High Speed Selective Jet Electrodeposition of Gold and Gold Alloys Using Single Circular Jets
High Speed Selective Jet Electrodeposition of Gold and Gold Alloys Using Single Circular Jets
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c C. Bocking
by
A Doctoral Thesis
Supervisor: Dr D. R. Gabe
Institute of Polymer and Materials Engineering
Loughborough University of Technology
m by C. Bocking 1994
ABSTRACT
High SpeedSelectiveJetElectrodeposition
(HSSJE)is a processin which metalsandalloysmay
be electrodeposited
at high ratesand in a selectivefashionwithout the needfor masking.Ile
jet of electrolyteat the surfaceto be
methodconsistsof directinga high velocitynon-submerged
platedandpassinga currentbetweenthe nozzleandthe substrate.Due to the natureof the flow
and the currentdistributioftwithin the jet, depositiontakesplaceat high ratesbut only in the
impingementand immediatelysurroundingregion. This techniquehas seenlittle commercial
withdeveloping
onlyasmallnumberofpapersonthesubject.7besewereconcerned
exploitationand
mathematicalmodelsfor the system.The purposeof this work was to examinethe structural,
produced
morphologicalandmetallurgicalcharacteristics
of bothgoldandgoldalloyelectrodeposits
undervariedconditionsofhighelectrolyteflow usingsmallgeometry(< Imm) nozzles.By relating
factorssuchaselectrolytevelocity, currentdensity,temperatureandmetalion concentrationetc
to the morphologyof the depositsproduced,an understanding
of the limiting conditionsfor
Resultsobtainedfrom depositsproducedby HSSJE
maximumdepositionrateswas ascertained.
As
those
to
made
under
conditions.
well as examiningthe
compared
more
conventional
were
deposits,attemptswere madeto gain informationon the electrochemicalfactors controlling
deposition.71ese factors, such as masstransfer characteristics,required the productionof
polarisationcurvesidentifyingthe limiting current densitiesof the systemunder study. Some
potentialapplicationsof the techniquearealsodiscussed.
ACKNOWLEDGEMENTS
The authorwould like to thankthe following peoplefor the invaluablecontributionto the work
carriedoutintheexperimental
phaseofthisTbesis.First,DrDavid Gabe,my AcademicSupervisor,
thatI undertakethis7"hesis
whooriginallysuggested
andwithoutwhom,it wouldneverhavebeen
Centre.Dr Brian Cameron,my GroupLeader
written. Also, my colleagues
at theHirst Research
and Mr Ian Christie, LaboratoryManagerof the MaterialsScienceLaboratoryas well as my
IndustrialSupervisor, for the freedomgiven to me in the pursuit of the aims of the BRITE
programmefrom whichthiswork wasderived.In addition,I wouldlike to thankDr BrianCameron
for carryingout the wear testingof connectorsin this study. Mr Alan Vale, for the chemical
analysisof theelectrolytesanddepositsproduced.Mr IanGunterfor thecomputercontrolprogram
that controlledthejet platingequipmentaswell asadviceandback-upon the electroniccontrol
systemsused.Mr Colin Dineen,who operatedthe X-Ray Diffraction equipmentand provided
enormousexpertisein the analysisand interpretationof the results.Mr David Prichardwho
producedsomeof the ScanningElectronMicrographsshownhere.Mr Chris Fisherfor themany
thatwe hadin trying to fathomthecomplexitiesof
varied,interestingandmostusefuldiscussions
the electrochemistry
of the system.
At Loughborough University my thanks go to Mr Frank Page, who produced some stunning and
prize winning Scanning Electron Micrographs of the more visually interesting deposits. Additionally, Dr Geoff Wilcox for the assistancehe provided concerningconventional electrochemical
procedures.
Finally, I would like to thank my wife Sueand children Laura and Lewis for their patienceduring
the writing of this Thesis.
inIndustrial
Theexperimental
workdescribedinthis thesiswastakenfrom aBRITE(BasicResearch
Technology)programmeNo. RI I B-304, "The improvementin the control andattainmentof high
processes".It was undertakenwith partnersCentro Svillupo Materiali,
speedelectrodeposition
Universityof Technology.Thework
GEC-MarconiHirst ResearchCentreandtheLoughborough
on HSSJEwascarriedout solelyat the Hirst ResearchCentreby the authorexceptwherestated
above.The other partnersworked on different aspectsof high speeddeposition.As such,the
its
For this reason,certainavenuesof
to
prior
commencement.
was
predetermined
programme
interestcouldnot be pursueddueto the needto obtaindefinitemilestoneswithin pre-determined
time periods.
11
Table of Contents
CHAPTER 1 INTRODUCTION
..........................................................
1.1 GENERAL BACKGROUND
.........................................................
1.2 SCOPE OF THIS STUDY
.............................................................
CHAPTER 2 GOLD ELECTRODEPOSITION
.......................................
2.1 GOLD PLATING IN THE ELECTRONICS INDUSTRY
.....................
2.2 ELECTROLYTE TYPES
.
.............................................................
2.2.1 Alkaline cyanideelectrolytes
.
...................................................
2.2.2 Acid gold electrolytes
.............................................................
2.2.2.1 Pure acid golds
..............................................................
2.2.2.2 Alloy acid golds
.............................................................
2.2.3 Structural characteristicsof gold deposits
.
.....................................
2.2.4 Ile influence of pulsed current on gold electrodeposition
. .................
CHAPTER 3 SELECTIVE PLATING TECHNIQUES
.............................
3.1 DIELECTRIC MASKING
00
...
................................................
00
......
3.1.1 Solvent based lacquers
..................................
o
.........................
3.1.2 Thick film inks
....................................................................
3.1.3 Photo-resists
........................................................................
3.1.3.1 Photoresistchemistry
.......................................................
3.1.3.1.1 Positive working resists
.............................................
3.1.3.1.2 Negative working resists
............................................
3.1.3.2 Outline of Printed Circuit Board Production Methods
..........
3.1.4 Pre-formed masks
...........................................
o
......................
3.1.5 Controlled depth immersion
......................................................
3.2 BRUSH PLATING
....................................................
$00
...............
3.3 ANODE PLACEMENT AND GEOMETRY
o
.................
.......
o
............
3.4 AUTOCATALYTIC (ELECTROLESS) DEPOSITION
........................
CHAPTER 4 HIGH SPEED ELECTRODEPOSITION PROCESSES
...........
4.1 THEORETICAL ASPECTS
..........................................................
4.1.1 Transport mechanismsand the diffusion layer
.
...............................
4.1.2 Realistic limiting current densities
.............................................
4.2 MEASUREMENT OF THE LIMITING CURRENT DENSITY
.............
4.2.1 Limiting current density measurementmethods
.
.............................
4.2.1.1 Galvanodynamicmethods
; .....................................
.
...........
4.2.1.2 Potentiodynamicmethods
.
................................................
4.2.1.3 Convective control methods
.
..............................................
4.3 PRODUCTION PROCESSES
........................................................
1
1
4
6
6
8
8
9
9
10
12
13
15
15
16
17
17
18
18
20
21
23
25
25
27
29
30
30
30
32
32
33
34
34
35
36
39
CHAPTER 5 ELECTROCRYSTALLISATION AND MORPHOLOGY
.......
5.1 SOME FUNDAMENTAL ASPECTSOF ELECTROCRYSTALLISATION
*... *0.........................
00*00
*.
0
...
.....
00*0
.....
9009*
*
0....
*00#0
0
.....
0
............
....
....
...
5.1.1 Electrocrystallisation at low current densities
.
...............................
5.1.2 Electrocrystallisation at high current densities
...............................
.
5.1.3 Mechanismsof surface irregularity amplification
...........................
.
5.1.4 Stability theories for roughnessdevelopment
.
.................................
5.1.5 Theories of needle, dendritic, densebranching morphology (DBM) and
fractal growth
. ..........................................................................
...
I
CHAPTER 6 HIGH SPEEDJET ELECTRODEPOSITION .......................
6.1 CHARACTERISTICS OF FLUID FLOW WITHIN JETS
....................
6.1.1 Flow within the freejet region
....................................................
6.1.2 Flow within the impingementregion
...........................................
6.1.3 Flow within the wall jet
..........................................................
.
6.2 MASS TRANSFER CHARACTERISTICS OF IMPINGING JETS
.........
lll
39
42
43
44
45
46
53
53
54
54
55
55
55
56
IV
106
107
107
108
109
ill
112
113
113
115
116
117
117
120
122
131
132
132
132
133
134
134
135
135
136
137
137
139
139
140
146
146
146
149
149
150
151
153
153
155
157
158
161
161
161
163
164
165
167
REFERENCES
...........................................................................................
PHOTOGRAPHS 1-39
.................................................................................
TABLES 1-27
............................................................................................
VI
169
174
198
NOMENCLATURE
Amps
Lattice parameter,A
a,.
C
&
CO
C
Cf
d
d'
D
Deff
Dvw
E
Hydrodynamic constantsec-I
io
JD
Diffusion flux,
k
KL
Litres
I
M
n
r
R
Re
Re,
Mol
CM-2sec-I
Vii
SC
Sh
Sh.
t
to
Transport number
t.
T
Cartesian coordinate
Cartesian coordinate
U.
Greekletters
Stackingfault probability,dimensionless
Twin fault probability,dimensionless
Symmetryfactor, oftentakenas0.5
a
P,
P
6
11
0
Overpotential,volts
Braggangle,degrees
1C
I-C
Specificconductivity
Kinematicviscosity,CM2sec-1
Viscosity, g cm-1sec
Density, g cm-1
Note: In the graphs presentedin this Thesis, the terms A/cm sq and kg/mm sq
in
limitations
is
due
This
the graphplotting software.The sq in
to
are used.
viii
CHAPTER 1
INTRODUCTION
is a processwherebymetalsare electrodeposited
Selectiveelectrodeposition
in discreteareas
of a substrate,preciselywherethat metalis requiredfor functionalor decorativepurposes.It is
widely practisedin boththe electronicsandengineeringindustries.Therearemanyreasonswhy
to alterthesurfacepropertiesof thesubstrate
a metalis depositedselectively.It maybe necessary
metal in a particularareain order to conferwear resistance,hardness,electricalconductivity,
in
somecases,to providea local form of corrosionresistance.In
and
solderabilityor weldability
materialssuchasgold, a considerable
costsavingcanbe achieved
addition,with certainexpensive
by platingthe minimumquantityof metaljust whereit is needed.
Examplesof selectivelyplatedmetals in the engineeringindustry can be seenin the re-building
of worn componentssuchas drive shafts,bearing surfaces,crankshaftsand piston sleeves.As part
of a manufacturing process, bearings are usually plated with the bearing material on the wear
surface only. Chromium is often plated selectively onto piston sleevesto confer wear resistance.
The electronics industry makesgreat use of selectiveplating. The printed circuit board (PCB)
industry usesselectively plated metals to act as etch resists. Thesemetals are plated onto regions
where tracks etc are required so that when the rest of the copper clad board is etched away, the
tracks remain. Electrical connectorsare usually plated with a gold alloy to confer wear resistance
and low electrical resistance.In order to minimise costs, only the region where contact is made is
plated with the gold. Another example is where componentsthat cannot easily be soldered are
given a tin or tin alloy coating to confer solderability. To minimise the spread of solder, these
componentsare plated selectively.
Many techniquesare available to produce selectiveelectrodepositionand theseare detailed in
subsequentChapters.However, aswith any process,they havetheir advantagesand disadvantages.
Most require the use of some form of dielectric mask to provide the edge definition which can
lead to cost penalties. Those that do not use masking are generally of poor definition but tend to
be lower cost processescomparedwith masking systems.Therefore there is a trade-off. Recently,
in
developed
has
been
that
technique
offers
overcoming the limitations of existing
some
promise
a
processes.This method will be referred to as High SpeedSelectiveJet Electrodeposition.
ZONE I
Free
ZONE II
ZONE III
Impingement
Wall jet
jet
zone
-NOZZLE
JET
III
II
SUBSTRATE
HYDRAULIC JUMP
Figure
Region I is the free jet region where flow continues in a similar fashion to that within the tube
is
known
II
Region
the
as the stagnation region. Close to the point of impingement, the
nozzle.
of
flow changes speed and direction from that of the free jet to that of region III, which is known as
the wall jet (after Glauert3. ). Finally, there occurs what is known as the hydraulic jump where the
flow
description
jet
increases
Further
the
thickness
and
changes.
momentum
of the flow will
wall
be given in Chapter 6.
is the metal ion. The maximum current density obtainableis therefore controlled by the situation
where the concentrationof metal ions at the surfaceapproacheszero. In other words, as soon as
a metal ion reachesthe surface, it is discharged.This situation is known as the limiting current
density, 'L. The limiting current density is given by;
nFDcb
(1)
= b(1-t')
It can be seenthat the thicknessof the diffusion layer 6 has a strong influence on the limiting
layer
is,
Migration
higher
limiting
density.
The
this
the
the
thinner
under the
current.
current
is
by
its
influence
dependent
for
(1
The
is
field
t').
on the total
magnitude
of
accounted
electric
ie
If
is
indifferent
there
a supporting
carriers,
an
charge
excess
of
carriers.
number of charge
insignificant.
be
Electrolyte agitation reducesthe thickness of the
term
then
this
will
electrolyte,
diffusion layer, the strongerthe agitation, the thinner the layer andthe higher the maximum current
density will be. By using a high electrolyte jetting rate, the interfacial agitation will be high and
the diffusion layer thicknesswill be low. It is very difficult to measurethe thicknessof the diffusion
layer directly but it can be measuredindirectly by meansof either a masstransfer coefficient, KLq
defined as
Kj
(2)
nFc
Sh,
dimensionless
Sherwood
the
by
the
masstransfer coefficient;
number,
or
Sh - KcD
(3)
In the electrodeposition
of metals,the limiting current densitycannotusually be achieved
form
is
deterioration
This
deteriorating
before
deposit
takes
the
this
the
reached.
quality
without
been
deterioration
has
S.
It
that
this
dendritic,
reported4.5.6.7.
or
powdery
growth.
nodular
of
for
0.9
'/'L
between
0.4
manyof the commonplatingelectrolytes.
of
and
at a ratio of
commences
However,little is knownaboutthe effectsof very high electrolytevelocitieson the ratio of "'L or
the metallurgicalstructureof depositsproducedundertheseconditions.
to this process. Chapter 2 details gold electrodeposition,the electrolytes used and the electrochemistry of the process. Chapter 3 examinesthe current methodsof selectiveelectrodeposition.
Chapter 4 deals with the mass transport mechanismsas applicable to high speed deposition
processes.Chapter 5 looks at electrocrystallisationand morphology and how the structure of the
deposit is related to the deposition conditions. Chapter 6 revues the current knowledge of jet
deposition theory and examinesthe characteristicsof fluid flow within jets. Chapters 7 onward
describe the experimentalresearchwork carried out for this thesis.
A number of papershavealready beenpublishedon work connectedwith this Thesis and these
have been addedas an Addendum.
CHAPTER 2
GOLD ELECTRODEPOSITION
The unique properties of gold are highly desirable in many spheresof life. Its chemical and
aesthetic properties have meant that gold has acquired a special position in society. The most
famous of theseare a function of the surface- its colour as well as its resistanceto corrosion and
tarnishing. In many respects,thin layers depositedonto basemetalscan function in the sameway
as if the whole article was madeof gold. Applying gold onto basemetalshas its roots in antiquity,
with gold leaf being applied ornamentally as far back as Egyptian times. In the 18th and 19th
deposited
items
by the application of a gold/mercury amalgam,the
onto
gold
was
metal
centuries,
mercury subsequentlybeing evaporatedoff. However, it did not escapethe attention of those
involved that the life of a gilder was not a long one as mercury poisoning took its toll. The first
in
V.
1802
by
Luigi
Brugnatelli,9.a colleagueof Allisandro
the
of
gold
was
of
electroplating
record
Volta. His work was not widely publicisedthough. Volta was invited with Brugnatelli to the French
Academyof Sciencesto discusstheir work. Unfortunately, whenVolta introducedhim to Napoleon,
the Academy President, as "the great Italian chemist, Brugnatelli", Napoleon insulted him by
Pavia
Italian
With
Brugnatelli
"there
10.
to
this,
chemists".
andpublished
returned
great
are
no
saying
his work there, which was not widely seen.It was not until 1840that Henry and George Richard
Elkington patented"- the forerunner of the modem gold electroplating solution, based on gold
potassiumcyanide. From 1845the processwas commercially available and was popular up to the
d'art
In
Russia
During
Victorian
this
time,
the
were
gold
plated.
grand
objets
period.
many
of
end
bases
large
For
the
a
very
out
on
and capitals of the
scale.
example,
carried
was
gold plating
interior columns of St Isaac's cathedral in St Petersburgwere gold plated, using 280 kg of gold.
However, becauseof a poor understandingof the chemistry of the process, successdependingon
"black book" recipes known only to a few, it fell into disrepute. Thereafter, gold plating was
largely relegated to the production of inexpensivenovelties or trinkets until its re-emergenceas
in
industry
1940's.
the
the
early
electronics
of
part
of 18,097 kg. For the sameyear, the world electronics consumptionof gold was 142,800 kg. 13.
This would indicate that approximately 110,000kg was electroplatedwith a value of just over $1.3
billion.
Within the electronics industry, the two major scale applications of gold are for electrical
connectors and printed circuit boards. It is estimatedthat in 1990,6,869 kg was plated onto
kg
deposited
2,440
was
onto printed circuit boards in Europe. The satisfactory
connectorswhilst
performanceof a connectoris crucial to the overall performanceof anypieceof electrical equipment.
It has to have a low contactresistance,as well as good corrosion and wear resistance.This latter
property is necessarybecauseconnectorsare frequently mated and un-matedduring the courseof
the equipment lifetime. Many specificationsrequire a connectorto remain functional through up
to 500 insertion/withdrawal cycles. In order to achieve this wear resistance, small quantities
(approximately 0.1 - 1.0 % by weight) of a transition group metal, such as nickel or cobalt, are
increases
This
the hardnessfrom about 80 Hv (Vickers Pyramidal
the
gold.
co-depositedwith
Hardness)for pure gold up to about 150 Hv with very little increasein the contact resistance.
Printed circuit boards (PCB's) are plated with gold in order to suppresscorrosion of the
improve
to
solderability. Many boardsstill usegold plated edgeconnectors.
underlying copperand
Theseare areasat one end of the board that act as connectingpadsthat can be mated with external
connectors. They are plated with the gold alloy to confer wear resistance.With the advent of
for
has
been
the
to
the production
use
systems,
gold
preferred
metal
communications
microwave
for
boards
high
frequency
needed
applications.The glassreinforced plastic
the
circuit
specialised
of
that is used for conventionalPCB's hasbeen replacedby either sintered alumina, quartz or PTFE
based materials for these applications. These are metallised using sputtering techniquesand the
tracks are built up using a combinationof photolithography and electroplatedgold. The remaining
metallisation is then removed.
4-12 g 1-'
Potassiumorthophosphate
Potassiumcarbonate
30 g 1-'
pH
Temperature
> 12
50 - 65 oC
Current density
1 -8 mA cm-2
30 g 1-'
30 g 1-1
The free cyanide is usually maintained at above 15 g 1-1.Due to their alkaline nature, these
in
been
have
the electronics industry particularly in the gold plating of
used
rarely
electrolytes
PCB's. As a result of the increasedrequirement for such applications during the 1950's, acid to
developed.
based
gold
on
potassium
cyanide
were
electrolytes
neutral
8.0 g 1-'
Au as KAu(CN)2
Citric acid
Ammonium citrate
40 g 1-'
40 g 1-'
EDTA
1-2g1-'
pH
Temperature
3.0-6.0
25-30oC
Current density
5- 10 mA cm-2
With the developmentof transistorsand integratedcircuits the needfor gold plating the device
for
barrel
The
the
electrolytes
were
suitable
acid
not
very
plating applications that
grew.
packages
these devices required and thus neutral electrolytes were developed. The acid electrolytes were
subject to metallic contamination and were able to co-deposit the contaminants. Nobel and
Thomson". demonstratedthe superiority of neutral electrolytes in a study of the barrel plating of
transistor headers. Subsequently,numerousproprietary formulations were developed, based on
mixtures of phosphatesand citrates, phosphateonly and pyrophosphates.To reducethe danger of
derivatives
Many
acid
such
organic
phosphonic
were
used.
agents
as
complexing
co-deposition,
of theseelectrolytesusedvarious addition agentssuchasorganic thio compoundsaswell astrivalent
arsenic to act as grain refiners and brighteners. Due to the wide variety of formulations for neutral
electrolytes, there is no "typical" formulation and the reader is referred to the literature for ftirther
information. 16-17.18.
In the early 1970's, it was discoveredthat the additive free acid and neutral baths worked quite
well when freshly made up but on use and with ageing, the deposit quality deteriorated, giving
rise to brownish deposits. Reinheimer'9-was one of the first to discover that the reasonfor this
was that freshly made electrolytes often containedsmall quantities of lead as a contaminant. As
the bath was used, so the lead was removed by co-deposition. It was only when more lead was
addedthat the quality of the depositwas returned. The addition of lead at a level of about 0.5 ppm
was patentedby him. At about the same time, it was found that thalliurn and arsenic were also
carried out a study on the depolarising effect of heavy
effective brighteners. McIntyre and Peck2Ometal ions including arsenic, lead, thallium bismuth and mercury. They demonstratedthat lead
and thallium depolarisedthe gold electrode. The proposedmechanismwas of adsorption of the
trace metal followed by an electrochemicaldisplacementreaction betweenthe adsorbedmetal and
Au(CN), This displacementwasthoughtto modify the crystallisationof gold allowing well formed
-.
fine crystals with a strong preferred orientation. This resulted in a bright appearance.However,
they discovered no depolarisationeffects with arsenic. Eisenman2l.examinedthe kinetics of the
reduction of dicyanaurateboth with and without lead. He explainedthat the effect of lead was to
lower the activation energy of the electrontransfer which gaverise to the acceleratedestablishment
of a preferred orientation. Rao andWeil22-and more recently Dinan and Cheh:73-studiedthe effects
Rao
to
electrolytes.
gold
and Weil thought that arsenicadsorbedonto the gold
additions
of arsenic
and acted as nucleation sitesbut at the sametime inhibited the lateral growth of the gold crystals.
As a consequence,the grain size was considerably reduced and this was responsible for the
brightening effect. Dinan and Cheh examinedthe effect of arsenicon the hardnessof gold. They
led
to an increase of hardness and that this was due to the
that
additions
arsenic
concluded
incorporation of the trace metal in the deposit.
One disadvantageof using these trace metals as brightening agents has been due to their
incorporation into the deposit and their subsequentinfluence on the performance of the gold. It
both
been
the thermocompressionand ultrasonic bondability was reduced in
that
shown24-25was
the presence of such incorporated additives, particularly when the gold was deposited at high
current densities. These workers concluded that low additive concentrations and low current
densities should be used for such applications.
2.2.2.2 Alloy acid golds
independently
discoveredtheacidstability
At thesametimeasEhrhardt'sdisclosure,Rinker26introducing
He
found
by
dicyanaurate.
that
also
suitablycomplexedbasemetals,the
of potassium
10
Au as KAu(CN)Z
Citric acid
4.0 g 1-'
120 g 1-'
Tetraethylenepentamine
Nickel (as nickel citrate)
20 g 1-'
2.5 g 1-'
pH
Temperature
4.0
Current density
20 mA cm-2
40 C
The most widely usedand studiedhard gold is one that usescobalt as an additive. In this case,
the bath formulations are similar to the abovebut the cobalt is addedasthe EDTA complex. There
have beenmany studiescarried out on the mechanismof hardeningand wear resistanceproperties
of this electrolyte. The addition of cobalt has been shown to increasethe hardnessfrom a value
200
kg
hardness
increase
It
150
kg
brought
80
100
to
thought
that
the
mm-2.
was
was
nun-1
of
in
Lo
by
the
reduction
grain
size.
et aP7. concluded that the hardnesswas a
a
significant
about
in
from
2
down
the
to 20 -30 nm. Eisenmann,21.in his
the
grain
size
about
of
reduction
itm
result
study of the kinetics of the reduction of gold concluded that the cobalt increasedthe activation
energy of the electron transfer reaction and gave rise to a high nucleation rate leading to a small
crystallite size. However, a high hardnessalone doesnot accountfor the good wear resistanceof
the cobalt and nickel hardened golds. Koch et aln. developed an additive free hard gold that
deposits.
itwas
However,
to
these
shownthatthe slidingwear resistance
similarhardness
exhibiteda
of the additive free depositswas not as good as thosecontaining cobalt in the absenceof a suitable
lubricant. Munier29-found an organic material co-depositedwith the cobalt gold and described it
as a "polymer". It was thought for sometime that this was responsiblefor both the increasedwear
increased
deposits
the
these
contactresistanceassociatedwith them.
as
well
as
slightly
of
resistance
11
However, there were many studies carried out subsequently and in one of them, 30.it was concluded
that the "polymer" discovered by Munier was in fact cobalt II hexacyanocobaltate III,
C03[Co(CN)J2. xH20. By using extraction with mercury instead of aqua regia as Munier had, it
was found that potassium cobalticyanide, K3Co(CN)6 was co-deposited. Of this, only 25 % of the
cobalt was in this state, the rest being in the form of metallic cobalt. In addition, only 21 % of the
carbon and 41 % of the potassium could be attributed to the K3CO(CN)6. The rest was later found
to be from incorporated AuCN. Later studies by Antler3l. showed that in addition to high hardness,
good wear resistance required a low ductility. Another study by DeDoncker et aP2. showed that
good wear resistance could only be obtained if the deposit contained at least 0.08 wt% of the cobalt
complex together with between 0.06 - 0.2 wt% of metallic cobalt. If the complexed cobalt was
below this value, then the wear resistance was poor. High levels of cobalt in the electrolyte tended
to suppress the co-deposition of the complex leading to high metallic cobalt contents. This resulted
in abrasive wear characteristics.
The useof cobalt asan additive hasa major disadvantagewhenusedfor high speeddeposition.33.
The CoII is readily oxidised to the inert CoHI complex, Co(CN)63-at the anode. However, nickel
does not suffer from this problem.
There are many reviews of gold electrodeposition technology in the literature and further
information can be obtained from them. 10.33.34.
12
The changesin the preferred orientation were reflected in the changeof morphology. The deposits
with a preferred (111) orientation exhibited a plate-like structure whilst those with the (220) and
(311) orientations showedwhat was describedas a "shell-like" morphology.
Wakabayashi25
reported that the presenceof lead or thallium favoured the growth of the (311)
planeswhilst the addition of arsenicleadsto a (111) preferred orientation. They also reportedthat
in the absenceof additives, the (111) plane was predominant.
DeBonteet a138.describedthe influence of current density on the structure of both the additive
free hard gold and a cobalt hardenedgold. In the caseof the additive free hard gold, low current
densities favoured a mixed (200) and (311) texture, the deposits having what they term as a
polyhedrical morphology. With increasingcurrent density, a (I 11) texture becamepredominant,
associatedwith a fine grained structure. With increasing current density, the deposits adopteda
mixed (200) and (211) texture which showedas a lenticular or plate-like morphology. Before the
onset of burning, a slightly nodular structure was observedthat exhibited a (200) texture. In the
caseof the cobalt hardenedgold, the structure at low current densitieswas a mixed (220) and (311)
texture. With increasing current density, this becamea (I 11) preferred orientation.
Antler39- reported a (311) major preferred orientation for a pure acid gold using XRD. In
addition, he reporteda (111) preferred orientation for a nickel hardenedalloy gold. The electrolyte
nickel content was 0.15 %. However, for cobalt hardenedgold, he reportedan un-oriented deposit.
13
It hasbeenpointed out42.that using very high peakcurrent densitiescan leadto grain refinement
and thus greater deposition rates than under DC conditions. However the rate can never exceed
the DC limiting current density. Therefore, whilst peak current densities can approachthe peak
limiting current densities with no degradationof deposit quality, the average limiting current
density cannot be surpassedwithout deposit deterioration. This meansthat for such high peak
current densities,there has to be an appropriateoff-time to allow recovery of the metal ions in the
diffusion layer so that the averagelimiting current density is not exceeded. One advantageof
using high peak current densitiesis that a thin, pulsating diffusion layer is produced adjacentto
the substrate.If this layer is small comparedto surface irregularities, then both the peaks and the
troughs of the irregularity are equally accessibleto diffusion. Sucha situation reducesthe tendency
of peaksto be magnified by excessivegrowth as would be the caseunder DC conditions where a
thicker diffusion layer inevitably forms. This will be discussedfurther in Chapter 5. As a consequence,by using very short, high peak current pulses, such a tertiary distribution is achievedand
the micro-distribution of the deposit is improved. Such an improvement in the microthrowing
power has beenshown by Andricacoset a143.using a citrate gold electrolyte. They depositedgold
onto a rotating disc electrodewith a small groove on it. They found that the microthrowing power
was significantly better using pulsed current of short duration than under DC conditions. The most
important criteria for such a current regime to be successfulis that the peak current density must
be such that deposition occurs under diffusion control. Another important condition for adequate
tertiary current distribution is that the mass transport rate should not vary across the electrode
surface. Such a condition is rarely achievedunder DC conditions but can easily be achievedwith
pulse plating.
One disadvantageof relying on tertiary current distribution to smooth deposits lies in their
susceptibility to hydrodynamic effects. If the pulsating difftision layer is disturbed by turbulent
flow conditions, the microthrowing power may be affected due to an uneven accessibility to
diffusion occurring.
As was mentioned previously, the use of very high peak current densities does require long
that the off-time can significantly influence the quality
off-times. It has been shown by PUippe42.
of the deposit. Working at average current densitieswell below the limiting current density, he
found that increasingthe off-time during pulsedgold depositionfrom a citrate bath led to an increase
in the grain size. He used a peak pulse current density of 100 mA Cm-2.With an off-time of 9
deposit
Increasing
ledtoanincreasein
the off time to 99 mswas
obtained.
smooth
a
IM,
surface texturing. He claimed that this was due to grain growth during the off-time.
14
CHAPTER 3
1. Dielectric masking
2. Brush plating
3. Jet or gelled electrolyte plating
4. Anode placementand geometry
5. Electrolessplating
Each of these categorieswill be discussedin greater depth, with the emphasison currently
used methods. Jet plating will be covered in Chapter 6 and will not be discussedhere. Gelled
electrolyte plating consists of placing a gelled electrolyte onto the surface to be plated where
deposition is required. It is a rarely used techniqueand will not be discussedfurther.
15
16
3.1.3 Photo-resists
Photoresistsare organic materials that can be applied to surfacesby a variety of methods to
form a chemically resistant,polymeric layer. They haveunique properties in that after application,
the chemical resistanceof the layers may be modified by ultra-violet light. By the use of light
blocking masks, the chemical activity of the areasexposedto the UN. radiation can be altered.
Photoresistsmay be classified into two main groups, namely positive and negative working. The
forms
hard
layer.
When this is exposed
when
applied,
a
chemically
resistant
resist,
working
positive
to UV light, the polymer becomessoluble in the chemicalsused for developing solutions. In the
UV
light,
forming
to
occurs
when
exposed
polymerisation
resists,
a more
of
negative
case
in
layer.
Photoresists
PCB
industries
the
are
and
used
mainly
microelectronics
resistant
chemically
boards
flat
the
and silicon wafers respectivelyare suited to the application
of
circuit
the
geometry
as
methods.
17
Photoresistsmay be further classified into two sub-divisionsbasedon the methodsof application. Liquid photoresists,as the namesuggests,are suppliedwith the photo-polymer dissolved
in an organic solvent. They are applied to the substratesby meansof spraying, dipping, roller
coating or spinning. After application, they are cured in an oven to remove the solvent and harden
the film. The dried film thicknesshas to be low (2.5 to 8.0 Jim) for adequatepenetration of the
UV light. Negative working liquid resistsare usually developedin chlorinated solvents. The main
disadvantagesof thesetypes of resist include their sensitivity to pin-holes in the mask that is used.
This can lead to spots of resist remaining on areasrequiring plating leading to broken tracks. In
addition, theseresiststend to plug the through holes in the board and are difficult to develop and
is
Controlling
the
thickness
resist
anotherproblem with the liquid resists.Positive working
remove.
liquid resists overcome the difficulties mentioned above with the exception of the control of the
film thickness.
The secondsub-division is the dry-film resist. Dry film resistsconsistof a thick (17 to 75 jim)
photo-polymer layer sandwichedbetweenMylar andpolyolefin films. Thesefilms allow the resists
to be wound into rolls in lengthsof up to 300 metreswithout the photo-polymer sticking to itself.
It is applied to the copper clad board by a hot roller process,the polyolefin film being removed
The
Mylar
film remainsin contactwith the resistup to the developing
to
rolling.
prior
automatically
from
damage.
developed
in
These
be
the
photo-polymer
resists
can
a number of
preventing
stage,
for
designed
Some
solvent stripping whilst others use aqueousor mixtures of aqueous
are
ways.
and solvent developers.The advantagesof the dry film resist include its relative easeof processing
liquid
from
"mushrooming"
being
they
than
the
the
thicker
resists,
prevent
subsequent
plating
and
over the resist layer.
18
be removedwith a suitable solvent or developer.Typical of the more modem liquid positive resist
systemsare basedon the photochemistry of diazonaphthoquinonesulphonateesters (NDS) in a
cresol-formaldehydecondensationpolymer binder (novolac). With exposureto near UV radiation
(360-440 rim), the NDS forms a keteneintermediatewhich reactswith residual water in the film
to form an indene carboxylic acid with the elimination of nitrogen. However, in the absenceof
water in the film, the ketenereactswith the phenolic -OH groups on the novolac to form pendant
ester linkages. As the resist is formulated with sufficient water in the film, the former reaction is
the most prevalent.
11
11
S_
Ht0
R
R'OH
i`
13
11
+N,
R=
R' = novolac
or
aryl
group
resin
19
__b
_o
bi
C=O
CH
CH
/
CH
\CH/
CH\
CH
Q
Q
---------------------"
Polyv. nyl cinnaMate
Cross
chains
(inked
duner
20
\
R-N, -+
azide
N-H
I
-C-
R-N,
nitrene
Insertion
R-N,
R
jH
C=C/
-c-
Addition
Abstraction
R-R-H+
C=c
c-
/\
Figure 4. The chen-Lical
reactionsinvolved in the photo-crosslinkingof cyclisized polyisoprene
using a bis(azide)photoactivecompound.
Photoinitiatedpolymerisationworks by the inclusionof a photoactivecompoundin a monomer
base. Irradiation of the photoactive compound creates free radicals that can polymerise the
monomer. A typical exampleof this is the polymerisationof vinyl monomersusing alkyl ethers
of benzoin. The radiation cleavesthe C-C a bond of the benzoinether creating the free radicals
that lead to the polymerisationof the monomer.
21
The additive processis further sub divided into three different classes,print, plate and etch,
panel plating and patternplating. Print, plate and etch consistsof defining the tracks etc by means
of a positive image mask and a negativephotoresist.The unexposedresist is removed in the
developmentleaving the copper exposedin the track regions. After suitablecleaning, the copper
is plated with a appropriatemetal etch resist such as tin, tin-lead, nickel or gold. After plating,
the resist is removedand the unwantedcopper is etchedaway leaving the tracks.
If double sided boards with plated through hole connectionsare required the panel plating
methodmay be usedin conjunctionwith print, plate and etch. Through-hole-platingis a technique
used where high componentdensitiesare required. This allows interconnectionsbetweeneither
side of the board, avoiding track cross-over. It consistsof drilling the appropriateholes in the
copper clad boardsprior to processing.In order to plate the non-conductingholes, it is necessary
to sensitisethe them by producing an adsorbedlayer of palladium on the hole walls. The board is
placedin an electrolesscoppersolutionandthe palladiumactsasa catalystto initiate the deposition
hole.
A
thicknessof between2 to 5 pin is appliedandthis is followed
the
the
of
walls
copper
onto
of
by electroplatedcopper to producea plating thicknessof 25tLmwithin the hole. This may require
a copperthicknessof up to 40jurn on the coppercladding. The print, plate and etchplating method
define
is
described
to
then
the features.However, this methodof panel followed by
used
above
as
has
significant disadvantages.Circuit featureslessthan0.4 mm cannot
plating
etch
print, plate and
be producedwith this technique.This is becauseof the total thicknessof unwantedcopper to be
etchedis very high andthis leadsto undercuttingof thetracksbeneaththe etchresist. This reduction
can be as much as 0.2 nun and slivers of etch resist metal can break away leading to subsequent
is
Where
tin
solder
used as the etch resist, this problem can be eliminated by
or
short circuits.
fusing with hot oil or infra-red heating.
The pattern plating process is the most widely used manufacturing process to produce
plated-through-holePCB's. It is suitable for fine feature geometriesas there is less undercut
involved. The manufacturingroute is the sameas that for panelplating up to the applicationof the
is
However,
the
the
after
electroless
copper,
photoresist
appliedand the image
copper.
electroless
produced as in the print, plate and etch method. Copper is then electroplatedonto the exposed
by
followed
After
holes,
into
the
the removal of the resist, the
the
etch
resist
metal.
and
areas
unwantedcopperis etchedaway.With this method,thereis muchlesscopperto etchandtherefore,
less undercutting occurs to the tracks. Dry film resistsare very applicableto this route as their
thicknessis of the sameorder as that of the plated copperand etch resist combined.
The masksused for the production of PCBs are critical to the final product. These can be
final
For
in
the
size may be drawn directly
prototyping,
a
mask
of
of
ways.
generated a number
onto a Mylar sheet but with obvious limitations to accuracyand tolerances. The artwork for
large
layouts
is
scale
produced
manually
using
with masterto final size
often
production purposes
22
23
its plating speedwaslimited by poor anodepositioning andtheuseof relatively low current densities
of between 50 and 100 rnA cnr2 were used. The processdid have the advantageof allowing the
plating of pre-punchedstrip lead frames. Mask spot plating was achievedby using a wheel mask
constructed from G10 fibreglass with appropriate holes for delineating the deposit. This had
problems with speedand registrationbut showedthe principle of operationvery well. Strip speeds
for the various processeswere describedand speedsrange from 2m min-I for intermittent wheel
spot platers up to 12m,min-'. for continuouslead frames, both receiving 50 u in. of gold.
At the sametime, Texas InstrumentS49.
reported the use of a spot plater for plating nickel and
gold onto continuouscontactstrip. A Teflon mask incorporating a platinised tantalum meshanode
was used. No mention was made on whether the mask was stationary or moving or of the strip
speedused.
Menziesm.describedreel-to-reelplating in 1978.The two techniquesmentionedwere controlled
depth immersion and stripe plating, similar to that describedpreviously. At the sametime, Rehrig5l.
described a step and repeat spot plating unit for the plating of lead frame bond pads in which the
in
The
that
closed
a
clarnshell
a
mask
opened
and
manner.
mask
out
using
carried
was
spot plating
was constructedfrom silicone rubber.
Theseincludedcontrolleddepthimmersion,
Hainet02- reviewedselectiveplatingtechniques.
fixed masksandmovingmasksaswell whatwastermedasfluid flow masking.This wasa method
limitations
They
HSSJE.
the
commented
on
various
advantages
and
to
of themethods,
equivalent
distortion
due
fixed
to
can
create
of
and
slow
problems
strip
speeds
that
systems
mask
noting
friction betweenthe maskandthe strip.
In 1982, Turner53-describedthe latesttechniquesfor the selectiveplating of connectorswith gold.
He describedhow high agitation rates and high metal ion concentrationsenabledhigh processing
in
densities
in
bath
250
He
Current
be
the
the
to
region
of
gold
were
mA
Crrr2.
achieved.
speeds
dielectric
flow
Oetting
fluid
in
that
of
masking
masking
and
air) was the
combination
a
claimed
for
high
Details
how
this was obtained
technique
speed
continuous
strip
plating.
of
successful
most
in
this reference.
given
were not
A more recent review of the selectiveplating of precious metals for connectorshas been given
by Wingenfeld. 54.He statedthat the moving masksystemin conjunctionwithjetting of the electrolyte
is the most widely used selectiveplating system. A wide range of configurations are describedfor
many connector configurations.
24
25
certain applications. The anodeis wrappedwith cotton batting of a long fibre variety. To reduce'
wear on the batting, it is sleevedwith surgical tubing made from Dacron. Polypropylene wool is
sometimesused as an alternative.
The tampon or stylus as it is generally called, is dipped into the plating electrolyte and rubbed
in
frequent
be
to
the
a
circular
motion,
with
replenishmentsof electrolyte.
plated
surface
across
For cylindrical shapeditems, thesemay be attachedto a slowly rotating lathe or turning head and
the stylus held in steadycontactwith the work-piece. In theseapplications, the electrolyte may be
fed directly to the stylus by means of a small pump. In this way, the process can be made
semi-automatic.
Control of the thicknessis basedon precise amp-minute meters. Due to the varying current,
distance
in
from
the
the
depends
the
the cathode
of
anode
the
stylus,
of
electrolyte
volume
on
which
is
It
is
usual to apply a voltage within a range specific
recommended.
not
the
ammeters
use of
etc,
to the electrolyte and monitor the current/time integral.
There are many advantagesclaimed for the brush plating technique. Refractory metals and
difficult to plate metals such as aluminium,are easily plated with this method. It is claiMed56.that
the adhesion is superior to conventional methods although the mechanismby which this occurs
has not been made apparent. It is also claimed that the hydrogen embrittlement of high tensile
deposition
brush
In
high
by
the
is
the
plating.
of
of
particular,
cadmium
use
onto
eliminated
steels
de-embrittlement
heat
is
This
does
treatment.
a
subsequent
require
confirmed
not
strength steels
by the fact that U. S. Air Forcehasapprovedtheprocesswithoutthe de-embrittlementheattreatment.
lists a very wide range of applications for the brush plating process. These
Rubenstein56.58.
flexible
deposit
through
to
from
that can
waveguides,
components
with
any
engine
aircraft
range
be conventionally deposited.Someof the more commonusesare in the repair of damagedor wom
by
brush
built
be
These
with
up
an
electrodeposit
means
of
plating and then
can
components.
be
Plating
instances,
high.
For
this
In
may
not
even
necessary.
rates
are
very
many
re-ground.
1.7
be
deposited
2.5
deposits
to
to
sec-1.
can
up
whilst
silver
at
Am
at
up
gold
Am sec-1.
example,
Deposit quality is very good becausethe high current densitiesemployed produce deposits with
a very fine grain size.
Selectivityis achievedbecause
only thoseareasthatcomeinto contactwith the electrolyteare
large
Components
fit
into
too
that
to
has
This
are
advantages.
conventionalplating
many
plated.
in
functional
For
the
be
areas.
enginecomponents,the entireengine
tankscan selectivelyplated
down
If
that
the
be
to
wom
region
needs
expose
re-plating.
an area
to
stripped
may not need
26
be
Because
is
there
masking
conventional
methods
can
cut
off,
applied.
a
sharp
no
requires
immersion in the electrolyte, theseconventionalmaskingsystemsremain in placemuch better than
if immersed.
Wingenfeld54.recently reported the use of the brush technique for the selective plating of
He
described
kinds
brush,
brush
two
the
of
moving
and the
connectors.
electrical
reel
continuous
in
brush58The
brush.
wrapped
consists
of
a
cylinder,
an absorbentmaterial,
moving
stationary
is
from
is
The
into
dipped
titanium,
the
cylinder,
which
made
platinised
used
electrolyte.
partially
as the anode. This slowly rotatesand the connector strip passesalong the cylinder with only the
is
it.
In
Plating
in
this
selective
plating
achieved.
with
rates of
way,
contact
area requiring plating
is
becoming
less
This
be
technique
this
6
with
method.
popular
achieved
can
up to gm/min. of gold
degree
become
the
the
contact
reduces,
required
and
area
of
of selectivity
smaller
as connectorsizes
brush.
brush
been
by
The
is
has
It
59.
be
the
longer
stationary
replaced
aV shaped
achieved.
can no
hollow platinised titanium block covered with an absorbentmaterial. The angle of the V is such
is
0.8mm.
The
into
low
has
electrolyte
of
about
pumped
at
area
pressure
the
a
contact
that
point
by
become
holes
the electrolyte by capillary
the
to
A
block.
wetted
material
allows
the
series of
block
V
the
the
they
touch,
then
The
of
and
where
along
passed
electrolyte
are
components
action.
is
block
but
The
constant
mounted onto an adjustmentplatform
rate.
slow
gently oozes out at a
block
be
By
block,
larger
tilting
tilt
to
the
the
the
of
set.
areas
angle
of
the
and
that allows
position
between
5-6
this
Plating
be
are
obtained
with
method.
of
rates
lim/min.
plated.
may
In general, the brushplating methodhasmany advantagescomparedwith conventionalmasking
deposition
be
in
deposition
High
can
are
obtainable,
carried
out
situ and many
rates
methods.
difficult to plate metals present few problems with adhesion. However, there are a few disadis
in
the
The
the
very
good
especially
process
not
absenceof additional
of
selectivity
vantages.
is
dependent
the
The
the
of
operator, exceptwhere automation
on
skill
operation
methods.
masking
is used.
27
28
3.4 AUTOCATALYTIC
(ELECTROLESS) DEPOSITION
29
CHAPTER 4
30
The region over which this directional diffusion occurs is known as the diffusion layer. The
thicknessof the diffusion layer is very dependenton the prevailing hydrodynamicconditions within
the bulk of the electrolyte, the convection.In unstirred solutions,the diffusion layer thicknesscan
flow,
it
high
0.05
conditions
of
electrolyte
can be as low as 0.002 cm.
under
cm whereas
reach
The diffusion flux J,) is relatedto the current density. It can be found using Ficks law of diffusion
is
ignored
if
migration
and
dc
dx)
nfJDs-D
(4)
: 'o
(Cs-co)
i
JD_-D
6
nF6
(5)
-i-
nFL(cb - co)
5
(6)
If the current density is raisedsufficiently, diffusion will not be able to re-supply the ions and
This
drop
limit
interface
density
to
the
represents
the
will
zero.
of
current
at
the concentration
hydrodynamic
be
conditions.
of
set
any
under
that can applied
nFDcn
t =b
dependent
is
be
from
temperature
diffusion
as
can
seen
Also, the
coefficient
31
(7)
D'_
T
constant
(8)
It can be seenfrom equation(7) that the magnitudeof the limiting current density is controlled
by the thicknessof the diffusion layer, the concentrationof metal ions and becausethe diffusion
by
(8),
The
difftision
is
the
temperature.
thinner
temperature
the
to
equation
related
coefficient
layer and the greaterthe metal ion concentration,the higher the value of 'L. There is a certain limit
to the metal ion concentrationthat can be used. This is dictated by the solubility of that particular
ion. However, the thicknessof the diffusion layer is dependenton the degreeof agitation of the
bulk electrolyte.
It follows that for high speedelectrodeposition,high metal ion concentrationsin conjunction
be
high
temperatures
high
used.
should
and
of
agitation
rates
with
is
deterioration
high
This
itself.
to
the
density
value,
certainly
related
with
exchange
current
"'L*
degradation
lower
It
logical
density
that
at
a
ratio
of
would
exhibiting
seem
systems
current
if the diffusion layer thickness could be reduced without affecting the critical ratio of '/'L then
higher deposition rates could be obtained from any particular electrolyte.
CURRENT DENSITY
32
Measurement
of 'L for any electrodereactionrequiresthat the surfaceconcentrationof the
reactingspeciesattheelectrodeis reducedto ascloseto zeroaspossible.By plottingtherelationship
betweenthe overpotential,tj andthe log of currentdensity,log 'LOthe limiting currentcondition
can be seenas a plateauwherethe currentdensityremainsalmostconstantwith increasing71.
Theseplotsmaybeobtainedbyapplyingincrements
of eithercurrentor overpotentialandmeasuring
the resultantchangein theuncontrolledvariable.Figure5 showsan idealpolarisationcurve.The
limiting currentdensityis clearlyvisible. The increasein currentat the endof the plateauis due
reductionprocesssuchashydrogenevolution.However,suchan
to a consecutive
electrochemical
68.Firstly, the surfacearea
idealplateauis difficult to obtainin practicefor a numberof reasons.
formation
deposition
deposits
in
during
due
increases
to
the
the region
of
rough
the
electrode
of
Secondly,
if
density.
'L*
This
the
true
current
competingelectrochemical
changes
effectively
Of
deposition,
hydrogen
as
evolution,thenthepartialmetal
with
such
simultaneously
occur
reactions
depositioncurrentis maskedby the currentdueto the secondaryreaction.Thirdly, at very high
is
found
high
transfer,
under
of
electrolyteagitation,the sizeof
as
conditions
such
ratesof mass
A similar effectis seenwith high metalion
the limiting currentplateauis reducedor disappears.
Both
due
in
these
to the onsetof the consecutive
the
are
phenomenon
electrolyte.
concentrations
'L
'L
in
these
the
circumstances,
of
occursat a much
as
under
region
overpotentials
at
reaction
higher valueof Tj. Finally, the rateof changein the perturbationappliedhasa stronginfluence
Too
fast
increment
lead
to non-steady
the
an
can
stateeffectsoccurring
plateau.
of
ontheappearance
diffusion
layer
be
do
to
state
established.
a
steady
allow
not
which
Log Current
Density
33
In addition, it is important when measuring'L that the effects of migration are reduced. The
contribution to the value of 'L of migration can be seenas the (I - t) term in equation (1). This
influence can be significantly reducedif an excessof a supportingelectrolyte is added, which will
then carry the major portion of the current. Such an electrolytic material should not influence or
be involved in the cathodic reaction of interest. Despite thesedifficulties, there are a number of
basic techniquesthat canusedto obtain the necessarydatato constructsucha polarisation curve.68.
60Sc"'w-'
(9)
This was found to be three times as high as for the equivalenttime using the potentiodynamic
it
despite
is
However,
to
the
below).
this,
(see
use
galvanodynamicmethod
often
preferable
method
for metal deposition reactionsas there is less rougheningof the deposit close to 'L than with other
methods.18.
34
rises more rapidly during a potential ramp comparedto a current ramp, this can lead to excess
surface roughening of the electrodewith the potentiodynamicmethod. As a result, excessively
high limiting current densitiescan be measured.
Relatedto the potentiodynamicmethodis the potential steptechnique.70-This method involves
separatelyestablishingthe approximatepotential, EL, at which OS found, by a potentiodynamic
by
is
followed
This
plotting the current-time relationshipat potentialsbelow, at and above
sweep.
this arbitrary value of EL. The value of EL used for the potential step analysis is that at which the
smallest variation in current magnitude is observed. Then, a potential step of magnitude EL is
applied to the electrodeand the current measuredover a period of time. The steady state current
'L.
is
is
This
by
the
this
value
of
claimed to have the advantageof being
method
method
measured
less sensitive to surfaceroughnessof the working electrode.
When measuringlimiting current densities,the problem of deposit growth can be serious. This
is especially so in convectivesystemsthat allow the rapid depositionof metals. In order to establish
in
hydrodynamic
flow, use is often
terms
the
of
such
a
system
of
transfer
characteristics
the mass
is
frequently
A
ferricyanide/ferrocyanide
the
used
redox
couple
alkaline
couple.
redox
made of a
ferrocyanide,
is
the
to
Ferricyanide
with
advantageof the system exhibiting
reduced
electrolyte.
have
been
Such
in
limiting
large
systems
used
extensively
plateau.
current
establishing the
a
in jet electrolysis.
flow
fluid
between
transfer
and
mass
relationships
35
Apart from the platingof steelstrip andwire, the most importantapplicationof high speed
depositionhasbeenwithin theelectronicsindustry.As mentionedin theprevioussection,gold is
industry.
The
this
mostcommonapplicationsof gold are for the plating
within
extensively
used
frames,
lead
PCB
edgeconnectorsandtransistorheaders.Other appliconnectors,
of electrical
for
bonding
deposition
bumps
include
the
the
of
gold
spots
or
of gold connectorwires to
cations
integratedcircuits. Sewell72.
reportedthe reel-to-reelselectivepuregold platingof leadframesat
high electrolytevelocityusinga mechanicalmaskandelectrolytejetting. Currentdensitiesof up
to 0.6 ACr1r2wereusedwith electrolytevelocitiesof up to Im see-'.Thecurrentefficiencieswere
found
It
for
differing
that althoughhigh depositionrates
concentrations
of
gold.
was
measured
%,
100
deposit
deteriorated
to
be
the
rising
efficiencies
quality
with
astheefficiency
achieved
could
This
the
maximumoccurredat currentdensitiesof around0.12 ACM-2
maximum.
approached
Above
ion
deposit
1-1
24
this
the
concentration.
value,
metal
appearance
g
changedfrom a
with a
brown
later
The
depositsshowedpoor eutecticdie
fine
to
a
rougher,
colour.
crystalline
yellow,
Plating
for
24
1-1
properties.
rates
a
g
gold citrateelectrolytewerereported
welding
attachandwire
factors
in
high
deposition
The
6
the
be
significant
most
speed
of gold werefoundto
to
inim'.
Itin.
be the flow rate, compositionandtemperature.
In contrast to the previous author, Dorey et 03. who examinedgold deposits produced in a
Chapter
flow
(see
5),
fluid
for
but
that
masking
concluded
thermocompression
using
similar way,
bonding, a gold with a distinctly "foxy brown" colour was optimum. Both a citrate basedelectrolyte
126
1-1
Au
1-1
Au
The
hardness
22
with
g
electrolyte
were
a
proprietary
used.
and
g
of the
with
200
Knoop.
Flow
137
between
39
deposit
to
to
rates
of
up
cm sec-1were usedalthough
was
optimum
36
the optimum was found to be 13 cm/secusing a current density of between0.58 to 0.86 A crn-2.
ScanningElectron Micrography (SEM) revealedthat the "foxy brown" appearancewas due to a
high degree of nodulation. This was not surprising considering the relatively low flow rates
employed.
The aforementionedwork was an extensionof the resultsof Rehrig.51-He describedthe deposit
both
DC
using
morphology
and an asymmetric waveform using high rates of
and
characteristics
electrolyte flow in a spot plating unit. Unfortunately, the electrolyte velocity was not mentioned.
Gold concentrationsof between30 and 40 g 1-1were used. The influence of the nickel undercoat
in
He
DC
for
included
bondability
the
that
claimed
assessment.
current
was
unsuitable
good
also
was
300
in
deposition
A
densities
mA
CM72.
of
wide
range
of
excess
conditions were examined
at current
using an asymmetric AC waveform, with a peak cathodic current density of between 1.0 A Cm-2
and 3.0 A CM-2.The AC frequency was tested between 60 and 50OHz. Anodic peak current
densities were examinedbetween0 and 0.4 A Crn-2.It was found that it was essentialto use an
Using
bondability.
for
an anodic current density componentof 0.25 A CM-2,
good
anodic current
The
deposit
bonds
morphology
such
of
a
showed a significant grain surface
satisfactory.
were
all
deposits
He
found
that a certain
cycle,
anodic
smooth
no
were
produced.
with
whereas
projection,
degreeof surfacemicro-Toughnesswas necessaryfor good bondability. The peak cathodic current
density also influenced the grain structure and bondability. At current densities of 3.0 A Cm-2the
deposit
but
lacked
high
the
was
powdery
and
adhesion.He concluded that
was
surface roughness
in
bondability
factor
important
obtaining
good
was the presenceand magnitude anodic
the most
for
If
low
the
the
the
this
too
nickel
of
plating
solution
used
undercoat.
pH
and
was
offset
current
then poor adhesion of the gold occurred. The frequency of the AC waveforin did not have a
bondability.
influence
the
on
significant
37
depositwas soft enoughto form a thermo-compressionbond. The real difference in the performance
defined.
in
flow
is
likely
different
to
the
clearly
which
was
not
rate
electrolyte
the
reside
methods
of
As flow rate affects the thicknessof the diffusion layer and thus the ratio of '/'LOthen this could
be the reasonfor the differences.
It is quite evident that high speeddepositionprocessesare required for rapid through-put of
for
I
deposition
(about
high
sec7l
Processes
that
of
rates
Jim
give
quite
are available
materials.
for
flow
further
by
increase
it
is
this
rates
and
but
to
electrolytes
optimising
still possible
gold)
particular applications.
38
CHAPTER 5
ELECTROCRYSTALLISATION
AND MORPHOLOGY
It was mentioned in section 4.1.2. that deposit quality deterioratesat some value of current
density below the limiting current density. This degradationtakes the form of rough, nodular,
dendritic or powdery deposits. It is obvious that the mechanismof growth goes through changes
as the current density is increasedand these changesare related to the rate of masstransport of
is
limitation
However,
ions
transport
the
to
the
not necessarilythe
mass
surface.
growing
metal
known
by
influencing
factor.
Electrodeposits
as electrocrysa
mechanism
are
produced
only
tallisation. An understandingof the mechanismsof electrocrystallisation is needed in order to
densities
high
how
are produced.
the
current
at
structures
observed
establish
various morphological
Crystallographic
planes
Surface
w
(2lmmmgEmm
Bulk
metal
Figure 6. A schematicrepresentation
of the surfaceof a metalshowingthe randomexposureof
crystalplanesat the surface.
39
A schematicrepresentationof the surface can be seen in figure 6. This is true even for single
crystals. This provides a depositingmetal ion with many different locations in which to join the
lattice. How it does so is dependenton the conditions at the interface at the time of deposition.
Having establishedgrowth sites,the depositwill then grow in a fashionthat is highly dependent
on the prevailing conditionssuch as current density, ionic form, temperature,nature of the metal
deposit etc. It is well known that electrodepositscan follow many different growth habits ranging
from compactepitaxial to single crystal needletypes. The first comprehensiveattempt to classify
His classificationwas basedon observationsmadewith
thesestructureswas madeby Fischer.75.76.
the optical n-dcroscope.He concludedthat there were six main forms of growth, with a number
of subdivisions of thesetypes.
Fischer concludedthat all thesedifferent growth forms were the result of differing degreesof
inhibition of the growth surfaceby foreign substances.Thesesubstancescould be organic molecules
deliberately addedto modify structures or impurities. In addition, anions could act as inhibitors
is
The
list
increasing
degree
the
the
reduction
of
above
ordered
with
process.
products
could
as
of inhibition.
40
Theseclassifications
providea goodguide-lineto depositstructuresalthoughthereare some
deposits
included
the
as
rounded
such
mound
and
nodular
structures
observed
with
not
structures
densities.
high
in
deposits
formed
Such
current
structures
often
observed
are
producedat relatively
In
have
been
diffusion
they
conditions.
controlled
addition,
also
observedwith
strongly
under
is
It
has
been
Fischer
hardened
that
the
although
now
accepted
model
electrodeposits.
gold
cobalt
it
individual
does
theory,
the
general
anomaliesthat may
as
a
not
explain
many
satisfactory
quite
be observedwhen studyingindividualsystems.An exampleof this is in the caseof hard gold
deposits.
Nakahara'n.studied the "rounded mound" structure of cobalt hardened gold. He found that
diameters
have
low
distributed
thicknesses
were
mounds
visible
and
even
at
of the same
uniformly
deposit.
found
increase
in
These
the
to
thickness
the
of
size as the deposit
mounds
were
as
order
thickened and ultimately impinged on one another. Transmission Electron Microscopy (TEM)
A
in
fine,
200-300
diameter.
deposits
In
that
the
consisted
of
uniform
grains
addition,
revealed
the grains had a preferred orientation of I 11 normal to the surface. According to the Fischer
Nakahara
should
not
possess
any
preferred
orientation.
grains
went on to
such
classification,
had
l5o
by
that
to
that
the
texture
the profile
that
a
spread
of
about
corresponded
extended
observe
from
inferred
bounded
He
by
III close
this
that
the
the
the
surface
of
mound
was
mound.
of
further
Transmission
Electron
Microscopy
growth
occurred.
which
also showed
onto
packedplanes
density
inclusions.
incorporation
high
He
the
of
of
a
non-metallic
concludedthat
of
clear evidence
these inclusions, presumably the potassiumcobalticyanide mentioned in Section 2.2.2, inhibited
41
42
RT (
-F In I-(
RT
(I-P)nF)
In
('io)crit
(to)
thus giving
)cru-
(!
0Nil
i_
`ii
'bb
(11)
t/
is small for
large values of i.. This is supportedby experimentalevidencethat nodular growth occurs for "'L
values of 0.9 for iron and nickel ( =2x 10,9)but for copper, '/'L is about 0.4 ( =4x 10-5)81.
Growth now proceedsthrough 3 dimensionalnucleation, in which nuclei form and grow not only
in the radial direction but also in the axial direction, ie perpendicularto the surface. This mode of
is exceeded. With
growth is responsible for the increasing nodulation of deposits as
increasing overpotential, a number of unique growths may be observed,such as dendrites, needles
and tip splitting branches(also known as densebranchedmorphology, DBM).
43
is
(iiiL),,.,,
occur
as
approached.In this way, it maybe possibleto understand
morphological changes
the way in which deposit deterioration occurs and may lead to a meansof increasing the rate of
deposition whilst maintaining the quality of the deposit.
Electrodeposits
formedat "conventional"currentdensitiesaregenerallysmoothandcompact.
However,as the currentdensityis increased,surfacerougheningis observedto increase.There
havebeenmanystudiesonthemechanism
examined
of surfaceroughening.GabeandRobinson82.
the formationof powderanddendritesin copperdepositionusinga rotatingcylinder electrode.
Theyfoundthattheincidenceof dendriticorpowderdepositionwas
relatedto thetransitionbetween
chargetransferto masstransfercontrol.Theyestimatedthatthecritical ratio, "'L9 for copperwas
0.4. Ibl83-reviewedthe subjectof powderformationby electrodeposition
andits relationto mass
transfer.He concludedthat powderformation(anextremeform of nodulation)occurswhen'L is
development
reached.He alsoconcludedthatroughness
wasattributableto instabilityof thedeposit
surfaceunderdiffusionlimiting conditions.Instabilityheremeansthe selectivegrowthof surface
perturbations,leadingto roughening.As explainedabove,underconditionsof diffusioncontrol,
3 dimensionalnucleationoccurswhichcanleadto noduleformation.It hasbeenshownby Kindler
that for copper,at currentdensitiessubstantiallybelow 'L, a largenumberof nodulescan
et a184.
form. Thesenodulesappeared
to be largefacetedcrystals,overgrownwith a fine microcrystalline
structure.They claim that the fine structuredepositspreferentiallyon the largecrystals,leading
to noduleformation.The numberof largecrystalsalsoincreases
with increasingcurrentdensity.
Therefore,surfaceperturbations
arecommonbelow'L.DegrezandWinandalstudiedthedeposition
of copperat high ratesusing a high speedflow channel.Under thesecontrolledmasstransfer
conditions,theyconcludedthatrougheningof depositswastheresultof 3 dimensionalnucleation,
the onsetof which was proportionalto the combinedkinetic and concentrationoverpotentials.
havealsoidentifiedthe factorsthat enhancepowderformation.Theseare a
DespicandPopov86decreased
of depositingions,anoverallincreasein theconcentration
concentration
of theelectrolyte
in thetemperature
(supportingelectrolyte),an increasein theviscosity,a decrease
anda reduction
in the electrolytevelocity. All thesefactorsresultin a loweringof the limiting currentdensity.
havepresented
Bockriseta166.
a simplifiedexplanationfor instabilityoccurringunderdiffusion
control in the presenceof surfaceperturbations.Figure 7 showsa schematicdiagram of the
interfacial regionwith a singlesurfaceperturbation,theheightof which is considerablylessthan
the diffusionlayer thickness.If depositionproceedsunderdiffusioncontrolanda linear diffusion
gradientis assumed(not strictly true), thenthe diffusioncurrentwill be givenby
44
iaDnFCa-Co
(12)
As the thicknessof 6Pk is less than that of 6.,, ip,,. will be greater than i.. due to both field and
f, k
f
diffusion distanceeffects. Therefore, the peakwill increasein height. In addition, the electric field
becomesconcentratedat a perturbation further increasingits rate of growth. This implies that any
slight surface perturbation will always lead to a rough deposit. It is obvious from practical
observationsthat this is not always the caseand there are other factors at work that can lead to
stabilisation of the surface. Therefore there have been many attemptsto analyse all the factors
responsiblefor surface rougheningand put these into a stability theory.
Bulk
D.Ffus. on
layer
electrolyte
S'..
s.,..
y
Figure 7. A diagram showing how the thickness of the diffusion layer is lower above a surface
perturbation provided the perturbation is small.
45
introduced to the plane. They also addressedthe morphological stability of a particle growing by
diffusion or heatflow. 88.Their conclusionwasthat althougha surfaceperturbationwill be amplified
and thus be unstable, stability could be achieved by the effects of the surface tension of the
crystallites, termed capillarity, providing the curvature of the perturbation was sufficiently small.
Aogaki89-extendedthis theory to the formation of electrodepositedmetal powders. Landau and
Shyu9Oapplied the theory to the developmentof surfaceroughness.This was further extendedby
The previous theorieswere claimed to be deficient as they did not take account
Barkey et al. 91-92.
of the ohmic overpotential. They concludedthat the morphological stability of the electrodesurface
is controlled by the electric field, the fraction of the limiting current and the surface energy.
However, the model developedby Barkey etal did not correctly predict the magnitudeof protrusion
spacing and were half that found by experiment.
Chen and Jorne93-included a damping factor to account for the degree of influence a perturbation
has on the diffusion layer thickness. They claimed that if the perturbation is very small compared
to the thickness of 6, then the diffusion layer boundary would be unaffected and could be taken as
being flat. This was not taken into account in the previous treatments. They went on to develop a
mathematical treatment and formulated a stability theory which agreed with experimental evidence.
They showed that the surface tension was the only stabilising factor in the system. Without the
influence of the surface tension, the perturbations would always grow with time. They pointed out
that the surface concentration of adions influences the stability by affecting the surface tension. In
the case of a zero surface concentration, the surface tension loses its stabilising effect and all the
surface perturbations will tend to grow. Instability is also encouraged by the magnitude of the
concentration gradient at the surface with large concentration gradients encouraging the growth of
increasingly smaller perturbations. In addition, increasing the metal ion concentration and reducing
the thickness of the diffusion layer both encouraged instability. This, in effect, is the same as
increasing the concentration gradient
5.1.5 Theories of needle, dendritic, densebranching morphology (DBM) and fractal growth.
Deposits produced above the critical ratio of "'L not only produce rough nodular deposits.
Under certain conditions of electro-growth, needles, dendrites, tip splitting dense branching
morphologies and fractal structureshave been observed. Figure 8 shows schematicdiagrams of
these morphological structuresproduced by electrodepositionin a2 dimensional Hele-Shaw cell
(Seelater). Whilst thesestructureshavebeenproducedin a two dimensionalcell, they sharemany
characteristics with those produced in the more conventional three dimensional systems. In the
caseof a needlegrowth, this is characterisedby a numberof thin needle-likecrystals with parabolic
tips exhibiting little or no lateral growth habit. This shouldnot be confusedwith whisker formation,
which are causedby the interaction of foreign molecules with a growing surface.75.A dendrite is
46
essentially a needlegrowth with lateral side arms growing at specific angles to the main growth
direction. Further lateral growths are often observedon theseside arms. The DBM structure is
characterisedby its lack of crystalline regularity althoughthe DBM also differs from a dendritic
structure in terms of its tip splitting habit. They also exhibit a regular growth front, with all the
leadingtips in the samespatialposition relativeto the electric field. Fractal growths arecharacterised
by their irregular growth fronts. Each of thesestructuresmay be produced electrochemicallybut
they are also observedin solidification from melts, precipitation from supersaturatedsolutions and
amorphousannealing.This would indicatethat thereare commoncausalprinciples to thesegrowths
irrespective of the nature of the growth medium.
The earliest theories of dendritic and needle growth are attributed to Barton and Bockris94.
.
They proposed that dendritic growth proceededfrom a surface perturbation by means of mass
transfer control. They startedwith the growth of a macrospiral (the growth of a spiral dislocation)
that has a very small tip radius (r -10-6cm). Under theseconditions, diffusion to the tip is controlled
by spherical diffusion as opposedto planar diffusion. The current density at the tip is given by
DnFc b/r insteadof DnFcb /6. Since r<<6, the limiting current density is much higher on the tip.
They also argued that becauseof the high step and kink density, the tip has a higher exchange
current density and the activation overpotentialwould be much lessthan on the surrounding planar
surface. This leadsto an acceleratedgrowth of the tip which subsequentlydevelopsinto a needle.
The important factors relating to the initiation of needleand dendritic growth have been identified
as being two critical overpotentials, the first being required to initiate the growth of the screw
dislocationsand the secondto producediffusion controlled conditionsat a rate necessaryto produce
the tip radius suitable for sphericaldiffusion. 95.An initiation period was identified in which these
identified
Critical
formation
for
both
dendrite
overpotentials
were
occurred.
and
powder
changes
for copper and cadmiumby Popov et al. 96-97-98,
using the Barton-Bockris theory. Whilst the theory
is able to explain the growth of needles,there still remained the question of the instability of the
individual
It
branching.
dendrites
treated
the
to
with no reference to the
also
as
needle growth
influence that other protrusions had on their neighbours.
Despic and Popovm.commentedin their review of transport controlled mechanismsthat as
twinning is frequently observed in dendrites, the regular angled sidearmsmay be due to growth
from twin sites. Twin sites represent low energy sites for lateral growth and as such enjoy an
enhancedgrowth rate. This would accountfor unique anglesobservedany particular metal as the
However,
by
is
the
twin.
they were unable to offer a
the
properties
of
crystal
controlled
angle
dendrite.
for
the
the
the
of
spacing
sidearms
on
regular
reason
47
--d-
in a Hele-Shawcell. (a)
Figure8. Typicalmorphologicalstructuresproducedby electrodeposition
(DLA)
A densebranchingmorphologystructure(DBM), (b) a fractalor diffusionlimitedaggregate
structure,(c) a dendriticstructure,(d) a needlestructure.
48'
One important distinguishing feature of a dendrite is the long range crystalline order present.
It has been suggested'03.
that a stacked plane structure provides the necessaryanisotropy that
stabilises the growth of a dendrite and prevents it forming similar but disordered fractal or tip
splitting structure.
Dense Branching Morphology structures occur if the influence of anisotropy is reduced by
other external factors. This type of morphology is characterisedby the formation of irregular
branching structuresthat undergo random tip splitting. However, there is generally a long range
has examinedthe differences between
order in that they follow a regular growth front. Barkey-11.
this type of morphology and dendritic structuresby examining Schlieren photographsduring the
growth of both dendritesand DBM structures.Thesephotographshighlight density differences in
liquids allowing the shapeof the masstransfer boundary layers to be seen.He concludedthat it is
the shapeof the masstransfer boundary layer that selectsthe developmentof either a dendrite or
a DBM structure. In the caseof a dendrite, the boundary layer resemblesa shock wave with the
tip of the dendrite being close to the boundary layer. In the caseof the DBM, the boundary layer
distance
some
advancing
aheadof the tip splitting branches.He went on to conjecture
observed
was
that in the caseof the DBM, a hydrodynamic instability is set up due to the fast growth of the tip
less
interaction
the
the
of
viscousboundary layer and the bulk. This createsa gradient stress
and
across the liquid interfaces that setsup a dynamic surface tension. It is this surface tension that
front
the
and prevents random variations in the growth velocity of different
growth
stabilises
branches.Thus, a continuous,regular growth front is preserved.The tip splitting results from the
growth of a surface perturbation via a Mullins-Serkerka type instability betweenthe fluid layers.
In the event of a significant protrusion, growth occurs of that protrusion resulting in tip splitting.
This type of morphology is rarely seenunder conventionalconditions of electrodepositionbut may
be realised under conditions of high overpotential and low metal ion concentration.
Fractal structureshavebeenlikened to Diffusion Limited Aggregates(DLA) observedin other
by
These
particle
aggregation.
characterised
a non-uniform growth
as
smoke
are
such
systems
front and a lack of symmetry. In addition, they havebeenshownto possessno long range ordering.
Such structures occur if the surface tension effects seenin DBM are reduced. As a consequence,
the Mullins-Serkcrka instability predominatesallowing surfaceperturbations to grow unchecked
in
This
a random structure that hasbeenfound to possessa fractal Hausdorf
results
and at random.
49
dimensioft*. One other important property of fractal objectsis what is known as scaleinvariance.
These objects are invariant under a transformation which replacesa small part by a bigger part,
that is, under a changein scaleof the object.
Recent work has been carried out on the morphology selection mechanisms of dendritic and
allied growth by means of two dimensional electrodeposition cells known as Hele-Shaw cells. 99.
The cell consists of 2 sheets of plexi-glass separated by a narrow gap of about
100.101.102,103.
0.001-0.01 cm which contains the electrolyte. A ring anode is set around the edge of the plates
and a small hole is supplied in the top plate for the insertion of the cathode. The cathodes used
vary but are usually copper wire. By applying a suitable potential across the cell, a variety of two
dimensional dendritic and fractal structures may be grown. The type of structure is highly dependent
on the nature of the electrolyte and the growth conditions. It has been found that for true dendritic
growth, crystalline anisitropy must be influential. If the influence of anisotropy is reduced, then
DBM and fractal growths predominate. The conditions controlling the type of structure produced
can be summarised by figures 9a and b. 101-100.
Me Hausdorf dimension, also termed the fractal dimension D can be derived as follows. Mic density correlation function c(r) of a
fractal may be defined as die averagedensity of an object at distancer from a point on the object and is an measureof the average
environment of an individual particle making up the object. Ile term c(r) reflects the scale invariance and it may be shown that the
only way in which c may vary is as a power law in r. Any other function would have an intrinsic scale. 71e term c may be written
in the following form:
e(r)-
kr'(d-
0)
Here, k is a constant and the exponent is written in terms of the dimension of space.d and D is the fractal or Hausdorf dimension.
Now, c(r) is a decreasingfunction of r as the averagedensity decreasesas the object becomeslarger. Consider how the mass of an
object, M, scaleswith the mean radius, R. We can estimatethis by multiplying a typical density from the above equation, by the
volume:
A,f(R)-
KRO'dRd- KR1
The termK is anotherconstant.It maynow be apparentwhy D is calleda dimension.For simpleobjects,D coincideswith the
a non-integer
usualnotionof dimension.But for fractals,D is not an integer.lberefore, if an objectcanbe shownto possess
Hausdorfdimension,it cantruly be calleda fractal.
50
For a quantitative description of this interaction between the microscopic and macroscopic
forces that dictate morphology selection,the readeris referred to reference 103. However, a brief
Under
be
here.
description
conditions of non-equilibrium growth, such as
given
will
qualitative
the formation of a snowflakeor the growth of a dendrite,the initial stablesolid phasewill propagate
into an unstableor metastablephase.In the caseof the snowflake, a collection of solid stablenuclei
it
In
dendrite,
into
the
the
the
case
of
supersaturated
water
vapour
phase.
unstable
propagates
ie
into
is
in
highly
into
tip
that
a
state
a
moving
a
non-equilibrium
an
electrolyte
propagates
continuously changing diffusion and hydrodynamic layer. The rate of growth of the stable phase
is limited in both casesby a diffusion process. As a result, the kinetics of the diffusion process
determine the macroscopicapproachof the solid phaseto equilibrium. In doing so, the system is
driven towards the formation of irregular or dendritic shapes.The exactform of the resultantshape
kinetics
depend
tension,
things
and anisotropy. and these are
as
surface
surface
such
on
will
determined by the exact conditions of growth and the nature of the growing material. Together
with diffusion kinetics, these microscopic forces determine the macroscopic approach towards
equilibrium and influence the structureson many length scales.
The reasonfor investigatingsuchnon-equilibrium crystallisationmodesis that under conditions
interface
high
is
due
far
from
to
the
the
overpotentialsapplied.
equilibrium
ofjet electrodeposition,
As such, it is to be expectedthat such structuresare likely to occur close to the upper deposition
limit during jet deposition. This is indeed observedand will be discussedlater.
51
lOM
CT
N
0.10M
O,O1M
1.0
5.0
APPLIEDVOLTAGE
10.0
(a)
LOM
OPEN
STRINGY
0,10M
N
DENDRITIC
HIM
1.0
HOMOGENEOUS
A
,
5.0
10.0
APPLIEDVOLTAGE
(b)
52
CHAPTER 6
There have been relatively few papers published on the subject of high speed jet deposition.
Of these, deposit morphology has not been given serious consideration. The emphasis in these
for
jet
been
has
the
transfer
mass
characteristics
of
models
mathematical
establishing
on
papers
Although under
deposition. Of these, a high proportion deal with a submerged jet, '. 104-105.106.107jet.
2.108.There
to
transfer
the
these
results
are
applicable
un-submerged
mass
certain conditions,
have been a number of papers published concerning the use of jets in electrochemical machining
but these are of little consequence to this study and will not be referred to. The earliest published
by
Zarb.
He
described
109jet
was
a system that made use of multiple
electrodeposition
work on
jets in order to produce selective gold deposits on lead frames. No masking was used. He claimed
in
15 seconds could be achieved using a pure gold electrolyte.
2
deposition
of
that
rates
tLm
In 1974, Fletcher,"O. describingan invention of G.D. Oliver, filed a Patenton behalf of NASA
describing a selectiveplating methodusing a pressurisedjetof electrolyte. Thejet could be moved
digitising
information
be
By
of
means
a
video
system,
on
a
pattern
could
under computer control.
introduced into the control system. The jet was scanned,raster fashion, acrossthe substrateand
In
in
the
this way,
times
the
with
control
pattern.
accordance
appropriate
at
the current was applied
in
dot-matrix
be
the
much
a
printer producesa picture.
same
way
as
written,
could
a plated pattern
No other publication by Oliver has been found and therefore few details of the process and the
deposits
the
produced are available.
of
morphology
Before examining the mathematical models for the mass transfer within jets, it is essential
hydrodynamics
the
the
of such a system.
of
nature
understand
6.1 CliARACTERISTICS
53
workers have divided the flow into four distinct regions as can be seenin figure 1. Theseregions
are termed 1) The free jet region, 2) The impingement region, 3) The wall jet region, 4) The
hydraulicjump. The hydraulicjump is uniqueto non-submergedjets. Whilst there are considerable
differences between the flow mechanisms,it has been shown that when the nozzle is within a
specific distancefrom the surface, then conditions of flow are similar for both the submergedand
un-submergedjets within the impingementregion. The wall jet characteristics,however are significantly different due to interaction betweenthe surrounding medium.
Thefreejet is theregionbetweenthenozzleandtheimpingement
zoneprior to anyinteraction
Schlichting"L
jet systemusing
target
the
studiedthe freejet within the submerged
surface.
with
boundarylayerequations.He foundthatajet will becomecompletelyturbulentat a shortdistance
from the dischargepoint asthe emergingjet becomespartly mixedwith the surroundingfluid at
flow
decreases
in
direction
jet
flow
Consequently,
the
the
the
mass
of
and
spreadsout with
rest.
However,
in
thetotalmomentumremainsthesame.Studiesof non-submerged
velocity.
a reduction
jets'12-haveshownthatthevelocityremainsnearlyconstantcloseto thenozzleexit. However,as
jet, at somedistancefrom the nozzle,turbulenceoccursdue to a
in the caseof the submerged
j
The
bell shapedwith themaximum
the
within
et.
velocityprofilebecomes
profile
varyingvelocity
jet
line.
This is a resultof entrainmentof thesurroundingair and
the
centre
on
velocityoccurring
discussed
thetheoreticalsolutionto the Navier-Stokes
equationfor
the flow breaksup. Squire'13laminarflow in a freejet.
54
havebeendevelopedby bothmathematical
Masstransfercharacteristics
modellingandtested
by experiment.Both submerged
andun-submerged
systemshavebeenevaluated.Much work has
beencarried out using the analogoussystemof heattransfer.Whilst the generalbehaviourof
from
different
jets
that of non-submerged
systems,undercertainconditions,
very
are
submerged
behaviourwithin the impingementregionis very similar. Therefore,some of the characteristics
be
will
revued.
system
the
submerged
of
6.2.1 Mass transfer in submerged jets.
Mass transfer and heat transfer are analogousin their behaviour. As such, work carried out
Work
by
to
heat
transfer.
experiments
transfer
and
are
applicable
mass
models
undertaken
using
Gardon and Akfirat' 16.
measuringheattransfer with airjets hasshownthat at large nozzle to surface
distances,the heat transfer decreasedin a monotonic mannerfrom the stagnationpoint. However,
in
heat
d'/d
0.5.
local
H/d,
transfer
at
was
observed
maximum
=
a
at small
55
Mass transfer in a submergedjet systemwas also shown to be highly dependenton the distance
betweenthe nozzle and the impingementsurface. Giralt'17- and Scholtz"s. have explained that
with large nozzle to surfacedistancesie H/d 2:8.0, the flow in the free jet has a fully developed
bell-shapedprofile. As a consequenceof this, the accelerationof the wall jet commencesat the
stagnationpoint and masstransfer is greatestat the stagnationpoint. At smaller values of H/d, the
jet still retains much of the flow characteristicsof the nozzle. Providing the flow within the nozzle
is uniform to begin with, then this profile is retained.Consequently,the accelerationof radial flow
is
d'/d
0.5.
This
the position at which the boundary
corresponding
with
at
a
position
commences
=
layer is thinnest and the masstransfer highest. In betweenthesevalues of H/d, the masstransfer
is relatively constant. Other experiments and theoretical calculations using controlled flow
conditions'19.have shown that with uniform flow distribution, the position correspondingto d'/d
= 0.5 exhibits the greatestmasstransfer. With a parabolic flo profile, this position corresponds
*w
to d'/d = 0.1.1M Mass transfer within the impingement region has been studied by Chin and
Using disc electrodesof various radii, they measuredthe masstransfer using the limiting
Tsang.105.
found
limiting
They
density
that
the
average
current
remained constantup to
method.
current
dI/d = 0.5 for laminar jet flow. However, under conditionsof turbulent flow, this value increased
to 1.0. These phenomenonmay be explained in terms of fluid acceleration.The fluid velocity of
the wall jet along the substratemay be derived from inviscid theoryl. as
U., - 1.161
r
U., -0.451611
r
f or
for
H/d -
0.25
H/d-
1.0
f or
non-unif
for
uniform
orm
flow
f low
(13)
56
Sh. - Re, Sc
1/3(c
1/2)
Chin and Hsueh'20usedthis equationto derivea form that is applicableto the non-submerged
impingingjet geometry.Local friction coefficientswereobtainedfrom the work by Nakoryakov
et al.
(i) in the impingementregion
C, - 0.662v
112U312XIU
2(d/2)
.
3/2
0.579u
112U312XIU2
x
(d/2)
1/2
(16)
U, - gd'
(17)
U, -U
(18)
By substituting equations(15) (16) (17) and (18) into the Chilton-Colbum equation and averaging
the local masstransfer coefficients over the electrodesurface, a set of correlations for the average
Sherwood number can be calculatedas
57
Sh = (0.936/a
*)Re
112SC113
(19)
5h - 0.767Re
.
112SC 113(r'ld)
-1/2
(20)
Sh - aRebSc'I(Hld)
(21)
The derivation of this equationcan be found in the excellent Chapterby Ibl and Dossenbach'23The value for c is generally acceptedto be 1/3. The masstransfer characteristicsare different for
jet
For
former,
it
has
been
found
by
to
the
the
impingement
wall
compared
region.
region
the
Giralt and Scholtz that the value of b is 0.5 for the submergedjet. The value of a is dependenton
but
is
between
0.5
For
degree
1.
turbulence
the wall
the
generally
of
and
and
the velocity profile
jet, b has been determined as 0.75 and is inversely proportional to the radial distance, d'. The
functional relationship betweenthe masstransfer coefficient and the nozzle to substratedistance
is generally expressedas a power relationship
f(Hld)-(Hld)-o
(22)
Valuesfor e' vary. Chin and Tsangfound a valueof -0.054 and -0.057 for the submerged
laminarandturbulentjet flow respectively.However,in a laterstudy,Chin andHsuehfoundthat
for 0.5 < H/d < 5.0, a valueof -0.09 wasappropriate.
58
The basic mathematicalmodel for the non-submergedjet has been determinedby Alkire and
Chen as applicable to electrodepositionsystems.They modelled the current and potential distribution along a cathodesurface in a high speedjet plating cell. The model was based on the
limiting current measurementof masstransfer using the reduction of ferricyanide in an alkaline
solution. They went on to study copper depositionfrom an acid sulphateelectrolyte both with and
is
ferric/ferrous
The
redox
couple
added.
reader
a
referred to this referencefor a detailed
without
description of the derivation of the model. They found that in the impingementregion, correlated
in dimensionlessform, gave the following relationship over the range 3000 < Re < 60000
Sh - 21.03Re
0,448
(23)
This, they claimed, agreedto within 10% of a semi-empirical correlation derived by Chin and
Tsang for a turbulent submergedjet. In this work the H/d was maintainedat a value of 2.0. This
in
impingement
the
transfer
characteristics
the
that
region were essentiallythe same
mass
ensured
jet
For
found
following
jet.
the
they
the
for
wall
region,
relationship
submerged
a
as
Sh., - 0.572Rex
O.5SCO.
33
(24)
Nakoryakov et al also derived a relationship for the wall jet basedon theoretical predictions of
Sh - 0.59Re
0.3scO.
33
(25)
dimensionless
Sherwood
to
the
number
notation.
after converting
Alkire and Chen, basedon both their theoretical and experimentalstudies, went on to establish
jet
From
the
behavioural
their
system.
of
experimentsusing the redox system,
properties
certain
following;
15%
theoretical
the
to
of
calculations
within
they established
59
Low currents led to high selectivity but a low plating rate whilst high currents give high
plating ratesbut low selectivity. Here selectivity is defined as
S-
metal
deposition
total
in
metal
impingement
deposition
region
rate
They claimed that the reasonfor this was that at low currents, the behaviour was controlled
by potential distribution and that as the impingement region was closest to the anode, the
favoured.
high
limiting
At
impingement
in
the
the
currents,
current was
region
was
reaction
by
the
controlled
masstransport.
system
was
achievedand
2.
The electrolyte conductivity influenced the behaviour. Electrolytes with a reduced conductivity led to an improved selectivity at low applied currents but at high currents had no
influence.
3.
4.
Whilst they found good agreement between the experimental results and the theoretical
found
high
ie
high
flow
that
under
conditions
selectivities
gave
were
rates,
errors
calculations,
high reactant concentrationsand low conductivity. They put this down to errors in the one
dimensional simplification they used for the theoretical calculations and had underestimatedthe
higher
These
than
predicted
a
selectivity
were actually observed.
errors
rates.
reaction
60
value. The reason for this was believed to be the difference in the exchangecurrent densities of
the two systems. During their studies, a dimensionlessnotation was derived to assist in the
mathematicalmodeling of the systemincluding a term t. This was defined as
rFa, d2io
xRT
(26)
where a, is the specific surfacearea and is a volume componentof the electrolyte involved in the
is
in
Its
derivation
given
reference(1) but is not importantto this discussion.The important
reaction.
aspectis the inclusion of the ratio of exchangecurrent densityto the conductivity i,,/x. This played
interpreted
be
in
This
important
the
could
selectivity
achieved.
as a ratio of ohmic
ratio
role
an
If
losses
transfer
this value was greater than unity, the current
to
charge
overpotential.
potential
distribution would be highly non-uniform andthusselectivity would be high. By way of illustration,
three values of t were plotted as selectivity vs total applied current for high rates of flow. These
values were 104,104 and 101.Of these, the intermediatevalue exhibited the poorest selectivity.
At low currents, a large value of k correspondedto ohmic control so that selectivity would be
expectedto be high due to non uniform current and potential distributions. Very small values of
k correspondto charge transfer control and thus a more uniform potential distribution. However,
the charge transfer overpotential must be very high in order to support the required current. Due
to the exponentialnature of the kinetic rate relationship (Butler-Volmer equation)modestpotential
distributions.
for
low
highly
Therefore,
non-uniform
current
currents,
generate
can
variations
is
increased.
For
high
depends
k
through
a
minimum
as
currents,
selectivity
on
selectivity passes
insensitive
in
is
to
t.
thus
variations
transfer
and
mass
Another term defined was r. This dimensionlessterm comprised
I_n2F2
kc"a, d2
xRT
(27)
This term included the ratio kclx and could be interpretedasthe ratio of masstransfer overpotential
dimensionless
limiting
be
Such
term
a
could
viewed
a
as
current. If r had a
to ohmic potential.
be
The
high
deposition
then
than
could
achieved.
very
mathematical
rates
unity,
greater
value much
high
deposition
be
if
both r
that
selectivity
could
achieved
rates
with
good
very
model predicted
and t had values greater than 10.
61
In the caseof copper depositionwith a redox couple, the chosensystemwas more noble than
the copper reduction. Therefore, at low current densities,the reduction of ferric to ferrous predominated.The current efficiency for copperdepositionthereforeincreasedwith increasingcurrent
density. Thus, the current efficiency was highestin the impingementregion. This led to a situation
in which the selectivity was low at low currents increasingto a maximum with increasingapplied
current. At very high applied currents, the selectivity reducedas copper was depositedoutsidethe
impingement region. It was found that by using the redox couple, the maximum selectivity was
increasedtwofold.
62
CHAPTER 7
63
r ------------------------------------------------
jr ---------------------------------------------
1286
PC
I!
I Kcrocompuler
LjCo
II
stant curren
power suppty
Stepper motor
Translator card
i L--
Stepper motor
driver supply
Pumpcontroller
Pump
Electrolyte
Reservoir
Heat Exchanger
64
Theelectrolytewaspassedthroughaheatexchanger
placedupstreamfrom thenozzleassembly.
This consistedof a Quickfit glasscondenserwith a spiral internaltube. The outerjacket was
from
hot
water
a separatereservoirdeliveredby a peristalticpump.The electrolyte
with
supplied
temperature
wasmonitoredon emergingfrom thenozzleby a fine thermocouple
wire placed3 cm
impingement
the
point on the substratemountingplate. Adjustmentof the hot water flow
past
control.
providedsuitabletemperature
Immediately upstream from the nozzle, a Titan Enterprises flowmeter, model No. 103 was
fitted to give a direct measurementof the flow asa back-upto the pressuretransducer.The computer
provided the measurementoutput for this meter.
As each electrolyte used in this study had a different viscosity, it was necessaryto calibrate
the flow measuringdevicesfor eachone. This wascarried out by measuringthe volume of discharge
over a range of pump settingsand producing a calibration curve. The computer output from the
flowmeter wasthen compensatedfor anydifferences,aswastheoutput from thepressuretransducer.
65
66
To computer
Putse
000
generator
Power
-0
supply
00
00
Digital ammeter
Resistor
F -54
Oscilloscope
0
Jet
Figure 11. The modification to the power supply to enablepulsed current electrodeposition.
7.1.1.6 The computer and control program
The computer usedwas an IBM compatible286 processorbasedsystem.The program usedto
following
"in
house".
jet
It
designed
the
the
was
written
unit
capabilities.
plating
was
with
control
1) A Computer aided design (CAD) user interface that allowed the computer to be programmed
to move the nozzle to appropriateplaceson the substrateand producedeposit spotsof the required
be
basis.
duration
interface
This
step
and
could
also
used to program the
on
a
repeat
and
current
jet
"directly
basis,
to
the
to
the
on
nozzle
a
continuous
write" the elecmove
allowing
computer
trodeposit. Figure 12 shows such a design as it appearedon-screen
67
10227
max- 25 0 25
ABSX= MEN
ARS V= 12.4250
REL X=8.028
REL Y=A. MO
fI 1`2 1`3 1`4 I'S 1`6 1`7 -
place node
radius 98
reset rel
del last node
terminal node
place spot
change view
f18- step=
0.02S8
polygons
save
merge
text
main menu
Figure 12. The computer "user interface" showing the CAD design screen.
7.1.2 Additional equipment
68
*Imastrip,suppliedby Enthone-OMI(UK)
69
For comparison, a series of control sampleswere prepared for XRD examination by conventional vat depositionmethods. Oneset were producedfrom a Ronovel N electrolyte containing
1.7 g 1-1nickel over the current density range 3.0 - 40 mA cnr2. A further set of sampleswere
produced over the samecurrent density range from an Auronal MRN bath also containing 1.7 g
1-1nickel, which is identical to the Ronoval N but containsno booster. Thesesampleswere used
to study the influence of the booster. Pure gold sampleswere producedfrom a typical acid citrate
These
density
1.0
20
0.06M
to
crrr2.
of
mA
over
a
current
range
gold,
containing
electrolyte
depositscovered the sametotal surfacearea of the substrateas that covered by the jet plated spot
array.
The X-ray diffraction datawasacquiredusing an SiemensD5000 X-ray Powder Diffractometer
(Bragg-Brentano geometry) equipped with a diffracted beam monochromator ((Cuka).
Measurementsof diffracted intensity were carried out over the 20 range 30* to 90*. Corrections
to the angular positions and breadth of the diffraction peaksderived from the samples, required
to compensatefor various instrumental and physical effects were applied. To determine these
in
dusted
The
fine
layer
(@
Ian
size).
sample
was
with
of
silicon
a
powdered
each
corrections,
bracketed
Widths
Half
Maximum
intensity
Full
(FWHM)
the
at
of
siliconpeaks
which
positions and
those from the gold were usedto calculatethe appropriatecorrectionsto position and width. Using
lattice
it
interpolate
known
to
parameter
of
silicon
was
possible
a correction to the
the precisely
for
lattice
for
thus
the
the
each
and
calculate
parameter
an
accurate
value
gold peaks
position of
line. The correction for line broadeningwas madeby assumingGaussianmodels for the observed
diffraction
instrumental
corrected
and
profiles.
profiles,
Data was derived from an analysis of the position, intensity and FWHM of the first five
diffraction peaksrecordedfrom the gold deposits. In the Bragg -Brentano geometry, the diffraction
from
those crystallographic planes which are essentially parallel to the
only
originates
pattern
derived
from
111,200,220
The
311
therefore
quite
the
reflections
are
and
sample.
of
surface
222
derived
deposit.
Only
III
distinct
the
the
within
reflections
are
and
crystallites
separateand
from the samecrystallites. Considerablecare therefore needsto be exercisedin interpreting data
from sampleswhich do not exhibit a true crystallographic random orientation.
Latticeparameters
werecalculatedfrom the angularpositionsof the first five lines(I 11,200,
220,311 and222) in the diffractionpatternfrom eachof the samples.
For thepurposesof this Thesis,crystallitesizewill bedefinedasa single,coherentdiffracting
D.,
be
below,
is
the
true
the
This
size,
as
will
as
crystallite
explained
same
not always
region.
intensity
half
full
The
for
of the Kcqline corrected
is
maximum
width at
but used convenience.
for instrumentalbroadeningwasusedto calculatethe crystallitesizeusingthe Scherrerequation.
70
(0.9k)
(tcoso)
(28)
where B= the broadeningof the diffraction line measuredat its half width maximum intensity
(radians), t= diameter of the crystal particle X= radiation wavelengthand 0= angular position
in degrees.
It was noted that the crystallite sizevaluescalculatedfrom the broadeningof the III reflections
using the Scheffer equation were significantly greater than the values derived from the 222
reflections. The crystallite sizes calculatedfor the two planes should be the same; that they are
not, suggeststhat the Scheffer model employed, which attributes all the intrinsic line broadening
to crystallite size effects, is an over-simplification. On the basis of this infonmtionsamples were
selectedfor a more detailed analysis in order to separatethe contribution to the observed line
broadening from crystallite size and strain (RMS) effects. This was undertakenusing the method
of Warren and Averbach-121.The successfulapplication of this type of analysisrequires as many
unique orders of reflection as possible. However, for an FCC metal examined using copper
radiation, the number of accessiblereflections with multiple orders is just 2, the 111 (222) and the
200 (400). In this study, line overlap problems combinedwith low peak intensities ruled out the
use of the hOOreflections so that only the 111 and the 222 peakswere used for the analysis.
In orderto accomplishtheanalysis,
a betterdefinedinstrumentalline broadeningstandardwas
by
This
achieved
producinga puregoldpowderandannealingit to thepoint where
was
required.
in
improvement
ka
ka2lines
be
is
It
further
the
the
resolution
of
and
could
achieved.
particularly
no
difficult to obtaina suitablegoldpowdercommerciallyandannealit in this waydueto its tendency
The observed
for grain growth andsintering. Therefore,a powderwas specificallyproduced%
diffractionlineswerecorrectedfor instrumentalbroadeningby dividingthe FourierTransformof
from
derived
lines
diffraction
thesampleby theFourierTransformof theappropriateline from
the
*A 50 g 1-1solution of gold chloride was produced by dissolving pure gold powder in aqua-regia and
Concentrated
dryness.
hydrochloric
to
acid was addedand re-evaporateduntil all oxides
near
evaporating
The
solution was then adjustedto the correct concentration using de-ionised
removed.
were
of nitrogen
in
10
it
to
the
produce
gold
grains
with
a
region
of
size
with
ordered
necessary
a
well
was
water.
jum
had
be
to
nucleated and grown very slowly. It had been shown that such a
structure. This meant they
by
be
100
A
the
temperature.
reducing
gold
chloride
using
acetone
at
room
achieved
ml
could
structure
sampleof the gold chloride was placed on a magneticstirrer at a temperatureof 35 *C and 30 ml of acetone
for
5
hours
Stirring
continued
a
after which the samplewas cooled to ambient
period
of
was
added.
was
3
days.
At
for
layer
the
this
to
a
period
end
of
period,
a
of gold powder was seenat the
stand
and allowed
bottom of the beaker that had merged to form a thin film. A piece of this film was cleaned in de-ionised
X-ray
diffraction
from
film
be
that
the
the
slide
so
pattern
glass
a
could
on
recorded.
mounted
and
water
The resolution of the ka doublet was determinedfor the first five lines in the X-ray diffraction pattern from
the film. The film was then subjected to a number of annealing operations at 350*C until no further
improvement resolution of the doublets was obtained. The total time of annealingto obtain this condition
was 5 hours.
71
The full application of this analysisyields the mean column length (noa) and its distribution
and the RMS strain and its distribution. The apparentcell size is a3and no, the number of cells
in the averagecolumn length, is determinedby a linear extrapolationof the real part of the Fourier
Transform of the (000) reflection.
The cell size (a) is deterrnined by the angular range over which the diffraction profile is
by:
is
given
and
analysed
-
1- 1/2-
I-
(2a,
(2a,
/X)
1+ 1/2-(2a.
/K)
sin 0,
sin 0.
/k)
sin 02
(29)
(30)
(31)
is
diffraction
is
the
q
the
q
x
the
the
and
end
q
start
of
are
and
profile,
position
of
peak,
where
the wavelengthof theradiationemployedandI is a reflectionorderasin hkl. In orderto simplify
it
is
convenientto choosescanrangesso that a3is the samefor all
calculations,
the subsequent
In
in
2.4
d,,,
this
the
analysis.
study,
used
a
cell
size
of
x
wasused.
reflections
Closeandcarefulexaminationof the diffractionpatternsfrom thesesamplesshowedboth the
III and222 diffractionpeaksoverlappedwith their nearestneighbours,the 200 and 311 peaks
for
determine
This
true
the
to
also
was
specially
reference
gold
sample
used
prepared
respectively.
instrumentalbroadening.In thepresentstudy,datawascollectedoveranangularrangeof 10
311/222
lines.
111/200
the
and
about
centred
In order to obtainadequate
representation
of thediffractionprofilesin the "tails" of thepeaks
(wheremostof the crystallitesizeandstraininformationis contained)a variety of mathematical
dataandtheparameters
for thebestfits usedto calculate
functionswerefitted to theexperimental
Split
Pearson
7
Pearson
7,
different
Voigt
(mixed
diffraction
three
and
pseudo
profiles.
model
Cauchyand Gaussian)type functionswereemployedin the modelling.
72
The modelled III and 222 diffraction profiles were calculated at 1024 data points over an
angularrangeof 16and20" respectively. Fourier transformswere calculatedusing anFFTroutipe.
The instrumentalcontributionto the diffraction datawasremovedby dividing the FT of the samples
by the FT derived from the precipitatedand annealedgold powder describedabove. The Fourier
coefficients of the 000 reflection were calculatedusing the extrapolationproceduresdescribedby
Warren and Averbach.121.This methodenablesthe individual contributions of crystallite size and
strain to line broadening to be evaluated. The contribution to broadening from crystallite size
(column length) is independentof the order of reflection whilst that from strain is dependenton
the order of reflection. Becauseof this, the two contributionsmaybe resolved. The meancrystallite
sizes were calculatedby extrapolating the linear region of the real part of the 000 transform to
obtain no. The mean column lengths (crystallite size) and RMS strains are listed in Table 23.
I+I.
Sa+P')F3
)T
a'
(32)
is
is
is
fault
D..
fault
true
the
the
[3
the
twin
crystallite
size,
probability
stacking
a
probability,
where
and a'is the lattice parameter. The stacking fault probability may be establishedby measuring
III
between
the
shift
and the 200 peaks. The probability may then be calculated.
any relative
Twin fault probabilities may be calculatedfrom any asymmetryof the diffraction peaksthat have
beenreconstructedfrom the inverseFourier transform producedduring the Warren and Averbach
it
fault
because
However,
to
the
twin
not
possible
was
accurately
calculate
probabilities
analysis.
the depositwas highly oriented in the III direction. Twin fault probabilities are usually calculated
for the 100 (200) reflections. Due to the high degreeof texture, the 200 signal was very weak and
could not be used for the analysis. Table 23 also includes the stacking fault probabilities where
thesewere significant.
73
74
75
76
To examine the influence of pulsed current, a series of deposit spots were produced over a
duty
from
0.02
The
cycles.
on-times
msecs.to 10.0 msecs. and
and
ranged
of
on-time
wide range
duty cycles between 5.0 and 90%. The averagecurrent densities used were between 6.0 A CM-2
A
10.0
Cm-2.
and
7.3.2 Gold alloy deposits
77
is
electrolytes
often a closely guardedsecret and it was not possible
composition of proprietary
to control all the compositional variables. However, despitethis, three electrolytes were chosen
to representthe three commonalloy systems.The cobalt and nickel electrolyteswere Ronovel CM
and Ronovel N, supplied by Lea Ronal. The gold/iron electrolyte was the Aurtma 7000 supplied
by Degussa.A seriesof plating trials were carried out on all three electrolytesin order to establish
which electrolytewasthe mostsuitablefor optimising forplating underhigh speedjettingconditions.
78
79
80
to choosea value of -r which correspondsto the point at which a steadystate diffusion layer has
formed. The value of -r will be dependenton the magnitudeof the potential and the current flowing
as this will influence the magnitudeof the diffusion gradient. The greater the current, the faster
the influence of diffusion. Also, at high overpotentialsand currents, depositgrowth becomesrapid
and this influences the surface areaof the electrodeleading to enhancedcurrents.
Charging
current
Deposit
growth
bi
ry
ry
D
u
Steady
state
rTIME
Figure 13. A typicalcurrenttransientproducedduringa singlepulseusingthe SCPVmethod.A
been
deposit
has
the
high
to
chosen
effect
of
growth.
show
overpotential
relatively
Below the limiting current density, the metal ions are not completely consumed. They are
however, lower than the bulk concentration of metal ions. At the limiting current density, the
increases
in
ions
be
further
lead
to
will
zero
and
potential
will
not
metal
of
surface concentration
This
in
further
technique should
a
secondary
reaction
unless
electrode
occurs.
current
rise
any
density
'LP
limiting
Tafel
identification
the
the
parameters
as
current
such
slope and
of
the
allow
the exchangecurrent density.
81
0.1 mm. The face of the block where the electrodesemergedwas polished flat to a mirror finish
thus providing a pair of flush mountedelectrodes.Severalof theseelectrodepairs were mounted
in the sameblock. A schematicdiagramof the electrodeblock is shownin Figure 14. The advantage
of this method of electrodearrangementwas that the referenceelectrodedid not interfere with the
jet. The gold wire referenceelectrodewas not ideal becausethe gold systemsused in thesetrials
were electrochemically irreversible. An ideal referenceelectrode should show complete reversibility with the ions in the electrolyte or there is the dangerof somecurrent flowing through it and
influencing the results. This was offset by ensuring that the potentiostathad an extremely high
input impedance.
Epox
lotock
82
83
00
Putse generator
00
0
Power
suppty
00
04?
D.q. tal
X-Y chart
recorder
Res.stor
IK
ommet r
1254
Oscitloscope
0
Yorking
tiectrode
I
Reference
etectrcWt
(a)
Putse
generator
00
00
V in
RE
99Y
WE
CE
e
Oscittoscape
I ou
Potentiostat
00
X-Y chart
recorder
=: I-j-e-t-71
Reference
etectrocle
Working
etectrocle
(b)
Figure 15. (a) The equipmentusedduring the SVPA experiments.(b) The equipmentused during
the SCPV experiments.
84
The resultsof this work will be presentedmainly in the form of graphsand micrographs.Where
in
form
Tables
is
data
towards the end of the Thesis.
the
the
of
shown
collected
relevant,
85
increasingly influential as the hydraulic jump occurred much closer to the nozzle exit. By maintaining the H/d value between I and 4, a constantselectivity could be ensuredeven when using
small diameter nozzles.
20
10
02
Dimensionless
distanceratio
Figure 16. The effect of the H/d ratio for a 0.4mm nozzle on the selectivity of the deposit.
8.1.2.1 Generalobservations
At a currentdensityof 0.25 A CM-2,
thedepositcouldnot be measured
within the impingement
difficulty
deposit
leading
differentiating
deposit
Dektak
the
to
the
thin
the
as
of
was
regionusing
from thebackgroundnoiseof thesubstrate.However,theexistenceof somedepositionwasvisible
in
4
diameter
was
observed
comparisonto the rest
change
as
a
colour
about
nun
subtle
to
of
up a
86
Width measuredoptically
II
Temp. 55 C
11
:3:
Velocity 18 m/sec
Efl
5
I)i
3
s
I
01
34
CurrentDensity A/cm sq
87
It was found that the presenceof dissolved oxygen had the effect of reducing the deposition rate
at current densities below 3.0 A crrr2. With the dissolved oxygen removed by de-aeration, the
deposition rates at theselow current densitiesincreasedby up to 60 %. In addition, the selectivity
30%.
by
around
reduced
was
88
10
Temp.25C
Li
Needle
type
Nodular
-----4=3-
Smooth
0
0
2000
4000
6000
No.
Reynolds
8000
10000
12000
Figure 18. Morphological diagram for the 0.041M citrate gold at a temperatureof 25oC.
40-C.
for
0.041M
diagram
temperature
the
at
a
Morphological
gold
of
19.
citrate
Figure
89
10
Temp.55C
Nodular
Smooth
0
0
2000
4000
6000
No.
Reynolds
10000
8000
12000
Figure 20. Morphological diagram for the 0.041M citrate gold at a temperatureof 55oC.
10
Temp.2SC
Fieldorientated
C.
C-,
Needletype
Smooth
0
0
2000
4000
6000
No.
Reynolds
10000
8000
12000
for
0.28M
diagram
25oC.
temperature
the
Morphological
gold
at
a
citrate
21
of
Figure
90
10
cs
0
0
2000
4000
6000
Reynolds
No.
10000
8000
12000
Figure 22. Morphological diagram for the 0.28M citrate gold at a temperatureof 40-C.
10
C.,
0
0
2000
4000
6000
Reynolds
No.
8000
10000
12000
for
0.28M
diagram
the
Morphological
citrategold at a temperatureof 55-C.
23.
Figure
91
axial direction. Suchstructureswere difficult to distinguish betweenfield oriented growth and the
recorded structure dependedon the relative magnitude of the axial and radial components.Low
temperaturesresulted in purely radial growth. High flow rates with low temperaturesincreased
the thicknessand regularity of the needlesfor the sameapplied current density. For the samelow
temperature and flow rate, increasingthe current density led to a finer, more filamentry type of
field
In
the
of
orientedgrowth, the structuresobserveddependedlargely
case
needle
growth.
radial
densities,
field
At
high
density.
orientedgrowths were nearly always
the
current
on
applied current
precededby needlegrowth.
From the above results, it was clear that the limiting factor to high speeddeposition was the
deterioration of the depositby nodulationor dendritic growth of various kinds. In order to establish
how such structures initiated and grew, a series of sampleswere prepared above the maximum
deposition
Each
for
density
the
conditions.
sample was prepared by
prevailing
useful current
incrementing the time of deposition slightly so that a picture could be built up of the mode of
deposits
(f)
density
10(a)
Photographs
to
show
a
series
of
produced
at
a
current
of 7.0 A
growth.
Photographs
II
(a)
(d)
3335.
but
to
Reynolds
the
show
some
of
of
same
no.
at a higher
CM-2at a
initiation
deposits.
These
the
of
show
and
growth
nodular
samples
magnification.
After a deposition time of 0.8 seconds,the substratewas fully covered with small nuclei
interspersedwith small nodules about 3.5 Am in diameter (Photograph 10a). Close examination
inhibition
larger
there
the
that
signs
surrounding
were
of
nuclei
this
nodules
revealed
sample
of
(Photograph Ila). After 1.5 seconds,the nuclei had grown to a size of about 2.5, um in diameter
having
7.5
(Photographs
10
b).
II
larger
Most
to
grown
about
and
nodules
Am
the
original
with
50
It
larger
the
a
outside
region,
presumably
stagnation
were
Am
these
zone.
nodules
was also
of
defects
After
2.5
larger
on
surface
such
as
scratches.
grew
that
nodules
seconds, there
noticed
larger
in
these
nodules
with
a
cluster
of
the same 50 Jim
of
appearing
number
were a greater
by
3
dimensional
be
that
It
growth
was
occurring
means
of
seen
nucleation, the
region. could
10c
I
Ic).
(Photographs
Deposits
and
appearance
taking
a
cauliflower
produced at a
on
nodules
time of 3.5 secondswere now distinctly nodular over the entire impingementregion with the fastest
(Photographs
10d
II
d).
the
By
5 seconds,
outside
stagnation
zone
and
occurring
of
nodules
growth
in
25
diameter
(Photograph
l0e). The growths in the stagnation
had
about
Am
the nodules
attained
but
their
distinct
3-dimensional
had
as
neighbours
growth
showed
the
size
a
more
same
attained
zone
forming
After
6
them.
on
and
growing
nuclei
seconds,whilst all the
mechanism with numerous
fastest
larger,
the
the
had
growth
occurred
at
centre of the spot, with these
slightly
grown
nodules
displayed
habit.
These
distinct
central
nodules
axial
a
columnar
a
powdery texture
nodulesadopting
(Photograph 10f). Some nodules towards the edge of the impingement region were obviously
influenced by the radial flow of the electrolyte as it enteredthe wall jet and had adopteda slightly
flow.
direction
following
the
the
of
elongated shape,
92
4
C,)
CD
CX,.
0
01
345
CurrentDensityA/cmsq
citrateelectrolyte.The
Figure24. Currentdensityvs platingratefor differentgoldconcentrations,
No.
12,000.
Re.
to
of
a
exit velocity corresponds
93
Figure 24 showsthe effect of current density on the depositionrate for different concentrations
of gold in the citrate electrolytes at a Reynolds No of 12,000. Tlere are several points to note.
Firstly, the rate bearsa linear relationship with the current density at current densitiesbetween I
and 5A cm-2.Above this upper value, the apparentrate varied, presumablydue to the increasingly
coarse deposits produced at these current densities. Ibis led to non-representativethicknesses
being measureddue to void and porosity formation. Secondly,the rate curves do not passthrough
the origin of the graph, indicating that at low current densities, the rate no longer has the same
linear relationship with current density. Similar results were observed with the phosphateelectrolyte.
It was found that the maximum deposition rate allowing smooth, high quality depositswas
obtainedfrom a 0.17M citrate electrolyte at 55-C and a ReynoldsNo. of 12,000. Ile rate obtained
from this electrolyte was 3.4, um/second.Photograph 13 shows a deposit 18
thick
produced
jum
deposit
14
By
these
of
comparison,
photograph
shows
a
of the samethickness
way
conditions.
under
be
It
deposit
that
the
can
seen
conventional
plating
conditions.
conventional
vat
under
produced
has an angular structure whilst the sample produced by jetting is comparatively smooth with a
hemispherical
mounds.
of
small
consisting
surface
The effect of the current densityon the current efficiency was establishedonly after the
Consequently,
it
be
had
been
increased
been
had
the
that
to
will
noted
pH
optimised.
electrolyte
8.1 comparedto 6.0 asshownin Table 1. for this setof experiments(seesection8.4)
Figure 25 showsthe relationship betweenthe current density and the current efficiency of the
0.17M citrate electrolyte produced at 550Cand a Re. No. of 12,000. It can be seenthat at current
densitiesabove2.0 A cm-2,the efficiency is in the region of 70%. Below 2.0 A cm-2,the efficiency
is reducedto 40% at a current density of 0.25 A cnr2. Experimentscarried out to remove dissolved
oxygen in the electrolyte revealedthat whilst oxygen, whenpresent,was electrochemicallyreduced
leading to a reduction in efficiency, this only accountedfor about 10%, averagedover the entire
current density range.
94
100
90
80
:2 70
Z::
L-3
60
so
40
30
0
34
CurrentDensityA/cmsq
Figure 25. Current efficiency vs current density for the optimised 0.17M citrate gold electrolyte.
95
220
200
HI
180
cn
Ul
160
140
HI
120
100
0
3456
Current density A/cm sq
10
96
20
k-
10
2
R Dimensionless
distance
Figure 27. A typical selectivity plot showing selectivity as a function of current density measured
using the Dektak.
97
4.1
I
11
-*-*.-200
220
-m-311
4.09
4. OB
4.07
4.05
r-
..&
222
a)
4.05
05
10
15
23
25
30
35
40
C.O. ffA/cm sq
100
goI
go
70
-*-III
-+-200
220
-311
60
40
t7
t: 7
loot=
10
113
20
30
25
35
C.D. ak/cmsq
98
Figure 28(b) showsthe degreeof preferred orientation of the deposit. It can be seenthat by
comparison with the expectedratios of the various planes (parallel lines) that there is a distinct
311 texture over the normal current density range of 1-7 mA CM-2.Above this, the deposit tends
towards a more random orientation.
The RMS strain of the conventionaldepositswas independentof current density over the range
analysedand was comparatively low, calculatedto be < e2>=0.000035.
The above measurementsof a conventionaldeposit were necessaryto compare and contrast
be
jetting
direct
Whilst
those
comparison
cannot
under
conditions.
a
made due to
produced
with
the orders of magnitudedifference in the current densitiesapplied, in terms of the morphological
increasing
density,
ie
the
that
current
a comparison
structural
changes
occurred
with
characteristics
was consideredto be valid. Figure 3 showssimilar graphsfor samplesproduced from the 0.17M
density
deposits
No.
12,000.
The
Re.
which
useful
of
maximum
current
under
a
using
gold
citrate
found
be
lattice
6.0
A
The
be
to
was
parameterof each of the crystallites
Crn-2.
produced
could
A.
bulk
in
4.075
However,
value, with an averagevalue the region of
was slightly smaller than the
below
2.0
lattice
A
densities
the
Cm-2,
parameterexhibited a smaller size.
at current
of
that this methodof estimatingthe crystallite size assumesall line broadeningis attributable to grain
indicate
222
III
fact
The
the
that this assumption
the
the
that
planes
were
not
same
as
planes
size.
line
broadening
difference
due
Further
incorrect.
the
to
that
this
of
analysis
was
revealed
was
density
0.0001275.
<e2>
the
current
over
measured
averaged
which
range
=
strain,
residual
There was no evidenceof either twin or stacking faults, except for a very low probability of a=
0.007 at a low current density. The crystallite size of the III plane as determinedby the Warren
A.
found
be
between
320
350
to
to
and Averbach method was
The preferred orientation of the jetted sarnplewas found to be strongly 220 above a current
density of 2.0 A crrr2. Below this value, aIII orientation predominated.
99
4.1
4.09
COB
4.07
-*-III
-+-203
--o-220
-311
-222
M6
a)
4.05
too
456
C.D. A/cmsq
10
90
-*-lll
-o-200
220
-4w-311
80
70
60
50
40
30
20
.0
loor
b)
456
C.D. Alcm sq
Figure 29. The relationship betweencurrent density and structural characteristicsas determined
by X-ray diffraction for a pure gold depositproducedby jetting in terms of (a) Lattice parameter
Reynolds
No.
Temp.
55-C.
12,000,
(b)
orientation.
preferred
=
=
and
100
101
C.D.- 4.0A/cmsq
Temp.
- SSC
Re.
No- 12000
0.28M
Citrateelectrolyte
K- 48.8mS/cm
Phosphate
A 0.27M
electrolyte
K- 90.02mS/cm
Citrateelectrolyte
v 0.28M
K- 97.6mS/cm
0.17M
Citrateelectrolyte
K- 88.2mS/cm
E
(I,
U,
C)
234
Rdimensionless
distance
ratio
102
higher conductivity citrate electrolyte. However, the depositquality deterioratedat a much lower
current density of about 3.75 A Crn-2.Despitethis, reasonablygood depositscould be producedat
a plating rate of 2.3 kLnVsecond.
8.1.8 The influence of nozzle size.
103
20
0.17MCitrate goldelectrolyte
100um nozzle
Currentdensity A/cm sq
0 4.0
Z 5.0
v 6.0
0 8.0
Temp.55 C
E
co
10
Re.- 3233
2
R Dimensionless
distanceratio
104
Diagram
Morphologicat
Dn-Time
vs
Duty
of
CycLe
Pulsed
AverQge
Temp. = 55 C
Rated
Jet
Gold
sq
100
nodular
slightly
80
60
very
nodutor
40
20
nodular
smooth
'rose'
0.1
0.02
0.2
(In-Time
0.5
1.0
20
5.0
10.0
mseconds.
Figure 32. Morphological diagram of on-time vs duty cycle at an averagecurrent density of 6.0
A Cm-2.
Diagram
Morphological
On-Time
Duty
vs
of
Cycle
Temp. = 55 C
Pulsed
AverQge
Jet
Plated
Gold
sq
100
very
80
noclutor
>1
60
noclutar
40
20
crown
t
--sr, o-o--
f ield
orientate
0.02
unknown
0.1
0.2
On-Time
Figure 33. Morphological
0.5
1.0
2.0
5.0
10.0
mseconds,
A Cm-2.
105
106
20
0 DCsample6.0 A/cm sq
A pulsesampleAUP4/22
Duty cycle= 20%
On-time= 0.02 sec.
AverageC.D. - 6.0 A/cm sq
Temp.z 55 C
Re.- 13545
C,,
e
10
-0
2
R dimensionless
distancefactor
Figure 34. A selectivity plot comparing a pulsed current deposit with the equivalent DC deposit.
107
CD
.11
AppliedcurrentdensityA/cmsq
10
100
Figure 35. Polarisation curve for the 0.17M citrate gold electrolyte using SVPA
Oneproblem with obtaining information using this techniquewas the influence of superimposed
5OHz noise on the signals, particularly at low applied current densities. The source was from
isolate
despite
but
the
to
and
cell and sensingresistors this
shield
efforts
equipment
surrounding
be
eliminated.
not
could
problem
108
0
4-JA
-Z:
C-)
1590
Csz
-I
L:::]
C,,
"411.
Z-'k .
4-.
C)
4-,
4-2
NY
-T-l
ZIA 'VIJU'
C] Re.No.= 13545
Re.No.= 3355
Re.No.= 1342
X\
_TZ
all 'I;?-119-1
EN
w
7
Temp.55 C
IN
-3
rsi
IN
kz-N
lu
V
/N
-4
001
.
LXI
w
P
01
.
.11
CurrentDensityA/cm sq
10
100
109
Reynolds No.
Lin-itingcurrent density
1843
0.367 A
CRr2
5252
0.470 A
Cnr2
7538
0.591 A
Cnr2
0.0
4-.
C,
4-.
[Z
-
-1.0
01
.
.1
Current density A/cm sq
10
110
0.448
(29)
the data from the turbulent flow experimentsagreedto 10% and 20% for Re = 7000 and Re =
10800. If it is consideredthat some deposit growth was experiencedduring the measurements,
if
be
Additionally,
a complete, steadystate equilibrium was not
expected.
some variations could
densities.
limiting
higher
lead
be
to
to
current
of
this
values
expected
would
achieved,
Other workers who have attemptedto measurelimiting current densitiesfor pure citrate gold
in
described
Chapter
2,
However,
been
have
the addition of a
as
unsuccessful.
also
electrolytes
few pprn of lead has been shown to interfere with the hydrogen evolution reaction and allow a
limiting current plateau to be observed. However, the addition of lead to the electrolyte was not
bythis
density
limiting
methodwould not necessarilybeapplicable
obtained
current
considered,asa
lead
lead.
has
been
described
As
in
the
and other metallic
earlier,
of
absence
to the results obtained
bonding
lead
to
performance.
wire
gold
poor
can
gold additives
Whilst the Auruna 7000 solution gave the greatestdeposition rate, examination of the deposits
fracturing
high
the
the
these
spots
were
underlying glass
rates,
that
plating
at
showed
produced
internal
high
levels
For
Auruna
indicating
tensile
this
of
stress.
reason,
substrateand exfoliating,
7000 was not used for further trials. In addition, whilst the cobalt and nickel alloy golds are
iron
the
are
golds
relatively
alloy
new
and
would
specifications,
existing
within
accepted
generally
Ronovel
The
CM
in
difficulty
commercially.
electrolyte
acceptance
gaining
present a greater
III
The basic Ronoval N electrolyte containing no nickel but with 60 n-J 1-1"booster" produced
semi-bright deposits.Optical examinationrevealedthat the deposittopographyexhibited a rounded
density
a
wide
current
over
range, the size of the mounds increasing with
appearance
mound
increasing current density. The nodules were approximately twice the size of the equivalent
thicknessof pure gold depositedunder identicaljetting conditions. As with the pure gold samples,
it was clear that surfacefeatureswere amplified asthe plating time and thus the thicknessincreased.
Photograph 30 shows an optical micrograph of a 17.2,um deposit from this electrolyte produced
Photograph
8.0
A
31
density
Cr1r2.
of
shows a microsection of a similar deposit but
current
at a
density
9.0
A
It
be
of
CM-2.
can
seenthat unlike the pure gold electrolytes,
a
current
at
produced
the nodulation would seemto have commencedas deposition proceededand not during the initial
density
9.0
A
Above
current
of
a
CM-2,the nodule size was reducedbut with an
of
growth.
stages
increasein the number of nodules.
112
8.2.2 The effect of the addition of nickel to the basic Ronovel N electrolyte.
The following additions of nickel additive were madeto the basic electrolyte; 0.5 g 1-1,0.7 g
1.1 g 1-1,1.5 g 1-1,2.2 g 1-1,2.5 g 1-1and 3.0 g 1-1.With each increment, deposit spots were
for
deposit,
hardness
topographical
the
examination,
nickel
content
of
and XRD
produced
examination. Two setsof sampleswere produced. The first set were plated to a thickness of >
16 jArnso that comparisonswith pure gold could be made. In addition, thick depositswere required
for the testing of the physical characteristicsof the deposit.The secondsetwere platedto a thickness
for
in
These
from
2.5,
:
value
use
realistic
production.
a
more
were
produced
an electrolyte
of
um,
1-1
1.9
g
nickel.
containing
8.2.2.1 Relationship betweennickel in the deposit, nickel in the electrolyte and current density.
Figure 38 shows the relationship between the nickel in the electrolyte and the nickel in the
deposit over a rangeof current densities.A linear regressionhasbeenapplied to the datapresented.
it can be seenthat a linear relationship exists for all concentrationsof nickel used. The error bars
indicate the analytical error of 6% of the nickel in the deposit. A further 5% error, not shown
for
in
the
solution.
analytical
error
nickel
the
represents
graphs,
on
113
.5
CurrentdensityA/cm sq
0 2.0
V 6.0
+ 12.0
Z 4.0
0 8.0
X 16.0
I Plotsdonot include
.3
5%error in Ni in soln.
determination
.2
0.0
2
Ni in solutiong/I
Figure 38. The relationshipbetweenthe nickel in solution and the nickel in the deposit for different
applied current densities
Figure 39 shows how the nickel in the deposit varied with the applied current density. A
data
best
has
been
fit.
Whilst
to
the
to
the
this
applied
provide
curve
analysis
regression
geometric
in
its
lower
is
for
be
the
concentrations
validity
of
nickel
solution,
quite clear at
questionable
may
believe,
is
be
different
There
to
therefore,
that
higher
such
a
relationship
will
no
reason
values.
the
for low values of nickel. The graph indicates that at low current densities, a greater quantity of
is
This
high
in
deposit
densities.
incorporated
the
than
understandableconat
current
nickel was
is
in
it
is
than
the
a
citrate
considerable
more
noble
that
electrolyte
gold
unless
nickel
sidering
strongly complexed.
114
68
10
12
14
16
18
20
Current densityA/cm sq
115
4
w
E
C>
N 60 ml/I boosternoNi
E] Ronovel
80
booster
Ronovel
N
Ni
ml/I
no
,0
Ronovel
N 60 mi/I booster
2.2g/l Ni
Ronovel
N 60 ml/I booster2.5g/l Ni
3.0 g/l Ni
N 60 ml/I booster
+ Ronovel
0
0
10
is
20
Currentdensity A/cm sq
Figure 40. Current density vs deposition rate for various concentrationsof nickel and booster in
the Ronovel N electrolyte.
116
100
90
80
e
.,.
>1
Iv
ZZ-3
60
so
40
30
10
Current density A/cm sq
is
20
Figure 41. Current efficiency vs current density for the Ronovel N electrolyte containing 1.9 g 1-1
Ni and 60 ml 1-1booster.
117
42, it is clear that at lower current densities,where the nickel in the deposit is greater, a lower
hardnessresults.This is in conflict with the well known effect of the hardnessincreasingwith the
addition of nickel seenwith conventionalgold nickel alloys.
34567
10
CurrentdensityA/cm sq
Figure 42. Deposit hardnessvs current density for different concentrationsof nickel in the electrolyte.
Figure 43 shows how the nickel in the deposit influenced the hardnesswhen depositedat
different current densities.It is evident from this graph that the quantity of nickel in the deposit
%)
hardness.
Low
(<
0.1
factor
the
the
contents
nickel
showedroughly the
affecting
only
was not
samehardnessvaluesirrespectiveof the current density. This did not vary by much for samples
below
increased
5.0
densities
A
However,
cm-2.
current densitiesexhibited
at
current
produced
different hardnessesfor the samevalue of nickel in deposit.The relationshipbetweenthe nickel
in deposit,current densityandhardnessis summarisedin Figure 44, which showsa 3-dimensional
surfaceplot of eachof the parameters.
118
220
Currentdensity
A/cm sq
200
cr
160
140
120
loo I
0.0
.1
.2
Ni in deposit
.3
.4
Figure 43. The relationshipbetweennickel in the depositand the hardnessfor different valuesof
applied current density.
119
20
Current density A/cm sq
No nickel
e-_
0 2.0
5.0
7.0
9.0
+ 16.0
lc-zzll
%\
Temp55 C
Re. - 10600
NQ-K-ll
14
0
23
R Dimensionlessdistance ratio
120
E
=
C,,
23
R Dimensionless
distanceratio
E
La
(I)
-d
23
R Dimensionlessdistance ratio
121
E
=
I,
-C
i-1
0
0
34
R Dimensionless
distanceratio
Figure 48. Selectivity of a deposit from a Ronovel N electrolyte containing 3.0 g 1-1produced at
1.0 A CM-2.
122
103
4.1
0111
90
-4-200
-a-220
311
Z! 2
4.09
#111
-4-220
-a-223
-311
80
70
4.OB
60
50
CL
do
-0
4.07
30
20
4.06
10
4.05
to
a)
30
20
C.D. rrAlcm
sq
40
50
10
b)
20
30
40
50
C.D. irA/cmsq
C)
Figure 49. The relationship betweencurrent density and structural characteristicsas determined
by X-ray diffraction for a conventionallydepositedgold nickel alloy from a Ronoval N electrolyte
in terms of (a) lattice parameter(b) preferred orientation and (c) hardness.
123
4.1
4111
200
220
4.03
-311
-222
4.09
CL
a)
.U4.07
4.06
05
a)
10
15
20
25
30
35
40
C.D. M/cmsq
10
20
30
40
50
C.D. ffAlcmsq
b)
i
leo
le
15 20
25
C.(L Wcmsq
30
35
40
C)
Figure 50. The relationshipbetween current density and structural characteristicsas determined
by X-ray diffraction for a conventionally deposited gold nickel alloy without booster from an
Auronal MRN electrolyte in termsof (a) lattice parameter(b) preferred orientation and (c) hardness.
124
a)
....
1
*111
-o-200
220
-*--311
90
70
60
50
C
.
40"
30
20
10
0
05
b)
10
15
20
C.D.A/cm
sq
Figure 51. The relationship between current density and structural characteristics as determined
by X-ray diffraction for jet deposited gold from an electrolyte containing 60 n-d 1-1booster in terms
(b)
lattice
(a)
preferred orientation.
parameter
of
125
a)
100
90
-+-200
220
-311
80
70
60
50
40
30
20
10
g
b)
10
15
20
C.D.A/cm
sq
Figure 52. The relationship betweencurrent density and structural characteristicsas determined
by X-ray diffraction for jet deposited gold containing 80 ml 1-1booster in terms of (a) lattice
parameter (b) preferred orientation.
126
a)
30rl
20t:
.6
10
0
05
b)
15
10
20
C.D.A/cm
sq
as determined
Figure 53. The relationshipbetweencurrentdensityandstructuralcharacteristics
by X-ray diffraction for jet depositedgold nickel alloy from an electrolytecontaining1.9 g 1-1
(b)
lattice
(a)
booster.
1-1
H
60
preferredorientation.
parameter
nickel and
127
a)
I
CO
80
-s-220
70 :.
60
50
40
30
20' ,
10
b)
0
10
15
20
C.D.A/cm
sq
Figure 54. The relationship between current density and structural characteristicsas determined
by X-ray diffraction for jet depositedgold nickel alloy from an electrolyte containing 3.0 g 1-1
(a)
lattice
(b)
booster.
1-1
60
preferred orientation.
parameter
ml
nickel and
128
The effect of the booster can be clearly establishedunder conventional deposition conditions
by comparing Figures 49 and 50. Figure 50(b) shows that in the caseof the Auronal MRN, a
distinct 111 texture is formed between 10 and 15 mA crrr2, the normal operating range of this
electrolyte. Indeed, below this range, the deposit appearancewas matt. Above this range, the
deposit showed signs of "burning" at the edgesof the sample. Figure 49(b) shows that with the
addition of the booster, the III texture was predominant above 5 mA Cm-2,with the apparent
suppressionof other growth directions. Pure gold, as has been seenearlier, possesseda distinct
3 11texture under conventionaldepositionconditions. It would appear,therefore, that a 111texture
is one of the necessaryconditions for the effective performanceof a nickel hardenedalloy gold.
Hardness measurementsshowed that the depositswith the booster were 15% harder than those
booster
be
density
15
It
the
that
to
reduced the
seen
of
mA
Cm-2.
can
also
a
current
up
without,
in
its
deposits
lattice
to
those
compared
produced
absence.
parameter
effective
The lattice parameter of the conventional depositswithout booster exhibited a mean lattice
%
less
0.27
than that of annealedgold and remainedessentiallyconstantwith current
parameter
density. The valuesfor all the planeswere comparablewithin the overall accuracyof measurement.
The lattice parameter of the conventional deposit containing booster was also lower than that of
being
less
-0.33%
than that of pure gold and showed a small
the
mean
value
annealed gold,
increasinglinear dependenceon current density. However the 220 planeswere significantly larger
and were comparableto those of the electrolyte without booster.
In both cases,the crystallite size of the III planesas determinedby the Scherrer equationwas
for
The
for
the III reflection was -350
the
than
value
other
measured
planes.
calculated
greater
A for depositsproducedat the lower current densities,decreasingto -200 A with increasedcurrent
density. The crystallite sizescalculatedfor the other planesmeasuredwere typically in the region
A.
booster,
from
In
the
the
100
elecirolyte
containing
samples
produced
the
closer
of
case
of
RMS
Averbach
Warren
that
the
a
significant
strain contributed
and
analysis
revealed
analysisusing
to this difference as canbe seenfrom Table 23. In addition, a slight asymmetryof the reconstructed
faulting
but
twin
that
some
was
present
as explained earlier, no accurate
suggested
peaks
be
their
could
magnitude
made.
measurementsof
Figures 51 and 52 show the data calculatedfrom samplesproducedbyjetting from electrolytes
1-1
booster
but
Figures
6(b)
80
7(b)
1-1
60
no
nickel.
n-J
respectively
and
show
and
ml
containing
increasing
be
It
that
can
seen
with
current density, the 111 component
the preferred orientation.
%
220
60
The
the
the
to
component.
expense
of
around
at
contributions
rapidly
of orientation rises
from the 200 and 311 remained fairly constant and close to their values expected in a random
is
This
consistentwith aIII
sample.
texture.
129
Figures 51(a) and 52(a) show the influence of the boosteron the lattice parameter. Thereisa
general trend of a reduction in the lattice parameterfor all planeswith increasingcurrent density.
It will be noted that the 200 plane exhibited a significantly smaller lattice parameterthan the other
planes. This would suggestthat a distortion of the lattice wasbeing createddue to the incorporation
of the booster (or breakdownproduct of it) within the 100 (200) planes.
As was observedin the previous samples,the 111planesexhibited a larger apparentcrystallite
size than the othersas determinedusing the Scherrerequation. For both concentrationsof booster,
A
be
in
found
300
III
to
the region of
the
whilst that of the other measuredplanes was
plane was
in the region of 150 A. This may be attributed to both stacking faults as well as residual strain as
can be seenfrom Table 23.
The presenceof nickel reducedthe lattice parameterof most of the planes examinedto below
A.
A
densities,
increasing
4.07
This latter value was about
low
4.07 at
to slightly above
current
the sameas that for the samplescontaining boosteralone. Examination of Figures 53(a) and 54(a)
increasing
density,
fell
200
lattice
the
the
that
current
similar to
with
parameter
of
plane
revealed
that of the samples with booster alone. With relatively large concentrationsof nickel in the
in
lattice
220
311
the
the
the
parameter, particularly at
and
also
exhibited
reductions
electrolyte,
high current densities.
130
C?
0
C?
-3
-4
001
.
01
.
.II
Appliedcurrent density A/cm sq
10
100
Figure 55. Polarisationcurve of the RonovelN electrolyteboth with and without nickel using
SCPV.
I
131
CHAPTER 9
There are a number of potential applications for which HSSJE would be suited. These are
mainly in the electronics industry. With a suitable scale-upof the system, it could be adaptedfor
engineeringuse, applying the principles outlined here to other metals. There are also areaswithin
the decorative market that could also be exploited. The following Sectionsoutline some of these
applications in more detail.
MICS are used extensively throughout the Telecommunicationsand Defence industries for
mounting active devices such as amplifiers, delay lines etc. The substratescan be made from
PTFE
by
These
or
composites.
quartz
are
metallised
sputtering a "keying" layer
alumina,
sintered
of chromium, followed by approximately 0.1 jim of gold. Circuit tracks are either defined by
photoresist and gold plated through the defined lines. Alternatively, the whole substrateis plated
with gold and the tracks defined by a print and etch process. Each processhas its disadvantages.
The additive processsuffers from photoresistattack by the gold depositionprocess.This is due to
the production of cyanideat the interfaceasa by-product of the depositionprocess.This effectively
failure
leading
definition
the
to
the
resist
a
complete
of the adhesionof
of
poor
or
edge
undercuts
the resist. There are a number of formulations that are claimed to overcome these problems,
including a tin brightened gold (111)electrolyte that operatesat a pH of 0.60. However, the
is
industry
doubtful
for
the
electrolyte
where very pure deposits
an
microwave
such
of
usefulness
high
definition
The
tracks as the photoresist is
process
can
produce
very
subtractive
are required.
does
into
However,
the
and
the
stage
not
come
contact
with
gold
electrolyte.
at
etching
up
applied
to 80% of the electrodepositedgold is etchedoff, constituting a considerablere-processingcost.
Consequently,thesemethodsare expensive.Apart from the gold, the main cost lies inthe production
form
in
These
However,
an
enlarged
and
are
produced
require
photo-reduction.
masks.
of suitable
by using the direct writing facility provided by HSSJE,the circuits can be written without the need
132
for masking directly from the CAD designs.A sputteredor electrolessplated layer is still required
in order to make the insulator conductive. After the direct writing process,thesethin metallised
layers canthen be removedby etchingwith virtually no attackon the written gold layer. Photograph
38 shows a simple ring oscillator producedby direct writing.
133
be
high
to
at
produced
very
production rates without the need for any
components
such
enable
'
form of masking. The size of the plant required and the volume of electrolyte will be considerably
reduced, thus reducing the capital expenditureand reducingthroughput times. Multiplejetsmay
be used for extra speedor where more than one area requires selectiveplating. The use of such a
small systemwill enablelarger numbersof connectorsto be producedin smaller floor areas.This
should considerably reduce the cost and lead to higher specification products being available at
currently commercial quality product prices.
As well as connectors,the gold plating of lead framesfor the semiconductorindustry is carried
for
Whilst
is
a number of applications, the use
systems.
silver
replacing
gold
on
reel-to-reel
out
of HSSJE could make gold more competitive as well as giving a high reliability product.
9.1.3 Bump plating.
Tape AutomatedBonding is a techniquethat is acquiring importancein the electronicsindustry.
The processconsistsof the production of lead frames on a metallisedplastic strip, similar to a 35
integrated
lead
frames,
film.
In
to
the
to
the
circuits
order
connect
ultrasonic
photographic
mm
bonding of gold or aluminiurn wires is used. To facilitate this, a gold bump is required at the end
for
in
However,
difficulties
lead.
There
technique
this.
a
photoresist
a
number
of
using
are
of each
selectivejetting can overcomemany of theseproblems.
9.1.4 The direct writing of etch resist for printed circuit boards.
The use of electrodepositedmetal etch resistshas beendescribedin Chapter 3. Using HSSJE
it will be possible to directly write the tracks using a metal etch resist. Although such a system
it
in
high
find
today,
techniques
the
use
could
conventional
volume
well
with
compete
not
could
PCB
Prototype
PCB's
in
the
of
prototyping.
are relatively expensiveas they
area
an application
By
direct
board
be
the
etch
using
writing
metal
resists,
of
a
could
photo-tooling.
need one-off
from
directly
design
By
design
(CAD).
the
a
computer
aided
using
as the
rapidly
very
produced
be
in
to
the
system
moved
the
control
will
enable
nozzle
relation to the board
computer
pattern,
be
The
of
such
a
system
would
relatively low in
pattern.
capital
cost
resist
thus writing an etch
Writing
Direct
Laser
PCB
systems
such
as
to
of photoresists.
manufacturing
comparison other rapid
However, it would have the disadvantageof not being able to produce through hole boards. This
there
be
as
are many existing processesthat can provide
a
prototype
with
a
problem
such
not
may
through hole connections,either manually or automatically.
134
There are other applicationsmore suitedto metalsother than gold but thesewill not be discussed
here. The electrochemicaland hydrodynamicconsiderationsthat apply to gold will most likely be
applicable to other metals.
135
would be necessaryto improve the selectivity of the deposition process in order to produce
microwave circuitry of an equivalentquality to thosecurrently being produced. Alternatively, the
impedencecharacteristicsof the HSSJEdepositscould be accommodatedby a small redesign of
the circuits basedon the deposit profile and accommodatingan increasedthickness. It would be
before
it
the
to
assess
economics
of
such
a
process
carefully
could be usedfor microwave
necessary
circuitry.
136
After testing, the wear scarswere examinedusing scanningelectron microscopy with an energy
dispersive X-ray analysisfacility. Copper X-Ray maps were produced of the contact regions to
determine the extent of the penetrationof the gold layer.
The results of contact testing indicated that in the caseof the jetted samples,higher contact
loads gave rise to lower contact resistanceswhereasthe conventional samplesonly showed this
effect with the 1.0 14mdeposit. The overall contactresistancefor both types of deposit was within
generally acceptedlimits, below 8.0 mOhms.
Examination of the wear scarsafter 200 cycles indicated that jetted 0.5 Am deposits showed
little apparentwear with loadsof 55g after 200 cycles, whereasthe equivalentconventionaldeposits
showed significant wear. However, at a thickness of 1.0 Am, the jetted samplesshowed severe
wear with penetration of the coating, apparently abrasivein nature. The equivalent conventional
depositsshowedlesswear althoughsomecoatingpenetrationwas apparent.No wear was observed
for any of the samplesafter 50 cycles.
.
These results are very limited but they do indicate the potential for the use of HSSJE for the
plating of connectorsand further work will be undertakento identify the optimum conditions for
good wear properties.
137
format. The tracks were written using pure gold at a linear tracking rate of 1.5 mm sec-1and at a
current density of 6.5 A Crn-2.It was found that a slightly higher current density could be used
when tracking the jet without any degradationto the deposit. A deposit thicknessof 3.5 lim was
measured. After completion, the thin background gold layer was chemically removed and the
un-coatedcopper cladding was etchedaway using a 500g 1-1ferric chloride solution at 60-C. Using
0.9
Virtually
jet,
400
track
of
nun
was
produced.
width
no undercutting of the
a
consistent
a
lAm
tracks were observed.
138
CHAPTER 10
10.1 GENERAL
139
of the hydrodynamic boundary layer adjacentto the diffusion layer. The maximum possible resupply of metal ions will be achievedwhen this boundary layer is of the samemagnitude as the
diffusion layer. However, limits are set by the way in which the growing electrodepositinteracts
with both the boundary and diffusion layers and this will be discussedin depth later.
140
in the caseof the pure gold masstransfer experiments,as no limiting current plateaucould be
seen,a graphical methodconsistingof extrapolatingboth the Tafel slopeandthe high overpotential
region was used. Extrapolations were obtainedusing a linear regressionprocessusing the points
that gave the highest correlation coefficient for eachregion. The point of imtersection represents
the limiting current density. Figures 56 to 59 show the extrapolationson the polarisation curves.
It was decidedto adopt the correlation derived by Alkire and Chin to comparethe results for the
gold as theirs was the more recent study. Table 27 shows the experimentally obtained limiting
currents for both SCPV and SVPA methodstogether with the values calculated from the Alkire
& Chin model.
Ibis data showsa very closeagreementwith the correlation of Alkire and Chin. Basedon these
diffusion
layer within
data
it
is
the
to
the
thickness
of
obtain
some
quantitative
on
possible
results
the impingement region.
141
ET
Ln
E
c
-:::
(
(N
IIIII
1111111
1' 11111111111!
I -A IIIII
Ln
";zv
C4
A-
IIIII
-L-
(N
C
-J
IIII
Ln
6
CD
14ua4odj, 3AO
Figure 56. Graphical evaluation of the limiting current density for jetted pure gold at a Reynolds
SCPV.
'L
data
by
3355
obtained
= 4.41 A cm-2.
using
number of
142
CT
Lfl
(Z)
D
L
C
-J
(N
C)
111
IIIIIIIfIItIIIIIIII.
-1
CN
Lr-)
Ln
CE
0
i
A-
(D
jejquaqodJ@Ao
143
AIIIIIIIII
IIIfII
q
llzv
(N
Cr)
uI-)
Ln
ci:)
jejquaqod-J3AO
Figure 58. Graphicalevaluationof the limiting cuffentdensityfor jetted pure gold at a Reynolds
'L
9.97
A
data
SCPV.
by
13545
cm-2.
obtained
using
numberof
144
(-D
ci-
(D
Ln
FE
cr
CA
cr s
Ln U
-J
L(i
LriII
IIE
2
LD
I
00
C: C:
C2r-ql
III
-I
IItIIIIIIIIIIIIIIIIIIIIIIIItIIIIIfIII
IZZI,
a
Ln
m
c10
L-A
m
A-
Lr-) (N
12TquaqodJBAO
Ln
0
Figure 59. Graphicalevaluationof the limiting currentdensityfor jetted gold from a RonovalN
Reynolds
10600
data
by
both
a
number
at
of
using
obtained
and
without
nickel
with
electrolyte
SCPV. Electrolytenickel concentration= 1.9 g/l, limiting current densityvaluesare shownon
the graph.
145
146
that in the deposition of the samples,a constantnumber of coulombs was passedfor each spot.
However, it was found that the measuredthicknessof the deposit at the jet centre-line increased
with increasingcurrent density. Figure 60 showsa typical exampleof the behaviour of a pure gold
deposit. There are a numberof reasonsfor this. Figure 17showsthe spreadof the depositmeasured
optically. It can be clearly seenthat the diameterof the depositwas high betweena current density
of 0.25 and 3.0 A cm-2although not readily measurableusing the Dektak. In addition, Figure 25
function
density.
If thesetwo effects are taken into
the
the
as
a
of
current
efficiency
current
shows
consideration together, the behaviour observedin Figure 60 would be expected.
20
10
0
01
345
Currentdensity A/cm sq
Figure 60. The relationship betweenthe measuredthicknessat the jet centre-line and the current
density for the 0.17M citrate gold.
A reduced current efficiency in the lower current density region, together with a decreased
density
thickness
the
the
to
over
current
measured
overall
range of
reduce
selectivity combined
0.25 to 3.0 A Cm-2.It can also be seenthat betweena current density of 3.0 and 4.5 A cm-2the
deposit
be
is
This
the
as
and
expected
efficiency
width
may
constant
constant.
thicknesswas almost
4.5
A
increase
in
in
increase
The
thickness
cm-2
coincided
roughly
with
above
an
this
range.
over
increase
in
A
The
in
5.0
density
the
thickness
cm-2.
of
was
current
the current efficiency above a
6.0
4.5
A
However,
density
between
the efficiency and
10%
and
of
Cni-2.
current
a
the region of
147
deposit width remainedconstantover this range. This would indicate that a changein the density
occurred either by micro-void or foreign matter incorporation into the deposit It was not possible
to measurethe density of the deposits,althoughmicrosectionsdid not show any signs of porosity
up to a current density of 7.0 A cm-2.Betweena current density of 5.0 and 7.0, a relative increase
in efficiency of 10% occurred. Over this range, an increasein thicknessof 10% also occurred.
This would explain the increasein thickness with increasing current density above 5.0 A crn-2.
Additionally, abovea current density of 7.0 A cm-2,the depositbecameincreasingly nodular, thus
artificially increasingthe apparentmeasuredthickness.
It is interesting to note that the width of the deposit passedthrough a maximum at a current
density of 0.75 A crrr2and thereafterreduced.The model developedby Alkire and Chin, together
with experimental results using a redox reaction indicates that low currents should lead to high
selectivity. In the case of copper deposition, they found that the opposite was true, with high
currents exhibiting better selectivity. This wassimilar to the depositionof pure gold. They attributed
this behaviour to the difference in the exchangecurrent densities of the copper and ferricyanide
electrolytes. If the Alkire model was correct, then in the caseof pure gold, the value of k (Equation
26) would have to be in the region of 10-1and the systemwould be operating under conditions of
mixed ohmic and charge transfer control. The polarisation data that closely correspondsto the
deposition conditions used to generateFigure 17 can be seenin Figure 36. It can be seenthat for
a Reynolds number of 13545, a current density of - 1.0 A Cm-2signifies the onsetof mixed charge
transfer and masstransfer control. This doesnot agreewith the Alkire/Chin prediction. However,
it should be notedthat the Alkire/Chin modelwasbasedon theoreticalcalculationsandexperimental
conditions over a "nozzle current density" of between0 and 100 mA crn-2.This is at least an order
in
lower
the
than
this work. Additionally, the reactive ion
experimental
values
used
magnitude
of
lower
in
Consequently,
than
this
this part of the
order
of
magnitude
an
work.
was
concentration
for
for
the
the presentstudy. The model and experimental
conditions
used
apply
may
not
model
data did show that at higher reactantconcentrations,the selectivity was increasedat higher currents.
This was becausethe impingement region operated under mass transfer control. Under these
in
improved
deposition
increase
the
the
concentration
an
rate within the impingement
conditions,
jet
led
increase
in
to
the
to
and
wall
a
significant
selectivity. The experimental
compared
region
in
this study agreewith such a prediction and therefore this part of the model was
obtained
results
Significant
improvements
in
to
the
studied.
conditions
selectivity were observed at
applicable
for
in
higher
ion
densities
the
the
control
region
mixed
relatively
metal
concentrationsused
current
in this study. At current densitiesbelow 0.75 A crrr2the selectivity increasedand this agreeswith
low
densities.
higher
The model predicts that a
for
concentrations
at
current
reactant
the model
be
in
increase
in
improvement
selectivity
would
observed
as
an
concentration increases
moderate
the exchange current density reducing the charge transfer resistance compared to the ohmic
be
Tafel
Such
the
the
at
appreciable
commencement
more
of
would
an
effect
region,
resistance.
density
increased.
This,
then, explainsthe shapeof the curve observed
the
was
current
reducing as
148
in Figure 17 with the maxima coinciding with the end of the Tafel region and the start of the mixed
charge transfer and masstransfer controlled region. Further discussionof the effects of current
density on the selectivity will be given later when the deposit interaction with the fluid flow is
discussed.
10.3.4. Temperature.
The temperature influenced the structure of the depositsin two ways. Firstly, an increasein
temperatureincreasedthe diffusion coefficient and enhancedthe rate Of masstransfer. This led to
density
increase
in
limiting
in
increase
the maximum useful current density.
the
current
and
an
an
Secondly, it influenced the flow characteristicsby altering the viscosity. This led to a significant
between
deposit
flow
be
interaction
discussed
in
the
the
this
the
and
electrolyte
and
will
alteration
in Section 9.6. The Alkire/Chin model did not include temperatureeffects and therefore a comdid
influence
The
be
temperature
the selectivity of the
significantly
not
made.
cannot
parison
deposits measured.
149
IncreasingthepH of thecitrateelectrolyteincreased
themaximumusefulcurrentdensity.This
would be expectedbasedon the stability theory.The citrateelectrolyteoperatedat a pH of 6.0
hasa lower currentefficiencycomparedto that at a pH of 8.1. This is becausethe hydrogenion
latter
in
deposition
lower
hydrogen
is
is
the
the
case
and
potential
of
morenegative
concentration
than at lower pH values.Therefore,moresurfaceadsorbtionsiteswill be availableat higherpH
andencourages
stability.
values.This effectivelyallowsa greatersurfaceconcentration
The role of the supporting electrolyte is also influential in the maximum deposition rate. The
both
decreased
density
a
maximum
current
exhibited
and deposition rate
electrolyte
phosphate
is
for
further
be
The
this
the
un-clear
and
to
work
reason
will
citrate.
required to establish
compared
differing
ions
degrees, with the phosphateions
to
is
It
the
that
adsorb
supporting
this.
possible
level.
higher
adsorbing at a much
150
151
A reduction in the nozzle size led to a reduction in the deposition rate of around 80 % as well
In order to ascertainwhy the deposition rate was
as a reduction in the selectivity to R=4.5.
reduced, it was necessaryto establishthe total massof gold depositedfrom both the 100 pm and
the 400 prn nozzle under similar conditions, exceptfor the Reynoldsnumber for reasonsdescribed
above. Deposit half profiles, similar to the selectivity plots except using thickness vs d' were
obtained from samplesproducedat a current density of 6.0 A Crn-2and a time of 5.7 secondsfrom
both nozzles. It was assumedthat there were no voids or inclusions that would reducethe deposit
density. A polynomial regressioncurve fitting routine was applied to each profile to obtain the
best fitting formula for eachcurve. The following data was obtained;
3_5.90SX4+
17.39
6.316
32.21
22.
OOSx
O.S67x3
+
yxX2 +
(30)
y-3.3
+ 0.107x
0.942
X2+ 0.264 X3_ 0.021 X4
-
(31)
Thesewere integratedin two axial directionsin order to find the volumeof eachdeposit.If
depositionconditionswere identicalfor eachdeposit,the ratio of the volumeto the numberof
be
very similar. It wasfoundthat for thedepositproducedfrom the400
should
coulombspassed
0.00156
However,
0.00108
obtained.
was
of
a
ratio
of
was obtainedfor the
a
ratio
nozzle,
pm
depositfrom the smallernozzle,30% lower than the larger nozzle.This is not as high as the
depositionratereductionof around80%wouldsuggest.Themassof thedepositswerecalculated,
The
19.3
deposit
density
theoretical
g
cm-3.
each
of
mass
of
was calculatedfrom
a
assuming
Faraday'sLaw. The cathodecurrent efficiencycouldbe calculatedfrom this data.It was found
that for the largernozzle,an efficiencyof 76% wasobtained.This comparesvery well with the
density
for
this
current
of 74% (Figure25). The efficiencycalculatedfor the
measuredefficiency
%.
for
There
53
in
two
the
are
possible
reasons
reduction
was
efficiency.The first
nozzle
smaller
lower for thesmallernozzleandasthemasstransport
is that the Reynoldsnumberis considerably
be
likely
ions
is
to
reducedas a resultof this, thenthe efficiencywill be reduced.The
of gold
interpretation
density.
Throughout
involves
the
the
theproject,thecurrent
of
current
reason
second
densityhas beengiven in termsof the nozzlediameter.This is not strictly valid as deposition
In
impingement
is
the
the
the
the
case
of
region.
smaller
nozzle,
selectivity
worse
outside
occurs
the true currentdensitywould probablybe lower
than with the largernozzle.As a consequence,
density
for
for
is
is
100
Evidence
this
the
the
useftil
current
maximum
taken.
nozzle
that
than
an
152
highef than for the larger nozzle, being 10.0 A crn-2,despiteoperating at a much lower Reynolds
it
is
is
likely
It
that
a combination of both possibilities that leads to the reduction in the
number.
deposition rate from small nozzles.
10.3.7. The effects of pulsed current.
153
crystallitcs as higher orders of reflection could not be obtained with this experimental method.
However, examinationof the lattice parameterswould suggestthat no stackingfaults were present
as they are all the samesize. These samplesexhibited the lowest RMS strain for the 111 planes
of all the samplesexaminedover the currentdensityrangeanalysed.The morphology of the deposits
produced may be describedas angular and crystalline.
When deposits are produced from the sameelectrolyte using HSSJE, both the structure and
morphology are significantly altered. This is due both to intrinsic changesin the deposit structure
due to the deposition conditions as well as the interaction with the electrolyte flow. The latter will
be discussedin the following Sections.The intrinsic changes-result from the very high rates of
deposition. The grain size is considerably reducedto a value in the region of 200 A, a tenfold
reduction. Such a reduction is the most likely causeof the increasein the deposit hardnessup to
featureless,
kg
The
200
and
mm-2.
surface
appearance
was
smooth
gradually
around
of
a value
developing smooth rounded mounds with increasingcurrent density. This rounded mound morphology is similar to that developedin the caseof alloyed golds. The mechanismof the growth of
these structures is discussedin a subsequentSection.
A (220) preferred orientation develops which, as has been suggestedby Lin et a137may be
is
in
be
lattice
A
the
observed,
which
slight
reduction
parameter
may
species.
caused adsorbed
due to the incorporations of small quantities of foreign species.This would not be surprising at
bury
deposition
high
the
takes
place
can
easily
surface
as
speed
at
growth
which
of
rates
such
is
important
both
jetted
deposit.
It
the
to
that
the
conventional
note
and
within
adsorbed species
This
lattice
deposits,
the
the
self
consistent.
parameter
of
of
measured
planes
was
each
gold
pure
faults
fairly
No
detected,
deposit
the
that
structure
was
ordered.
structural
were
well
would suggest
low
densities.
This
D,
low
for
true
that
the
at
current
means
and
probability
=D
very
a
except
ff
23.
in
Table
is
as
crystallite size
Some pure gold depositswere produced for trials of thermocompressionbonding properties.
The results of thesetrials indicate that despitethe relatively high hardnessof the gold, good bonds
frequent
failure
breakage
Such
the
as
most
mechanism.
results would
wire
with
were achieved
ductility
despite
that
the
adequate
was
maintained
pure
and
an
relatively
the
was
that
gold
suggest
hardness. These results indicate that pure gold HSSJE deposits would not be suitable for wear
being
despite
hardness
the
the
of
connectors
same order as alloy
as
such
applications
resistant
deposits. Failure would inevitably occur due to cold welding. However, this would allow pure
deposition
lead
frames
for
be
the
deposits
selective
of
such
as
where good
to
applications
used
gold
bondability is required.
154
155
jetted pure gold depositsmanifest a hardnessof between 160 kg mrn-2atlow current densities and
200 kg Mm-2at high current densities. Deposits produced from electrolytes containing booster
exhibited a consistenthardnessof around 200 kg 1=2 over the current density range examined.
When nickel was added to a conventional electrolyte as in the case of the Auronal MRN, the
hardnessincreasedfrom 100 kg Mrrr2 to between 150 and 200 kg mm-2.Similar hardnessvalues
were observed when nickel was addedto the Ronovel N electrolyte containing only booster. In
the caseof the electrolyte containing only nickel, there was a tendencyfor an increasing deposit
hardness with increasing current density. In the case of the electrolyte containing booster and
nickel, the oppositetrend was seen.The hardnessof the nickel containing depositproduced using
HSSJE, is reduced proportional to the quantity of nickel added to the electrolyte, from 200 kg
Mm-2 down to as low as 110kg mm-2.There is no direct evidenceto explain this behaviour as the
jetted samplescontainingboosterboth with and without nickel exhibited similar structuresin terms
of RMS strain and stacking faults. The main difference was the reduction in the crystallite size in
the caseof the nickel containing sample. This alone was insufficient to account for the changein
hardnessas no current density dependencewas seenin terms of the crystallite size. However, a
linearly increasing current density dependencewas observedin the lattice parameters.The nickel
in the deposit reduceswith increasingcurrent density and there is an empirical linear relationship
for alloys whose individual componentstructuresare similar betweenthe lattice parameterand the
atomic percent of an alloy constituent (Vegards Law) This would imply that some of the nickel
lattice
in
incorporated
being
the
the form of metal atoms.It is known that when transition
within
was
metals are addedto a gold electrolyte, conventionally produceddepositsincorporate the majority
in
form
A
in
in
the
the
transition
of
a
cyanothe
complex.
change
metal
way
which the transition
of
is
deposit
interacts
the most likely explanationof the reduction in hardnessobserved.
the
with
metal
It is clear from Figures 39 and 43 that the changein the hardnessis a function of the nickel in the
in
deposit.
This tendsto confirm the inhibition mechanismas the main
the
that
not
electrolyte and
influence on the hardnesschangesobserved.
The wear properties of gold alloy depositsproducedby jetting have already been describedin
Chapter 9. It is further suggestedthat the changein the inhibition process is responsible for the
difference in the wear characteristicsobservedbetween conventional and jetted deposits. It was
found that jetted depositsshowedsome reduction in the wear resistanceparticularly with thicker
coatings. There was also evidencethat the wear mechanismwas abrasivein nature. Such abrasive
deposits
from
in
is
alloy
produced
properly controlled electrolytes under
gold
observed
not
wear
DeDoncker
Vanhumbeek32have
deposition
conditions.
and
suggestedthat in the
conventional
behaviour
is
the
strongly relatedto the proportion of cobalt present
wear
alloys,
cobalt
caseof gold
ion
high
latter
being
the
complex,
with
to
that
as
a
cobalt
values
of
present
required for
as metal
in
If
high,
incorporation
the
the
too
the
electrolyte
cobalt
concentration
was
resistance.
wear
good
leading
high
deposit
to
too
the
suppressed
was
a value of metallic cobalt in
the
within
complex
of
the deposit. Such depositsexhibit abrasivewear behaviour. In addition, Antler31-has found that
156
in order to obtain good wear resistance,the deposit must have a low ductility as well as a high
hardness. Sucha combinationwould not be expectedfrom a depositin which the alloying constituent
has suggestedthat it is the inhibition due to
was presentpurely in the metallic phase.Nakahara77.
the nickel complex and its incorporation into the depositthat is responsiblefor the crystallographic
structure observedin gold nickel alloys. It would seemto follow, therefore, that due to the high
rates of deposition achieved in HSSJE, the inhibition processis changed, with much less of the
incorporated
into
deposit
but
being
the
asmetal within the gold lattice. This would
complex
nickel
explain the reduction in the wear resistanceobservedby Bocking and Cameron.
157
10.6.1 Interaction of the flow below the maximum useful current density
Most of the models for the impinging jet have been basedon fluid thickness and limiting
limiting
The
current methodmakesuseof a ferricyanide/ferrocyanideredox
measurements.
current
system. Sucha systemprovides a very good meansof establishingthe masstransfer characteristics
of thejet as it doesnot producea solid product that would interfere with measurements.However,
in electrodeposition, the product is a growing layer of metal. Figure 61 shows how a pure gold
depositgrew with increasingtime. The conditionsof depositionweresuchthat a smooth, featureless
deposit was produced. The growth rate at the centre of the deposit showed a linear growth rate
with time.
0.28Mcitrate gold
Temp.= 40 C
Re. 10458
C.D. 3.0 A/cm sq
Depositiontime, secs.
Cl)
cn
W
1.0
2.0
0
+
C]
X
4.0
8.0
15.0
20.0
2
R dimensionless
distance
158
has
fully
developed,
"dome"
the
the ratios are virtually constant.
shape
characteristic
when
However, during the initial stagesof growth, there is an accelerationin the rate of growth of the
stagnationzone comparedto the wall jet region, particularly at high values of R. It is proposed
that there is a suddenincreasein the rate of deposition in the stagnationzone due to an increase
in the local current density at this point. This is becausethe distancebetweenthe deposit and the
substratehas been reducedand becauseof the highly non-uniform current distribution within the
jet, the electric field is enhanced.The depositgrows at an enhancedrate within the stagnationzone
with respectto the wall jet region. This can be seenby the significant increasein the ratio at low
deposition times.
24
0.28MCitrate gold
Temp.= 40 C Rez 10458
20
nnti",
I
ZA
r
Ratio
of R=0
to R=1.0
0 Ratioof R=0 to R =1.5
v Ratioof R=0 to R=2.0
16
co
10
20
30
Time
Figure 62. The effectof increasingtime on the ratio of centre-linethicknessto variousvaluesof
R.
Additionally, due to this increasein current density, the walljet operatesat a lower current density
deposit
happen.
is
lower.
As
First,
two
things
the
the position at
grows,
the
efficiency
at which
from
is
be
flow
longer
jet
forms
the
the
away
stagnation
region
shifted
as
no
will
the
wall
which
becomes
larger.
into
Secondly,
flow
In
the
the
region
stagnation
effect,
the
substrate.
normal to
This
increase
in
to
the
becomes
aerofoil.
jet
of
an
effects
acceleration
similar
accelerated,
wall
boundary
layer,
in
the
the
thickness
have
turn would reduce
of
the
which
of
reducing
effect
would
159
Graph
30
0 Ratioof R=0
L Ratioof R=0
17 Ratioof R=0
Ratioof R=0
0.28Mcitrate gold
Re. 10458
C.D. 3.0 A/cm sq
Temp.= 40 C0
to R=0.5
to R=1.0
to R=1.5
to R=2.0
20
0
10
0
01
H/d
Figure 63. The effect of the nozzleto substratedistanceon the ratio of the centre-linethickness
R.
of
to variousvalues
160
10.6.2 Interaction of the flow above the maidmum useful current density.
As hasbeenshownearlier, thedepositslosetheir featurelessappearanceunder certainconditions
of current density, flow or temperature.The depositsthentakeon a nodular, needle-likeor dendritic
character. The morphology diagramsshow suchtransitions. There are many factors that influence
these transitions and it is certain that the interaction of the flow with the deposit will dependon
such factors as the interplay betweentemperature,current density, flow rate, nozzle to substrate
distance and chemical composition of the electrolyte. Such complex interactions are difficult to
evaluatebut each individual growth structure will be discussedseparately.It should be noted that
in the case of the alloy golds, no structures other than nodular types were observed under the
be
limited
discussion
As
to that of pure gold.
the
consequence,
a
will
examined.
conditions
10.6.2.1NoduIar deposits.
As the current density exceedsthe maximum useful current density, the deposit growth habit
changes from a relatively smooth surface, exhibiting small rounded mounds, to a true nodular
is
just
it
fact,
In
that
the
a coarserversion of the rounded
appear
structure
would
nodular
structure.
is
fixed
dimensions
for
There
transition
to
the
simply
grow
greater
point,
mounds
no
mound.
density.
formation
different
for
The
creates
current
of
nodules
a
applied
surface
of
greater values
the impinging electrolyte. Surfaceimperfections reach length scalesof the diffusion and boundary
layers and local interaction with these become likely. If the magnitude of the nodules does not
diffusion
layer,
layer
boundary
the
then nodular growth will
the
thickness
the
of
either
or
exceed
interaction
As
direct
fluid
flow
this
type
the
of
growth,
with
with
no
occurs,
unhindered.
proceed
this subject will be discussedin greater depth later.
161
lower
formed.
Examinationof depositsexhibiting needles
low
flow
the
number
of
rates
needles
with
in the processof formation has indicated that the tip radii are very small (<0.1 Am). However,
have
tips
that
reachedtheir "maximum" length of around 225 Am show radii in
examination of
the region of 1-2,um. This suggestsa mechanismby which the needlesgrow and what limits their
length. It is proposedthat the needlesgrow by a mechanismof sphericaldiffusion. With low metal
ion concentrations,increasingthe current density rapidly leadsto a nodular deposit formation due
to ion depletion. Once the nodule size exceedsthe thicknessof the local boundary layer, needle
structures form by creating a wake in the direction of the flow. This wake causesturbulent eddies
that disturb the boundary layer leading to enhancedlocal agitation that allows a preferred growth
in the direction of the flow within the wake. Once the growth tip attains the critical radius for
in
direction
flow
behind
diffusion
the
the
then
of
growth
proceeds
via
spherical
growth,
needle
eddy. Higher current densitiespromote the onsetof needlegrowth by generatinglarge nodulesat
increaseddistancesfrom the centre-line. Additionally, an increasein the current density promotes
the rapid growth of thesenodules, leading to a greater number of needlesto be formed.
The type of needle structure strongly dependson the prevailing temperatureas described in
Section 8.1.2.2. At low temperatures,flow rates and current densities, the needlesare varied in
flow
have
high
larger
At
there
they
of
needles
and
a more
rates,
are
a
number
size and shape.
in
both
leads
Increasing
the radial and axial
the
temperature
to
needles
growing
size.
regular
direction. At low flow ratesunder theseconditions the needlesgrow mainly in the axial direction
form
The
from
jet
form
the
the
stagnation
region.
usually
emanating
within
structures,
core
and
layer.
interaction
boundary
It
is
dependent
highly
is
their
the
suggestedthat
on
take
with
needles
the variance in size and shapeof the needlesseenat low flow rates and temperaturesis due to the
increasedviscosity of the electrolyte when comparedto higher temperatures. Due to the viscous
form
damped
dependent
local
highly
This
flow,
that
the
the
are
on
conditions.
and
eddies
of
nature
low
high
flow
in
At
lead
the
temperatures,
the
and
size
rates
and
to
shape
of
needle.
a
variation
will
due
increased
to
the
size,
shear stresseswithin the flowing
consistent
a
more
the needlesare of
liquid. This leadsto a less dampededdy formation beyond the protruding nodulesand therefore a
High
habit.
due
temperatures
to
the
to
also
proceed
allow
eddies
undamped
growth
regular
more
High
flow
increase
the number of needlesbecauseof
lower
the
electrolyte.
rates
of
the
viscosity
boundary
layer.
As
between
interaction
the
thinner
the
and
nodules
well as radial growth,
a greater
is
leads
limit
It
this
that
to
the
they
of radial growth. As the
grow.
process
thicken
as
the needles
needlesthicken, they effectively shield the growing tips and rob a greaterproportion of the current.
This shielding effectively reducesthe overpotentialat the growing tip and the critical overpotential
for needle growth is reduced. In addition, it is likely that the metal ion concentrationavailable to
local
limiting
density.
lowering
it
has
been
Indeed,
the
is
thus
current
reduced
the tip
seriously
ion
low
concentrations,considerablenodule growth occurs on the needles
that
metal
at
observed
Henceforth,
is
but
to
the
tip
impingement
tip.
the
this
close
seen
needle
not
no
the
region
within
162
longer grows in a radial direction. However, althoughno further increasein length occurs, some
growth in the diameter of the needlesmay still take place. This would explain why fully formed
needleshave comparitively large tip diameters.
163
The mechanismof growth of the ferri-like forms that grow along the edge of the free jet are
not so clear. Examination of all the depositswould indicate that centre line forms tend to grow at
lower values of Reynoldsnumber, lower current densitiesand lower temperaturescomparedwith
the former. It is thought that the crown-like structures developas a result of additional turbulence
in the edgesof the free jet due to the greater velocities but the exact mechanismwould require
further investigation.
Oneof the featuresof the depositsformedat high currentdensitiesis their lack of crystalline
regularity. Many of the fern-like or crown-likeforms resemblefractal structureswhilst others
resembledensebranchedmorphology(DBM) types.Generally,therewouldappearto bea regular
growth front like that observedwith DBM structures.However,closerexaminationrevealsa
significant numberof irregular growthswithin them. Becauseof the highly non-equilibrium
conditionsof deposition,it is not surprisingthat a mixtureof both maybe present.The presence
of a regularlygrowthfront wouldsuggestthattheseareDBM typeforms.The methodof growth
in
5.1.5),
by
Barkey
(Section
whicha thick boundarylayer existsat the growingtips,
suggested
during growth. Tip splitting is certainlya
is unlikely underthe high ratesof flow experienced
featurebut it is morelikely that this occursdueto nucleationandgrowth on or closeto the tips
leadingto secondary
andmultiplearmsforming.Thisprocessis repeated
creatinga multi-branched
front
induced
be
by
Stability
the
growth
may
of
meansof theconstancyof the impinging
growth.
flow togetherwith the effectsof the electricfield, which would alsobe constantacrossthejet.
However,therearemanyexamplesin whichcertainbranches
growattheexpense
of othersleading
to a non-uniformgrowth front. The most likely explanationis that all the structuresare fractal
(DLA) and that in somecases,regularityis produceddue to the
diffusion limited aggregates
flow
interaction
the
of
andtheelectricfield. Indeed,undertheseconditionsof growth, the
overall
depositionis truly diffusioncontrolled.
OF NODULAR DEiOSITS.
Whilst the fractal structuresproducedat very high current densitiesare an interesting field of
limitation
deposits
do
to
the
that possess
they
a
major
of
smooth
constitute
production
not
study,
lower
densities
All
by the formation
the
above
phenomenon
are
at
current
preceded
useful properties.
deposits
have
been
be
Smooth
deposits.
to
shown
produced at rates as high as 3.4
of nodular
density
is
increased,
if
deposit
becomes
increasingly
However,
then
the
the
current
,um/second.
It
has
been
for
therefore,
applications,
useless.
shown that smooth deposits of
most
nodular and
both gold and gold/nickel alloy, exhibit rounded mounds. Microsections have shown that these
With
increasing
densities,
to
the
to
the
substrate.
a
close
region
current
extend
mounds
rounded
height.
At
in
both
density,
depending
and
some
radial
size
current
grow
mounds
on the
rounded
164
prevailing conditions, the mounds becomenodules, that is they no longer exhibit integrity with
their neighbours.This is thetrue limiting condition to high speedjetdepositsof gold. Thernechanism
by which thesestructuresform will now be discussed.
165
166
adsorb on a surface such as gold particularly as it is formed on the surface. Further studies are
required to establishthe actualmechanismof noduleformation, particularly with regardsadsorption
phenomenon.
167
of a pulsating diffusion layer that followed the micro-profile of the surface. As a consequence,
tertiary current distribution wasaffected.A further factor wasthat eventhoughequitabledeposition
rates to DC could be achieved, the depositswere more porous due to gaps between the mound
structures. Thesealmost certainly result from inhibition of the lateral facesduring the off-time by
speciessuchas AuCN or CN. It is worth exploring other pulse regimesbut there are theseintrinsic
problems to be overcome.
168
References
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
12.
13.
Industries, third quarter and whole year, 1991", C. G. Wedgewood Consultancy Service, London, December, 1991
"Gold 1991", Gold Field Mineral ServicesLtd, London, 1991
11.
14.
15.
16.
17.
18.
19.
21.
22.
23.
24.
20.
25.
26.
27.
28.
29.
169
30.
31.
32.
33.
34.
35.
36.
37.
R.T. Page,Met. Fin. Journ. 19,274 1973;!bid, 19,338,1973; !bid; 20, ibid,
K. Lin & R. Weil, J. Electrochem.Soc., 133,690,1986
S.T. Rao& T. Weil, J. Electrochem.Soc., 127,1030,1980
K-L. Lin, W-C. Liu, M.H.M. Lin & Y. W. Hu, J. Electrochem.Soc., 138,3276,
1991
EastReport,EugenG. Leuze
M. DeBonte,J.P.Celis,J.R. Roos& J. Vanhumbeek,
Verlag, Saulgau,1992
38.
39.
40.
41.
D. L. Rehrig, H. Ledheiser & M. R. Notis, Plat. & Surf. Fin., 64,40, (12), 1977
J-C. Puippe & F. Leaman (Ed), "Theory and Practice of Pulse Plating% American
42.
44.
45.
9,1977
York,
46. N. S. Allen (Ed), "Photopolymerisation and photoimaging Scienceand Technology",
Elsevier, London 1989
47.
F. I. Nobel & R.T. Hill, American Electroplaters Society, 'Second Continuous Plating Seminar', 75,1977
48.
49.
"Texas instrumentsusesspot plating of gold to cut costsof keyboards", Plat. & Surf.
Finish., 62,9,846, (1975)
50.
51.
52.
53.
54.
56.
57.
Idem,lbid, 29,3,7
58.
55.
(1976)
170
59.
60.
61.
62.
63.
64.
65.
66.
67.
68.
69.
70.
71.
72.
73.
74.
75.
76.
77.
79.
80.
81.
London, 1970
R. Piontelli & G. Poli, Comite International de Thermodynamiqueet de Cinetique
78.
82.
83.
84.
85.
171
86.
87.
88.
89.
90.
U. Landau& 1. H. Shyu,ReportEM-2937,ElectricPowerResearchInstitute,Palo
Alto, Calif. 1983
D.P. Barkey,R.H. Muller & C.W. Tobias,J. Electrochem.Soc., 136,8,2199,1989
D. P. Barkey,R.H. Muller & C.W. Tobias,J. Electrochem.Soc., 136,8,2207,1989
C-P. Chen& J. Jorne,J. Electrochem.Soc., 138,11,3305,1991
J.L. Barton& J. O'M. Bockris,Proc. R. Soc.London,Ser. A, 268,485,1962
J.W. Diggle, A. R. Despic& J.O'M. Bockris,J. Electrochem.Soc., 116,11,1503,
1969
K. I. Popov,LJ.M. Djukic, M. G. Pavlovic& M. D. Maksimovic,J. Appl. Electrochem.9,527,1979
K. I. Popov,M. D. Maksimovic,D.T. Lukic & M. G. Pavlovic,Ibid, 10,299,1980
K. I. Popov,M. D. Maksimovic,J.D. Trnjacev& M. G. Pavlovic,Ibld, 11,239,
1981
D. Barkey, J. Electrochem.Soc., 138,10,2912,1991
Y. Sawada,A Dougherty& J. P. Gollub, Phys.Rev. Letts, 56,12,1260,1986
R. Clarke& L. M. Sander,Phys.Rev. Letts., 56,12,1264,
D. Grier, E. Ben-Jacob,
1986
M. Matsushita,M. Sano,Y. Hayakawa,K. Honjo & Y. Sawada,Phys.Rev. Letts.,
53,3,286,1984
& P. Garic, Nature,343,523, Feb. 1990
E. Ben-Jacob
F. Coeuret,Chem.Eng. Sci., 30,1257,1975
91.
92.
93.
94.
95.
96.
97.
98.
99.
100.
101.
102.
103.
104.
105. D-T. Chin & C-H. Tsang, J. Electrochem. Soc., 12S, 9,1461,1978
106. A. A. Sonin, J. Electrochem. Soc, 130,7,1501,1983
107. D-T. Chin &M Agarwal, !bid, 138,9,2643,1991
108. R. C. Alkire & T-J. Chen, ibld, 129,11,2424,1982
109. G. A. Zarb, Proc. 8th Congressof the International Union for Electrodeposition and
Surface Finishing, Basel, 5th - 9th September, 1972
110. U. S. Patent No. 3810829, J.C. Fletcher, NASA, May 1974
111. H. Schlichting, "Boundary Layer Theory", 4th Ed., McGraw-Hill, New York, 1960
112. T. Tanaka & E. Tanaka, Bull. JSME, 19,133,792,1976
113. H. B. Squire, Quart. J. Mech. App. Math., 4,3,321,1951
114. D. A. Dawson & 0. Trass, Can. J. Chem. Eng., 44,121,1966
115. E. J. Watson, J. Fluid Mech, 20,481,1964
116. R. Gardon & J. C. Akfirat, Int. J. Heat Mass Transfer, 8,1261,1965
172
117. F. Giralt, C-J. Chin & 0. Trass, Ind. Eng. Chem. Fundam., 16,21,1977
118. M. T. Scholtz & 0. Trass, AlChE J., 16,82,1970
119. T. Strand, Am. Inst. Aeron. Astronaut., Paper No. 62,144,1964
120. D-T. Chin and K-L. Hsueh, Electrochim. Acta, 31,561,1986
121. B. E. Warren & B. L. Averbach, Journ. Appl. Phys., 21,595,1950; 23,497,1952
122. A. R. Stokes, Proc. Phys. Soc. (London), B61,382,1948
123. "ComprehensiveTreatise of Electrochemistry Vol 6", Ed. E. Yeager, J. O'M Bockris and S. Sarangapani,Chapter 3 "Convective Mass Transport", N. Ibl & 0. Dossenbach,Plenum Press (New York) 1983
124. J. Newman, "ElectrochemicalSystems", Prentice Hall, Engelwood Cliffs, N. J. 1973
125. F. Walsh, PhD Thesis, Loughborough University, Loughborough, 1982
173
Photograph 1. The X-Y table (in the fume cupboard) with the control computer and ancillary
equipment.
174
Photograph 2. SEM micrograph of a pure gold deposit produced using H/d = 4.375.0.27M phosphate gold electrolyte.
Photograph 3. SEM micrograph of a pure gold deposit produced at a current density of 0.75 A
is
The
deposit.
"dull"
topography
to
that
similar
of
a
conventional
appearance.
typical
a
of
CM-2,
0.17M Citrate gold, 55oC
175
Photograph4. Optical micrograph of a pure gold deposit produced at a current density of 4.75 A
"rounded
0.17M
typical
mound"
a
appearance.
citrate gold, 55-C.
showing
CM-2
Photograph 5. Optical micrograph of a pure gold deposit produced at a current density of 7.0 A
55-C
0.17M
gold,
2
citrate
structure.
CM showing a nodular
176
177
Photograph 8. SEM micrograph of a structure growing into the edgeof the jet.
178
Photograph 9. SEM micrograph of a jet core structure. The colour has been addedby computer
enhancement.
179
oex
$sun
211(U 410NO
382X
laeum -
P--69497.
$losses
P'Sesis
leoum-
51u wo i9mm
SA0800
25KU WD:14NM
S: 00909 PIS0029
321X
leou"
".,
.-
'-
..;
I-- I-
--
b,
Vw . 4w .-,
W. 4.,
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ter
-.
-, *
-IV
P-80014
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MUM
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szooese
V09821
- s .--,
jz,.
F'
Zw
low
%v
r"'.
lit
: A'
IM
74(-V.
0.17M
increasing
time.
deposit
with
the
growth
of
the
Photograph 10. SEM micrographs showing Re. 3335. (a) 0.8 secs. (b) 1.5 secs. (c) 2.5 secs. (d)
==
A
7.0
density
CM-2.
Current
=
gold.
citrate
6.0
(f)
secs.
5.0
(e)
3.5 secs.
secs.
180
1,27KX
20um-
25KV WD 18MM
s 00000 P: 08812
0 UM_
25KU WD JeMm
s 00000 p 00011
higher
but
10
deposits
in
Photograph
at
the
shown
Photograph 11. SEM micrographs of some of
denCurrent
deposition
0.17M
increasing
times.
gold.
citrate
magnification showing the effects of
3.5
(d)
2.5
1.5
(c)
(b)
secs.
0.8
(a)
secs.
3335.
secs.
Re.
secs.
A
7.0
=
cm-1.
sity =
181
L- SE1
cm
tv
W, 10.10
mia
Tm
,
mwlaamo
Photograph 12. SEM micrographs showing the growth of the deposit with increasing time at a cur0.17M
Current
density
jet
density
produced.
are
citrate
gold.
structures
core
rent
at which
= 10.0
A CM-2.Re. = 12078. (a) 0.6 secs.(b) 2.0 secs. (c) 2.0 secs. (d) 3.5 secs. (e) 6.0 secs. (f) 8.0 secs.
182
Photograph 13. SEM micrograph of a pure gold deposit produced at the maximum useful deposition
rate of 3.4 jAm/secondat a current density of 6.0 ACM-2. Deposit thickness = 18.0 Arn.
Photograph 14. SEM micrograph of a conventionaldeposit produced at a current density of 5.0 rnA
18.0,
Deposit
thickness
=
um.
cm-1.
183
Photograph 15. Microsection of a pure gold deposit produced from the optimised citrate gold electrolyte. Current density = 2.0 A CM-2.Re. = 12078. Temperature = 55oC. X 2000
Photograph 16. Microsection of a deposit produced from the optimised citrate gold electrolyte. CurTemperature
Re.
55oC.
A
12078.
X 2000
4.0
density
CM-2.
=
=
rent
=
184
Photograph 17. Microsection of a deposit produced from the optimised citrate gold electrolyte. Current density = 6.0 A CM-2.Re. = 12078. Temperature = 55oC. X 2000
Photograph 18. Microsection of a deposit produced from the optimised citrate gold electrolyte. CurTemperature
55oC.
X
2000
Re.
12078.
7.0
A
density
=
cm-1.
=
rent
=
185
304X
LI 0,100ti
00
Photograph 19. The effects of electrolyte velocity. 0.28M citrate electrolyte. Current density
4.75 A CM-2.Temp. = 55oC. Re. = 1044.
Photograph 20. The effects of electrolyte velocity. 0.28M citrate electrolyte. Current density
4.75 A CM-2.Temp. = 55oC. Re. = 5220.
186
Photograph 21. The effects of electrolyte velocity. 0.28M citrate electrolyte. Current density
4.75 A Crn-2.Temp. = 55oC. Re. = 9396.
density
5.0
Current
ACrn-2.
0.17M
influence
The
22.
citrate
gold.
=
Photograph
pH.
of electrolyte
Temp. = 55 -C. Re. = 12078. pH = 5.3.
187
Photograph 23. The influence of electrolyte pH. 0.17M citrate gold. Current density = 5.0 A rM-2.
Temp. = 55 oC. Re. = 12078. pH = 6.1.
Photograph 24. The influence of electrolyte pH. 0.17M citrate gold. Current density = 5.0 A CM-2.
Temp. = 55 oC. Re. = 12078. pH = 8.1.
188
ENT-9.80 KY Wo 20
200
v
UNYJETPLATEINGSAu
L- SE1
Photograph 25. A typical exampleof a "rose" type morphology produced using pulsed current in
conjunction with HSSJE.
Photograph 26. A typical exampleof a "crown" type morphology produced using pulsed current in
HSSJE.
with
conjunction
189
Photograph 27. A typical exampleof a "field oriented random" type morphology produced using
HSSJE.
in
with
pulsed current conjunction
L- ', EI
EHT- 10.0 KV
10. Ommi1
Wu- 15
PHOTO- 11
mm
1TI1;
i]
-kA'
--cal.
1,LE4
k"m
';
in
using
pulsed
current
"smooth"
type
produced
morphology
Photograph 28. A typical exampleof a
HSSJE.
conjunction with
190
in
"nodular"
type
produced
current
A
using
pulsed
29.
morphology
typical exampleof a
Photograph
HSSJE.
with
conjunction
from
deposit
Ronoval
N
17.2
gold
produced
a
eleca
prn
of
An
Photograph 30.
optical micrograph
X
A
Re.
10800.
8.0
density
Current
but
CM-2.
"booster"
1-1
=
=
no nickel.
trolyte containing 60 ml
2000
191
from
Ronoval
N
deposit
produced
a
A
electrolyte containing
32.
gold
Photograph
microsection of a
60 ml 1-1"booster" and 3.0 g 1-1nickel. Current density = 6.0 A cm-1.Re. = 10800. X2000
192
Photograph 33. An optical micrograph of a 17.6 pLmgold/nickel alloy deposit produced from a
Ronoval N electrolyte containing 60 ml 1-1booster and 0.7 g 1-1nickel. Current density = 8.0 A
CM-2.Re. = 10800. X 1000
Photograph 34. An optical micrograph of a 17.9 fzrn gold/nickel alloy deposit produced from a
Ronoval N electrolyte containing 60 ml 1-1booster and 2.2 g 1-1nickel. Current density = 8.0 A
1000
X
Re.
10800.
CM-2=
193
3, OSKX
leum
26KV W0115MM
S: 00000 P: 0189I
Photograph 36. SEM micrograph of a 2.5 jAmgold/nickel alloy deposit produced from a Ronoval
Current
1-1
density
ACM-2.
1-1
1.9
12.0
Re. = 10800.
60
nickel.
g
and
n-d
=
electrolyte containing
194
018000 P: 00004
Photograph 38. An example of a directly written ring oscillator produced by HSSJE with both a 400
layer.
"seed"
the
1001im
metallised
of
nozzle after removal
Itm and a
195
Photograph 39. The connector wear test configuration as used by the GEC Contact Tester showing
an actual contact pair under test.
196
DATA TABLES
Thesetables list the most relevant data obtainedduring this study.
197
8.2 g 1-1
45.0 g 1-1
15.0g 1-1
to pH 6.0
Kinematicviscosity
25-C
40oC
55-C
0.0100203cm%w,
0.0073904cm%wI
0.0058590CM2SeC-1
Conductivity
25-C
55-C
49.6 mScnrl
83.12mScnrl
54.0 g 1-1
45.0 g 1-1
15.0g 1-1
to pH 6.0
Kinematicviscosity
25-C
40-C
55-C
0.012284cm2se%-,
'
0.009221cm,2sec-I
0.0076567cm2sec-I
Conductivity
25-C
55-C
55.3 mScar'
97.6 mScnrl
33.5 g 1-1
45.0 g 1-1
15.0g 1-1
to pH 6.0
Kinematicviscosity
25-C
0.005906cm2swI
Conductivity
55-C
92.3 mScra-I
54.0 g 1-1
1.0 g 1-1
1.0 g 1-1
to pH 6.0
Kinematicviscosity
55-C
0.04232cm2sw,
Conductivity
0.27M PHOSPHATEGOLD ELECTROLYTE
55-C
48.8 mScnrl
Gold (aspotassiumgoldcyanide)
hydrogenphosphate
Di-potassium.
Potassiumdi-hydrogenphosphate
Potassiumhydroxide
53.1 g 1-1
40.0 g 1-1
10.0g 1-1
to pH 7.1
Kinematicviscosity
25oC
40oC
55-C
0.009164cm2sec-I
0.006891cm2sec-I
0.005426cm2sec-I
Conductivity
25-C
55-C
52.44mScnrl
90.02mScurl
TABLE 1. Composition and someproperties of the pure gold electrolytes used in this study.
198
SAMPLE NO.
Awl
To".
PH .
ELECTROLYTE
l
25 C
Nozzle
al
0.041M Citrals
tywas
:02
Total-coulo,
ribe
05
54
)0041
rate uissic
1
0oposit quality
0 Obe
SAMPLE NO.
so
lie
0 ISO 0.381
- 4
Terro. .
PH .
Total couiornbe
Thick, @" um
Plating rote U/2*C
0 675
0 942
ELECTROLYTE
25 C
1
025
031
123
2
4
05
075
11
003
094
1 26
625 41 45 31 25
Omas
0
0
am, 1, offla
So
46
0 074 0 207
o
106
0 339
PH -
I$
7
a
1 225
15
1 75 12
1 68 220 f 251 1 283
208 1782 11583 1388
125
-1 57
249
ome. 2 m"
M, 9
T-77
1288
161i
is
0
0 774 0 970
502
7*8
am's
amp,
I)MV6
I
:, 49010W"
Is
a
7.54
52
Is
17
am's
ReynoldsNo.
;9- 31 235
10
it
121
13
14
25
275 13
3 14 345 1 377 1 5.02
125 11 35 1042
78
em, p Ums
WIS
190
ww
offloo
0041,
kle
a"
on*
14
5
625
025
is
a
754
52
is
17
I
is
am*
one
arm
0.041M Cluraft
Nozzle area cm eq
101
al
14
5
028
825
10
ELECTROLYTE
25 C
To".
coasis emai,
13
4
Nozzle area cm aq
00,11
Aull
to
1,
12
25
275 13
314
345 1 377
125 11.35 io 42
am'?
-:
15
D*pc)ot quality
SAMPLE NO.
0.041M C41rals
Ol
an*
13
Spot nurnber
Curnsmidensity Alcm eq
Current applied mill,
Tornesacs
lee
Au2
9
225
283
1388
a am'?
lea
::
7
0
15
1.75 12
1 88 220
251
208 1782 1563
00"GaP *",
1
00010"02
1 25
1 57
249
Thickness um
Plating
2
3
4
025 1 05
075
1
031 1 003
094
1.20
123 625 4145 31.25
04
15
Spot number
Current density A/cm eq
Cufront applied mA
Tirm sees
00.4
0-10110
1
Spot number
Cu"nt density AJcr, sq
Current applied rriA
Tornipsocis
Total coulornbt
Thickness Urn
plating rate u1soc
IDepolat Quality
I
ELECTROLYTE
an
naion n*/sn
I
cm Iq
raw W
one
004
0 001INS
25
0 04
63
106
83
0 256
0 152
0 426
I
i
is
one
1
11
0 520
136
0 793
140
0 963
t
156
1 126
ow
185
132
4
Z/sn
n
on
PE
1 no
I
T
is00,
Viscosity cm eqtsee.
21
3
4
51
a
7
1
9
10
il
12
05 1 075
1 1 25
115 1.75
2 225
025
25
275
31
--1 26 1 57 188
220
0"
251
063
293
3.14 345
377
V 31
123 625 4145 31 25 249 208 1782 1503 1388
125 11 35 1042
emoi, omini omas 0-as smair @"to essIty amirs om, r aa0-oe
0
0
anis
171
Is
I1
1-
somesurnent
only
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Nozzle or" em eq
15
Nozzle sz* cm
qualffi,
14
13
15
5
L
4
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628
754
78
625
52
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OM?a 00.1.
0.041111,11
Chraw
Nozzle
@I
am
PH
7hicknissioum
vi"
d1
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25 C
is
=-P.
Awill
Temp.
-Plating
9
I
SAMPLE NO.
Spot nurnber
Current density
Cu"nt applied
T.rns, soice
Total coulombs
a
7
a
4
a1
9
10
It
12
1 1 25
15
1175
2 225
25
275
3
_075
094
2SI
1 26 1 57 1188 220
263
314
345
377
208 1782 IS63 1388
4145 31 25 240
125 11.35 1042
a50,30,11
eMall am's 00MIF 0mol am'? a00Irs
99
so
120. 144
154
ISO
T 126
0 let 0317 0357 0"
084)8 7"s
2
1
025
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083
031
123 82S
0-al
0
33
0 0053
rid
one
13
14
is
5
4
6
502
626
754
78
025
52
am"
aam"
17
P4
one
TABLE
199
is
11
ELECTROLYTE
Am$
SAMPLE NO.
Tonw. -
25 C
pH .
61
0.041M Civals
Nozzle imelocity"Wift
18
Nozzle size em
C,04
rate u1sec
I
qual Ty
0.00126
Viscosity cm sq/ooc
001002
0035
0118
0256
0414
0 41 4 0591
10
no
Tomp. -
40 C
pH .
61
07199
dl
AwS
1 162
1017
De
rid
SAMPLE
no
end
no
Nozzle area em oq
40 C
pH
@I
We
: 00120
0027
4
to
74
44
0106
104
0 418
0 237
d, s
103
Nozzle velocity
14
0 786
0 40
an
0"
91
10
11
12
is
14
15
is
25
225
215
3
4
5
a
a
263 3 14 345
377
502
628
754 1005
78
1358 12 5 11 35 10 42
025
52
39
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0
coniars od"19 00,tirm om's 0-9
157
1 004
an
ELECTROLYTE
Tornp.
Au7
NO.
Is
17
0.04 1m Chre's
--
Nozzle are cm
0
42
0 0067
urn
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f tw*o u0
15
14
is
5
a
a
028
754 1005
025
52
30
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1 352
junt"I
13
4
502
78
ELECTROLYTE
Nozzle Velocity RV;
9
10
11
12
225
25
275
3
28.3 314
345
3 77
13 88 12 5 It 35 10 42
oml? down 001*20 ottiddi,
i6o
is I
2
4
5
7
1
6
a1
05
075
21
025
1 1 25
15
1 75
064
2 51_
063
1 26 157 1 as 220
031
208 1782 1563
I Z3 62 5 41 45 31 25 249
a00=
60
oo:vsoe0"10 omly 00-
Thickmess
7185
13
Spot "Uniber
Curretif doriory Iklem so
Current aDpl-ed mA
Tirne socs
Total coulonnom
ReynoldsNo.
1a
SAMPLE NO.
2
3
4
5
0
7
1
05
075
025
1 1 25
15
1 75 1
2
094
15
157
1 be 220
251
031
083
128
123 825 4145 31 25 2499 20 6 17 82 15 63
G
Do10"i"if . 41m od'Sof
a o"If
oGd.? . 0m,f
0
2.2
a 103
10 3 123
137
49
ISO
Spot mumbor
Curreml density Aicm sq
Curremtappied mA
Time mcs
Total coulorrtos
Thlekn*64 Urn
Plabrig
i0opost
an
223
1 784
174
1M
9m
21 1
1 859
20
1 919
am
on
1 on
11
18
207
26538
In,
0.04 1M Citrade
Nozzle ares cm eq
rrvm
Reynolds
I.
No.
2706
Is
a
17
Viscosity
0,51
crn
sq/90c.
1
Spot
Toialcoulo,
Thmkiiegl
4
1
1 20
1 25
157
15
1 88
62 5 41 45 31 25
249
20 8 17 82 15 63 1386
05 1 075
004
0 63
025
031
123
Time socs
urn
Platilmo rate U,
d/s
0. 117
225
263
11
275
34S
12
3
3 77
13
4
502
14
5
628
is
a
7S4
12 5 It 35 10 42
76
a 25
52
149
d/9
40 C
Nozzle velocity
at
Cox,?
174
is a
do
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tn1
an
I
ELECTROLYTE
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pH
ed
2
251
10
1 25
314
0 154 0 262 0 418 0 S63 0 &M 1 062 1 255 1 496 1 656 1 Till
Q-Al, ty
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1 75
220
0 006
F-
SAMPLE NO.
01
104
! D"wt
71
oiqws e. 64
82
00-1
nbs-
21
numbs,
r,
mj otmety !, cm sq
Current Opp', #a n, ,
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90W, 0 *. is 8
179
o"If
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an 1 on 1 en I
Thlelintes urn
plat'r, o rote ul
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in
to
er" eq/80C
0om
otittdii
ootddil
71
71
00
"
24
0
0 0036
Co...
0.041M Career
5
227
0 121 00227
0 22
5
1 25
1 57
a
15
1 ba
249
208
39
004
4
3
11
1
1
0 25 1_2ES 075
1
i 031
0"
1 26
26
31 1 063
123
123 1 GE S 41 45 3
1005
k125
Spot MUMb9f
_
current oonwty Aicm so
71
9
a1
1 7S
2 225
220
251
283
1782
IS63
1388
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94
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128
143
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142
1025
10
25
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11
275
345
13
14
Is
Is
17
11
a
4 1 5M1a
0055 000
1005
502
6 201 17 54 to
12
3
377
11.35
75
1042
COWN 101010 0
Is
161
1 26 1410
don't
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1.777
151
19015
on
an
825
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52
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0-
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2592
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8
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on
1
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on
an I. on
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no
TABLE
200
Is
057
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AR
I
nd
Is
11
SAMPLE NO.
ELECTROLYTE
AuD
Tamp*
40 C
Nozzle
15
sty md"
16
4
Spot number
075
05
1 1 25
025
031 ES3_ 094
1 20 1 5Z.
123 .62 5 41 45 31 25 249
omal, OM,011omaa omlPf om, *
72
0
47
93
11
0 0018 0 113 0 23 0 373
Z
Z
Z
Dopoestquality
004
13
0.041M C411rale
Nozzle size cm
11111
PH
we
15
1 88
20 8
-1,
TOM
03
0 49S
E
1 75
220
17 82
am"
- Tr1 -2
0 029
Z
Awl 0
T".:
40 C
as
VOco:
ty Cm Sq/98C
Diiistoot Qua"
11
13
12
2 225
275
25
251
283 3 14 345
15 63 13 as 125 11 35
ot-, a om" aI129
14 7 148
176
0 825 1 061 1 168 1551
E
0 11
d
is
17
0.041M Cities*
fly in/@*
Nozzle art em
"d
16
Nozzle ve
01 0 021
Is
14
3
5
4
a
a
3 77
502
754 1005
628
52
1042 78
025
39
am, 11 amiss 00W,G 00"'. am"
184
lea
164
1574 21538 2624
Is
004
0001"
Viscouslyem lics/96c.
as
0 ODrM
0 21_4_ 0357
a
0 457
8
0 564
Wall
0 774
1 025
1 232
1 4Z?
3
2
4
5
1
1
a
9
10
"
12
05
075
025
In15
175
2 225
25
275 13
063
094 -11 26 157
031
1"
220
251
283 3 14 345
3 77
20 8
82 1503 13 58 12 5 11 35 10 42
123 82 5 41 45 31 25 249
_17
aa.
"
asomall
003019
a 0-17 1a. amlKi *M, a
46
67
80
0
13
95 -0mly
104 -0-s,
121
142
154
162
163
8110
17
Spot numbes,
Current devty A,/cm 9q
Cumitnt applied mA
Time sects
Total Coulombs
h,cks,v*** um
FleynoldisNo.
ion
ELECTROLYTE
61
pH
area ern aq
10
SAMPLE NO.
Nozzl
19
ia
all
Mal
DATA
13
4
is
is
4
5
a
a
502
628
754 1005
7a
625
52
39
amill 00"24 omill 00"19
182
148
2 0769
1W
am
17
2 366
an
am
1
--
SAMPLE
ELECTROLYTE
Aull
NO.
Tornp.
55 C
Nozzle velocity m/
Nozzle
1111
PH
Spot number
Cumiint density Alcm so
Cumism app,, *a mA
Time space
Total couiombe
11
025
031
123
21
O.L
063
625
A
0-
Th, cksivssswm
Plasma so
01 0 01a
u,
Doposist quai. ty
SAMPLE
nd
NO.
Tamp. .
PH .01
3
0 75
094
4145
a mm
-a
0145
0.041M
; "
72
Nozzle or"
-".
1.20 cm
Cilrose
Viscosity
51
4
1
1 26
31 25
1 25
157
249
, -ft74
omt*
0237
0381
15
1 88
208
175
220
1? 82
00-6
100
051
1-11
123
069
d_
ob
Aul 2
ELECTROLYTE
55 C
a1
91
2 R 225
751
283
ll
-.
cm all
CM SQ196C.
10
25
iS 63
1388
418
3 14
125
10
om'?
01.1?
21
1 51S
151S
omn
to
1 52
14
0898
e,.,
11
275
345
11 35
Current
appiped mA
Time sisace
Total Coulombs
Th,clinsi,se u,, s
Piatimic;rate uisoc
IDepositausil, ty =
I
No.
1363
is
a
754
5 2
16
a
17
- -J
12
3
777
-
13
4
502
76
1042
14
5
628
825
1005
39
on
M
am
0 04 1M Chrove
Nozzle area cm aq
as
11.49
Reynolds
21
3
4
51
a
71
1
a1
1 1 25
15
05 1 075
1 75 1
025
2
1 20
57 188
220
003
094
251
031
-1
200 17 82 15 63
123 025 4145 31 25 249
00,01,1asam's
a`s*1pto"
003M 0
oo
71
74
9 10 3 , 117
52
0
13
0 171 0237 0381 0495 0857 0832
03
.
[
j
E
EE
d
d
d
so
I
I
9
10
11
225
25
275
283
314
345
13 56 12 5 11 35
a. ",? I-,, % 1185
1 19
n
a. A
3414
12
1
3
1 3 77
110 42
1
13
14
15
5
4
a
a
502
020
7S4 1005
76
625
52
30
_
0 10 00"
00"19 L=11,
o
n
on
I
am
I
TABLE
201
No.
Viscously CM eq/
1
Spot number
Cument clonstv kc,,, 90
Reynolds
17,
55 C
Tomw. :
al
pH
0.041M Chrele
ELECTROLYTE
Kul 3
SAMPLE NO.
Nozzl area cm aq
:
04
"101
Total Coulomb$
ea
Thickness um
Plating rate u see
0
05
0 0008
no
Quahly
am,?
as
42
0101 0,188 0301
83
0399
94
0539
0?
61
6
53 C
Temp.:
004
Nozzle size cm
Total Couiornbs
0-
. -
55 C
Torrip.
pH
00.11
is
185
183
162
2 84 3 $to 4 IS4
a-
I
,
Reynolds
No.
10241
w
1M
N
13
4
5 02
78
14
5.
6 26
0 25
001"
619
15
IS
a
a
a
7 54 10 05
52
39
00"'9
17
18
I
00-9
76
18 7 17 1
17
2 1923 2 816 3 596 4 385
85
125
13 137
1 1 145 1 315
--
0.041M Citrals
00mi
01
go
117
109
too
03419 0556 0697 0844
ELECTROLYTE
Aul 5
SAMPLE NO.
011
71
53
0 17 0285
1
I
al
Pal
00"
17
em, q
51
7
a
a1
91
12
10
it
31
1 75
2 225 1 25 275
1 25 1 15
2Si K 263
314
345
377
157
1 88 220
20 8 17 82 15 63 1388
249
13 SO 12 5 11 35 10 42
a-ti
't-i
32
03
0
0 01
0005
005
05 0077
Thickness urn
plat'no at* u1swc
soc
2
4
1
05 1 075
0"
063
126
625 All 45 31 25
1
025
031
123
00-
167
2141
V'scosity cm altsee
13
Spot number
Current density A)Cm
Cm so
Cu", t apphed MA
Time soce
0-
0amit
is
16
6
a
754 1005
52
30
Nozzle area cm eq
15
at
PH
0.041M Citrate
ELECTROLYTE
14
5
628
625
i - - FPI
=
bn
P
P
E
- . -
ObIA
I
Aul 4
'time
oes-
.......
SAMPLE NO.
13
4
502
78
12
3
377
1042
US
13.3 156
107
0 71 0 772 1008 1 172 1 497
01
071
asso-a
10
"
25
275
3U
345
125 1135
it 1
It
al
so
tion's
kitpowt
tiainte
00toes 0
a-
00
%Awo: ty cm sqlaw.
7
51
a
a
a9
2 225
125 1 15
1 75
2 51 293
157
le$
249
20 8 17 82 15
6 " 13 86
633
1563
3
4
21
1
05 1 075
004
083
1 26
02 5 41 45 31 25
1
025
031
IZ3
Spot numbw
Current density A/cm oq
Current appl, *d mA
Time socs
Is
Nozzle area cm eq
1104
Viscosity
a
15
1 88
7
175
_220
61
91
10
2 225
25
251
203 3 14
20 8
17 82
15 63
-,
00m.; oowr
em Weec.
1
:0*-
122M
ON"
_:
lileynoide No.
Spot murnber
Cu"t density A,c- so
Current applied MA
T, ffw socs
Total coulombs
1
- O25
031
05
063
3
075
094
23
123
1
62 5
41 4S
31 25
Ir"
It-,
24 9
54
7173
24
04
0
0
0
0 OB7
Thmkqls
um
platiria rate Ufsec
5
4
11 1 25
1 26 1 57
058
71
0285
84
10
0_404_ 0561
L
I
I
D"wt
nd
It 0
124
0 850 0 992
-9
Aul 6
To
25 C
ELECTROLYTE
Nozzle
fly rrdw
Nozzleare ef"
pH
Spotnumber
Current sopowd
T, rne we*
Totefcoulombs
mA
1 26
31 25
251
15 03
10 42
0ams
Dopos
00-41
Plating
60-,
un
?at* u1swe
visual
Assess"W"t
only
Th, cknes*
51
075
025
-F3 - 1 - W-94
123 4 45
00:iiot
100
Deposit quality
I
rid
I
I
ZZ
625.
52
39
a. -
133
1 172
14
1 344
168
2 1538
178
2 848
154
2 962
too
4250
am
an
on
am
an
I
is
Nozzleareacm sq
Viscositycm sq/0@c
.2
004
6
325
35
408
Go
440
so
00:019 =WI
11
10
3 75
ReynoldsNo. 651.3
12
1
13
a
425
45
4 711_ 502
83
78.
534
74
565
597
828
so
057
00:aite
00WIS 00
475
L. ""
4
I14
Is
55 16
025
Sol
568
754
521
0 tims
a. m.
'am.
00""
to
17
as
a is
401
879
Dom?
coml
446
E-n.
Z
me
.
I
78
377
10 42
17
14
is
Is
5 a
a
628
7 54 1005
0.29M Carsup
11 35
19
21
13
4
502
ww
-I
SAMPLE NO.
12
-- 3
377
L-
.i
11
0704
12 5
13 8a
Ill
275
345
-a .
en
swic
I
TABLE
202
is
1
Aul I
SAMPLE NO.
Temp. :
0.25M Citrate
ELECTROLYTE
25 C
@I
PH
Nozzle at?@cm
Spot number
Current density A/cm aq
Current applied mA
1
025
031
2
075
004
123
41 45
Const
Depowl
quality
SAMPLE
NO.
31 25
oonol 00"WI
75
024
0
0
4
3.
1
1 26
V'scoory
15 83
o0n`?C 00"I'M
97
156
0 621 1 467
Cm "/vive.
Total Coulomb$
ThICkneso Um
Nozzle velocity
aI
025
0.31
123
075
094
;1 as
1
1 26
31 25
oo
54
oo57
p &I'Mit rate u
13
0 182
to
11
425
534
45
4
5
855
565
So
69
78
00,
2`1 7
2614
0-19
2173
.
74
0-
00""'
00-
121
13
14
475
55
507 -5 625 -691
15
a
754
is
17
65
7
a is
Is41 879
657
521
48I
481
I. nrN
o'nol
0
'nilt,
on*/
on i
arel
625
onoo
558
Conn
no
one
010
04
Reynolds
0001
%necooty cm actlese.
25 C
1a
2 13
2 51 13 77
15 63
3 25
35
4 06 440
96
so
10 42
Conn
117
0 749
00"
141
1 353
are
00",
going
ZI
no
91
375
otin't
10
4
502
78
4 71
63
*0-
o"Wo
425
534
74
00-
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12
13
4 75
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5
028
14
15
55 1
a1
691 1 754
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568
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45
555
so
025
031
075
094
lZj
4`145
IInC6
54
C0".
83
h. ckness u
Plating rate u/sac
Deposit
0 13
0266
00"
I'M.
Temp.
pH
so
Total Coulombs
Tfilckreal
uill
40 C
01"
14 7
094
i0tima felt
N rz
al
5
3
3771
1042
a
7
325
_35
408
440
98
so
C-
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1
7.1
0
we
375
4 71
83
eynoldsNe.
Depowt
quality
nd
oonl? '
0171
Conn
- 98
0314
Sul
1
101
4 1 425
S02 1 534
78 174
11
12
45
585
69
13
14
55
5
828
825
475
Sol
057
Conn
Conn
one
riliss
size Cm
004
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172
11
Conn
as
1 $04
Can'.
204
2 125
35
440
so
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2 326
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754
05
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7
879
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446
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one
so
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0.26M Citraie
5
21
3
4
1
31 325
2
075 1
1
025
377
408
1 26 251
031
094
90
123 4145 31 25 1563 1042
u1sec
879
1w*11c l
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Is
01229
It
a
375
4 71
8L
: 00121
NAscowly Cm sti/sec
009"
Spot number
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Current acipi,ed
Time sacs
00m,
17
7
4
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-1
1
004
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Au2O
NO.
a is
4 at
521
Nozzle area cm eq
nVas
31
- 7n e
quahty
SAMPLE
Is
85
i -0 i -0
0.25M Citraw
4
2
11
1 20 1 251
31 25 is 83
-1
3258
N zz: velocity
Nozz
90
No.
"a
1
Current do's-WAICMI
current app"ed
fA
Tim@ secs
Total Co. iombs
446
35
Nozzle area cm eq
ELECTROLYTE
pH
Spot number
is
0.211M Citrow
mise
ObIns
Aul 9
Temp.
83
10
1N
1
9
Qualfty
SAMPLE NO.
00"C's 1-11
182
18,
1 677 2 045
1_O
1=
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ELECTROLYTE
15
Spot number
Current demo? y Adem 9q
Current sop,, ed mA
Time sacs
9
a
3.75 1 4
02
5.02
471
'I
35
440
an.
25 C
PH
"
10 42
a/n*
Aull
Temp.
5
a
3 325
377
408
4
2
251
I
00012"
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Nozzle area cm aq
Ime sect
Well Coulomb$
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Plating rate U/sm
Reynolds
k
9
1
4
4
502
50 2
7a
7a
10
4 25
534
74
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C. M..
21 8
245
225
2 627 3 141 3 041
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1
nj
nine
n
11
45
585
69
K
12
475
475
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5
85
857
as
13
14
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625
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521
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00"',
PC
IC
t
on
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TABLE
203
17
7
879
440
408
I
No. 887.6
18
SAMPLE NO.
ELECTROLYTE
Au21
0.20M Citrate
1
Temp. :
pH
40 C
Nozzle *z* cm
$I
0,
area
VOco:
ty em
10
Spot number
Current density A/cm so
Cumerlt sophed mA
Time set: s
Total Coulomb*
Thickness urn
2
075
0 04
1
025
031
123
3
1
1 26
31 25
41 45
flow?
oonas
a1
00"A
83
5
4
2 K
3
2 51 377
15 03
a
325
4 08
42
1042
10
ao"
155
10"IN
jonn
Is
II 1
1
Is
8
-9
00"Vil
18 7
7
35
4 40
a
375
4 71
so
Nozzl
cm
IC3190C
!Deooo.t quai ty
SAMPLE NO.
Ik
4
5 02
10
425
S 34
11
45
5 65
83
78
74
so
0010TI 0T 89
183 - -AQ
con's
194
all-
10nM
Temp.
pH
40 C
Nozzle velocity
61
12
475
5 97
13
5
6 28
is
is
55
5
6 911 7 54
057
825
568
521
481
446
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on/nd
---
no
004
Tomp.
%)H
Spot numoor
C,,ri,enj oon$.ty A C- So
-,, ent soooeo MA
T"to
Total coulombs
Th-'ess
.,, 11
plalino rate u1sec
to C
Viscosity
Nozzto size cm
181
0 04
Temp.
55 C
DH
61
Nozzl: area cm sa
Vaco lycmea/soc
14
55
691
Sao
is
is
15
Is
6
15 as
5
a Is
7 54
521
51
481
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11.11
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17
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7
a
8 70 IC 05 1
39 1,
4 46
0-1.
11-1
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no
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124
10
11
12
13
14
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4 25
45
4-, 5
5
55
9
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565
7 54
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528
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74 -6 i- -6-S-7-r- a 25 5 8-8 5 21
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ELECTROLYTE
Reynolds No
00072
-no
2
3
41
5
7
6
11
a
91
1
075
3 25
1
35
375
025
4
0 9A 1 26 25,
377 4 08 A 40
031
4 71 502
9a
89
83
78
123 41 45 31 25 1563 11042
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as
157
155
155
161
154
0 896 11 507 1015 1742
0 0099 0
104 2 103
Au24
I.
::
0.28M Carate
09powfous"
SAMPLE NO.
on.,
an*,
cm @a/sec
-; -fne
so"
som
at
0,911c,
M
7
a
aI
111 10
11
12
13
13
35
3 75
3 25
41 425
5
45
4754 1
47
71_ 502
534
440
4 71
565
408
59 7
597
628
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go
89
83
74
69
a 57
057
625
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onn 00"19 oenooo o1noo C.
I_ 162
167 is?
17 175
Is I
2012 2 170 236S 2333
1 687 1 $76 2012
ELECTROLYTE
Au23
SAMPLE NO.
one
Nozzle area cm oq
10
Nozzle are Cm
0.25MCitram
/me
2
3
5
4
-1
075
025
1 Z 2
3
031
094
1 26 2511 377
5563 1042
123 4145 31 25 1563
irW2
0 030 0""
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Inn ....
73
49
14 7 159
094
520
0
520
0 0 118 0234
94 111526
04
17
is
7
a
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20
Spot numb*f
IS
05
6
ELECTROLYTE
Au22
tiorn
737 1W
0 0 147 0 266 0 992 1
2 054 2 777 i 48-7 T703
1737
!= :
no
*D
"
am
on
sm an
I
f
II
f
Wing 810 wc
: -ze
oq
2
0 04
Nozzl area cm so
Reynolds No
1045
is
is
a
as
7 54 5 is
521
2 1 481
i1o"M
onn oo"P,
on.
17
7
11
8 79 110CS I
4 46 139
V,Oco: tv cm sa'soc
#
Spot mumber
A,cm on
Current con"
Current aDDItedmA
Tirne sees
Total coulomt's
Th ck, ess urn
jPlating rate u sec
Gus,-tv
71
2
3
5
a
a
1
a
1 0 2 10 75
2
3 3 25
35
3 7L
1
3 77 408
4 40 4 71
094
1 20 251
031
e9
98
! 3_
4145
145 31 25 1563 1042
123 45
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C1.11, 'Inn
InIS io"r
76
203
14 2 189
19 7 206
49
0 Ila
0"
118 0 243 0909 1814 2052 2 15 2446
Is
is
9
10
11
12
4 425
45
4 75
502
534
565
So
7a
74
9 657
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214
206
202
27 44 2764
28
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On
wonsi sr%,
n*
c
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1
1
13
s
It
55
691
Go
5 25 55,
515
581
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on,
sn'sne
snoen.
1
c
1
TABLE
204
Au2 5
SAMPLE NO.
ELECTROLYTII
55 C
Temp. .
pH .aI
Spot mumber
cu"ent de8. noA cm oq
Cu"M
opphod
Tn'*
MA
c,
Total coulombs
Th. ckeas um
plotong rate U'soc
00.
nd
55 C
Nozzle velocity
pH .
61
Nozzle size cm
2
075
T V
29
007
um
rate womic
Depostt cuaittv
i"A
-0
w748 1
12
13
0
4
10 4511 4 75
4 25
534
502
78
on't
's
74
00"19
10
.011
DM#
OM.
o"m
wMe
on
000121
000788 1
12
13
5
628
625
area crn eq
375
440
471
Ton,
I? "
10 45II
4 75
565
597
425
534
502
74
go 89 63 78
2 -"It
17
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IC je
10.10
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18
so
7
17 7
12269 2527 2609
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657
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14
0"12
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5.224
L-IL is
55
591 LL54
521
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9.
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81
8 79
446
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39
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15
Is
18
5
55
a
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a
754
628
679
691
a
16 446 1005
481
825
568
521
39
on
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I
35
408
ELECTROLYTE
55 CI
14
em w
Noule
004
a
3 25
1042
fl
567
657
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0.28M Citrate
.
3 77
t-
es
so w
Au27
Tomo -
4 71
17 1
158
173
ss
108 516 781 iz_,
933 1084
176
0 05911 1 1
nd
SAMPLE NO.
O..
5
3
-4s-
t . -)
Viwoe, ty cm sa,
a
375
440
5
83
98 so
so
I223 0
00- 0 00"" 0 ,
168
la1 [L3jgL
1872595
19 2739
ISO2007
191 3195
75 2506
12
1
I'll,
mtso
04
26 251
031
31 25 IS83
123 ILI
Total couiomos
408
Temp. .
A cm so
I
35
a
325
ELECTROLYTE
I
025
004
ob
Au2d
C. rwt
appimA
T,, ',
ecs
Plating
cm
038 10o
4 0
154
53
11
478
092 0202 0729
0
1
number
Th, ckess
SAMPLE NO.
Spot
Current o9miury
Nozzte gre
D*povt 0.61'ry
.5
4
2
02,
075
3
004
26 251
377
031
123 41 45 13125 1563 1042
0 25M Citrato
ll
DATA
Nome
aroa crn sq
VISCOWTVem go, we
Roynolds No
000126
; 404
"
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III113
4
mubo,
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A emi "stv
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Spot
so
F--"c
9
Totai coulomos
10
10
25 10 75
31 10 94 11 26
123 14, AS 131 25
... "A
1 61
48
039 10 154
.. -,!
-"I
rT-h,
emmegs um
0 10
Id
DeDowt Q. S"N
1a
11
T*mo DH -
251
1563
a
3 25
3 77
1042
T-
fl
14 9
43
10
0653
4 08
4 71
4 25
534
74
502
7a
45
ses
69
I
0-3
17
,
168
12
4 75
S97
$57
227
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17 0
2725
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14 1
13
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is
5 55 754
1
6 691
15
568
21
25
625
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118 81
153
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18 2
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3 31 13 493 13 805
2928
tm
i
i
i
S"
S,
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0 27M Phosphaw
71
9
4
9a a9T783
TI- 17 4 176
la ISO2096 2 256
667
1 1899
ELECTROLYTE
25 C
440
3 75
I"
so
Au2I
SAMPLE NO.
7
5
2
.
: 00124:
i
coolill
Nozzle area cm go
00
Viscolviv
cl" 90'wc
I
N
Spot muber
A cm so
Curntni cerivy
Curnp,? spol, ed mA
Tmw secs
Total co. lovs
Th, cKmess wM
Plating rate U'vec
1
025
0 31
123
oW2
No mic
075
094
1 25
41 45 131 25
3
3 77
251
1563
1042
325
3S
406
06
440
89
11"
3 75
4 71
93
-9
4
502
78
ton'*
10
- 425
534
74
I o1w
II
12
- 45 , 4 75
565
69
. 0-
5 97
0 57
to""
13
14
is
a
a
5
55 .
6 28 , so,
754
a 25
568
5 21
0"
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17
as
04
4 at
5 79
4 48
o..
i
Depost
cual-tv
no
9 so
s- smooth
& bnght
sb - wrr4-bnght
visual seseswriont
oniv
sn*
d- w"ooth
?II
IC
lit
& dull
n- slight noculaton
TABLE
205
Is
ai
1005
39
1
1
11
SAMPLE NO.
Au29
Temp. al
25 C
pH
71
Total Coulombs
Nozzle
-3
51
is
Nozzle area cm eq
Viscowry cm sq/
size cm
0-
16
7
35
440
so
325
408
go
."
. 0-9
a1
9
3 75
4
4 71 502
87
7-8
0-
- =!.
10
425
534
74
06"it
It
12
13
14
15
is
17
eolllliti
No th,c
no
quality_
SAMPLE
0.27M Phosphate
so-?
Thickness um
Wing rat uioac
Deposit
ELECTROLYTE
9
1
2
3
4
2
025
05
1
3
063
031
1 26 251
377
123 4145 31 25 1563 1042
Spot number
Current bill
Aicm so
Current sopised mA
Time sacs
NO.
aII I anIw/cr
l
-W=I.
ELECTROLYTE
Au3O
25 C
Temp..
Nozzle w1ocity
71
PH
Nozzle
13
miss
are cm
025
Curremi appited
Time sece
031
mA
Total coulombs
h, ckness um
Plaiing rate w9ec
10
Nozzle area cm aq
OlDtfs
.0
04
Viscosity
00,181
cm go Igoe
1
5
05 11
12
71
91
3 25 1 351 3 75
0 e3 f1 26 1 261
41 45 131 25 11563
1"..
123
141
Spot number
0.27M Phosphate
377
4 08
96
1042
Otis"
V-lr
onlef
S. 17
4 40
89
1
11
12
1-
502
$34
78
74
No.
4350
I
is
13
is
is
is
41 4 25
4 71
e3
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10
Reynolds
I'M$
No th. c
#a
DeDowl
:=
'a
quailtv
silsn,
cr
SAMPLE
NO.
ELECTROLYTE
Au3I
25 C
Temp.
Nozzle velocity
71
pH -
0 Z? M phosprists,
m/se
is
Nozzle size em
Nozzle area cm aq
004
Viscosity
19
number
Currant oertsin,
Cur, e, t ii
Time WCS
Total couiomos
Thickness um
Spot
Plating
025
031
A cm 90
-A
123
3 1A
21
OS 1
1
063 1 1 26
41 as 131 25
2SI
IS63
Reynolds
: 001":
cm sq'see
No
7S56
11
R*yno, d$No.
'101
1
to
4 25
534
74
4
502
78
.2
I1
45
565
is
14
is
No m, c
rate u sec
E
7e-0,
cost
51
a
18
3
3 25 -7 35
3 75
T -7-7 - 7 -08 - 7
40
4 71
1042 - 9 6 - eq
8-3
11
OU
vH
Spot number
Cumem aeriviv A cm so
Current sow, eo mA
Time sect
Total coulombs
Th, ckmess um
JPl8l.r,Q late u, wc
I-
o
66
Nazz
air* cm
-0.01
`10 2
we
!=
ic
0.27M Phosphate
1119
2
3
075
025
1
-03 - 1 I rg -4 - T -26 - 2 5 1 - T -77
7745
31 25 1563
1042
123
We
ELECTROLYTE
40 C
Temp. x,
Au32
SAMPLE NO.
no
11tv
0 1".
186
n -"
21
004
71
325
35
4 OF 74 - 0
go ' - 8 9
i0itill
Nozzle area cm so
10
it
12
3 75
4 71
4 25
SS4
74
as
565
4 75
597
657
63
C. "
00
I-
502
78
5",
so
, 03s"o 0 Q-ti
C-
13
1
a 25
- t-
14
Is
6 5
691
6
7 54
566
5 21
1
i
! "A
0 0 159 0 326 1 1 19
D#=Coos-l
Quality
so"
me
We
C
I
s. 9mooth&bnghI
sb - wnw. bnght
id-wTooth&dYll
n- might noduisticin
in. veremodulabon
no-aiighinciegrowin
en@ - vort
mcie gromm Je - let core Clenerite
er - elecks d - "0 es, elt cleoost
TABLE
206
SAMPLE NO.
ELECTROLYTE
AuU
Temp. -
40 C
pH .
7.1
0.27M Phoshate
51
Nozzle size em
Nozzleareacm
00,
Mwos,
13
Spot number
Current density A/cm so
Current applied mA
Time socc
Total coulombs
Thickness um
Plating
5
71
2
4
a
a1
9
1
10
11
2
3 325
025
075
1
351 375
4 425
45
31 094
3 77 408
440 4 71 702 - 534
1 26 251
585
_O 1123 41 45 31 25 1563 1042
06
89
83
78
74
60
00u001,00
Dii"OUPil 0"19 . -1
06
cGlOll 00M0 00le0l
5
84
164
20
rate Wairc
Dirposit quality
0 269
pH .
'a ine
Is
17
Como
n/n*
snin*
is
Nozzle or* cm
Nozzle or"
004
viscowly cm so 2"
Reynolds No.
:, '"I
cm eq
Ooom
13
Spot number
Current density
Current applied
Time sacs
Total coulombs
Alcm so
mA
025
031
123
eami
Thickness
um
rate u/sec
Plating
075
11
094 11 26
41 45 131 25
00,rioeii1"..
77
46
0 111
a
no
SAMPLE NO.
0 246
40 C
Total couiomtev
Thick, @" um
Plating rare u/saic
N
N
3
--377
3 25
_408
10 42
98
cemit . 0-9
174
Is
1 a7
1 024
e
LMOMS
sirim
*v aloe"ty
21
3
0 75 1
1
094 1 1 26
1
0 25
031
00-a
Ozzie or*
123
ELECTROLYTE
pH .7
A/cm eq
IM-52%ty
Currant applied mA
Time sacs
Au33
Tomp.
4
251
15 63
41 45 131 25
100mil
00
3
431
0 104 0234
cm
1
a1
-? 35
37S
4
502
71
4 71
83
440
89
otui, "
snino
91
00-
'
wine
0-0
Vin-e
10
11
12
13
425
534
45
565
4 75
597
5
628
74
so
657
625
..
00, roe .. we
14
Is
17
is
-1
us,.
SAMPLE
mlaa
iS 63
042
10
42 1
cow,
151
10 11
, 0766
17
T-77
1 569
1669
1 813
Is
091
568
0 0
0-em.
:=F
,ne
w-,.
Nozzle
area
cm
qq
004
V'scilely
Reynolds
No.IOWA
Closer
cm gal
1
71
6
35 1 375
440
4 ?1
96
so
9
4
502
10
425
534
I'l
45
565
78
74
at
83 *
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12
4 75
597
13
5
628
14
55
Sol
is
17
is
is
7
a 1 65
1
754
a is , 879 1-0
$57
625
568
521
481
440
39
elm.
00ml!
10.21
2em,
on-tl
"me
Temp. .
pH .
55 C
N zzle velocity
71
Nozzle size cm
onsier
W*, c, iw*ecfl
wir
eno
tlno
$no
, ; 7*
one
0.27M Phosphate
21
"v"
004
v1scosayernia;
Reynolds
000543
cm aq
No.
1474
see
191
Spot number
Current density A/cm ;7
Current applied mill,
Time secs
3
4
5
2
2
3
1
0 25 0 75
377
094
1 25 251
031
123 Ali 4S 31 25 1563 1042
Total coulombs
Thickness um
P =a
109posit
ae
52
0 3
rate weac
Quality
no
coml
81
0 259
149
0 03
So
a
325
; 08
96
'Qm11 00W.
20
205
1 919 2 135
n
1
I
ELECTROLYTE
AU36
NO.
0.27M Phosphate
51
4
a
2 1
31 325
251
3 771 408
Is
55
f
no
Is
0.27M Phosphate
Nozzle ireloocity"Viss
71
15
ZZI I I
ELECTROLYTE
Temp. -0C
14
E EI
l
Au34
13
1 919
1040
- 9
no
SAMPLE NO.
0 121
12
475
597
SS7
7
35
440
89
a
375 14
4 71 502
78
om, f .03
aeaq
an
10
4 25
534
74
00
7/n;
11
45
565
so
0.
+qnin*
12
475
597
13
5
628
_057
0 0"M
jqnwlc
14
55
091
568
15
Is
_625
004iir?
'I 00m.
1
sneepc
PC
TABLE
207
10
17
is
SAMPLE NO.
A07
70".
55 C
PH .
71
Nozzle
I-Ity"Ves
0-
31
OW5
id
rate uoties:
i
Deposit quality
SAMPLE NO.
PH .
124
Is 8
16 4
0 202
0 703
1 812
1 017
hickritses um
Rating fam u1see
Deposit
om's
111
12
45
475
505
507
69
057
is
2 Oil
n1
0.27M Phosphate
10
as
17
15
251
Is 63
34
58
0082
0166
3
377
12
0768
1a
1 375
4 71
83
10 42
325.
408
of
440
"
00"
150
1 497
""If
Is$
1 729
-11,
179
2 Oil
. M?
2_182
193
wn
'0=
omit
nq
...
"
is
2 -308
10
:, sts'.
005.0
10
isis
10
11
41 425
502 1 534
761
74
QsMe
161
17
is
71
65
8
a is
870 11005
39
481
448
0M.
1
91
35
one
%siscosity,
cm sqfwc.
a
2
15
6
754
621
004
14
55
Sol
568
2 649
n
I
13
5
025
025
oix,,m,
Is r , 719-2 19 8
110
ELECTROLYTE
11
11 26
41 45 31 25
a. -
10
4 25
S34
74
502
78
14
075
094
123
1 Qss
02S
031
a
375
47,
L3
Nozzle size cm
*",
Be
13
Current dentistry A/cm so
Current appt, od mA
Time sects
Total coulombs
0"19
71
Spot number
ii
7
35
440
89
a
325
408
96
63
Id
I
MC
cm 9qf*ke
15
ss
Au3I
T"..
vlwo"
04
OOD543
"d
I
Nozzle area cm aq
:5
Nozzle size cm
h,ckn*ss um
Plating
1
3
2
025
075
2
3
1
031 094
1 20 251
377
123 4145 3125 1563 1042
Total coulombs
0.27M Phossilphate
ELECTROLYTE
14
Spot numbw
Current density AJcm 9q
Current applied mA
Timessece
45
56S
80
0-
12
475
597
657
0-
13
5
14
1 55
is
85
a1
754 1 a Is
521 1 481
i 01
Sea
628
625
0
15
00303"1 iiiin"
0 "J"
17
7
879-
I
is
6
446
1005
39
00m,
10"It
quai, ry
no
19
Ea
"
an*
Ic
sea ss
aissis
s
si ssessi
SAMPLE NO.
ELECTROLYTE
Au3fi
Tamp. -
55 C
Nozzle "
styIwee
0.27M Phosphate
.
Nozzle area cm aq
is
Nozzle size cm
pH sis
Reynolds No.
1,019cosity
cm sq/
13me
000543
I
SM
"u
Alcm
025
031
123
Current so ited mA
Torne sece
Total cou, ombs
075
094
41 45
51
2
3
1
251
77
1 28
31 25 1563 _3
1042
0
325
408
96
OW's 10 A OWW" 00
01.11
17
44
It 3
is
is I
0041
0141
0723
1 4a- 1677
Thickness um
Plating rate u1sec
Deposit
21
00"',
00
Is 1
185
2034
2229
--
Temp.
PH
Spot number
Current
density
AJcm so
Current applied mA
Time secs
40
Nozzle ve
7.1.1
1
025
031
0I-P
4
025
031
123
123
02-2
iss, ". -1
-
25
_M
60
9
-
a 0"',
1170
2205
VII
51
00183
2473
45
565
as
-
13
4 75
597
5
6 2a
025
its?
18 2
2638
I Q
187
2 846_
I. -lleg
3024
wn
It
14
SS
091
56S
0-1.
q?
Is
7
a Is , $79
481
446
a
1005
39
Is
is
6
7 54
5 21
65
M
11-1
em'.
I
"/00
n.
we
of dissolved
Oxygen
a1
as
.1-01.
Reynolds
No.
7372
Is
Is
i?
91
10
11
12
13
14
00-2
55
TABLE
208
10m,
425
534
74
12
1-
010
04
---
11
10
wn
0.27M Phosphate
sty fill"
21
3
025 1 025
031
03
0311
123
123
sailcouicimbe
h.ckneas urn
plating rate u1sec,
6-M
urge time mine
Quallty
lAwal
ELECTROLYTE
Aw 40
NO.
91
375 1
4
4 ?1
502
83
78
3S
440
so
SAMPLE
a1
no
quality
11
Is
SAMPLE NO.
Aw4l
Tomp. -
40
PH .
7.1
ELECTROLYTE
1
Velocity nVolic
Total coulombs
60-s?
Thickness um
Plating rate uivok:
0mall
0
d
lot Qu
SAMPLE NO.
Temp.
55
Velocity
an
Cuff"t
C
had ,A
mA
LaIaapplied
; .1
c
Im*
IL
'a INICS
Total coulombs
Thickne se u
m
um
00
Do-
Plat'n
P1
35
440
89
375
471
83
0=11
00"
to
4
502
78
*=I'
0,
161
45
565
69
OM60
0aaaa
QsX*0
=a
no
IS
15
13
Is
14
5
55
020 Sol 00. DO 000
025 568
325
408
96
000
000
an.
nitrogen 40 mine
Reynolds No. 13259
0.00i"
cm sq)
81
$1
10
375
41 425
4711 502 1 534
83
78 1 74
0031WO00.10
Is
=I
1
7
35
440
- 89
17
-1
Semple do-swaraledvft
Viscosity
00(wai) atia"a"
Nozzie are@ cm sq
004
121
475
597
057
425
534
74
0
no
it
14
a-
role u
Usarc
U,see
ac
sling role
.1
1
2
5
4
025
075
2
1
3
377
031
094
1 20 251
123 4145 3125 1583 1042
A/cm sq
A/c?
.0
0.27M Phosphate
West:
13
Spot
S
r I number
density
C
Current
Z nt d*mw
linscositycitisq/voc.
in
Nozzle size cm
04
ELECTROLYTE
7.1
PH is
0
an
Au42
tool"
19
025 075 11
2
3 1 325
031 094 1.26 251 3.77 408
123 41 45 31.25 1563 1042 as
CumontdensityA/cm sq
CurrentappliedmA
Timeask:9
Do
Nozzle W" cm aq
1a
'4
10
:S
Nozzle size cm
13
Spot number
0-27M Phosphate
omilo
11
45
565
69
a-
1
121
475
597
857
a. -
13
5
026
625
Is
15
a1 05
754 1 610
Is
IS
521
at
481
14
55
Sol
568
Co..
*a-.
a.a-?
-?
10
Olin'.
11-1
wine
*me
17
is
7
a
879 1005
39
446
#
d
Deposit qual-tv
an
Aw43
SAMPLE NO.
Temp..
40
ELECTROLYTE
I
pH
0.27M Phosphate
Velocity Wdowic
181
Nozzle or"
Nozzle size cm
04
Mocovity
em aq
cm sq/mc
Spot Muni
09MINty Aicm 94
applied MA
Time soce
Current
Current
Thickness
st'no
fate
025
075
031
123
094
41 45
1
1 20
31 25
1563
IM"S
. 07M
a. "
90AW4
Total coulombs
4
2
251
3
377
1042
7
35
3S
408
98
a-
8
375
4 71
440
89
9
4
S02
78
"
0-11
om
0-19
10
425
534
74
ImsO
It
12
45 , 4 75
SOS
597
, 657
.
"
003sat)
u1sec
Temp.
me
me
me
Nozzle
PH
00,1WHI
0MV4
one
ans,
is
is
a 1 65
754
a is
17
7
$79
521
481
446
01.21
00.21
emIrl
t /Cm liq
.
mA
app,, ea
T.rne wee
Total coulombs
Thickness um
rate wome
21
075 1J
3
4
2
1
094 1 1M
1 26
031
26 251
IZ3 41451 3125 I563
00
00301400"M ..
74
0
02
151
03
0 0024 0 179 0
0 2914
20,4 0 964
1
025
0 04
51
6
3 325
Viscosity
7
35 1 375
1-10
-aam
--
cm aq
cm sq/90C
11
13
11
12
13
t
5
45
475 15
408
440 1 471
534
565
597
62 a
628
565
0
25
go
89
1042
83
so
19
11, ' 057
025
otaiiiil
*
..., # em, fl easke 0"'s
omea 0moti 0
eiriviqi
1
19
1 823
0
01
0
0
0
0
0
0
0
0
10
425
1
4
14
is
5
55
a
Sol k 75 4
568
568
52,
521
0
0""
00
am"
a"
0
0
0
is
So
quality
-.
70 - `71 =-'c'
1
-#In.
n".
win*
"n.
anins
no0,
n
w
nw
ale
8 79 110 05
481
cam,
39
448
otoqri, am, *
no,
"a,
1
.
A dull
d- mooth
9- wnooth A beqhl
ob - serri. bnght n- lilight nodulation
TABLE
209
17
is
7 1a
0
1
--
line
1
9
4
502
50 2
78
7
!
Depolpt
is
a
1005
39
1
Spot number
Current don E
$no
w,*
Nozzle or"
101
2.2s, cm
1-
0.27M Phosphate
Velocity Rveac
40
0
1
ELECTROLYTE
Au44e
SAMPLE NO.
plating
14
55
691
568
um
1i
Current
OMM,
13
5
628
625
12
0
21
AU44b
SAMPLE NO.
TeW.
ELECTROLYTE
ViRkpovyWave
10
71
pH
0.27M Phosphels,
Nozzle area em aq
101
0 04
Nozzle lure em
Viscosity cm sqlasc
Spot numbeir
Current density A/cm sq
Current applied mA
Time sacs
Totalcoulombe
'Thickness um
1
025
031
2
075
094
3
1
1 26
123
41 45
414
4145
31 25
ca'sa?
-
5
3
377
0
325
408
7
35
440
10 42
go
89
00"Pall
lisReas00"'I'V5 "Cul0a etrlaaf
52
a1
15S
179
1"19
4
2
251
15 83
0.125
0
125 0259 0092
F = =T
plabrog rate
Temp.
pH Is
WRIR .
ELECTROLYTE
40
Vl.,
71
Nozzle are cm
am"
T =
10
425
534
11
45
585
74
09
0. VM Phosphate
Y N.
Is
[an
-I..
Viscosity
025 1= 05
05 1
1 1.25
0625
25 3 125
1 25
Temp.
40
pH
71
T
225
5 S625 , - 7 5
0.27M Phosphate
3
377
05
am. "
Thickness um
08
wma
-2
Velocity missic
IS
Nozzle are em
004
521
481
44e
36
cow?
etrier.
0IMe'll
lua, q
15 1 33
4
3
377
4
n ....
as
a
3
3 77
3
3 77
a
....
1`-,
127
I
rate ulooc
$Mai
on
Wei
SiReFigureld
Reynolds No. 10448
!
81
13
15 1
a
3
377
9
3
377
20
30
1
-5
14
is
17
is
SeeFigurs6i
I
:, -
liflaccaty, cm siqlasic
3
377
6
193
tl
121
112
00M.
Dom
1
31
3
3 77 1 377
2
11
ON3,1 11aam.
'
568
Effectolincressinglims
1
Spot num
625
I NaL disteme mm
ELECTROLYTE
057
15
em sq/9ve
3
2
41
a
a
0
1
o1
aI
3
3
3
3
3
3
3
31
31
3
377
377
377
77 3 77 377
377
3 77 3M
378
go _396
of
go
go _ 96
96
96
96
so
a. 'r
00.21 Do-, 011 a*.,? as"" as%'? am'? 00"'i, am'?
IS2
148
149
145
146
146
138
137
174
152
Au,117
---a
754
17
a
16
aI
65
005
065
a Is _7
a 79 E10
"W"Ic fil
71
SAMPLE NO.
14
55
Sol
Effewoffoozzledistance
Spot number
Current density A/cm sq_
Current applied MA
Time since
Total coulombs
Thickness urn
I H/d
13
5
625
Nozzle orse em eq
004
1.5 1 75 2
3 75 4 37S
121
475 1
507
QWaW 0a,waa
78
83
4 e
ne
Aw"
SAMPLE NO.
a
9
3 75
4
471 502
it
10
12
13
14
Is
Is
17
Is
0 0f
Orion ait
a! *-
224
308
1 493
1 S4
6powl
quality
ELECTROLYTE
Aw4l
SAMPLE NO.
Temp. -
40
pH 1
I
!: %tV
Ajcm sq_
C!
,,!
Current applied MA
Time sees
Total coulombs
Thickness um
plating
at* uivac,
0.27M Phosphate
Velocity rivesc
IS
Nozzle area CM aq
is
Norris size cm
04
linscouty cm salsisc
is
*0:-
I
1
25
3 14
05
0.111,
O.
's,
07
07
14
2
25
314
1
a. ".
14
14
3
25
3 14
2
4
25
3 14
4
5
25
3 14
a
6
25
3 14
12
a-. .
a_
28II
-O'M
a
1 25
M, l
96
12
00".
15 3
1 275
13
7
25
314
Is
..
"a
191
1 273
314
20
..
204
1 32
9
25
3 14
30
10
11
IL
13
14
Is
a-.
408 1 38
Is
TABLE
210
13
11
Is
IF-P-UREGOLD
SAMPLE NO.
Aw49
ELECTROLYTE
Temp. -
55
Velocity M/SK
PH .
53
Norzi* aze cm
Total Coulomb*
018
04
16
2
1
4
5
025
075
2
3
1
031
094
3 77
1 26 251
:25 15*63 1042
123 41 45 314
0-r
00
-
Th,citness um
st'ng rate ul"c,
k
'0
'0
-
-=
-
DoDo_
a
0
ol'-"
v1scowly cm siqlftc
Day"
IF
a
35
375
440
4 71
89
a3
60"19
-1
- 4
Is 7 - 17
1 74 1 V's
I
01
10
4 425
502
534
78
74
00-
. 0wo
00
=8
MT7a
if
45
585
69
12
475
597
057
13
5
628
625
oow, ci 0
"..
18 a 165
Igo
2 12 2 321 2 541 2 881 2 983
an
14
55
891
568
-'.
104
3104
an
AuSO
ELECTROLYTE
Temp. ar
55
Velocity in/me
pH
Nozzle Sze cm
0.25M Citrate
Is
Is
81 as
754
BIG
5V
481
'0""
0"2'
IC
- -
SAMPLE NO.
Nozzle area cm aq
325
408
96
9 162
14
411
16 2
0 0034 0 131 0576 1
555
1555
epowt quailty
The affect of PH
13
Spot number
Current denwtv A/cm so
Current sopiied mA
T,"w sect
0.25M Citrate
1-it
'0M,
is
17
7
a
879 1005
39
446
IC
-. --
The efhw-l of PH
Nozzle area cm so
18
004
Oco"
-V',
: =261
00706
cm sofsec,
15
Spot number
4
2
41 45
1
1 26
31 25
Current denstv A, cm so
Current soo,. ea mA
Time sacs
Totalcowo-os
075
094
025
031
123
cow;
ThICKMOSSUM --
vetlm c";.
36
0 115
0 0024
Plat, no rate u, sc
DeDosil oublory
SAMPLE
a
3
777
325
35
4
502
78
4 71 _
83
08
10 42 -4- go
'0..
'oMit
11 8
0 75S
ISO
1 526
164
1 708
ELECTROLYTE
V*Iccrty
55
3 75
440
80
a5
1 854
Nozzle
*q*
0 04
cm
- 45
_12
4 75
565
so
So?
657
14
__13 a
628
625
ialqm . 0"M
- 55
_156
as
Sol
S68
754
a is
4al
: 031A
18
5 21
"x
is
17
7
---a 0
to
39
4 46
879
1t"?'
0f
In.
"'.
Sri
In
on "c
Ic
?c
Reynoics
No
Effect of pH
Nozzle
IS
:_
425
534
74
IGO
173
2 let
2338
Fn
1=
0 17M Carsta
rn'sec
11
10
Otto's 0-
16 8
2 024
Aw5l
Temp
251
15 63
NO.
ow
V'qcostv
cm
em
so
so
ra
avc
: 00126
9399
I
Go
3
1 26 1 2 2 11 3 71
3
41 45 131 '25 11 6
,6 12
3 25
4 08
96
3S 13 75
4 40 14 71
a9
83
I L2
Spot riumoor
A Cm w
Current cc""V
Curr"t
sopiiaanA
T, ma sitcs
41
21
075
094
02S
031
123
Torsi cowo-tis
Th, cxnass um
plaung 819
Depowt
10
4
S02
7a
4 25
5 34
74
13
5
12
11
4 75
5 67
a 57
45
505
Go
14 2
628
825
a 911
a9
5 68a
56
.61
a
Is 6
IS
23923
2
9 23
2
2 576
Temp
5:
mloac
Is
:-
Nozzie size cm
cH
Current
A Cm .0
Current sops-od n, A
T, mv secs
Totat couiombs
0.1.11
Qua, 'nr
075
025
031
004
'23
41 45
13
0 0031
Th.ctqess um
plat'no rate U1110tC
I1
IC)OPowt
no
1
126
31 25
2
251
325
35
10 42
408
go
4401
a01
377
7
1 375
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55
ELECTROLYTE
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SAMPLE NO.
1a
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A*vnoics
1
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534
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TABLE
211
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.:
cm atl, see
10
No
14
,n
SAMPLE NO.
AuU
Temv. :
ELECTROLYTE
56
vow"
So
PH
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13
Current dor M
cur, rwril go
cm GQ
A
4
Time sece
Total coulomos
Thickness unl
Plating rate weec
h
epowl quality
1 075
025
Temp.:
pH
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2
075
325
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11
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Aw54b
SAMPLE NO.
Ternpi. :
pH
55
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all
071
345
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3
11
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10
1
9
Spot number
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377
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901
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Total coulorms
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rate u "a"
21
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212
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TABLE18B
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216
Ueposition
C. D.
Sample
mA cm
Ni Dep.
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Ni Scin
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conamons
Hard.
Boom.
N At
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kg mm
ml I
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XAUP I
XAUP 3
1
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Ronoval N
ConvenbonaJ
Auronal MRN
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0
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0.259
1230
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3
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134
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17.6
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17.3
RNXII
RNX12
RNX13
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7
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127
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1.9
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2
0
167
Jet plated
samples
Jet
samples
plated
75
130
10
TABLE 19
217
=
SPOTS.
DEPOSITED
PLATING
PARAMETER DATA
ALLOY GOLD
11
RNI &2
SAMPLE NO.
Temp.
pH .
55
Velocity nVook:
46
Nozzle size cm
1
025
031
246
Spot number
Current density A/cm, so
Current applied MA
Time *act
Ronoval N
ELECTROLYTE
20
BOOSTERm1A .
Nozzle or"
cm sq
7
61
91
10
1`1
12
5
6
a
9
10
628 754
879 1005 1130 1258
125 1042 892
78
69
624
00M.
00"
05
0002
20
28
138
17.3 172
174
L8 182 178
IGO 163
0 031 0 042 0 441 0 835 1 154 1 456 1 589 1 039 2 205 2 435 2 612
011M
OOM3 oomv
conse
00m,
do-$
O. Mill
80
0WIM21
dr
Total coulombs
00,0.0
is
%Avcowry cm sq/ooc.
004
51
0
3
4
3
1
3
4
377 502
1 25 377
625 31 26 2084 156
2
075
094
829
NICKEL IN ELECTROLYTE911
17
is
13
14
Is
Is
11
13
14
15
is
12
1382 1507 1833 1758 11164 2010
30
568
521
40,
4 4a 410
con, do 00,10,
001
00-2
7MIT
do, 042 DOM,
_ T4_
ao
0
3 821
is 1 167
2 8345 3 205 3 202
it %
2
205 2
12001
II
J
_.
SAMPLE NO.
RN3
Temp. pH .
I
_
_I
Ronoval N
ELECTROLYTE
12126
203 6
NICKEL IN ELECTROLYTE94 -
55
Velocity misoc
2D
Nozzle arms cm aq
46
04
BOOSTERmin -
0.5
I
OW?
Or'S3'
50
1
2
11
075
025
031
094
246 B29
Spot number
Current density A/cm eq
Current applted mA
Time 99ce
Total Coulomb$
Th, ckness urn
00,12.
3
51
0
4
4
1 3
1 26 377 _3377 502
625 31 28 20 84 150
. mj
eorVIO, d0-0
10075
1
004 1
11623 11
Temp. -
Velocity
55
1
02S
031
240
101W
,w
--",
Temp.
SE2t number
:M go
Current appi. od rnA
Time sacs
Total coulomb$
Thickness urn
Plating role um
.
wnlrii.
katmm2
2
1
025 1 075
031 1 0 94.
246 1 a29
00,11.
low$
atim
19
1
12
13
14
is
Is
10
1256
624
11
12
1507
521
13
14
17 58
446
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0059
Z)
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oomi
venii?
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0 129
1374
_
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0 114
148
1864
4 Is
20 10
0.72
gA
BOOSTER
Reynolds
A.
Im
mlA -
me
90
No. 10824
1
11
12
10
a
9
to1005 11.30 1256
78
so
0 24
is
17
13
15
'a
14
0
14
is
11
13
12
1362 1507 1833 1758 1884 =.
39 1
568
521
4a
481
446
00-7
00M.,
'a-
10082
1
Q-,
00-9
Dom.
. 0-,
don't
1
0 055
11734
TABLE20
218
000753
cm vQ190c,
1
013
is
19
7
17
5 16
625
7S4
879
892
125 1042
oo
1633
481
is
dO3
I'm ' '
NICKEL IN ELECTROLYTE
Viscosity
1382
558
17
F
:
I. 1
Nozzle area cm aq
004
1a
0047
jeo a I
Ronoval
No. 10624
Reynolds
11
ooni"
I 51
10
oa?"!
3
4
14
3 13
I1
377 1 502
1 26 377
62 5 31 26 20 84 ISO
iW? t
Tycrnsq/60C
00,101,
on, , ! ""1
0
15
I
I_
visco
oml
Nozzle size cm
N
: 00124
1005
78
Velocity milask;
PH
9
11 30
69
ELECTROLYTE
55
aroa cm aq
508
ANS
NO.
so
0.72 BOOSTERml/I -
Nozzl:
6 17
7S4 18 79
692
1042
oom3y
NICKEL IN ELECTROLYTE9A is
Ronoval N
3
5
4 N
3 77 1 5 02
0 28
2084
5O
158
125
SAMPLE
oeigno
832
020
04
oom,,
is
17
Is
13
15
14
Is
14
15
il
13
12
1382 1507 10 33 17 58 1864 2010
446
568
521 481
1@ 39
-4
oofto
oom?
con'r
I~
DOM3
corew
0025
misec:
3
0 75 1
1
377
094
1 26
G
829
25 31 20
0rli, f
loniat
I-,
164 2
Nozzle size cm
1
Zbe a
CM
did, " A, cm so
Current 8000ird rnA
Time secs
Total coulombs
Thickness urn
draso
0 033
ELECTROLYTE
AN4
SAMPLE NO.
00MI,
7
a1
91
io
11
12
5
1
a
8
9
10
6 28 754
879 1005 11 30 1255
75
125 1042 892
69
824
'em"
SAMPLE NO.
RNS
T".
55
voCcity"vc
20
pH .
46
Norzie ipze cm
004
Spot number
Current
domimj_m
Cuffent appited mA
Ti sees
ITotai coulombs
4
075
3
094
26 377
820 Le25 31 26 2064
I
025
1
011
246
0""
55
Velocity rNsec
pH .
40
Norzle are cm
I
025
Currtnt
031
246
094
829
secs
Total Coulomb$
Theknese um
00M.00of
0007
Velocity misec
pH .
461
Nozzle size cm
mA
I
025
0
094
031
246 1 829
Im.
um
-i
pH
Spot number
Current
demwty A/cm $0
appited
mA
T,nw socs
Total couioos
Th, ckten
Pisting
um
role um/mc
FNTc-k*lin deposit %
Fvaesv ko-2
9
3
1
00-1
i IA
S02
7
5
628
125
1159
1 011
248
00,12.
2D
829
oo
004
3
3
377
26 377
625 31 20 2084
11
Olft,
0032
I'M
1042
Ranov&IN
Nozzle size cm
094
9
7
12
879
892
. . -F
101 11
a 3-0
9 1256
10
1005
,1eg 024
78
. . -I
oo
00.11
181
13
a
4
502
156
1362
ro-1---"l
r, 7-5-r
1505
NICKEL IN ELECTROLYTEg/l .
2.2
Nozzle are& cm aq
000124
m9covirer"
0 007W
9 L-1
II
a
9
N
30
679 1005
892
7a
1'
0
0.
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I.
1063
123 8
M.
I
194
176 oom"
192
11a 0845 244 1536
0377
1031
044
11
is
le
Is
01.1,10-1
155
oei
BOOSTERPnIA-
60
12
I?
15
1 15
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ELECTROLYTE
2
075
a
7540
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46
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OM)
004
a
4
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176
11
9
le 00381
0
028
381 0645
845
0028
Tomp.
1042
20
117
1
"I 2e 2084
625
AN9
SAMPLE NO.
6
7546
Ronoval N
.
4
3
26
owl
piat.,,
piat.,, G
rate umlsec
umlsec
G rate
FN-ickel
Nickel In
In depooll
depoml %1
lHardneso
kol-2
srcness koi-2
[Curr*nt
2
75
621
125
lo
ELECTROLYTE
55
T, vcs
Total coulo,, os
Th. cknete
0034
lom?
7
5
0001"
oomt
omil 175
-11"
194
131 0
192 a
183 0179
las
188
0419
B88
244
804 2052 2295 2536
536
0 0167
1 1 1128
019 136 1
0098
148
1686
Temp. -
Spot numbor
[Cvrrent comsity A,cm sq
itopited
21
004
502
156
OM3
-M,
RNO
SAMPLE NO.
1042
2D
a
4
1255
caqw,,2
Current
5
4
3
3
377
26 377
625 F31-26 2084
0308
IM deposit
e
754
Ronaval N
Temp. -
soptsed mA
628
125
ELECTROLYTE
2
075
Nickel
502
BOOSTERmIA -
1.5
Nozzl* area cm aq
m sq/c
0. -1
RN?
Spot number
Current density Alcm so
7
5
6
4
NICKEL IN ELECTROLYTE9/1 .
ISO
oil 770
, DM,00-1le137
19
0438 1
52
1 01351
025 1
0168
1406
1289
oo
SAMPLE NO.
I'll
oo
Thickness um
Ti
Rcmaval N
ELECTROLYTE
54
Dy
ao
cow.
. l
ion"
TABLE21
219
Omll
11
SAMPLE NO.
Ternp.
ELECTROLYTE
ANIO
63
Velocity nvwc
48
Nozzle size cm
Ronov&IN
20
NICKEL IN ELECTROLYTE9/1
BOOSTERrrg/l -
80
- ;7zzis
Reynolds No. 10624
ar" crn sq
004
viscowly em qq1q*c
V1
07iVI
N
Spot number
Cumont 43*nwty A/cm aq
C. Iftnt opphed mA
Time sece
Tollif coulombs
21
025
031
246
075
094
829
001?71 ll
Thickness um
lating row u/sec:
r l ckel In el*eosl t%1
'mm i
a rdne;;
1
3
377
1 20
62 5 31 20
come
5.3
0 'so -85
0
1
377
20 84
0111'ro coml
13
1144
1
1528
4,
502
5
8
628 - 754
7
a 79
156
125
1042
892
lama
lam?
aof
comly
138
142
37 716
-- 5 601
1
T-91- 7104
1
134
132
-1 48
2=6
1148 3
1 1154
10
11
12
13
a
9
10 OS 11 30
78
at
10
12 50
024
11
13 82
568
low,
00,11,C) Dow?
135
127
125
1 079
1 957
2 035
2 2007
h595
IS
Is
12
13
14
15 07 . 16 33 1758
17 58
5 211 4 111 446
44 6
_
am)_ oo
1-7
lie
122
121
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131
Is
14
2 342
I
2 516
I
17
is 1
16
is 84 120 10
39
4 '16
0MI,
2O 46
.
TABLE22
220
la
114
2 74
left),
It 5
75-5
S&NIPLE
C. D.
Do A
D,, )L
(111)
(111)
D,, A
(222)
<e3>
(111)
a
(111)
2 ". 3
Ni
Booster Hardness
CM3
CIM-3
kg MM-1
Pure u Conv.
3.0 nLAJcmz
2332
744
540
0.000035
n/d
101
Pure Au Conv.
7.0 mA/crn2
2321
860
551
0.000035
n/d
01
102.4
Pure Au Jetted
2.0 A/cm2
324
326
198
0.00011
0.007
163.9
Pure Au Jetted
4.0 A/rn.'
350
349
206
0.00015
n/d
198.9
Pure Au Jetted
6.0 A/cm2
335
327
215
0.000115
n/d
203.5
Pure Au Jetted
8.0 AIcm2
328
304
205
0.000133
n/d
204.1
Ronoval N Con
10.0 mA/cn-s2
261
104
128
0.00015
n/d
1.7
60
198
RonovalN Conv.
40.0 mA/cmP
254
107
128
0.000135
n/d
1.7
60
130
Jetted
3.0 A/crn2
324
340
209
0.000115
0.021
60
Ronoval N Jetted
9.0 A/cm2
289
307
189
0.00013
0.022
60
Ronoval N Jetted
3.0 AIcm2
191
182
104
0.00017
poorpeak
1.9
60
127
1.9
60
170
Ronoval
resolution
Ronoval N Jetted
9.0 A/cm2
200
201
128
0.
TABLE 23. Crystallite size, RMS strain and stacking fault probabilities for some samplesfor the (I 11)
planes only. Note n/d = not detectable.
221
ELECTROLYTE
NIAX.USEFUL
C.D.
3.0 A Cm-2
1.7,um sec-I
5.5 A cm-2
2.9 Am sec-I
6.0 A CIIr2
3.4 Am sec-I
5.0 A cm-2
2.9jum sec-I
3.75 A cm-2
2.2, um sec-I
TABLE 24. The maximumuseful current densitiesanddepositionratesfor the pure gold electrolytesstudied.
ELECTROLYTE
Ronovel CNI
1.6, um sec-1.
5.0 A =2
Ronovel N
6.7 A czw2
Auruna 7000
10.0 A crrr2
MAX. C. D.
TABLE 25. The maximum useful current densitiesand deposition rates obtainedduring the initial study of
the alloy gold electrolytes.
222
Reynolds nurnber
Limiting C. D.
1893
5252
7538
0.367
0.47
0.591
953
1220
1535
618
976
1148
461
768
923
956
1145
Sherwoodnumber
Alkire, & Chin
Chin & Hsueh
Chin & Tsang
Sh = 21.03ReO-"
Sh
Sh
0.9ReJSc.33(Hld)-0.09
1.51Re-5Sc. 33(H/d)-0-0-14
774
(Laminar flow)
Sh
33(H/d)-0.057
1.12Re-ISC.
(Turbulent flow)
Diffusion coefficient
Viscosity 0.014M Cu
TABLE 26. Limiting current density and Sherwoodnumber data obtained using the 0.041M copper electrolyte, together with calculatedvalues using modelsderived by other authors.
Reynolds No.
3355
iL(SCPV) A cm-2(pure)
'L(SVPA) A cm-2(pure)
i, (SCPV) A cm3 (R.N. no ni)
4.41(-8%)
6710
13545
9.97(+10%)
6.3(-3%)
5.1(+B%)
'L(SCPV) A cm 2 (R. N. + r)
'L(Correlated)
10600
5.03(+6%)
Sh - 21.03RO
4.78
6.52
8.94
4.71
TABLE 27. Limiting current density data for the 0.17M citrate gold and the Ronoval N, together with
Percentage
&
Chin
deviation
from
based
Alkire
the
the
the
model.
values
on
represent
values
calculated
model.
223
ADDENDUM
224
TEXT
BOUND
THE SPINE
INTO
SUMMA RY- High speedselective jet electrodeposition is a process whereby electrodeposits may
be produced in a selective manner without the needfor masking. The principle is that a nonsubmersed, free standing electrolyte jet impinges onto a substrate and deposition occurs within the
impingement region, with little or no deposition occuring in the surrounding areas. The deposition
of copper from an acid sulphaie electrolyte has been examined and deposit structure and quality
has been related to the prevailing hydrodynamic conditions of deposition. The selectivity or
resolution of the process has been examined. Further work has been carried out using an acid
citrate gold electrolyte and some initial results are presented, and also relating deposit structure
and quality with the hydrodynamic conditions of deposition. Examples of applications are
discussed.
INTRODUCTION
High Speed Selective Jet Electrodeposition
(HSSJE) is a process whereby electrodeposits may be produced in a selective
manner without the need for masking. The
principle is that a non-submersed, free
standing electrolyte jet impinges at a high
velocity onto a substrate and with the application of an electric current, deposition
occurs within the impingement region and
the immediately surrounding region. Due to
the resistive nature of the electrolyte and
the properties of the hydrodynamic flow
surrounding the impingement region, the
spread of the deposit is limited. Whilst
Selective Jet Deposition is not a new technique, the principle being patented by
NASA' in 1974, there has not been a
significant commercial exploitation of the
process. The NASA patent refers to feeding
an electrolyte at high pressurethrough a jet
nozzle onto the surface to be selectively
plated. An image of the pattern to be plated
was scanned using a video scanner in a
raster fashion in the same way as an
electron beam is scanned on a television
screen to obtain pattern defining signals.
The nozzle was scanned in the same way
and the pattern defining signals controlled
the amplitude of the plating voltage. Thus,
in regions where plating was required, the
voltage was modulated to give the plating
current. In this way, the pattern was built
up in a similar way to a dot matrix printer.
A forced flow selective plating system
was described by R. Haynes el a12 in 1978
and Dorey ef al used a modified version to
gold plate conncctors3 in order to evaluate
thermocompression bonding characteristics
of the deposits produced. The maximum
flow rate used was 39 cm/sec and current
densities of up to 1.3 A/CM2. With a nozzle
diameter of 0.5 cm, the flow under these
deposit
However,
is
laminar.
circumstances
quality deteriorated at current densities in
formaby
A/CM2
0.86
nodule
the region of
tion. It was claimed that nodular deposits
did not necessarily reduce bondability.
that
describe
the
hydro-
119
in
RIIB-0304Parnersh'P With
*BRITEPrOject
Italy
Materialli
of
and
Svillupo
Centro
Loughborough University of Technology.
control
program developed "in-house".
The computer program could also take plot
Files from computer aided design packages
(CAD) and convert them to output f iles for
the X-Y table, allowing very elaborate
designs to be directly written by clectrodeposition.
I-
"I
TABLE
MICRI]COMPUTER
II
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raft, vs current
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/ jpjf,' 15 1
formed wili,ti /11(,
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it-pe %fruourv%[hill
(o m/m/rale dwance win
mm 0
MaNgARMORAUC
123
hydrogen
ion
a.
s
Such
react
ing
com pet
Jhe effect
reduction.
or
oxygen
evolution
by deestablished
was
reduction
of oxygen
by bubbling
nitrothe
electrolyte
aerating
it for 30 rninute,,
to
prior
through
gen
deposits
It %%a found
that
deposition.
dc acrated
did
oluhom
produced
deposit of 0.3 pin at
mewmah1c
a
produce
A/c,, )-' In addition,
0.25
an
of
a(
-D
in deposit
thickness
of approxiincrease
1), of'
101"o
to
up
a(
seen
"as
nialcls'
.
incicase
1.0 A/cm2
alter which no I'miliel
tiom
was Well.
C0jjVCljtiOljjI
conditions,
90
1'. p SbC
Y. l. ly le
i-
OH 01
(0
t)41
"0
101
0
)46
Cii
D.itily
Alt.
tq
carilly
current
deposits
structure
alfccted
densities
Figure
17. Current
Inaxinnort
denstit,
spread
11.1/d
if
/)
aw
60
opt/w,
p/l
%-%(lopo%il
v%,,
(/jjj
of %poi%.
wAll
/ Ipule
10 ( ... low
domiti
.
diflo-rew
pold corn cfill o/ 14,11
1,14 ltSI,.
platim,
Iti(Ile
for
taic
wll of vir.
41/4
l. I.,.
OOIM
" 01I
44
041
44
I.. p
(
I
S.
234
Ciii..
I Doilly
AIrs
.q
kv
. 11-..
'0 1
.
0-11,
Ah.
. 11 '...
40
1
Q
66
on
I10n
A 76
D41 M
a 11 .
I
.* [0
...........
Figure
N-ow
'rhe Effed
exhibits
ol current
(tensity
on
-1-he cll'cct
be seen ill Figure 18. It can be
can
selectivity
low current densities, the
al
filar
seen
is poor. As the C. D. is increased,
%eleclivitv
structure
than
gold
maximurn
maximum
was
the
creasing
plating
obtained
8.1 was
3.4
A/cm2.
in
obtained
structure
At
maximurn
current
19.
0.17M
this
series
of'
deposit
this
It
can
the
and
a slight
density
and
seen
much
plating
pi I
of'
rate
The
be
that
less
vent ional
late
at
density
experiments.
call
a
in-
to
clectiolytc
be
coil
tile
where
pialing
at a current
pin/sec
This
was tile highest
of
Figure
useful
current
The
maximurn
the
so
However,
the
rate.
from
ill
seen
jetted
(lie
angulai
deposit.
of" 0.28M,
tile
plating
rate was 2.9 uni/sec
a( a
density
]'his
of' 5.0 A/CM2.
effect
concentration
i,
21
Iffle
clifoll.
ertnt
ol
com ('1111411foll
(Off
Rold
density
at 0.17M
led
reached
1.1gurf,
Ae/tIclivill'.
increased,
was
concentration
in
reduction
6.0
content
useful
curient
increased.
rate
plating
derusils, t)ll
of Gold Conceniration
deposit
the
Is
improves.
As
61.0,
... d
tile selectivity
1'. 0 *,[
4,
1'. 0 Y, C
front S111001111
and (full to
changed
then to bright ;is the C. D.
arid
serni-brighi
followed
by either a
This
was
increased.
growth
or ncedle
arid
Structure
nodular
above 6.0 A/C1112 (lie growth pattern
finally
dendii(ic
a pronounced
with
becallic
I lowcver,
lield cuientated
growth.
dendlitic
(4] no dcndrific
electrolyte
of'
it, tile case
It should be remembered
seen.
was
growth
deposit
thickness
also increased
the
that
density
incicasing
current
arid this
illi
,A,
have had all influence
oil the deposit
would
(See tile Fflect of
and appearance.
structure
Thick ness).
Increasing
124
-11 [it,
1 /l/d/1111, fill"
Irml,
s(
8/
being
The
//1,
1Y
p/m/m
i'd fit Ifle Ilf"'ll".
(( ltrale
ele-, troh ie-,
A/cipy. '. Re, 0.078.
plation,
Wi(Il
low
al
Observed
low efficiencies
incicamny, a,, tile
densities
and
curiew
*Ilii.
iiicrcitscdl4.
%%%,
otil(ibc
(iciisityi,.,
cullcui
F" (rest potential) value of
[lie
as
expected
V. A( a pil of 6.0, the
is
about
-0.61
gold
V.
j:, 1 value of hydrogen is about
-0.3
a signiat low overpotentials,
'I-hereforc,
be
hydrogen
cowill
of'
ficant quantity
deposited, rcclucing as the overpotential is
been
it
has
In
shown
addition,
increased.
that the reduction of' oxygen also occur. %at
It
densities".
would appear that
low current
behaviour occurred under jetting
ilmlat
a
condition",.
denwi
%-%
rurrent
glow
laigel,
I III',
cffccl
IN alNo
Clillank-ed
VC10(.111C.
flial
N. llll
Inklikatcs
lucclialli"Ill
and law of nodule
glowth
dillivoon
connollcd.
I-iguic 20 shows tile plating
late,, lot
difTereril
conccimationN
of gold om
glealel
by
(lie
is
life
file
at loll
Clectlokles
"llowing
all
1'111 wits
appaicnily
gicatei
plaiing
iatc.
lacl
to tile
(tile
flim
al high
ClIfIC111(
dcII1, IfiCS, (lie delIMIN' of' file deposit
fell as
delvimiated
tile deposit
qualif\
(life to an
inclease
ill %olds. 11 call he well Illat tile
CUIVCS I'01 thc 0.0411\1 and 0.28M
electrolytes show a "ignilicant
deviation
m (Ile Iligh
(1)'
Ilk
') II
11"
I I] I"CII
IhI
ill
I C1)1
01
II RIS
111C
%N1111
pool d(-po'l(N
11(1w depm II (I II; j IIik
k it I, ('' %%
Icill'Imcd
I\ )'41( dm
I c. I ' 11.11)
cl II It, IIIII, t 'h, m 11
Md III I'l III CtI III . 11111t)NIIllic'11 I clal I(
I WHIC
21
I Ilk.
till
I Ilc
IIJL'
NIIWA
CII('kj
Il
wIk-kIl\II\
twl
! hc -p
I lic
(h)
lwl
)', l hIt.
il
(
mil
ol
I(),,
1)
I Ilk
I
I ll(.
(k
p(
)111
tl lay
mc
N(.
k
ill
lit-,
;I
)I
I
Id.
11
p[
)d
11, cd
Ollw
"1111 pIt
11111),
11 11, Mw
Ilm%ll
ht.
(-Ilk"
III
"t-cli
II .
(
[I),
1"
I,
, .,
Ilt
)
Rc.
N (. 1),
R
I.,
wurg, .15(a)
fitati, kold,
of I emperalure
I plit
Af"rphofiwi,
lefrip.
Ilic
al thavi, im 1w 0 041 if
2s (
othel
mere
strucitiro
at ,, (
W
II
It lat IIIrtILIIIICA
,A)HI
(lie
illii\lllltllll
uwful
culrelif
den,
2S Cand all Re.
tl it[ it lempeialmeof
6(XX) %%ii 2.0 A, cm-' lot (lie 0.28M
k% a"
,II
1 11,111,
111.1t
. 111
I he V fled
uwahle
1N
cI t 1,11
11111 c
2,
n 11 Ill
h IpIk
'Ind
clilliel
Icd
%vII)AIIN
It
Im
IIIIIIIIIIc.,
'wc
lit
AIII
111al
. 111c,
I", I
Ilodillal
I I\
hc
all
Ipfilllk'llllk
11
M)d
I ItvLIf
1111111 It IC
wen
I"
Needle
clc,: ITokIcs,
onk
C'
at loA
Re.
It'
NCCT1
ivpc
altjcs
of III
1)0IIIIIILItIreS
\N.ttI[IIIIiIc
1111111'1ckl
; it a I)II (it 8.1 lot hoth 111(-0.28%1
I IIIN AlMkCd a
and Ilic 1). 17M
gicalcl
plaimp
Itic to he t1wd. I lvulc 20,
27 and 28 I)o\k (j(: pojj,, lioni ilic 0.28M
,
eleMokic
and 81 icj)cctal JAI S. 1,6.1
i%cl\. An inticawd
plaling iaicai ilichipher
JAI \; Iltle %kotild bc C\I)k. ctckl a Ihc I% altic
lot Imito. mi
( 0.5V) IIIIICLI 11OW1 10 IIIC
dCl)(1111011
101 )'Old,
Olal
a lo%%
colldllcllll\
oltllioll (ould hc lc(Cd. Ilic
conducli%1IN wa aboul hall Ilial ol (tic
I
(,
it'/
lemp
fl"I
) (,
11,'/I
//
I ,t1,1/
(/
i-old i, imitt,
llm
__I_7"
.. 4" . ",
--
v , - -/// ;, T'l
Vi
"I
* \
1.
... 1h
-:.4
Ai
1W,i, \Nj Wt
lph 1. OlM,
1, - 1r
,,
A.
11,
/ 11!141(- '(II)
-'
(Iffalckold.
Aforld'oh
/em/p.
wl, al dwi-fam
40 (
for 0.04 / Af
T,. p 40 C
A
N,, dl, 1".
N. d. U.
Iff
"l,
Wo
.",
1000
Inm
Rc
malc
aldiavram
1w 0 041M
EI
U
s"I'll
i)
II
4,W
llo
170DO
125
%elective plating
omponents.
u 4aruiv
gold deposit from
conventional
tinder
vIt" produced
electrol.
C. D. 5.0 PnAlcrn2.0.06M
gold.
conditions.
ThicknesIv 18 vIn.
A
I 11furl, 3"
A 11flill"'I
,M lilt 1""Ild
direct
wramp
wi a if(dd (-t( h rcmt
held
belweell
Component%
i tibber
maA%. 'I lie direct write system will enable
to be produced
such componen1%
at very
high plOdtJCIiOo MICS Oil ;I L'OlIlintrous
basis
tile liced lot CXI)Cll%ive nla%k% as tile
without
The
spread of tile dCpO..,il is sell limiling.
of clcctrosize of tile plaill and tile quaillity
lytc ie(jukcd
will be significantly
reduced
leading
to lower
capital
and
expendilure
tile
II
tatci
throughput
linics.
on plating
FIKule
im(tiowave
(weitil
deposition
understanding
of' how
(ak"
place under free flow jetting
ill
collditiolls
terms of useable dcl)osi(
'I'lli%
situctuics.
will
cnablc
thc systcul
to be applicd
to
production
or prototype
processes. Some of*
tile possible applications
are listed below.
1) The
direct
printed
writing
of
boards.
circuit
c(ch
resist
for
The
densif of?
The
current
31.
of
effect
i., gure
,v
Lowconduclivit, electrol-vie.
selectivity.
30 shows a com1--igure
other electrolytes.
between the apparent plating rate
Parison
the
and
electrolyte
low
conductivity
of the
be seen that the
It
can
gold.
0.28M citrate
exhibited a
electrolyte
low conductivity
plating
rate.
apparent
greater
Much
Figure 31 reveals that the
of'
1.xamination
,
low
better
is
the
with
much
s, leclivity
electrolyte and this explains
conductivity
This electrolyte
rate.
plating
tile greater
best selectivity of all tile clectrotile
gave
R
2.5.
maximum
of
a
with
tested,
lyt's
deposit structure was not as
the
jIowcvcr,
higher
conductivity electrolyte,
tile
as
1ood
large incoherent nodules occurring at
with
densities as low as 3.75 A/CM2. At
current
density, a plating rate of 2.3
this current
/%cc was achieved.
,,,,
'A'I IONS
I(
APPI,
is to achieve a full
this
work
of
,1.1,c ptlrl, ()s(.
possibility
of the direct
writing
of a
metal etch resist for PCB prototyping
has
been examined
using gold as (lie resis( metal
(Figure
32). The
in this
tracks
written
example
were 3.6jan thick and written
al it
linear velocity
of" 1.0 nun/%cc. 1; xanlillation
*
of the tracks
revealed
a very good edge
definition
even when using it I'ciric chloride
etch. Whilst this process may not lend it. sell
to high volume
it is very
production
work,
for prototyping
low volume circuit
suitable
boards
direct
from
design.
a CAD
Eventually,
it is intended
to dcvelop a high
speed
tin
electrolyte
as
in
etch
resist
material.
2) The
direct
writing
of' Microwave
Integrated Circuit Substrates
Microwave
Integrated
recl-to-reel
;. -
2v,
Of
Circuit
Substrates
are
throughout
used
the
teleconumini
I'or the mounting
cations industry
of' active
devices such as amplificts
etc. 'lliese
;nc
usually inade f*rom sintered alumina,
quaw
or PTFF
The
composites.
ciictfits
are
by niciallising
produced
by
the substrate
sputtering
in
and the nacks are pioduced
the conventional
by gold
way
clectiodeposition,
either by [lie addative
oi sit[)
Either
tractive
method.
way,
expensive
kknds
indusity
IFlic electronic
makc. % u.%c of
bonding of' thin gold
thermocompi-mion
Wiles from inlegimed chcuit% to the lead
franic connection% within tire IC housing.
This requires at gold "hunip"
to be plated
onto tire connecting leads of the lead franic.
At present, this is carried out using cithcr
pholo-lithography
or rubber masks. The jet
plating process will allow tire production of
tire need for
these "butups"
without
masking.
There arc a number of'other applications
of this technique Which are Company Confidential but it may be concludcd that any
selective plating [equilcuncill Inay be Carried
out Willi (lie direct Write jelling technique,
even on complicated geomeny componcrits
and Willi any metal or alloy, provided thal a
fotniulafion
suitable electrolyte
can be
pioduccd that allows high speed deposition
and is not chemically aggiessivc to either
file sub%trate or the dcposi( produced.
CONCLUSIONS
It ha% been shown that the behaviour of
both a simple salt copper sulphatc electrolyte and a complexed salt gold electrolyte,
behave in a similar way when deposited
high
under
sliced jetting
conditions.
However, (fie copper electrolyte exhibits a
slight chemical attack on the deposits
produced by the electrolyte wash.
The fac(ois that influence the maximum
densities
useful ctmew
and thus the
maximum plating imes that produce high
quality (icl)o,, it,, aic:
a) The electrolyte tempeiature - tile higher
tile temperature,
(tic greater the plating
had tile greatest
rate. This pitiametcr
itil'Itience oil (tic gold system, presumably
because ol' (tic reduction in thickness of* tile
dil'I'lision layet. It has yet to be established
wilethel Copper electrolytes exhibit it Similar
tempeiaturc dependence.
b) The electrolyte velocity
the greater the
velocity (of' Re), the higher (lie plating rate
that can be achieved.
(III-, value,
no improvement
or a
Fcdtiction fit meful plating imes I,, ot)%crvcd.
both
3)
4)
5)
0)
7)
8)
ACKNONVI
11-
K. Ramachandran
R. Hayncs,
I inebefg,
"'I'lle
I echniquC
How MwAing
Selective
We.%tvrn Electric
Engineer,
(1978).
& D. J.
of Fluid
Dit,
22,61,
9)
R. E.
Dorey
Haynes.
J. K.
11, R.
Sinitski & R. F. Woods, "ThcrmocomSpecd
Ifigh
Bonding
Using
prcssion
Mal. & Surf.
Plating-,
Selective (iold
Fin. 67,81,
(1980).
Speed FlectroW. H. Safranek,
"Ifigh
Ibid, 69.48 (1982).
plating",
I-A. 'Natson,
-The Radial Sprcad of a
J.
Platic",
Liquid
Over a Horizontal
I-Imel Afech. 20,3,491.
&
6. G. Pokusaev
V. F. Nakoiyakov,
F. N.
I royan,
"Impingenicni
of all
Jet oil a Barrier,
Axisymmetric
Liquid
21,1175
MI. J. Heal Mass Transfer",
(1979).
1. 'Imi,
Layer".
(1948)
T.
'I a na kit
"Fxpeimmital
Turbulent
Jet",
792 (1970).
If.
Schlichimp.,
F.
Ta nak it,
&
Study
of' a Radial
19,133,
Bull. JSAM,
Layer
"Boundmy
Nc%
Mc(; raw Hill,
Theotv",
4th cd.
Yolk (1900).
J. Clicn, "llighSliml
10) R. C. Alkirc&'l
Single
Selective
1; lectroplaling
Willi
,
Soc..
J. h7ectrochern,
Circular
Jels-,
129,11,2424
(1982).
I]
Tsang,
"Ma11) D-T.
Chin
&C
Jet
Tran. -d'er
Impinging
to
all
Flectrode",
Ibid. 125,9,1461
(197M).
Uni12) ,FA Chen,
Ph. D. Disscrtation,
UrbanaIllinois
vcrsity
at
of
Champaign,
11. (1981).
13)
14)
Enhanced
C. C. flocking,
"Laser
and
Ifigh Sliced Jet Selective Dcposition"
Tran. v. IMF, 1988,66,50.
Gold
RA
Page,
Review
"A
of
.
Llcctroplating
Part 4".
Solutions
Met. Fin. J. 20,229,4
(1974).
127
EdelmetalleModerne Technologien
Anwendungen
und
tra U41I
eLlf Of)VdII%,
academy
of surface
technology
schw,ibisch gmund
If wnIi kil 0I
iA )( 11-11
hvv.)bl( h C'mund v V.
I utivri G Lewiv Veilaq.
f,
B est,,
",
I.
.,
Available
-Co
py
High speedselectivejet electrodepositionis a process wherebymetalsmay be depositedin a selective mannerwithout the need formasking. Theprinciple is that a free standingjet of electrolyte impinges on a substrateata high velocityandan electric currentis oassed.Due to both electrochemical
and hydrodynamicpropertiesof thejet, metalis deposited only within the impingementregionand the
immediatelysuffounding region. In this way, the
spread of the deposit is limited. By use of suitable
engineering,thejet can be moved under computer
control allowing the direct writing of tracks, spots
etc. This paper discussesthe factors that govern
the way in which a gold deposit produced in this
way grows and how the dimensionsof the deposit
may be controlled. Thepaper also discusses the.
factors that control the rate of depositionand possible applicationsof the technique.
Introduction
High Speed Selective Jet Electrodeposition
(HSSJE)is a process in which metal may be
deposited selectively without the need for
masking. The principle of the process is that
a free standing, non-submersedjet of electrolyte flowing at a high velocity impinges
onto a substrate.The applicationof a suitable
voltage betweenthe substrate (cathode)and
the nozzle(anode)causesmetal to be deposited within the impingement region and the
immediately surrounding region. Due to the
properties of the hydrodynamic flow sur-
rounding the impingement region, the electrolyte forms an extremelythin radial layeras
it flows away. Becausethis layer,termed the
wall jet region (I], is so thin, the electricalresistance of the electrolyte is comparatively
high. This means that under certain conditions, deposition is limited to the impingement region, with little deposition occurring
within the highly resistive wall jet region. In
this way selectivity is achieved. Figure I
shows a schematic view of the electrolyte
flow. Due to high electrolyte velocity, high
current densities can be applied and therefore high plating rates can be achieved.
I
III
NOZZLC
I 41-JET
II
SUBSTRATE
HYDRAULIC JUMP
Selective Jet Deposition is not a new process, with the principle being patented by
NASA [2] in 1974. This patent described a
forced electrolyte flow system in which the
nozzlewas scannedacrossthe substrateand
current applied at appropriate times in accordancewith a control pattern. In this way, a
plated pattern could be written, much in the
same way as a picture is formed on a dotmatrix printer. The process described here
however uses a "direct write" system more
like the way a plotter produces an image.
Since 1974, there has been comparatively
little information published on the subject of
HSSJE,possibly due to commercial confidentiality reasons. Hayneset al [3] described a
forced flow jet plating system in 1978 and
Dorey et al [4] used a modified version of this
equipment to gold plate connectors for the
evaluationof the thermocompression bonding characteristics of the deposits. The
maximumflow rate used was 39 crn/sec. and
current densities of up to 1.3 A/cM2. They
found that the deposit quality deterioratedat
20
Bocking.,
TheHighSpeedSelectiveJetElectrodepositionof Gold
to correlate
DerS DublishedafteMDtina
-plating
systems
rnathenatlcallmodels oi let
with experimentalresults [5,6,7,8].However,
little work has been published on the morphological characteristics of deposits produced in this way.
Bocking [9] describedselectivepure gold deposition using both laser enhanced jet deposition and HSSJEusing small bore nozzles
or
w.
m
th.
mn
_
--i
1.
- -.. " "J. I--..
I. - I I.w.
phology of the deposits produced and reUlUbt: i -LU 'LIM
t: ItA; LlUlYLt;
VUIUULY.
lilt;
-M.IdLVU
-. -A ---
current efficiency of deposition was also described. He went on to show a "direct write"
facility wherebythe jet could be moved in relation to the substrate by means of a computer controlled X-Y table, producing plated
tracks and lines.
The selectivedeposition of both copper and
gold deposits has beendescribedin depth by
Bocking [10] focusing on the relationshipbetween depositionand deposit morphology.
This paper describes pure gold desposition
using HSSJE.The morphologiesof deposits
produced are briefly described. The way in
which these deposits grow is discussedand
the factors that control the dimensionsof the
deposits are given.
Previous Studies
Previouswork by the author [10] had enabled
the relationship between the conditions of
deposition and the deposit morphologiesto
be established.It will be helpfulto summarise
the results of this previous study in order to
provide a starting point for the results of this
work.
It was found that the deposits produced had
a gaussianprofile.This shape can be seen in
Figure 2which showsa typical selectivityplot
of deposits produced under different conditions. Selectivity is a measureof the deposit
thickness within the impingementzone compared with the thickness produced in the wall
jet region. The dimensionlessdistance, R, is
the ratio of the radialdistancefrom the centre
of the impingementregionto the radiusof the
nqzzle. By plotting the thickness against the
dimensionlessdistance,the selectivityunder
different deposition conditions can be compared irrespective of nozzle size. A dimensionlessdistanceof 1 indicatesthe end of the
impingementregion and the start of the wall
jet region.
Bocking.TheHighSpeedSelectiveJetElectrodepositionof Gold
1. Theeffect of currentdensity,
temperatureand ReynoldsNumber
The structure and spread of the deposit is
significantly affected by the current density.
At low currentdensities(< 1.0 A/cm the deposits were found to have a poor selectivity
and low thickness. Deposits were up to 11
rirnin diameter but had thickness in the region of about 1 Am or lesswithin the impingement region, reducingto less than 0.1 Am in
the wall jet region. This thickness reduction
appears to be asymptotic. At higher current
densities, (> 2.0 A/cm the selectivity was
improved with a diameterof between 1.1 and
1.2 mm, depending on the precise conditions. Thicknesses were in the region of
18 Am, again dependingon the precise conditions used.Figure5shows the effect of current density on the current efficiency.At low
current densitiesthe efficiency is low (approx
40 %) but increasesto about 70 % with increasing current density. Neither temperature or flow ratehad much effect on the selectivity.
21
uta149
IHM
V---v
thodif type
soms
2DOO
4WD
60M
wq. w N&
ON
loom
12ma
18 M/IK
i-I
to
60
50
I
30 1
012345
Curroalknoty
A/cm 54
22
very dependenton the current density,temperature and flow rate. High flow rates and
temperatures allow high current densities
that still enablesmooth, pore free depositsto
be produced.However,it was noticed that at
very high flow rates or ReynoldsNumber,the
maximum current density was slightly reduced.
2. Theeffect of gold concentration
It was found that increasingthe gold concentration of the electrolyte increased the
maximum current density and thus the plating rate at which smooth deposits could be
produced. However,at concentrationsmuch
above 0.17M, the maximum current density
and plating rate was reduced slightly. Selectivity was not significantly affected by the
gold concentration.
3. Theeffect of conductivity
Electrolyte conductivity influenced both the
selectivity and the structure. Reducing the
conductivity by half improved the selectivity
such that the deposit diameterswere in the
region of 0.9 mm. However, the deposit
structure deterioratedat much lower current
densitiesand a maximumplating rate of only
2.9 jzrn/seccould be achieved.
4. Theeffect ofpH
The effect of pH was studied over the range
5.3 to 8.1. It was found that at the higher pH,
slightly higher plating rates could be
Experimental
A complete description of the equipment
used has been given in a previouspaper [101.
However,a schematic diagram of jet plating
system is shown in Figure 9. The nozzlecon3
X-Y-Z
TABLC
MICROCOMPUTER
I
r- -------.
I
STEPPER
M0713RC13NTR13LLER
r-'
II
II
II
II
/M RIVER
7RANSLA713R
-'----------------
*-*
702RTE-*
I
r-r
PWSSL*C
TPMACA
!I
I;
!i...
:
.............
........
1-,
I
L1i
CONSTANTCURRENT
RPiY
:H
-
"0
G---4-
FZW61T i
SWITCH
1i1
.1H
------------------------------------
FILTER
PLAIM
CLCCIRCL"t
Bocking:
The High SpeedSelective JetElectrodeposition of Gold
platinumwire, 200 ILM in diameter also embedded and separated from the working
electrode by a distance of 100 gm. This
acted as the reference electrode. Prior to
measurements,both the working electrode
and the reference electrode were polished
and pre-platedwith gold at current densityof
5 mA/cM2for 2 minutes. Whilst this type of
referenceelectrode was not ideal due to its
poor reversibilityin the system understudy, it
was justified by the necessityto use a small
diameter,flush mountedreferenceso that the
flow patternswere not disrupted.
Polarisation curves were produced by
sampledcurrent pulse voltarnmetryat different electrolyte velocities. Because the deposit growth was so rapid at these high current densities, conventional steady state
polarisationtechniquescould not be used. It
was foundthat a steadystate condition could
be achieved within 20 to 40 milliseconds
underjetting conditions.A series of potential
pulses of 40 milliseconds duration were
applied and the current measuredat the end
of each pulse.The substratewas re-polished
and re-plated prior to each measurement.
Prior to the application of the pulse, a preelectrolysisfor 30 seconds at 0.3 volts vs the
gold referenceelectrode (GRE)was applied.
Results
DepositMorphology
Figures 10a to 10e show a typical range of
structures produced by the jetting process.
Lower flow rates and temperatures also affected the type of structure but they all followed a typical pattern. At low current densities (< 1.0 Alcm the deposits were of a
plate-like structure as in Figure 10a.As the
current density was increased, the deposits
adopted a closed, pore free structure with
few surfacefeatures.Highercurrent densities
23
54.09/1(0,28M)
45.09/1
25*C
40*C
55*C
15.0 9A
to pH 6,0
0.012284cml/sec
0.009221 cm'/sec
0.0076567 CM2/sec
55'C
33.5g/1(0,17M)
45.0g/l
15.09/1
to pH 8,1
0.005906cm2/sec
24
Bocking:
The High SpeedSelective Jet Electrodeposition of Gold
Fig. 10: A typical range of structures produced In ascending order of current density. Whilst the deposits were produced under different sets of
conditions, they present the growth changes as the current density is inmased for any single set of conditions
The series of deposits produced with increasing time show this pattern of growth
develop. Figures 1la to 1ld and 12a to 12f
show typical deposits produced at 7.0 A/cM2
and 10 A/cM2 for increasing deposition
times. Both samples show that certain sites
produced faster growing nodules. Depending on the current density, these then developed into either needle like structures in
the radial flow direction or field oriented dendrites in the direction of the jet in the case of
the higher current density. The lower current
density samples simply produced larger
nodules that eventually became powdery and
non-adherant. At low temperatures, dendritic
growth was less field oriented and adopted a
finer, filamentry structure as in Figure 13.
Bocking:
The High SpeedSelective Jet Electrodeposition of Gold
25
FFM
Aulk
., -1
?i
-, -
TI
.-.,
--
Mot
31- Allk
l"
tm
_aq;
increasingtime
Fig.12: The growth of the deposit with
(b) 1.5
(e) 6-0
26
Bocking.TheHighSpeedSelectiveJet Electrodeposition
of Gold
evidence of preferred orientation of the deposit Under these conditions, no needles or
dendrites were produced. Figure 15 shows a
typical diffraction pattern. Deposits produced at higher current densities showed
evidence of a decreasing grain size with increasing current density, the maximum grain
size occuring at a current density of 0.75 A/
cm 2.
PolarisationStudies
Figure 14shows the polarisationcurves for a
0.17M citrate gold at velocities of 2,10 and
20 m/second. It can be seenthat at a velocity
of 20 m/second, up to a current density of
2 A/cM2, deposition proceeds under activation control. TheTafel slope is -355 mV/dec.
Above this value, mixed activation and diffusion control occurs. No clearly defined limiting current is observed.This could be due to
the fact that hydrogen evolution competed
with gold deposition and the limiting current
plateau was hidden or that mass transfer
within the jet was so high. However,it can be
seen that the deposit beganto deteriorate in
the mixed control region. This applied to the
other velocities except that deteriorationoccurred at lower current densities.
C. D. -I
A/CM2
Discussion
Based on the evidence obtained to date, a
mechanismof growth and deteriorationof the
depositscould be postulated. It is beyondthe
scope of this paper to develop a rigourous
mathematicalmodel of the growth mechanisms involved.However,a l5ossiblemechanism could be empirically clevoloped.At low
current densities (< 1.0 Alcm) the mechanism of growth was similar to conventional
gold. Because the deposit spread was so
0VRe. 13515
20 M/Re. 33SS
7 V-SM/W
these low current densities (up to
great
at
Re. 1342
.1 V-2m1w
11mm diameter)It Is reasonableto assume
that the true current density was much lower
T-p 55C
than that based on the impingement zone
area. This was confirmed by the marked
similarityto conventionaldeposits of gold of
similar thickness that have been published
-I previously.It is likely that the spread observed here was due to the long time periods
used to pass the required number of cou0lombs
(up
to 140 seconds). This allowed a
100
10
01 Ncrent DNvty A/CMsq
001
build up of deposit beyond the Impingement
However,
it
be
that
zone.
must
remembered
Fig.14: Polarisationcurvesfor a 0,117M
citrate gold,
this
deposit
surrounding
was extremely thin
Temp. - 55'C
(< 0.1 Am). It can also be seen from the efficiency measurementsthat secondary reactions such as oxygenreductionand hydrogen
X-ray diffraction Studies
X-ray diffraction studiesshowedthat overthe evolutionwere occurring.
As
0.75
to
the current density was Increasedabove
between
density
of
range
current
1 A/cM2,all of the deposition occurred wi7.0 A/cml and a Re. of 12078,there was no
.0
Bocking:
TheHighSPeedSelectiveJetElearodeposition
of Gold
thin a region of 3 times the jet diameter, the
actual spread depending on the prevailing
conditions of deposition. Most of the deposition occurred within the impingement zone.
The deposits produced at these higher current densities showed a slight hemispherical
surface texture. It can be seen from Figure 14
showing the polarisation curves that in the
case of the curve corresponding to a Reynolds number, Re. of 13545 that deposition
assumed mixed activation-diffusion control
at a current density of about 2.0 A/cM2. Lower Re values showed this transition at lower
current densities.
27
thickness occurs in the centreof the impingement zone. This is known as the stagnation
region as axialflow is negligible.Dawson[14]
has estimated the transition between the
stagnationzone and the walljet to be x/d - 4,
where x- radial distance from the centre of
the jet and d- the jet diameter.In the present
case, this transition occurred at r- 50 i4m.
Beyondthis region,the boundary layerthickness increaseduntil it obtained the thickness
of the walljet At this point,the hydraulicjump
[12] occurred.
The behaviour of the diffusion layer is complex under these circumstances. Although a
measure of the thickness of the diffusion
layer cannot be made directly, as the value of
the limiting current density, I,, could not be
obtained, a maximum value can be estimated
approximately from the polarisation curve. At
a Reynolds number, Re. of 13545, high quality deposits are obtained up to a current
density in the region of 6.0 A/cM2. It is known
that deposits produced above the limiting
current are dendritic or powdery and nonadherant. Therefore, if a value of 7.0 A/cm' is
taken arbitrarily as the limiting current, the
thickness of the diffusion layer can be found
from a derivation of Ficks first law of diffusion;
DCb
nF
0
28
Bocking.
The High SpeedSelectiveJet Electrodeposition of Gold
Id't.
rj,
2) Theselectiveplating
of reel to reel components.
Largequantitiesof strip or pressedstrip components such as connectors and lead frames
are currently being produced either by controlled depth Immersionor by submersedjet
deposition with the reel being held between
Bocking.
The High SpeedSelectiveJet Electrodeposition of Gold
29
References
[I I M.B. Glauert.J. Fluid Mach. 1,626 (1956)
(21US Patent No. 3,810,829,May 1974.James Fletcher.NASA
[31R. Haynes,K. Ramachandran& D.J. Fineberg,The Western
Electric Engineer,22,61, (1978)
[4] J. K. Dorey11,R. Haynes,R.E. Slnltskl and R.E.Woods, Plat. &
Surf. Fin.67.81 (May 1980)
[51R.C. Alkire & T.J. Chen. J. Electrochern.Soc. 129,11,2424,
(1982)
[61K-L Hsueh& D.-T. Chin, Ibid, 133.1.75. (1986)
M D.-T. Chin & C.-H. Tsang, Ibid. 125.9,1461, (1978)
18]R. Alkire & J.-B. Ju. Ibid, 134.2,294, (1987)
191C.C. Bocking, Trans. IMF, 66,50, (1988)
[101C.C. Bocking, Proceedingsof the 59th Intnl. Conf. On Surf.
Fin.Torquay.2,51. (1991)
1111E.J. Watson.J. Fluid Mach., 20,3,481, (1964)
(121H. Schlicting, "Boundary Layer Theory", 4th ad., McGrawHill, Now York 0 960)
[131V.E. Nakoryakov.B.G. Pokusaev& E.N. Troyan. Int J. Heat
Mass Transfer.21.1175. (1978)
[14] DA Dawson & 0. Tress, Can. J. Chem. Engng, 44,121.
(1966)
1
.1-
130
NOMENCIATURE
B
Proportionality
Concentration
(Mol/CM3)
Cb
CO
Diffusion
Faraday constant
iL
Limiting
AD
Diffusion
n
R
Rd
coefficient (cm2/s)
Pimen iI
ssspreadparameter,y1r'
r
Re
I
Rtynolds number
Stagnationzoneradius(cm)
Nozzle radius(cm)
Temperature (K)
Yd
131
JD - -D(dc)
&x0 ..
(1)
17
(cb
JD
- -D
- Co)
(2)
132
C. BOCKING
Solvingfor i gives
(Cb
i=
- CO)
-nFD
(3)
nFDch
IL = -6
(4)
(5)
where B is a constant.
It can be seen from eqn. (4) that the magnitude of
the limiting current density is controlled by the thicknessof the diffusion layer, the concentration of metal
ions and the temperature. There is a certain limit to
the metal ion concentration that can be used. This is
dictated by the solubility of that particular species in
the electrolyte. However, the thickness of the diffusion layer is dependent on the degree of agitation of
the bulk electrolyte.
It follows that for high speedelectrodeposition, high
metal ion concentrations in conjunction with high
rates of agitation and high temperatures would appear
to give the highest rates of deposition.
Despite the fact that the limiting current density
determines the maximum deposition rate for a particular set of conditions, it has been found by a number of
workers(") that the deposit quality begins to deteriorate at some value below iL. This deterioration is
apparent froni the formation of either dendritic
growth or nodular powdery deposits. It is important,
therefore, to ascertain the fraction of the limiting current density at which deposits begin to deteriorate
rather than the limiting current density itself.
There is a further factor that limits the maximum
deposition rate. For many electrodeposition reactions,
not all the current is used for depositing the metal.
Some of the current is expended in reducing hydrogen
ions, which are plentiful in aqueous electrolytes, to
form hydrogen gas.There are a number of reasonsfor
this, but these are beyond the scope of this paper.
However, the tendency for this side reaction to occur
increases with increasing current density because of
the resulting reduction in the surface concentration of
metal ions. The current efficiency of the reaction is a
measure of this secondaryreaction and can be defined
as the. fraction of the current used for metal deposition, given as a percentage. This is a further reason for
maintaining as high a surface metal ion concentration
as possible by means of agitation.
-5
-4
li Re.= 13550
3350
&Re.
=
,
o Re.= 1350
TEMP=55C
-3
-2
-1
04001
.
61 -0.,
. CURRENTDENSITY/A/CM2
10
100
CFr
InURNA
I nF PF-VFA RCH
ML
QNO. 3.1992
133
3. BACKGROUND
Selective jet deposition is not a new process, with
the principle having been patented by NASAM in 1974.
This patent described a forced electrolyte flow system
in which the nozzle was scannedacross the substrate
and current applied at appropriate times in accordance
with a control pattern. In this way, a plated pattern
could be written, much in the sameway as a picture is
formed on a dot-matrix printer. Tlie processas subsequently described, however, uses a 'direct write' system in the manner that a plotter produces an image.
Since that time, there has been comparatively little
information published on the subject of HSSJE, presumably for reasons of commercial confidentiality.
Haynes et al.(6)described a forced flow jet plating sys0)
Dorey
in
1978
et al. used a modified version
tem
and
for
to
the
plate
connectors
gold
this
equipment
of
bonding
thermocompression
the
charof
evaluation
flow
The
deposits.
the
maximum
velocity
acteristics of
densities
39
the
current
and
were up to
cm/s
was
used
1.3 A/cm2. In this work, it was found that the deposit
densities
in
the region
deteriorated
at
current
quality
formation.
However,
because
A/cm2
0.86
nodule
of
of
it was claimed that nodular deposits did not detract
from bondability. There have been severalpapers published that attempt to correlate mathematical models
4. EXPERIMENTAL DETAILS
Fig. 3 showsa schematic diagram of the equipment
used in this study. A platinum tube nozzle with a diameter of 400gm was sealed into a lead/soda glass tube.
This was connected to the pump outlet and was
mounted onto the X-Y table. The table was driven by
two stepper motors in half-step mode allowing
increments of 2.5gm/step. The controlled current
...............
:I,
***"*****I*.
X-Y-ZTABLE
II
Iii
Iii
II
Iii
II,
Iii
II,
r-
-.
-I-----I.
II-
IIi_
IL....
----
--
---.
-.
i--. Im.
%.-M-
rLUMNIt IW
-----
II.
:iI
I; -. ---,
PRESSURE
.
-TRANSDUCER
III
II,
I Ij
II,
Iii
II
IIj
II,
--
1,'PULSErD-AMPER
I,
Li1
%JFILTER
::
f. %- .-.
--
-. ---0
RELAY.
_..
__
----------I
_j
II
SITO-RT
11
I
CIRCUIT;
SWITCH'
- _-Il
134
C. BOCKING
Table 1
Details of electrolytes used
1. Gold electrolytes
sample [1]
sample [21
sample [31
Gold (g/litre)
(as potassium
gold cyanide)
54.0
(0.28 M)
33.5
(0.17M)
54.0
(0.28M)
Diammonium
hydrogen
citrate (g/litre)
45.0
45.0
1.0
Citric acid
(g/litre)
15.0
15.0
1.0
Potassium
hydroxide
to pil 6.0
to pI 16.0
(initially)
to p1l 6.0
Parameter
Kinematic
viscosity
(CM21s)
Conductivity
(MS/cm)
88.2(55
fl
28 2 (25
O)
8
48.8(55
.
_
2. Copper electrolytes
Copper
(as copper sulphate)
0.08M
0.204M
0.8M
Sulphuric acid
5. RESULTS
is
in
m/s,
The electrolyte jet exit velocity, measured
different
electrocomparing
of
means
an
accurate
not
lytes. This is because of the differences in viscosity
between
frictional
S.ZZ
135
It was found that increasing the metal ion concentration of the electrolytes increased the maximum current density and thus the plating rate at which smooth
deposits could be produced. However, above a certain
value of concentration, the maximum current density
and maximum plating rate were reduced slightly. This
can be seen in fig. 5 which showsa plot of the maximum
useful current densities against Reynolds number for
different metal ion concentrations of copper. Similar
effects were observed for gold, particularly at a temperature of 250C. Selectivity was not significantly
affected by the metal ion concentration.
S.Z3.7he effectof electrolytePelocity
'Me velocity of the electrolyte, or more precisely, its
Reynolds number, has a significant effect on the morphology of the deposits produced. Figs. 6 to 8 show a
seriesof simple morphological diagramsfor the 0.28M
gold system.These relate the Reynolds number to the
current density and show the range of morphological
structures observed. Other gold concentrations
showeddiffering morphological habits but the general
trends were similar. Increasing the velocity allowed a
130.8MCOPPER
* 0.204MCOPPER
* 0.08MCOPPER
Z
LU
Z
LU
Ir
.9
-6
REYNOLDS
NO,
Fig. 5. Maximum current densities for acceptable
deposits from various copper concentrations, as a
function of Reynoldsnumber
10
TEMP=25*C
E
.2
Z
ui
Z
LU
cc
cc:
ui
960
&AU-
LLJ50
0
-0
40
304
01278
CURRENTDENSITY/A/CM2
Currentefficiencyvs currentdensity,0.17M
4.
Fig.
,
gold
2000
4000
136
C. BOCKING
10
TEMP= 40'C
30
FIELD
ORIENTATED
CO
z
NEEDLE
TYPE
LLJ
a 5
FNODULAR
z
LLI
tr
cc.
SMOOTH
01..
0
2000
' 12600
io6oo
TEMP
= 55'C
V5
Z 5.
w
z
w
cc
cr
123
R,DIMENSIONLESS
DISTANCE
little
had
distance
Increasing
the
selectivity slightly.
deposit
the
but
the
of
effect on selectivity
morphology
altered. The deposit becamemore nodular towards the
wall-jet region and some needles were observed,
oriented in the flow direction.
S.Z6. Ae effectof electrolyteconductipity
C-)
040
2000
4000 6000
8000
REYNOLDS
NO.
10000 12000
137
138
C. BOCKING
The structure of both gold and copper deposits produced at current densities above 6.0 A/cm2 indicated
that the mode of growth was by 3D nucleation. Fresh
nucleation occurred on existing grains forming a cauliflower-type structure. Ibis type of nucleation generally occurs at high overpotentials in the region of
mixed activation/diffusion control. The polarization
curves show that relatively high overpotentials are
required to achieve the current densities applied and
that deposition is controlled by mixed mechanisms.
X-ray diffraction studies could not provide any cvidence of preferred orientation in the samples examined. However, these samples did not include any
deposits containing needles or dendrites, which have a
strong, preferred orientation. During electro-crystallization, growth occurs faster in certain crystallographic
directions than in others. Becauseof this, certain areas
for
faster,
deposit
sites
the
of
providing
grew
subsequent needle or dendritic growth.
It was also observed that nodulation wasparticularly
prevalent in the region of surface impetfections such
as scratches etc. This is not surprising as these sites
for
lowest
presented the
energy requirements
nucleation and subsequentgrowth. It wasat these sites
that growth occurred most rapidly, at least in the initial
stages. Above a critical ratio of flow rate to current
density, the growth of these nodules was accelerated,
especially those towards the edge of the impingement
it
is
for
To
this,
necessary
the
zone. understand
reason
to examine the behaviour of the flow and the diffusion
layer during deposition under these conditions.
The hydrodynamicsof an impinging free jet on a surface normal to the flow has been described by several
In brief, when the jet hits the surface,
authors('- 14-16).
the flow decelerates rapidly in the axial direction and
jet.
forming
the
in
direction
wall
accelerates the radial
This gives rise to a region where a viscous boundary
layer of constant, but low, thickness occurs in the
centre of the impingement zone. This is known as the
Dawsod")
flow
is
negligible.
stagnation region as axial
has estimated the transition between the stagnation
zone and the wall jet to be y1d = 4, where y- radial
distance from the centre of the jet and d- the jet
diameter. In the present case,this transition occurred
layer
boundary
5OAm.
Beyond
the
this region,
at r=
thickness increased until it reached the thickness of
the wall jet. At this point, a hydraulic jump(15)occurred
in order to conserve the electrolyte momentum.
0)
b)
cl
dl
el
139
fl
0.1
7M.
12
100,
Re
density
OAlcm
Current
10.
gold
increasing
deposit
time.
with
Fig. 13. ThegroKlhof the
6.0s])
&Os
3.5s
d)
Os
2.
1.5s
b)
e)
0.6s
c)
a)
140
C. BOCKING
D of
the diffusion
calculation,
coefficient
1.68xIV cm2/sat 600C as given by Cheh(11),has been
used. This value was derived from a citrate type gold
electrolyte with a gold concentration of 0.007M. It is,
known that an increase in concentration decreasesthe
value of D but this decreaseis relatively small and will
be ignored in this instance. More accurate values of D
for the concentration of gold being used are being estimated at the present time. Under the conditions specified, the maximum diffusion layer thickness is
calculated to be 4gm. However, this value is likely to
be high becauseof the arbitrary choice of the limiting
current density value and the high value of AA diffusion layer thickness of closer to 2gm is more realistic.
Whilst a fast growing nodule is confined to the diffusion layer, its growth will be controlled by planar diffusion. Its growth will be enhanced by the fact that its
local current density will be higher than that of the
surrounding deposit. If the nodule penetrates the bulk
diffusion layer, a local diffusion layer will develop
around it. If the radius of the nodule is much less than
the thickness of the local diffusion layer, then spherical diffusion will take over as the dominant mass
transfer mechanism. As spherical diffusion occurs at a
rate which is several orders of magnitude faster than
planar diffusion, then the growth of the nodule will be
accelerated even further. As the nodule grows, the
field intensity will increase and the local current density will increase,accelerating growth even further. On
penetrating the static hydrodynamic boundary layer,
the nodule will disrupt the flow, causing a local
increase in turbulence in its wake. This will lead to a
further increase in diffusion in the direction of the
flow. In this way, a structure such as that seen in fig. 14
will develop.
If the current density is sufficiently high, when a fast
growing nodule penetrates the diffusion layer, the
deposit will grow in the direction of the electric field
and thus will grow in the axial direction of the jet along
the jet wall as well as in the radial direction. Such
growths are dendritic in nature and the structure
assumesa crown-like appearance,as in fig. 15.Current
densities higher than those that produce this structure
3,1992
NO
9,
VOL
GEC JOURNALOF RESEARCH,
141
needles can be observedadjacent to these field-orientated growths. In many of the examples shown, it will
be noted that, in the stagnation region, there is no
flow-directional growth apparent. The radius of this
region is about 50gm and supports the claim of
Dawson(") mentioned earlier.
Temperature and metal ion concentration also
affect the morphology as they both influence the diffusion coefficient and thus the limiting current density.
Small differences in morphology have been recognized
at lower temperatures and concentrations, but these
are caused by differences in the ratio of the diffusion
and boundary layer thicknesses.
7. APPLICATIONS OF HSSJE
circuit
tu!
142
C. BOCKING
GLAUERT,
M B., 'The Wall Jet', J. Fluid Mech. 1, p. 625,1956.
ROBINSON,
D. J. and GABE,DR., 'I figh SpeedElectrodeposition
with
11 ALKiRE,R. andJu,J-B, 'Iligh speedselective
electroplating
impinging two dimensionalslot jet flow'. Ibid, 134,2,
p. 294,1987.
14 WATSON,
E.J., 'Theradialspreadof a liquidjet overa horizontal
plane',J. Fluid Mech.,20,3, p. 48191964.
17 DAWSON,
DA. andTRAss,0., Can.J. Chem.Engng,44,p. 121,
1966.
18 CHEH, II. Y. and SARD, R., 'Electrochemical and Structural
Aspects of Gold Electrodeposition from Dilute Solutions by
Direct Current', J. Electrochem. Soc. 118,11, p. 1737,197 1.
C. Bockingand B. Cameron,
Trans.IMF, 1994,72(l),33.
INTRODUCTION
Most electrical devices interconnect with
other devices and the outside world by
means of the ubiquitous electrical connector. Vast quantities of connectors are
produced throughout the world, many are
very low cost particularly in the Far East.
ne satisfactory performance of a connector is crucial to the overall reliability of
any piece of electrical equipment. It has to
have a low contact resistance, good corrosion resistance and good wear resistance.
This latter property is necessary because
connectors are frequently mated and unmated during the course of the equipment
lifetime. Many specifications require a connector to remain functional through up to
500 insertion/withdrawal cycles. In order to
achieve such a performance, they arc
usually electroplated with gold, alloyed
with small quantities (- 0.1-0.3%) of
This increases the
cobalt or nickel.
hardness whilst maintaining a satisfactory
contact resistance. Despite competition
from the Far East, Europe maintains a
healthy production record in connector
in
1990,
It
is
that
estimated
production.
6,869 kg of gold was plated onto connectors
in Europe alone'. The gold plating on a
connector constitutes a significant part of
the manufacturing cost. As a consequence,
there has been a trend to reduce the
quantity of gold used either by reducing the
thickness or by limiting its application to
the functional region by means of selective
plating or both. This paper describes a
further advance in the selective plating of
The method requires no
connectors.
masking and can deposit suitable gold
alloys at much higher speeds than have
been achieved previously.
ABRIEF IIISTORYOFTHE
SELECTIVE PLATING OF CONNECTORS
Early high reliability connectors were
plated all over with gold. It soon became
clear that by limiting the required
thickness of gold to the functional contact
area, great cost savings could be made. In
fact, by the use of selective plating of gold,
tonnes of the precious metal have been
saved. Non-functional areas were given a
much thinner coating to provide a degree
of tarnish and corrosion resistance. One
of the earliest and still commonly used
methods is the use of controlled depth
immersion, which is a relative simple
The conselective plating technique.
tinuous strip is fed vertically into a plating
electrolyte at a controlled depth. The
immersed region therefore gets plated
The
whilst the remainder does not.
solution level is maintained by means of a
weir at each end of the plating tank. The
electrolyte is pumped into the tank from a
reservoir to provide a rapid flow past the
work allowing high current densities to be
used. Hain el ar- described the advantages
of the system as being simple and versatile
but listed as disadvantages surface turbulcnce and capillary action which reduce
the selectivity. As a consequence, the fccdthrough rates have to be low. Also, as
many components such as connectors
require plating on one face only, and as
the whole of the immersed component is
plated, there is a considerable wastage of
gold.
The use of selective plating of continuous strip became popular in the early
In 1975,11ciestad' described a
'70s.
variety of selective strip plating cquipment
34
ZONE I
ZONE 11
ZONE III
Free jet
Impingement zone
Walt jet
N
Ronoval
from
deposit
jet
the
Optical
a
of
micrograph
F*
re2
I
'!feuctrolyte.
2.2 g1l,
Ni
in
Alcm2,
6.0
density
electrolyte
=
Current
=
E
deposit thickness = 17 Lm.X1000.
35
N,
Ej Ronovel N 60 mill booster no
Ni
booster
8o
N
no
Ronovel
mill
0
2.2 g/l Ni
booster
N
60
Rono'vel
ml/I
A
Ni
2.5
booster
g/l
N
60
Ron
MI/I
0vel
,7
Ni
3.0
booster
g/l
60
N
Ronovel
ml/I
+
for
deposition
various concendensity
Current
Z
rate
Figure
vs
N
Ronovel
in
electrolyte.
booster
the
trations of nickel and
36
/I
I
te
in
and
Figure 7. The relationship between the nickel so ution
densities.
nickel in the deposit for different applied current
250
Nickel in SobL
05 g/l Irl
: 0.7 g/l Ni
Li
Ni
: 1.5 g/l Ni
2.2 9A Ni
: 7-5 gA DR
3.0 gA NI
200
c2,
100
4
50
68
20
12
14
16
18
20
10
05
15
-410
:5
30
35
43
C. D. nA/cm sq
deposit
in
between
the
the
and
nickel
The
Figure 9.
relationship
in
different
for
density
of
nickel
concentrations
the applied current
the electrolyte.
*
t-11-41.
i#, '
iIQ
. '..
ao'*k'o
,
,-,,.
* 14
,,
J-1-1
,
-, '-
*. PL
-44
1
34567
Qa-rent densityA/cm sq
10
different
for
density
conhardness
current
Deposit
vs
10.
Figure
in the electrolyte.
nickel
of
centrations
-.
il#7.
-.
a-
-,.
k,
-b
--S
, -7
-C
I'
. 'N
ut...
.-,
0-
4 -. * 91-6
-, r
-'%'-
"-
analytical controls of the nickel in the electrolyte and the applied current density
(See the next Section).
The relationship between nickel in the
deposit and the current density
measurements
revealed
significant differences in the influence of
nickel additions between conventional and
jet deposits.
Ordinarily,
the addition of
nickel to a gold electrolyte
causes an
increase in the hardness of the deposit.
However, examination of Figure 10 shows
the opposite trend. The basic electrolyte
with no nickel produced deposits with a
hardness in the region of 200 kgIMM2-
1*
20 -;:::
i7
10
15
10
23
C. D. A/cm sq
100
90
100
so
--*-Ill
90
-a-220
-311
80
-4-200
70
GO
50
40
60
30
SO
20
In.
10
0
40
10
20
30
40
C. D. nIA/CmSq
38
30
10A/cm
Current densitY
15
20
sq
and
efficiency
between
the
The
current
16.
Figure
-relationship
HSSJE.
N
using
for
Ronoval
density
electrolyte
the
current
400.5 um/55g W
-0.5 um/IOD9 lot
14 um/53 g A
1.0 um/1009 Jet
M5 um/53 g com
-0.5 um/100 a corw.
- 1.0 um/55 g conv.
- 1.0 um/loog coew.
50
100
150
200
No of cyck)s
by
the
as
used
test
The
configuration
wear
18.
connector
Figure
test.
under
Testershowing
contactpair
an
actual
Contact
GEC
CONCLUSION
It has been shown that the use of HSSJE
with a modified Ronoval N electrolyte
allows high quality gold deposits with
similar properties to thoseobtained under
deposition
conditions. The
conventional
deposits exhibit strong structural similarities as well as hardnesses. The wear
from
differ
thoseof convencharacteristics
tional deposits when applied to real
of
conditions
simulated
under
connectors
X-ray
maps of a
Cu
Figure 22. SEM micrographs and
radiation
1.0
allo
V
goldlnickel
Lm
with
plated
contact pair, conventionally
100g.
load
200
of
cycles under a
after wear testingfor
London,
Consultancy Service,
December,1991.
2. W.R. Hain and L.W. Rudolf, Western
ElectricEng.,1978,April, 91.
3. D. Heiestad, '8th Annual Connector
NJ.
Hill,
Cherry
symposium',
Electronic Computer Study Group.
337,1975.
4. "Texas Instrumentsusesspot plating
keyboards".
of
costs
of gold to cut
Plating & Surf. Finish., 1975,649).
846.
197&
Prod.
Electronic
Menzies,
5. G.
May, 38.
Eng..
Electric
Western
Rehrig,
L.
6. D.
1978,April, 48.
7. D.R. Turner, Thin Solid Films, 1981
95,1443.
91,
Connectors
Proc
8. P. Wingenfeld,
1991,91.
Na
Patent
U.
S.
NASA,
9. J.C. Fletcher,
May.
3810829,1974
DJ.
and
Ramachandran
K
10. R. Haynes,
Fineberg, WesternElectric Eng. 1978.
April, 22,61.
E.
Sinitski
R.
Haynes,
R.
11,
11.J.K. Dorey
Plating & Surf.
Woods,
E.
R.
and
Finish.,1980,May, 67,81.
J.
Tsang,
C-H.
12. D-T. Chin and
1461.
1978,125(9),
Soc.,
Electrochem.
1983.
Soc.
Electrochem.
1.
Sonin,
13. A. A.
130(7),1501.
1991.
ibid,
Agarwal,
M
Chin
14. D-T.
and
138(9),2643.
1%e
ibid,
Chen,
T-J.
15. R.C. Alkire and
129(11),2424.
1988,66,
IME,
Trans.
16. C.C. Bocking,
50.
Conf.
Intnl.
59th
Proc.
17. C.C. Bocking,
2,51.
April,
1991,
Fin.
Surf.
On
G.
Eugen
Report,
East
18. C.C. Bocking,
1992.
Saulgau,
Verlag,
Leuze
To be
Dineen,
C.
19. C.C. Bocking and
published.
Vanhumbeek
J.
20.R. DeDonckerand
Trans.IMF, 1985,62,59.
Coinponents
Trans.
IEEE
21.M Antler,
CBMT4,1981.
Tech.,
Man.
&
Hybrids
1,15.
Roos
R.
J.
and
Celis,
P.
J.
22. M.DeBonte,
Eugen
Report,
EAST
J. Vanhumbeck,
1992.
Saulgau,
Verlag,
G. Leuze
Copyright
Reserved
C. BOCKINGGradEff,
C. DINEEN
MSc,BSc
nAff
ABSTRACT
.1 INTRODUCTION
High SpeedSelectiveJet Electrodeposition(HSSJE)is a processby which e'lectiodepositscan
be produced at very high deposition rates, selectively, without the need for masking. In
HSSJE, a jet of electrol yte is pumpedat high velocity from a small nozzle (< Imm) through
'
'
an air gap onto the substratewhilst applying a suitable electrical potential. The nozzle is
is
deposited
is
Metal
in the impingementregion
the
the
substrate
cathode.
anodic
whilst
made
is
The
deposit
its
immediate
limited becausethe electrolyte
the
of
surroundings.
spread
and
forms a very thin radial layer as it flows away from the impingement region. Ibis radial
layer is highly electrically resistive in comparisonto the jet and the'ref6rem6st of the metal
is deposited in the impingement region. Bocking'." has described in detail the electrodeposition of copper and pure gold using this method. More recently, Bocking and Cameron4
have describedthe electrodepositionof nickel alloyed hard gold. Such depositsare widely
used for the selective electrodepositionof electrical connectors. They presenteddetails of
the hardnessandwear characteristicsof the depositsproduced. They also describedthe results
deposits.
It
initial
these
the
crystal
of
of
structure
studies
was establishedthat whilst
of some
there were manysimilarities betweenHSSJEdepositsandthoseproducedby more conventional
in
behaviour.
differences
the
there
wear
some
were
methods,
This paper describesthe results of the examinationof both pure and nickel aNoyedhard gold
depositsproduced by HSSJE using X-ray diffraction techniquesCARD) and comparesthese
by
Possible
those
conventional
more
methods.
reasonsfor the differences in
produced
with
the wear behaviour are suggested.
2BACKGROUND
References 1-3 give a complete background to experimental studies on the HSSJE of both
information
However,,
deposits.
some
necessary
on the mechanismsof
pure gold and copper
deposition and the types of deposit will be given here. When electrodepositionis carried out
jet
impingement
in
is
7le
deposit
HSSJE,
the
region.
spot thickness
produced
a
spot
using
85%
Gaussian
is
over
of 'deposition occurring within the
with
approximately
profile
impingementregion. The maximum depositthicknessis obtainedat thejet centre line. Figure
I shows the profile over one half of a typical deposit and is presentedas thicknessagainst R,
from
line
distance
the
defined
to the nozzle radius.
is
the
R
centre
the
radial
of
ratio
as
where
20
It was found that by using a citrate based electrolyte containing 0.17M, gold, pure gold
deposition rates at thejet centreline as high as 3.4 pm sec-1at a current density of 6.0 A cm-2
could be achievedwhilst maintaininga high quality deposit. In order to attain thesedeposition
rates, a high electrolyte velocity was required. Most of the work in thesestudieswas carried
jet
0.4mm
diameter
highest
deposition
out using a
rates were obtained with
nozzle and the
has
It
Re
120000.
18
Number,
This
Reynolds
to
velocities of
=
m sec-1.
was equivalent a
also been shown4that gold alloy deposits can also be produced at deposition rates of up to
3.0 pm sec-1at cuff ent densitiesof up to 9.0 A CM-2.
3 EXPERIMENTAL
21
deposited
by
the
spotswere strippedusing commercially availablestripping solutions.
covered
As the metallised layers were extremely thin, the stripping operation left the HSSIE spots
in
'Ile
thickness
the array was maintainedabove
the
centre-line
of
spots
virtually unaffected.
15.0,um and confirmed by measurementusing a Dektak SurfaceProfilometer after the XRD
examination had taken place.
For comparison, a series of1control samples were prepared for XRD examination by conOne
from
deposition
methods.
set
were
produced
a Ronovel N electrolyte
vat
ventional
3.0
density
40
1.7
din-3
ftirther
A
the
over
cuff
range
g
nickel
ent
mA
CM-2.
set
containing
density
from
Auronal
MRN bath
the
over
same
cuff
ent
range
produced
an
were
samples
of
is
identical
Ronoval
dm-3
N but contains no booster.
1.7
the
to
nickel,
g
which
also containing
These samples were used to study the influence of the booster. Pure gold samples were
0.06M
from
density
typical
itrate
electrolyte
containing
gold,
acid
over
a
a
current
produced
These
deposits
20
1.0
to
covered the same total surface area of the substrate
CM-2.
mA
of
range
as that covered by the jet plated spot array.
22
23
I,
where B =the broadeningof the diffraction line measuredat its half width maximum intensity
(radians),t =diameter of the crystal particle X= radiation wavelengthand0= angularposition
in degrees.
It was notedthat the crystal]ite sizevaluescalculatedfrom thebroadeningof the III reflections
using the Scherrer equation were significantly greater than the values derived from the 222
reflections. Ile crystallite izescalculatedfor the two planes should be the same; that they
are not, suggeststhat the Scherrer model employed, which attributes all the intrinsic line
broadeningto crystallite size effects, is anover-simplification. On the basisof this information
in
for
detailed
a
more
analysis
order to separatethe contribution to the
selected
were
samples
observedline broadeningfrom crystallite size and strain (RMS) effects.- 71is was undertaken
using the methodof Warren ad Averbachs. Ile successfulapplication of this type of analysis
However,
for
FCC
as
possible.
orders
of
reflection
an
unique
metal examined
as
many
requires
is
just
2,
the
reflections
with
the
of
accessible
multiple
orders
number
copper
radiation,
using
111 (222) and the 200 (400). In this study, line overlap problems combined with low peak
intensitiesruled out the useof the hOOreflections so that only the iII and the 222 peakswere
used for the analysis.
In order to accomplishthe analysisa better defined instrumentalline broadening standardwas
required. This was achievedby producing a pure gold powder and annealing it to the point
where no further improvement in the resolution of the ka, and k% lines could be achieved.
It is particularly difficult to obtain a suitable gold powder commercially and annealit in this
way due to its tendencyfor grain growth and sintering. Therefore, a powder was specifically
produced*. Ile observed diffraction lines were corrected for instrumental broadening by
dividing the Fourier Transform of the diffraction lines derived from the sampleby the Fourier
Transform of the appropriate line from the standardas describedby Stokes6. It Wasfound
necessaryto subtractthe signalderived from the blank glasssubstratesfrom that of the samples
prior to calculating the transform, in order to obtain a level baseline required for an accurate
analysis.
The full application of this analysis yields the mean column length (riA) and its distribution
and the RMS strain and its distribution. The apparentcell size is a3and no, the number of
cells in the averagecolumn length, is determinedby a linear extrapolation of the real part of
the Fourier Transform of the (000) reflection.
The cell size (a) is determined by the angular range over which the diffraction profile is
analysedand is given by: -
I- Ih = 2a3/Xsin(q)
1= 2a3tAsin(q)
I+ Ih = 2a3tAsin(q)
25
diffraction
is
q
the
cl
the
q
the
are
start
and
and
end
of
profile,
the
positionof
where
peak,
,
x is the wavelengthof the radiation employedand I is a reflection order as in MI. In order
to simplify the subsequentcalculations, it is convenientto choosescanrangesso that a3is the
same for all reflections used in the analysis. In this study, a cell size of 2.4 x d,,, was used.
Close and careful examinationof the diffraction patternsfrom thesesamplesshowedboth the
III and 222 diffraction peaksoverlappedwith their nearestneighbours,the 200 and311 peaks
for
This
true
the specially prepared reference gold sample used to
also
was
respectively.
determine instrumentalbroadening, In the presentstudy, data was collected over an angular
range of 10% centredabout the 111/200and 311/222 lines.
In order to obtain adequaterepresentationof the diffraction profiles in the *tails" of the peaks
(where mostof the crystalI ite sizeandstrain information is contained)avariety of mathematical
functions were fitted to the experimental data and the parametersfor the best fits used to
calculate model diffraction profiles. Pearson7, Split Pearson7 and three different pseudo
Voigt (mixed Cauchy and Gaussian)type functions were employed in the modelling.
The modelled III and 222 diffraction profiles were calculated at 1024 data points over an
Fourier
FI-7
20"
16
transforms
using
an
were
calculated
and
respectively.
of
angular range
diffraction'data
instrumental
Ile
to
the
contribution
was removed by'dividing the
routine.
,
FTof the samplesby the FTderived from the precipitatedand annealedgold powder described
000
The
Fourier
the
reflection were calculatedusing the extrapolation
of
coefficients
above.
procedures describedby Warren and Averbach'. This method enablesthe individual contributions of crystallite size and strain to line broadening to be evaluated. The contribution
is
independent
length)
(column
from
broadening
of the order of reflection
to
crystallite size
is
dependent
Because
from
the
on
order
of
that
of this, the two
reflection.
strain
whilst
contributions may be resolved. Ile mean crystallite sizes were calculatedby extrapolating
the linear region of the real part of the 000 transform to obtain N. The meancolumn lengths
(crystallite size) and RMS strains are listed in Table 1.
In addition to-crystallite size and RMS strain, layer sequencefaults on the III plane may also
faults
line
broadening
The
broadening.
line
to
twin
of
stacking
and
to
contribution
contribute
have
been
Ile
identified
be
the"strain
contributions
established.
effective
and
size
once
may
for
(I
11)
D.
the
plane
comprises
crystallite size, fr
I /D.
ff=
I/ D+
(I.
Sa+f3)*F3/4
where D is the true crystallite size, a is the stacking fault probability, p is the twin fault
probability and a is the lattice parameter. The stacking fault probability may be established
by measuringany relative shift betweenthe III and the 200 peaks. The probability may then
becalculated. Twin fault probabilities maybe calculatedfrom any asymmetryof the diffraction
peaks that have been reconstructedfrom the inverse Fourier transform produced during the
Warren and Averbach analysis. However, it was not possibleto accurately calculatethe twin
fault probabilities becausethe deposit was highly oriented in the III direction. Twin fault
probabilities are usually calculatedfor the 100 (200) reflections. Due to the high degreeof
texture, the 200 signal was very weak and could not be used for the analysis. Table I also
includes the stacking fault probabilities where thesewere significant.
Metallurgical Microsection was carried out on a number of samples in order to observe any
resolvable microstructures. The gold deposit was etched using a proprietary gold stripper
dissolved in an alcohol/water mixture.
4 RESULTS
The results of the XRD analysisare presentedin Figures 2 to 9 and Table 1. - As would have
been expected,there were considerabledifferences betweenthe pure and alloy gold deposits
so each will be presentedseparately.
4.1 Pure gold deposits
Figure 2 shows the lattice parameters and orientation of the major first and second order
reflections for a deposit produced under conventional conditions. The normal operating
current density range for this electrolyte was between3 and 7 mA CM-2.
Analysis of the data from Figure 2(a) showed that all plane generally exhibited the same
lattice parameter, although a slight increase was observed with increasing current density.
Ile averagelattice parameter of 4.077 was close to that of pure gold, which is generally
acceptedas being 4.0786 A at 25-C. It is thought that the single point of the 220 plane that
deviatesfrom this is due to experimental error.
27
It was noted that, on calculating the crystallite size using the Scheffer method, a significant
depending
This
the
observed,
on
reflection.
was particularly evident at the
was
variation
higher current densities. An analysisof this is difficult as the line broadeningobservedhas
been assumedto be purely due to crystallite size and ignoresthe existenceof strains and faults
that may also contribute. Analysis of the III reflection using the Warren and Averbach
method indicated that such an assumptionwas invalid as the crystallite size was found to be
(See
Table
1).
The
for
crystallite
size
actual
after
correcting
strain was
greater
considerably
in the region of 0.23 Wn. No evidenceof faulting was observed.
Figure 2(b) showsthe degreeof preferred orientation,of the deposit. It can be seenthat by
comparison with the expectedratios of the variousplanes(parallel lines) that there is a distinct
'31 Itexture over the normal current density range of`11-7 mA cm-1., Above this, the deposit
tends towards a more random orientation.
The RMS strain of the conventional deposits was independentof current density over the
be
low,
< e2>=0.000035.
to
calculated
comparatively
and
was
range analysed
The above measurementsof a conventionaldeposit were necessaryto compare and contrast
Whilst
direct
be
jetting
comparison
a
cannot
those
conditions.
made
under
produced
with
due to the orders of magnitude difference in the current densities applied, in terms of the
increasing
ie
that
the
changes
occurred
current
structural
with
characteristics
morphological
density, a comparisonwas consideredtobe valid. Figure 3 shows similar graphs for samples
-*producedfrom the 0.17M citrate gold using a Re.. No., of 12,000. The maximum current
density under which useful deposits could be produced was found to be 6.0 A CM-2. The
lattice parameterof eachof the crystallites was slightly smaller than the bulk, value, with an
A.
densities
2.0
A
below
However,
4.075
in
cm-2,the
the
current
at
region
of
value
average
lattice parameterexhibited a smaller size.
The crystallite size of the jetted sample calculated using the Scheffer equation was in the
'
A.
A
300
It
be
III
for
but
200
a
size
of
the,
showed
around
must
which
plane
all
region of
is
line
broadening
the
size
this
assumes
all
crystallite
that
of
estimating
method
remembered
III
222
fact
The
the
the
that
the
same
as
planes
were
not
planes
to
size.
attributable grain
.
indicate that this assumptionwas incorr ect. Further analysisof the line broadening revealed
that this difference was due to residual strain, which over the current density range measured
faults,
There
1275.
twin
evidence
of
either
or
stacking
no
>-=0.000
wasaveraged < e2
low
Ile
low
for
a
cuffentdensity.
crystallite size
at
probability of a=0.007
a very
except
*
found
be
between
Averbach
Warren
by
to
determined
III
and
the
method
was
plane as
of the
320 to 350 A.
Ile preferred orientation of the jetted samplewas found to be strongly 220 above a current
density of 2.0 A CM-2.Below this value, aIII orientation predominated,
The RMS strain observedin thesesamplesgiven in Table I was nearly an order of magnitude
greater than for depositsproducedunder conventionalconditions. There was, however, no
clear relationship with current density.
Polishedand etchedmicro-sectionsof jetted samplescan be seenin Figures 12 and 13. These
showedthat there were few structural featuresapparentat current densitiesbelow 6.0 A cm-1.
Above this value, fan shaped,cell-like structures could be observed. These cells became
apparentafter a thicknessof about 8 um had been achieved. Figure 13 shows examplesof
thesecells. Below 8 lim, the cell structure was integral with the rest of the deposit but as the
thickness increased,the cell "wall" exhibited a discontinuity. Extrapolation of the wall line
showeda coinciding point closeto the substratesurface. Topographically, thesecells appear
as nodules, increasing in size with increasing current density as well as deposit thickness.
Thesestructuresclearly resemblethe "rounded mounds"describedby Nakahara7whostudied
the structureand morphology of gold alloy deposits. He concludedthat suchstructuresformed
as a result of an inhibition processthat forced a small crystallite size to be produced as well
as forming the rounded mound structure. .
4.2 Alloy gold deposits
Figure 4 shows the data obtained from depositsproducedconventionally using a Ronovel N
electrolyte, whilst Figure 5 shows that obtained from the Auronal MRN. In addition to the
XRD data, the deposit hardnessis shown.
'T'heeffect of the booster can be clearly establishedunder conventional deposition conditions
by comparing Figures 4 and 5. Figure S(b) shows that in the caseof the Auronal MRN, a
distinct III texture is formed between 10 and 15 mA CM-2,the normal operating rangeof this
electrolyte. Indeed, below this range, the deposit appearancewas matt. Above this range,
the deposit showed signs of *burning* at the edgesof the sample. Figure 4(b) shows that
with,the addition of the booster, the III texture was predominant above 5 mA CM-2,with the
apparentsuppressionof other growth directions. Puregold, ashasbeenseenearlier, possessed
a distinct 311 texture under conventional deposition conditions. It would appear, therefore,
that aIII texture is one of the necessaryconditions for the effective performance of a nickel
hardenedalloy gold. Hardnessmeasurementsshowedthat the deposits with the boosterwere
29
15% harder than those withot, up to a current density of 15 mA CM-2. It'Can also be seen
that the booster reduced the effective lattice parameter compared to those deposits produced
in its absince.
The lattice parameterof the conventional depositswithout booster exhibited a mean lattice
less
0.27%
than that of annealedgold and remained essentially constantwith
parameter
current density. Ile values for all the planeswere comparablewithin the overall accuracy
of measurement. The lattice parameter of the conventionaldeposit containing booster was
being
-0.33%
less
lower
that
the
than that of pure
than
mean
value
of
annealed
gold,
also
gold and showeda small increasinglinear dependenceon current density. However the 220
larger
and were comparableto those of the electrolyte without
significantly
were
planes
booster.
In both cases,the crystAite'size of the III planes as determined by the Scherrer equation
The
for
for
III
than
the
calculated
the
value
other
planes.
measured
reflection
greater
was
A for depositsproduced at the lower current densities,decreasingto -200 A with
-350
was
increasedcurrent density. The crystallite sizescalculatedfor the other planesmeasuredWere
A.
in
100
In the caseof the samplesproduced from the electrolyte
the region of
typically
Warren
Averbach
booster,
the
and
analysis revealedthat'a
closer
analysis
using
containing
difference
be
from
Table
1.
In
RMS
to
this
as
can
seen
strain
contributed
addition,
significant
a slight asymmetry of the reconstructedpeakssuggestedthat some twin faulting was present
but as explained earlier, no accuratemeasurementsof their magnitudecould be made.
Figures 6 and 7 show the data calculatedfrom samplesproducedby jetting from electrolytes
but
dm-3
booster
80
Figures
6(b)
60
dm-3
respectively
no
nickel.
CM3
crn'
and
and
containing
7(b) show the preferred orientation. It can be seenthat with increasing current density, the
III componentof orientation risesrapidly to around60% at the expenseof the 220 component.
The contributions from the 200 and 311 remained fairly constant and close to their values
expectedin a random sample.Ibis is consistantwith aIII texture.
Figure's6(a) and 7(a) show the influence of the booster on the lattice parameter. There is a
for
increasing
in
lattice
the
all
trend
planes
with
current
parameter
a
of
reduction
general
density. It will be noted that the 200 plane exhibited a significantly smaller lattice parameter
lattice
distortion
being
This
the
that
a
of
the
suggest
was
created
would
than
other planes.
due to the incorporation of the booster (or breakdown product of it) within the 100 (200)
planes.
30
Figure 10 showsthe effect of current density and nickel in the electrolyte on the hardnessof
thejetted deposits. It can be clearly seenthat a decreasein the current density as well as an
increase in the nickel in the electrolyte reduced the hardness. This is unusual as under
conventional deposition conditions, it is generally acceptedthat increasing the nickel in the
electrolyte leadsto an increasein the hardness.Figure II shows the relationshipbetweenthe
hardnessand the nickel in the deposit for different concentrationsof nickel in the electrolyte.
It is evident that the quantity of nickel incorporated in the deposit is not the only factor
governing the hardnessbut is also a function of the nickel concentrationwithin the electrolyte.
Figure 14 showsa microsection of a typical alloy gold deposit producedusing HSSJE. As in
the caseof a pure gold jetted deposit, fan-like cells leading to a rounded mound structure can
be seen. No other internal structural featurescould be resolved using optical microscopy.
5 DISCUSSION
Someof the more important physical and structural properties of pure gold depositsproduced
using HSSJE have been examined during the course of this experimental work. These
properties have been compared to deposits produced under more conventional deposition
conditions. Conventional pure gold depositsfrom a citrate electrolyte exhibit a crystallite
for
faulting)
for
0.2
(after
III planes and have
the
strain
and
accounting
of
around
size
jum
hardnessvalues of around 100 kg mm-2. Thesedepositsexhibit a 311 preferred orientation.
Such a texture has beenobservedby other workers.9-9.It was not possibleto obtain data on
the 311 crystallites ashigher orders of reflection could not be obtainedwith this experimental
lattice
However,
the
parameterswould suggestthat no sticking faults
examination
of
method.
These
they
the
samplesexhibited the lowest RMS strain
same
size.
as
are
all
present
were
for the III planesof all the samplesexaminedover the current density range analysed.
When depositsare produced from the sameelectrolyte using HSSJE, both the structure and
from
both
intrinsic
This
results
changesin the deposit
altered.
are
significantly
morphology
interaction
flow.
deposition
due
the
the
to
the
as
as
well
with
conditions
electrolyte
structure
The intrinsic changesresult from the very high rates of deposition. Ile crystallite size is
A,
200
Such
in
tenfold
the
of
a
reduction.
a reduction
to
region
a
value
reduced
considerably
is the most likely causeof the increasein the deposit hardness,increasingto a value of up to
33
'rounded
mounds observed exhibited a strong III orientation with a
was found that''ihe
A.
between
200
300
it was concludedthat such a structure formed as
and
crystallite size of
a result of inhibition of lateral growth by adsorbedspecies, presumably transition metal
complexes. Mie sameinhibiting moleculesadsorbedon the top surface of the growing planes
and causedcontinuous nucleation leading to the small crystallite size and high hardness.A
high number of twins were observedwithin the structure. It is evident that gold nickel alloy
depositsproduced conventionally shareda numberof morphological featureswith bothjetted
deposits
but
gold
some significant differences were observed in the microalloy
and
pure
structure.
In the case of the jetted samples, similar values of Dff were observed for the conventional
Ronovel N and jetted depositscontaining only booster. The presenceof nickel however led
to a reduction of -25% in this value. There appearedto be no direct dependenceof D., on
is
increasing
density.
It
the current density in simple electrolyte
that
generally
accepted
current
systemsleads to a reduction in crystallite size. These results would suggestthat in the case
inhibition
by
deposits,
Nakaharawas operative.
the
as
envisaged
an
process
conventional
of
The fact that a similar crystallite size was observed under jetting conditions suggeststhat
inhibition processeswere also responsiblefor the small crystallite size and not an influence
is
density.
The
increased
this
of
unclear anddifficult to identify
cuff
ent
exact
process
nature
of
as there are a number of possible inhibiting species.These include AuCN, CN-, booster and
transition metal cyanide complexes.It is most likely that there is an'equilibrium betweenthe
depending
deposition
the
concentration
on
prevailing
and
alters
conditions.
which
adsorbates
Tbestructural propertiesare therefore altered,dependingon the natureof the inhibiting species
incorporated within the deposit.
One of the most significant .differences in physical propertiei between the conventionally
is
influence
byjetting
deposits
the
those
of nickel additions.
and
produced
alloy
produced gold
Conventionally produced pure gold depositsexhibit a hardnessin the region of 100kg mm-2,
in
200
kg
do
hardness
deposits
the
those
region
of
MM-2
as
a
manifest
whilstietted pure gold
When
booster.
from
nickel was added to a conventional
containing
electrolytes
produced
increased
hardness
from
kg
MRN,
100
in
Auronal
the
the
the
nun-2to
case
of
electrolyte as
between 150 and 200 kg MM-2.Similar hardnessvalueswere observedwhen nickel was added
In
booster.
the caseof the electrolyte containing
N
Ronovel
only
to the
electrolyte containing
increasing
hardness
deposit
increasing
for
current
with
there
tendency
an
was a
only nickel,
density. In the caseof the electrolyte containing booster and nickel, the opposite trend was
HSSJE,
deposit
is
hardness
The
using
the
produced
containing
reduced proof
nickel
seen.
portional to the quantity of nickel addedto the electrolyte, from 2W kg mm-2 down to as low
as 110 kg mm-2.There is no direct evidenceto explain this behaviour as the jetted samples
containing boosterboth with and without nickel exhibited similar structures in terms of RMS
strain and stacking faults. The main difference was the reduction in the crystallite size in the
caseof the nickel containing sample.This alone was insufficient to account for the changein
hardnessas no current density dependencewas seenin terms of the crystallite size. However,
a linearly increasing current density dependencewas observedin the lattice parameters.The
nickel in the deposit reduceswith increasingcurrent density and there is an empirical linear
relationship for alloys whose individual componentstructuresare similar between the lattice
parameter and the atomic percent of an alloy constituent (Vegards Law) This would imply
that some of the nickel was being incorporatedwithin the lattice in the form of metal atoms.
It is known that whentransition metalsare addedto a gold electrolyte, conventionally produced
deposits incorporate the majority of the transition metal in the form of a cyano- complex. A
changein the way in which the transition metal interacts with the deposit is the most likely
explanationof the reduction in hardnessobserved.It is clear from Figures 10 and II that the
deposit.
in
in
hardness
is
function
in
the
the
that
change
a
of the nickel the electrolyte and not
This tendsto confirm the inhibition mechanismas the main influence on the hardnesschanges
observed.
It is further suggestedthat the changein the inhibition processis responsible for the change
in the wear characteristicsobservedin the study by Bocking and Cameron 4. They found that
.
jetted depositsshowedsomereductionin the wear resistanceparticularly with thicker Coatings.
There was also evidencethat the wear mechanismwas abrasivein nature. Such abrasivewear
is not observed in gold alloy depositsproduced from properly controlled electrolytes under
in
deposition
have
that
Vanhumbeek'2DeDoncker
conventional
suggested
conditions.
and
the case of gold cobalt alloys, the wear behaviour is strongly related to the proportion of
cobalt presentas metal to that presentas a cobalt ion complex, with high values of the latter
being required,for good wear resistance. If the cobalt concentration in the electrolyte was
too high, the incorporation of the complex within the deposit was suppressedleading to too
high a value of metallic cobalt in the deposit. Suchdepositsexhibit abrasivewear behaviour.
In addition, Antler13-has found that in order to obtain good wear resistance,the deposit must
have a low ductility as well as a high hardness. Such a combination would not be expected
from a deposit in which the alloying constituent was present purely in the metallic phase.
Nakahara7hassuggestedthat it is the inhibition dueto the nickel complex and its incOrPOration
into the deposit that is
in
for
gold nickel
the
observed
crystallographic structure
responsible
alloys. It would seemto follow, therefore, that due to the high rates of deposition achieved
I
35
It has been shown that theuse of HSSJE ran significantly alter the micro-structure of both
harder,
become
deposits
deposits.
Pure
to
the
much
proportional
gold
gold
alloy
and
pure
in
being
despite
density.
However,
there
a
reduction
crystallite size and an
current
applied
increase in RMS strain, no direct dependenceon current density could be observed in the
from
311
for
deposits
in
HSSJE
texture,
a
the
conventional
a
change
causes
micro-structure.
from
in
Such
jetting
220
orientation
preferred
results
usually
a
change
conditions.
to a
under
deposits
Gold
inhibit
the
that
process.
alloy
electrocrystallisation
the use of organic additives
Whilst
the texture
to
those
conventionally.
produced
the
compared
change
greatest
showed
both
deposition,
for
III
the
methods
of
orientation
a
preferred
generally
remained
found
It
that although the morphology and
was
altered
considerably.
micro-structure was
300A
in
200
in
being
for
both,
to
the
the
the
of
and
nickel
region
crystallite size was similar
deposit was similar, the microstructure exhibited significant changes. Under conditions of
HSSJE,a high stackingfault probability wasobservedwhich wasnot seenin depositsproduced
in
is
It
the surface
this
thought
that
as
a
comes
about
result
of
a
change
change
conventionally.
high
deposition
densities.
As
from
at
very
current
a
adsorption/inhibition processresulting
incorporated
is
into
deposit.
71is
the
in
form
less
the
complex,
of a cyano
nickel,
result,
incorporation
jetted
deposits
in
the
the
as
of
of
wear resistance
would explain the reduction
the non-metallic inhibitor is responsiblefor the good wear characteristicsof conventional
deposits of this type. On the basis of the evidencepresentedin this and previous work on
HSSJE, that whilst pure gold deposits were found to be harder and possessa finer grain
bonding
thermocompression
characteristicswere not
structure, physical properties such as
in
differences
the
the
However,
structure
of
observed
were
significant
affected.,
significantly
Indeed,
influence
their
to
of
physical
properties.
under
some
that
appeared
nickel gold alloys
HSSJEdeposits
4
in
resistanceof
wasreduced.
theprevious
wear
study,
thetest conditionsgiven
be
to
the gold plating of
the
applied
that
does
cannot
process
This
mean
not necessarily
is
however,
the
be
understanding
mechanisms
of
What
greater
a
required,
will
connectors.
by which the nickel and nickelo-cyanide complex is incorporated within the deposit and the
factors that control the ratio of metal to complex within the deposit.
REFERENCES
1.
2.
C. C. Bocking, Proc. 59th IntnI. Conf. On Surf. Fin. 2,51, April 1991
3.
4.
5.
6.
7.
8.
9.
S.E. Craig Jr, R.E. Harr, J. Henry and P. Turner, J. Electrochem. Soc, 117,1450,1970
10. K-L. Lin, W-C. Liu, M. H. M. Lin & Y. W. Hu, J. Electrochem. Soc., 138,3276,1991
11. E. T. Eisenman,J. Electrochem. Soc., 125,717,1978
12. R. DeDoncker & J. Vanhumbeek,Trans. Inst. Met. Fin., 62,59,1985
13. M. Antler, IEEE Trans. Components,Hybrids & Man. Tech., CHMT-4,1,15,1981
ACKNOWLEDGEMENTS
37
C.D.
SAMPLE
PureAu Conv.
3.0 mA/cml
D.,, k
D,, )L
D.. A
(111)
(111)
(222)
2352
744
540
< e3>
(111)
O.OOW35
Booster Hardness
g dnrs
cm,
dn3,-s
kg inrrra
n/d
101
PureAu Conv.
7.0 mAlcm2
2321
960
551
0.000035
u/d
Pure Au Jetted
2.0 Alcm2
324
326
198
0.00011
Pure Au Jetted
4.0 A/ml
350
349
206
PureAu Jetted
6.0 A/cml
335
327
1
Ka
cl
(111)
I
1
0.007
163.9
0.00015
n/d
198.9
215
0.000115
nld
203.5
304
205
0.000135
n/d
204.1
n/d
1.7
60
198
102.4
PureAu Jetted
8.0 A/cm2
329
Ronoval N Conv.
10.0 mA/cm2
261
104
128
Ronoval N Conv.
40.0 mA/cml
254
107
128
0.000135
n/d
1.7
60
130
Ronoval N Jetted
3.0 A/cm'
324
340
209
0.000115
0.021
60
200.1
Ronoval N Jetted
9.0 A/cm2
289
307
189
0.00013
0.022
60
212.2
Ronoval N Jetted
3.0 A/cml
191
182
104
0.00017
pocwpcak
1.9
60
127
0.00015
-
ramAdiou
1.9
60
170
Ronoval N J:;
9.0 Alcml
200
1 201
128
1 0.00015
1 0.027
TABLE 1. Crystallite size, RMS strain and stacking fault probabilities for some samplesfor
the (I 11) planes only. Note n/d = not detectable,n/m = not measurable.
38
Current DensityA/cm sq
0 0.75
2.0
,
,74.0
0 6.0
+ 8.0
03
012
R Dimensionless
distance
39
4.1
-*-III
200
-*-a-220
-311
--w-222
4.09
4. OB
4.07
4.0&
a)
4.05 'III
05
to
15
20
25
30
35
40
C.D. FrA/cmsq
Wo
CA
80
200
220
-311
10 rl
4a E30
ION
15
05
10
Figure 2. (a) Lattice
20
25
30
35
40
C.D. M/cs sq
40
a)
90 GO 10 -
200
-.*-220
-311
Go io -
40
30
20
le
b)
456
C.D. A/cmsq
41
100
go
0111
Re
-ZM
-311
S
S
a
so
-0
40
30
20
10
0t
0
10
b)
20
33
C.11 irA/cmsq
40
50
g
I
c)
42
'20
4.1
9a
:: 200
220
-311
-222
4.09
Z20
311
83
70
re
4. OB -9
60
4.07
39
.3
4.06
20
05M
15 20 25
C.0. M/cm sq
30
35
10
10
3)
3B
40
50
C.D. aVcm sq
le
z
IsLM 20
kk. sq
30
35
c)
43
4.1
4.0)
COB
4.07
4.06
a)
4.05
5
20 '
15
10
C.D. A/(m-,q
100
9a
-*-III
-200
so
-220
-311
40
30
201
10 r.
-_Zz
b)
--i---I
is
28
C.D. AVCM
Sq
data
for
HSSJE
Ronovel
N
(b)
Lattice
6.
(a)
orientation"
Figure
preferred
and
parameter
but no nickel.
depositsproducedfrom an electrolytecontaining60CM3dM-3booster
44
4.1 1
-*-III
-200
220
-311
-222
4.03
. -K
4.08
4.07
-J
4. Ob
a)
4.05
0
too
15
10
C.O. A/cmsq
20
90
-200
220
-311
80
70
60
50
40
30
20
to
b)
10
Is
20
C. D. "CM Sq
45
-1
a)
"0
o
b)
46
a)
20
sq
1a3
.33
-*-III
-200
220
-311
10
60
le
Z
40 33
23:
10
b)
15
la
C.o. &/Cosq
20
47
3456789
10
Figure 10. Ile effect of current density and nickel in the electrolyte on the hardnessof gold
*
nickel alloy depositsproduced by HSSJE.
-: ,I-
48
Figure11.Therelationshipbetweenthehardness
diff6rent
for
in
deposits
HSSJE
the
and nickel
concentrations
of nickel in the electrolyte.
49
Figure 12. A microsection of a pure gold deposit produced using HSSJE. Current density
6.0 A CM-2,Re. = 12000, Temp. = 55-C. X 1000.
50
Figure 13. A microsection of a pure gold deposit produced using HSSJE. Cuff ent density
7.0 A CM-2,Re. = 12000, Temp. = 55-C. X 1000.
51
Current
HSSJE.
using
deposit
prWuced
alloy
nickel/gold
a
of
dm-3.
Figure 14. A microsection
3.0
g
=
in
the
electrolyte
Nickel
55,
Temp.
-C.
10600,
=
Re.
A
=
6.0
cm-2,
density =
x 1000.