Art 10.1007 BF03214646
Art 10.1007 BF03214646
Peter Wilkinson
Engelhard Limited, Cinderford, Gloucestershire, United Kingdom
For effective operation, gold plating baths must require the minimum of attention in respect of replenisbment and replacement,
and mustproduce as little sub-standard or reject work aspossible.
To acbieve this, an understanding of the processes involved and
thefactors affecting them is advantageous. Tbis article attempts to
provide such an understanding in a simple manner. Special attention is given to the plating of gold from acid baths containing
monovalentgold complexes.
Au(CN);
Au+ + iC
a constam
[Au+][c )'
where [Au(CN);], [Au+] and (CN-] are the concentrations ofthe
respective ons in solution .
This constant (4) provides a measure of the stability of the
Au(CN);complex anel is referred to as its stability constam {32
(the subscript 2 indicates that the reaction is two stage).
The value of {32 for the Au(CN); ion has been determined as
10383 . This is exceedingly large anel implies that the equilibrium
in reaction (1) is far to the left and that the Au(CN); ion is a
very stable one. Moreover, it indicares that the concentration
[Au+] of Au+ ons is given by equation:
[Au(CN);)
[Au + ] = [CN-2 ]
. 10-383
These may be operated under alkaline, neutra! or acid conditons. Under acid conditions, the value of [Au +] is increased as
a result of the equilibrium reaction:
Sulphite Baths
Dissociation of the gold(I) sulphite complex occurs by the
reaction:
Au(SO);- ;:= Au+
+ 2SO -
It is much less stable than the gold(l) cy:micle complex anel its
stability constam is of the orcler of 1010 or about 1028 times less
than that ofthe Au(CN); complex:
[Au(SO);-J
10-10
[S0 -)2
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The formaton ofthe dlthionate ion sp -, which is a powerful reducing agent, leads to a gradual reduction of the gold
complex to metallic gold (14). Below pH 4.7 the sulphite ion
breaks down.
Reduction of the gold compiex between pH 4.7 and 8.0 can
be clecrased considerably by strengthening the sulphite complex with ethylenediamine (16) or by adding an oxidising
agent, like picric acid, that will react with the dithionate at a
faster rate than the gold sulphlte complex. However, the use of
these additives makes the bath contrai difficult and is not completely effective.
Brighteners
Although brightness in itself is not importam in gold plating
for electronic applications, it is associated with other desirable
qualities such as wear resistance and lack of porosity.
Brighteners for gold electrodeposits are of three types:
O Organic substances such as polyethyleneimines and high
molecular weight polyamines. TI1ese operate by selective
absorption within the Helmholtz double layer, usually
causing an increase in polarisation. They are adsorbed
onto the more prominent growth points so that the gold
is deposited preferentially on other parts of the cathode
surface, producing a levelling and brightening effect. Invariably the organic additive is incorporated into the
structure of the deposit with adverse effects on its physical properties, especially wear resistance. The wear resistance can, however, be improved by co-depositing a
second metal such as cadmium.
O Co-deposited metais and semi-metais such as arsenic,
thallium, selenium, lead etc. The use of these causes depolarisation and they produce only lustrous deposits
from cyanide baths but fully bright deposits from sulphite
baths. They operate at extremely low concentrations of a
few ppm and this has resulted in a number of theories as
to how they work, but only one the01y withstands examination. In this theory the semi-metais are regarded as
being adsorbed evenly on the cathode surface where they
catalytically enhance the nucleation of the gold. In the absence of these brighteners the gold nucleates at growth
points such as crystal dislocations on the cathode, but the
catalytic effect of the semi-metal encourages more even
deposition by creating more growth points (17). The
effect can be termed catalytic because the charged
species, for example TI , is available for readsorption.
The mechanism is even more efi:lcient for sulphite golds.
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Temperature
Increasing ternperature increases the solubility of
KCo(Au(CN) 23) , and this leads to decreasing brightness. Chelating strengths are also temperature dependem. The effects of
higher temperature can usually be corrected by increasng the
gold and cobalt concentrations .
Darrel PJating
A barrei can act like a semi-permeable membrane by creating a separate catholyte within the barrei. Within the anolyte
compartment the cd+ concemration increases, whilst within
the catholyte the pH and free cyanide increases . When the barrei is removed and allowed to drain, the two solutions mix and
there is a rapid formation of cyanocobaltate. These effects can
be cmmtered by maint.aining a low pH, increasing the flow of
electrolyte through the barrei and by using the largest possibl e
volume of electrolyte.
High Speed PJating
High speed acid gold solutions are designed to produce the
same type of deposit as convemional vat plating . In order to do
this it is usual to increase the gold and cobalt contem so as to
prevent local depletion around the cathode. For the same
reason agitation in, high speed plating becomes critica!: jet
plating is necessary to produce thc required turbulence for
very high current densities. Higher temperatures are needed to
reinforce the effect ofturbulence.
The main characteristics of high speed plaing are the high
anodic and cathodic current densities. Various effects result
from this: the pH rises faster; more Co3+ is produced; conversion to cyanocobaltate is faster; anel organic chelates tend to be
anodically oxidised. As far as brightness alone is concerned,
semi-metais are better additives at very high current densities.
Recently, a number of acd gold processes have been developed which make use of organic addltives to increase the cu rrem density range of baths for deposition of cobalt and nickel
brightened acid golds. This enables high speed plating to be
done at lower concentrations than was previously possible.
79
Efficiency
By efficiency we mean that proportion of the applied current, usually expressed as a percentage, that results in the deposition of gold. The remaining current s responsible for the
reduction of other species.
The reacton below is of little importance in terms of current consumption but the formation and adsorption of
KCo(Au(CN) 2\ increases the polarisation and thus encourages
the deposition of hydrogen:
Stress
There are a number of theories that attempt to explain stress
in electrodeposits; none of them are entirely satisfactory and
only two will be considered.
The excess energy theory (23) states that an on must pass an
energy barrer in arder to leave its ligand field and become an
atom in a solid lattice. This additional energy barrier is respmsble for polarisation . Once over this energy barrier, the atom
will have excess energy which is converted into heat so that
each freshly deposited layer s hotter than the rest of the sold.
On cooling this gives rse to tensile stress. The relatively high
stress in aciel golds anel the low stress in sulphite golds is explained in this way. On this basis, however organically
brightened gold should be high in tensile stress anel this is not
necessarily so.
The dislocaton theory (24,25) states that impurities cause
extra dislocations in the metallattce , which cause stress in acid
golds and sulphite golds. In terms of this theory certain
organics should give rise to compressive stress because they
disguise some of the surface vacancies which lead to dislocations.
It is known from empirical observations that a deposit containing more than 0.3 per cem w/w Co or Ni will probably be
too highly stressed, and ths would fit in with the second theory.
Stress s probably generated in more than one way and it is
unlikely, therefore, that one theory wll ever supply ali the
answers.
Deosity
Table 11 shows the densities of acid gold deposits. The figure
for pure gold deposit s induded .
The much lower density of cobalt anel nickel brightened
acid gole! deposits cannot be explained on the simple assumption that the deposit contains 0.2 per cent cobalt or nickel_. For
the density to have fallen so much, the structure of the gold deposit must have been expanded by the inclusion of relatively
lightweight material.
It has been indicated above that in acid gold deposits up to
10 per cent of the atoms are not gold but are much lighter elements. This explains their lower density.
Conclusion
The early acid gole! processes were developed empirically
and it is only in the past few years that the relationship between
the composition anel operating parameters of the electrolyte,
and the composition anel performance of the deposits have
begun to be understood. If significant advances are to be
achieved, a more rigorous theoretical basis is required as a
guide in exploring avenues of future development . O
References
1 ]. Souter, Trans.I.E.E.E. Part 1,Hybrid Pack, March 1974, 18
2 G.U. Munier,Plating, 1969,56,1151-1157
3 P. Wilkinson, Trans.lnst.Met. Finish., 1981,59,57-60
4 'Stability Constants', Chem. Soe., Special Publcation No . 17, 1964, 111
and 109
5 A. Knodler ,Meta llobeiflache , 1979, 33, 7
6 Y Okinaka, West.Elect. Eng., 1978,22, (2), 72-81
7 E.Freedman and].N . Shea, U.S.Pat.3598706, 1971
8 A. Fletcher and W.L. Moriarty, U.S.Pat. 4168214, 1979
9 Oxy Metallndustries, GeJmanPat. DE-OS 2658003, 1976
10 W. Zilske, GennanPat. DE-OS 3012999 Al, 1981
11 ].M. Deuber and HJ. Luebke, '72 nd nn. Tech. Conf. Proc., Am. Electroplaters' Soe.,' 1985, G3
12 Arakawa KakoKKJpn. Pat.Appl. 57174487,1981
81