Passivation (chemistry)

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For the concept in nonlinear control, see Feedback passivation. For the concept in spacecraft,
see Passivation (spacecraft).
Passivation, in physical chemistry and engineering, refers to coating a material so it becomes
"passive," that is, less readily affected or corroded by the environment. Passivation involves
creation of an outer layer of shield material that is applied as a microcoating, created by
chemical reaction with the base material, or allowed to build by spontaneous oxidation in the
air. As a technique, passivation is the use of a light coat of a protective material, such as metal
oxide, to create a shield against corrosion.[1] Passivation of silicon is used during
fabrication microelectronic devices.[2] In electrochemical treatment of water, passivation
reduces the effectiveness of the treatment by increasing the circuit resistance, and active
measures are typically used to overcome this effect, the most common being polarity reversal,
which results in limited rejection of the fouling layer. [clarification needed][citation needed]
When exposed to air, many metals naturally form a hard, relatively inert surface layer, usually
an oxide (termed the "native oxide layer") or a nitride, that serves as a passivation layer. In the
case of silver, the dark tarnish is a passivation layer of silver sulfide formed from reaction with
environmental hydrogen sulfide. (In contrast, metals such as iron oxidize readily to form a
rough porous coating of rust that adheres loosely and sloughs off readily, allowing further
oxidation.) The passivation layer of oxide markedly slows further oxidation and corrosion in
room-temperature air for aluminium, beryllium, chromium, zinc, titanium, and silicon
(a metalloid). The inert surface layer formed by reaction with air has a thickness of about
1.5 nm for silicon, 1–10 nm for beryllium, and 1 nm initially for titanium, growing to 25 nm after
several years. Similarly, for aluminium, it grows to about 5 nm after several years.[3][4][5]
Surface passivation refers to a common semiconductor device fabrication process critical to
modern electronics. It is the process by which a semiconductor surface such as silicon is
rendered inert, and does not change semiconductor properties when it interacts with air or
other materials. This is typically achieved by thermal oxidation, in which the material is heated
and exposed to oxygen. In a silicon semiconductor, this process allows electricity to reliably
penetrate to the conducting silicon below the surface, and to overcome the surface states that
prevent electricity from reaching the semiconducting layer.[6][7] Surface passivation by thermal
oxidation is one of the key features of silicon technology, and is dominant in microelectronics.
The surface passivation process was developed by Mohamed M. Atalla at Bell Labs in the late
1950s.[6] It is commonly used to manufacture MOSFETs (metal-oxide-semiconductor field-effect
transistors) and silicon integrated circuit chips (with the planar process), and is critical to
the semiconductor industry.[6][7] Surface passivation is also critical to solar cell and carbon
quantum dot technologies.

Contents

 1Mechanisms
 2History
o 2.1Discovery
o 2.2Surface passivation
 3Specific materials
o 3.1Aluminium
o 3.2Ferrous materials
  3.2.1Stainless steel
o 3.3Titanium
o 3.4Nickel
o 3.5Silicon
 4See also
 5References
 6Further reading

Mechanisms[edit]

Pourbaix diagram of iron.[8]

There has been much interest in determining the mechanisms that govern the increase of
thickness of the oxide layer over time. Some of the important factors are the volume of oxide
relative to the volume of the parent metal, the mechanism of oxygen diffusion through the
metal oxide to the parent metal, and the relative chemical potential of the oxide. Boundaries
between micro grains, if the oxide layer is crystalline, form an important pathway for oxygen to
reach the unoxidized metal below. For this reason, vitreous oxide coatings – which lack grain
boundaries – can retard oxidation. [9] The conditions necessary, but not sufficient, for
passivation are recorded in Pourbaix diagrams. Some corrosion inhibitors help the formation of
a passivation layer on the surface of the metals to which they are applied. Some compounds,
dissolved in solutions (chromates, molybdates) form non-reactive and low solubility films on
metal surfaces.

History[edit]
Discovery[edit]
In the mid 1800s, Christian Friedrich Schönbein discovered that when a piece of iron is placed
in dilute nitric acid, it will dissolve and produce hydrogen, but if the iron is placed in
concentrated nitric acid and then returned to the dilute nitric acid, little or no reaction will take
place. Schönbein named the first state the active condition and the second the passive
condition. If passive iron is touched by active iron, it becomes active again. In 1920, Ralph S.
Lillie measured the effect of an active piece of iron touching a passive iron wire and found that
"a wave of activation sweeps rapidly (at some hundred centimeters a second) over its whole
length".[10][11]

Surface passivation[edit]
The surface passivation process, also known as the Atalla passivation technique, [12] was
developed by Mohamed M. Atalla at Bell Telephone Laboratories (BTL) in the late 1950s.[6][13] In
1955, Carl Frosch and Lincoln Derick at Bell Telephone Laboratories (BTL) accidentally
discovered that silicon dioxide (SiO2) could be grown on silicon. They showed that oxide layer
prevented certain dopants into the silicon wafer, while allowing for others, thus discovering the
passivating effect of oxidation on the semiconductor surface.[14] In the late 1950s, Atalla further
discovered that the formation of a thermally grown SiO2 layer greatly reduced the concentration
of electronic states at the silicon surface,[13] and discovered the important quality of SiO2 films to
preserve the electrical characteristics of p–n junctions and prevent these electrical
characteristics from deteriorating by the gaseous ambient environment. [15] He found that silicon
oxide layers could be used to electrically stabilize silicon surfaces.[16] J.R. Ligenza and W.G.
Spitzer, who studied the mechanism of thermally grown oxides, managed to fabricate a high
quality Si/SiO2 stack, with Atalla and Kahng making use of their findings. [17][18][19] Atalla developed
the surface passivation process, a new method of semiconductor device fabrication that
involves coating a silicon wafer with an insulating layer of silicon oxide so that electricity could
reliably penetrate to the conducting silicon below. By growing a layer of silicon dioxide on top
of a silicon wafer, Atalla was able to overcome the surface states that prevented electricity from
reaching the semiconducting layer.[6][7] For the surface passivation process, he developed the
method of thermal oxidation, which was a breakthrough in silicon semiconductor technology. [20]
Before the development of integrated circuit chips, discrete diodes and transistors exhibited
relatively high reverse-bias junction leakages and low breakdown voltage, caused by the large
density of traps at the surface of single crystal silicon. Atalla's surface passivation process
became the solution to this problem. He discovered that when a thin layer of silicon
dioxide was grown on the surface of silicon where a p–n junction intercepts the surface, the
leakage current of the junction was reduced by a factor from 10 to 100. This showed that the
oxide reduces and stabilizes many of the interface and oxide traps. Oxide-passivation of silicon
surfaces allowed diodes and transistors to be fabricated with significantly improved device
characteristics, while the leakage path along the surface of the silicon was also effectively shut
off. This became one of the fundamental isolation capabilities necessary for planar
technology and integrated circuit chips.[21]
Atalla first published his findings in BTL memos during 1957, before presenting his work at
an Electrochemical Society meeting in 1958.[22][23] The same year, he made further refinements
to the process with his colleagues E. Tannenbaum and E.J. Scheibner, before they published
their results in May 1959.[24][25] According to Fairchild Semiconductor engineer Chih-Tang Sah,
the surface passivation process developed by Atalla's team "blazed the trail" that led to the
development of the silicon integrated circuit.[21][24] Atalla's surface passivation method was the
basis for several important inventions in 1959: the MOSFET (MOS transistor) by Atalla
and Dawon Kahng at Bell Labs, the planar process by Jean Hoerni at Fairchild Semiconductor,
and the monolithic integrated circuit chip by Robert Noyce at Fairchild in 1959.[22][23][21][24] By the
mid-1960s, Atalla's process for oxidized silicon surfaces was used to fabricate virtually all
integrated circuits and silicon devices.[26]
In solar cell technology, surface passivation is critical to solar cell efficiency.[27] In carbon
quantum dot (CQD) technology, CQDs are small carbon nanoparticles (less than 10 nm in
size) with some form of surface passivation. [28][29][30]

Specific materials[edit]
Aluminium[edit]
Aluminium naturally forms a thin surface layer of aluminium oxide on contact with oxygen in the
atmosphere through a process called oxidation, which creates a physical barrier to corrosion or
further oxidation in many environments. Some aluminium alloys, however, do not form the
oxide layer well, and thus are not protected against corrosion. There are methods to enhance
the formation of the oxide layer for certain alloys. For example, prior to storing hydrogen
peroxide in an aluminium container, the container can be passivated by rinsing it with a dilute
solution of nitric acid and peroxide alternating with deionized water. The nitric acid and
peroxide mixture oxidizes and dissolves any impurities on the inner surface of the container,
and the deionized water rinses away the acid and oxidized impurities. [31]
Generally, there are two main ways to passivate aluminium alloys (not
counting plating, painting, and other barrier coatings): chromate conversion
coating and anodizing. Alclading, which metallurgically bonds thin layers of pure aluminium or
alloy to different base aluminium alloy, is not strictly passivation of the base alloy. However, the
aluminium layer clad on is designed to spontaneously develop the oxide layer and thus protect
the base alloy.
Chromate conversion coating converts the surface aluminium to an aluminium chromate
coating in the range of 0.00001–0.00004 inches (250–1,000 nm) in thickness. Aluminium
chromate conversion coatings are amorphous in structure with a gel-like composition hydrated
with water.[32] Chromate conversion is a common way of passivating not only aluminium, but
also zinc, cadmium, copper, silver, magnesium, and tin alloys.
Anodizing is an electrolytic process that forms a thicker oxide layer. The anodic coating
consists of hydrated aluminium oxide and is considered resistant to corrosion and abrasion.
[33]
 This finish is more robust than the other processes and also provides electrical insulation,
which the other two processes may not.

Ferrous materials[edit]

Tempering colors are produced when steel is heated and a thin film of iron oxide forms on the surface.
The color indicates the temperature the steel reached, which made this one of the earliest practical uses
of thin-film interference.
Ferrous materials, including steel, may be somewhat protected by promoting oxidation ("rust")
and then converting the oxidation to a metalophosphate by using phosphoric acid and further
protected by surface coating. As the uncoated surface is water-soluble, a preferred method is
to form manganese or zinc compounds by a process commonly known
as parkerizing or phosphate conversion. Older, less-effective but chemically-similar
electrochemical conversion coatings included black oxidizing, historically known
as bluing or browning. Ordinary steel forms a passivating layer in alkali environments,
as reinforcing bar does in concrete.
Stainless steel[edit]

The fitting on the left has not been passivated, the fitting on the right has been passivated.
Stainless steels are corrosion-resistant, but they are not completely impervious to rusting. One
common mode of corrosion in corrosion-resistant steels is when small spots on the surface
begin to rust because grain boundaries or embedded bits of foreign matter (such as
grinding swarf) allow water molecules to oxidize some of the iron in those spots despite the
alloying chromium. This is called rouging. Some grades of stainless steel are especially
resistant to rouging; parts made from them may therefore forgo any passivation step,
depending on engineering decisions.[34]
Common among all of the different specifications and types are the following steps: Prior to
passivation, the object must be cleaned of any contaminants and generally must undergo a
validating test to prove that the surface is 'clean.' The object is then placed in an acidic
passivating bath that meets the temperature and chemical requirements of the method and
type specified between customer and vendor. While nitric acid is commonly used as a
passivating acid for stainless steel, citric acid is gaining in popularity as it is far less dangerous
to handle, less toxic, and biodegradable, making disposal less of a challenge. Passivating
temperatures can range from ambient to 60 degrees C, or 140 degrees F, while minimum
passivation times are usually 20 to 30 minutes. After passivation, the parts are neutralized
using a bath of aqueous sodium hydroxide, then rinsed with clean water and dried. The
passive surface is validated using humidity, elevated temperature, a rusting agent (salt spray),
or some combination of the three.[35] The passivation process removes exogenous iron,
[36]
 creates/restores a passive oxide layer that prevents further oxidation (rust), and cleans the
parts of dirt, scale, or other welding-generated compounds (e.g. oxides). [36][37]
Passivation processes are generally controlled by industry standards, the most prevalent
among them today being ASTM A 967 and AMS 2700. These industry standards generally list
several passivation processes that can be used, with the choice of specific method left to the
customer and vendor. The "method" is either a nitric acid-based passivating bath, or a citric
acid-based bath, these acids remove surface iron and rust, while sparing the chromium. The
various 'types' listed under each method refer to differences in acid bath temperature and
concentration. Sodium dichromate is often required as an additive to oxidise the chromium in
certain 'types' of nitric-based acid baths, however this chemical is highly toxic. With citric acid,
simply rinsing and drying the part and allowing the air to oxidise it, or in some cases the
application of other chemicals, is used to perform the passivation of the surface.
It is not uncommon for some aerospace manufacturers to have additional guidelines and
regulations when passivating their products that exceed the national standard. Often, these
requirements will be cascaded down using Nadcap or some other accreditation system.
Various testing methods are available to determine the passivation (or passive state) of
stainless steel. The most common methods for validating the passivity of a part is some
combination of high humidity and heat for a period of time, intended to induce rusting. Electro-
chemical testers can also be utilized to commercially verify passivation.

Titanium[edit]

Relation between voltage and color for anodized titanium.

Titanium can be anodised to produce a passivation layer of titanium oxide. As with many other
metals, this layer causes thin-film interference which makes the metal surface appear coloured,
with the thickness of the passivation layer directly effecting the colour produced.

Nickel[edit]
Nickel can be used for handling elemental fluorine, owing to the formation of a passivation
layer of nickel fluoride. This fact is useful in water treatment and sewage
treatment applications.

Silicon[edit]
In the area of microelectronics and photovoltaics surface passivation is usually implemented by
oxidation to a coating of silicon dioxide. The effect of passivation on the efficiency of solar cells
ranges from 3-7%. Passivation is effected by thermal oxidation at 1000 °C. The surface
resistivity is high, >100 Ωcm.[38]

See also[edit]
 Cold welding
 Deal-Grove model
 Dental implant
 Pilling–Bedworth ratio

References[edit]
1. ^ "Passivation vs Electropolishing - What are the differences?". https://www.electro-
glo.com/passivation-vs-electropolishing-what-are-the-differences/
2. ^ IUPAC Goldbook
3. ^ http://www.semi1source.com/glossary/default.asp?searchterm=native+oxide
4. ^ O'M. Bockris 1977, p. 1325
5. ^ Fehlner, Francis P, Low-Temperature Oxidation:The Role of Vitreous Oxides, A
Wiley-Interscience Publication, John Wiley & Sons, New York , 1986 ISBN 0471-87448-5
6. ^ Jump up to:a b c d e "Martin (John) M. Atalla". National Inventors Hall of Fame. 2009.
Retrieved  21 June 2013.
7. ^ Jump up to:a b c "Dawon Kahng".  National Inventors Hall of Fame. Retrieved 27
June 2019.
8. ^ University of Bath Archived 3 March 2009 at the Wayback Machine & Western
Oregon University
9. ^ Fehlner, Francis P, ref.3.
10. ^ Lillie, Ralph S. (20 June 1920). "The Recovery of Transmissivity in Passive Iron
Wires as a Model of Recovery Processes in Irritable Living Systems".  The Journal of General
Physiology. Physiological Laboratory, Clark University, Worcester.  3 (2): 129–
43. doi:10.1085/jgp.3.2.129.  PMC 2140424. PMID 19871851. Retrieved  15 August 2015.
11. ^ Macinnes, Duncan A. (1939).  The principles of electrochemistry. Reinnhold
Publishing Corporation. pp. 447–451.
12. ^ Maloberti, Franco; Davies, Anthony C. (2016). A Short History of Circuits and
Systems: From Green, Mobile, Pervasive Networking to Big Data Computing  (PDF).  IEEE
Circuits and Systems Society. p. 66.  ISBN  9788793609860.
13. ^ Jump up to:a b Black, Lachlan E. (2016).  New Perspectives on Surface Passivation:
Understanding the Si-Al2O3 Interface.  Springer. p. 17.  ISBN  9783319325217.
14. ^ Bassett, Ross Knox (2007).  To the Digital Age: Research Labs, Start-up Companies,
and the Rise of MOS Technology. Johns Hopkins University Press. pp.  22–
23. ISBN 9780801886393.
15. ^ Saxena, A (2009). Invention of integrated circuits: untold important facts. International
series on advances in solid state electronics and technology. World Scientific.
p.  96. ISBN 9789812814456.
16. ^ Lécuyer, Christophe; Brock, David C. (2010).  Makers of the Microchip: A
Documentary History of Fairchild Semiconductor.  MIT Press. p. 111.  ISBN  9780262294324.
17. ^ Huff, Howard R.; Gösele, U.; Tsuya, H. (1998).  Silicon Materials Science and
Technology: Proceedings of the Eighth International Symposium on Silicon Materials Science
and Technology. The Electrochemical Society. ISBN 978-1-56677-193-1.
18. ^ Lojek, Bo. (2007). History of semiconductor engineering. Berlin: Springer. ISBN 978-
3-540-34258-8. OCLC  317626839.
19. ^ Morris, Peter Robin (1990). A History of the World Semiconductor Industry.
IET. ISBN 978-0-86341-227-1.
20. ^ Huff, Howard (2005). High Dielectric Constant Materials: VLSI MOSFET
Applications.  Springer Science & Business Media. p. 34.  ISBN  9783540210818.
21. ^ Jump up to:a b c Wolf, Stanley (March 1992). "A review of IC isolation technologies".  Solid
State Technology: 63.
22. ^ Jump up to:a b Lojek, Bo (2007).  History of Semiconductor Engineering.  Springer Science
& Business Media. pp.  120& 321–323.  ISBN  9783540342588.
23. ^ Jump up to:a b Bassett, Ross Knox (2007).  To the Digital Age: Research Labs, Start-up
Companies, and the Rise of MOS Technology.  Johns Hopkins University Press.
p.  46. ISBN 9780801886393.
24. ^ Jump up to:a b c Sah, Chih-Tang (October 1988). "Evolution of the MOS transistor-from
conception to VLSI"  (PDF).  Proceedings of the IEEE.  76  (10): 1280–1326
(1290). Bibcode:1988IEEEP..76.1280S.  doi:10.1109/5.16328.  ISSN  0018-9219. Those of us
active in silicon material and device research during 1956–1960 considered this successful
effort by the Bell Labs group led by Atalla to stabilize the silicon surface the most important and
significant technology advance, which blazed the trail that led to silicon integrated circuit
technology developments in the second phase and volume production in the third phase.
25. ^ Atalla, M.; Tannenbaum, E.; Scheibner, E. J. (1959). "Stabilization of silicon surfaces
by thermally grown oxides".  The Bell System Technical Journal. 38 (3): 749–
783. doi:10.1002/j.1538-7305.1959.tb03907.x.  ISSN  0005-8580.
26. ^ Donovan, R. P. (November 1966). "The Oxide-Silicon Interface".  Fifth Annual
Symposium on the Physics of Failure in Electronics: 199–231.  doi:10.1109/IRPS.1966.362364.
27. ^ Black, Lachlan E. (2016).  New Perspectives on Surface Passivation: Understanding
the Si-Al2O3 Interface  (PDF). Springer. ISBN 9783319325217.
28. ^ Wang, Youfu; Hu, Aiguo (2014). "Carbon quantum dots: Synthesis, properties and
applications". Journal of Materials Chemistry C. 2  (34): 6921–39. doi:10.1039/C4TC00988F.
29. ^ Fernando, K. A. Shiral; Sahu, Sushant; Liu, Yamin; Lewis, William K.; Guliants, Elena
A.; Jafariyan, Amirhossein; Wang, Ping; Bunker, Christopher E.; Sun, Ya-Ping (2015). "Carbon
Quantum Dots and Applications in Photocatalytic Energy Conversion". ACS Applied Materials &
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76. doi:10.1038/nbt994. PMID 15258594.  S2CID 41561027.
31. ^ Aluminum Passivation [1]
32. ^ Chemical Conversion Coating on Aluminum [2]
33. ^ Aluminum Anodizing Process [3]
 34. ^ "Stainless Steel Passivation". Arrow Cryogenics. Archived from  the original on 4
March 2014. Retrieved 28 February 2014.
35. ^ http://www.cartech.com/techarticles.aspx?id=1566
36. ^ Jump up to:a b "Stainless Steel Passivation Services - A967 & A380 | Delstar Metal
Finishing, Inc".
37. ^ "Archived copy"  (PDF). Archived from  the original  (PDF)  on 12 September 2012.
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38. ^ Aberle, Armin G. (2000). "Surface passivation of crystalline silicon solar cells: A
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487. doi:10.1002/1099-159X(200009/10)8:5<473::AID-PIP337>3.0.CO;2-D.

Further reading[edit]
 ASTM (1 March 2010), ASTM A967: Standard specification for chemical passivation
treatments for stainless steel parts (Rev 05e2 ed.), doi:10.1520/A0967-05E02. The most
common commercial spec for passivation of stainless steel parts. Used in various
industries; latest revision is active for new designs; legacy designs may still require older
revisions or older standards, if the engineering has not been revisited.
 SAE (8 July 2011), AMS 2700: Passivation of corrosion resistant steels. (Rev
D ed.). AMS specs are frequently used in the aerospace industry, and are sometimes
stricter than other standards. Latest revision is active for new designs; legacy designs may
still require older revisions or older standards, if the engineering has not been revisited.
 SAE (16 February 2005), AMS QQ-P-35: Passivation treatments for corrosion-
resistant steel (Rev A ed.). AMS-QQ-P-35 superseded U.S. federal spec QQ-P-35 on 4
April 1997. AMS-QQ-P-35 itself was canceled and superseded in February 2005 by AMS
2700.
 U.S. government, QQ-P-35: Federal specification: Passivation treatments for
corrosion-resistant steel (Rev C ed.). U.S. federal spec QQ-P-35 was superseded by
AMS-QQ-P-35 on 4 April 1997 as part of the changeover instituted by the Perry memo.
Both are now outdated; they are inactive for new designs, but legacy designs may still
require their use, if the engineering has not been revisited.
 Chromate conversion coating (chemical film) per MIL-DTL-5541F for aluminium and
aluminium alloy parts
 A standard overview on black oxide coatings is provided in MIL-HDBK-205, Phosphate
& Black Oxide Coating of Ferrous Metals. Many of the specifics of Black Oxide coatings
may be found in MIL-DTL-13924 (formerly MIL-C-13924). This Mil-Spec document
additionally identifies various classes of Black Oxide coatings, for use in a variety of
purposes for protecting ferrous metals against rust.
 Budinski, Kenneth G. (1988), Surface Engineering for Wear Resistance, Englewood
Cliffs, New Jersey: Prentice Hall, p. 48.
 Brimi, Marjorie A. (1965), Electrofinishing, New York, New York: American Elsevier
Publishing Company, Inc, pp. 62–63.
 Bockris, John O'M.; Reddy, Amulya K. N. (1977), Modern Electrochemistry: An
Introduction to an Interdisciplinary Area, 2, Plenum Press, ISBN 0-306-25002-0.
 Passivisation : Debate over Paintability http://www.coilworld.com/5-6_12/rlw3.htm

https://en.wikipedia.org/wiki/Passivation_(chemistry)