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ChemInform Abstract: Electrodeposition Science and Technology in the Last

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 Journal of The Electrochemical Society, 149 (3) S9-S20 (2002)
An ECS Centennial Series Article
Electrodeposition Science and Technology in the Last Quarter of
the Twentieth Century
D. Landolt*
Materials Department, LMCH, Swiss Federal Institute of Technology Lausanne, CH-1015 Lausanne EPFL, Switzerland
© 2002 The Electrochemical Society. All rights reserved.
On the occasion of the fiftieth anniversary of the Electrochemical
Society in 1952, William Blum published a review on electrodepo-
sition in which he regretted that its theoretical basis was largely
insufficient and “the great advances that have been made in elec-
trodeposition are therefore largely empirical”.1 Twenty-five years
later, Mc Kinney and Faust2 published a follow up report in which
they presented a detailed account of many technological advances
achieved during that period. From today’s perspective, it is interest-
ing to note that the authors mentioned electronics applications just
briefly, and they devoted only a single paragraph to fundamentals.
Apparently, electrodeposition was still perceived as a mostly empir-
ical technology serving primarily for surface finishing and corrosion
protection. Of course, electrochemists and electrochemical engi-
neers had studied the scientific principles governing plating process-
es for many years before, and an impressive amount of knowledge
was available. However, it would seem that this knowledge had not
yet made a decisive industrial impact. At present, the situation has
dramatically changed. Some of the most advanced experimental and
theoretical modeling work in electrochemical metal deposition and
dissolution is performed in industrial research laboratories and elec-
trodeposition and dissolution processes have found a firm place in
electronic device fabrication.3
Electrodeposition as an industrial activity has been practiced for
over 150 years, one of the first applications having been the electro-
forming of printing plates.4 Subsequently, electroplating gained
major importance as a cheap and versatile surface finishing process
for decorative applications and for corrosion and wear protection.
Typical examples include chromium plated automobile trimmings,
gold plated brass jewelry, nickel-plated steel, gold plated electrical
contacts or hard chromium plated bearings. Traditionally, the auto-
motive industry has been a big user of electroplating (Fig. 1).5 While
this industry used large integrated plating facilities, much of the plat-
ing for other applications was performed by specialized shops of rel-
atively small size. Indeed, a characteristic of the traditional plating
industry has been its fragmentation to which several factors may
have contributed. On one hand, before strict environmental regula-
tions came into effect, the investment needed to start a commercial
* Electrochemical Society Fellow.
S9
plating activity was relatively modest. Furthermore, the availability
of fully formulated commercial plating electrolytes reduced the
development efforts needed to start production. Success of a plating
operation then depended mostly on the skill and ingenuity of the
electroplater. Because electroplating depended largely on empirical
know-how and involved handling of aggressive chemicals and solu-
tions, it did not fit well into mechanical production lines and many
manufacturing industries preferred to subcontract plating operations
to specialists. At the end of the twentieth century though, the elec-
troplating industry is undergoing fundamental changes, which are
likely to continue in the future.
On one hand, due to ever more severe regulations concerning the
emission and final disposal of heavy metal ions and chemicals, the
electroplating industry today needs advanced water recycling and
purification schemes that drastically increase investment cost.
Environmental pressures also require that certain established plating
processes be substituted by more environment friendly technologies
that often require closer control and better scientific understanding.
A well-known example is the replacement of cadmium coatings for
corrosion protection by other metal or alloy coatings. Hexavalent
chromium widely used for chromatation of zinc and in chromium
plating has come under attack, as well as lead containing electro-
plated solder alloys. On objects that enter into contact with the
human skin, notably jewelry and watches, traditional nickel barrier
coatings must be replaced, because nickel causes allergic reactions
in some people. A second driving force for change is the emergence
of electrodeposition as a large scale manufacturing process involv-
ing fully automated high throughput installations. Examples are
found in the steel industry and in the electronics manufacturing
industry. In these and other applications electrochemical processes
compete with dry processes and to be competitive they must exhib-
it the same degree of reliability and control. Interestingly, the prin-
ciples governing scale up and scale down of electrodeposition
processes are perhaps better understood at present than those of
competing plasma deposition processes. Finally, the general trend
towards globalization modifies the market conditions for the elec-
troplating industry and creates new types of partnerships between
the manufacturing companies and their subcontractors with ever
higher demands on technical competence, cost effectiveness and
product reliabilitiy.
Figure 1. Corrosion of autobody panels
has been drastically reduced by the use of
zinc and zinc alloy coated steel. Fully
automated plating lines have been
designed to produce coated steel sheet in
a fast, continuous process. The figure
shows a high throughput reel-to-reel zinc
plating installation where the steel strip
moves at a speed of up to 137 m/min.10
S10 Journal of The Electrochemical Society, 149 (3) S9-S20 (2002)
The period covered by this report coincides with the emergence
of information technology, the first personal computers appearing on
the market in the late 1970s and early 1980s. They were made pos-
sible by the invention of cheap and powerful microprocessors based
on integrated circuit technology and of low cost data storage and
retrieval systems. The dramatic pace of progress in information tech-
nology and its enormous impact on human society is common
knowledge. Perhaps not so well known is the fact that electrodepo-
sition and related electrochemical processes have had a decisive
impact on the development of computer technology.6 The present
review will retrace significant scientific and technical achievements
in electrodeposition science and technology made during the last
part of the twentieth century, without any claim to completeness.
During this period electroplating, historically considered a “black
art”.7 has evolved into an exciting field of high technology with
numerous new applications and challenges in micro and nanotech-
nology. Fundamental research carried out by electrochemists, elec-
trochemical engineers and materials scientists made this develop-
ment possible. Continuing research will permit to sustain it in the
future.
Electrodeposition Technology
Decorative and functional coatings.—Traditional applications of
electrodeposition include decorative and functional coatings, elec-
troforming of three-dimensional objects and plating of printed cir-
cuit boards. Many metal winning and refining processes are based
on electrodeposition. These and other applications were thoroughly
reviewed by McKinney and Faust.2 The fourth edition of “Modern
Electroplating” published recently under the auspices of the
Electrodeposition Division of ECS gives a comprehensive overview
of the current practice of electrodeposition and electroless deposi-
tion of different metals and alloys.8
Decorative chromium coatings have been produced by electrode-
position for many years. Traditionally, the automobile industry has
been the largest user, but due to changing fashion trends the impor-
tance of decorative chromium plating has diminished in this indus-
try.5 On the other hand, electroplating has found new applications in
the field of corrosion protection of automobile bodies. Starting in the
1970s, the automobile industry introduced zinc coated steel sheets
for body panels replacing plain steel. In response to the new demand,
the steel industry developed high throughput continuous reel to reel
plating installations for the production of coated steel sheet.9,10
Metallic Zn or Zn-Ni alloys are plated on one or on both sides of the
steel sheet.5 Apparently, the introduction of Zn coated steel was
delayed somewhat by the fact that the salt spray corrosion test which
has been widely used in industrial corrosion testing, initially indi-
cated poorer performance of Zn coated than untreated steel.11 More
realistic tests had to be developed to get better agreement with field
experience which showed that the use of zinc coated steel panels
drastically reduced perforation of automobile body panels by rust.
Hard chromium coatings plated from chromic acid electrolytes
are extensively used for wear protection of bearings and other
machine elements. Since hexavalent chromium is believed to be car-
cinogenic, alternatives have been sought in recent years. Sputter
deposited ceramic coatings are a possible alternative for many tribo-
logical applications. Electroless nickel-phosphorous coatings are
also widely used for corrosion and wear protection. Electroplated
nickel-tungsten alloys or chromium plated from trivalent chromium
electrolytes have been investigated as alternatives to hard chromium,
but as of now have not had a major commercial impact. The auto-
mobile industry uses electroplated Ni/SiC dispersion coatings for
wear protection of cylinder linings and piston rings in car engines.
These materials were originally developed in Germany for the
Wankel motor and they were introduced in car engines between
1978 and 1980 in Europe and Japan.12 Electroless Ni-P/SiC com-
posite coatings find many applications in different kinds of machines
similarly as electroplated Ni/SiC coatings. Self-lubricating metal
Figure 2. Magnetic recording heads fabricated by through mask electrode-
position were introduced in the late 1970s. Continuing miniaturization of
electrodeposited magnetic heads has permitted an astonishing increase in
storage density. The figure shows an inductive head fabricated by electrode-
position comprising a Permalloy horseshoe magnet and a copper coil. The
size of the entire head is comparable to the diameter of the human hair shown
schematically for comparison.6
matrix composite coatings such as Ni-P/PTFE fabricated by electro-
less plating are used in the mechanical and process industries for
valves, injection molds or sliding contacts.13
Electrodeposited noble metal coatings made of gold, silver, plat-
inum, rhodium and their alloys are extensively used for decorative
purposes in the watch and jewelry industries. Gold and gold alloy
coatings also serve to avoid corrosion and oxidation of electrical
contacts. In the late 1970s and early 1980s the price of gold
increased manifold. This led to great efforts to reduce the thickness
of gold coatings in electrical contacts or to replace gold by other
materials such as silver-palladium and nickel-palladium alloys. In
recent years, the price of gold has substantially decreased while that
of palladium went up and is now almost twice that of gold. Not sur-
prisingly, the economic motivation for replacing gold with palladi-
um alloys has vanished.
It is well known that only a limited number of metals and alloys
can be plated from aqueous solution. The use of organic solvents or
molten salts, in principle, should permit to plate a larger number of
metals. In Europe a process for fabricating aluminum coatings by
electrodeposition from aluminum alkyl complexes in toluene has
been brought to an industrial scale.14 Because of technological dif-
ficulties and safety issues the process has not found wider applica-
tion so far. To the authors knowledge no other processes for elec-
trodeposition of coatings from organic solvents or molten salts have
gained industrial importance.
Electronics manufacturing.—One of the first applications of
electroplating and electroless plating in the electronics industry
involved the fabrication of printed circuit boards and electrical con-
tacts. Impressive progress recently achieved in these fields include
fast speed (several meters per minute) reel to reel plating of electri-
cal contacts and high throughput processing of lead frames. In the
1980s and 1990s electrodeposition and related technologies have
found new applications in electronics manufacturing, notably in
packaging and magnetic recording. Several recent overviews discuss
specific aspects of electrochemical technology in electronics and
microsystems manufacturing and the reader is referred to these for
more detailed information.3,6,15-23 Progress in the field is also docu-
mented in several ECS Proceedings Volumes.24-26 Compared to
competing vapor phase technologies, electrodeposition and electro-
less deposition offer several advantages for device fabrication. First
of all, electrochemical processes are relatively cheap and they are
 Journal of The Electrochemical Society, 149 (3) S9-S20 (2002)
Figure 3. Interconnects are multilevel structures which carry electrical sig-
nals between chips in multichip modules. Copper plating is an important
technology for the fabrication of interconnects in electronic packaging. The
SEM shows a via stack with 11 levels. The experimental structure was fabri-
cated by through mask plating of copper in a number of subsequent steps. For
better visibility the dielectric was removed prior to taking the picture.27
highly selective in that metal is deposited only on those places where
it is needed. Electrodeposition has a better throwing power than
physical vapor deposition (PVD) and it allows one to produce high
aspect ratio structures with good precision. Also, the laws governing
scaling up and scaling down of electrochemical processes are rela-
tively well understood. While electrodeposition requires water treat-
ment and recycling installations, the cost of these is not a critical fac-
tor for high-throughput production plants.
Of the many applications electroplating has found in electronics,
through mask plating of thin film magnetic heads has perhaps had
the highest impact. Development of electroplated thin film magnet-
ic heads started at IBM in the 1960s. The process, which included an
electroplated permalloy (81Ni-19Fe) horse shoe magnet and electro-
plated copper coils was introduced into production in 1979 (Fig.
2).6,17 Continuing progress achieved in through mask plating tech-
nology has led to an increase in the magnetic storage density by one
order of magnitude every eight years.6 Lately, the rate of growth has
accelerated even further due to the development of new magnetic
alloys and electroplated combined inductive-resistive heads.21
Progress in through mask plating of magnetic heads has significant-
ly contributed to the fast paced improvement of the performance of
modern computers.16
Packaging of advanced electronic systems constitutes another
important application of electroplating. Packaging serves for signal
and power transmission, heat dissipation and for protection against
mechanical or chemical damage. A typical packaging hierarchy may
include chips, chip modules and printed circuit boards. Advanced
computers contain multilevel chip modules, which are connected by
S11
fine wiring located on the top of the transistor circuitry of logic or
memory chips (Fig. 3).27 In 1997 IBM announced that it would use
electroplated copper wiring in advanced IC chips, replacing the
vapor deposited aluminum used previously. Compared to aluminum,
copper has a higher conductivity and a better resistance to deteriora-
tion by electric migration at high current densities. An additional
advantage is the easier scalability of electroplating. The electro-
chemical manufacturing process relies on the so-called damascene
plating technology.28,29 Contrary to through mask plating, where
metal is selectively deposited into the features of a patterned pho-
toresist, in damascene plating pattern generation precedes the appli-
cation of a conducting seed layer. Plating is performed on the entire
surface and unwanted metal is subsequently removed by chemical
mechanical planarization (CMP). Damascene plating permits one to
plate simultaneously the via holes and the overlying line trenches
(dual damascene plating), making it well suited for interconnect fab-
rication on an industrial scale. Barrier layer between the seed layer
and the insulator prevent unwanted interactions.
Chips must be attached to a substrate. Different technologies
compete in this field such as wire bonding, tape bonding or con-
trolled collapse chip connection (4C). The latter technology uses sol-
der bumps, which permit short interconnection distances for fast
signal response and low inductance. In the mid 1990s an electro-
chemical route for producing lead-tin alloy solder bumps for inter-
connects was developed.30 The process also includes electroplating
of tin-lead alloys as well as a controlled etching step of the seed lay-
ers in order to achieve the desired shape of the bumps. Compared to
the earlier PVD technology, electroplating presents not only eco-
nomic advantages but it is also considered to be a more environment
friendly technology.28 The reason is that in sputter deposition metals
deposit indiscriminately on the reactor walls, whereas in electrode-
position metals deposit only on those spots where they are needed.
This reduces the need for cleaning and waste material disposal.
Microelectromechanical systems.—Electroforming of three-
dimensional structures has been one of the oldest applications of
electrodeposition.4 Recent years have seen the emergence of elec-
trochemical fabrication technologies for micro-electromechanical
systems (MEMS). For these applications electrochemical through
mask plating offers high precision and the possibility to achieve high
aspect ratios. The technology has been pioneered in Germany start-
ing in the early 1980s and has become known under the name LIGA,
which stands for the German “Lithography, Galvanoformung und
Abformung” (Fig. 4). LIGA is a through mask plating process using
thick resist masks with high aspect ratio features. Originally, the
resists were patterned by X-ray lithography. Through mask plating
was performed to produce metallic masters for use in injection
molding of precision polymer parts. More recently, high aspect ratio
through mask electroplating has been applied to the fabrication of X-
ray masks, sensors and tiny turbines among other. Overviews of the
LIGA process and similar processes are available,31,32 as well as a
discussion of early experimental work on X-Ray lithography per-
formed in the U.S.6 At the time of this writing the indistrial impact
of the LIGA process is still limited, but as the technology matures
one may expect that many uses will rapidly develop. Resists have
recently been developed for LIGA applications, which permit the
irradiation with much cheaper UV instead of synchrotron radiation.
They allow fabrication of high aspect ratio structures by several sub-
sequent irradiation steps.32 At present, predominantly nickel is used
in the LIGA process, but Ni-Fe alloys and copper have also been
plated. In the US a complete thin film magnetic micro motor was
recently built by through mask electroplating with the aim to demon-
strate the outstanding capabilities of this technology.6
Electrochemical Phase Formation
The kinetics and mechanisms of single metal deposition were
studied extensively in the 1950s and 1960s and reaction paths for
many systems were established.33,34 Most metal deposition and dis-
S12 Journal of The Electrochemical Society, 149 (3) S9-S20 (2002)
solution reactions proceed through several consecutive steps involv-
ing adsorbed reaction intermediates that are often partially
hydrolyzed. Complexing species play an important role for the dis-
charge mechanism because they change the thermodynamic equilib-
rium and the rate determining step of the charge transfer reaction at
the electrode surface.33,35 These early investigations laid the foun-
dations for later modeling studies of alloy deposition and additive
effects and they provide a solid basis for current studies of electro-
chemical phase formation using scanning probe techniques. The sci-
entific study of electrochemical phase formation developed in
Europe some 50 years ago.36 Of particular interest was the develop-
ment of a method for the fabrication of almost defect free single
crystal electrodes by electrodeposition. It permitted to perform ele-
gant experiments on the energetics of 2D nucleation and to study the
role of crystal defects.37 Many authors studied three dimensional
nucleation using potentiostatic transient techniques. Formation and
growth of three dimensional nuclei on a foreign substrate produce
characteristic overshoots in the current transients and their shape can
be compared to predictions of theoretical nucleation models. A
recent summary of results obtained with this approach is found in
Ref. 38. Underpotential deposition (UPD) is another important topic
in electrochemical phase formation that has found much attention.
UPD implies the formation of a metal monolayer on a foreign sub-
strate at potentials positive to the reversible potential calculated
from the Nernst equation. Typically, UPD is observed when the
binding energy between the depositing atoms and the substrate
exceeds that between the atoms of the deposit material. The phe-
nomenon was observed for the first time in the 1960s.39 The study
of UPD became quite popular in the 1970s and 1980s, when several
groups used single crystal substrates in combination with linear
sweep voltammetry and other techniques for quantifying UPD phe-
nomena. The use of single crystal substrates led to the discovery of
the formation of UPD superlattice structures.40 Furthermore, it was
found that the nature of the UPD layers depended on the anions pre-
sent. For more details the reader is referred to recent reviews.41,42
Electrochemical phase formation has been most widely studied on
metal substrates, but electrodeposition on semiconductors, notably
silicon, is also of great interest, both from a theoretical and from an
industrial point of view. The subject has recently been reviewed and
three charge transfer mechanisms have been identified, which can
lead to electrodeposition of a metal on an n-type semiconductor.43
They involve an electron transfer from the conduction band to the
metal ions in solution, the injection of holes into the valence band or
an electron transfer from surface states. For a given metal deposit the
dominating mechanism depends among other on the prevailing
redox potential which can be adjusted by complexing ions.
The invention of the scanning tunneling microscope (STM)44
and of the atomic force microscope (AFM)45 in the early 1980s
marked a decisive step forward in the study and understanding of the
initial steps of electrochemical phase formation. The STM opened
up entirely new possibilities for the observation of the structure of
metal-electrolyte interfaces on the microscopic and atomic scales
(Fig. 5). The first in situ STM studies of electrode surfaces were
published in 1986-1988.46-48 In subsequent years scanning probe
techniques became important tools for the investigation of adsorp-
tion on metal surfaces and for electrochemical phase formation.49-51
Using single crystals, reconstruction of metal surfaces in solution
could be imaged in situ with atomic resolution. For example, the
atomic structure of a gold single crystal electrode was found to
depend on the applied potential and on the type of anions present.52
The STM also confirmed the existence of super lattice structures
deduced previously from indirect techniques. The STM and AFM
provided new insight into the role of step and kink sites for electro-
chemical phase formation and growth. For example, it was found
that after formation of an initial UPD layer copper atoms deposit
preferentially on monatomic steps of a gold single crystal surface,
Figure 4. The LIGA process for microelectroforming of metallic components
by electrodeposition was developed in the 1980s. Originally, synchrotron
radiation was used to irradiate PMMA masks suitable for the fabrication of
high aspect ratio structures. More recently, UV sensitive resist materials have
become available, which permit similar results without the need for synchro-
tron radiation. The figure shows an microturbine made by electrodeposition
of nickel using the LIGA process. The diameter of the turbine is ~0.25 mm.
Also shown is a glass fiber speed monitor.31
whereas deposition of silver on the same gold crystal led to a Frank-
van der Merve type epitaxial growth up to 10 monolayers.52 The dif-
ference was attributed to the fact that the lattice mismatch between
copper and gold is much larger than between silver and gold. It has
been known for many years that step and kink sites as well as bulk
crystal defects, notably screw dislocations, play an important role
for nucleation and growth of electrodeposits at small overvoltage.53
Using the AFM, copper deposition on a screw dislocation on a (111)
single crystal substrate could be followed in situ.54 The literature on
the study of metal electrodes using the STM has been reviewed cov-
ering publications up to 1998.55 Other in situ methods for character-
izing electrode surfaces are described in Ref. 56. The scanning probe
techniques in conjunction with other in situ methods have led to an
impressive amount of knowledge concerning adsorption phenomena
and electrochemical phase formation on the nanometer scale.
To produce an image by STM or AFM the surface viewed must
be scanned and this is a relatively slow process. For this reason the
STM and AFM techniques are suitable only for studying relatively
slow electrodeposition phenomena. In spite of this limitation, inter-
esting information on step motion and surface diffusion has been
obtained recently, by analyzing the fuzziness of growth steps in
STM pictures.57 The STM can also serve as a tool for the local ini-
tiation of electrochemical phase formation. Local metal deposition
can for example be initiated by producing a surface defect with the
STM.58 In another method metal atoms are first deposited on an
STM tip, then the tip is approached to the polarized substrate surface
in order to initiate a transfer of atoms from the tip to the substrate
surface. Using this technique arrays of well-defined copper or palla-
dium clusters were produced.59,60 Similarly, cobalt clusters were
produced by anodically dissolving the metal from an STM tip posi-
tioned close to the substrate.61
Several groups used the STM or the AFM to study the effect of
additives on the formation and movement of atomic steps during the
growth of electrodeposits. In an early study with copper it was found
that benzotriazole (BTA) did not affect the nucleation, but inhibited
growth of certain planes.62 The observed influence of BTA and
thiourea on the growth morphology of copper deposits was attrib-
uted to their effect on surface diffusion.51,63 The role of substrate
structure was also investigated and it was found that inhibiting addi-
tives adsorbed preferentially at defect sites.64 Most commercial plat-
 Journal of The Electrochemical Society, 149 (3) S9-S20 (2002)
Figure 5. The invention of the scanning tunneling microscope in the 1980s
opened exciting new possibilities for observation on an atomic scale of elec-
trode surfaces and electrodeposition phenomena. The figure shows copper
nuclei on a gold [111] surface obtained by electrodeposition from an acid sul-
fate solution by stepping the potential. The figure suggests that, under the
conditions of the experiment, copper nuclei are formed exclusively at the
monoatomic height steps on the substrate surface.52
ing electrolytes contain not one but several additives. For example,
many copper plating solutions contain small quantities of chloride
ion together with two or three organic additives having different
functions.51,65,66 These additives act in conjunction through adsorp-
tion processes that inhibit or accelerate electrochemical reaction
steps. A strong synergistic effect between polyethylene glycol and
chloride ion was recently reported, copper deposition being inhibit-
ed only when both additives were present.66 Similarly, during pulse
plating of copper-cobalt alloys it was found that a surfactant (SDS)
added alone had a very different effect on the deposit morphology
and the current efficiency than when it was added together with sac-
charin, a stress relieving agent.67 Different mechanisms by which
additives may influence the electrochemical reactions at the elec-
trode-solution interface have been discussed in a recent review from
a chemical point of view.68 The author distinguishes blocking addi-
tives, complex-forming additives, ion pairing additives, surfactants
and insoluble film forming additives. Acid-base concepts have also
been considered.69 Using scanning probe techniques the evolution of
deposit morphology in presence and absence of additives was stud-
ied with the aim to find scaling laws permitting to relate atomistic
growth mechanisms to macroscopic models.51,63,70 Only a limited
number of additives have been studied so far with scanning probe
techniques and the different interaction mechanisms between addi-
tives are not yet well understood. As scanning probe and other sen-
sitive in situ techniques become more widely used, one may expect
that the scientific understanding of how synergistic and antagonistic
effects of additives influence electrochemical phase formation will
significantly improve. This could open the prospect of formulating
plating electrolytes on a more rational basis in the future.
Electrochemical Engineering Aspects of Electrodeposition
Electrochemical engineering concerns the application of the prin-
ciples of thermodynamics, kinetics, mass transport and current dis-
tribution to the scaling, optimization and control of electrochemical
S13
processes. Mastering these subjects has been crucial for the success-
ful introduction of electrodeposition technology in electronics man-
ufacturing. The theoretical foundations of current distribution and
mass transport in electrochemical systems were laid in the 1940s and
1950s. Since then electrochemical engineering has developed into a
recognized branch of electrochemistry71 and excellent textes
describing the underlying principles are available.72,73 In the years
covered by this report a large number of studies adressed problems
of current distribution and mass transport in electrodeposition.
Current distribution is of critical importance for the design of
plating cells and for the operation of industrial plating processes. It
determines the thickness and uniformity of an electrodeposited coat-
ing and the shape evolution of the cathode in electroforming, level-
ing and superfilling. In alloy plating the distribution of the partial
current densities on the cathode determines the uniformity of the
chemical composition of the deposits. The current distribution pre-
vailing on the cathode during an electrodeposition process is the
result of several parameters such as cell geometry (primary current
distribution), charge transfer kinetics (secondary current distribu-
tion) and mass transport conditions (tertiary current distribution).
Numerical simulations involving all these effects are quite involved
and require a detailed knowledge of prevailing hydrodynamic con-
ditions. For this reason complete current distribution calculations
have been performed for a limited number of electrochemical sys-
tems only, the rotating disk electrode being the classical example.74
For cell design purposes it is often sufficient to consider the limiting
cases of primary current distribution or entirely mass transport con-
trolled current distribution. Using these principles, a number of new
designs for electroplating cells were developed in recent years. They
include the rotating cylinder Hull cell,75 the uniform injection cell,76
the recessed rotating disk electrode77 and different types of jet cells
with submersed or emerged electrolyte jets.78-81 The paddle cell82,83
developed for through mask plating of wafers on a laboratory or
industrial scale offers a uniform current distribution over the entire
surface. Mass transport conditions are fairly uniform although the
mass transport rate may vary periodically with time as the paddle
moves back and forth.84 Through hole plating poses difficult current
distribution problems because the metal must be deposited uniform-
ly into a high aspect ratio geometry. The current distribution in
through hole plating using direct current85,86 and pulse current87,88
has been studied extensively. Another current distribution problem
in electronics concerns the terminal effect that may occur when plat-
ing seed layers on an insulating substrate. In these applications the
electrode resistance is not always negligible and potential gradients
may develop in the cathode parallel to the metal-electrolyte inter-
face. As a consequence, more material is plated in the vicinity of the
electrical contact to the cathode than far from it. Dimensionless cri-
teria have been proposed for estimating the importance of this
effect.89
In through mask plating different scales must be taken into
account with respect to current distribution and mass transport; the
workpiece scale, the pattern scale and the feature scale.90 At the
workpiece scale the primary current distribution depends essentially
on the overall cell geometry. In some cases it can be improved by
using auxiliary electrodes.91 On the pattern scale, the current distri-
bution between the individual features forming the pattern depends
strongly on their spacing and their geometry.92,93 Generally, the cur-
rent density on a given feature tends to be higher when it is spaced
farther away from a neighboring feature. The “active area density”
which is the ratio between the area of the features and the geometri-
cal area of the wafer has been found a useful concept for describing
the current distribution on patterned surfaces.92 On the feature scale,
the current distribution determines the shape of the growth front in
through mask and in damascene plating and the shape of the disso-
lution front in electrochemical micromachining.90,94-96 Depending
on experimental conditions, the current distribution on the feature
S14 Journal of The Electrochemical Society, 149 (3) S9-S20 (2002)
scale is governed by the concentration field of the reacting species
and/or by the potential field in the feature. Convection in cavities
exposed to fluid flow has been theoretically modeled and it was
shown that it can lead to asymetric concentration fields.97,98 In elec-
troplating one controls the current distribution on the feature scale
most often by using suitable additives.90
The effect of additives on the current distribution on micropro-
files and the mechanism of cathodic leveling has been studied by a
number of authors as early as the 1950s.97,98 The topic has found
renewed interest in the 1990s because of its importance in electro-
chemical microfabrication and because numerical methods such as
finite element and finite boundary element methods became avail-
able that facilitated quantitative modeling of shape changes. A quite
unique feature of electroplating is that under certain conditions more
metal is deposited into recesses than on protruding parts of a micro-
profile. This permits to achieve leveling of rough surfaces by
cathodic metal deposition. The same behavior can be used to selec-
tively fill small cavities on a patterned surface in Damascene plating
(Fig. 6). It is generally accepted that leveling requires an inhibiting
additive which is consumed at the cathode under mass transport con-
trol. Since recesses in a surface are less accessible than protrusions,
metal deposition is less inhibited there and as a consequence the
local deposition rate is higher than on the rest of the surface.
Several groups have proposed quantitative models based on this
concept.99-101 Leveling experiments with nickel using model pro-
files agreed well with theoretical predictions and confiremd that the
rate of leveling depends on three dimensionless quantities, which
characterize the ratio between mass transport and reaction rate of the
additive, its reaction kinetics and its adsorption properties.102 The
shape evolution during electrodeposition of copper bumps has been
studied both theoretically and an experimentally.103,104 The Peclet
number and the resist angle were found to be the most critical quan-
tities determining the resulting shape. Superfilling in Damascene
plating has been modeled assuming that the additive reacts under
diffusion control and that the metal deposition is activation con-
trolled.90,105 By optimizing the reaction conditions in presence of
additives it was possible to achieve a flat growth front in the fea-
tures. More recently, a different model for superfilling of narrow
deep cavities was proposed, which includes not only inhibition but
also an accelerating effect of additives, the extent of which was
assumed to depend on curvature.106,107
The use of pulse current or pulse reverse current provides an ele-
gant way to influence the current distribution in electrodeposi-
tion.108 In the absence of significant mass transport effects, the cur-
rent distribution in pulse plating is less uniform than in dc plating
because of the lower Wagner number. On the other hand, plating
under conditions where nonsteady state mass transport controls the
rate of deposition can lead to a more uniform current distribution
compared to dc plating.109 Using a rotating disk electrode it was
shown that with pulse reverse current a more homogenous current
distribution can be achieved than with simple pulse current, because
conditions can be chosen such that during the anodic cycle the metal
dissolves preferentially from the outer part of the disk.110 By the
same mechanism, pulse-reverse current was found to be a viable
method for improving the deposit uniformity in through hole plat-
ing.86,111
Electrodeposited Materials
Structure and properties of electrodeposits.—Materials science
deals with the relationships between processing, structure and prop-
erties of materials. Materials science aspects of electrodeposition
have been the subject of several recent ECS symposia.112-114 Indeed,
a wide range of metals and alloys with different structure and com-
position can be electrodeposited. Electrodeposition normally takes
place far from equilibrium, and therefore microstructures and alloy
compositions can be achieved that are not accessible by convention-
al metallurgical means (Fig. 7). For example, X-ray amorphous
Figure 6. Electrodeposition is unique in that it permits, under certain condi-
tions, the preferential deposition of material into the recesses of a surface.
The behavior is used to achieve leveling in plating of coatings and superfill-
ing in damascene plating. The figure illustrates filling of a hemispherical
groove by electrodeposition of nickel in the presence of a leveling agent. A
cross section of the actual deposit is shown together with numerical simula-
tions of the shape change for increasing amounts of charge passed. The cal-
culation takes into account mass transport and adsorption of the leveling
agent.102
alloys115-117 or nanocrystalline metals and alloys118-120 have been
obtained by electrodeposition. Another particularity of electrodepo-
sition is that small changes in process conditions, for example the
presence or not of tiny amounts of additives or of complexing
agents, can have enormous consequences for the resulting
microstructure and composition of the deposited materials and hence
for their properties. If not controlled, this behavior can lead to repro-
ducibility problems in laboratory experiments and in production.
Careful monitoring of electrolyte composition therefore is a critical
factor for success in industrial electrodeposition.121 On the other
hand, if processing conditions are rigorously controlled electrodepo-
sition offers the possibility to fabricate materials with tailor made
structure and properties.113 Frequently, internal stress develops in
electrodeposits. Several factors may contribute to this, such as mis-
match between substrate and deposit, grain coalescence during
growth and incorporation of electrolyte species or of hydrogen.122-
125 Internal stress can cause cracking of deposits or loss of adhesion.
A good review of different methods for measuring stress in elec-
trodeposits has been published in the early 1970s.126 Several more
recent papers discuss methods for in situ measurement of internal
stress during electrodeposition including X-ray diffraction,127,128
bending of thin film substrates,129,130 strain gauge,131 and the use of
the electrochemical quartz crystal microbalance.132
Copper is probably the most widely studied metal in electrode-
position, because of its industrial importance and because its noble
equilibrium potential makes it well suited for fundamental studies
without interference of hydrogen formation. The 1990s saw an enor-
mous increase in the number of studies on copper electrodeposition
stimulated by its use in electronics packaging. Much knowledge
therefore is available on the mechanism of copper deposition and
how deposition conditions affect deposit structure and properties. A
survey of early work on the electrocrystallization of copper can be
found in Ref. 133. Most of the research in the 1960s focussed on the
study of interfacial kinetics and transient phenomena. An important
result was the establishment of the reaction mechanism of the cop-
per electrode.134 Copper deposition and dissolution in sulfate solu-
tion was shown to involve two consecutive charge transfer steps, the
copper(I)-copper(II) step being rate-limiting. More recent studies
deal with the interactions of additives with the monovalent copper
intermediate.135,136 The role of inhibition and of applied current
density on deposit morphology has been studied extensively.
Increasing inhibition and/or increasing current density was found to
 Journal of The Electrochemical Society, 149 (3) S9-S20 (2002)
Figure 7. Most electrodeposition processes take place far from equilibrium
and for this reason materials not readily obtained by classical metallurgical
methods can be made, including nanocrystalline and amorphous materials.
Generally, the structure and properties of electrodeposited metals and alloys
vary strongly with the deposition conditions. The figure shows in a ternary
diagram the fcc-bcc phase boundaries of CoNiFe alloys electrodeposited
from solutions containing different additives, namely (A) saccharine, (B)
thiourea, and (C) a nonsulfur containing compound. The data show that the
phase boundary and therefore the magnetic properties of the alloys are
strongly affected by the nature of the additive.21
favor formation of fine grained deposits. The microstructures
observed with copper have been summarized in a schematic diagram
having as its y-axis the degree of inhibition and as the x-axis the
applied current density divided by the copper ion concentra-
tion.133,137 It has been known for some time that electrodeposition
under limiting current conditions leads to dendritic or powdery
deposits.138 Therefore, the value of applied current density with
respect to the mass transport limited current density is a critical para-
meter for deposit morphology. Similarly, the degree of inhibition can
be expressed as the ratio of applied current density to exchange cur-
rent density.139,140 Several papers discuss various aspects of the
relationship between deposit microstructure and electrochemical
conditions for deposition of copper and other metals.43,122,139-141
Quite generally, kinetically limited growth tends to favor compact
columnar or equiaxed copper deposits while mass transport limited
growth favors formation of loose dendritic deposits.
Additives, typically small amounts of chloride in conjunction
with two to three organic compounds, are widely used in industrial
copper plating from acid sulfate solutions.51,101 The additives are
not only needed for leveling and superfilling, but they also affect the
structure and roughness of the deposits. Inhibiting additives tend to
promote the formation of small equiaxed grains142 which may lead
to increased internal stress. Many additives are incorporated into the
deposit.143 The incorporation of additives was found to change the
microstructure of copper deposits and to lower their electrical con-
ductivity.144 Copper deposition from sulfate solutions can lead to the
formation of nonequilibrium grain structures, which spontaneously
recristallize even at room temperature. As a consequence, structure
dependent materials properties such as electrical conductivity or
internal stress may change slowly with time after deposition.145
Pulse plating is an interesting method for controlling the
microstructure of electrodeposits.146 Early studies on copper, gold
and cadmium suggested that pulse plating leads to refinement of the
S15
grain structure of copper, which was attributed to the high instanta-
neous current densities favoring nucleation.147 A later study of the
effect of pulse current parameters on the microstructure of copper
deposited from sulfate electrolytes indicated that nonsteady state and
steady state mass transport conditions are the most crucial parame-
ters.148 Well below the pulse limiting current and the steady state
limiting current the deposit structure was not affected by the applied
pulse parameters, because copper atoms were apparently added at
step and kink sites rather than forming 3D nuclei. Several studies
found that for nickel deposition the use of pulse plating leads to
deposits of finer grain size119,120,149 and increases their hardness and
their corrosion resistance.120,149 In another study, pulse plating was
found to affect the crystal structure of chromium deposits because of
different hydrogen charging.150 It would appear from the mentioned
literature that the deposit structure in pulse plating depends on the
nucleation mechanism and adsorption phenomena as well as on
mass transport conditions, but a general theory in this field is still
lacking.
Fundamentals of alloy deposition.—A comprehensive compila-
tion of electrolytes and electrochemical conditions for alloy deposi-
tion has been published in the early 1960s.151 Most of the practical
information given therein remains of interest today. More recent
overviews on electrodeposition of different metals and alloys are
found in the fourth edition of Modern Electroplating published
under the auspices of ECS.8 Reviews covering fundamental aspects
of alloy deposition152,153 or electrodeposition of functional alloys
for magnetic applications16,20 are also available. During the last thir-
ty years research on alloy deposition was stimulated greatly by the
needs of the electronics industry for functional alloys and by the
search for new coatings for corrosion protection. The availability of
new tools and methods for electrochemical experimentation, materi-
als characterization and theoretical simulation provided a further
stimulus. From a fundamental point of view, alloy deposition can be
understood by considering the thermodynamics and kinetics of the
partial electrode reactions in a system involving multiple reac-
tions.153 Often, the partial electrode reactions do not proceed inde-
pendently but are coupled through adsorption processes or solution
equilibria. The quantitative investigation of codeposition phenome-
na therefore usually requires numerical modeling. The mechanism
of so called anomalous codeposition, has been extensively studied,
because of the industrial importance of iron group alloys for mag-
netic heads and of zinc alloys for corrosion protection. In anomalous
codeposition a higher proportion of the less noble metal is found in
the deposit than in the solution,151 a behavior typically observed
with iron group metals and with zinc. Different groups studied the
anomalous codeposition of Fe-Ni alloys and proposed models for
explaining the codeposition mechanism and for predicting alloy
composition as a function of different variables such as potential or
convection conditions.154-160 Originally, the anomalous effect was
attributed to the formation of an oxide-hydroxide layer at the cath-
ode surface.154 A later model considered mostly the effect of solu-
tion equilibria in the cathodic diffusion layer.155 More recent papers
explained anomalous codeposition of Fe-Ni alloys by the competi-
tive adsorption of reaction intermediates, which leads to inhibition
of nickel deposition.156,160 Of late, it was observed that in addition
the codepositing nickel enhances the rate of codeposition of
iron158,159 and a theoretical model was proposed that takes into
account both inhibiting and accelerating effects.157
Certain metals like tungsten or molybdenum, which can not be
deposited from an aqueous solution, readily codeposit with iron
group metals forming an alloy. The phenomenon known as induced
codeposition151 has recently been theoretically modeled by postulat-
ing a mechanism that involves an adsorbed mixed reaction interme-
diate of the codepositing metals.161 Alloy formation during codepo-
sition of small amounts of Pb and Sn with copper162 as well as of Ni
with Al in a molten salt electrolyte163 has been attributed to under-
S16 Journal of The Electrochemical Society, 149 (3) S9-S20 (2002)
potential deposition. Since no underpotential deposition of molyb-
denum on iron group metals has been observed such a mechanism
can not explain induced codeposition of these metals. Quite general-
ly, significant progress in the theoretical understanding of alloy
deposition has been achieved in recent years thanks to theoretical
modeling based on numerical simulation. Theoretical models for
codeposition typically take into account mass transport and chemi-
cal equilibria, competitive adsorption and charge transfer kinetics.
They permit to simulate how experimental parameters such as
applied potential or convection conditions affect the composition of
electrodeposited alloys and many such predictions were successful-
ly tested by experiment. However, most alloy deposition models
proposed in the literature require knowledge of rate constants
derived from codeposition experiments under similar conditions and
in addition they usually involve assumptions as to the nature of
adsorbed species.157 At this time, codeposition phenomena involv-
ing coupled partial reactions can not be quantitatively predicted
from the electrochemical properties of the participating metals
alone.
Pulse plating provides additional means to influence composition
and structure of electroplated alloys.146,153,165,166 In the 1980s and
1990s several groups used numerical modeling for the study of pulse
plating of alloys.167-171 These models usually consider steady state
and nonsteady state mass transport as well as interfacial kinetics. It
has been found that displacement reactions during the off time can
have an important effect on resulting alloy composition.171
Theoretical models were proposed which take into account this
effect and they were successfully tested with copper-nickel and cop-
per-cobalt alloys.172
Alloys for magnetic applications.—Electroplated alloys are wide-
ly used in magnetic read and write heads. Several Proceedings of
ECS symposia provide evidence for the impressive progress
achieved in regard to processing technology and properties of elec-
trodeposited magnetic alloys.112,173 A recent review presents a
detailed discussion of materials requirements and deposition condi-
tions of promising alloys.16 Magnetic writing requires magnetically
soft materials with high saturation magnetization, low coercivity and
low magnetostriction.174 Originally, permalloy was used, which is a
Ni-Fe alloy containing 19 % Fe with a saturation magnetization of
about 1 Tesla. Much research over the years was carried out to devel-
op alloys with higher saturation magnetization. Increasing the Fe
content of Ni-Fe alloy or replacing nickel by cobalt can be used
towards this end. Still higher values of saturation magnetization are
achieved with electroplated ternary alloys.16 The magnetic proper-
ties of electrodeposited CoNiFe alloys were found to depend on their
composition and microstructure.21 Among other, they are modified
by the presence of sulfur containing additives such as saccharin or
thiourea.175 The line separating the bcc and fcc phases in the ternary
diagram Fe-Ni-Co is shifted depending on the additive used. Sulfur
containing additives lead to incorporation of sulfur into the deposit.
While this permits to influence phase formation and grain size, it
may negatively affect the corrosion properties.176 By careful opti-
mization of deposition parameters nanocrystalline ternary alloys
with a grain size on the order of 10 nm were produced that exhibit-
ed saturation values of 2 Tesla or more.21
Multilayer alloys have been an important field of research during
the last 20 years. The first electrodeposited multilayer alloy films
(also referred to as composition modulated alloys or CMA in the lit-
erature) were reported in 1983.177 By periodically varying the poten-
tial, well-defined Ag-Pd multilayers could be produced from an elec-
trolyte containing both silver and palladium salts. The films were
intended for electrical contacts having a good corrosion resistance
and good electrical conductivity. The same technique was applied in
the mid 1980s to the deposition of Ni-Cu multilayer alloys178 to
study their mechanical properties. Decreasing the layer thickness to
below 0.4 micrometer resulted in a strong increase in tensile
Figure 8. Multilayer alloys with alternating layers of magnetic and a non-
magnetic materials, each layer just a few nanometers thick, exhibit the so-
called giant magnetoresistance effect, meaning that their resistance changes
markedly when a magnetic field is applied. These materials are used in a new
generation of magnetic heads for high density magnetic storage. Multilayer
alloys can be electrodeposited from a suitable electrolyte by periodically
varying the current or the potential. The figure shows a TEM micrograph of
a nanomodulated Co-Cu multilayer alloy electrodeposited on a silicon [100]
substrate. The deposits exhibit columnar growth mode as confirmed by elec-
tron diffraction.229
strength. A few years later the potential interest of Cu-Ni and Co-Ni
multilayer alloys for magnetic applications was discovered.179 This
led to a considerable number of studies on structure and properties
of multilayer alloys and to the investigation of how the structure and
spacing of the layers influence the magnetic properties, especially
the magnitude of the giant magnetoresistance (GMR) effect (Fig. 8).
A comprehensive review of the literature on electrodeposited mag-
netic multilayer alloys was published in 1996.180 The same potential
modulation technique used for fabricating multilayer alloys can also
be applied to fabricate composition modulated nanowires using a
porous polymer membrane or a porous aluminum oxide as a tem-
plate.181 Three-dimensional nanostructuring of pulse plated Cu-Co
multilayers was recently achieved due to columnar growth of copper
rich and cobalt rich phases.182
Materials for corrosion and wear protection.—Electrodeposited
and electroless coatings find a wide range of industrial applications
for corrosion and wear protection. In particular, zinc and Zn-Ni alloy
coatings with about 15 to 20% Ni are extensively used in the auto-
mobile industry for corrosion protection of steel. Codeposition of
zinc with iron group metals involves anomalous codeposition, the
deposition of the iron group element being inhibited by the code-
positing zinc in chloride as well as sulfate electrolytes.152,183 A num-
ber of papers deal with the mechanism of electrodeposition of Zn-Ni
alloys and different sometimes contradictory models have been pro-
posed.184-187 In one paper impedance data are interpreted in terms of
a mixed adsorbed reaction intermediate.184 Another study found that
the polarization curve for deposition of Zn-Ni alloys exhibits an
inversion before the onset of anomalous codeposition. To account
for this behavior and for observed impedance data a reaction model
with twenty-five parameters was developed.185 A different theoreti-
cal model considering transport by convective diffusion and migra-
 Journal of The Electrochemical Society, 149 (3) S9-S20 (2002)
Figure 9. In electroless plating a reducing agent supplies the electrons for
reduction of metal ions. The process exhibits a high throwing power and it
can also be used for plating on insulators. Electroless nickel-phosphorous
alloys and nickel-phosphorous composite materials containing hard or soft
phases are widely used for corrosion and wear protection. In recent years,
electroless plating has become an important technology in the electronics
industry. The figure shows the cross section of a circuit board with a high
aspect ratio through-hole plated with electroless copper. The thickness of the
board is 4 mm, the hole diameter 0.25 mm] corresponding to an aspect ratio
of 16. The figure demonstrates the excellent uniformity of the deposit thick-
ness over the entire length of the through hole.210
tion at a rotating disk electrode attributed the anomalous codeposi-
tion behavior to an increased exchange current density of Zn.186
Codeposition of hydrogen was thought to enhance nickel deposition
during the first stages of Zn-Ni alloy formation which apparently
involved discrete nuclei of zinc and nickel.187 The phase structure of
electrodeposited zinc alloy coatings differs from that of thermally
produced alloys and it strongly depends on deposition conditions.188
Similarly, the phase structure and composition of pulse plated Zn-Ni
alloys varies with the applied pulse parameters.165 Generally, the
corrosion resistance of Zn-Ni alloy coatings is superior to that of
zinc metal coatings, permitting to apply a smaller coating thick-
ness.5,184 Electroplated Zn-Fe alloys are less corrosion resistant than
Zn-Ni alloys unless they are subjected to a chromate treatment.189
Electroplated and electroless composite materials can be fabri-
cated by codeposition of a metal and a powder suspended in the elec-
trolyte. Ni/SiC composite coatings obtained by electrochemical
codeposition of SiC powders with nickel are used for cylinder lin-
ings in the automobile industry.12 During the 1970s electroless Ni-
S17
P/SiC composite alloy coatings were developed for various tribo-
logical applications. Generally, the incorporation of hard particles
such as carbides, oxides, borides or diamond leads to dispersion
hardening and thus permits to improve wear resistance of the matrix
material.190 The mechanism of codeposition has been studied by a
number of groups and theoretical models of varying degree of com-
plexity and sophistication have been proposed.191,192 It is generally
agreed that codeposition of SiC involves transport processes193 and
adsorption.194,195 However, many phenomena associated with parti-
cle codeposition are not yet well understood. For certain tribological
applications such as self-lubricating bearings, it is advantageous to
incorporate soft rather than hard particles into metal deposits. The
soft particles act as solid lubricants that reduce friction. Electroless
or electrodeposited metal matrix composite coatings containing
MoS2 196 or PTFE13,197exhibit self-lubricationg properties.
Electroless Ni-P/PTFE coatings are well established in industry.
Interestingly, they exhibit satisfactory friction and wear behavior
only under oxidizing conditions, which permit the formation of a
passive oxide film on the surface.198 Recently, nontribological prop-
erties of electrodeposited composite coatings have become of inter-
est. Among other, the catalytic properties and electrochromism of
electroplated metal-oxide and similar materials have been studied199
and the suitability of electrodeposited Ni/PTFE coatings as
hydrophobic electrodes for organic reduction and oxidation reac-
tions has been explored.200 Nontribological applications of elec-
trodeposited composite coatings could well become more important
in the future.199
Electrodeposited semiconductor materials.—Electrodeposition
of chalcogenide semiconductor compounds from aqueous solution is
a potentially simple and cheap process. An inherent problem, how-
ever, is the comparatively low purity of electrodeposited semicon-
ductors compared to those produced by vapor phase deposition,
especially molecular beam epitaxy. The most promising application
of electrodeposited semiconductor compounds is thought to be in
large area solar cells where economy of scale is more important than
uttermost control of purity. Electrodeposition of CdTe was reported
in 1978 and theoretical aspects of codeposition leading to compound
formation were discussed.201 Since then a number of different
selenides, sulfides and tellurides have been electrodeposited such as
ZnSe, CdSe, PbSe, CuSe, In2Se3, ZnS, CdS, ZnTe, and mixed com-
pounds such as Cd(Hg)Te, (CdZn)S, CuInSe2, and CuInTe2.202 The
deposition mechanism of CdTe is typical for the cathodic reactions
leading to semiconductor compound formation by electrodeposition.
Reduction is thought to proceed in two steps. In a first step the tel-
lurium is formed by reduction of telluric acid. In a second step the
Cd undergoes underpotential deposition on tellurium sites on the
surface.202 A similar mechanism apparently applies to electrodepo-
sition of zinc oxide in presence of oxygen or hydrogen peroxide.203
The electrodeposition mechanism of ternary compounds such as
CuInSe2 involves several reaction steps, but the deposit composition
depends to a large extent on the relative magnitude of the diffusion
fluxes of the codepositing species.204,205 Electrodeposition has also
been used to produce epitaxial deposits of semiconductors. The tech-
nique involves the use of two electrolytes, which are alternatively
admitted to the deposition cell.206,207 The potential of the cathode is
chosen such that alternatively each element of the compound semi-
conductor undergoes a UPD reaction forming a single atomic layer.
At the time of this writing the practical applicability of this proce-
dure for device fabrication appears to be limited, however.
Related Electrochemical Processes
The interests of the Electrodeposition Division of ECS include
not only electrodeposition and its different applications but also
related processes such as electroless plating (Fig. 9) and anodic dis-
solution applied to electropolishing, electrochemical machining and
electrochemical etching. To keep this review within a reasonable
length these processes will be mentioned only briefly and the reader
S18 Journal of The Electrochemical Society, 149 (3) S9-S20 (2002)
is referred to the indicated literature for more information.
Electroless plating uses chemical reducing agents such as hypophos-
phite or formaldehyde as a source of electrons in place of a cathod-
ic current. The process, which can be considered a corrosion process
in reverse, is best described by mixed potential theory.208 Recent
overviews of the theory and applications of electroless plating are
given in Ref. 209 and 210. Electroless plating of nickel-phosphorous
alloys is widely used to produce coatings for corrosion and wear pro-
tection. More recently, electroless plating has found many new
applications in electronics manufacturing, especially for packaging
and for producing diffusion barriers.211,212 Electroless plating
requires a more elaborate bath control than electroplating, but on the
other hand, it provides better throwing power and it does not require
conducting substrates.
Electropolishing finds numerous applications in the manufactur-
ing industry for polishing of metallic objects of complex shape.
Fundamental aspects of the process have been reviewed covering the
literature up to 1987.213 More recent studies of electropolishing are
found in Ref. 214-219. Electrochemical machining (ECM) was
developed in the 1960s for machining of complex shapes in hard to
machine alloys used mostly by the aerospace industry.220 Current
densities applied in ECM are two to three orders of magnitude high-
er than in electrodeposition and therefore the process requires
intense electrolyte flow for evacuating reaction products and heat
generated in the inter electrode gap. For most metals and alloys
anodic dissolution under these conditions takes place in the transpas-
sive potential region.221 During the 1980s and 1990s electric dis-
charge machining has taken over many tasks of ECM, because it is
easier to control and does not need elaborate electrolyte pumping
and filtering installations. On the other hand, during this period elec-
trochemical micromachining (EMM) has emerged as a new manu-
facturing technology for micromechanics and electronics.3,222-227
EMM is based on controlled anodic dissolution through masks. The
process does not require heavy installations and permits precision
fabrication of microstructures using well established photolitho-
graphic techniques. Recently, a mask free electrochemical microma-
chining process has been described, which uses laser irradiation for
forming a pattern on an anodically grown oxide film that acts as a
mask during anodic dissolution.228
Concluding Remarks
This review describes significant developments in electrodeposi-
tion science and technology that took place during the last part of the
twentieth century. Electrodeposition has become a broad field with
many ramifications making it extremely difficult for a single person
to be aware of all important developments. The selection of topics
and references in this review therefore necessarily contains some
subjectivity, reflecting the authors own experience and limitations.
Readers are kindly asked to forgive unavoidable shortcomings and
omissions. According to W. Blum,1 “a historian must in some degree
also be a prophet”. Keeping in mind the popular wisdom “predic-
tions are always difficult, especially when they concern the future”
let us therefore conclude this review with a short glance at what
could be future trends and developments.
Sustained environmental pressures, emerging nanotechnology
and the need for tailor made functional materials for microsystems
will be strong driving forces for future research, innovation and
process development in the field of electrodeposition and related
processes. The economic importance of electrochemical microfabri-
cation technology will likely continue to grow in the coming years,
including not only electrodeposition but also electroless deposition
and electrochemical micromachining. Continuing miniaturization in
information technology and the emerging nanotechnology, will lead
to an increasing need for understanding the kinetics of electrochem-
ical phase formation and electrochemical reaction mechanisms on an
atomic scale. This will further increase the importance of in situ
experimental methods capable of providing information on phenom-
ena at solid-liquid interfaces on a nanometer scale, including power-
ful physical and spectroscopic methods and new types of scanning
probe techniques. Such research should eventually lead to a better
understanding and control of electrodeposition processes with and
without additives, and it may offer new opportunities to electrode-
posit not only metals and alloys, but also nonmetallic materials such
as compound semiconductors or functional oxides on a variety of
substrates. The importance of numerical modeling will further
increase, including ever more realistic assumptions concerning
chemical and physical mechanisms involved in metal and alloy
deposition and an ever wider range of length scales. This should
eventually permit to link atomic scale phenomena with macroscopic
process models and materials properties. Powerful and user friendly
software for simulating metal and alloy deposition kinetics will
increasingly become available. As a consequence the plating indus-
try will be in a position to routinely apply numerical modeling for
electrolyte development and process optimization. This should facil-
itate the development of new environment friendly processes and
functional materials for specific applications.
During the last part of the twentieth century, electrodeposition
science and technology contributed significantly to the emergence of
our modern information society. There are many reasons to believe
that in the twenty first century electrodeposition and related tech-
nologies will have an equally important or even more important
impact. The Electrochemical Society through its symposia and pub-
lications has contributed to the development of electrodeposition
science and technology in the past and it is expected that it will con-
tinue to stimulate advancements in the field also in the future.
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