10.1007@0 306 47604 52

2
Electroless Deposition of Metals and Alloys
Stojan S.
The Westaim Corporation, Fort Saskatchewan, Alberta, T8L 3W4, Canada
I. INTRODUCTION
Electroless deposition of metals and alloys has a very significant

practical importance in modern technology especially in the production
of new materials for applications in electronics, wear and corrosion
resistant materials, medical devices, battery technologies, etc.
This process supplements and in some cases replaces
electrodeposition for several practical reasons. The solutions for
electroless deposition have excellent throwing power and allow plating
on articles of very complex shapes and plating through holes. Deposits
obtained by electroless deposition are more dense (more pores-free)
and exhibit better properties for corrosion and electronics applications.
Other important advantages of electroless deposition over
electrodeposition include its applicability for metallization of non-
conductive surfaces (glass, ceramics, polymers, etc.) and the ability to
selectively deposit thin metal films only on catalyzed areas of the
substrate. Finally, for electroless deposition processes, an external
current source is not needed.
In spite of relatively intensive studies in recent decades, electroless
deposition is still not clearly understood. Attempts have been made to
Modern Aspects of Electrochemistry, Number 35, Edited by B.E. Conway

and Ralph E. White, Kluwer Academic/Plenum Publishers, 2002
51
52 Electroless Deposition of Metals and Alloys
explain the mechanisms and kinetics of electroless deposition;

however, a fully accepted model is not yet established. It is obvious
that much more research is needed to advance scientific understanding
in order to ensure successful operations of the process.
The aims of this chapter are to review achievements in the field of
electroless deposition of metals and alloys, and to examine in some
detail the mechanisms that have been proposed for the processes
involved.
II. ELECTROLESSLY DEPOSITABLE METALS

AND ALLOYS
The first scientific description of electroless deposition processes

by von Liebig in 1835 was related to the reduction of Ag(I) salts to Ag
metal using aldehydes.1 Later in 1844, Wurtz observed that ions
2
can be reduced by hypophosphite ions. However, he obtained only a
black powder. This discovery can be considered as the beginning of the
development of the electroless deposition process. In spite of its early
start, process development in this field remained slow until 1946, when
Brenner and Riddell described the proper conditions for electroless
deposition of smooth Ni films from an aqueous solution containing
nickel and hypophosphite ions. 3,4
Over the past few decades, significant progress in this field has
been made because of rapid developments in modern technology
related to electronics, corrosion protection, batteries, decorative
purposes, biomedical applications, etc.
It seems that all metals electrochemically depositable from aqueous
solutions can also be deposited electrolessly under proper conditions
(bath composition, pH, temperature, and corresponding catalytic
surface), using suitable reducing agents.
Table 1 presents a survey of metals and alloys that have been
deposited electrolessly hitherto. In the first group are listed commonly
deposited single metals such as Ni, Co, Cu, Ag, Au and Pd. Other
metals from this group do not have significant applications at the
S. Djokic 53
present, but it should be noted that there are reports on their deposition
in the published literature. For example, it has been reported that Cd
can be deposited using as a reducing agent5 and Pb can be
deposited using thiourea or titanium chloride7 as reducing agents. Bi8
6
and Sb9 have been deposited by In10 by and Pt11, Ru12

and Rh13 by hydrazine. Although there are no other reports, it is worth
noting the claim that Cr can be electrolessly deposited from an aqueous
solution of and sodium hypophosphite as the reducing agent.14
The second group lists elements, which cannot be deposited alone.
However, they can easily be codeposited with nickel or cobalt. Typical
examples are Mo and W. The phenomenon is somehow analogous to
induced electrodeposition as Brenner defined it.15
The third group represents alloys based on the first and/or second
group of elements. These alloys have been deposited for various
applications, mainly in the electronics industries. There is a high
probability that other alloys (which are commonly electrodeposited)
can also be electrolessly deposited, but there are no published data so
far.
III. BASIC DEFINITIONS, SIMILARITIES AND

DIFFERENCES AMONG ELECTROLESS PROCESSES
Brenner and Riddell3,4 were the first authors to introduce the term
electroless metal deposition when describing an autocatalytic process
of depositing a metal in the absence of an external source of electrical
current. Since there are other metal depositions from aqueous solutions
that are carried out without an external current, this process can be
divided into three main groups:
1. displacement deposition
2. contact deposition
3. autocatalytic deposition
1. Displacement Deposition
Displacement deposition is a heterogenous galvanic process in

which the noble metal ions are reduced and deposited at the surface of
an active metal, as a consequence of dissolution of that metal. The
process is sometimes called immersion plating, although this term it is
not a specific description, and therefore should be avoided, or
cementation. The overall displacement reaction is quite simple16 :
and involves the displacement half-reaction of a more active metal
by a more noble metal,
Typical cementation systems in practice are Ag/Zn, Ag/Cu, Cu/Zn,

Cu/Fe, Cu/Al, Sn/Cu etc. The displacement reaction stops immediately
S. Djokic 55
after the reduced metal (more positive metal) covers the surface of the
immersed metal (more negative metal). Accordingly, the thickness of
the deposited metal is always limited. The time of immersion is
particularly critical for achieving a uniform coating layer. Very often,
the adhesion of the deposited films is not as good as that of films
prepared by electrodeposition or by autocatalytic deposition. The
displacement deposition differs from all other plating processes from
aqueous solutions without an external source of electrical current,
because it does not require a reducing agent. Similarly to autocatalytic
processes, displacement deposition has the advantage of nearly
unlimited throwing power. Because of lower quality and thinner
coatings, displacement deposition has found applications mainly in the
refining metals. To a certain extent, however, there are other
applications such as coatings for porcelain enamelling17, zincate
coatings18, decorative finishing, soldering19, etc.
2. Contact Deposition
Contact deposition is equivalent to electrochemical deposition with

the exception that the current is derived from the chemical reaction and
not from an outside source. The metal on which deposition takes place,
and the auxiliary metal with which it is in contact, form a galvanic
element. In this galvanic element, the auxiliary metal acts as an anode
and dissolves; the other metal is a cathode. Consequently, the
dissolved metal is deposited on the cathode (metal on which deposition
takes place) at a mixed potential.
The importance of contact deposition for industrial applications is
relatively small. Sometimes the process is used with autocatalytic Ni to
initiate Ni deposition on copper and its alloys.18 This is achieved by
coupling the Cu or Cu-alloys with Al, Fe or Ni. The contact deposition
is applicable only to a limited extent, and uniform thicker deposits
cannot be obtained. On the other hand, the constant increase of
dissolved metal concentration in the solution may cause instability of
the solution. It should be noted, though, that contact deposition is very
suitable for the initiation of autocatalytic deposition on some surfaces,
(e.g. Ni on Cu). The metals that can be plated by the contact deposition
process include Ni, Co, Cu, brass, Ag, Pt, Sn.18
3. Autocatalytic Deposition
Autocatalytic deposition is the most commonly used chemical

method for the deposition of metallic films from aqueous solution
without an external source of electrical current. The metal films are
formed only on catalytically active surfaces without an external source
of electrical current and by the chemical reduction of metallic ions in
an aqueous solution containing a reducing agent. Autocatalytic
deposition is defined as a process for deposition of metallic films by a
controlled chemical reaction that is catalyzed by the metal or alloy
being deposited.20,21 If the metal ion, is reduced by the reducing
agent ion, the process can be simply described by the following
reaction:
Although the term electroless deposition broadly describes all

processes of metal and alloy deposition without an external source of
electrical current, it should be noted that this term is commonly used
the for autocatalytic deposition process. Consequently, in this chapter,
the term electroless deposition is used only for the autocatalytic
deposition processes.
The development of electroless deposition is mainly connected with
Ni or Cu deposition. However, other electrolessly depositable metals
and/or alloys such as Ag, Au, Co, Sn, AuSn, NiWP, etc. have also been
studied because of their important applications.
IV. SOLUTIONS FOR ELECTROLESS DEPOSITION
All solutions for electroless metal deposition have many similarities,

but depending on the metal or alloy to be deposited, there are also some
S.Djokic 57
differences. Typically, the constituents of a solution for electroless

metal deposition are:
1. Source(s) of metal ions

2. Complexing agent(s)
3. Reducing agent(s)
4. Stabilizer(s) and inhibitor(s)
1. The Metal Ion Sources
Table 2 presents sources of metal ions in electroless deposition of

common metals. Generally speaking, the metal ion sources can be any
water-soluble salts such as sulfates, chlorides, acetates, cyanides, etc.
The nature of the metal ion source is usually determined by the stability
of the solution, properties of the deposited films and also by
environmental issues. Chloride ions are used for limited applications,
since they act deleteriously when these salts are used to coat Al or
ferrous based alloys.20
In the case of Al, the chloride ion can promote its dissolution, and
the coating will exhibit poor adhesion. Similarly, in the case of ferrous
metals, adsorbed chloride ions at the substrate surface can provoke
corrosion. A recent report22 on the effect of nickel salts used in
electroless deposition showed the best overall results (in terms of rate
of deposition and desirable properties of the deposit) had been
accomplished using and then or
The best nitric acid resistance and the highest hardness of
electroless deposited nickel coatings was obtained using nickel fluoride
as the source of nickel ions.
In electroless copper deposition, is used mainly as the
source of copper ions. In electroless gold or silver deposition, cyanide
salts are still employed. However, environmental problems related to
the use of cyanide solutions, create permanent pressure towards using
other non-toxic solutions.
2. Complexing Agents
The majority of complexing agents used in electroless metal

deposition are organic acids or their salts, with a few exceptions of
inorganic ions such as or Cyanides have never been
used in electroless nickel deposition. Pyrophosphates are exclusively
used in alkaline electroless nickel solutions. Ammonia and ions,
in the case of nickel solutions, are mainly used for pH control.
The choice of the complexing agents is dependent, first of all, on
the nature of the metal ion used for deposition. The principal functions
of complexing agents are: buffering action, prevention of precipitation
of hydroxides and salts, and reduction of the concentration of free
(aquo) metal ions. In addition, complexing agents affect the rate of
reduction and the properties of metal deposits. In some cases,
complexing agents apparently form strong complexes with metallic
contaminants, thereby making them less susceptible to react with
reducing agents.
Complexing agents used for the electroless deposition of common
metals are listed in Table 3. Commercial solutions for nickel
electroless deposition operate in the pH range 4.5 to 6. The
complexing agents are most effective in this pH range. However, in the
S. Djokic 59
electroless deposition of Cu, Au, Ag, Pd and in some cases Ni,

solutions with pH > 8 are used. In these cases, different complexing
agents are needed (Table 3). For an extensive review of the stability of
solutions and the effect of complexing agents on hydrolysis of cations,
the reader is referred to field-related monographs (e.g. see References
23- 25).
3. Reducing Agents
Choice of reducing agent depends on conditions of electroless

deposition and, of course, on the metal or alloy being deposited,
including their physico-chemical properties. Use of reducing agents
containing phosphorus or boron leads unavoidably to the incorporation
of these elements, which can dramatically affect the properties of the
metal deposit. On the other hand, electroless deposition of pure metals
is also possible, using reducing agents such as hydrazine or
formaldehyde. Individual reducing agents, used for electroless

deposition, are discussed in the following sections.
(i) Hypophosphite
Hypophosphite is mainly used for the electroless deposition of Ni,

Co, Pd and their alloys. The deposits are not purely metallic as they
usually contain phosphorus. Utilization of hypophosphite in electroless
metal deposition is considerably less than 100 %. The reduction
reaction takes place only at certain surfaces - such as metals belonging
to group VIII of the periodic table (Fe, Co, Ni, Rh, Pd, and Pt). It also
takes place on Au.
Initial reactions in electroless plating depend on the nature of the
metal being deposited and on the nature of the substrate on which
deposition takes place. For example, when electroless Ni plating takes
place on metals such as Fe or Al, the initial reaction in the deposition
process is the displacement reaction:
or
At the formed Ni layer, further reduction of with hypophosphite

proceeds independently. A similar initial process takes place when Cu
or its alloys are plated with gold. The first reaction is displacement of
Cu with
On the other hand, when Cu or its alloys are plated with Ni, pre-
treatment with catalyst or contact deposition20 is required.
The most studied reaction among electroless processes is definitely
deposition of Ni with hypophosphite. The overall reaction for nickel
deposition with hypophosphite can be represented as:
S. Djokic 61
Similar reactions are applicable for Co or Pd deposition with

hypophosphite.
Generally, if the concentration of hypophosphite is increased, the
phosphorous content in NiP alloy is increased.26-30
The concentration in most acid-type solutions (pH 4 to 6) is
0.09 to and molar concentration for sodium
hypophosphite is 0.18 to With a constant concentration
of the other constituents and constant pH, the Ni deposition rate is
proportional to the concentration of hypophosphite.26,31 Similar
behaviour has been reported for alkaline solutions: the rate of
deposition increased with an increase in hypophosphite
concentration.20,32
Lloyd and Mallory investigated kinetics of Ni electroless deposition
with hypophosphite from an acidic solution (pH=4.8) in the presence of
hydroxyacetate, lactate, malate and citrate.33 They found for
all investigated complexes that increasing hypophosphite concentration
up to leads to an increase in the deposition rate. Typical
dependence of the deposition rate on the hypophosphite concentration
for the case of used as a complexing agent is presented in
Figure 1. The reaction order in respect to the hypophosphite
concentration depended on the nature of the complexing agent.
An increase in the hypophosphite ion concentration in the solution
leads to an increase in phosphorus content in electroless deposited CoP
films. 34 Feldstein and Lanscek reported linear relationships between
the deposition rates of Co or Ni and the steady-state potential in the
electroless deposition of NiP or CoP alloys with hypophosphite as the
reducing agent. 35 Similarly, the rate of phosphorus deposition
increased linearly as the steady-state potential increased.
An electrochemical investigation of electroless NiP deposition from
ammoniacal solutions shows the existence of strong interactions
between the reduction of ions and oxidation of hypophosphite
36
ions. The rate of reduction of ions increases the rate of
hypophosphite oxidation. This behavior is attributed to deprotonation
of the hypophosphite anion, which occurs on the catalytic surface of the

growing layer.
Electroless deposition of Cu with hypophosphite is still doubtful. In
the presence of nickel, however, NiCuP alloy films have been
deposited successfully. 37-42 In Ref. [38], it was claimed that in spite of
small amounts of Ni was not
deposited (i.e. "pure" CuP films were obtained). The reaction of Cu
deposition with hypophosphite takes place in the alkaline region (pH 8
to 10) and was described as:
Chassaing et al. reported that an increase in hypophosphite

concentration from 0.1 to during autocatalytic deposition
of NiCuP alloys at pH=9 leads to an increase in both the phosphorus
42
content (2 to 9 %) and the rate of deposition (0 to It seems,
according to these results, that further increase in the hypophosphite
concentration leads to a decrease in the rate of alloy deposition, which
is explicable by the increase in bath instability.
Electroless Au deposition solutions, with hypophosphite as
reducing agent, are described in literature. These solutions are first of
all convenient for Au deposition onto Ni-based substrates.43-46 As
shown by Brenner46 and later by Kurnoskin et al.44, these processes are
not autocatalytic. Kurnoskin et al. showed that in the initial stages, the
process primarily proceeds by the galvanic displacement mechanism.
In the later stages, exposed areas of nickel serve as the catalyst surface
for the hypophosphite oxidation, causing gold deposition onto the
remaining areas of the surface.
Solutions for electroless deposition of silver with hypophosphite
have been reported in the literature, although, it seems that they provide
deposition rather by the galvanic displacement mechanism than by a
truly autocatalytic process.46
S. Djokic 63
There are several solution formulations for electroless Pd

deposition using hypophosphite as the reducing agent.47-51 All these
solutions are alkaline with pH higher than 8. The results show that
only 31 % of hypophosphite used in the process is consumed for the
reduction of the remainder decomposes with evolution of gaseous
hydrogen from the solution.48 The rate of deposition increases with an
increase in hypophosphite concentration up to Above this
concentration the solution is unstable.
(ii) Boron-containing reducing agents
Boron-containing reducing agents used in electroless Ni deposition

are mainly borohydrides and amine boranes. Deposits usually contain
90 to 99 % metallic phase, depending on the composition of the
solution and operating conditions. The rest is usually boron and other
occluded reacting agents. The-boron containing reducing agents are
used for electroless deposition of common metals, such as Ni, Co, Pd,
Pt, Au, Ag and their alloys.
Borohydride ion
The electroless deposition of Ni with borohydride takes place in

alkaline solutions. Theoretically, each borohydride ion can reduce four
nickel ions:
However, experimental results show that one mole of borohydride

reduces approximately one mole of nickel ion.20 The reduction to
boron, according to literature data, proceeds according to the following
reactions:20,52
or
or
or
S. Djokic 65
Gorbunova et al. investigated the conditions for electroless nickel-

boron deposition using sodium borohydride as a reducing agent.52,53
They found that an increase in the concentration in solution
without a stabilizer or with stabilizers such as lead chloride, 2-
mercaptobenzothiazole or thallium nitrate, leads to an increase in the
rate of Ni-B deposition (Figure 2). Using a solution containing
as a stabilizer gives a faster rate of Ni-B deposition.
In the electroless deposition of gold, Okinaka assumed that the
reducing agent of is not itself, but the species
formed as a result of hydrolysis according to the reactions:54
and
Since the utilization efficiency of borohydride in electroless Au

deposition is very low (less than 2 %), Efimof et al55,56 proposed that
another hydrolysis product, participates as a reducing
agent This result is attributed to the decomposition of borohydride.
The overall reactions for Au deposition were described as follows:55,56
and
The maximum rate of Au deposition with borohydride is obtained with

57
concentration of about This unusual
dependence is attributed to the competitive adsorption of and
on the gold surface. An increase in concentration

acts as a catalytic poison, thus preventing the adsorption of the
reducing agent.
If is formed because of hydrolysis, according to a

polarographic investigation carried out by Gardiner and Collat58-60, the
overall reaction describing gold deposition from a borohydride solution
can be presented as
S. Djokic 67
Using borohydride as the reducing agent, gold-based alloys such as

Au-Ag61 and Au-In62 have been produced. Other metals deposited using
borohydride as a reducing agent are Pt63 and In64. Electroless cobalt
deposition with borohydride has also been reported. 20,65,66
Amine Boranes
Whereas borohydrides such as are completely ionic, the

amine boranes are covalent compounds. The electrons in the amine
boranes are displaced toward the boron atom, giving the boron atom
negative character, while the nitrogen atom displaces positive charge as
is illustrated by the following formula:
In practice, the application of aminoboranes is limited to

dimethylamine borane, Dimethylamine borane
(DMAB) is used for the electroless deposition of Ni67-71, Cu72,72, Co74-76
and Ag77. In alkaline and neutral solutions, the preceding chemical
reaction of dimethylamine borane with ions can be represented
as:57,78
The acid-catalyzed hydrolysis of dimethylamine borane occurs

according to the following equation:79
Most authors believe that the major species supplying electrons for
67,68,71,72
metal-ion reduction is The investigation of hydrolysis
71
of DMAB shows that hydrolysis is pronounced at pH’s below 5. In
this way, a significant amount of DMAB is wasted by the hydrolysis,

and consequently the electroless deposition in this region should be
avoided. In the pH region above 5, the consumption of DMAB by
hydrolysis approaches a minimum. The rate of Ni deposition increases
with an increase in DMAB for all investigated pH's within the range 6
to 11.71 However, it should be noted that an increase in pH within this
range leads to a decrease in the rate of Ni deposition. This can be
attributed to the increase in the solution stability (probably because of
the tendency of to hydrolyze at very high pH). Under these
conditions, the reduction reaction may start in the bulk solution and the
rate of deposition (at the corresponding substrate) decreases.
Consequently, the deposition efficiency decreases. Mallory suggested
that the preferred operating pH range for Ni deposition with DMAB is
6 to 7 (near neutral). 20
DMAB has three active hydrogen atoms bonded to the boron, and
theoretically should reduce three metal ions for each ion of
The boron reduction can be represented by the following reaction:71
Based on the experimental results, in the electroless nickel

deposition the molar ratio of nickel ions reduced to DMAB molecules
consumed during the process is approximately 1:1.71
Parlstein and Weightman investigated electroless deposition of Co
with DMAB from acid solutions containing cobalt sulfate,
sodium succinate, sodium sulfate and
DMAB.76 Cobalt-deposits obtained at 70 °C and pH 5.0 contained 96
% Co, 1.7 % B, 0.97 % C and 0.05 % N. Dependence of deposition
rate on DMAB concentration is presented in Figure 3. As illustrated in
this figure, the rate of Co deposition increases almost linearly up to
S. Djokic 69
DMAB concentration of about A further increase in DMAB

concentration results in a rapid decomposition of the solution.
(iii) Formaldehyde
Formaldehyde is mainly used for electroless copper and silver

deposition; however, there are reports that this reducing agent can also
be used for electroless deposition of AuCu alloy80 or Co81.
An overall reaction for electroless copper deposition with
formaldehyde was proposed by Lukes82
Dumesic et al. studied electroless copper deposition from an

EDTA alkaline solution, using formaldehyde as a reducing agent.83
They reported that an increase in the formaldehyde concentration from
0.03 to leads to a linear increase in the initial deposition
rate (Figure 4).
On the other hand, the final rate of copper deposition, according to

the results of these authors, is almost independent of formaldehyde
concentration. Paunovic investigated the effect of complexing agents
such as
and
on electroless copper deposition.84 The rate of copper deposition as a
function of ligand, increased in the order: tartrate, EDTA, quadrol,
S. Djokic 71
CDTA. The addition of a second complexing agent to the solution that

already contains alters the rate of deposition.85 In this case, the second
complexing agent is treated as an additive. The dependence of
deposition rate on formaldehyde concentration passes through a
maximum, when only CDTA (cyclohexane-1,2-diamine-N,N,N',N'-
tetraacetic acid) is used as a complexing agent of ions.86
However, when 50 %of CDTA and 50 % of EDTA are present, a linear
increase in the deposition rate with an increase in the formaldehyde
concentration is observed (see Figure 5).
Electroless Ag deposition with formaldehyde is fast, but either a

cloudy film of silver metal is obtained or peeling occurs. Silver
deposition with formaldehyde can be described by the following

reactions:
or
It seems that the last reaction is more probable, since the hydrogen
evolution reaction has not been observed during the electroless
deposition.
From other metals, as mentioned earlier, the electroless Co deposition
is carried out using formaldehyde as a reducing agent.81 The rate of
cobalt deposition increased in a linear way, with an increase in
concentration within the range to On the
other hand, the dependence of the rate of Co deposition on the
formaldehyde concentration is found to pass through a maximum for
the formaldehyde concentration at about In the alkaline
solution (NaOH concentration 7 to is
formed.81 Reduction to Co is accompanied by hydrogen gas evolution.
The overall reaction for Co deposition is described by the following
equation:
(iv) Hydrazine
Hydrazine has long been recognized as a very powerful reductant of

metallic ions.87-89 Hydrazine and its salts are excellent reducing agents,
as indicated by their standard redox potentials:90
S. Djokic 73
(E° =1.16 V, alkaline conditions)
and
(E° =0.23 V, acidic conditions).

As shown by these reactions, the hydrazine is a better reducing agent
under alkaline than under acidic conditions.
Hydrazine has been used for electroless deposition of metals and
alloys onto metallic and non-metallic surfaces. Examples include
electroless Cu90,91, Ni92-94 , Au95, Ag87,89,96,97, Pt-group of metals and
their alloys98-102, NiSnW89, NiFe89 and alloys resembling stainless
steel.103 There are also reports on electroless deposition of Co with
hydrazine.104,105 Levy proposed the following reaction for the reduction
of with hydrazine.93
However, this reaction does not account for the hydrogen evolution
reaction, which is unavoidable during electroless Ni deposition with
hydrazine. In order to explain the hydrogen production, Mallory20
proposed the following reaction:
The above reaction does not explain a decrease in pH21

(accumulation of during electroless deposition. The overall reaction
accounting for the formation and consequent decrease in pH, can
therefore be proposed as:
The rate of electroless deposition of Co with hydrazine, increases

with an increase in concentration, which is presented in Figure 6.
105
The net reaction for electroless deposition of Co with hydrazine is
described as:
Similarly to other reducing agents, increasing hydrazine

concentration leads to an increase in the rate of electroless deposition.
Moskvichev et al. studied electroless Au deposition with hydrazine
at Ni substrates.106-108 They showed that the first reaction is galvanic
displacement:
The continuous, substrate-catalyzed deposition was described by

the following reactions:
and
Finally, the overall autocatalytic reaction for gold deposition is

described as:
In the initial stages, when the displacement and substrate-catalyzed

reactions are in progress, the rate of deposition is faster. The rate of
deposition slows down when the surface is covered with Au and the
deposition becomes entirely autocatalytic.
S. Djokic 75
Tetramine Pd(II) complex solutions were used for Pd electroless

deposition with hydrazine by Rhoda.98 The overall reaction is:
The rate of deposition linearly increased with temperature and the

deposit contains 99.4 % Pd. Hydrazine is often used in the spray
method for mirror production as the deposition rate is fast.109 The
deposition of Ag from an complex solution can be described
with the following reaction:110
4. Stabilizers
Stabilizers are chemical compounds used in electroless deposition

of metals in order to avoid the decomposition of the solution. Addition
of these compounds to the plating solution assures, under proper
conditions, operations over an extended period of time. Bath
decomposition occurs as a precipitation of metallic particles in the bulk
solution. These particles act as a highly efficient catalyst for further
metal reduction because of their large surface area. The choice of a
stabilizer depends on the metal being deposited and its compatibility
with the process.
Stabilizers, used in the electroless deposition of Ni, have been
divided into the following classes: 20
I) compounds containing elements such as S, Se, Te;

II) compounds containing oxygen
III) heavy metals cations and
IV) unsaturated organic acids (maleic, itaconic acid, etc.)
The concentration of stabilizers is very important, since it

determines the rate of deposition. An increase in the concentration of
stabilizers of classes I or II above 2 ppm may completely inhibit the
deposition reaction. The concentration of class III stabilizers is in the
range to and the concentration of class IV
stabilizers is in the range to
35
Feldstein and Lancsek investigated the effect of three distinct
classes of accelerators on electroless deposition of Ni and Co from
hypophosphite-based solutions. Thiourea and thyocianate were
investigated as accelerator-inhibitor substances (class AI). The
dependence of the rate of deposition on the additive concentration
reached a maximum at about 300 ppm. A further increase in the
additive concentration led to a decrease in the rate of deposition, which
was explained by inhibition due to an adsorption-poisoning
S. Djokic 77
mechanism. In the class API (accelerator with partial inhibition)

glycine was investigated. An initial acceleration in deposition rate with
an increase in the concentration of glycine was observed. With further
increase in glycine concentration, incomplete inhibition in the rate of
deposition was observed. A plateau was reached at higher accelerator
concentrations. In the third class were investigated compounds
designated as AO (accelerator only). Contrary to the behavior of
classes AI and API, the rate of deposition approached a maximum
value asymptotically with increasing additive concentration. This type
of behavior was noted for formate and fluoride ions.
A presence of oxyanions such as etc. may
inhibit electroless deposition of Ni.111 With an increase in
concentration from 0 to 400 ppm, the steady-state potential sharply
decreases, resulting in a decrease in the rate of deposition. This
behavior is explained by a surface adsorption mechanism.
Substances reported as stabilizers in electroless deposition of Cu are
mercaptobenzothiazole, thiourea, cyanide or ferrocyanide salts,
mercury compounds, methyl butynol, propionitrile, etc.112 These
compounds are usually employed at low concentrations, typically 1 to
100 ppm.
Solutions for electroless deposition of Ag are usually very unstable.
There are many different stabilizers used in the electroless deposition
113
of Ag. They include metal ions ,sodium-2,3-
mercapto-propane sulfonate , cystine, cysteine and NaSCN115,
114
tetrabutylammonium nitrate and dodecylammonium acetate. 116 Small

amounts of 3-iodotyrosine or 3,5-diiodo tyrosine
significantly increased the stability of solutions for electroless
deposition of Ag (pH 10 to 10.5).117
In electroless deposition of Pd, compounds such as
and N,N'-p-phenylsulfonic acid-c-

mercaptoformazan are reported to act as stabilizers. 101
During electroless deposition of Au with borohydride, the loss of
borohydride due to hydrolysis is expected. The accumulation of the
hydrolysis products will cause the instability of the gold-borohydride
solution. 118 Compounds recommended as bath stabilizers in electroless

deposition of Au are nitrilotriacetic acid and mercaptosuccinic acid. 119
Kato et al.120 investigated the effect of dithizone, 1,10-
phenanthroline hydrochloride, sodium N,N-diethyldithiocarbaminate
and mercapto compounds on the rate of deposition from a non-cyanide
solution. They found that solution for electroless deposition of Au in
the presence of these compounds is stable for over 20 hours.
However, all other additives, except mercapto compounds, rapidly

decreased the rate of deposition, suggesting that they cannot be used as
stabilizers. Mercapto compounds such as 2-mercaptobenzothiazole
(MBT), 2-mercaptobenzoimidazole (MBI) and 6-ethoxy-2-
mercaptobenzothiazole (EMBT) significantly stabilized solution for
S. Djokic 79
electroless Au deposition. The effect of MBT concentration on the rate

of Au deposition and bath stability is presented in Figure 7. The
optimum concentration of MBT, recommended for electroless Au
deposition is about 2 ppm.
Metallic ions such as and are known to catalyze
the reduction of Au through their specific adsorption on the Au surface
and subsequent underpotential deposition. 120,121 The results on the
effect of metal ions on the rate of deposition show that only is
effective as an accelerator (Figure 8).120 On the other hand,
electrochemical measurements show that all three ions, and
accelerate the cathodic production of Au. The rate of Au
deposition increased by a factor of 2, with a concentration of 1
ppm.
V. DEPOSITION KINETICS AND EMPRICAL RATE LAWS
The rate of electroless deposition can be determined by several

techniques, such as gravimetric, electrical resistance and optical
transmission measurements. The later two procedures have been
adopted for process control in order to continuously determine rates of
deposition. There are also methods such as electrochemical techniques
(polarization resistance122, a.c. impedance123 and coulostatic
methods124,125), which authors claim may be useful tools for automatic
control of various electroless processes.
The empirical rate law for the electroless deposition, can be
expressed as:
where K is the frequency factor from the Arrhenius law, the

activation energy, T the absolute temperature and R is the universal gas
constant; etc. are concentrations of the species A, B, C
acting as reagents or products in the deposition reaction; and
etc. are the reaction orders of the respective species. The individual
time derivatives, etc., are referred to as the rate
of the reaction with respect to the species A, B, C, etc., and
is the overall reaction order.
Based on literature data, the exact empirical rate laws for the
electroless deposition of a given metal differ. These differences are
attributed to the use of different experimental conditions such as bath
composition, pH, types of reducing agents, etc. On the other hand,
there are also some similarities.
The rate of deposition is independent of nickel ion concentration in
the range where most hypophosphite-based solutions are employed.20
Gutzeit126 reported that the rate of electroless Ni deposition is the
first order in respect to the hypophosphite ion concentration. Mallory
and Lloyd127 showed that for several solutions, reaction order, in
S. Djokic 81
respect to the concentration, was -0.4. The rate of electroless Ni

deposition, r, for this case can be expressed as:
Mimani and Mayanna studied electroless nickel deposition from an

acidic tartrate solution.128 On the basis of the observed data, they
proposed the following kinetic equation for the electroless nickel
deposition:
For the activation energy, the authors reported a value of 68.6 kJ/mol.
Lloyd and Mallory reported that the reaction order and the
activation energy depend on the nature of the complexing agent.129
Their results are summarized in Table 4.
The activation energy for all complexing agents had values between
50 and 100 kJ/mol. However, some differences in the reaction order, in
respect to the corresponding species, appeared. Differences in the
activation energy and reaction orders are obviously due to use of
different solutions (different complexing agents) in the experiments.
Mallory and Lloyd investigated electroless Ni deposition with

dimethylamine borane (DMAB).130 The overall deposition reaction for
this system can be represented by the following equation:
The deposition rate was considered to be a function of the

concentrations of complexing agent,
and temperature. Since and
form a complex131, the number of parameters was reduced from seven
to six, and deposition rate, v, was studied in terms of the following
equation:
where DMAB and L are dimethylamine borane and complexing agent

respectively, and AB is the dimethylamine/boric acid complex.
For their studies Mallory and Lloyd used three different complexing
agents: glycolate, malate and citrate.130 They found that the glycolate
has no effect on the deposition rate. In cases of malate or citrate, the
values for reaction order, are near zero or negative. The effect of
complexing agent concentration on the deposition rate is shown in
Figure 9.
Three empirical rate laws were developed for three electroless
nickel-boron deposition systems, depending on the nature of the
complexing agent. These are represented below:
S. Djokic 83
Glycolate:
Malate:
Citrate:
As can be seen from these equations, the deposition rate is

independent of which was confirmed experimentally, but only for
pH ranging from 6.0 to 7.0. This is also illustrated in Figure 10, which
shows that the rate of deposition is independent of pH within the range
6.0 to 7.0. On the other hand, increasing in pH from 4.0 to 6.0 leads to
S. Djokic 85
an increase in the rate of deposition. Accumulation of the byproducts

of DMAB oxidation (AB concentration) has little or no effect on the
deposition rate. These laws are valid only for a limited range of
DMAB and concentrations, pH, and only for the respective
complexing agents. However, the method suggested by Mallory and
Lloyd130 may be applied to any other electroless deposition reaction to
optimize the behavior of the system of interest.
For the overall Cu electroless deposition reaction:
according to data obtained by Shippey and Donahue132, for the case of

alkaline tartrate solutions, the following empirical rate law equation can
be written:
where [L] is the tartrate concentration, d is the empirical reaction order

in respect to tartrate at 40 °C), k is the rate reaction
constant; and is the activation energy (E = 49 kJ/mol).132
Molenaar et al. 133 investigated electroless deposition of Cu from a
solution containing EDTA. They found that at high
and high ECHO concentrations, the
deposition rate is controlled by the concentration in the range
from to For this case, Molenaar et al.133,
proposed the following kinetic equation:
where L is the EDTA concentration and E is the activation

energy At lower and HCHO
concentrations, the deposition rate is controlled by the
concentration of these species, and is independent of
concentration. The empirical rate under these conditions was expressed

as:
Values for k, d and E for this case were not reported.

For the partial anodic and cathodic processes during the electroless
Cu deposition, Donahue and Shippey134 proposed a method for deriving
the rate laws. Based on measurements of mixed potential, and
corresponding current, for various concentrations of the reactants, they
reported the following rate laws for the respective anodic and cathodic
partial reactions:
and
where and are rates and constants of anodic and cathodic

reactions respectively. These equations demonstrate that is not
involved in the anodic partial reaction but that and HCHO are
involved in both partial reactions (anodic as well as cathodic).
For different solutions used in electroless deposition of Cu, based
on mixed potential theory, Donahue et al. obtained the following
empirical rate law equation:135
Their results showed that predicted and measured values of deposition

rate agreed to within 20 %.
S. Djokic 87
According to these results, it is obvious that different conclusions

have been reached by different authors. This is probably a consequence
of using different reaction conditions, as well as different bath
compositions, including the presence of complexing agents and
additives.
VI. MECHANISTIC ASPECTS OF ELECTROLESS

DEPOSITION
In spite of relatively intensive study of the electroless deposition of

metals and alloys, there is still some disagreement in the treatment of
mechanistic aspects of these processes. In order to explain electroless
deposition of metals and alloys, five different mechanisms have been
proposed, as follows:
1. "atomic hydrogen" mechanism

2."hydride ion" mechanism
3. "pure electrochemical" mechanism
4. "metal hydroxide" mechanism
5. "uniform" mechanism
These mechanisms involve various attempts to explain electroless

deposition. However, according to some experimentally observed
characteristics, it is difficult to use any one of these mechanisms for a
general explanation of an electroless deposition process. The following
are discussions of the proposed mechanisms.
1. The Atomic Hydrogen Mechanism
This mechanism was originally postulated by Brenner and

and later supported by others.52,126,136-140 The atomic hydrogen
mechanism was developed for electroless Ni deposition with
hypophosphite. Brenner and Riddell postulated that the atomic
hydrogen reduces and acts by heterogenous catalysis at the
catalytic Ni surface. Atomic hydrogen is generated by the reaction of

hypophosphite with water, and is then desorbed at the catalytic surface
according to the equation below:
At the catalytic surface, the adsorbed hydrogen reduces ions:
The hydrogen evolution reaction, accompanying the catalytic nickel

reduction is described as the recombination of two H atoms, according
to the equation:
Gutzeit136 supported Brenner's assumption that ions are

reduced by atomic hydrogen. He attributed the formation of H atoms to
the dehydrogenation of hypophosphite during the formation of
metaphosphite ion:
According to the atomic hydrogen mechanism, all of the evolved

hydrogen gas must originate from H bonded directly to phosphorus in
hypophosphite.
Formation of elemental phosphorus (its deposition) is explained by
a secondary reaction between hypophosphite and atomic hydrogen:
In general terms, the atomic hydrogen mechanism, according to

literature data137-139, can be described by the following equations:
S. Djokic 89
Anodic:
where RH is formaldehyde, hypophosphite or borohydride

Cathodic:
Recombination:
The reduction of ions by H is theoretically possible in a certain

pH range for which the calculations are published. 141 However, the
atomic hydrogen mechanism fails to explain many of the features of
electroless deposition such as the simultaneous hydrogen evolution
reaction. In this mechanism, deposition of phosphorus and
involvement of hydrogen evolution reactions are explained as side
reactions. Furthermore, this scheme does not explain why the
stoichiometric utilization of hypophosphite is always less than 50 %.
In an attempt to explain why the utilization of hypophosphite on
reduction cannot exceed 50 %, Ivanovskaya and Gorbunova142
proposed the following reaction for electroless Ni deposition from
alkaline solutions:
According to this equation, the pH of the reacting solution will

decrease, and the reduction of one Ni atom leads to production of one
molecule. The atomic hydrogen formed in this reaction does not
reduce but is evolved as gas. These authors claimed that, in
agreement with their experimental results, the above equation predicts
that the hypophosphite utilization for reduction cannot exceed

50%. Ivanovskaya and Gorbunova142 did not examine reduction paths
of phosphorus codeposition, or discuss electroless Ni deposition in
acidic solutions.
2. The Hydride Ion Mechanism
The hydride ion mechanism was first suggested by Hersch. 143

According to Hersch’s hypothesis, the hypophosphite acts as the donor
of hydride ions. The hydride ion is the reducing agent of both
and ions. This mechanism, originally proposed by Hersch143,
was later modified by Lukes 144 who applied it both acidic and alkaline
solutions. In acidic solutions, formation of the hydride ion was
described by the reaction:
In alkaline solutions, the formation of Lukes described by the

following reaction:
Two hydride ions from the above reactions can then react with
or one ion with either a hydrogen ion or water:
Acid solutions:
Alkaline solutions:
S. Djokic 91
In broad terms, the hydride ion mechanism can then be described

by the following general equations:
where RH is formaldehyde, hydrazine or hypophosphite as previously.

The proportion of hydrogen gas evolved that can be attributed to
hydrogen originally bonded to phosphorus in hypophosphite will vary
from 50 to 100 %. Lukes did not discuss the reactions and mechanism
by which phosphorus is included in the electroless Ni deposition by the
hypophosphite reduction. He suggested that phosphorus codeposition
should not materially affect the hydride generation and reduction
reactions.
From Lukes’ theory arises a question of the reality of a hydride ion
formation having a standard reduction potential of - 2.08 V in a
hypophosphite solution with standard potential of -1.57 V. 142 Both
potentials are reported for pH=0. The change-over from standard
conditions to those in which metals are reduced by hypophosphite does
not alter the difference between these potentials. On the other hand, the
existence of hydride ions in an alkaline medium, even in an
intermediate state, appears very unlikely.128
3. The Electrochemical Mechanism
The so-called electrochemical mechanism was first proposed by

Brenner and Riddell3,4 and later modified by other researchers.145-150 In
this mechanism, electroless deposition is considered to result from

mixed anodic and cathodic reactions. In the case of electroless Ni
deposition, the oxidation of hypophospliite with water generates
electrons, and is considered as the partial anodic process:
with
The electrons formed in the above reaction are utilized in the

coupled cathodic processes for deposition of Ni and P:
with and
with
According to the electrochemical mechanism, the evolution of

hydrogen gas is a result of the secondary reaction which follows:
with
The electrochemical mechanism does not explain reduction of

metal ions in the bulk solution (i.e. without the presence of a metallic
substrate). It also does not explain the reduction of metal hydroxides
(formed as precipitates) to a metallic state. As experimental results
show, the presence of any metallic surface is not a sufficient condition
S. Djokic 93
to start electroless deposition. It is very well known that electroless

deposition takes place only at catalytically active surfaces. Examples
include non-conductive Pd activated surfaces.
In terms of mixed potential theory, electroless deposition was first
described by Paunovic.145 According to this theory, electroless metal
deposition can be considered as the superposition of anodic and
cathodic curves crossing at the mixed potential, Electroless
deposition of metals takes place at the mixed potential. The mixed
potential, and the deposition current, are obtained by the
intersection of the partial anodic and cathodic polarization curves, as it
is schematically shown in Figure 11. This theory predicts that the rates
of anodic reactions do not depend on the cathodic processes occurring
simultaneously at the cathodic surface. The rates of separate reactions
(anodic and cathodic) depend only on the mixed potential at which they
have the same values.
For the case of electroless deposition of copper from an alkaline
solution of copper sulfate, containing EDTA as a complexing agent and
using formaldehyde as a reducing agent, Paunovic145 determined the
rate of Cu deposition in three different ways. Firstly, the rate of Cu
deposition was determined from the intersection of the polarization
curve for the oxidation of formaldehyde and polarization curve for the
reduction of at single electrodes. This value of was
which corresponds to the value of a mixed potential of 0.65 V
vs SCE. On the basis of Faraday's law and the mixed potential theory,
the rate equation for electroless copper deposition was written as:
Using the value for obtained for the single electrodes

(1.9 mA and the above equation, the rate of electroless copper
deposition was derived as
In the second experiment, the rate of electroless copper deposition
was determined from the extrapolated current density at the mixed
potential obtained from the cathodic polarization curve for the mixed
electrode. The value for was at the mixed potential of

-0.66 V vs SCE, and the consequent rate of Cu deposition was
Finally, the rate of electroless copper deposition was determined

gravimetrically, and had a value of The comparison of
these three values 2.2, 2.1, and showed that there was
very close agreement among the methods used in this work.
The application of the mixed potential theory to the electroless
deposition of Ni by hypophosphite can be described by the following
reactions. The oxidation of hypophosphite:
S. Djokic 95
is an anodic process, with the hypophosphite oxidation current,

designated here as The cathodic processes are related to the
deposition of Ni and P, and hydrogen evolution, as described by the
following reactions:
with the Ni deposition current
with the P deposition current and
with the H evolution current
At the mixed potential, the rate of reduction is equal to the

rate of oxidation, i.e.
Since the rate of reduction, is:
Using Faraday's law the rate of Ni deposition is:
The equation (83) is derived for the case of deposition of Ni (the

constant 1.09 is calculated from M(Ni)/zF for Ni only, and does not
take into account the deposition of P), although,
Furthermore, the same equation was used to describe electroless

deposition of Ni with DMAB but did not consider the deposition of
boron. 68
In order to propose mechanism of electroless deposition, van den
Meerakker151 investigated anodic oxidation of formaldehyde in alkaline
solutions. Based on the assumption that the anodic oxidation of
formaldehyde and the cathodic reduction of metal ions are independent
processes in electroless plating solutions, he investigated the effect of
electrode material, pH and potential. The experimental results were
explained by a mechanism in which methylene glycol anions
are dehydrogenated at the electrode surface, thereby
producing adsorbed hydrogen atoms. The adsorbed hydrogen can
either be oxidized to water or be desorbed as a gas. He reported that
electroless Cu, Pt and Pd solutions behave according to the same
mechanism.
By the applying the mixed potential theory it was suggested that the
mechanism can be predicted from the polarization curves for the partial
processes. However, the extrapolation of partial polarization curves
and application of the mixed potential theory is not often realized, since
the two partial processes are independent of each other.152
An application of the mixed potential theory153 led to the
development of a technique by which electroless process may be
classified according to their overall mechanisms.154
The overall mechanism of electroless Cu deposition was
determined by a technique based on the application of the mixed
potential theory to a rotating disc electrode. In this theory, the mixed
potential is considered to be a function of agitation, concentration of
the reducing agent and, concentration of metal ions. 154 Based on the
assumption that each partial reaction is either under electrochemical or
under mass-transfer control, Bindra and Roldan154 developed four
cases.
Case1. Cathodic partial reaction is diffusion-controlled and the
anodic partial reaction is electrochemically controlled. The equation
which describes this case is:
S. Djokic 97
where is the mixed potential, is the standard potential for

HCHO, is the Tafel slope for the anodic reaction, is the exchange
current density for HCHO oxidation, is diffusion parameter for
complex, is the rotation rate of electrode and is the
bulk concentration of ions. This equation shows that mixed
potential is a linear function of and ln The Tafel slope ,
may be obtained by plotting vs or vs ln
Case 2. Cathodic partial reaction is electrochemically controlled

and the anodic partial reaction is diffusion controlled. The equation
describing this case is:
where is the standard electrode potential for the Cu deposition

reaction, the Tafel slope for cathodic partial reaction, the
exchange current density for metal deposition, is the diffusion
parameter for HCHO and is the bulk concentration of HCHO.
Case 3. Both partial reactions are electrochemically controlled
Case 4. Both partial reactions are diffusion controlled
Cases 3 and 4 were not discussed by the authors; they explain that
in both cases mixed potential is independent of the rotation rate, and
that such cases are rarely encountered in electroless processes.
Measurements were performed in the complete electroless bath, as well
as in the catholyte and in the anolyte separately. The theory developed
by Bindra and Roldan154 was experimentally verified by a comparison
of mixed potentials for different rotation rates and concentrations.
As shown in Figures 12 and 13, there are linear relationships
between and and between and which is in
agreement with equations (84) and (85).
For the oxidation of formaldehyde in complete solution (with all
constituents), the polarization curve is illustrated in Figure 14. The
Tafel slope for formaldehyde oxidation obtained from Figure 14 has the
value +210 mV per decade at 70 °C. The large value of the Tafel slope
is attributed to the electrochemical oxidation of formaldehyde under
Temkin adsorption conditions. For electroless Cu deposition, they
showed that the formaldehyde partial reaction (oxidation) is
electrochemically-controlled, while the metal deposition partial
reaction is diffusion-controlled which is in an agreement with their
theoretically proposed model.
Mital et al.70 investigated the validity of mixed potential theory for
electroless Ni deposition. The results for Ni deposition with DMAB
show the predominance of an electrochemical mechanism. These
authors stated that the mixed potential theory is applicable only for
S. Djokic 99
systems where the reduction of metal ions and oxidation of the

reductant is electrochemically feasible at the mixed potential, perhaps
an obvious requirement.
According to Mital et al. 70, in the case with DMAB, reduction of
metal ions and oxidation of the reductant is electrochemically feasible
at the mixed potential. However, in the case of they reported
that a chemical mechanism predominates.
Although the results obtained for the electroless Cu deposition
showed strong agreement with the theoretical approach based on the
mixed potential theory68,131, there is no strong evidence that this theory
works for the case of electroless Ni deposition with hypophosphite (see
above discussion) . It is the opinion of this author that the mixed
potential theory works perhaps for the case when cathodic processes
are related only to the deposition of single metals (e.g. electroless Cu
deposition or electroless deposition of metals by hydrazine). The

mixed potential theory does not explain reduction of metal ions in bulk
solution. Also, when the cathodic processes represent a combination of
several reactions such as electroless Ni deposition with hypophosphite,
or electroless deposition of alloys, a simple combination of mixed
potential theory and Faraday's law does not work. To prove this,
however, further intensive experimental studies are required.
4. Metal Hydroxide Mechanism
The metal hydroxide mechanism was originally proposed by

Salvago and Cavallotti. 27,32 For the example of electroless Ni
S. Djokic 101
deposition with hypophosphite, they proposed a mechanism based on

experimental observation. Electroless deposition of Ni is possible in
both acidic and alkaline solutions. In the acidic solutions, the reaction
is experimentally significant only at pH>3, and its rate increases
sharply with pH. The process occurs in a pH range where hydrolysis
phenomena are involved. Hydrolyzed species of Ni ions can also react
directly with hypophosphite. The metal hydroxide mechanism
proposed by Salvago and Cavallotti27,32 can be described briefly by the
following scheme.
At the catalytic Ni surface, the ionization of water takes place
according to the reaction:
Hydrolysis of and formation of hydroxo-complexes takes place

as follows:
and
The hypophosphite ions interact directly with hydrolyzed species,

as is indicated below:
Deposition of phosphorus was explained in terms of the reaction:
This reaction also explains non-homogenous distribution of P and

lamellar morphology of deposits. The hydrolyzed Ni(I) species
interact directly with water:
Evolution of hydrogen can be explained as:
or by the reaction of hypophosphite ions with water:
According to the reactions (91) and (92) Savago and Cavallotti27,32

explained lamellar morphology of electroless NiP deposits. It is
obvious that any periodicity between the reactions (91) and (92) will
produce deposits having layers richer with P, and then layers richer
with Ni (lamellar morphology). Cavallotti and Savago reported that
when nickel hydroxide is precipitated, inhibition phenomena are
evident.
The results of calorimetric studies of electroless deposition of Ni,
obtained by Randin and Hintermann155, supported the mechanism
proposed by Cavallotti and Savago.27,32 The molar ratio
] in the overall reaction for electroless nickel deposition is 0.25,
according to the following equation:
S. Djokic 103
supported the metal hydroxide mechanism for electroless

deposition of Co, using hydrazine as the reducing agent. 105 In this
work, electroless deposition of Co powders is explained by the metal
hydroxide mechanism, according to the following reactions:
or
Finally, the overall reaction for electroless Co deposition with

hydrazine is represented by the following equation:
The observations in this work105 support the metal hydroxide

mechanism as a means of explaining the electroless deposition of Co by
hydrazine. Hydrolyzed species of can react directly with
hydrazine producing metal powder. The reaction occurs in bulk
electrolyte, when a precipitate of cobalt hydroxide is formed and
production of Co powder takes place. The SEM micrographs show
that the Co powder produced under these conditions was dendritic in
terms of surface morphology (Figure 15).
XRD patterns in Figure 16 show that the Co powder contained the

70 % Co having the hcp structure and 30 % Co the fcc. Co powder of
similar morphology and structure can also be obtained by an electroless
reduction of alkaline Co(III) solutions.143
Although the metal hydroxide mechanism explains most of the
characteristics of electroless Co deposition by hydarzine, particularly
the reduction of precipitated cobalt hydroxides and deposition of
dendritic Co powder, there are still some doubts about this mechanism.
For example, it does not explain the oxidation of at a Pd-activated
surface in Co(II)-free solutions. In order to explain deposition of shiny
105
and smooth coatings at flat surafces, suggested that
contributions from both the electrochemical and the metal hydroxide
mechanisms should be considered.
S. Djokic 105
5. The Universal Mechanism
Based on similarities among electroless processes, van den

Meeraker proposed a mechanism that accounts for both the
electrochemical and the catalytic nature of the process.157 This
mechanism was developed according to the following features which
are common to different electroless systems:
(a) The electroless deposition process proceeds only on certain
catalytic metals that are known as effective hydrogenation-
dehydrogenation catalysts;
(b) Electroless deposition is always accompanied by evolution of
hydrogen gas;
(c) Poisons for hydrogenation-dehydrogenation reactions, such as

thiourea and mercaptobenzothiazole, act as stabilizers in practically all
electroless processes; and
(d) The deposition rate increases with an increase in pH.
The reactions taking place during electroless deposition were

described as follows:
Anodic:
Dehydrogenation: RH = R + H
Oxidation:
Recombination:
Oxidation:
Cathodic:
Metal Deposition:
Hydrogen Evolution:
In this scheme, RH represents the reducing agent. It dissociates to a

radical R and atomic hydrogen. The electrons for reduction of metal
ions are supplied by the oxidation of R and/or reaction of H with
The universal mechanism is not adequate for the explanation of all
electroless processes. It fails to explain electroless deposition of metals
on non-conductive surfaces, and also deposition of metal particles in
solution.
In spite of intensive studies on mechanistic aspects, it is obvious
that there is still not enough experimental data to confirm proposed
theoretical approaches for electroless deposition of metals and/or
alloys.
The proposed mechanisms explain most of the characteristics of
electroless deposition. However, as discussed above, there are some
characteristics which cannot be explained using these mechanisms. It
seems that major problems arise when attempting to generalize the
proposed models for electroless deposition. A more realistic approach
would be to look for specific reactions, for particular conditions and
S. Djokic 107
substrates. It is very unlikely, in spite of the similarities of electroless

processes, that a general mechanism will be developed explaining
features for all electroless deposition of metals. Nevertheless, this
literature review suggests that intensive experimental studies are
required in order to develop and/or prove existing models for
electroless deposition of metals.
VII. RECENT DEVELOPMENTS
Development of electroless deposition of metals and alloys in the

past years has been remarkable and still continues. This process was
investigated for various applications such as magnetic disks158-159,
printed circuits160-165, selective plating and semiconductors166-174,
batteries175-177, medical devices178, etc. Most of these applications are
related to electroless deposition of copper or nickel. It is beyond the
scope of this section to review all published literature related to the
topic of electroless deposition. However, a few important points
related to new developments and basic research will be presented here.
Considering the fact that many of these applications use similar
approaches and in a way overlap, the further discussion in this section
is presented as follows:
1. metallization of non-conductive surfaces

2. electroless deposition of composite coatings
3. electroless deposition of gold and other metals
4. new developments and basic research
1. Metallization of Non-Conductive Surfaces
Metallization of non-conductive surfaces (polymers, ceramics and

glass) requires specific treatments prior to electroless plating. Usually,
these surfaces are first etched, then sensitized by a simple immersion in
an solution. During the sensitization process, the adsorption
of ions takes place. Senzitized surfaces are then exposed to a
solution containing and HCl. This process is called activation.

The activation process can be described by the following equation:
The Pd sites formed during the activation step allow chemical

deposition of Ni or Cu. In some cases, sensitization and activation
steps are combined in one step. In other words, solutions for the
sensitization and activation are combined and represent mixtures of
and HCl.
Other processes recommended for the activation of non-conductive
surfaces for metal deposition from aqueous solutions (electroless
deposition or electrodeposition) are carbon/graphite systems,
conductive polymers, and non-formaldehyde based electroless
processes. For details on these processes, the reader is referred to Ref.
[179] and references therein.
The metallization of alumina surfaces with electroless NiP is used in
the electronics industry for printed circuits and sensors applications;
however, on metallized alumina substrates, failure is often observed at
the metal-ceramic interface. In order to increase adhesion of the
metallic layer to the ceramic substrate, several approaches are found in
the literature. In one example180, alumina substrates were cleaned with
a surfactant (amino perfluoroalkylsulfonic acid), etched with HF,
sensitized with solution and activated first with
then with solutions. Metallization of pre-treated alumina
substrates was carried out using an acidic, chloride-based solution. The
thin NiP films on alumina substrates exhibited a columnar structure.
This layer plays a crucial role in adhesion for all cases where interfacial
failure is observed. The same authors181 recommended a very different
approach to solve adhesion-related problems. On clean alumina
substrates, a thin layer of Ti (about 20 run) was deposited by vacuum
deposition. A thin Pd film of approximately the same thickness (20
nm) was then deposited on the Ti layer, also by vacuum deposition. On
these surfaces, NiP was deposited by electroless deposition; a
thick layer of Ni was then electrodeposited from a sulfamate solution.
S. Djokic 109
The resulting very strong adhesion was attributed to chemical binding

of the first Ti monolayer with the substrate oxygen atoms.
For the metallization of piezoelectric ceramic surfaces, based on
lead titanium zirconate, electroless deposition of NiP182 or Cu183 was
recommended. Surfaces were senzitized with and activated with
in the standard way.
Electroless deposition of palladium on a ceramic substrate
consisting of 70 % 29 % and 1% was carried out
from a solution containing EDTA, and hydrazine as
the reducing agent. 184 Prior to the electroless deposition of Pd, the
ceramic substrate was sensitized and activated with and
acidic solutions.
For applications where metallization of advanced devices on
titanium silicide substrates takes place, Cu is deposited by a low
pressure CVD from copper (II) hexafluoroacetylacetonate. 185 The
substrates with Cu films were then ready for further metallization.
Graphite samples were sensitized and activated with and
and plated with Cu or Ni using formaldehyde or hypophosphite
as reducing agents, respectively. l86 A complete coverage of graphite
was not observed and this result was attributed to the porosity of the
graphite material. However, when electroless plating of Cu followed
by electroless plating of Ni was applied, the surface became completely
covered.
An interesting approach for the pre-treatment of non-conductive
surfaces prior to electroless plating was recommended by Calvert et al.
187-191
This process is based on the application of tin-free, aqueous
Pd(II) catalyst in conjunction with chemisorbed ligating organosilane
films. Typical ligating systems include organosilane precursors
containing pyridine, alkylamine and arylphosphine ligands. Most
substrates of technological importance, such as silicon, metals, metal
oxides, ceramics, plastics, polymers and diamonds, are suitable for
silane attachment (adsorption). 190,191 A self-assembled monolayer is
used as a ligating surface to bind a Pd(II) catalyst. The Pd(II) catalyst
can covalently bind to ligands containing nitrogen, sulphur and
phosphorous atoms. The Sn-free, Pd catalyst is made by dissolving
11.4 mg of sodium tetrachlorpalladate in 1 mL of 1M NaCl. To this
mixture MES (2-morpholinethane sulfonic acid) buffer (0.1M, 10 mL)

at pH 5 is added, followed by dilution with water up to 100 mL. The
solution is left at 22-23 °C for about 20 hours. Under these conditions,
the polymerization takes place, and Pd-oligomers are formed. Silicon
substrates are first immersed in 1:1 solution for 30
minutes, followed by a rinse in water and immersion in
for 30 min. After rinsing, the substrates are immersed in boiling water
for 10 minutes, dried with and then transferred into 1 %
organosilane solution. The organosilane compounds used in this work
were 2-(trimethoxysilyl)ethyl-2-pyridine, N-(2-aminoethyl)-3-amino-
propyltrimethoxy silane, and (aminoethylaminomethyl)-
phenethyltrimethoxy silane.
Silicon samples are immersed in organosilane solutions for 1 hour
at room temperature. Substrates are then removed from solutions and
baked on a hot plate for 3 to 4 minutes at 120 °C. A 20 % catalyst
coverage is attained when substrates with organosilane films are
immersed for 10 min in the Pd catalyst solution. 192 For treatment
times over 2 hours, 100 % coverage is observed. On activated
substrates, the NiB alloy is electrolessly deposited from a commercial
solution. Metallized surfaces exhibited broad particle size distribution
with the maximum Ni particle size exceeding 120 nm.
A similar approach for the activation of surfaces with Pd(II)
catalyst dispersion solution with HC1, hydrolyzed at pH 7) for
electroless Ni deposition in nanolithography applications is
recommended by Brandow et al. 193 The metallization of catalyzed
surfaces with Ni led to the deposition of Ni particles with an average
size of 21 ± 5 nm.
The first stages of platinum electroless deposition on Si substrates
were investigated using atomic force microscopy. 194 Silicon substrates
are etched in 40 % HF solution. To this solution, is
added to yield a 1.0 mM concentration of Pt(IV) in solution. During
the immersion of silicon in an aqueous HF solution containing Pt(IV),
platinum is nucleated at the surface, while the silicon is etched.
Deposited nuclei are polycrystalline and highly pure. The process is
represented by the following reaction:
S. Djokic 111
The etching of silicon with HF solution containing ions is a

galvanic displacement process composed of two reactions:
cathodic
with
and anodic
with
A similar process for electroless deposition of Pd onto Si substrates

has also been published.195 This process, based on a
solution, is represented by the following reaction:
Metallization of aluminum nitride ceramics is necessary for

applications in the electronics industries. Prior to electroless deposition
of copper, A1N substrates are etched with a 4 % NaOH solution. 196
The etching process is described by:
A1N substrates are sensitized and activated with and

respectively, then metallized with electroless copper from an alkaline
solution using formaldehyde as a reducing agent. Adhesion of Cu to a
substrate increases as the etching time is increased.
et al. 197 reported a procedure for metallization of ceramic

substrates, including AIN. After proper substrate preparation, they
recommended direct electroless NiP deposition onto A1N substrates.
Cu was electrodeposited up to a thickness of onto these
substrates. Adhesion of the Cu layer plated onto A1N substrates was
very good.
The activation of diamond surfaces for electroless metal plating (Cu
and Ni) is achieved by laser-induced modification of the film surface
during ablative etching. 198 Encapsulation of the electroless copper
lines into diamond films is obtained.
Metallization of polymers and plastics has also attracted significant
attention from researchers because of its various industrial applications.
Different pre-treatment steps before metallization of polymeric
substrates were disclosed. Polymers of interest included polyimides199-
203
, polystyrene204,205, olycarbonates205-207, polyetherimides208, ABS
plastics206,209, aramid fibres210,211, A-PPE (allylated poly-2,6-dimethyl-
1,4-phenileneether) resin212, fluoropolymers213 etc.
Two different ways of activation of polyimide resins for the
electroless plating will now be discussed. According to patents granted
to IBM201 and Monsanto Company202, a precursor polyamic acid film is
deposited at the surface. The film of polyamic acid is exposed to a
solution containing Pd(II) ions then heat treated to imidize the polymer.
Samples with Pd seeds are used for electroless deposition. This
procedure is further recommended as a pre-treatment step for
electroless deposition on substrates such as metals, ceramics, glass,
silicon, high heat polymers, and thermoset polymers.
Direct metallization of polyimide resins is proposed according to
the following procedure.199 Polyimide resin substrates are immersed in
fuming sulfuric acid at 25 °C for 15 to 30 seconds. The sulfonated test
samples are then dipped in solution for 3 minutes to
adsorb ions. After a careful water rinse, the samples are exposed
to solution to reduce ions and form a thin
copper film. The thickness of the thin Cu film formed after the
reduction process is recommended for the metallization ofA-PPE resin.
212
S. Djokic 113
Prior to metallization, polycarbonate and polystyrene polymers are

treated with and plasma. 205 After treatment with
plasma the amount of oxygen significantly increases, while treatments
with or plasma increases the amount of nitrogen. When the
surface of polymers contains nitrogenated and oxygenated groups, it
can chemisorb palladium directly. However, when the surface of
polymers contains only oxygenated groups it chemisorbs palladium
only through previously chemisorbed stannous ions. This sequence is
used for direct or treatments, in order to eliminate the use of
This process is recommended not only for polycarbonates and
polystyrene, but for any other polymers, including fluorinated ones.
2. Electroless Deposition of Composite Coatings
Codeposition of solid, inert particulates within a metal matrix

during electroless deposition of that metal matrix (single metal or alloy)
leads to production of composite coatings. In typical composite
coatings, the fine particulates' diameter size ranges from 0.1 to
20
Their content in the coating can exceed up to 40 vol.%. The metal
matrix in this class of composite coatings is usually electroless NiP or
NiB. These materials are used for the improvement of wear and
corrosion resistances, friction coefficient and hardness. Inert
particulates, depending on applications, may include chromium
carbide, alumina, titanium carbide, silicon carbide, boron carbide,
diamonds, PTFE etc.
There is renewed interest in coatings with exceptional hardness,
wear and friction properties for automotive and other mechanical
applications.214 High performance coatings include alloys of cobalt and
tungsten, composites with fluoropolymers etc. These coatings have
potential for replacement of hard chromium.
Composite NiPSiC coatings are obtained by electroless deposition
of NiP alloy from a solution containing dispersed SiC particles (1 to
215
Such particles can be homogenously incorporated into a
deposit through a proper agitation of the plating solution. The amount
of SiC incorporated into the deposit is estimated to be about 30 vol. %.
During the heat treatment of electroless deposited NiPSiC coatings at

650 °C for 1 hour, a new phase of is identified by structural
analysis. Electroless deposition of NiB matrix composite coating,
containing Al/SiC particles, is also reported.216 These composites have
very good adhesion after treatment at temperatures above 400 °C.
The inclusion of fluoropolymeric materials in nickel-based coatings
requires the addition of surfactants which block the aggregation of the
particles and provide conditions for their incorporation in the coating.
217
The influence of the nature of different surfactants in electroless
deposition of NiP-PTFE composite coatings is reported by Nishira and
Osamu.218 They found that anion-active and cation-active surfactants
have no effect on the formation of composite coatings. If a solution for
electroless NiP deposition contains only non-ionic surfactants,
incorporation of PTEF into deposit is not observed. Uniform coatings
are obtained when combined cation-active and non-ionic surfactant are
added to the solution.
The relationship between the Zeta potential and codeposition of
PTFE particles suspended in electroless Ni solution was investigated by
Hu et al. 219. Their results showed that PTFE particles, with more
positive potential, codeposit more easily with NiP. Consequently, their
content in coatings is greater. These composite coatings contain about
25 vol. % of PTFE.
Commercial acceptance of composite coatings has increased in a
number of applications, especially since productivity, quality and
environmental concerns continue to expand at increasing rates. 220
3. Electroless Deposition of Gold
Electroless deposition of Au is used for applications in the

electronics industries (deposition on semiconductors and circuit
patterns), as well as for decorative purposes. Solutions for electroless
deposition and properties of deposited Au films were reviewed
recently. 221
The classical electroless Au solutions utilize as a source
of Au and or DMAB as reducing agents. These solutions are
S. Djokic 115
autocatalytic, and it is possible to deposit sufficiently thick layers of

gold.
In order to replace cyanide-based solutions, two different systems
for electroless deposition of Au were developed in recent years. Both
use gold thiosulfate as their source of gold. The main difference is the
reducing agent. The first system uses thiourea, while the second uses
ascorbic acid. Typical baths for electroless Au deposition contains
120
The electroless
deposition is carried out at 60 °C at pH 6, using ascorbic acid as the
reducing agent. In the presence of thiosulfate and sulfite, Au(III) from
is reduced to Au(I), according to the reactions below:
and
According to the results from polarization curves, Au(I) is reduced

to the metallic state from the thiosulfate complex. If the plating
solution contains sulfite alone Au can still be deposited; however, the
deposition rate is very slow.
In a search for a reducing agent Koto et al. 120 found that the
reducing power of boron-containing compounds DMAB and
tributhylamine borane) is so strong that the solution decomposed
immediately upon the addition of these compounds at near-neutral pH.
The reducing power of other agents decreases in the following order:
ascorbate>thiourea>hydrazine. Hydroxylamine and formaldehyde are
not effective as reducing agents in the system investigated.
Deposition of Au using ascorbate as the reducing agent, is
explained as
the combination of an anodic reaction (oxidation of ascorbic acid):
coupled with the cathodic reaction (reduction of Au(I) to Au):
The effect of ascorbate concentration on the rate of Au deposition is

shown in Figure 17.
In deposition of Au with thiourea as the reducing agent, the anodic
reaction is:
while the cathodic reaction is described by equation (113).

Heterocyclic mercapto compounds, especially 2-mercapto-benzo-
thiazole (MBT), stabilize the solution and do not significantly influence
the rate of deposition. Sullivan and Kohl222 investigated the
autocatalytic deposition of Au from thiosulfate solution using sodium
L-ascorbate as the reducing agent (at pH 6.4 and 30 °C). They found
that ascorbic acid reduces gold thiosulfate at a deposition rate of
approximately The rate of deposition decreases with time
which was attributed to the accumulation of thiosulfate in the reacting
solution.
The activity of the bath and the deposition rate are partially restored by
adding to the reacting solution. decomposes thiosulfate to
trithionate and sulfate. In this way, the accumulation of thiosulfate is
slowed, and the rate of deposition is restored.
Other developments include improvements of non-cyanide
solutions (gold(I) thiosulfate with ascorbic acid as a reducing agent) for
the electroless deposition of gold, which prevents the formation of any
precipitates during the storage of the bath223, and solutions with
chelating agents, such as diethylenetetraaminepentaacetic acid224,
dimethylamine225, etc.
S. Djokic 117
4. Electroless Deposition of Other Metals
Among other metals, studied from the aspect of electroless

deposition, should be mentioned Ag226-230, Sn231-234, Sb-Pb235-237, Bi 8 ,
Sn-Bi solder238,239, Pd240, Ni-Sn-P alloys241, etc.
Molenaar reported that the autocatalytic Sn deposition is possible
by a disproportionation reaction of tin(II) ions in alkaline solutions.231
An increase in the mass of an autocatalytic Sn layer on a Cu substrate,
as a function of plating time, is observed when the deposition is carried
out from a solution containing 3.85 M NaOH,
and t =75 °C (Figure 18).
The deposition reactions were described as follows:
(a) displacement reaction:
(b) reduction of tin(II) by hypophosphite:
(c) disproportionation of tin (II) ions:

S. Djokic 119
(i)
(ii)
(iii)
Concentrations of tin (II) and hypophosphite determine the plating rate.

In the later work232, Molenaar reported that the autocatalytic
deposition of Sn can be carried out through a disproportionation
reaction in alkaline solutions without hypophosphite. The thickness of
deposited tin layer as a function of time, when the deposition is carried
out from the solution containing 2.5 M NaOH,
at 75 °C is presented in Figure 19. They suggested that
other metal derivatives such as Pb(II), Pt(II), Pd(II), Hg(I), Cu(I), In(I),
T1(I) and Au(I) will give this type of disproportionation reaction.
It is first reported by Rutkevich et al., that Bi can be reduced by
Ti(III) complexes in an autocatalytic mode.8 The main characteristics
of the process are explained in terms of pure electrochemical
mechanism. The reduction of Bi(III) to Bi is represented as:
The authors also claimed a possibility of using Ti(III) complexes to

reduce Ni(II) and Co(II), as well as application of V(III) for
autocatalytic Cu(II) reduction.
NiSnP and NiSnB alloys are deposited from alkaline solutions
containing as a complexing agent, using sodium
hypophosphite and DMAB as reducing agents, respectively. 241 For

electroless deposition of NiSnP a source of Sn is and for
NiSnB, a source of Sn is Sn(IV) gluconate.
The maximum contents of Sn in the deposit are estimated at 30 at.%

for NiSnP and 42 at.% for NiSnB alloys. The crystallinity of alloys
increases as the Sn content increases.
S. Djokic 121
5. New Developments and Basic Research
Several publications related to new developments and basic

research in the field of electroless deposition will be discussed here.
Hatsukawa et al. 242 reported that during electroless deposition of
NiP films, carbon can be codeposited only if the solution contains
complexing agents having or =NH groups (e.g.
diethylenetriamine or -alanine). Carbon cannot be incorporated, if the
solution contains only -COOH or other carbon-containing groups. The
deposition of carbon is explained by the adsorption of or =NH
groups, followed by incorporation of carbon from the main chain of the
compound via codeposition with nickel. Deposited NiPC films contain
about 3 atom. % of C when electroless deposition is carried out from
solutions containing diethylenetriamine or at pH 6 (90 °C).243
These films exhibit very high resistivity. Heat treatment of NiPC films
leads to crystallization of as-deposited amorphous alloys.
Crystallization occurs at temperatures higher than the crystallization of
pure NiP alloys.
For electroless deposition of Cu, the glyoxilic acid is used as an
alternative reducing agent of ions. 244 Electroless deposition is
carried out from a solution containing 0.24 M
EDTA, 0.2 M lactic acid, at 60 °C and pH 12.5 (adjusted with NaOH).
The solution also contains 10 ppm of 2, The reaction for
deposition of Cu is described as:
with a standard redox potential of 1.01 V for the reaction:
The deposition rate and solution stability are superior to that of

commonly used formaldehyde solutions. The rate of deposition
increased with an increase in temperature, pH, concentrations of

and reducing agent (Figure 20). The use of KOH for pH adjustment,
instead of NaOH, significantly suppressed the reaction.
A low-temperature electroless deposition of Ni from an alkaline
solution is recommended by Chen. 245 A decrease in plating
temperature was attributed to the addition of sodium tungstate to the
plating solution. The composition of deposited films was not reported.
It seems, according to this work, that the authors deposited NiWP alloy,
rather than NiP.
A process for electroless deposition of metals and alloys on large
parts is disclosed. 246 This process is based on sequences of
simultaneous spraying of two aqueous solutions; one containing the
reducing agent and the second containing metallic ions. The authors
claimed the process can be carried out at room temperature, because the
electron exchange reactions can occur in a very thin aqueous layer at
the surface. Metals that can be deposited by this method are classified
in four groups: a) pure metals (Ni,Co, Cu), b) binary alloys (NiB,
CoB), c) ternary alloys (CuCoB, CuNiB and NiCoB) and d) quaternary
alloys such as CuNiCoB.
There are several other publications related to mechanistic aspects
of electroless deposition. 247-250
Mishra and Paramguru247 investigated mechanisms of electroless
deposition of copper from an alkaline solution containing tartrate and
using formaldehyde as a reducing agent. In this study, they used
potentiostatic and galvanostatic curves, as well as steady-state plots.
They found that the mechanism of electroless Cu deposition changes
from anodic to cathodic control, as well as from diffusion to activation,
depending on the concentration of and HCHO in this solutions.
Based on the morphological evolution via AFM for the electroless
deposition of Co with hypophosphite as the reducing agent on highly
activated pyrolytic graphite, Hwuang and Lin248 concluded that this
process follows the electrochemical mechanism.
Electroless deposition of NiP alloys is described by a mathematical
model which is based on steady-state convective diffusion equations
with non-linear boundary conditions and overpotential equations. 249
The results are explained in terms of the mixed potential theory. On
S. Djokic 123
the other hand, Abrantes and Correia250 found that the mixed potential
theory is unable to describe the electroless deposition of NiP alloys.
They investigated the initial stages of electroless deposition of NiP

alloys from a chloride solution by means of potentiodynamic and open-
circuit potential measurements. The authors assumed that the process
was initiated by adsorption of hypophosphite at the surface and the
homolysis of its hydrogen bond with formation of radicals. These
radicals promote and hypophosphite reduction in order to form the
NiP deposits.
It is obvious, according to these papers that there is still
disagreement among researchers on the mechanistic aspects of
electroless deposition. To fully understand the process of electroless

deposition, further investigations are required.
Several patents in the field of electroless deposition have appeared
recently. They are related to electroless deposition of Pd251, activating
solution based on a mixture of zinc lactate, copper lactate and
palladium chloride in alkaline medium252, Cu or Ag plating on textile
for electronics and biomedical applications253, and a method for
depositing NiP alloys254.
VIII. CONCLUSIONS
In spite of development of other competitive technologies, it is

obvious that applications of electroless deposition of metals and alloys
will continue to grow in the future. Applications of electroless
deposition of metals and alloys are related to developments in the
electronics industries, battery technologies, medical devices, and
protective and decorative coatings. According to literature review,
more work is required to understand fundamental issues related to the
reaction mechanisms of electroless deposition, the influence of
processing parameters on properties of deposited coatings, etc. This
knowledge is needed to ensure the successful operation of the process.
The new electroless deposition-based technologies should improve
selectivity, satisfy quality requirements of deposited coatings, and
assure the consistency of the process. The environmental concerns
related to the solutions used for electroless deposition must also be
investigated, in order to develop environmentally-friendly technologies,
and to allow successful competition with other available processes.
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2

Electroless Deposition of Metals and Alloys

Electroless deposition of metals and alloys has a very significant

Modern Aspects of Electrochemistry, Number 35, Edited by B.E. Conway

explain the mechanisms and kinetics of electroless deposition;

II. ELECTROLESSLY DEPOSITABLE METALS

The first scientific description of electroless deposition processes

and Sb9 have been deposited by In10 by and Pt11, Ru12

III. BASIC DEFINITIONS, SIMILARITIES AND

Displacement deposition is a heterogenous galvanic process in

and involves the displacement half-reaction of a more active metal

by a more noble metal,

Typical cementation systems in practice are Ag/Zn, Ag/Cu, Cu/Zn,

Contact deposition is equivalent to electrochemical deposition with

Autocatalytic deposition is the most commonly used chemical

Although the term electroless deposition broadly describes all

IV. SOLUTIONS FOR ELECTROLESS DEPOSITION

All solutions for electroless metal deposition have many similarities,

differences. Typically, the constituents of a solution for electroless

1. Source(s) of metal ions

1. The Metal Ion Sources

Table 2 presents sources of metal ions in electroless deposition of

The majority of complexing agents used in electroless metal

electroless deposition of Cu, Au, Ag, Pd and in some cases Ni,

Choice of reducing agent depends on conditions of electroless

formaldehyde. Individual reducing agents, used for electroless

Hypophosphite is mainly used for the electroless deposition of Ni,

At the formed Ni layer, further reduction of with hypophosphite

Similar reactions are applicable for Co or Pd deposition with

of the hypophosphite anion, which occurs on the catalytic surface of the

Chassaing et al. reported that an increase in hypophosphite

There are several solution formulations for electroless Pd

(ii) Boron-containing reducing agents

Boron-containing reducing agents used in electroless Ni deposition

The electroless deposition of Ni with borohydride takes place in

However, experimental results show that one mole of borohydride

Gorbunova et al. investigated the conditions for electroless nickel-

Since the utilization efficiency of borohydride in electroless Au

The maximum rate of Au deposition with borohydride is obtained with

on the gold surface. An increase in concentration

If is formed because of hydrolysis, according to a

Using borohydride as the reducing agent, gold-based alloys such as

Whereas borohydrides such as are completely ionic, the

In practice, the application of aminoboranes is limited to

The acid-catalyzed hydrolysis of dimethylamine borane occurs

this way, a significant amount of DMAB is wasted by the hydrolysis,

The boron reduction can be represented by the following reaction:71

Based on the experimental results, in the electroless nickel

DMAB concentration of about A further increase in DMAB

Formaldehyde is mainly used for electroless copper and silver

Dumesic et al. studied electroless copper deposition from an

On the other hand, the final rate of copper deposition, according to

CDTA. The addition of a second complexing agent to the solution that

Electroless Ag deposition with formaldehyde is fast, but either a

deposition with formaldehyde can be described by the following

Hydrazine has long been recognized as a very powerful reductant of

(E° =1.16 V, alkaline conditions)

(E° =0.23 V, acidic conditions).

The above reaction does not explain a decrease in pH21

The rate of electroless deposition of Co with hydrazine, increases

Similarly to other reducing agents, increasing hydrazine

The continuous, substrate-catalyzed deposition was described by

Finally, the overall autocatalytic reaction for gold deposition is