CHAPTER 3

Electrolytes for the Deposition of Metal Coatings

Introduction Electrodeposition Electrolytes 3.2.1 Electroplating Electrolytes 3.2.2 Electroless Deposition Electrolytes References 3.1 3.2

56

Electroplating- Basic Principles, Processes and Practice

3.1 Introduction
Aqueous electrolytes, used in metal finishing for electrodeposition of metal coatings, are principally solutions of metal salts, which, in solution, dissociate to form electrically charged anions and cations. These ions can be simple metal cations, Me z positively charged complex ions or hydrogen ions, H Also present will be ionised acid species, negatively charged complexes or hydroxyl anions, OH-. Figure 3.1, which shows by way of illustration, the copper-sulfate ion system, also makes clear that the charged ions themselves are surround by an outer sheath of water molecules, held by electrostatic forces to the ions themselves. The orientation of these water molecules is seen to differ according to whether they surround a positively or a negatively charged ion. The reason for this lies in the dipole nature of water molecules. The same is also true for complex ions which, in comparison to simple ions, have a more complex structure. The reason for this is that complex species are higher-order compounds, built up from first-order species. In many of their properties, they differ markedly from the simple compounds of which they are formed. The build-up of a complex can be described as follows. Around a central ion, in many cases, a heavy metal, are spatially arranged other ions or uncharged molecules (Fig. 3.2). These are often referred to as ligands. The central ion can coordinate, in this way, a greater number of outer ions or radicals than its normal valency would imply. This being the case, the conventional, simple means of formulating a chemical compound is no longer adequate. The bonding between the central ion and the ligands is predominantly electrostatic or also non-polar bonding. The number of ligands is expressed as the so-called coordination number. There is no correlation between the valence number of the central ion and the coordination number, which is often 4, 6 or 8 in value. The reason for this lies in rules, which are an expression of steric ordering. Figure 3.3 shows the three most commonly found spatial configurations. Since the ligand species are usually larger than the central ion, the latter is more or less completely shielded, with the result that its chemical properties are usually extensively modified.

Figure 3.1 Formation of hydration sheaths around a positively and a negatively charged ion, as illustrated by copper (cation) and sulfate (anion).

Electrolytes for the Deposition of Metal Coatings

57

Figure 3.2 Schematic arrangement of a complex. ZA m+ is the central ion, L- the ligands (m, n are the charge numbers, k can be positive, negative or uncharged) [1].

I I

, I

,"/

",,
. \ \\

l/

II I

XX
__,

\\
.... i" I

------ T . . . . .

I
, ,

," c~--.
1/11"~j~.~ 111 I

',x

"
I

'
II I

'
II I I
l

,,

',

I /,'
iI

"',',I/,,'
Four-coordinate Six-coordinate Eight-coordinate

Figure 3.3 The most commonly found coordination structures of metal complexes ( 0 = central ion, C) = ligands) [2].

Many electrolytes used in Metal Finishing are based on complexes. A typical example would be potassium hexacyanoferrate(II), in which six CN ligands surround a central iron ion. The species dissociates as shown below:
CN CN K4[Fe(CN)6] > 4K + + CN Fe C CN 4-

(3.1)

CN In addition to ligands which possess only one coordination site used in complex formation, there are other species with more than one coordination points allowing them to envelop the central ion. Complexes formed on this basis are known as 'chelated' and the ligands are known as 'chelating species' or 'chelants' (from the Latin, crab's pincers). Examples of these include ethylenediamine tetraacetic acid (EDTA) and ethylenediaminetetra-2-hydroxpropane (quadrol), with chemical formulae {(HOOC-CH2)2N-CH2-CH2-N(CH2-COOH)2 }

58

Electroplating- Basic Principles, Processes and Practice

or {CH3CH(OH)CH2)2-N-CH2-CH2-N(CH2CH(OH)CH3)2}. The structural formulae of these are shown below:

HOOC-H2C HOOC-H2C

CH2-COOH -CH2-CH2-N ~

~N

CH2-COOH

EDTA OH H3C-CH-CH2 H3C_CH CH2''~/N-CH2-CH2-N I

-

OH H2C-CH-CH3

CH2-(~H-CH3
OH

OH Quadrol

Using EDTA as example, it is seen that the two nitrogen atoms bond at two coordination sites, the four oxygen atoms of the acetate grouping bond at four coordination sites [3, 30].

3.2 Electrodeposition Electrolytes

The electrodeposition of metal coatings in industrial metal finishing is usually based on aqueous electrolytes, known in the industry as electrodeposition baths or simply, baths. Their primary constituent is the metal salt of the metal to be deposited, then in most cases an acid or alkali to promote conduction. In some cases the bath is buffered. In addition, there will be additives to promote the electrodeposition process or optimise the deposit properties. The metal deposition is brought about either by current flow from an external power source, or by addition of a strong reducing agent, which sets up a coupled anodic and cathodic reaction. Depending on which of these is the case, the terms 'electrodeposition' or 'electroplating' or 'electroless deposition' are used (see Chapter 4). The term 'plating' usually refers to electroplating, but retains a degree of ambiguity.

3.2.1 Electroplating Electrolytes

Over the last few decades, hundreds of different plating baths have been developed to allow or optimise the deposition of metals or alloys. A useful means of characterising such baths is in terms of their operating pH. In terms of this, one has acid, neutral and alkaline baths, where the pH values are usually < 3,= 7 and >9, respectively. In the following, examples of each of these three are detailed. In all three cases, it is vital to avoid significant pH changes during the electrodeposition process. For this reason, all plating electrolytes have added acid, alkali or buffers.

Electrolytes for the Deposition of Metal Coatings 59 3.2.1.1 Acid electrolytes

Acid electrolytes are usually based on simple metal salts such as sulfates or chlorides, less commonly are phosphates or sulfamates encountered. Also present is a high concentration of the parent acid, partly to optimise electrical conductivity, partly to minimise pH changes. The metal salts will dissociate as usual, into their constituent anions and cations. A typical example is the so-called 'acid copper' [4] typically constitutes as: 150-250 g/1 copper(II) sulfate pentahydrate CuSO4"5H20 30-75 g/1 sulfuric acid (d = 1.84 g/cm 3) 30-150 mg/1 chloride (C1- ion) The copper salt is the source of the metal ions. From a copper sulfate solution alone, copper deposits will be mossy, coarse-crystalline and brittle. Only after the parent acid is added will a compact, fine-grained and ductile deposit be formed. In addition, by increasing electrolyte conductivity, the process can be carried out at a lower voltage, reflecting a smaller ohmic drop in solution. To this acidified sulfate solution, brightening additives are usually added (see Section 3.2.1.4.1), whose function is self-evident. Addition of chloride ions is critical for the correct functioning of such brighteners, and the concentration of this is usually in the range 30-150 mg. At chloride concentrations < 2 0 mg/1, striated and rough deposits are formed. Above the higher limit, matt deposits are found and the covering power falls off (see Section 3.2.1.5.2). This type of electrolyte is usually operated in the temperature range 20-45~ and at current densities of 1-20 A/dm 2. Another example of an acid deposition bath is the high-chloride nickel electrolyte, typically of composition: 200 g/1 nickel(II) chloride hexahydrate NiC12-6H20 up to 1 O0 g/1 nickel(II) sulfate heptahydrate NiSO4" 7H20 30-50 g/1 boric acid, H3BO3 The pH in this system lies in the range 2.5-4 [5] with the boric acid as buffer to maintain a constant pH. Operating conditions are 40-70~ and deposition current density of 3-10 A/dm 2. There are also electrodeposition baths using organic or inorganic complexes as source of the metal ions. Thus, fluroboric acid H[BF4] is the basis of well-know fluroborate electrolytes, while hexaflurosilicic acid H2[SiF6] is likewise the parent acid of flurosilicate baths [5]. In both cases, the metal is present in cationic form. Equally, however, there are metal ion complexes where the metal is anionically charged [5]. These include hexavalent chromic acid (for chromium plating) and acid gold baths, based on the anion [HCr207]- and [Au(CN)2]-, respectively.
3.2.1.2 Neutral electrolytes

Under this heading are included systems which operate in the weakly-acid to weakly alkaline range. Since these are poorly conducting, they are not in common use. (hydrogen cations and hydroxyl anions have far the greatest electrolytic conductivity).

60 Electroplating- Basic Principles, Processes and Practice An important exception to this, however, are the neutral zinc plating baths, operating in the pH range 7.5-8.8. They contain two or more zinc-containing complexes, which must be maintained in a given concentration ratio. The first of these are complexes of ammonium chloride zincate, of composition Zn[(NH3)2C12] or Zn[(NH4)2C14], with the second category being zinc chelated with polyhydroxycarboxylic acid. Thus a typical composition of such an electrolyte would be [6] 26-52 g/1 zinc (as the metal) 105-165 g/1 chloride (as C1- ion) 4 5 - 9 0 g/1 chelating agent Another example of a neutral electrolyte is that used for electrodeposition of precious metals, which incorporate added salts to increase their conductivity. So a typical composition for a neutral (pH 6.8-7.5) gold bath might be [7]: 7 g/1 gold (as the potassium dicyanoaurate(I), K[Au(CN)2]) 7 g/1 copper (as potassium cyanocuprate(I) K2[Cu(CN)3]) 28 g/1 sodium dihydrogen phosphate NaH204 This bath is used at 65-75~ with a deposition current density of 0.5-1 A/dm 2. One final example of a neutral electrolyte is that for forming gold-palladium-nickel alloys in which both cationic and anionic metal ion complexes are present as [Pd(NH3)4] 2+ or [Ni(NH3)6]2+ and [Au(CN)2]- or [Au(SO3)2] 3- [5].
3.2.1.3 Alkaline electrolytes

This category is best sub-divided as cyanide-containing and cyanide-free types. It might be noted here that in both cases, alkaline electrolytes react slowly with carbon dioxide in air to form alkaline metal or other metal carbonates. Anything that increases electrolyte-to-air contact, such as agitation or air-sparging, will accelerate the rate of carbonate formation. Above a certain concentration, carbonates in solution will adversely affect the metal deposition process and will have to be removed, using either a physical or chemical approach.

3.2.1.3.1 Cyanide-containing electrolytes

Electrolytes are designated as 'cyanide-containing' when they contain significant amounts of so-called 'flee cyanide', that is, an excess of the simple KCN or NaCN. This will dissociate in solution, to form the constituent ions. It is vital that such solutions be at all times kept sufficiently alkaline, for if this is not so, HCN, the deadly hydrocyanic acid will form and be liberated in gaseous form (also known as 'Prussic acid gas'). In fact, accidents due to this are extremely rare. In spite of this, metal finishers are under on-going pressure to replace cyanide-based processes with those not containing this species. Citing an example, such as cyanide copper solution [4], is helpful. The copper(I) cyanide, CuCN, which acts as the source of the metal, is not soluble in water, but can be made so by addition of an alkali metal cyanide (NaCN or KCN).

Electrolytes for the Deposition of Metal Coatings 61

This leads to the formation of a cyanide complex, as: CuCN + 2NaCN~Na2[Cu(CN)3 ] CuCN + 2KCN~K2[Cu(CN)3 ] (3.2a) (3.2b)

Dissociation of the complex salt sodium (or potassium) tricyanocuprate(I) takes place as shown: Na2[Cu(CN)3]~2Na + + [Cu(CN)3]-~2Na + + Cu + + 3(CN)K 2 [ C u ( C N ) 3 ] - - ) 2 K + [ C u ( C N ) 3 ] 2 - ~ 2 K + + Cu + + 3(CN)-

(3.3a) (3.3b)

It follows that the presence of a significant amount of 'free cyanide' (as the sodium or potassium salt) as well as free alkali are necessary for the functioning and safe operation of this system, not just to solubilize the copper cyanide, but also for the following reasons:

(a)

(b)

(c)

Cyanides will slowly break down, either by anodic oxidation or homogeneous or heterogeneous (catalysed) air oxidation. Alkali is removed, as explained above, by carbonate formation. If there is insufficient free cyanide to solubilise the copper salt, the anodes will become encrusted with the insoluble metal cyanide, their rate of dissolution will be reduced and the electrolyte may become depleted of copper ions. In some cases, because the effective anode area is reduced, the current density will increase and polarisation or passivation may occur. In the absence of sufficient cyanide in solution, the electrodeposited copper will be powdery rather than forming a dense adherent layer.

A typical cyanide copper electrolyte (low copper type) would have the following composition: 25 30 3 6 g/1 copper(I) cyanide CuCN g/1 sodium cyanide NaCN g/1 sodium sulfite Na2SO3 g/1 sodium carbonate Na2CO3

Such a bath operates at pH 12, at a temperature of 20-30~ and a current density of 2-2.5 A/dm 2. The particular characteristics of this electrolyte lend themselves to copper-plating of undercoats on zinc diecastings. A similar copper electrolyte, but with higher copper content, is made up as [8]: 2 70 g/1 potassium tricyanocuprate(I) K2[Cu(CN)3] 10-30 g/1 sodium cyanide NaCN 10 g/1 potassium cyanide KCN 5 g/1 sodium sulfite Na2SO 3 5 g/1 sodium hydroxide NaOH This electrolyte too, has pH 12, and will also include brightening additives. It would normally be operated at 65~ and at a current density of 1.5-4 A/dm 2.

62

Electroplating- Basic Principles, Processes and Practice

Table 3.1 Composition of alkaline cyanide zinc plating baths [6, 9].

Constituents High cyanide

Concentration [g/l] Medium cyanide Low cyanide

Zn NaCN NaOH

30-50 75-150 75-150

15 40 90

17-15 10-30 80-150

Other examples of alkaline cyanide baths are used for deposition of zinc, silver and gold. In the case of zinc, cyanide electrolytes are categorised as low, medium or high cyanide. Typical compositions for these are shown in Table 3.1. In many cases, some 2 5 - 3 0 g/1 of sodium carbonate is also added, to increase bath stability, and small quantities of sulfides may be added, in order to precipitate out, as the highly insoluble metal sulfide, any metallic impurities. Of the greatest importance, when operating cyanide zinc solutions, is not only the zinc ion concentration, but also the ratio of NaCN and NaOH to the zinc ion concentration, in order to ensure uniform thickness distribution. In practice, one uses the so-called 'M-factors', which are defined as follows: NaCN Zn
--

Mc N

M~

Na0H Zn

Such M-factors can be used to determine the trade-off between highest useable current density and optimum throwing power. Thus, a high MCN- factor, that is, high NaCN content, implies a lower useable current density but good throwing power (see Section 3.2.1.5.3). Thus, when zinc plating components of complex geometry or with pronounced profiles, a high MCN factor is desirable. By contrast, a high Moll factor, that is, high NaOH concentration, is preferred when high deposition rates are desired, even at the expense of covering power [9]. Being able to 'fine tune' such zinc electrolytes for a particular application is thus a useful attribute. In addition to examples of cyanide electrolytes cited above, one might also list those in use for deposition of a range of alloys, including copper-zinc, copper-tin, gold-copper-cadmium or gold-copper-zinc [5].

3.2.1.3.2 Non-cyanide alkaline electrolytes

Under this heading, one could list a range of zinc baths used for rack or barrel plating of small parts. Cited compositions for such electrolytes are 1 2 - 1 4 g/1 zinc and 1 2 0 - 1 6 0 g/1 NaOH, or 1 1 - 1 3 g/1 zinc and 1 1 0 - 1 5 0 g/1 NaOH [9]. The optimum ratios of NaOH to zinc are 8-10. The higher the zinc and NaOH concentrations, the higher the current efficiency, other things being equal. These cyanide-flee alkaline zinc electrolytes lack the stability of their cyanidecontaining counterparts, and are mainly used where (for whatever reason) it is desired to avoid the use of cyanides, but without sacrificing the benefits of uniform

Electrolytesfor the Deposition of Metal Coatings 63

deposit thickness distribution. These systems are usually operated at 18-3 5~ and at a deposition current density of 0.5-6 A/dm 2 [9].
3.2.1.4 Electrolyte additives

In addition to metal salts, electrodeposition electrolytes usually contain various other species. Thus both inorganic and organic salts, acids or alkalis will be added to increase electrolyte conductivity. Other species, both organic or inorganic, may be added for specific purposes, for example, to increase bath stability, or improve levelling or metal distribution, or to optimise the chemical, physical or technological properties of the deposited metal (corrosion resistance, brightness or reflectivity, hardness, mechanical strength, ductility, internal stress, wear-resistance or solderability). In working with such additives, it should be recognised that they are often effective over only a defined concentration range, and should their concentrations fall outside this range, all kinds of problem can arise either in the deposition process or the deposit properties. In the following sections, such addition agents are considered in greater detail.

3.2.1.4.1 Brightening agents

In metal finishing, bright or highly reflective surfaces (the terms are usually synonymous) can be of both decorative and functional importance, if for no other reason that bright surfaces require less mechanical finishing, after plating, if indeed any at all. Defining brightness or reflectivity of a surface as the extent to which incident light is reflected, it follows that surface roughness and unevenness are antithetical to good reflectance. Reflective surfaces are characterised by a crystallite size at the surface of less than 0.3 p~m2. Thus, highly reflective deposits are found under conditions where fine-grained deposits are formed. To achieve this, it is long-established practice to add metallic or organic compounds, known as brighteners or brightening agents. Their use is based on empiricism, there being no certain means of predicting their effects. In the same way, selecting the most appropriate such compound(s) will usually be based on trial-and-error. Two different types of brightener are recognised, the first being brightener carriers, the second, brightener additives [ 10-12]. Addition of brightener carriers, also known as primary brighteners or Class I brighteners, leads to a significant grain refining action in the deposited metal. While this greatly increases the brightness of the metal, it will not impart a mirror-finish or anything close to this. Among the best-known brighteners of this type are [13] sulfonamides sulfonimides benzenesulfonic acids (mono-, di- or trisulfonic acids) napthalenesulfonic acids (mono-, di- or trisulfonic acids) alkylsulfonic acids sulfinic acids - arylsulfonesulfonates.
-

These primary brighteners are essential components of a complete brightening system, in that they reinforce the efficacy of Class II or secondary brighteners, the

64

Electroplating- Basic Principles, Processes and Practice

Table 3.2

Some commonly used brighteners [14].

Designation Thiourea

Structural formula
s

II
s

H2N - C - NH 2

Acylthiourea Mercaptoalkylsulfonic acid Bis-(sulfoalkyl)-disufide

II

II
2

R-C-NH-C-NH

HS - C n H 2 n - SO3H
[S - CnH2n- S03H]2

Thiocarboxylic acid amide

II

R > N - C - S - C n H 2 n - SO 3 R1 s

Thiocarbazone

H
H2N - C - 0

Thiosemicarbazone

R,

>C = N - N H R 1~

-C-NH

s II

Thiohydantoin

=s

latter being rarely used without the former. Class II brighteners, even at very low concentrations, impart a near-mirror finish to the deposited metal. The most important of these are listed in Table 3.2. Out of a very large number of potential Class II brighteners, only a few are used in practice, largely b e c a u s e - although many such species are highly effective in their brightening action, they can adversely affect process or deposit properties in other ways. In order to minimise this, secondary brighteners are usually employed with a primary brightener in a combination known for the compatibility and synergy of both. A number of electrolytes form bright deposits only in a comparatively narrow temperature and current density operating window. Figure 3.4 shows this for chromium deposition. As Fig. 3.4 shows, at any given temperature, a range of current densities exists, within which bright deposits can be formed. Alternatively, at any given current density, there is range of temperatures in which the same is true. Figure 3.4 is valid only for a particular chromium electrolyte system, and depending on concentrations of species used, and the catalyst, similar diagrams can be drawn, though the general shape of these is similar. At a given temperature, the widest possible range of operating current densities is desirable, especially when items of complex geometry or with deep profiles are involved, as in such cases, there will be marked variations in

Electrolytes for the Deposition of Metal Coatings 6 5

Figure 3.4 Operatingwindow for bright chromium deposition as function of deposition temperature and current density [8, 15].

current density at different locations on the work, An approach such as that shown in Fig. 3.4 is essential in ensuring that bright deposits are formed over the entire surface, however complex this might be. There are many theories to explain the brightening action of this class of additive. Most probably, the effect is due to a controlling effect, and perhaps a rate-limiting action, on the electrocrystallisation step. Such theories link with the accepted mechanism for metal electrodeposition, based on a nucleation and growth at a series of centres. From the growth nuclei, grains develop with a range of sizes and orientations. It is assumed that the brighteners are preferentially adsorbed on the developing growth peaks, thereby inhibiting further growth at these points. Having no alternative, the electrocrystallisation is forced to continue in the valleys rather than the peaks, whereby a levelling action results. The end result is a smooth and shiny surface. It follows that brightening is associated with a levelling action as well. 3.2.1.4.2 Levellingagents Either before or after electroplating, it may be necessary for the work to be mechanically finished, using grinding, then polishing stages, and these can significantly add to the overall cost [16], especially when the deposited metal is hard, for example, hard chromium. Levelling agents can act to smooth pre-existing irregularities in the surface, such as pits or scratches and thus they compensate for poor surface quality of incoming work. The levelling action of an electrolyte, that is to say its ability to form a smoother surface than that of the original substrate, is defined as 'levelling power' [11, 17-19]. By levelling action is implied the deposition of a greater thickness of metal in the depths of a groove than at its outer edge. This can be quantitatively expressed as: E = dt-d R: "100% (3.4)

66

Electroplating- Basic Principles, Processes and Practice

Figure 3.5 Illustration of levelling action: (a) geometric levelling; (b) true levelling; (c) levelling as function of deposit thickness.

In Eqn (3.4), E is the levelling effect, dt the deposit thickness at the base of the groove, d the overall deposit thickness and Rz the roughness of the substrate. A distinction is made between geometric and true levelling. In the former case, the key factor is that the deposit is thicker at the bottom of a groove than at the edge (Fig. 3.5a). The effect is measured in terms of the geometry and shape of the groove. The hallmark of true levelling is a higher metal deposition rate in the groove than at the adjacent areas (Fig. 3.5b) and this results when the so-called levelling agents or levellers are added to the electrolyte. The manner in which these additives work is by restricting the rate of metal deposition, but only at those locations where they are freely supplied, specifically at peaks and edges. The levelling action of such species can vary quite widely, apart from which it is usually temperature dependant and can often be enhanced by work movement or solution agitation. Levelling action is a function of deposit thickness and increases as thickness increases (Fig. 3.5c). Certain electrodeposition electrolytes are specially effective in their levelling action. These include bright nickel, whose levelling action is shown in Fig. 3.6. On a polished surface of a copper-zinc alloy, grooves were formed using a scribing diamond with loading 0.5 N. Onto this scribed surface, bright nickel was deposited at 58~ pH 4.0 and a cathodic current density of 4 A/dm 2. From this sequence of cross-sections, it can be seen that as a result of the pronounced levelling action of the bright nickel, deposition occures initially in the

Electrolytes for the Deposition of Metal Coatings

67

Figure 3.6 Dependence of bright nickel levelling action on deposition time. From top down, 7, 14 and 21 min v = 350:1 [5].

grooves. The levelling effect increases as the deposit thickness grows so that, after sufficient time, the troughs and peaks have been effectively levelled. A negative levelling action is defined as a situation where less metal is deposited in the depths of a groove than at the outer surfaces, that is to say that the electrodeposition enhances the surface roughness. This effect is observed with some cyanide electrolytes. 3.2.1.4.3 Surfactants (wetting agents) Plating baths will usually contain wetting agents, also known as surfactants. These are characterised by their asymmetry and dipolar nature (o--). They have a hydrophilic ('water loving') 'head' (o) and a hydrophobic ('water-repellent') 'tail'-. Surfactants can be 'anionic', 'cationic' or 'non-ionic' depending on the charge at the hydrophilic end. The polar hydrophilic radicals are typically-COO- or-SO3 groupings, while the hydrophobic part of the molecule might be a non-polar aliphatic long-chain hydrocarbon [20, 21]. Non-ionic surfactants are themselves uncharged, acquiring their charge from ions present in aqueous solution [ 17]. Wetting agents are surface-active species, that is, they act by accumulating at a surface or interface. At an air-electrolyte interface, they are oriented with hydrophilic head into solution, the hydrophobic tail to the air-side. In this way they reduce the surface tension of a liquid. Chromium plating afford a good example of the working of such wetting agents. In this process, chromium deposition is accompanied by a substantial evolution of hydrogen gas at the cathode (work) surface. These bubbles rise to the electrolyte surface and there explode, thereby forming a mist of the chromic acid

68 Electroplating- Basic Principles, Processes and Practice

Table 3.3 Classification of surface-active agents (n 10-20; m 8-16; o 5 - 2 0 ) [20].

Type Anionic

Hydrophilic grouping
-CO0 @
--0 -- SO2-- 0 E) -S02-O e

Example
CH3-(CH2)n-CO0@ with Na| basic soap with K+: lubricating soap
CH3- (OH2)n- O-SO2-Oe CH3-(CH2)n- S 0 2 - 0 e CH3-(CH2)m'-~'- S 0 2 - 0 @

Designation Soaps Fatty alcohol sulfates Alkyl sulfonates Alkylarylsulfonates

Cationic

OH3 -N -CH 3

OH3 CH3-(CH2)n-N -CH 3 Ci @

Ie I

Ie I

Alkyltrimethylammoniumchloride

CH 3

CH 3 OH3 CH 3- (CH2)n-N - CH2-CO-O 0

Amphoteric, zwitterionic

(~
I

H3

N-alkylbetain

-N@-CH2 - c O - O0 CH3

I
OH3

Non-ionic

-O-(CH2-CH2-O-)L-H

a) CH3-(CH2)m-O-(CH3-CH2-O-)L- H

Polyethyleneglycol adducts of 7 with b) CH3-(CH2)m--~O-(CH2-CH2-O-)L- H 0 (a) alkyl alcohols c) CH3-(CH2)n-~ -O-(CH2-CH2-O-)L-H (b) alkylphenols (c) fatty acids 0

electrolyte 1, which is extremely hazardous to health, and indeed to nearby equipment. As a result, powerful air-extraction facilities are essential. If, however, a wetting agent is added, usually a fluorinated type capable of withstanding the powerful oxidising action of chromic acid, the surface tension will be reduced from, typically 70 to 2 0 m N / m and the extent of chromic acid mist formation is greatly reduced [22]. At the same time, a thin and compact layer of foam is formed at the surface which substantially reduces evaporative losses from the electrolyte. Wetting agents or surfactants also build up at the solid-liquid interface of the work, immersed in the electrolyte. The hydrophilic groups are hydrated and drawn towards the aqueous phase, with the hydrophobic end being weakly adsorbed onto the work surface. With this degree of ordering imposed at the interface, the interfacial tension is reduced, that is, the work surface becomes more easily wetted by the electrolyte, with several resulting benefits to the electrodeposition process. In metal finishing, anionic or non-ionic surfactants are most often used. The lowering of surface tension facilitates the release of gas bubbles adhering to the work surface, whether these be cathodically evolved hydrogen or trapped air. Where such bubbles adhere to the surface, their shielding action results in little electrodeposition occurring and they can be the cause of pitting or deposit porosity. Table 3.3 gives a classification of surface-active agents. 1 Hexavalentchromium compounds are toxic and carcinogenic.

Electrolytes for the Deposition of Metal Coatings 69

Addition of surface-active agents also results in the following: 9 9 9 9 certain organic compounds, insoluble or poorly soluble in water can be solubilised or their distribution in solution made more uniform; coagulation and sedimentation of suspended solid matter as dirt in solution which would otherwise lead to rough or porous deposits, is reduced; crystal growth is inhibited and a brightening action of the deposit results; draining of adherent electrolyte, on withdrawing the work from solution is improved, drag-out losses are reduced.

It should be noted that the type of surface-active agent best used is very much linked to the particular electrolyte employed, and a poor choice can result in all manner of adverse consequences in process operation. Maintaining the optimum concentration is also critical. If too low, some or all of the benefits listed above may not come into play, while if too high, the deposit properties may be adversely affected. Finally, the choice of wetting agent may be influenced by the type of electrolyte agitation being used, whether air-sparging, work-movement or eductor.
3.2.1.5 Electrolyte properties The aim of the electrodepositor will usually be to form dense, uniform and adherent metal coatings. Of the countless factors which are important for this, the electrolyte and its properties are vital, and this is discussed below.

3.2.1.5.1 Electrolytic conductance Whereas, in a metal, electric current flows by means of free electrons, the passage of current in an aqueous solution of ionised species is due to the migration of ions, molecules or atoms bearing a positive or negative charge. In some important aspects, these two mechanisms behave differently, and conduction of the latter type is therefore known as electrolytic conductance, as opposed to electrical conductance found in a metal. Electronic conductors are sometimes known as Class I conductors, electrolytic conductors as Class II. Worth noting that under a wide range of conditions, both types of conductors obey Ohm's law. Arguably, the key feature of aqueous electrolytes is that the compounds dissolved in them, have partly or completely ionised. It is by the movement of such charged ions that electric current can be passed through the solution. For further details and data, see Refs. [8, 23]. The key issues are the degree of dissociation of the dissolved species in solution, and the so-called ionic mobility, reflecting the fact that under a given potential gradient, some ions travel faster than others, and are thus a more effective means of carrying charge. In broad terms, it is usually assumed that inorganic acids, alkalis and metal salts are close to 100% dissociated (see Table 3.4), metal salts of organic acids, such as copper acetate, are partly dissociated, while, for example, organic acids range from being highly dissociated (formic, acetic) to being almost undissociated (butyric, oleic acids). Ions formed by dissociation of the parent species travel across the electrolyte between anode and cathode, under the influence of the potential gradient established by application of a voltage. Cations (positively charged) travel to the cathode (the negative pole) and anions, negatively charged, move in the opposite direction to

70 Electroplating- Basic Principles, Processes and Practice

Table 3.4 Degree of dissociation of selected acids and salts.

O,1 N solution of H2SO4 HNO3 HC1 H3PO4 NaOH KOH ZnC12 Na2SO4 NaC1 ZnS04 CuS04

Degree of dissociation [%] 96 92 91 81 80 73 24 13 12 0.17 0.01

Table 3.5

Ionic mobility values for selected ions.

Ion H+ OHCIK+ SO2NO3 Ag+ Fe+ Na+ Cu2+

v [cm/h] 11.34 6.01 2.25 2.18 2.13 2.09 1.76 1.73 1.32 1.04

the anode. Their ionic mobility is defined as rate of travel (in cm/s) under unit potential gradient (volt/cm = 1). It should be noted that since all ions in aqueous solution carry a hydration sheath, what is actually measured is the rate of travel of the hydrated ion. This explains why, for example, in the alkali metal series, the larger ions such as Rb + travel faster than the apparently smaller ions such as Li+, the reason being that the latter carries a larger hydration sheath. A selection of ionic mobility values is shown in Table 3.5. It will be noted that the hydrated proton and hydroxyl ions have the highest mobility values, and this is due to the fact that, for these two species, an additional charge transport mechanism operates. It should be emphasised that the foregoing description is greatly simplified. Factors such as solution viscosity (itself linked to temperature) and ionic activity (a measure of concentration, but corrected for other effects) are also important. In terms of the simplified theory presented here, one might expect a solution undergoing electrolysis to become depleted, as ever more anions migrate in one direction to the anode, and cations to the cathode. In practice, such effects are only significant under very special conditions. Working against ionic depletion are effects such as solution agitation (including natural convection) and diffusion under the effect of a concentration gradient (Fick's law). Chapter 4 provides further insights.

Electrolytes for the Deposition of Metal Coatings 71

Table 3.6 Specific conductivity of selected electrolytes [19].

Electrolyte Zinc, sulfuric acid Nickel Copper, sulfuric acid Copper, cyanide Zinc, cyanide Chromium

X X 10- 5[m/f~ mm 2] 0.49 1.04 1.10 2.15 2.52 6.57 (at 25~ (at 50~ (at 25~ (at 60~ (at 25~ (at 50~

These explain the apparent paradox that chromium can be electroplated (at a cathode) from hexavalent Cr202- ions when in fact one might expect such ions to be repelled from a cathode. For electrolytes, as for metallic or inorganic conductors, the concept of specific conductivity, X or its reciprocal p, specific resistivity, is useful. These can be visualised as the conductivity (or resistivity) of a cube of the material or liquid, to which Ohm's law is applied, that is, current is measured across opposing faces of the cube under a voltage gradient of 1 V/cm. Conductance is thus expressed as (m/tl mm 2) or (mS/cm) where S (the siemens) = [1/11]. Some examples of specific conductivity are given in Table 3.6. It is seen that the electrical conductivity of metals, for example silver, with = 63, and copper with = 60 is of order 106 higher than the best conducting electrolytes. Thus, 30% sulfuric acid solution at 18~ has a conductivity 800,000 times lower than copper. In order to increase the conductivity of electrodeposition baths, acids or alkalis or salts are often added, and these are known as 'supporting electrolytes'. In the case of acid electrolytes, chloride and acids are used for this purpose, with chlorides alone being used with neutral solutions and, for alkaline solutions, sodium hydroxide or cyanide. In order to compare the conductance of several electrolytes, a rational basis for doing so must be established. In practice, this is done by comparing values for 1 M solutions (also known as CMol)or as CAethe molar equivalent concentration. 2 In the first case, molar conductivity is expressed as:
Am _ X [cm2/O,.mol] CMol

(3.5)

and in the second case as the equivalent conductance XAe (3.6)

AAe = ~Ae[Cm2/~"~.val]

The conductivity of an electrolyte is a function of the degree of dissociation, the mobility of the individual ions, the temperature (and thus viscosity) and the electrolyte composition. It should be noted that not only the ionic mobility but also the charge carried by each ion, as well as their concentrations. The hydration sheaths on
2 The equivalent weight of an atom is its atomic weight divided by valence value.

72

Electroplating- Basic Principles, Processes and Practice

800

700

600
5OO

.9.o E

/
I I

0:04

'400 3O0 NaCI 200 100

10 15 20 25 Concentration [wt%]

30

Figure 3.7

Conductivity of various electrolytes as functions of their concentration [24].

the ions play no part in the overall charge transport process. Some values for specific conductivity of selected electrolytes are plotted versus their concentrations in Fig. 3.7. It is seen that conductivity initially increases with concentration, after which a maximum value is reached. In the gradients of these plots and also the concentration values at which maximum conductivity is reached, there are significant differences between the various species shown. The reason why, at higher concentrations, the linear relationship between conductivity and concentration breaks down, is ascribed to electrostatic interactions between neighbouring ions. These become more significant as concentration increases and this interaction decreases the effective rate of ionic mobility. The marked decrease in conductivity at the highest concentrations is due to the greater coulombic forces acting between the ever-closer ions in solution. This can lead to a loose association of oppositely charged ions, which are effectively neutral and thus no longer contribute to the overall solution conductivity. While, in principle, the electrolytic conductivity of a solution has no effect on the properties of the deposited metal, in cases where it is too low, certain adverse effects will appear. These include: 9 Primary current distribution deteriorates, with the result that disproportionately heavy deposition occurs at leading edges and corners of the work. More generally, the outcome is less uniform metal distribution. Because the resistance is higher, more heat will be generated by the passage of the same current t h r o u g h the electrolyte (i2R effect), the result being

Electrolytes for the Deposition of Metal Coatings

73

increased electrical energy required, and perhaps more cooling of the solution being necessary. High concentrations of alkali metal or alkaline earth metal cations, as well as cationic impurities in solution, all adversely affect solution conductivity. 3.2. ] .5.2 Covering power The term 'covering power' is used to describe the extent to which an electrodeposition electrolyte can cover the entire surface of an object being plated, with reasonably uniform thickness, including at least some deposition in recesses and cavities. It is accepted that metal deposition begins only above a certain deposition potential, the value of which depends on the surface, and the metal being deposited. For an electrodeposition bath to exhibit covering power, the so-called minimum coveringpower current density must be applied. Estimation of covering power is frequently determined using the so-called Hull cell, named after its American inventor [DIN 5095 7, 5, 17]. As Fig. 3.8 shows, this is a miniature electrodeposition tank, but one in which the cathode is angled with respect to the anode. As a result, when a voltage is applied across the anode and cathode, the resulting current density will vary along the length of the cathode, being highest at the point it is closest to the anode. In this way, one can, within a single test run, assess the effect of varying current density. After such a run, the cathode is removed and inspected. At the highest current densities, the deposit may be burned. At the lowest current densities, no deposition may be observed. Thus the Hull cell allows the determination of the so-called 'operating window', the current density range over which acceptable deposition occurs. An electrolyte is said to have good covering power when satisfactory metal deposition extends into the lowest current density range. Covering power is largely a reflection of the energy of nucleation at the work surface. Among the parameters affecting it, are the nature of the substrate surface, its composition and the operating conditions. Covering power usually increases with increasing current density and decreases with increasing temperature. Covering power is specially important in the case of chromium plating, since it is generally poor for this metal anyway. A uniform deposit will result only when high

Anode

Figure 3.8

Hull cell for experimental determination of covering power of electroplating solutions.

74

Electroplating- Basic Principles, Processes and Practice

current densities are used and total current densities can be up to 100% greater than the actual chromium deposition current density [ 19] with copious co-evolution of hydrogen. Typically, a uniform chromium deposit will form in 1-3 min. Further deposition is then carried out at reduced current density. In general, alloy steels with high carbon content as well as cast iron and aluminium and its alloys all require relatively high current densities to achieve covering, as compared with unalloyed steel, copper and nickel [19]. 3.2.1.5.3 Macro-throwing power In the electrodeposition of metals, the depositing metal film does not grow uniformly at the same rate across the surface, reflecting the various factors which influence the rate of crystal growth. Macro-throwing power is a term used to describe the ability of an electrolyte to lay down as nearly as possible, a uniformly thick deposit across the surface of an object. The more this is so, the better the throwing power, and thus throwing power can be used as a predictor for the uniformity of a deposit. It will be clear that good covering power is a pre-requisite for good macro-throwing power. The macro-throwing power of an electrolyte is a manifestation of the extent of primary and secondary current density distribution in the system [ 17, 19]. Primary current distribution is the outcome of Ohm's law, applied to the dimensions and geometry of the spatial anode-cathode configuration and the shape of the electrolyte container. As seen in Figs. 3.9(a) and (b), there is a concentration of electrical lines of force at edges, points and corners. The result is a higher current density at these points and, in most cases, heavier deposition. The higher the electrolyte resistance, the greater such enhanced effects at edges, etc., will be. The parallel field lines shown in Fig. 3.9(c) are never achieved in practice. Secondary current distribution reflects the electrochemical behaviour of the system, mainly in terms of the overvoltage at the cathode (polarisation). This is total overvoltage, and thus includes the various types of overvoltage which impede the rate of metal deposition. Overvoltage, or polarisation, is thus an expression of the difference between actual potential and the theoretical, reversible potential under conditions of current flow. The higher the overvoltage, the more uniform is metal distribution and anything that results in increased overvoltage will thus result in

(a)
m +

(b)

(c)

~ ~ ~ ~ .

I:::::

!:
Figure 3.9

Primary current density distribution as a~unction of the electricalfield between anode and cathode.

Electrolytes for the Deposition of Metal Coatings 75

Cathode Anode Cathode

,..

Figure 3.10 Haring-Blum cell for experimental determination of throwing power of electrodeposition electrolytes [25].

more uniform current density. Included in such effects are electrolyte composition, electrical conductivity and electrolyte agitation as well as deposition current density. The experimental determination of macro-throwing power can be made either using a Hull cell or a Haring-Blum cell (Fig. 3.10). A rectangular, open-topped electrolyte container is equipped with two cathodes, one at each end, of the same size, shape and material. Between these, is positioned an anode made of perforated mesh or similar construction. This anode is placed closer to one cathode than to the other, typically 1:5 in terms of the two anodecathode spacings. The aim, though it is never completely achieved, as a result of edge-effects, is to replicate the uniform field shown in Fig. 3.9(c). Assuming that the electrolyte resistances in the two compartments reflect the respective anode-cathode spacings, and are thus 1:5, one would expect, on the basis of primary current distribution effects, five times more metal distribution at the cathode of the shorter of the two compartments. In such a case, the macro-throwing power would be taken as zero. In practice, various electrolyte effects intervene and rather different values are obtained. These alter the amount of electrodeposited metal on the more distant cathode and result in positive values of macro-throwing power. Macro-throwing power is defined using the equation L-M S = L + M2" 100% (3.7)

where S is the throwing power, L the distance between anode and cathode and M the ratio of deposited metal on the nearer and farther cathodes. It should be noted that two Haring-Blum cells, each with anode positioned in the ratio 1:5 vis-~i-vis the two cathodes, but of different total length will give different results. Some authors, especially when using poorly conducting electrolytes, advise against perforated anodes, since current can flow through the perforations, creating spurious effects. Instead, a planar anode giving a seal between the two electrolyte compartments is suggested. For cyanide- or sulfuric acid-based copper electrolytes, this method gives values of 25-30% and 2-5%, respectively [26] showing that cyanide copper electrolytes have a macro-throwing power far superior to that of acid copper. In general, it can be

76

Electroplating- Basic Principles, Processes and Practice

asserted that complex-type electrolytes and those containing brightening additives have good macro-throwing power. Thus, in the case of copper plating components with complex geometry, cyanide copper or cyanide-flee alkaline copper are the electrolytes of choice, where a uniform deposit is desired. In practice, it is clear that the uniform electrical field which the Haring-Blum cell sets out to create, is rarely achieved. The electrical field is distorted by the shape of the work being plated, and by the means by which the work is attached to the racks, the configuration of anodes, etc. In practice, despite its poor performance in the Haring-Blum cell, a satisfactorily uniform deposit can be obtained using an acid copper electrolyte. A far more challenging situation, in terms of macro-throwing power, is found with hexavalent chromium electrodeposition [2 5], which is inferior even to acid copper. In some cases, this requires that the chromium be electroplated from the trivalent electrolyte. In this case too, electrolyte agitation and increased temperature can lead to reduced macro-throwing power. 3.2.1.5.4 Micro-throwing power Given that many components being electroplated have far from perfectly smooth surface, micro-throwing power is important. This is the extent to which metal electrodeposition occurs at the outer plane of the substrate or at the base of valleys or cracks. In principle, electrodeposition at these latter sites is hindered, in that access of flesh electrolyte and dispersal of exhausted electrolyte are hindered. Microthrowing power becomes important in such situations, and is an expression of tertiary current distribution. The less metal that is deposited on peaks and outer planes, the better is the micro-throwing power. Micro-throwing action is achieved by preferentially activating the metal surfaces at the base of cracks or valleys, ensuring that those species which promote electrodeposition are concentrated there, while at the same time inducing inhibitors to adsorb at the outer surfaces [2 7]. In many cases it is found that micro-throwing power is inversely related to macro-throwing power. When the one is good, the other is not, and vice versa. Micro-throwing power thus acts to bring about a levelling (see also Section 3.1.4.2).

3.2.2 Electroless Deposition Electrolytes

Electroless deposition, also known as chemical deposition (see Chapter 4) is brought about when, to an electrolyte similar to those used in electroplating, a chemical reducing agent is added. Metal ions are thus reduced to metal at the surface of the work, not by externally applied current, but by the oxidation of the chemical reductant at the metal surface [3 ] ]. Examples of such systems include the widely used electroless nickel, where the deposited nickel includes a significant amount of phosphorus, when hypophosphite is the reducing agent used. Though such systems are used to deposit metallic coatings over metal substrates, they are also able to deposit a metal on non-conductors, such as plastics, once these have been activated. The basis of this hugely important activity, so-called 'metallising of plastics' is described in Chapter 4. In the case of electroless nickel, the deposits typically contain from 3 to ] 5 wt% phosphorus. After

Electrolytes for the Deposition of Metal Coatings 77

heat-treatment, a range of Ni-P intermetallics are formed, whose hardness and corrosion resistance are superior to those of conventionally electroplated nickel. The nickel salt used is usually the sulfate hexahydrate, NiSO4" 6H20, with sodium hypophosphite as reductant. This is usually in the form of colourless hygroscopic crystals, molecular weight 107 and readily water soluble (100 g NaH2PO4" H20 per 1 O0 g water at 2 5~ Table 3.7 shows the composition of commonly used electroless nickel systems and the deposition conditions used. These so-called hypophosphite electrolytes have a pH of 4.6-5.6. Operated at 85-95~ they deposit N i P coatings at a rate of 1 0 - 3 0 Ixm/h. Operating under the simplest conditions, they have a finite life, typically expressed as 2 - 1 0 MTO (metal turnover) [28] where 1 MTO implies a complete depletion of the nickel content of the bath. It is clear that to achieve this, the bath will need to be several times replenished with flesh nickel salts to make good the nickel removed from solution. In the past, accepted practice was to dispose of the bath after 3 0 - 8 0 g/1 nickel had been deposited from it [28]. One can continue to use the bath for m u c h longer, but the deposit properties will suffer. However, more recently, n u m e r o u s processes for bath life extension have been published, many based on removal of the orthophosphite ions formed. The so-called EDEN (electrodialysis of electroless nickel) process claims that when used, the life of an electroless nickel bath is virtually infinite. As Table 3.7 suggests, the Type III system is in many ways the best of the three. It uses lower nickel and hypophosphite concentrations, has higher stability, that is to say is less prone to spontaneous deposition. It has a high deposition rate and longer bath life. Bath life is here defined as the age of the bath before metal deposits exhibit properties inferior to those from a virgin bath. The Type III system can be operated at high pH and temperatures to give greater deposition rates. Against this, it must be noted that the lower phosphorus content gives a deposit with somewhat reduced corrosion resistance, as compared to that from Type I and Type II systems.

Table 3.7 Compositions and operating parameters for three proprietary electroless nickel systems.

Bath constituents and operating parameters Nickel content [g/l] Sodium hypophosphite [g/l] pH Bath temperature [~ Deposition rate [Ixm/h] Bath life [MTO](metal turn over)1 Bath life (g/1Ni) Bath loading [dm2/1] Agitation/air sparging Filtration Bath stability P content of deposit [%]

Type I 7.3 40 4.6-5.2 86-92 12-14 5-6 37-44 up to 2 Required Continuous High 10-11

Type II 7.3 40 4.6-5.2 86-92 13-15 5-7 37-50 up to 2 Required Continuous High 11-12

Type III 6.3 30 4.8-5.6 88-95 18-25 9-12 57-63 up to 3 Required Continuous Very high 8-9

1 MTOequates to the depletion of the entire nickel content of the bath.

78

Electroplating - Basic Principles, Processes and Practice

In order to avoid too high a concentration of free nickel ions in solution, complexants are added at concentrations up to 0.2 M. These form stable nickel complexes, reducing the concentration of free nickel ions while providing an available reservoir of the metal. This represses the tendency for nickel ions to precipitate as the hydroxide, which otherwise readily occurs in weakly acid solutions. The stability of nickel hypophosphite baths can be compromised by local overheating in solution, by too high a concentration of reactants and by the presence of trace impurities in solution. The formation of suspensions of insoluble species such as nickel hydroxide or nickel phosphate can have the same effect, since such solid particles can act as nucleation sites for spontaneous electroless deposition to occur. For this reason, such solutions usually include stabilisers (cadmium, lead, tin, thiourea, etc.) to prevent spontaneous metal deposition. The concentration of these species must be carefully adjusted. At too low a concentration they will not have any effect, at too high a concentration, they will make any metal deposition difficult to initiate. Their concentration depends on the nickel ion concentration and the ratio of work surface area to bath volume. Where excessive nickel deposition on the walls of the tank is observed, a higher concentration of stabiliser is called for. In the opposite sense, when a discolouring is observed on the edges of work, indicating too thin a nickel deposit, the stabiliser concentration should be reduced. Typically, stabiliser concentration lies in the range 1-6 ppm. Also present in most electroless nickel formulations is a so-called accelerator which activates the hypophosphite anions and increases the availability of free nickel ions. The effect is to accelerate film growth kinetics without detriment to the action of the stabiliser. A further bath constituent, in many cases, is a wetting agent, to increase the wettability of the work surface, thereby aiding the release of adherent bubbles and promoting more uniform deposit growth. The concentrations of these species, and also the pH buffer used, are in practice reached on the basis of a compromise, in which bath stability and high deposition rates are the primary aims. Another very widely used electroless deposition system is electroless copper, used to metallise plastics, which include the substrates of printed circuit boards. The main constituents are the copper salt, the reducing agent, alkali and the complexing agent. The copper salt used is normally the Cu(II) sulfate pentahydrate. The reducing agent is a 3 7% aqueous solution of formaldehyde. NaOH is added to reach a pH of 11-13. The complexant depends on the system used, but is usually EDTA, quadrol or tartaric acid [29]. Stabilisers are adsorbed at the copper nuclei, otherwise surrounded by solution, thereby minimising their further growth. Copper deposition from this solution takes place at 20-35~ typically with deposition rate of 5 p~m/h. The main bath constituents are 10 g/1 copper sulfate pentahydrate; CuSO4" 5H20 10 g/1 sodium hydroxide: NaOH 50 g/1 potassium sodium tartrate KOOC-CH-CH-COONa 10 g/1 formaldehyde: HCHO, 37% 10-100 mg/1 stabiliser

Electrolytes for the Deposition of Metal Coatings 79

3.2.2.1 Electrolyte additives In theory, it should be possible to operate an electroless bath containing nothing but metal salt and reducing agent. In practice, the result would be either a system so unstable that spontaneous metal deposition occurred, and/or that the deposited metal would not possess the desired properties. Spontaneous deposition can be triggered by catalytically active foreign particulates, suspended, often homogeneously, in solution. Metal ions are reduced at such suspended particles, which act as nucleation sites. Following an initial metal deposition, often no more than a few atoms, an uncontrolled metal deposition follows. To repress such effects, a range of organic or inorganic additives are included in such bath formulations, to increase bath stability, to control the metal deposition process and to regulate the metal deposition rate, both too fast or too slow being undesirable. At the same time, such additives are used to optimise deposit properties such as hardness, ductility, solderability, wear- and corrosion-resistance, as well as minimising internal stress and increasing deposit brightness. No single additive can bring about all of these modifications and in practice, a combination of addition agents is used. The selection of such additives and the combinations and concentrations in which they are used, make the difference between successful and unsuccessful operation of such baths and the resulting deposit properties. Some of the additives act diametrically opposite ways to one another, and some act (for example) as accelerators at low concentrations, and inhibitors at higher concentrations. It would be no exaggeration to suggest that the remarkable advances in plating bath formulations in recent years have been the result of development of improved additives and combinations of these. The composition and nature of such additives lies at the core of intellectual property, and they are rarely disclosed, save in the patent literature. In what follows, the most important bath constituents are discussed.
3.2.2.1.1 Reducing agents Apart from the metal salt, the reducing agent is the most important constituent of electroless deposition systems, and the following key points should be made: 9 9 9 The concentration of reducing agent is critical. Increasing this will usually lead to an increase in metal deposition rate. The reducing agent plays a critical role in determining the bath stability. The composition and microstructure of the deposited metal and thus its properties, are largely determined by the nature of the reducing agent.

The importance of the choice of reducing agent is indicated by the fact that it is usually indicated when describing a deposition system, for example, as 'Electroless nickel-phosphorus'. Some of the best-known electroless deposition systems are listed in Table 3.8. The power and ranking of reducing agents is indicated by their redox potential value and for a chemical reduction to take place, this value must be more negative than the redox potential value of the metal/metal ion couple. However there should not be too great a potential difference between the two values, if a deposit with

80 Electroplating- Basic Principles, Processes and Practice

Table 3.8 Frequently u s e d electroless metal d e p o s i t i o n systems [28].

Reducing agent

Chemical formula

Molecular Available Redoxpotential Usedfor: weight [g/moll electrons [V] 2 8 2 6 4 - 1.57 alkaline - 1.38 acidic - 1.24 alkaline - 1.11 alkaline - 1.18 alkaline Nickel, Cobalt

Sodium hypophosphite NaH2PO 9H20 106.90 2 Sodium borohydride NaBH4 Formaldehyde HCHO Dimethyl-aminoborane (CH3)2NH. 3 BH Hydrazine N2H4 3 7.80 30.03 58.90 32.00

Nickel, Cobalt Copper, Silver Nickel, Copper, Silver - 1.16 alkaline Nickel

satisfactory properties is to be formed. Thus sodium hypophosphite (E = - 1 . 5 7 V) is ideal for reducing nickel ions (E = - 0 . 2 5 V) though it is not suitable for reducing the more noble copper ions (E = 0.34 V). The latter require an alternative reducing agent with a higher redox value, and formaldehyde (E = - 1 . 1 1 V) is used in this case.
3.2.2.1.2 Stabilisers A constant preoccupation in operation of electroless plating systems is to avoid spontaneous and uncontrolled metal deposition. Unlike electroplating baths which cannot operate unless electrical energy is supplied, electroless deposition systems are thermodynamically unstable, and spontaneous metal deposition is prevented only so long as a catalytically activated surface is absent. To minimise the danger of this happening, so-called stabilisers are added and form an essential part of all electroless metal deposition systems. The concentration of these species is very low, and were this not the case, their effectiveness would be so great that metal deposition would not occur even when this was desired. Stabilisers operate by masking off those nuclei which would otherwise act as initiators for the reduction process, and it is generally assumed they do so by adsorbing at the surface of these finely divided particles, which are often held in suspension, thereby impeding further nucleation reactions. Of course, there will also be adsorption of the stabiliser on the work surface, where it can likewise impede any metal deposition. Stabilisers can be metallic or non-metallic. In the former category, are found lead, c a d m i u m and tin, and in the latter class, divalent sulfur c o m p o u n d s such as thiourea, lead or tin sulfides or sodium methyl xanthates are used.

3.2.2.1.3 Complexing agents Though they act in quite another way, metal complexing agents are used in electroless deposition systems for various reasons, one of which is to prevent spontaneous metal reduction and deposition. By complexing the metal, the danger of its precipitation as an insoluble compound is largely avoided. Complexing agents are species which form ionic compounds with the metal to be deposited. These ionic complexes often behave quite differently from the simpler ions of the metals they include. The complexation of a metal can be seen as a means of stabilising it, and making it less readily available for any form of reaction. Indeed, the metal ion will not be available

Electrolytes for the Deposition of Metal Coatings 81 Table 3.9 systems. Some commonly used complexing agents for electroless deposition

Designation EDTA NTA EDTP

Chemical formula
(HOOC-CH2)2N-CH2-CH2-N(CH2COOH) 2 N(CH2-COOH)3 ((HO)2PO-CH2)2N-CH2-CH2-N(CH2-PO(OH)2)2 (CH3CH(OH)CH2)2N-CH2-CH2-N(CH2CH(OH)CH3)2 HOOC-CH(OH)-CH2-COOH HOOC-CH2-C(OH)(COOH)-CH2-COOH HOOC-CHCOH-CH3

Quadrol Malic acid Citric acid Lactic acid

unless the complex is decomposed. If the metal ion is too strongly bound in such a complex, it will not be released for reduction and no metal deposition will take place. The strength with which the metal is locked up in a complex is expressed in terms of the stability constant of a given metal-ligand system. Though complexation cannot change the total amount of metal ions in a closed system, it will lower the concentration of 'flee metal ions'. The greater the stability constant, the more that metal ions will be complexed and the lower the concentration of 'flee' metal ions. There are no firm rules for assessing the concentration of complexing agents, though this is often much lower than that of the other main bath constituents. Complexing agents affect bath stability, ease of deposition initiation and deposition rate. Since they will be slowly but systematically lost from the system by drag-out, their concentration must be monitored and losses made good by dosing. Recognising that the deposition conditions can critically affect the mechanical and other properties of the deposit, it will be recognised that the complexation process offers a key to control of the deposition reaction. Complexing agents would appear to form an essential part of many aqueous metal finishing and surface treatment processes. On the debit side, however, these species can be environmentally harmful and a number of them call for special effluent treatment techniques in order that they are broken down and made harmless. 3.2.2.1.4 pH buffers Electroless metal deposition systems operate in a relatively narrow pH window, and this must be strictly maintained if the deposit properties are not to be compromised. However metal deposition is almost invariably accompanied by hydrogen evolution and the loss of this hydrogen will drive the solution to become more alkaline as hydrogen ions are lost from the system. In some cases, the redox values of the metal ion, or the complex holding it, or the reducing agent can be affected by change in pH, and so influence the overall process. Such effects are minimised by including in the bath formulation, a pH buffering system. These are described in most physical chemistry textbooks. Such buffer systems operate in a defined pH range and will normally be effective over about 2 pH units within that range. They are usually based on a weak acid or weak alkali and its metal salt and as long as at least some of both buffer species remain in solution, they will prevent any marked excursions of pH.

82

Electroplating- Basic Principles, Processes and Practice

3.2.2.2 Electrolyte monitoring

When operating electroless deposition systems, the following rules should be followed. The chemicals used in electroless bath formulations must be of higher than normal purity, and as such, will be more expensive than lower quality grades. This has to be accepted as an inherent part of the process cost. The deposition rate for most electroless processes is rather lower than that for the analogous electrodeposition reaction. This implies that for thicker deposit, relatively longer tank times are involved. Maintaining the recommended concentrations of metal ions and other species in the bath, is critical. When depositing very thick layers, there should be sufficient metal in the bath (in ionised form) to allow such deposit to form without significant depletion of the bath. After such deposition, the bath must be replenished, but doing so in the middle of a deposition operation is not recommended. Satisfactory deposit quality will only be obtained when the concentration of all species in the system lie within the permitted ranges. When this is not so, and indeed when the concentrations of by-products such as phosphite, accumulates above permitted levels, not only will deposit quality suffer, but spontaneous metal deposition may occur or the electrolyte may become inactive. In either case, the electrolyte becomes unusable with financially adverse consequences. In summary, the composition of an electroless plating bath will change during operation, becoming depleted in reactants, accumulating impurities and reaction products and all of these will affect deposit properties, usually adversely. For this reason, monitoring bath composition, density, pH and deposition conditions such as temperature, is absolutely essential. Some comments on these are made below.
3.2.2.2.1 pH value pH (defined as - l o g CH+) is a measure of the hydrogen ion concentration in solution. In all but the most dilute solutions, the concept of concentration is usually replaced by that of 'activity' which can be seen as a measure of concentration, but with adjustment to take account of interaction of neighbouring species in solution. At higher concentrations, a given ion will be less 'active' than would be the case in dilute solutions. The above definition can then be replaced by pH = - l o g all+. The pH value of a metal deposition electrolyte is critical, because it can influence:

9 9 9 9 9

the the the the the

electrical conductivity of solution, extent of corrosion of the substrate immersed in solution, deposition rate, co-evolution of hydrogen, deposit properties.

Figure 3.11 illustrates the effect of pH on metal deposition rate for the electroless nickel-phosphorus system. Such solutions are buffered, as described above, to

Electrolytes for the Deposition of Metal Coatings 8 3

rE

30-

pH 5.5 pH 5.2

t_

g 20
~ a 10

pH 4.9

0 80
Figure 3.11

8'5
-I~ Temperature [~

9'0

Effect of pH on deposition rate of electroless nickel-phosphorus.

7-

~6t.O

r -~ 5 -

70~ 60oc 50~

4-

~_3

0
Figure 3.12

15 3 5 - - ~ Deposition time [min]

60

Effect of bath temperature on deposit thickness for electroless palladium deposition.

maintain the correct pH value. Even modest pH changes can affect not only the deposition rate but also the amount of phosphorus included in the deposit. The latter exerts a considerable influence on the mechanical and chemical properties of the deposit.
3.2.2.2.2 Electrolyte temperature

Maintaining close temperature control of the deposition bath is one of the most important criteria in operating electroless deposition processes. It determines deposition rate and bath stability, as Fig. 3.12 shows. Under actual operating conditions (e.g. components from a cold storeroom being introduced into a hot bath), bath temperatures can vary by several degrees celsius. Increase in temperature will result in a higher electrolytic conductivity, and because all reaction rates are accelerated, will increase the rate of consumption of additives in solution.

84

Electroplating- Basic Principles, Processes and Practice

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Electrolytesfor the Depositionof Metal Coatings 8 5

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