PROCESSES AND APPLICATIONS FOR TIN AND TIN-BASED ALLOY SURFACE COATING TECHNOLOGIES

A Technical Review and Assessment of Recent Developments Compiled for Tin Technology
'

STAGE 2 CHEMICAL DEPOSITION

1

PART 1 IMMERSION AND ELECTROLESS PLATING

B Y L. M. Baugh, BSc, MSc, PhD, Chem, FRSC Consultant

November 2005

0
CONTENTS

0
1

Introduction

2.

............................................................................. Fundamental Studies of Plating Processes ..................................... 2.1 Immersion Plating .............................................................
2.1.1 2.1.2 2.1.3

5 7

0
2.2

Sn onto A1.............................................................. 7 Sn, Ag and Sn-Ag onto Cu .......................................... 10 Underpotential Deposition of Sn onto Cu ........................ 13

EZectroZess Plating ........................................................... 2.2.1 2.2.2 2.2.3

15

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3

SnontoCu............................................................ 15 Sn-Ni onto Cu ........................................................ 18 Sn onto Miscellaneous Substrates ................................. 20

Experimental Conditions and Applications in the Field of Solders/Electronics

3.1

................23
23

Immersion Plating 3.1.1

...........................................................

Sn ...................................................................... 3.1.1.1 3.1.1.2 3.1.1.3 3.1.1.4 3.1.1.5 3.1.1.6

23

0
3.1.2

Plating Solutions and Methodology.................... 23 23 Immersion Tin Thickness ............................... Plating Adhesion and Bond Enhancement....... ....24 WhiskerDendrite Control ............................... 25 Ageing Studies ............................................ 27 Organic Metals ............................................ 28 30

0 0

Sn-Ag..................................................................

3.1.2.1 Plating Solutions and Methodology.................... 30 3.1.2.2 Plating Adhesion and Bond Enhancement............ 30 3.1.3 Sn-Bi ........................................................................................ 3.1.3.1 Plating Solutions and Methodology.................... 3.1.4 Sn-Zn .................................................................. 3.1.4.1 Plating Solutions and Methodology.................... 30 30 31 31

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2

3.1.5

Sn-Pb .... . ..... ....... ...... ... ... ............ ..... .... ... ...... ... ....31 3.1.5.1 3.1.5.2 Substrate Surface Pretreatment.. . . .. .. . . .... . . . ...... ..32 Plating Solutions and Methodology.. . . .... . . . ... .. . ...32

3.1.6

Complexing Agents. . . . ... . ..... . . .. .. ...... . .. . .... . .... .. . ... ..... 32

3.2

Electroless Plating..

.........................................................33

. 3.2.1 Processes involving Sn2+. . . ... . .. . ... . . . . .. .... . ... . . . ... .. .. .. . ...33
3.2.1.1 3.2.1.2 3.2.2 3.2.3 Coating of Plastics.. . . . .. . . . .. . . ... .... . .. . . ...... . .. . . .. 33 Lead-Free Alloy Electroless Plating. . . . . . . . .... .. . .. ..34

Sn-Zn.. ..... .... .. . .. . ...... ... .. ... . ... .. . .. . ,. .... .. ... ...... . ... ... .34 Sn and Sn-Pb.. .. ....... .. ............... . .. . .. .... ...... ..... . ... ... .34 3.2.3.1 3.2.3.2 3.2.3.3 Plating Solutions and Methodology. . .. . .... .... . ......34 Adhesion and Compactness.. ... . .... . . . ... . . . .... . . . ... 35 Joining Strength .......................................... 35

4.

Experimental Conditions and Applications i the.. ....... n Field of Corrosion Protection 4.1 Immersion Plating of Copper Tube...... .
4.1 . l . 4.1.2 4.1.3 4.1.4 4.1.5

..................36

. ...............................36

Optimisation of Pre-plating Processes.. . .... . . . . .. . . . . . . ... . ., . ..36 Initiation and Formation of Immersion Layer.. .... .. . . .... . .. .. 39 Uniformity of Immersion Sn.. .. . ... . . . . .... ... . .... . .... ... ... ... .42 Effects of Surface Contamination.. , ... .. .... . .... .. ..., ... ..... . .43 Other Processes. . . . . ... . .... . .. . . . ... .... .. .. . . .... . . ... . ... . . . . . ... .45
45

4.2 Electroless Plating of Copper Tube...................................................

4.2.1 4.2.2

Autocatalytic Process.. .. ... . .. . . . . .. .. . . . . . . . . . . . .. . . . .. . . . . .. . . ....45 Other Processes. . . . ...., .. .. . .. . ...... .. .. . . . . ... . . .... . .... . . .., .. . .5 1

4.3 Immersion Plating of Aluminium.

4.4

....................................... 51

Immersion Plating of Steel

.................................................51

5.

Experimental Conditions and Applications in the ...... Field of Power Sources

5.1 Immersion Plating

.....................53
53

...........................................................

5.1.1 Alkaline Manganese Batteries.. . . . . . . . . . . .. .... . ... . . . .. . . . . . ... .. 53

5.2

Electroless Plating.. 5.2.1

........................................................ 53

Lithium-Ion Batteries.. . . .. . . . . ... .. . . . . . . . .. .. .. . ... . . .,... .. .......53 5.2.1.1 Tin Coated Graphite.. . .. . . .. .... ... . ... . . .... . . . . . . . . . ...54 5.2.1.2 Mesocarbon Microbeads.. . .. ....... .. . ..... .. . . . .. . . ....57 5.2.1.3 Miscellaneous TidCarbon.. .. . . . . .... . ..... .. . . . .. . . . ..59

5.2.2 Photovoltaic Cells.. ...... .. . .. ....... . . ... .... . . . ... . . ... . . . ... ... . .60 5.2.3 Fuel Cells.. .,.. . . ... ...... .. . ..... ... . .. . .. . .... . . .. . ... .. .... ... ... .. 60

6.

Extended Summary ............................................................... References ....................................... Acknowledgements.. ........ .............

67

7.
8.

....................................78

........................................83

1. Introduction

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The current review forms part of a series concerned with detailed analyses of recent progress in the science and technology of tin and tin alloy coatings. Earlier works [ 11 covered developments in Electrolytic Plating (Stage 1). These included: the electroplating ofpure tin (Stage 1, Part 1); corrosion resistant tin alloys (Stage 1,Part 2); the use of electrodeposited tin alloys in electrochemical power sources (Stage 1, Part 3) and the formation of solders and applications in electronics (Stage 1,Part 4). Stage 2 of this exercise is concerned with Chemical Plating and the current report (Stage 2, Part 1) focuses on the very important topics of immersion and electroless processes. Both of these processes occur spontaneously without the need to apply an external current. Immersion plating (sometimes known as displacement or substitution plating) is a process where deposition is by displacement of elemental metal from a substrate by 2. metal ions in a plating solution [ ] Since plating is by displacement, immersion plating is an electrochemical reaction that depends upon the position the substrate metal occupies in the electrochemical/electromotive series relative to the metal to be deposited from solution. Plating occurs when the metal from a dissolved metal salt is displaced by a more active (less noble) metal immersed in the solution. For example, when a steel part is immersed in a copper sulphate solution, the following reaction occurs: Fe + Cu

Cu + Fe

The iron displaces the copper from its solution and the copper is deposited on the steel. Similar reactions can be written for the case of the immersion plating of copper onto zinc and aluminium. However, the reverse of these processes may be contrived with the careful choice of solution composition. For example, since copper is more noble than tin, tin would not be expected to be plated by immersion onto a copper substrate. But when the solution contains complexes under acidic conditions, the electrode potentials of the tin complexes relative to copper are reversed, making immersion plating possible. This is clearly a very important reaction in the field of solders/electronics. The thickness of depositsobtained by immersion plating is limited, because the deposition ceases when the entire surface of the metal is coated. Higher temperatures increase reaction rates of immersion baths and stirring is sometimes beneficial. Parts must be properly cleaned prior to immersion. Immersion baths are usually inexpensive and have excellent coverage. They permit plating on difficult surfaces, such as the insides of tubing or in cases where there is difficulty in making electrical connections to isolated areas of the base metal.

0 0 0

Electroless plating (sometimes known as autocatalytic plating) differs from immersion plating because additional reducing agents are required to reduce the metal ions of the depositing metal, since the base metal does not act as a reducing agent [3]. This process also differs in that thicker deposits can be produced, since the only requirement is for the replenishment of the reducing agent consumed and the removal of reaction products in the solution. However, there appears to be much

confusion in the literature concerning the differences between immersion and electroless processes and the terms are often used interchangeably, namely in Japanese and certain American patents. In this report, the two processes will be considered separately where possible. The components of an electroless plating bath include an aqueous solution of the metal ions, one or more reducing agents, one or more complexing agents and bath stabilisers operating in a specific metal ion concentration, temperature and pH range. The base substrate being plated must be catalytic in nature. A properly prepared workpiece provides a catalysed surface and, once introduced into the electroless solution, a uniform deposition begins. In electroless plating, metal ions are reduced to metal by the action of the reducing agents which are simply electron donors. The metal ions themselves are electron acceptors which receive electrons from the reducing agent. The catalyst is the workpiece or metallic surface, which accelerates the electroless reaction. During electroless plating, by-products of the reduction, together with dissolved metal salts, can accumulate in the solution. These can affect the performance of the plating bath. The metal ion and reducer concentrations must be monitored and controlled closely in order to maintain proper ratios, as well as the overall chemical balance in the bath. The electroless plating deposition rate is controlled by temperature, pH and metal iodreducer concentration. Each of the particular plating ractions has optimum ranges at which the bath should be operated. The complexing agent, also known as a chelator, acts as a buffer to help control pH and maintain the free metal salt ions available to the solution, thus allowing solution stability. The stabiliser acts as a catalytic inhibitor, retarding the potential spontaneous decomposition of the plating bath. The latter compounds determine the composition and brightness of the deposit. Trace impurities and organic contamination in the plating bath, e.g. degreasing solvents, oil residues, mould releasers, etc., will affect the properties and appearance of the deposit. An improper balance and control will cause deposit roughness, porosity, changes in final colour, foreign inclusions and poor adhesion.
An assessment of the applications of immersion and electroless plating processes involving tin and tin alloys has shown that they fall into three major categories: viz. solders/electronics, corrosion resistant coatings and uses in the field of power sources (batteries, photovoltaic cells and fuel cells). These applications are discussed in separate sections of the report. However, the investigations reported in some of the scientific and much of the patent literature, though important, are somewhat empirical in nature. In view of the complexity and diversity of the chemical reactions that pertain in immersion and electroless plating, it was considered instructive to commence the discussion with a consideration of recent fbndamental studies of the mechanisms involved, in order to provide an initial basic level of understanding.

e a a a a a e a a a a e e a e e e e e a a e a

2. Fundamental Studies of Plating Processes

2.1

Immersion Plating Sn onto A1

2.1.1

Aluminium and its alloys offer many advantages as construction materials in several major areas of mechanical engineering. The basic shortcoming of these materials, restricting a wider application, is their relatively poor corrosion resistance in different hostile media. However, the highly negative potential of aluminium and its pronounced chemical activity render the metal and its alloys a very difficult substrate for plating protective (or decorative) coatings. Stoychev et al. [4] have camed out a systematic investigation of the immersion and deposition processes of thin tin coatings used as an 'underlayer' for the deposition of the 'multilayer' system Cu/Ni/Cr onto a typical aluminium alloy, applied in the automotive industry and other branches of mechanical engineering. The tin coatings were deposited from an alkaline stannate electrolyte containing sodium stannate (90 g/l); sodium hydroxide (1 1g/l) Rochelle salt (20gA); and a chelate compound (1 5g/l). Rectangular substrates 30 mm x 20 mm x 4 mm were prepared from an aluminium alloy type 1917 (1.3 - 1.8 wt % Mg; 3.4 - 4.0 wt % Zn; 0.15 - 0.22 wt % Zr; 0.2 - 0.6 wt 'YOMn; 0.08 - 0.2 wt % Cr; and impurities of Ti up to 0.1 wt %; Cu up to 0.1 wt 'YO;Si up to 0.3 wt % and Fe up to 0.4 wt %). The amount of deposited tin (the current yield) and the quantity of dissolved aluminium were determined by atomic absorption analysis of the solutions before and after the depositions. The morphology of the tin coatings was monitored by means of routine electron microscopy. Some of the results of these investigations are presented below. Fig. 1 (curve 2) shows that the rate of immersion deposition of tin up to the 30th g cm-2s-' and after that it increased and became established at second was 7 x about 1.5 x lo-' g cm-2s-'. In parallel with this process, the aluminium dissolution dependence followed an inverse relationship. After the 30thsecond, the aluminium dissolution rate suddenly fell and reached 2 x lo-*g cm-2 s-1 . It was conspicuous that the change in the slope of both curves commenced almost'at the same instant, viz. approximately the 30thsecond.

a a e
10

0
30
50

70

90 T ! ,

a
Fig. 1. Dissolution rate of aluminium vs. time (curve 1) and immersion deposition rate of tin
vs. time (curve 2) [4].

a
7

The aluminium dissolution process became significantly inhibited with the continued deposition of tin. It was concluded that after the 30thsecond, an adequately dense tin film was formed on the aluminium substrate, so that only those aluminium atoms, which were required for the substitution reaction with tin and situated at the base of the pores in the film, were active. Fig.2 shows a plot of the thickness of the film vs. time in the immersion process. Also shown is a plot of film thickness vs. time when an electrodeposited coating was It produced using a current density of 0.25 A dmm2. can be seen that under these im conditions the rate of growth of the fl produced by the two methods was very similar. For plating durations of practical importance (15-60s) the thickness of the film varied between 120-54OA. It is clear from Figs. 1 and 2 that the rate of growth of the tin film shows no signs of decreasing within the time scale of the experiments,

Fig.2. Thickness of the tin coating vs. time: curve 1, electrodeposited at a cathodic current density of 0.25 A dm-2; curve 2 immersion plated [4]. Fig. 3 shows SEM micrographs for samples plated for different times. The initiation (Figs. 3b-3d), growth (Fig. 3e) and complete coverage of the film (Fig. 3f) can be discerned. Tin deposition onto aluminium alloy 1917 is compounded by the presence of iron impurities. These are segregated at the surface of the alloy where they function as active sites for the deposition process. The iron particles are ideal sites for the cathodic reactions of tin deposition and hydrogen evolution. Any oxide film present on the alloy is also broken at iron-rich sites due to local alkalization. Clearly a large number of parallel processes occur during the immersion plating of the alloy and the exact electrochemical mechanism and its time dependence is somewhat complex. The background to this subject has been discussed by Stoychev and Stoyanova [ 5 ] .

e e e e e e e e e e e e e e a a e e e a e e
Fig. 3. SEM micrographs of tin coatings deposited onto aluminium alloy 1917 at deposition durations: (a) Is; (b) 3s; (c) 5s; (d) 10s; (e) 20 s; (f) 30s. (Magnification x 20,000) [4]. It can be assumed that the nature of the reactions that occur are basically electrochemical and they represent a system of two partial electrode reactions. In the case of stannate immersion treatment, they can be represented as: Anodic Cathodic 4A1- 4A13++ 12e 3sn4++ 12e + 3 ~ n
(1)

(2)

This indicates that for every 4 anodically dissolved aluminium atoms, 3 tin ions will be reduced. However, this is an oversimplification of the overall processes because corrosion reactions, occumng in parallel with the above, must also be taken into account. These are continually attacking the substrate metal and give rise to the

evolution of hydrogen throughout the course of the deposition. The overall reaction for the corrosion of aluminium can be represented

The partial currents for all the processes have been measured under the same experimental conditions as those described above [ 5 ] . Fig. 4 shows the results.

10

30

50

70

90

110

r,s

Fig. 4. Relationship between the currents of: A dissolution (curve l), Sn deposition (curve 2), 1 hydrogen evolution (determined by two different methods, curves 3 and 4) and the overall cathodic process (curve 5) and the duration of the immersion treatment [ 5 ] . It is clear from these considerations that during the immersion treatment of aluminium and its alloys in stannate solutions that, depending upon the duration of immersion and the formulation of the stannate immersion solution, the ratio between the rate of the two cathodic reactions (tin deposition and hydrogen evolution) can vary over a wide range. The possibility therefore exists to control these processes according to a predetermined pattern and exert a beneficial effect on the characteristics of the tin coating. 2.1.2 Sn, Ag and Sn-Ag onto Cu -

Lead-free solder joint technology has become an urgent issue in the electronics industry. In particular, the choice of surface treatment procedures for coating electronic and semiconductor parts has become an important concern. The development of lead-free solder electroplating technologies, for example, Sn-Cu, Sn-Bi and Sn-Ag, has been significantly advanced (see previous reports [ 13 for a detailed discussion). However, very few attempts have been made to study the immersion plating of these alloys in any fundamental detail. Arai et al. [6] have recently developed a process for the immersion plating of Sn-Ag . The bath contained potassium pyrophosphate (lGP207) and I as complexing agents U for Sn and Ag, respectively, and thiourea (CS(NH&) as the complexing agent for the

10

0
Cu. The metal salts were derived from AgI (0.008 M) and tin pyophosphate (0.1 M). Thiourea (TU) could only be dissolved in the baths to approximately 1 M at room temperature. Higher concentrations were produced by heating them to 90C. The pH of the baths was adjusted to 5 by addition of HC1 before the TU was added. Pure copper plate (3 x 5 x 0.03 cm) was used as the substrate. This was degreased in alkaline solution and then activated with 10 wt % sulphuric acid. Electroless plating was conducted by fully immersing the Cu substrate into the plating bath for 60 minutes. The temperature was 90C and no stirring was carried out. The volume of the plating bath was 0.1 dm. In order to explore the mechanism of the plating process, anodic and cathodic polarization measurements were made in the plating solutions. To aid an understanding of the reactions, separate experiments were conducted to determine the characteristics of the individual Sn plating and Ag plating processes on the Cu substrate. Fig. 5 shows the relationship between the composition of the Sn-Ag films deposited and the concentration of TU.

0
Concentration of TU / M

0
Fig. 5.Relationship between the concentration of thiourea and the composition of the deposits [61.

All deposits obtained in the range of TU concentrations from 2 to 8 M were codeposits of Sn and Ag. The content of Ag in the deposits decrease with increasing TU concentration. However, the minimum value of the Ag deposit was 24 at.%, which was considerably larger than the eutectic composition (Sn-3.8 at.% Ag). Fig. 6 shows the SEM micrographs of the films deposited. The grain size of the deposits decreased with increase in TU concentration (decrease in Ag content).

0
11

Fig. 6. SEM micrographs of the copper substrate after the immersion test for 60 min at 90 "C. (a) TU = 2 M (Sn-52 at.% Ag); (b) TU = 3 M (Sn-47 at.% Ag); (c) TU = 5 M (Sn-42 at.% Ag); (d) TU = 8 M (Sn-33 at.% Ag) [6].
-

Fig. 7 shows the X-Ray diffraction pattern of the Sn-24 at.% Ag alloy f l . the i m All peaks from the film were attributed to the p-Sn phase and the E (Ag3Sn) phase.

Fig. 7. X-Ray diffraction pattern of Sn-24 at.% Ag alloy film [6]. Fig. 8 illustrates the anodic and cathodic polarization curves that represent, respectively, the dissolution of copper (curve a) and the deposition of Sn-Ag (curve b). The anodic curve was determined with the copper substrate as the working electrode and the cathodic curve was determined with a silver working electrode. The current increase in curve (b) at -0.7 V was attributed to the deposition of Ag. The abrupt current increase from -0.8 V was attributed to the codeposition of Sn-Ag. It was also considered that the plateau in curve (b) in the range -0.9 to -1.1 V indicated a limiting current for the codeposition for the Sn-Ag alloy of 0.8 A dm-2.Finally, the current increase at more negative potentials than - 1.1 V was considered to be due to hydrogen evolution. Polarization curves of the type shown in Fig. 8 are extremely useful as a means of illustrating the approximate magnitude of the currents flowing during the immersion plating process. However, it should be noted that the cathodic curves can only be obtained using a working electrode consisting of the plating metal (or one of them in the case of alloy plating) and not the substrate metal itself. This means that serious errors can occur if attempts are made to interpret the data quantitatively. The approach

12

a a a a a a a a a a a a a

described in this study therefore contrasts with that described previously in the case of the immersion plating of aluminium by tin (Section 2.1.1) where an aluminium substate was used throughout the investigations and the deposition and hydrogen evolution rates were determined by non-electrochemical methods.

a a a a a a

Fig. 8. Anodic and cathodic polarization curves: (a) 0.4 M K4P207 + 1.5 M KI + 8 M thiourea, worlung electrode Cu; (b) As in (a) + 0.1 M Sn2P207 0.008 M AgI, working electrode Ag + [61.
2.1.3

Underpotential Deposition of Sn onto Cu

Very recently, Fujiwara [7] has described the special experimental conditions that can give rise to the underpotential deposition of Sn onto a Cu substrate by a contact immersion process. Fig. 9 shows the experimental arrangements schematically.
Short-qircuit

a a a a a a a a a a a a a

Fig. 9. Experimental setup for two types of contact immersion processes: (a) Cu substrate dipped in Sn(1I)-citrate solution with suspended Sn powder, (b) Cu substrate and Sn sheet short-circuited and both sheets dipped in Sn(I1)-citratesolution. 1-Thermometer; 2-Silicon rubber lid; 3-Thermostated Water; 4-Condenser; 5-Cu substrate; 6-Sn(II)-citrate solution containing Sn powder; 7-Magnetic bar; 8-Glass fnt; 9-Polyethylene coated Cu wire; 10Sn(1I)-citrate solution; 11-Sn sheet [7].

13

The solutions contained 0.1 M SnS04 and 1.O M trisodium citrate. The pH was adjusted to 6.2. Two series of contact immersion experiments were carried out. In the first, a Cu substrate was dipped into the Sn(I1)-citrate solution containing 90 g/1 of suspended Sn powder (99.9%, diameter < 150 pm). In the second, a Cu substrate and a Sn sheet were dipped into Sn(1I)-citrate solution without the metallic powder suspension, but were electrically short-circuited to each other. The solutions were deaerated with NZand vigorously stirred. The Cu substrate was degreased by cathodic electrolysis in a 100 g/1 I(4P207, 50 8/1 KOH solution, dipped in a diluted H2S04 solution and rinsed with purified water just before the deposition experiments. The results obtained by these conditions produced quite different deposits from those discussed earlier. In particular, the deposition of a Sn film was not observed, but rather intermetallicphases, CusSnS, CuloSn3 and Cu3Sn. It was proposed that the formation of these phases at the copper surface was initiated by site changes between the underpotentially deposited Sn atoms and the Cu substrate atoms. It was also proposed that the growth rate was determined by solid-state difhsion of Sn and Cu atoms through the intermetallic phase layer. The solid-state diffusion mechanisms were confirmed by the activation energy of the diffusion process, 98 kJ mol- K, estimated from the parabolic rate constants, which agreed well with the literature value of the difhsion controlled growth of a Cu3Sn layer of 96 kJ mol- K-I. A parabolic rate law generally indicates the diffusion controlled growth of the film and is expressed by the equation

Ax = d2Dt
where Ax is the film thickness at time t and D is the mutual difhsion coefficient through the film. The law was confirmed as shown in Fig. 10.

(4)

v)

i 0.10 0

rc

CJ, .a,

t u

1s

112

Fig. 10. Weight of deposited Sn as a function of the square root of immersion time, t2.Open symbols: Cu sheet dipped in a solution containing metallic Sn powder. Closed symbols: Short-circuited immersion in a solution without Sn powder [7].

14

Fujiwara claimed that the alloy film formation processes described above have the following advantages compared with electrodeposition, autocatalytic deposition or displacement reactions: (i) an external current source is not needed, (ii) accumulation of the oxidation products of the reducing agent does not occur, and (iii) accumulation of the metal ions dissolved from the substrate does not occur. However, the limitations of these processes are that the deposited films essentially contain constituents of the substrate and that the deposition rate is determined by the relatively slow solid-state diffusion mechanism. 2.2 2.2.1 Electroless Plating

0
Sn onto Cu
Electroless (or autocatalytic) plating gives the possibility of selective deposition of metals to unlimited thickness. Molenaar and Couman [44] developed an autocatalytic deposition process by a disproportionation reaction in which the oxidation of one tin(I1) ion at the surface supplies the two electrons for the reductiuon of a second tin(I1) ion to metallic tin. The metallization solution contains tin(I1) chloride, sodium hydroxide, sodium citrate as a complexing agent and sodium hypophosphate as a reducing agent, at a temperature of 70C. Accordingly, tin could be plated from the stannate ion as follows: 2Sn(OH)3- + Sn + %(OH):However, the details of this process remained obscure. Later, Koyano et al. [8] attempted to investigate the reaction more thoroughly and improve the method of practical application. It was found that very specific conditions were required to produce satisfactory results. Rolled copper sheet (30 x 30 x 0.4 mm) was used as the specimen. A special surface preparation procedure involving alkaline degreasing and acid cleaning was first applied. It was found that the electroless plating process occurred preferentially on a tin surface. Hence, prior to the main electroless plating, a very thin film of tin (0.5 pm) was formed on the copper substrate by conventional plating. Following this, the surface was activated in HC1 solution and then plated by the disproportionation reaction. The electroless plating solution consisted of KOH ( NaOH or LiOH), SnC12 and further additions of sodium hypophosphate and sodium citrate in certain experiments. The alkaline solutions were added into the stannous chloride solutions to prepare the plating solutions. A large number of experiments using different alkalis and mole ratios [MOH] / [Sn(II)] were required to determine suitable bath compositions where the solution remained transparent and therefore stable under the plating conditions of 70C for 1 hour. Only a small composition window was found to be available (< 0.6 M SnC12 and [MOH] / [Sn(II)] ratios of 10-13, 10-20 and 9-16 for Li, Na and K baths, respectively).
(5)

In order to explore the plating mechanism, preliminary experiments were performed to establish the materials balance of the reaction. Ten sheets of the specimen were immersed in 250 ml of the plating solution for 2 h at 80C whose Sn(I1) and [MOH] / [Sn(II)] ratio were fixed at 0.3 M and 13, respectively. The change in weight of the samples and the change in the concentration of Sn(I1) and Sn(N) were then

15

determined. In .any solution it was found that the molar ratios of ASn(II):ASn(IV): ASn became 2: 1:1, where A signifies the change in concentration observed. This confirmed the validity of the disproportionation reaction (5). Fig. 11 shows the relationship between the weight of tin deposited and plating time when [MOH] / [Sn(II)] = 13 for different [Sn] values between 0.2 and 0.4 M and Fig. 12 shows the effect of Sn(I1) concentration on the plating rate.

T iiiie ( 11
Fig. 11. Variation of Sn weight with time: closed symbols K bath, open symbols Na bath [8]. Fig. 1 1 indicates that the coating weight increased linearly with time. The disproportionation proceeded continuously at a high rate especially in the potassium bath. The rate in the latter bath was twice that in the sodium bath. Fig. 12 shows that the rate of plating increased exponentially with increase in Sn(I1) concentration. The plating rate was also found to increase exponentially with temperature. A relatively Furthermore, the hypophosphite bright and smooth coating was obtained at 70-75 "C. reducing agent had only a marginal influence on the rate of plating and it was concluded that the presence of a reducing agent was unnecessary in this type of disproportionation plating. However, the citrate complexing agent was found to be effective as an 'accelerator'.

16

e
IS

I I

2
M

10

0
0 ) .

c,
4

.-

; n
U4

r 5
0

s
0

0
Fig.12. Influence of Sn(1I) concentration on plating rate [8]. The authors claimed that the plating methods described above could be satisfactorily applied for practical purposes, especially in the plating of electronic parts necessary for soldering. In this regard they investigated the morphology of the deposits on two copper surfaces, firstly, using the preparation procedure described earlier, and secondly, that involving an additional electroless copper plating treatment to a thickness of 3p.m directly following the acid cleaning of the rolled copper sheet. Figs. 13a and 13b present scanning electron micrographs of the tin surfaces without and with the additional plating step, respectively. A smoothing effect of the additional electroless plating step on the morphology of the deposit is evident.

0
Fig. 13. Scanning electron micrographs of tin plate: (a) without underplated copper layer, (b) with additional underplated 3p.m electroless copper layer [8].

0
17

2.2.2 Sn-Ni onto Cu The preparation of Ni-Sn alloys by an electroless deposition method has been described by Shimauchi et al. [9]. Ni-Sn is used as a hnctional material because of its excellent corrosion resistance, wear resistance and solderability. Electrodeposited Ni-Sn films are used as a decorative coating, an etch resist in printed circuit board manufacture, a connector-finish with a thin gold overlayer, etc. They usually contain 40 50 at.% tin and it is a metastable compound that corresponds closely to the formula NiSn [9]. However, electroless plated Ni-Sn films contain only small amounts of tin compared to the electrodeposited alloy films, eg. ca. 25 at.% tin using dimethylaminoborane (DMAB) as a reductant and ca. 10 at.% tin using sodium hypophosphite or hydrazine. The objective of the work of Shimauchi et al. was to investigate the factors and operating conditions of electroless Ni-Sn plating in order to increase the tin content. Because of the phosphorous and boron contents of the reducing agents used, the alloys actually generated were Ni-Sn-P and Ni-Sn-B, respectively. Experiments were also conducted to produce NI-P and Ni-B coatings. The solderability and corrosion resistance of the films were determined.

The Ni-Sn-P basic bath consisted of nickel sulphate (0.10 M); trisodium citrate (0.12 M); sodium hypophosphite as the reductant (0.20 M); and sodium stannite (0.003 M) as the source of tin. The normal bath temperature was 90C and the pH was 10.0. The Ni-Sn-B basic bath consisted of nickel sulphate (0.10 M); trisodium citrate (0.20 M); DMAB (0.04 M) as the reductant; and sodium stannate-gluconate complex (0.05 M) as the source of tin. The normal bath temperature was 70C and the pH was 9.0. Copper sheeting (20 x 20 x 0.1 mm) was used as the substrate material. This was degreased and then catalysed in a single step process using PdC12 dissolved in HC1. Electroless Ni-Sn-P and Ni-Sn-B platings were camed out for 10 and 30 min, respectively. In the studies of structural properties, solderablity and corrosion resistance, the film thicknesses were adjusted in the range 1.8-2.5 pm by adjusting the plating duration.

In the case of the Ni-Sn-P alloy, the most effective factor for tin codeposition was the trisodium citrate concentration. Fig. 14 shows the effect of this parameter on the deposition rate and the film composition of this alloy. The tin content in the deposit increased with an increase in the trisodium citrate concentration in the bath and the maximum value was ca. 30 at.%, whereas the phosphorous content decreased. The deposition rate decreased with an increase in trisodium citrate concentration and at values above 0.25 M there was no deposition.

18

0
Naj citratc conc. / mol dm"

Fig. 14. Effect of trisodium citrate concentration on the deposition rate (o), tin content (A) and phosphorous content (A)of Ni-Sn-P films [9].

0
In the case of the Ni-Sn-B alloy, the most effective factor for tin codeposition was Sn4+-gluconateconcentration. Fig. 15 shows the effect of Sn4'-gluconate concentration on the deposition rate and the film composition of this alloy. The tin content in the deposit increased with an increase in Sn4+-gluconateconcentration in the bath and the maximum value exceeded 40 at.%. This was approximately equal to the value in an electroplated deposit. By comparison, the boron content was c 0.7 at.% in all deposits. The deposition rate was approximately constant in the range of experimental Sn4+-gluconateconcentrations, but at a value above 0.07 M, no deposition occurred.
Fig. 16 shows SEM images of the Ni-Sn-P alloy films with various tin contents, where the films were prepared from baths of varying trisodium citrate concentrations. The 'dome-like' projections became smaller with increase in tin content in the film. Similar morphologies and dependence upon tin content were observed in the case of the Ni-Sn-B alloys when the concentration of Sn4'-gluconate was varied.

0 '

E .-

0.25 F B content 6 0.7 at%!

-f

50

.
2
0 ..0 e

i;"
O - b

0.02

0.04 0.06 0.08

Sn4'-gluconateconc. I mol dm"

0
Fig. 15. Effect of Sn4'-gluconate concentration on the deposition rate ( 0 ) and tin content (A) of Ni-Sn-B films [ 9 ] .

0
19

Fig. 16. SEM images of Ni-Sn-P films with various tin contents [9]. Extensive corrosion tests were carried out on the various alloys in a range of corrosive media including sulphuric (0.5 M), hydrochloric (1 .O M) and nitric (1.O M) acids and also sodium chloride (- 1.O M). Dissolved oxygen was removed before these tests. The anti-corrosion ability in the inorganic acid and brine solutions produced the following ranking: Ni-P 2Ni-Sn-P > Ni-Sn-B > crystalline Ni-P Solderability tests using the meniscogram method and Sn-Pb (60 / 40) solder revealed the following ranking: NI-B > Ni-Sn-P 2 Ni-Sn-B > amorphous and crystalline Ni-P

2.2.3 Sn onto Miscellaneous Substrates

Comparatively early and detailed studies relating to the autocatalytic deposition of tin onto steel, nickel, copper, Al3S and poly(propylene), were conducted by Warwick and Shirley utilizing titanium(II1) salts as reducing agents [ 101. Specific surface preparation methods were described for all substrates. The composition of the normal plating electrolyte was as follows: tin(I1) chloride (7.5 gA); trisodium citrate (100 gA); sodium acetate (1 0 gA); benzene sulphonic acid (32% w/v; 1 ml/l); and titanium (111)

20

0
chloride (30% w/v;15 mV1). The pH of the bath was adjusted to pH -9 and the plating temperature was 90"C . The process of plating was assumed to take place through the reduction of Sn2+ ions at an active surface by a reducing species thought to be a complex of the Ti3+ion in which one of the ligands could be a tin-containing entity. The deposition onto steel and nickel proceeded at ap roximately 4 g m -2 h-1 . Copper could be plated at approximately 7.5 g m-2h- . The plastic substrate poly(propy1ene) was successfully coated at 3.7 g m-2 h -1 . Conspicuously, no apparent limit for tin coating thickness was observed under the experimental conditions imposed.

Fig. 17 shows the growth of the tin coating thickness on the three metals: steel, nickel and copper, and Fig. 18 that on the plastic, poly(propy1ene.

0
70 -

- 10
-8

60-

0
0

-1
0

-6

0
Steel
A Nickel

-4
0 Copper

6'

s 5

0
l ~ l ~ l ~ l

- 3
-2
l , l , l , l

e
~ l *

8 10 12 Plating time ,h

l 4

16

18

Fig. 17. The growth of tin coating thickness as a hnction of time onto steel (o), nickel (A) and copper (0) [ 101.

%t
0

/
1
1

14

6 .

Plating t i i ,h

Fig.18. The growth of tin coating thickness as a function of time onto poly(propy1ene) [101.

21

The morphology and growth of the deposit obtained from the normal plating solution is shown in Fig. 19 for steel and Fig. 20 for poly(propy1ene). An X-ray diffraction analysis showed the coating to be the standard room temperature p-tin allotrope.

(0)

(bl

(4

Fig. 19. Scanning electron micrographs of the tin deposit on steel after: (a) 5 min, (b) 30 min, ( c ) 3 h. The scale markers are 2 pm [ 101.

Fig. 20. Scanning electron micrographs of the tin deposit on poly(propy1ene) after: (a) 5 min, (b) 30 min, (c) 3 h. The scale markers are 2 pm [ 101.

22

3. Experimental Conditions and Applications in the Field of SoldersElectronics 3.1

3.1.1 Immersion Plating

Sn

3.1.1.1 Plating Solutions and Methodology

Coatings of tin (lead, bismuth and their alloys) have been applied to the surfaces of copper and copper-based alloys by displacement plating such as by immersion plating techniques. Chemical displacement plating has been used in the manufacture of printed circuit boards (PCBS) and particularly multilayer printed circuit boards. Printed circuit boards mainly comprise a non-conducting or dielectric layer such as fiberglass/epoxy sheet which is clad with a metal conductive layer such as copper on one or both surfaces. The metal layer on the PCB, before processing, typically is a continuous layer of copper which may be interrupted by a pattern of plated through holes linking both surfaces of the board. During processing, selected portions of the copper layer are removed to form a raised copper circuit image pattern. Multilayer PCBs are typically constructed by inter-leaving imaged conductive layers such as one containing copper with dielectric adhesive layers such as partially cured B-stage resin i.e. aprepreg, into a multilayer sandwich that is then bonded together by applying heat and pressure. Since the conductive layer with a smooth copper surface does not bond well to the prepreg, copper surface treatments have been developed to increase the bond strength between the layers of the multilayer PCB sandwich. One example of copper surface treatment is the use of immersion tin (or tin alloys) as a bonding media for multilayer circuits. Various patents have been filed in which an immersion tin composition has been disclosed containing thiourea compounds and urea compounds to displacement plate the copper surface of each PCB with tin prior to laminating them to form a multilayer board. Recently, Bokisa and Willis [ 11,121 have described in detail the solution compositions and methodology. The process is claimed for a variety of other metals including lead, bismuth, indium, gallium and germanium. The plating bath contains (A) the metal salts, (B) at least one complexing agent selected from the group consisting of thiourea compounds and imidazoles, and (C) at least one amidine. The baths also contain at least one acid and optionally one or more surfactants. The thiourea compounds may be represented by the general formula RIRZNC(S) NR& where R1-4represent a large number of potentially useful substituents, including alkyl; alkenyl; aryl aralkyl; cycloalkylalkyl groups; etc. A considerable number of combinations and permutations of suitable compounds for the plating bath are documented in the patents. 3.1.1.2 Immersion Tin Thickness

The technology of surface finishes for printed circuit boards is seeing a dramatic shift fiom hot air solder leveling (HASL) towards alternative finishes such as electroless nickel, immersion gold, immersion tin, immersion silver and organic solder preservatives. This trend is driven by the worldwide environmental pressure to ban the use of lead for electronic assemblies, as well as the demands of modem assembly

23

technology, which require higher co-planarity o f the surface finish for surface mount assembly. One of the main benefits of HASL is its extremely good resistance to ageing under high temperature conditions. Alternative finishes, due to their thickness, offer excellent co-planarity, but can result in inferior surface protection. As the thickness of the surface finish is critical to the performance, a good understanding of the true thickness deposited onto the copper substrate is essential with the existing and new finishes. In addition to measuring the true thickness, the effects on performance during assembly need to be determined. Lamprecht [ 131 has described the different thickness measurement techniques that enable reliable thickness assessments and the determination of the recommended immersion tin thickness for lead-free soldering. Immersion tin layers were prepared with systematically varying layer thicknesses. The samples were annealed at different reflow profiles, used in assembly for Sn-Ag-Cu alloy soldering. The layers were characterised with X-ray fluorescence, electrochemical stripping coulometry and by examining the cross-sections using scanning electron microscopy. The solderability was measured with a solder balance. It was shown that if all the pure tin is converted into S d C u intermetallic, so that no pure tin is left as a solderable layer, the wetting behaviour decreases dramatically. Especially for the multiple soldering processes, two reflows followed by wave soldering, it is essential to have a pure tin layer covering the S d C u intermetallic before going to the final soldering process. Owing to the higher temperatures used in lead-fiee soldering and therefore the greater tin consumption during the S d C u intermetallic compound formation, Laprecht concluded that the required tin thickness for multiple reflow soldering is 1.2 pm. 3.1.1.3 Plating Adhesion and Bond Enhancement Many highly varied processes of chemically or physically treating the surface of a metal substrate, such as copper, to improve the bonding of the metal to a polymeric material, such as epoxy or polyimide, are used in industries such as printed circuit board fabrication. The dielectric adhesive layer in a PCB is often a partially cured Bstage resin, referred to as a prepreg. Since the conductive layer that has not been treated does not bond well to the prepreg, various surface treatments have been developed to increase the bond strength between the layers in a multilayer PCB system . Dickson et al.[ 141 have devised a method of treating a metal substrate to improve adhesion of polymeric materials thereto. The process comprises the steps of intergranular etching a surface of the metal substrate and applying an immersion plating composition consisting of tin, (or certain other metals). The embodiment hrther comprises a step of adhering the immersion metal plated surface to a polymeric non-conductive material. The polymeric material may be PTFE, an epoxy resin, a polyimide, a butadiene terephthalate, etc. A further step involving the use of a silane coating over the immersion plated metal may also be included in the overall process.

24

0
Recently, McKenny et al. [ 151 have devised a process of multiple tin coatings that are claimed to have superior chemical resistance and enhanced adhesion in the fabrication of printed circuit boards. A sheet comprising at least a layer of copper is initially immersed in an acid tin solution containing a complexing agent for a time sufficient to produce a first heavy tin deposit. The sheet is then immersed in a second tin solution comprising stannous tin ions and stannic ions for a time sufficient to produce a thin tin deposit on the sheet. A rough texture providing mechanical adhesion sites results. The board is then treated with a coupling agent, such as a silane, for enhanced bonding to a subsequent epoxy or other polymer prepreg.

3.1.1.4 WhiskeriDendrite Control

In addition to problems associated with adhesion of copper to laminating materials, PCBs must also be treated in order to preserve the solderability of exposed conductors. PCBs are generally fabricated in a finished form by a board fabricator and shipped lacking certain circuit elements, which are added later by an assembly house. Therefore, in a finished PCB, some circuitry must be left exposed for later attachment, usually by soldering, of further circuit elements. It is critical that such conductors retain good solderability. Copper and copper alloy conductors have previously been coated with tin or tin alloys to preserve solderability. However, electrodeposited pure tin is subject to whiskering, a phenomenon well known in the PCB industry. Tin alloys such as Sn-Pb have been used to avoid the whiskering problem, but have the environmental disadvantage.
Bosika and Bishop [ 161 have shown that by applying to a substrate , e.g. a finished PCB, a first coating of tin from an immersion tin plating solution followed by a cap layer of an alloy of at least two immersion platable metals, a high degree of solderability can be preserved and the problem of tin whiskering can be avoided. The immersion platable metals in the alloy cap layer may be at least two metals selected from tin, silver, bismuth copper, nickel, etc. Full details concerning the bath compositions proposed, are given in the patent. Typical alloys in the cap layer include Sn-Ag, Sn-Bi, Sn-In, Sn-Ge, etc. Tin whiskers are hair-like growths of near perfect single crystalline structures of tin that grow from pure tin surfaces independently of plating character, i.e electroplated or immersion plated tin. Tin whiskers are believed to grow in order to relieve mechanical stresses acting within the tin layer. Over time (days or months to years), some whiskers have reached lengths capable of creating electrical short circuits between closely spaced conductors. Whisker growths are frequently defined as spontaneous in order to distinguish them from a completely different type of phenomena known as dendrites, which require the presence of moisture, an ionic species and an electric field in order to form. They have in fact been known to form in inert atmospheres and in vacuum with or without the presence of an electric field. Meeh [ 171 has recently described a state-of-the-art process for immersion tin plating of PCBs which is used to preserve solderability prior to assembly. The process sequence is described and preventative measures for handling the final surface finish documented. A solderability test method and basic requirements for fluxes and soldering parameters are also described. Quantitative results on the formation of intermetallic Sn-Cu phases are shown and their influence on the formation of tin

a a a

25

whiskers explained. Using newly developed additives or by heat treatment, whisker growth can be reduced to an acceptable level. Superior whisker-reduced immersion tin technology has been described by Schroeder [ 181. The latest findings on whisker formation on pure tin finishes are discussed and effective methodology for whisker suppression outlined, together with other benefits for the use of this new immersion tin generation. When tin is placed directly over a copper substrate, there will be intermetallic formation at the copper-tin interface with time. It has been found that the intermetallic formation occurs by copper diffusion into tin. Furthermore, the diffusion front is not evenly distributed throughout the coating and is dominated by grain boundary diffusion. There are areas where the intermetallic formation is fast and areas where it is slow. Since more matter is placed into a fixed volume, a compressive stress is generated in the tin film. The presence of tin oxide prevents the stress from being released. With time, this compressive stress keeps building up. Because the tin oxide layer is not perfect, there is always some defect present. Hence, when the compressive stress becomes high enough, it will break through the defect in the oxide layer and a whisker will form to release the compressive stress. Besides intermetallic growth, grain size and cleanliness of the deposit are also reported to contribute to the compressive stress. Stress build-up is due to the grain boundary diffusion of copper into tin. Hence, large grained tin is more stable regarding whisker formation because copper diffuses more slowly into these grains than into small ones. Furthermore, grain size also affects activation energy. Tin with a large grain size is thermodynamically more stable and less susceptible to recrystallisation. At the same level of compressive stress, it is more difficult to squeeze out a whisker from a large grain size tin than from tin with small grains. Schroeder [ 181 has shown that a nano-layer deposit from an organic metal-based pre-dip significantly reduces the diffusion by creating a unique sandwich layer with smooth concentration gradients. A drastic reduction in diffusion and stress is produced, eliminating the driving force for whisker formation and prolonging the layers shelf life and temperature stability at the same time. The organic metal used in an aqueous dispersion as a pre-dip prior to plating, catalyses the tin deposition and initiates the deposition of tin with a large grain size (cf. Figs. 21 and 22). The above discussion concerns the inhibition of whisker formation. However, an equally important requirement is the inhibition of dendrites. Tsuji et al. [ 191 have developed a solution composition containing phosphorous compounds which are claimed to suppress dendrite formation during the immersion plating of tin or tin alloys. The phosphorous compound is selected from inorganic phosphorous compounds such as orthophosphoric acid, pyrophosphonc acid, polyphosphoric acid, hypophosphorous acid, phosphorous acid and their salts and organic phosphorous compounds such as methylene phosphoric acid, alkyl phosphate and their salts. The compounds may be used singly or in combination.

26

a a a

a a a a a

Traditional Immersion Tin

a a a a a

Fig. 21(a) FIB images of a whisker. Fig. 21(b) Standard plating reaction and grain size of a common tin immersion process [ 181.

a a a

ORMECON CSN FFIFF-W Immersion Tin

0
Fig. 22. Tin deposition reaction with organic metal catalyst and resulting morphology [ 181. 3.1.1.5 Ageing Studies

a a

Options for solderability preservative coatings on printed circuit boards include organic (azole or rosinhesin based) films and tin based metallic coatings, Ray et al. [ 191 have compared the solderability performance and corrosion protection effectiveness of immersion tin coatings and organic azole films after exposure to a

27

series of humidity and thermal cycling conditions. It was shown that the solderability of immersion tin is directly related to the tin oxide growth on the surface and is not affected by the formation of Sn-Cu intermetallic phases as long as the intermetallic phase is underneath a protective tin layer. Thin azole films decompose upon heating in the presence of oxygen and lead to solderability degradation. Evaluations of leadfree solder pastes for surface mount assembly applications indicated that immersion tin significantly improved the spreading of Sn-Ag and Sn-Bi alloys as compared to mole finishes.

3.1.1.6 Organic Metals

Schroder (Omecon Chemie GmbH and Co.) has recently described the properties of a new generation of immersion tin as a solderable surface finish for printed circuit boards [ZO]. The new process combines the unique technology of organic metals with the well established technology of immersion tin. Organic metals have been developed from the group intrinsically conductive polymers. The organic metal ORMECON@belongs to the family of poly(ani1ines). This polymer is purely organic and consists of elements C, 0, H and S. It is electrically conductive and has a potential of a noble metal (between Ag and Cu). It has catalytic properties and can be reduced and oxidized without changing its form. The polymer is also largely insoluble and can be processed by dispersion. Omecon have integrated an aqueous dispersion of the organic metal into a classic immersion tin process as a pretreatment. Two important effects have lead to quality improvements in the tin layer:

1. Due to its property to switch repeatedly between different oxidation states (which means it can take and give away electrons) and the higher potential compared to copper, the polymer initiates a defined oxidation of copper surfaces. By taking electrons away from the copper surface it initiates the formation of only Cu' whilst Cu2+is avoided. This leads to a reproducible state of the board's copper surface prior to the immersion step. Since the quality of a surface finish is dependent upon the quality of the initial surface pretreatment, this is the first basic feature that helps to improve the quality of the tin deposit.
2. Because of the catalysis of the tin deposition reaction, the organic metal has a direct influence on the deposit morphology. In contrast to conventional immersion tin technology, the tin deposits in the new process form large flat crystals building a dense and compact layer. The form of these crystals leaves almost no room for impurities, which may be nucleation sites for whisker formation. Furthermore, large crystals provide a smaller area than small crystals, so the active area for oxidation processes is reduced for an organic metal immersion tin. The high density also slows down difhsion processes. The result is a slower transformation of pure tin into intermetallic compounds which are not solderable under usual process conditions.

Figs. 23 and 24 compare and contrast electron micrgraphs for the conventional tin
immersion and organic metalhmmersion tin deposits.

28

a a a a a a a a e a a e a a a e e

Fig. 23. Conventional virgin immersion tin surface finish. There are already signs of oxides on the surface and the deposit consists of small grain size crystals. The deposit is porous and provides a high surface area. Ideal conditions for encapsulation of impurities and diffusion and oxidation processes [20].

a a

e
Fig, 24. Organic metal/imrnersion tin surface finish. Flat crystals can be seen. They present a very dense and compact layer with a high resistivity against diffusion and oxidation [20]. The most important criterion for the quality of a surface finish of a printed circuit board is its solderability under various conditions. Schroder evaluated the parameters of solderability and wettability for different surface finishes including: hot air leveling (as standard); electroless nickel/immersion gold; immersion silver; immersion tin; and organic metaVimmersion tin. Accelerated ageing was conducted under the following conditions: 155C for 4 h; steam ageing; and 85% r.h./85"C/24 h. It was found that HAL was the most stable surface finish under any ageing conditions. Ni/Au only exposed a weakness under steam ageing conditions. Immersion tin, and especially organic metal/immersion tin, gave good results. Immersion silver gave poor results at

a a a e a a a a a a

29

155C for 4 h. In conclusion, it was claimed that the new process could act as a very good alternative surface finish in terms of cost effectiveness and quality.
3.1.2 Sn-Aq

3.1.2.1 Plating Solutions and Methodology Nishihama et al. [21] have devised a bath for the immersion plating consisting of SnAg alloys containing a water soluble tin compound such as tin oxide; a water soluble silver compound such as silver oxide; a water soluble sulphur containing organic compound having two monosulphide groups in the molecule; and a hypophosphorous compound. The pH is controlled to 5 7 with an acid such as hydroborofluoric acid and methanesulphonic acid. This combination is claimed to produce good bath stability. By adding to the plating bath thiourea compounds, the precipitation rate is improved and a thick deposit is possible at low temperatures. Arai et al. [22] have developed a Sn-Ag plating bath which again is claimed to have a high stability. The bath contains an oxyalkylene type aliphatic sulphide having an oxyethylenic group or an oxy(hydroxy1 propylene) group singly or repeatedly in the molecule. Thioureas are used as complexing agents. Instead of the above aromatic sulphide compound, alpha-mercaptomonocarboxylic acids such as alpamercaptopropionic acid or mercaptoalcohols such as thiglycolic acid may be used.

3.1.2.2 Plating Adhesion and Bond Enhancement

In order to improve the adhesion of a silver layer deposited from an immersion plating bath, Preznik and Jacques [23] have suggested a pretreatment method that involves bringing a less electropositive metal than silver (Zn, Fe, Ni, Pb, Cu, or their alloys) into contact with an azole compound before bringing it into contact with the immersion plating bath. The contact between the azole compound is preferably performed in the cleaning process or the etching process after cleaning. Such methods are claimed to be particularly useful in the manufacture of electronic devices.

3.1.3

Sn-Bi

3.1.3.1 Plating Solutions and methodology Melton et al. [24] have devised an immersion process for depositing Sn-Bi solder onto a copper surface. The method involves immersing the article into an acidic aqueous solution comprising a tin alkane sulphonate compound, preferably tin methane sulphonate, and a bismuth alkane sulphonatecompound, preferably bismuth methane sulphonate. The solution also contains thiourea. The bismuth compound is added in an amount sufficient to produce a bismuth concentration that is less than about 1.O g/l. Furthermore, the ratio of tin to bismuth in the solution is at least 30: 1 and preferably 50: 1. The process is claimed to deposit a dense adherent plate composed of a tinbismuth alloy containing at least 50 wt.% tin and preferably greater than 70 wt. %.

30

Tsuji et al. [25]have developed a method for producing eutectic Sn-Bi alloy films having bonding strength and appearance claimed to be comparable to a tin coating. The plating bath contains a soluble stannous salt, at least one organic acid such as sulphonic acid or an aliphatic carboxylic acid and an inorganic acid such as hydrofluoroboric acid or sulphanic acid, together with a complexing agent comprising a thiourea derivative or a mixture of a thiourea compound, a polyamine or an aminoalcohol. Cooper et al. [26] have proposed a complex method for the immersion plating of metals onto various substates, including the plating of Sn-Bi solders. A metal (designated metal 1) is plated onto a substrate (designated metal 2) by immersing the substrate into a bath comprising a compound of metal 1 and an organic diluent. Metal 2 is more electropositive than metal 1. The organic diluent has a boiling point higher than a eutectic point in the phase diagram of either of the metals. The bath is operated above ,the eutectic point but below the melting point of metal 2. For example, Bi can be plated onto lead-free tin-based solder balls and subsequently redistributed by fluxless reflow. The diluent can be selected from the group consisting of polyols, sulpholane, dimethyl sulpholane, dimethyl sulphoxide and tetraglyme or mixtures of these compounds. Ionic liquids and alkylpyridinium salts can also be used.

3.1.4

Sn-Zn

3.1.4.1 Plating Solutions and Methodology

Sn-Zn solders may be considered to be more desirable than many other potential substitutes for Sn-Pb, because their operating temperature is closer to that of the traditional Sn-Pb solders. However, zinc is a very reactive metal and oxidizes very quickly. This reactivity creates problems when used in solder compositions. Firstly, oxidized zinc creates wetting problems. Secondly, the zinc tends to react quickly with other components typically found in solder pastes, such as flux, thereby significantly reducing the shelf-life of the solders and solder pastes. Therefore, in order to take advantage of the beneficial properties of Sn-Zn solders, active steps need to be taken to keep zinc from oxidizing and reacting. Mei [27] has provided a substantially lead-free solder composition with improved wetting properties and extended shelf-life which comprises a solder material and an immersion coating having a thickness between 0.5 and 2 pm disposed about the solder material. The solder composition is preferably a Sn-9Zn eutectic alloy coated with another metal, e.g. Cu, Ag, or Au, but preferably a 1 pm thick layer of tin. A melting point suppressant may also be added to the alloy, e.g. In, Ag or Bi, to lower the melting temperature below 192C. The resulting Sn-Zn alloy powder has a spherical shape of particle diameter 30 pm.
3.1.5

Sn-Pb

Although Sn-Pb solders are gradually being replaced by lead-free materials, during the past 10 years some attention has been focused upon the development improved immersion plating techniques for these alloys. Some of this technology is also claimed

0
31

to be applicable to the immersion plating of pure tin and possibly other alloys. The following is a summary of some of these patents.

3.1.5.1

Substrate Pretreatment

Iantosca [28] has proposed a pretreatment step for the immersion plating of Sn-Pb alloys. This is performed immediately preceding contact of the part to be plated with the immersion plating solution. The pretreatment step comprises rinsing the part to be plated with a solution containing pH adjustors and buffers compatible with those contained in the plating solution either in lieu of the conventional water rinse or subsequent to the same. Following this pretreatment step, the part is then contacted with the immersion plating solution, without use of an intermediate step of water rinsing. In this way, only solution components from the pretreatment solution are dagged into the immersion plating solution, and in a preferred embodiment of the invention, in an amount approximating to the amount lost by drag out. This assures a uniformity in at least solution pH during use, avoids drag in the contaminants into the plating solution and thereby contributes to the uniformity of the depositfrom part to part during extended use of the plating solution. 3.1.5.2 Plating Solutions and Methodology Uchida et a1.[29] have suggested a process for the immersion plating of tin, lead or tin-lead alloys on copper or copper alloys. The tin andor lead content in the bath is maintained high enough to chemically deposit thick films by replenishing the tin andor lead salt in proportion to the increase in concentration of copper ion dissolving out in the bath. Tin-lead immersion baths usually contain sources of divalent tin and lead ions in the form of water-soluble salts, are strongly acidic, either by use of particular tin andor lead salts (e.g. fluoroborates) andor by provision of acids or acid-engendering materials separate and apart from the tin and lead salts. Another essential component of tin-lead immersion baths is thiourea, serving the hnction as a complexing agent for the tin and lead ions in the bath. Most commercial tin-lead immersion baths also contain hypophosphite ion, e.g. hypophosphorous acid andor alkali metal salts thereof, typically sodium hypophosphite, as an essential component for stabilizing the bath and providing denser, more uniform deposits. Efforts to eliminate hypophosphite from tin-lead immersion baths have not always proved successful. In particular, elimination of hypophosphite from tin lead immersion baths tends to result in deposits having a high tin concentration irrespective of the balance between tin and lead ions in the bath. Ferrier [30] has developed tin-lead immersion plating baths free of hypophosphite ion, comprising a strongly acid solution of thiourea, water soluble sources of divalent tin and lead (fluoroborates); a weak acid (citric, acetic, tartaric); and a weak base (ammonia or water soluble amines). 3.1.6 Complexing Agents Commercial displacement tin plating processes, and many of the plating baths described above, use thiourea as the complexing agent of choice. However, thiourea is a toxic substance and has been identified as a carcinogen. Strict measures are needed

32

0
in disposing of the process wastes and rendering them innocuous to the environment. Such waste treatment processes add to the overall costs of circuit board production. Hence, there is a need for a complexing agent which is innocuous to the environment and which can safely replace thiourea in its plating characteristics. Dodd et al. [3 11 have proposed a replacement complexing agent consisting of an unsymmetrical dialkylimidazole-2-thione compound. Of this class of compound, 1-methyl-3-propyl-2-thiocarbonyl-2, 3-dihydroimidazole is preferred for immersion tin plating.

3.2
3.2.1
3.2.1.1

Electroless Plating Processes Involving Sn2+ Coating of Plastics

0 0

0
In printed circuit board techniques, metal coatings are utilized to render boards
electrically conductive, the boards being made of cross-linked epoxy resins normally being reinforced by glass fibres or other reinforcing material. The metal coatings are made to form circuit traces, connectingpads or for through hole plating.

To produce metallic coatings on plastic parts, these are usually submitted first to a pretreatment in order to remove any contamination such as grease from the surfaces. Moreover, in most cases, etching processes are performed to roughen the surfaces so that efficient bonding to them is possible. Then the surfaces are treated with so called activators to form a catalytically active surface for subsequent electroless metal plating. For this purpose, so called ionogenic activators or colloidal systems are utilized. For activation with ionogenic systems, the plastic surfaces are treated with stannous ions first, tightly adhering gels of stannic acid formed during the process of rinsing with water that takes place after treatment with stannous ions. During further treatment with a solution of a palladium salt, palladium nuclei form on the surfaces through reduction of tin@) species that function as catalysts for electroless metal plating. For activation with colloidal systems, solutions of colloidal palladium are generally utilized that are formed by reaction of palladium chloride in the presence of excess hydrochloric acid. Following the process of activation, the plastic parts are metal plated utilizing a metastable solution of a metal plating bath. These baths contain the metal to be deposited in the form of salts dissolved in aqueous solution, together with a reducing agent for the metal salt.
Brandles et al. [32] have proposed a method for electroless metal plating of substrates, more specifically having non-conductive surfaces, by which the substrates may be reliably metal plated at low cost under manufacturing conditions. The method involves the following steps: (i) pickling the surfaces with a solution containing chromate ions; (ii) activating the pickled surfaces with a silver colloid containing stannous ions; (iii) treating the activated surfaces with an accelerating solution in order to remove the tin compounds from the surfaces; and (iv) depositing, by means of an electroless nickel plating bath, a layer that substantially consists of nickel to the surfaces treated with the accelerating solution, the electroless nickel plating bath containing at least one reducing agent selected from the group comprising borane compounds.

0
33

Nishimura et al. [33] have discussed a copper electroless plating process using a preliminary treatment consisting of a colloidal solution of a noble metal compound and a primary tin compound. 3.2.1.2 Lead-Free Tin Alloy Electroless Plating

Tsuji et al. [34] have patented a process for the electroless deposition of tin alloys which are claimed to have excellent joining strength and corrosion resistance and are formed with increased rate of precipitation. The lead-fiee alloy film is produced fiom a plating solution containing a mixture of a stannous salt and the salts of one or more kinds of metals e.g. Bi, In, Sb, Zn, CO,Ag, and Cu; one or more kinds of organic acids such as sulphonic acid and carboxylic acid; and inorganic acids such as hydrochloric acid, sulphuric acid or borofluonc acid; and a complexing agent. Furthermore, the composition ratio of the above metals, such as Bi, is regulated to 23 wt.%. The velocity of precipitation and the quality of any plated film are improved by further adding a reducing agent and a surface active agent. 3.2.2 Sn-Zn

A method and bath for the autocatalytic chemical deposition of a Sn-Zn alloy on a catalytic surface has been proposed by Cavallotti and Sirtori [35]. The method is claimed to be particularly useful in the manufacture of electronic components. When the deposition of a thin layer of Sn-Zn alloy is needed before the deposition of the Sn-lead free alloy necessary to improve the solderability characteristics of the Cu surface. The Cu surface must be made catalytic before immersion in the autocatalytic bath, e.g. by depositing a thin film of metallic tin.

In a specific example, the initial solution contains 0.2 M sulphuric acid; 0.3 M thiourea; 0.15 M sodium hypophosphite; 0.01 M tin sulphate and ).l M zinc sulphate. The copper substrate is immersed in this solution for 3 min at 25C and then rinsed with deionised water. This has the effect of depositing a thin film of metallic Sn onto the Cu substrate, which activates the autocatalytic process of deposition of Sn and Zn. The catalytic surface is then immersed in an alkaline autocatalytic bath containing Sn and Zn salts. The composition of the second bath is as follows: Zinc salt (0.1-1 M); Sn salt (0.01-0.5 M); complexing agent (0.1-1.5 M); and alkali 1-5 M. The preferred embodiment for the tin salt is tin sulphate (0.03 M) and the preferred zinc salt is zinc acetate (0.5 M).
3.2.3 Sn and Sn-Pb

3.2.3.1 Plating Solutions and Methodology Uchida et al. [36] have sought bath compositions for tin and tin-lead alloy electroless plating processes which can produce uniform deposits consisting of fine grains. A tin or tin alloy electroless plating bath containing a soluble metal salt component in the form of a stannous salt (organic sulphonates, borofluoride, acetate, chloride, carboxylate) or a mixture of a stannous salt and a lead salt ; an acid ; thiourea; and a reducing agent ( hypophosphorous acid or sodium hypophosphite). This formulation can be improved by (1) adding one or more non-ionic surfactants, preferably in

34

combination with one or more members selected from a cationic surfactant or a heterocyclic compound having a nitrogen atom in the ring and a derivative thereof or (2) adding an ammonium ion andor quaternary ammonium ion. The pH is preferably 2 or lower. The non-ionic surfactants include polyoxyalkylene ether series such as polyoxystearyl amide ether. Examples of the cationic surfactant include alkylamine salts and examples of the heterocyclic compound include alkyl pyridines. 3.2.3.2 Adhesion and Compactness Nishikawa and Tanaka [37] have proposed another bath composition for the electroless plating of tin and tin-lead alloys containing thiourea derivatives formed by linking a substituent to more than one nitrogen atom or sulphur atom in the molecule. The nitrogen substituents consist of imidazoline betaine, carboxybetaine and alkylamine oxide. This bath composition is claimed to increase the adhesion and compactness of the deposit and enhance the high temperature ageing stability of thebath. 3.2.3.3 Joining Strength Tsuji et al. [38] have patented a solution composition which contains a substituted naphthol for increasing the joining strength of an electroless plated film. The substituents have the form S03M or COzM, wherein M is hydrogen; an alkali metal an alkaline earth metal; ammonium or amine.

a a

35

4. Experimental Conditions and Applications in the Field of Corrosion Protection

4.1

Immersion Plating o Copper Tube f

Recent concerns over copper dissolved in drinking water have posed the question of controlling the internal corrosion of copper water tubes by coating the inner tube surface with an immersion tin deposit. Restricted copper release combined with other environmental pressures and the quality criteria set on products by consumers enhance the importance of a reliable perfonnance and, thus, uniform coating structure. This structure is influenced by three preliminary attributes, which all act independently to form an integrated system: pre-plating procedures, the actual coating process, and post-plating treatments. In a series of papers [39-421, Huttunen-Saarivirta et al. have conducted extensive studies relating to the pre-plating procedures and immersion coating of copper tube by tin and the role of contamination in determining coating morphology, thickness and integrity. 4.1.1. Optimisation of Pre-Plating Processes

In pre-plating process optimization, the complete production route of the uncoated component has to be taken into consideration in order to understand the sources of surface contamination. In general, the fimctional metal surface usually consists of several contaminant layers on the base metal itself. These contaminant layers have a detrimental influence on the production or the properties of the tin coating.

An outermost contamination layer consists of oil, soil and greases from prior processing. In hard-drawn copper tubes, this layer comprises drawing oils from the production sequence. Trichloroethylene has traditionally been used to clean the copper surface of drawing lubricants, but due to its inefficiency in preparing the copper surface for plating and environmental aspects, alternatives are being sought. Other cleaning procedures suggested to be capable of removing drawing oils from the copper surface 'include emulsion cleaning, acid cleaning and alkaline cleaning. An innermost contaminant film is the reaction layer of oxides, sulphides and hydroxides formed as a result of chemical reactions with the ambient environment over a long period of time. The inner layer of the copper tube surface is mainly made up of a mixture of cuprous and cupric oxides, the predominant one being the former. Cuprous oxide can be eliminated by pickling in relatively dilute sulphuric acid solutions.
Huttunen and Tiainen have investigated the influence of pre-plating processes on the buildup of immersion tin coatings and subsequent deposit structure by scanning electron microscopy [39]. Hard drawn copper tube of size 15 x 1 mm wall thickness was used. In the first part of the study, the efficiency for the removal of grease from the copper surface was studied with water-soluble cleaning media of which five were alkaline cleaners and two acidic. A study was also made of the cleaning efficiency of two solvent cleaners and acetone. The oxide layer was eliminated with an oxidizing pickling solution containing sulphuric acid and hydrogen peroxide. The pickling bath was maintained at 40C. In the second part of the work, the coating structure achieved after the above

36

pre-plating treatments was evaluated. The temperature range during the deposition varied from 60C to 85C. The baths used in the coating process were acidic in nature. The cleaning and plating solutions were pumped through the copper tubes. The following conclusions were drawn from the investigation:1. Organic drawing lubricants can be effectively removed from the copper substrate with alkaline degreasers, of which those containing phosphates are the most efficient. Oil removed by trichloroethylene was found to be inappropriate from an environmental viewpoint and also inefficient, whilst acid cleaning was considered too costly. 2. Too weak a cleaning efficiency lead to hindered nucleation and growth of the tin coating. 3. Adequate rinsing after degreasing was found to be particularly important. A dramatic change in the in the coating structure occurred in the presence of degreaser residue.
4. Successful pickling was found to be controlled by the selective etching of grain boundaries and localized corrosion, which took place with a too weak or a too powerful pickling procedure, respectively. A completely oxide-ffee copper surface resulted in an even and uniform tin coating structure with pleasing deposit appearance.

a a a

Some of these conclusions are illustrated in Figs. 25 and 26. Fig. 25(a) represents the tin coating structure after successful cleaning with the phosphate based cleaner, (main components: inorganic salts, nonionic emulsifiers and fatty alcohols). The tin coating nucleated uniformly over the entire surface leading to good adhesion properties. Surface roughness and variations in the tin grain size were attributed to the drawing flutes, which played an important role in determining the accessibility of the plating solution to different areas of the substrate surface. Fig. 25 (b) illustrates the tin coating structure where coating nucleation was restricted by organic residues. Fig. 25 (c) shows the influence of cuprous oxide layer on tin deposit formation. The oxidized areas exhibit no tin deposit, whilst the oxide-free areas are coated normally. If rinsing is poor, the residues of surfactants and surface modifiers originating from the cleaning solutions remain on the copper surface. Surface active agents act as leveling agents serving as nucleation sites for tin grains, but simultaneously hindering the further growth of the grains. This is shown in Fig. 25 (d) and leads to smooth but very thin tin coatings provided that the surfactant residues are homogeneously distributed. However, surface irregularities, pores and flaws tend to be difficult to reach by the rinsing solution. The role of the drawing flute on tin nucleation and growth is illustrated in Fig. 25 (e). The grains nucleate on the sharp edges and projections of the drawing flute, since these are the areas of more efficient rinsing. The deposit around the surface irregularities was found to be poorly adherent to the copper surface. Finally, Fig. 25 ( f ) shows that trichloroethylene is unable to remove organic soil uniformly, leaving most of the grain boundaries unpurified. The additional carbon layer on the grain boundaries acts as a barrier for nucleation

37

of coating grains leading to discontinuous coating structure. Subsequently, the coating nucleates inside the grains with no deposit on grain boundaries. Such irregular coating formation gives rise to the poor adhesion properties of the subsequent tin coating.

Fig. 25. SEM images of immersion tin coated surfaces after different cleaning procedures: (a) Cleaning carried out by phosphate based cleaning agent (x 6400); cleaning performed with alkaline cleaner ( x 3200); (c) tin coating on oxidized copper (x 800); (d) tin coating after poor rinsing of phosphate based cleaning agent (x 12,800); (e) the role of drawing flutes on tin coating nucleation in the case of poor rinsing ( X 1600); (f) tin coating deposited on copper surface degreased with tnchloroethylene (x 800) [39]. Fig. 26 depicts the influence of different pickling and plating sequences on the microstructure of the tin deposit.

38

Fig. 26. SEM images of immersion tin coatings on a copper substrate cleaned with a phosphate based cleaner after different pickling and plating sequences: (a) Coating deposited after successful pickling and at a slow plating solution circulation rate (x 6400); (b) coating deposited at a slow plating solution circulation rate (x 6400); (c) coating deposited after successful pickling and at a faster plating solution circulation rate ( X 6400); (d) coating deposited at a faster plating solution circulation rate, no pickling ( ~ 3 2 0 0 ) [39].

The influence of pickling on the immersion tin coating structure was dramatic, as coating smoothness was radically increased by pickling. Pickling serves to reduce surface roughness and thus to eliminate the role of drawing flutes in coating formation. The surface is also simultaneously activated. This gives rise to tin grains of equal size in the entire coating structure, in contrast to coating at the unpickled surface where grain size varied widely. A hrther conclusion was that the coating solution velocity affects the coating porosity, with a denser deposit formation obtained at an increasing solution flow rate. 4.1.2 Initiation and Formation of Immersion Layer

Ln further work, Huttunen-Saarivirta et al. [40] studied the initiation and formation of
the immersion tin layer in more detail. The surface preparation procedure was the same as that described above, but in addition to the acid bath, a methanesulphonic acid based bath was studied for comparison. The former bath contained hydrochloric acid for pH adjustment, sodium citrate for buffering, thiourea for complexation, sodium hypophosphite for bath stability and stannous chloride for delivering the Sn2+ ions. Plating times from 15 to 1800 s were used for the tin coating deposition from the hydrochloric acid based bath in the temperature range 50 to 80C. The methane sulphonic based bath was a commercial tinning solution (Schlotter, Germany). The

e
39

main components were methanesulphonic acid for pH control, thiourea for complexation and tin methanesulphonate for supplyng Sn2+ ions. For this commercial plating solution, deposition times of 60, 300 and 600 s were used and the bath was operated at a temperature of 40 to 80C. The immersion coating phase was followed by rinsing with warm water. The following conclusions were drawn from this work: 1. The formation of immersion coating crystallites from the hydrochloric acid based bath takes place semi-coherently with the underlying substrate. The coating initiation process is sensitive to substrate condition and controls the build-up of immersion coatings from the hydrochloric acid based bath up to 60"C, where the prevalent process to regulate the coating formation is shifted to grain growth. Grain growth proceeds both in a vertical and a horizontal direction, which introduces equiaxed grains in the tin coatings. 2. The immersion deposition from rnethanesulphonic acid based solutions proceeds via the formation of nanocrystals exhibiting the {220), { 112) and (312) preferred orientation. Due to the formation of nanocrystals, immersion tin coating nucleation from the methanesulphonic acid based bath is independent of operating temperature and insensitive to surface condition. During grain growth, these nanocrystals form columnar grains with prevailing (220) texture. This enhances the development of tin coatings with a regular and compact surface morphology. The coating growth process is facilitated by an increasing plating bath temperature. 3. The atomic-scale bonding between the tin coatings deposited from both the hydrochloric and methanesulphonic acid based plating baths and the copper substrate make the achievement of very good adhesion properties possible.

4. There is no evidence for noble intermetallic compound formation between the

tin coatings and copper substrate. The potential presence of pores in the tin coatings does not therefore present a corrosion hazard of the kind w h c h would exist if such noble phases were present. The SEM characterization of the immersion coatings produced in the hydrochloric acid bath disclosed the sensitivity of immersion coating morphology to temperature. Temperature was shown to regulate both the coating nucleation and growth behaviour of the coatings. Below 60"C, the nucleation sites for coating build-up are few in number, leading to a heterogeneous coating formation mainly into surface irregularities. At a temperature of 60C, optimal conditions for coating nucleation and growth phenomena were achieved. Usually for immersion tin coatings, coating thickness increases linearly with time until a critical thickness is achieved. For immersion produced in the current study, a linear dependence of tin coating thickness on plating time was also observed. However, at short times the coating nucleation and growth concentrated on the sites of the easiest plating solution accessibility yielding surface irregularities. At longer plating times, coating growth took place more evenly throughout the surface. This leveling behaviour can be seen in Fig. 27.

40

0
Fig. 27. SEM images showing the influence ofplating time on the initiation of immersion tin coating structure deposited from the hydrochloric acid based bath at 60C: (a) Plating time 15 s, coating thickness 0.2 pm (x 1000); (b) plating time 60 s, coating thickness 0.3 pm (X 200); (c) plating time 300 s, coating thickness 0.8 pm (x1000); (d) plating time 600 s, coating thickness 1.3 pm (x 1000) [40]. The SEM characterization of the immersion coatings produced in the methanesulphonate bath revealed the independency of the coating nucleation process to temperature (Fig. 28). In the studied temperature range from 40 to 80" the deposition was uniform despite the presence of drawing flutes present in the substrate surface, reflecting the low sensitivity of the plating process to substrate condition. However, the coating growth process was found to be very sensitive to the plating temperature. Fig. 28 also addresses the value of plating bath temperature in the coating growth process. High temperatures favour effective grain growth yielding to surface roughness and, thus, changing the overall coating morphology. An increase in coating thickness is also associated with higher deposition temperatures. These results show that the coating nucleation occurs independently of operating temperature, while the temperature sensitivity of the grain growth is evident. The coating grain growth process in the methanesulphonic acid based bath exhibited a linear trend with time, in common with the observations in the hydrochloric acid bath. The coating rate reached at its best a value of 10 pm h-', which was claimed to be high for immersion plating. Also, this rate was observed to be three times higher than that produced by the hydrochloric acid bath.

0
41

Fig. 28. SEM images showing the development of surface morphology on the immersion tin coating structure developed after 600 s from the methanesulphonic acid based bath as a function of operating temperature: (a) Processing temperature 40C, coating thickness 0.1 j m (x 800); (b) processing temperature 60C, coating thickness 0.2 pm (X 1600); processing temperature 70C, coating thickness 1.5 pm (X 1600); (d) processing temperature 80C, coating thickness 1.6 pm ( ~ 1 6 0 0 [40]. )

4.1.3 Uniformity of Immersion Sn

In a later study, Huttunen-Saarivirta continued to explore the role of bath composition in determining the plating characteristics of immersion tin coatings, but in particular, the question of the role of surface condition was addressed [41]. Despite the fact that the tin coatings develop in different ways in the hydrochloric and methanesulphonic acid baths, uniform coatings could be plated fi-om both baths when the substrate was clean and smooth. However, differences in the 'surface sensitivity' were observed when plating was attempted on improperly cleaned substrates. The essential difference between the two situations is shown schematically in Fig. 29.

42

a
Contaminutioii or iqulrrjry of

0
Fig. 29. Schematic representation of the structural development of immersion tin coatings on cleaned and regular copper and the suggested influence of contamination or irregularity of the copper surface on the uniformity of the coatings: (a) The initiation and formation of tin coating from the hydrochloric acid based bath on cleaned copper. (b) The initiation and formation of tin coating from the hydrochloric acid based bath on contaminated or rough copper. (c) The initiation and formation of tin coating from the methanesulphonicacid based bath on cleaned copper. (d) The initiation and formation of tin coating from the methanesulphonic acid based bath on contaminated or rough copper [41].

a a a

The hydrochloric bath yielded non-uniform coatings on irregular or improperly cleaned substrates, since large size grains developed immediately after coating initiation. These large size grains were suggested to orientate to follow the contours of impurity particles or surface irregularities introducing misalignment in grain columns and, thus, non-uniformity into the coatings. In contrast, a methanesulphonic acid based bath was still able to produce uniform tin coatings on contaminated or rough surfaces, as the coating was proposed to accommodate to substrate surface irregularities by the build-up of a nanocrystalline zone at the early stages of tin coating deposition. Sulphur containing elements in the methanesulphonic acid plating bath were claimed to play the central role in the nanocrystalline layer formation.

4.1.4

Effects of Surface Contamination

In the latest investigation, Huttunen-Saarivirta has addressed the topic of surface contamination with drawing lubricant in more detail [42]. The hydrochloric acid based bath was used in these studies. SEM micrographs of immersion tin coatings on clean and contaminated copper surfaces are presented in Fig. 30.

0
43

Fig. 30. SEM images showing the influence of substrate contamination on the inhibition of immersion tin coating formation at short and longer plating times: (a) Successful tin coating formation on clean copper surface, plating time 15 s, coating thickness 0.2 pm. (b) Successful tin coating formation on clean copper surface, plating time 600 s, coating thickness 1.3 pm. (c) Inhibited tin coating formation on contaminated copper surface, plating time 15 s, coating thickness indeterminate due to thinness. (d) Inhibited tin coating formation on contaminated copper surface, plating time 600 s, coating thickness 0.5 pm [42]. It is clear from these micrographs that the nucleation and growth processes and the overall appearance of the coating were modified by the carbonaceous layer on the substrate. The nucleation ceased in areas where the carbonaceous film remained due to poor cleaning, whilst successful nucleation was concentrated on the areas of better degreasing. The coating growth, in turn, was almost totally restricted in the case of improperly cleaned copper, because the coating thickness was only a fraction of that deposited on clean copper. The following conclusions were drawn from this study:

1. A discontinuous, thin, nanocrystalline and irregular tin coating forms on the contaminated copper substrate instead of a continuous, crystalline, regular tin coating of reasonable thickness, which builds up on a clean copper surface. 2. The nucleation mechanism of the immersion tin deposition is equivalent on clean and contaminated surfaces. However, the oily contamination layer effectively blocks the accessibility of the aqueous plating solution onto the substrate because of the dissimilar polarities of the contaminant and the plating bath, thereby hindering the coating nucleation at the areas of poor cleaning.
44

a a a a a a a a a a a a a a a a a e a a a a a a a a a a a a a a a e

3. The inhibited tin nucleation is not succeeded by a grain growth process. The tin coating is thus suggested to be introduced on the poorly cleaned copper by aprogressive nucleation process. The chain of sequential nucleation processes also brings about a nanocrystalline coating structure.
4. In immersion tin coating deposition on copper, the higher sensitivity of the grain growth process to the substrate surface contamination as compared to the nucleation process can be explained by the relative activation energies involved in these processes.

4.1.5

Other Processes

In a commercial copper tube tinning process it is necessary for the plating solution to be circulated for a long time, particularly if a long tube is considered. The effectiveness of the coating depends upon careful choice of the parameters of solution composition and the rate of flow of the solution through the tube. Clearly, severe concentration gradients will prevail when the tube length exceeds some critical value. Ito et al. [43] have devised a method for the manufacture of copper tube with a tinned inner surface by circulating a substitution-type plating solution inside the tube. The process is characterized by afimt plating step wherein the rate of deposition of the film is adjusted so that the total copper ion concentration emanating from the tube divided by the tin(I1) concentration is equal to 0.8 or less, and a second plating step wherein plating is carried out at a plating temperature considerably higher than that in the first step. The plating solution comprises 0.05-0.3 M Sn2+,0.5-2.0 M thiourea, 0.5-2.0 M sulphuric acid, 0.05-2.0 M alkyl benzene sulphonic acid and 0.5-5.0 g/1 nonionic surface active agent. It is claimed that the process ensures quality manufacture of long coiled tubes with tinned internal surfaces used as water supply tubes, hot water supply tubes and tubes for heat exchangers. The tin plate film is also claimed to have a uniform thickness and exhibit superior adhesion properties and corrosion resistance.
4.2

Electroless Plating o Copper Tube f Autocatalytic Process

4.2.1

Besides the immersion tinning processes describes above, an autocatalytic tin coating process provides possibilities to deposit tin chemically from solution onto the inner surface of copper tubes. In the autocatalytic tin deposition process, the coating forms as a result of a disproportionation reaction [44, 451 where two stannous ions dissociate to form metallic tin and stannate ion. However, this autocatalytic tin deposition only occurs successfully and yields uniform coating structure when applied to existing tin surfaces [46]. This necessitates the employment of a two-step coating process, first to trigger the autocatalytic plating by the utilization of a thin immersion tin coating, which is then followed by the autocatalytic plating step. This two-phase coating process has been considered somewhat complex, which is suggested to be the main reason for the limited use of autocatalytic tin coatings. The advantage of autocatalytic tin coatings is their unlimited thickness as compared to immersion tin coatings. The thickness of immersion tin coatings is mostly limited to values below 1 pm.

45

Nevertheless, a minimum thickness of 1 pm is required for chemical tin coatings intended for water tube applications. To cope with this discrepancy, an autocatalytic tin plating step may be utilized after the immersion deposition phase. In addition to the increased coating thickness, autocatalytic tin coatings can be applied for modifying the surface properties of existing thin tin coatings. Huttunen-Saarivirta and Tiainen [47] have very recently described in detail the autocatalytic plating of copper tube by the two step process. The structural evolution of the autocatalytic tin coatings was examined and the optimal plating parameters explored. The influence of the autocatalytic tin coating step on the corrosion properties of immersion tin coated copper tubes was also addressed. The hydrochloric acid based bath was used in the immersion timing procedure. This bath, introduced by Koyono et al. [46], contained 1.5 M hydrochloric acid for pH adjustment, 0.2 M sodium citrate for buffering, 3.25 M sodium hypophosphite for bath stabilization and 0.4 M stannous chloride for delivering Sn2+ions. The temperature of the bath was maintained at 60C during this catalytic immersion phase. A very short immersion plating time of 15 s was used. This was deliberately chosen to ensure that all the structural and corrosion properties of the tin coated surface could be attributed to the subsequent autocatalytic tin coating process. Those related to the initial immersion process in the fabrication of tin coated copper tube have been described previously (Section 4.1). The fabrication of tin coated copper tubes was completed by the utilization of the autocatalytic deposition step. This takes place by a disproportionation reaction, where two stannous ions dissociate to form metallic tin and stannate ion according to [44, 45, 481 2Sn(II) + Sn + Sn(1V) The actual process advances by the formation of soluble hydroxides by the reaction:
-

2Sn(OH)3

Sn + Sn(OH)62-

which necessitates the use of an alkaline pH. The pH of the autocatalytic plating baths ranged from 10 to 11. Baths contained sodium hydroxide for pH adjustment in the range 7.5 to 13 M, either 1.25 or 2.25 M sodium citrate for buffering and 0.75 M or 1.O M stannous chloride for delivering Sn2+ions. The components of the bath were added to distilled water in the above mentioned order and this solution was further diluted with distilled water to meet the required molar concentrations. The precise sodium hydroxide content in the bath was determined by the [Sn2'] to [OH-] ratio, which was kept at either 1:10 or 1 :3. Deposition cycles of 30-120 min were carried out at operating temperatures ranging from 60 to 95C. The study showed that tin coatings with a uniform structure could be obtained up to a temperature of 85C. However, an operating temperature of 80C was found to be optimal for autocatalytic tin coating development. The surface morphologies of tin coatings plated at different temperatures in a bath containing 1 M stannous chloride, 10 M sodium hydroxide and 1.25 M sodium citrate are presented in Fig. 31.

46

0
Fig. 3 1. SEM images showing the influence of plating temperature on the morphology of tin coatings deposited for 90 min in a bath containing 1 M stannous chloride, 10 M sodium hydroxide and 1.25 M sodium citrate: (a) 6OoC,coating thickness 520 nm, (b) 70"C, coating thickness 900 nm, (c) 80"C, coating thickness 1.05 pm, (d) 95"C, coating thickness 1.1 1 pm
[471.

At 80C, tin coating nucleation and grain growth processes were found to be at equilibrium so that a completely compact layer of tin grains was formed. At lower temperatures, an excessive coating nucleation was favoured instead of grain growth, resulting in a discontinuous coating structure. A similar influence was brought about by too high a sodium citrate concentration. In contrast, above 85C the disproportionation reaction to deposit the coating started to become uncontrollable, resulting in an unstable plating bath and reduced bath efficiency. These results highlighted the need to carefully control the processing variables of temperature and citrate concentration. However, the amount of sodium hydroxide and stannous chloride in the plating bath did not have a marked influence on the coating structure. The plating time determined the final thickness of the coating. A linear response between the plating time and coating thickness was observed, the slope being determined by the operating temperature and bath composition (Fig. 32). When process conditions promoting nucleation were used, the grain growth was only concentrated on some grains and rather thick coatings were subsequently produced. In contrast, if process conditions favoured grain growth, an even coating layer of reasonable thickness was gained.

0
47

Coating thlcW8 YS. coatlng tlme for autocatalyttc

Cdng8

E,
*L U

6
a
50

104

Time, minutes

Fig. 32. Thickness of autocatalytic coatings as a function of plating time obtained for various plating compositions and temperatures [47].

Fig. 33. SEM micrographs showing the morphologies of tin coatings deposited for different plating times in a bath containing 1 M stannous chloride, 13 M sodium hydroxide and 1.25 M sodium citrate at 60C: (a) 30 min, coating thickness 1.9 pm, (b) 60 min, coating thickness 2.0 pm,(c) 90 min, coating thickness 2.4 pm,(d) 120 min, coating thickness 2.6 pm [47].

48

0
Besides coating thickness, plating time influenced the structure of the coatings. This is illustrated in Fig. 33. After nucleation, grain growth was observed to advance until a completely compact layer of tin grains was formed, which was followed by a new nucleation and growth phase. At long plating times, the role of surface irregularities was emphasised. This was due to the nucleation of new tin grains after a complete tin layer; nucleation taking preference in the vicinity of surface irregularities, (Fig. 33d). This phenomenon was observed on the surface of all tin coatings deposited for 120 min independently of the plating temperature and other processing parameters. Such surface irregularities were considered to have a detrimental influence on corrosion resistance and therefore an upper limit of 90 min deposition time was chosen to avoid unnecessary secondary nucleation processes. The corrosion properties of the autocatalytically tin coated copper tubes were explored by potentiondynamic polarization experiments. In these measurements, a sample holder specifically designed for tubular samples was used. The electrolyte was chosen so that it caused moderate aqueous corrosion to bare copper. Cyclic polarization responses were measured from -800 up to 1200 mV and back to - 800 mV with respect to the corrosion potential of the sample. The scanning rate was 0.5 mVIs. The cyclic polarization curves (Fig. 34) were found to give some indication of the density and structure of the autocatalytic coatings. For example, a sudden increase in the corrosion potential values when turning from the initial polarization curve to the return curve could be interpreted as a signal for the presence of porosity, as shown in Figs. 34(b) and 34(d). In these cases the low operating temperature coupled with the high sodium citrate concentration of the plating bath seemed to enhance the uneven coating structure and hence the inefficient corrosion protection of copper. These findings were supported by the microstructural studies of the type shown in Fig. 3 1. The build-up of uniform and compact autocatalytic tin coatings on copper maintained the corrosion potential of the initial and return polarization curves at a constant value or even shifted the return corrosion potential to lower values. At its best, the application of autocatalytic tin coatings on copper reduced the corrosion current to less than one tenth that of the uncoated copper and shifted the corrosion potential from - 0 V vs. Ag/AgCI (for uncoated copper) to a maximum of 350 mV negative (Figs. 34a and 34b). These values indicate even better shielding properties of the autocatalytic tin coatings as compared to earlier reported coatings produced by immersion alone. Therefore, copper is more effectively protected from corrosion by the autocatalytic coatings than by immersion coatings provided that the coating structure is dense and continuous. The highest corrosion protection for copper was achieved from a bath depositing for 90 min containing 0.75 M stannous chloride, 7.5 M sodium hydroxide and 1.25 M sodium citrate at a temperature of 80C (Fig. 34b).

a e

0
49

15.30 .

T-

...._..____.____________ 123min

.-.- --..-..-... ................................ .... .. ..

-95%

. . . . . . . ~ . . I . . . .

......_......_..

......... ...._.. . . ...

i
-1503

j
1.OE-07
I, A/crnz

3 .OE-O9 (c;

1.OE-05

I .OE-03

Fig. 34. Cyclic potentiodynamic polarization curves for autocatalytic tin coatings produced under a variety of operating conditions. The arrows indicate the initial and return curves. (a) 0.75 M stannous chloride, 7.5 M sodium hydroxide and 1.25 M sodium citrate at 80"C, varying time, (b) 0.75 M stannous chloride, 7.5 M sodium hydroxide and 1.25 M sodium citrate for 90 min, varying temperature, (c) 0.75 M stannous chloride, 9.75 M sodium hydroxide and 1.25 M sodium citrate at 80"C, varying time, (d) 0.75 M stannous chloride, 9.75 M sodium Hydroxide at 70C for 120 min, varying sodium citrate concentration [47].

In relation to the corrosion testing of tin plated copper tube, it is interesting to note that Huttunen-Saarivirta and Tiainen have utilized the electrochemical current noise method in previous studies [49]. Few investigations of this type have been made to characterise the corrosion resistance of metallic coatings. Huttunen-Saarivirta and Tiainen have explored the use of this method to determine the quality of tin coatings on the inner surface of copper tubes. The study included scanning electron microscopy, open-circuit potential surveys and actual electrochemical current noise measurements. The results obtained by electrochemical current noise were consistent with the microstructural examination and thermodynamic corrosion studies of chemically produced tin coatings on copper. The statistical analysis of electrochemical current noise data presented either in time or infrequency mode was shown to be capable of characterising the chemical tin coatings in terms of uniformity, surface morphology and porosity. The peak shapes of current noise transients reflected the electrochemical phenomena taking place in the tin coating system when exposed to drinking water.
50

4.2.2

Other Processes

A process for tin plating the inner wall of copper or copper alloy tubes, which is claimed to be an electroless process and produce a uniform plating film, has been proposed by Kuroda [50].The electroless plating solution is prepared by mixing a pH controlling agent, bivalent tin ion, complex forming agent with the copper ion, reducing agent and surfactant. The latter is a poly(oxyethy1ene octyl phenyl ether) and/or poly(oxyethy1ene nonyl phenyl ether). The weight ratio of bivalent tin ion to the non-ionic surfactant is regulated in the range 10 to 130.

0
4.3
Immersion Plating of Aluminium A pickling/activating solution for the pretreatment of aluminium-steel composites before dip tinning has been formulated by Eberhardt et al. [ 5 I]. Examples of aluminium-steel composites are sliding bearings, bushes, wear disks, dry sliding bearings, etc. for pumps, motors and gearboxes. After pickling and activation, uniform, particularly strongly adhering tin coatings must be obtained on the substrate in the subsequent dip tinning process. The pickling solution contains sulphuric acid, hexafluorosilicic acid, at least one wetting agent, at least one transition metal cation and nitrate andor nitrite ions. One of the significant problems in the plating of aluminium castings resides in the aggressive nature of hot alkaline @H 13) tin plating solutions, wherein the solution tends to attack the porous cast aluminium substrate producing excessive accumulations of corrosion products and severe etching; both constituting problems which result in severe blistering, peeling andor flaking of the plated deposit. Daily et al. [52] have provided an alkaline plating composition which incorporates an effective amount of a sludge controlling compound that is an organic chelating agent. This compound is a polyamine.

a
4.4 Immersion Plating of Steel Van and Vijayan [53] have described the processes involved in producing galvanized steel and in particular the problems that are encountered when producing galvanized coatings containing a high aluminium content. This galvanize treatment imparts outstanding corrosion resistance and excellent mechanical properties. The steel has a coating comprising an inner layer consisting of intermetallic iron-aluminium compounds, e.g. Fe2A15,and an outer layer of a Zn-A1 alloy containing 17-40% Al, and preferably about 22% Al, the eutectoid composition. The galvanized steel can be made, for example, using a hot-dip batch galvanizing process consisting of two steps: (i) fluxing the steel article by an immersion process involving a variety of metals, but preferably tin, (ii) galvanizing the steel by dipping the article in a bath comprising molten zinc and aluminium. Numerous immersion treatment methods are cited in this patent. In one variant, steel panels are degreased in 10 wt. % NaOH solution heated at temperatures in the range 65 to 80C for 5 minutes. The panels are then rinsed and pickled in 12 wt. % HC1 at room temperature for 5 minutes. The aqueous flux bath is composed of 10 wt. %

a a a

51

stannous chloride and 5 wt. % HC1 and is maintained at a temperature of 75C. The panels are immersed in the fluxing bath for one minute and then rinsed and dried prior to hot-dip galvanizing.

52

0
5. Experimental Conditions and Applications in the Field of Power Sources

0
5.1

0
Immersion Plating 5.1.1 Alkaline Manganese Batteries A brass pin constitutes the negative current collector in alkaline manganese batteries. This is indirect contact with the zinc anode which in turn consists of a powdered zinc dispersion in a gelled alkaline electrolyte. In early technology, the zinc electrode was amalgamated with up to 6 wt.% mercury. However, environmental concerns have now eliminated the use of mercury in these batteries. In order to control zinc corrosion and minimize gassing from hydrogen, other metals having a high hydrogen overvoltage must be incorporated into the zinc matrix. Watabe [54] has proposed the use of tin (or indium) as replacements for.mercury. These metals can be plated onto the zinc spontaneously from the alkaline electrolyte via a simple immersion coating process. 5.2 5.2.1 Electroless Plating Lithium-Ion Batteries

e e

0
Carbonaceous materials are widely used as anode active materials for lithium-ion batteries and the background to their use, coupled with that of tin, has been recently been described by Wang et al. [ 5 5 ] and Veeraraghavan et al. [56]. Carbon can be lithiated to form LiC6 with a theoretical capacity of 372 mA h g-, but carbon anodes usually deliver a reversible capacity of 280-320 mA h g-. The carbons can exist in various forms. The carbon anode materials used in lithium-ion batteries are categorized into three types: (1) hard carbon which does not graphitize at high temperature, (2) soft carbon which is changeable by heat treatment, and (3) graphite. Amongst these, the gruphitized mesocurbon microbeads are the industry benchmark anode materials for lithium-ion batteries. These have stable lithium intercalation and de-intercalation characteristics with a reversible capacity of 300 mA h g-. Current research is focused upon developing either cheaper or higher performing alternatives.

In order to increase the capacity of the anode, tin-based composite oxides and tin-based alloys have been developed. (For a review of the latter, see Stage 1, Part 3 of this series [ 11). These new anode materials can deliver a lithium storage capacity exceeding by 2.5 times that of carbonaceous materials. The potentials for lithiation of the tin based alloys are higher than that of carbonaceous anodes, significantly reducing passivation of the lithium and improving the safety characteristics of the anodes. The amorphous tin based composite oxides have a first insertion capacity of 1030 mA h g- and a reversible capacity of 650 mA h g-. However, both the tin-based oxide anodes and tin-based alloys suffer from poor cyclability. This is mainly caused by the large volume changes in Li,Sn alloys.

0
53

The increase of the volume associated with the formation of different Li-Sn phases during the charging process (tin expands as much as 259% when alloying with lithium) and the reverse of this (contraction) during discharging, eventually leads to the disintegration of the anode and rapid capacity decay with cycling. This problem can be significantly alleviated by embedding active Sn, Sn-based oxides or tin-based alloys, in ductile graphite matrices. The following discussion summarises recent investigations to improve the performance of tidgraphite materials or composites as anode materials for lithium-ion batteries in which electroless tin deposition processes have been utilized in the initial production of the materials. . 5.2.1.1 Tin Coated Graphite Veeraraghavan et al. [56]have developed tin-graphite composites as an alternative anode material for Li-ion batteries using an autocatalytic deposition technique. The specific discharge capacity, coulombic efficiency, rate capability and cycle life of the Sn-C composites was studied using a variety of electrochemical methods. The amount of tin loading and the heating temperature were shown to have a significant influence upon the composite performance. The synthesis conditions and Sn loading were optimized to obtain the maximum capacity. Heating the composite converted it from an amorphous to a crystalline form. In addition to a higher capacity, the Sn-graphite composites possessed a higher coulombic efficiency, better rate capability and a longer cycle life compared with bare synthetic graphite. Synthetic graphite, commercially known as SFG10, was used in this work. Sn particles were embedded on the host graphite by an electrocatalytic process. The substrates were pretreated in a reducing hypophosphite bath. Tin coating was carried out at 50-60C for 0.5 h from an alkaline bath of SnClz (6.38 g/l) in NaOH (38 g/l). Sodium hypophosphite (8 g/l) was used as the reducing agent and sodium citrate (30.8 g/l) served as the complexing agent. Altering the SnCl2 concentration in the plating bath varied the amount of tin loading on the graphite. Typical graphite negative electrodes were prepared by adding 10% liquid poly(tetrafluoroethy1ene) binder to a 50 % (vh) solution of isopropyl alcohol. The resulting slurry was then mixed in an ultrasonic cleaner for 1 h. Pellets of the finely mixed encapsulated carbon samples were prepared by the cold rolling technique. Disk electrodes, 1.4 cm2 in area, were cut from the cold pressed material. Since the graphite was coated with tin, no additional conducting additives were included during the electrode preparation. Electrochemical characterization studies were performed using a three-electrode T-cell setup. These cells were prepared in a glove box filled with ultrapure argon. The electrodes in the T cells were prepared by cold pressing material on both sides of metal current collectors. Pure lithium metal was used as the counter and reference electrode. 1 M LiPF6 was used as the electrolyte in a 1: 1 mixture of ethylene carbonate and dimethyl carbonate. A Whatman fibre membrane was used as a separator. Further details of the procedure are given elsewhere [57].

54

e
Initial studies were performed to check the dispersion of tin over the graphite substrates and the results are shown in Fig. 35.

e e e
Fig. 3 5 . SEM Iimages of (a) bare SFGlO graphite and (b) 15% tin on SFGlO [56].

The autocatalytic deposition of tin lead to dispersion of fine particles of tin on the flake-like graphite structure (shown by bright spots). Further studies were undertaken to optimise the heat treatment of the material in terms of discharge capacity. It was

55

found that a treatment in which the composites were dried in a vacuum at 200C for 24 hours was optimal. Tin combines extensively with.lithium to form alloys of the form Li22Sn5,which gives rise to a theoretical capacity of 991 mAh g-'. The reversible reaction of lithium with tin can be given by Li+ + Sn + e 4 Li,Sn (x 5 4.4)

The addition of tin significantly improved the discharge capacity of the electrode when compared to that of bare carbon. Figs. 36 and 37 show the effect of increasing the tin loading on the discharge capacity of the composite. An optimal figure of 433 mAh g" (obtained at a cut-off voltage of 0.005 volts) for 15 wt.% Sn is evident (Fig. 36) and this constituted an increase of 50% in the reversible capacity (Fig. 37).

1.8

s%Sn

Ban:.--.

E
* >
C

. 4 . ;3
2
e

1.3 -

,lO.;/O 20% . , . ~+ ! I !15% : ! I : . II I : . ' i ! I !

: ! I :

2.
08 .
'

e 0

0.3 -

0 0

-0.2

Fig. 36. Comparison of charge/discharge curves for graphite composite loaded with different amounts of tin. Curves for bare SFGlO graphite are also shown for comparison [56].
70

b 60

Y O

.I
t

.a

30
2o

l0

10 15 CCUDpbOf9n()9

25

Fig. 37. Percentage increase in the reversible capacity of the Sn-coated SFGlO as a function of Sn loading [56].

56

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

a a a a a

Extended charge/discharge studies were conducted to characterize the cycle life performance of the tin composite and bare graphite anodes (Fig. 38). The former exhibited a particularly stable capacity after about 15 cycles and a consistently higher capacity (by a factor of > 2) compared to the bare graphite electrode. Earlier studies camed out on Sn-C composites prepared through a chemical precipitation route exhibited considerable loss in capacity during cycling. This was attributed to the presence of large particles of crystalline tin that crumbled and became detached from the main body of the electrode during cycling. By contrast, the electroless deposition method of electrode fabrication produces amorphous tin and this improves the utilization and stability of the system.

0
500

a a a

'

400

a a

300

200

100

0
0

a a a

10

IS

20

25

30

35

Cycle n u d a

Fig. 38. Cycle life studies on bare and 15 wt.% Sn coated SFGlO samples at C/15 rate [56]. 5.2.1.2 Mesocarbon Microbeads Wang et al. [ 5 5 ] have very recently studied the electrochemical characteristics of tincoated mesocarbon microbeads (MCMB) graphite as an anode material in lithium-ion cells. Several of these materials were prepared by microencapsulating nanosize Sn particles in MCMB. The particles were homogeneously dispersed in the MCMB matrix via an electroless in situ chemical reduction process. The tin coated MCMB electrodes demonstrated an improvement in lithium storage capacity. The tin loading of the MCMB powders was achieved from a plating bath consisting of NaOH and SnC12 at 55C. The powders were added to the solution under magnetic stirring. In order to enhance the dispersion of the powders, ultrasonic vibration was also applied. Sodium hypophosphite and sodium citrate were added to reduce Sn2+to Sn. The sodium citrate served as a complexing agent for the reduction process. The amount of tin loading was altered by changing the concentration of the SnC12 in solution. After the electroless coating, the Sn-MCMB powders were thoroughly -washed by de-ionised water, then dried in a vacuum oven. Sn-MCMB powders with different Sn contents were prepared in the range 10-20 wt.%.

a a a a a a a

57

Teflon type testing cells were assembled for electrochemical characterization. The testing electrodes were made by dispersing 95 wt.% active materials and 5 wt.% polyvinylidine fluoride binder in dimethyl phthalate solvent to form a slurry. The slurry was then spread onto a copper foil and dried in a vacuum oven. The electrodes were then cut to12 mm diameter discs. The cells were assembled in an argon filled glove box. The electrolyte was 1 M LiPF6 in a mixture of ethylene carbonate and dimethyl carbonate (1 : I by volume). The cells were galvanostatically charged and discharged in the voltage range 0-1.5 volts vs. a Li/Li+ counter electrode. Fig. 39 illustrates SEM images of both the bare and Sn-coated MCMB powders. The MCMB agglomerates have a spherical shape consisting of many small graphite crystals (Fig. 39a). The spherical agglomerates have an average particle size of 10-12 pm. After coating, bright spots appeared representing deposited tin (Fig. 39b). The presence of tin was confirmed by EDS analysis.

Fig. 39. SEM images of (a) bare MCMB powders and (b) 15 wt.% Sn-MCMB powders [ 5 5 ] .

58

0
Fig. 40 shows the discharge capacity vs. cycle number data for cells cycled under a low current density of 0.015 mA cm-*.The bare MCMB electrodes were very stable on cycling and could deliver an average reversible discharge capacity of 320 mAh g-'. The 10 wt.% and 15wt.% Sn-MCMB electrodes exhibited an almost constant cycle life performance. However, the 20 wt.% electrodes showed a significant capacity loss during cycling. The alloying of tin with lithium accompanies a substantial volume increase. The chemically deposited particles are amorphous or nanosize in nature and are uniformly dispersed in the ductile MCMB graphitematrix. .The volume increase can be effectively absorbed by the matrix, preventing the crumbling and ultimate disintegration of the electrode. This happens when the tin loading is comparatively low (0-15 wt.% Sn)..

0
Fig. 40. Lithium insertion capacity vs. cycle number [ 5 5 ] . However, at higher levels, the electrode is not able to accommodate the large volume changes (e.g. 20 wt.% Sn). Therefore, the tin coating can enhance the electrode performance in a limited concentration range 10-15 wt.% Sn, where an optimal capacity and cycle life is achieved. 5.2.1.3 Miscellaneous TidCarbon Composites Guidotti et al. [58] have examined a number of S d C composites as anode materials for Li-ion batteries prepared by different methods including pyrolysis and electroless deposition techniques. The best overall electrochemical performance was obtained with a composite material produced via an electroless deposition process of 10 % tin onto KS-6 platelet graphite (Lonza). This system yielded the full capacity of 450 mAh g-' for graphite and tin. It also exhibited good cycling performance at the C/5 rate and higher. Tin acetylacetonate was dissolved in dimethyl sulphoxide and shaken with the KS-6 graphite. Two equivalents of anhydrous hydrazine were added to the slumes and the mixture was shaken for 25 h. The slumes were then precipitated into diethyl ether.
59

a a

a a

After collection of solids by filtration, they were washed with diethyl ether and then dried under vacuum for 24 h. Tin acetylacetonate reduces to tin metal and 2,4-pentanedione. The solvent and byproducts are removed under vacuum to yield the S d C composite . 5.2.2 Photovoltaic Cells BP Solar has been manufacturing the buried contact solar cell under the product name Saturn since 1992. A huge number of individual cells are required in this form of energy conversion. The company is currently investigating improved processes for the fabrication of the cells, including a more environmentally friendly method for the metallisationof the cell. These include copper plating and cyanide-free metal coating processes as capping layers on the copper to avoid tarnishing and improve solderability. In regard to the latter, various electroless silver and tin electroless coatings have been investigated as suitable candidates [59]. It was found the tin coatings proved to be particularly effective, passing all the applied tests, and therefore provide an alternative to the current cyanide-based coatings. The silver coatings, by contrast, were shown to be less suitable and failed several of the tests. 5.2.3 Fuel CeIls The CO tolerance of the anode catalysts for low temperature polymer electrolyte membrane fuel cells (PEMFC) can be markedly improved by combining Pt with a less noble metal component, allowing oxidation of the poisoning CO,d, species. This process involves surface reaction with OH species, electrosorbed onto oxophilic metal sites, at a lower potential compared to that for Pt alone. The latter reaction sequence is usually referred to as a bfunctional mechanism. This has stimulated enormous efforts (both experimentally and theoretically) to formulate novel PEMFC catalyst materials with an improved performance and the subject has recently been reviewed [60].Stalnionis et al. [61] has also provided a detailed categorisation of the literature. The most promising compositions for electrocatalytic applications are Ru, Os, Ir, Sn, Bi, MO,V, W, Re, etc, binary or ternary/quatemary combinations with Pt. These can be divided into two major groups with respect to catalyst preparatiodcomposition, i.e. (i) bimetallic alloys and (ii) surface-modlJied catalysts. The first group (i) deals with metal alloys, ensuring an intimate intermixing of the constituent atoms and uniform chemical structure. Electrochemically deposited; chemically formed; sputter deposited; or single crystal alloy electrodes; have been extensively studied in PEMFC related electrocatalytic reactions to achieve important kinetic and mechanistic insights concerning the relationship between composition, structure and activity. The second group (ii) deals Pt surface modification by oxophilic metals. Three basic methods are involved here: (a) underpotential deposition and electrodeposition of monolayers or submonolayers, e.g. Sn on the Pt surface; (b) physicochemical deposition of modifying metal through an organometallic route, e.g. thermal decomposition of organyl complexes of non-noble metals on Pt, photolithography, ion implantation, or epitaxially grown overlayers under ultra high vacuum conditions; and

60

a a a a a a
(c) surface modification through spontaneous deposition. Very recently, Stalnionis et al. [61] have undertaken a detailed investigation of the surface modification of Pt by a spontaneous dip coating approach involving the generation of both tin oxy-species and tin metal, based on hydrolysis of a tin chloride complex and autocatalytic deposition of tin. The method consisted of (i) Pt immersion into SnC12/HC1solution under open-circuit conditions and (ii) subsequent rinsing of the surface by pure water. The resulting tin modified Pt surfaces were characterized by atomic force microscopy, X-ray photoelectron microscopy and cyclic voltammetry. Two types of tin species, namely, tin oxidehydroxide species and metallic tin were identified at the Pt surface. The former were assumed to be derived as a result of Sn(I1) chloride complex hydrolysis, while the latter were most likely deposited spontaneously due to disproportionation of Sn(I1) to Sn(IV) and metallic tin, competing with the dissolution of tin in the strongly acid media. The modifying tin species exhibited a satisfactory stability in 0.5 M H2S04 solution at potentials relevant to low temperature fuel cell operating conditions, i.e. below 0.6 V vs. standard hydrogen. A solution of H2SnC14(ca. 3.5 M) was freshly prepared by dissolving SnC12.2H20 in concentrated HC1 to avoid hydrolysis of tin chloride. A spontaneous modification of the clean polycrystalline Pt surface was carried out by (i) immersing the sample into SnC12/HCl solution under open-circuit conditions at room temperature for 2 min, and (ii) subsequent extensive rinsing of the sample by pure water. All procedures were performed at ambient temperatures under a naturally aerated environment. Fig. 41 shows AFM images of the Pt surface following various treatments. In each case, representative areas of the surface were randomly selected (5,000 x 5,000 nm) and zoomed in to higher magnification (up to 1,000 x 1,000 nm). The tin-modified surface images (Fig. 41 d-f) showed several differences compared to the clean Pt. (It should be noted that, due to the ex situ modification, the AFM images displayed different areas of the surface before and after modification). The shape of the tin-modified crystallites became more rounded compared to the rectangular domains on the clean Pt. The fine structure of the lower height crystallites became smoothed and less clearly resolved. On the other hand, the underlying structures of the Pt crystallites can still be clearly resolved.

a a a a a a a a

a a

0 0

a a

a a a a a a a a e a

61

72 18 1000

1000'

24 69

2030

2coo

,108 61

5000

5000

Fig. 41. Representative atomic force microscopy images (in nm) for a clean mirror polished polycrystalline Pt surface (a-c), after spontaneous modification by Sn species (d-f) and after etching in 0.5 M H,SO, solution (g-i). Zoomed areas are highlighted accordingly [6 11. For the acid-etched Pt surface (Figs. 41 g-i) the underlying Pt crystallite surface became better resolved compared to the Sn-modified Pt, although still not as clear as that for the clean Pt surface. The topography of the surface became smoother, as can be discerned from the images at higher magnifications. Moreover, at higher magnifications the occurrence of the ill-resolved nanosize features can be visualized over the crystallites surface for the acid etched Sn-modified Pt. Due the inert nature of the Pt substrate against exposure to a moderately acidic solution (0.5 M HzS04) under open-circuit conditions and at room temperature, such corrosion-induced features could be attributed to the selective dissolution of the modifying film rather than the substrate. This could be rationalized in terms of a different stability of the film component sin acidic media, leading to preferential dissolution of certain species constituting the film and resulting in variations in composition.
As a result of their AFM and X P S analyses, together with the supplementary evidence gained from the cyclic voltammetry, Stalnionis et al. [61] proposed a mechanism for the deposition of the modifying tin layer as follows:

62

0
A Sn(I1) tetrachloro complex, formed due to dissolution of tin chloride in concentrated hydrochloric acid:
SnC12 + 2HC1SnC1d2-+2Hf
(1)

disproportionates spontaneously to metallic tin and Sn(IV), the Sn plating out on the Pt surface via an electroless process: 2Sn(II) + Sn + Sn(1V) (2)

The specific feature of this process is that electrochemical half-reactions occur simultaneously on a Pt surface under open-circuit conditions according to mixed potential theory. These reactions are: an anodic reaction consisting of the oxidation of Sn(I1) to Sn(1V) and a cathodic reaction consisting of the reduction of Sn(I1) to metallic tin (or the discharge/reduction of protons). The reactions require a conductive and catalytically active substrate, such as Pt. Moreover, in strongly acidic solution, a growing non-noble tin deposit is partly dissolved according to the reaction

Sn + 2HC1-+ SnC12 + HZ

(3)

preventing continuous growth of the tin film, (i.e. complete Pt surface blocking) and apparently resulting in the formation of metallic tin nano-structures at submonolayer amounts. Evidently, the amount of metallic tin deposited is controlled by the rate of the tin deposition/ dissolution reactions as exemplified by reactions (2) and (3) and can be varied by changing the concentration of SnC12 and HC1. The formation of tin oxidehydroxide species on the Pt surface was postulated to result most likely from the hydrolysis of the Sn(I1) chloride complex by the rinsing of the surface by water during electrode prepararation. The hydrolysis of the Sn(I1) chloride complex resulting in a tin oxide/hydroxide deposit is well known and widely used for the pretreatment of dielectric surfaces prior to activation with Pd ions and electroless deposition of desired metal films and can be described by the following reactions : SnC12 + 2H20
--$

Sn(OH)2 + 2HC1

(4)

Sn(OH)2+ SnO + H 2 0

(5)

0
63

In further work, Stalnionis et al. [62] have assessed the effectiveness of the above treatments in enhancing the catalytic activity of Pt in direct methanol fuel cell applications. The electrocatalytic activity of the spontaneously Sn-modified Pt was compared to that of a polycrystalline Pt electrode in the electrooxidation of pre-adsorbed CO and the simple so-called C-1 molecules methanol,formic acid and formaldehyde. The spontaneously Sn-modified Pt catalyst exhibited a superior activity towards adsorbed CO oxidation and could thus be considered promising for polymer electrolyte fuel cell applications operating on CO-contaminated hydrogen oxidation. Although the methanol oxidation rate was hardly changed on the Sn-modified Pt surface, compared to the Pt electrode, it was shown that the formic acid oxidation rate could be enhanced and that for formaldehyde could be dramatically increased. The latter was observed at the most negative potentials where anodic formaldehyde oxidation is normally completely suppressed on a pure Pt electrode. The experimental data is summarised in Figs. 42 and 43, which show potentiodynamic and potentiostatic electrooxidation curves, respectively. In Fig. 42(b) it can be seen that the formaldehyde oxidation rate on the Sn-modified Pt catalyst (solid line) was increased considerably compared to that on a Pt electrode (Fig. 42a, solid line), resulting in an anodic peak centered at ca. 0.3 V (SHE). This was in agreement with previously reported data for electrodeposited Pt-Sn alloy [63] and microfabricated tin island arrays pre-formed on a Pt surface [64]. Comparative current transients for a potential step from 0 to 0.6V on the Sn-modified Pt electrode are shown in Fig. 43. The formaldehyde oxidation current transient on the Sn-modified Pt electrode (Fig. 43b, solid line) exhibited an increase with time, similar to that of formic acid (Fig. 43b, dashed line), but in contrast to the observed decrease in formaldehyde oxidation current for the untreated Pt electrode (Fig. 43a, solid line).The formaldehyde oxidation current on the Sn-modified Pt surface after 30 min electrolysis at 0.6 V was -5 fold larger compared to that on the Pt electrode, demonstrating that the Sn- modified Pt is a good catalyst for formaldehyde oxidation in agreement with the potentiodynamic measurements in Fig. 42 and literature data [63,64]. In conclusion, Stalnionis et al. postulated that submonolayer amounts of tin on Pt surfaces facilitate oxidation of formaldehyde, known as a by-product of methanol electrooxidation, and thus increase the current efficiency of the overall methanol oxidation reaction and decrease toxic formaldehyde emissions. However, the coverage of tin. species must be optimised to prevent significant blocking of Pt sites required for the initial catalytic dehydrogenation of methanol. Overall, the catalytic effect of tin oxy-species can be explained in terms of oxidation of poisoning adsorbed CO species, either pre-adsorbed from CO saturated solution or derived during dehydrogenation of organic molecules.

64

0
3

0
1

F-a
, ,'

". .
.

,,

.. ' ./ A.

, 5 . ...... A 7 ...

-1

...

.I_.----'

....

..

0
1.o

0
0.0

02

0,4

0,6

a a a

E / V (SHE)

Fig. 42. Potentiodynamic electrooxidation of methanol (dashed-dotted lines), formic acid (dashed lines) and formaldehyde (solid lines) on Pt (a) and Sn-modified Pt (b) electrodes in 0.5 M H2S04solution containing 1 M CH30H,HCOOH, or HzCO, respectively. Potential scan rate 50 mV/s. Dotted lines: base cyclovoltammograms in the supporting electrolyte [62].
4 .

(a)

31i/I'
'

----__

0
0
10

20 time I rnin

30

Fig. 43. Potentiostatic electrooxidation of methanol (dashed-dotted lines), formic acid (dashed lines) and formaldehyde (solid lines) on Pt (a) and Sn-modified Pt (b) electrodes in0.5 M H2S04solution containing 1 M CH30H,HCOOH, or HzCO, respectively. Potential step from 0 to 0.6 V (SHE). Dotted lines: potential step in the supporting electrolyte [62].
65

6. Extended Summary

1.

Immersion plating (sometimes known as displacement or substitution plating) is a process where deposition is by displacement of elemental metal from a substrate by metal ions in a plating solution. Since plating is by displacement, immersion plating is an electrochemical reaction that depends upon the position the substrate metal occupies in the eIectrochemicaI/electromotive series relative to the metal to be deposited from solution. Plating occurs when the metal from a dissolved metal salt is displaced by a more active (less noble) metal immersed in the solution.

2.

Electroless plating (sometimes known as autocatalytic plating) differs from immersion plating because additional reducing agents are required to reduce the metal ions of the depositing metal, since the base metal does not act as a reducing agent. This process also differs in that thicker deposits can be produced, since the only requirement is for the replenishment of the reducing agent consumed and the removal of reaction products in the solution. However, there appears to be much confusion in the literature concerning the differences between immersion and electroless processes and the terms are often used interchangeably, namely in Japanese and certain American patents.

A) Fundamental Studies

1.

Several fundamental studies relating to the mechanism of immersion plating have been carried out: (i) Aluminium and its alloys offer many advantages as construction materials in several major areas of mechanical engineering. A systematic investigation of the immersion and deposition processes of thin tin coatings used as an underlayer for the deposition of the multilayer system Cu/Ni/Cr onto a typical aluminium alloy, applied in the automotive industry and other branches of mechanical engineering, has been conducted. It can be assumed that the nature of the reactions that occur are basically electrochemical and they represent a system of two partial electrode reactions. In the case of stannate immersion treatment, they can be represented as: Anodic Cathodic 4A1- 4A13 + 12e (1) (2)

3sn4++ 12e + 3 ~ n

This indicates that for every 4 anodically dissolved aluminium atoms, 3 tin ions will be reduced. However, this is an oversimplification of the overall processes because corrosion reactions, occurring in parallel with the above, must also be taken into account. These are continually attacking the substrate metal and give rise to the evolution of hydrogen throughout the course of the deposition. The overall reaction for the corrosion of aluminium can be represented

0
66

It was shown that during the immersion treatment of aluminium and its alloys in stannate solutions that, depending upon the duration of immersion and the formulation of the stannate immersion solution, the ratio between the rate of the two cathodic reactions (tin deposition and hydrogen evolution) can vary over a wide range. The possibility therefore exists to control these processes according to a predetermined pattern and exert a beneficial effect on the characteristics of the tin coating. (ii) Lead-free solder joint technology has become an urgent issue in the electronics industry. In particular, the choice of surface treatment procedures for coating electronic and semiconductor parts has become an important concern. The development of lead-free solder electroplating technologies, for example, Sn-Cu, Sn-Bi and Sn-Ag, has been significantly advanced. However, very few attempts have been made to study the immersion plating of these alloys in any fundamental detail. A process has recently been developed for the immersion plating of Sn-Ag onto copper. The bath contained potassium pyrophosphate (&P207) and KI as complexing agents for Sn and Ag, respectively, and thiourea (CS(NH2)z) as the complexing agent for the Cu. The metal salts were derived from AgI (0.008 M) and tin pyrophosphate (0.1 M). Thiourea (TU) could only be dissolved in the baths to approximately 1 M at room temperature. Higher concentrations were produced by heating them to 90C. The pH of the baths was adjusted to 5 by addition of HC1 before the TU was added.
2.

Several fundamental studies relating to the mechanism of electroless plating have been carried out. (i) Electroless (or autocatalytic) plating gives the possibility of selective deposition of metals to unlimited thickness. An autocatalytic tin deposition process has been developed utilising a disproportionation reaction in which the oxidation of one tin(I1) ion at the surface supplies the two electrons for the reduction of a second tin(I1) ion to metallic tin. The metallization solution contains tin(I1) chloride, sodium hydroxide, sodium citrate as a complexing agent and sodium hypophosphate as a reducing agent, at a temperature of 70C. Accordingly, tin can be plated from the stannate ion as follows: 2Sn(OH)3---f

Sn + Sn(OH)62-

(5)

Recent studies have attempted to investigate the reaction more thoroughly and improve the method of practical application. It was found that very specific conditions were required to produce satisfactory results on a copper substrate. A special surface preparation procedure involving alkaline degreasing and acid cleaning was first applied. It was found that the electroless plating process occurred preferentially on a tin surface. Hence, prior to the main electroless plating, a very thin film of tin (0.5 pm) was formed on the copper substrate by conventional plating. Following this, the surface was activated in HC1 solution and then plated by the disproportionation reaction. The electroless plating solution consisted of KOH ( NaOH or LiOH), SnCl2 and further additions of

67

sodium hypophosphate and sodium citrate in certain experiments. The alkaline solutions were added into the stannous chloride solutions to prepare the plating solutions. A large number of experiments using different alkalis and mole ratios [MOH] / [Sn(II)] were required to determine suitable bath compositions where the solution remained transparent and therefore stable under the plating conditions of 70C for 1 hour. Only a small composition window was found to be available (< 0.6 M SnC12 and [MOH] / [Sn(II)] ratios of 10-13, 10-20 and 9-16 for Li, Na and K baths, respectively). (ii) Ni-Sn is used as a functional material because of its excellent corrosion resistance, wear resistance and solderability. Electrodeposited Ni-Sn films are used as a decorative coating, an etch resist in printed circuit board manufacture, a connector-finish with a thin gold overlayer, etc. They usually contain 40 50 at.% tin and it is a metastable compound that corresponds closely to the formula NiSn. However, electroless plated Ni-Sn films contain only small amounts of tin compared to the electrodeposited alloy films, eg. ca. 25 at.% tin using dimethylaminoborane (DMAB) as a reductant and ca. 10 at.% tin using sodium hypophosphite or hydrazine. Recent work has investigated the factors and operating conditions of electroless Ni-Sn plating in order to increase the tin content. Because of the phosphorous and boron contents of the reducing agents used, the alloys actually generated were Ni-Sn-P and Ni-Sn-B, respectively. Experiments were also conducted to produce Ni-P and Ni-B coatings. The Ni-Sn-P basic bath consisted of nickel sulphate (0.10 M); trisodium citrate (0.12 M); sodium hypophosphite as the reductant (0.20 M); and sodium stannite (0.003 M) as the source of tin. The normal bath temperature was 90C and the pH was 10.0. The Ni-Sn-B basic bath consisted of nickel sulphate (0.10 M); trisodium citrate (0.20 M); DMAB (0.04 M) as the reductant; and sodium stannate-gluconate complex (0.05 M) as the source of tin. The normal bath temperature was 70C and the pH was 9.0. A single step process using PdC12 dissolved in HCl was employed to catalalyse the surface of the substrate prior to electroless plating.

In the case of the Ni-Sn-P alloy, the most effective factor for tin codeposition was found to be the trisodium citrate concentration and in the case of the Ni-Sn-B alloy, the Sn4+-gluconateconcentration. Extensive corrosion tests were carried out on the various alloys in a range of corrosive media including sulphuric (0.5 M), hydrochloric (1.0 M) and nitric (1.0 M) acids and also sodium chloride (- 1.O M). Dissolved oxygen was removed before these tests. The anti-corrosion ability in the inorganic acid and brine solutions produced the following ranking: Ni-P 2 Ni-Sn-P > Ni-Sn-B > crystalline Ni-P Solderability tests using the meniscogram method and Sn-Pb (60 / 40) solder revealed the following ranking: Ni-B > Ni-Sn-P >_ Ni-Sn-B > amorphous and crystalline Ni-P (iii) Comparatively early and detailed studies relating to the autocatalytic deposition of tin onto steel, nickel, copper, ABS and poly(propylene), were

68

0
conducted by utilizing titanium(II1) salts as reducing agents, Specific surface preparation methods were necessary for all substrates. The composition of the normal plating electrolyte was as follows: tin(I1) chloride (7.5 g/l); trisodium citrate (100 gA); sodium acetate (10 gA);benzene sulphonic acid (32% w/v;l mV1); and titanium (111) chloride (30% w/v;15 ml/l). The pH of the bath was adjusted to pH -9 and the plating temperature was 90C. The process of plating was assumed to take place through the reduction of Sn2+ ions at an active surface by a reducing species thought to be a complex of the Ti3' ion in which one of the ligands could be a tin-containing entity. The deposition onto steel and nickel proceeded at approximately 4 g m -2 h-1 . Copper could be plated at approximately 7.5 g m -2 h-1 . The plastic substrate poly(propy1ene) was successhlly coated at 3.7 g m -2 h-I . Conspicuously, no apparent limit for tin coating thickness was observed under the experimental conditions imposed.

a
1.

0
B) Applications in the Field of Solders/Electronics
A large number of publications have emerged concerning the plating bath formulation and the quality of immersion plated tin.

(i) Plating methodology has continued to be developed. One example of copper surface treatment is the use of immersion tin (or tin alloys) as a bonding media for multilayer circuits. Various patents have been filed in which an immersion tin composition has been disclosed containing thiourea compounds and urea compounds to displacement plate the copper surface of each PCB with tin prior to laminating them to form a multilayer board. Detailed solution compositions and methodology have been described. One process is claimed for a variety of other metals including lead, bismuth, indium, gallium and germanium. The plating bath contains (A) the metal salts, (B) at least one complexing agent selected from the group consisting of thiourea compounds and imidazoles, and (C) at least one amidine. (ii) The thickness of the surface finish is critical to the performance, a good understanding of the true thickness deposited onto the copper substrate is essential with the existing and new finishes. In addition to measuring the true thickness, the effects on performance during assembly need to be determined. Different thickness measurement techniques have been described that enable reliable thickness assessments and the determination of the recommended immersion tin thickness for lead-free soldering. It has been shown that if all the pure tin is converted into SdCu interrnetallic, so that no pure tin is left as a solderable layer, the wetting behaviour decreases dramatically. Especially for the multiple soldering processes, two reflows followed by wave soldering, it is essential to have a pure tin layer covering the S d C u intermetallic before going to the final soldering process. Owing to the higher temperatures used in leadfree soldering and therefore the greater tin consumption during the Sn/Cu intermetallic compound formation, it was concluded that the required tin thickness for multiple reflow soldering is 1.2 pm. (iii) Many highly varied processes of chemically or physically treating the surface of a metal substrate, such as copper, to improve the bonding of the

69

metal to a polymeric material, such as epoxy or polyimide, are used in industries such as printed circuit board fabrication. One method comprises a process of multiple tin coatings that are claimed to have superior chemical resistance and enhanced adhesion in the fabrication of printed circuit boards. A sheet comprising at least a layer of copper is initially immersed in an acid tin solution containing a complexing agent for a time sufficient to produce a first heavy tin deposit. The sheet is then immersed in a second tin solution comprising stannous tin ions and stannic ions for a time sufficient to produce a thin tin deposit on the sheet. A rough texture providing mechanical adhesion sites results. The board is then treated with a coupling agent, such as a silane, for enhanced bonding to a subsequent epoxy or other polymer prepreg. (iv) Tin whiskers are hair-like growths of near perfect single crystalline structures of tin that grow from pure tin surfaces independently of plating character, i.e electroplated or immersion plated tin. Tin whiskers are believed to grow in order to relieve mechanical stresses acting within the tin layer. Over time (days or months to years), some whiskers have reached lengths capable of creating electrical short circuits between closely spaced conductors. Whisker growths are frequently defined as spontaneous in order to distinguish them from a completely different type of phenomena known as dendrites, which require the presence of moisture, an ionic species and an electric field in order to form. They have in fact been known to form in inert atmospheres and in vacuum with or without the presence of an electric field. Superior whisker-reduced immersion tin technology has been described in detail. It has shown that a nano-layer deposit from an organic metal-based pre-dip significantly reduces the diffusion by creating a unique sandwich layer with smooth concentration gradients. A drastic reduction in diffusion and stress is produced, eliminating the driving force for whisker formation and prolonging the layers shelf life and temperature stability at the same time. The above discussion concerns the inhibition of whisker formation. However, an equally important requirement is the inhibition of dendrites. A solution composition containing phosphorous compounds has been developed which is claimed to suppress dendrite formation during the immersion plating of tin or tin alloys. The phosphorous compound is selected from inorganic phosphorous compounds such as orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid, hypophosphorous acid, phosphorous acid and their salts and organic phosphorous compounds such as methylene phosphoric acid, alkyl phosphate and their salts. The compounds may be used singly or in combination. (v) The properties of a new generation of immersion tin as a solderable surface finish for printed circuit boards have been discussed. The new process combines the unique technology of organic metals with the well established technology of immersion tin. Organic metals have been developed from the group intrinsically conductive polymers. The organic metal ORMECON@ belongs to the family of poly(ani1ines). This polymer is purely organic and consists of elements C, 0, H and S. It is electrically conductive and has a potential of a noble metal (between Ag and Cu). It has catalytic properties and

70

0
can be reduced and oxidized without changing its form. The polymer is also largely insoluble and can be processed by dispersion. Omecon have recently integrated an aqueous dispersion of the organic metal into a classic immersion tin process as a pretreatment. (vi) In addition to a considerable amount of literature concerning immersion tin in soldering/electronics applications, a substantial amount of information pertains to the immersion plating of tin alloys. These include Sn-Ag, Sn-Bi, Sn-Zn and Sn-Pb. Although the determination of improved bath compositions, plating solutions and methodology have remained the main thrust of this work, information relating to deposit adhesion and bond enhancement has also been forthcoming.

0
2.

Fewer publications have emerged concerning the plating bath formulation and the quality of electroless plated tin, although the electroless plating of alloys has received some attention. (i) A bath compositions for tin and tin-lead alloy electroless plating processes which can produce uniform deposits consisting of fine grains. A tin or tin alloy electroless plating bath containing a soluble metal salt component in the form of a stannous salt (organic sulphonates, borofluoride, acetate, chloride, carboxylate) or a mixture of a stannous salt and a lead salt ; an acid ; thiourea; and a reducing agent ( hypophosphorous acid or sodium hypophosphite). This formulation can be improved by (1) adding one or more non-ionic surfactants, preferably in combination with one or more members selected from a cationic surfactant or a heterocyclic compound having a nitrogen atom in the ring and a derivative thereof or (2) adding an ammonium ion andor quaternary ammonium ion. The pH is preferably 2 or lower. The non-ionic surfactants include polyoxyalkylene ether series such as . polyoxystearyl amide ether. Examples of the cationic surfactant include alkylamine salts and examples of the heterocyclic compound include alkyl pyridines. (ii) A method and bath for the autocatalytic chemical deposition of a Sn-Zn alloy on a catalytic surface has been proposed by Cavallotti and Sirtori [ 3 5 ] . The method is claimed to be particularly useful in the manufacture of electronic components. When the deposition of a thin layer of Sn-Zn alloy is needed before the deposition of the Sn-lead free alloy necessary to improve the solderability characteristics of the Cu surface. The Cu surface must be made catalytic before immersion in the autocatalytic bath, e.g. by depositing a thin film of metallic tin.In a specific example, the initial solution contains 0.2 M sulphuric acid; 0.3 M thiourea; 0.15 M sodium hypophosphite; 0.01 M tin sulphate and ). 1 M zinc sulphate. The copper substrate is immersed in this solution for 3 min at 25C and then rinsed with deionised water. This has the effect of depositing a thin film of metallic Sn onto the Cu substrate, which activates the autocatalytic process of deposition of Sn and Zn. The catalytic surface is then immersed in an alkaline autocatalytic bath containing Sn and Zn salts. The composition of the second bath is as follows: Zinc salt (0.1-1 M); Sn salt (0.01-0.5 M); complexing agent (0.1-1.5 M); and alkali 1-5 M. The

0
'

a
'

0
71

preferred embodiment for the tin salt is tin sulphate (0.03 M) and the preferred zinc salt is zinc acetate (0.5 M).

C) Applications in the Field of Corrosion Protection

1.

The main focus of immersion plating work has been in the development of improved corrosion resistant tin coatings for the interior of copper drinking water supply tubes. (i) Recent concerns over copper dissolved in drinking water have posed the question of controlling the internal corrosion of copper water tubes by coating the inner tube surface with an immersion tin deposit. Restricted copper release combined with other environmental pressures and the quality criteria set on products by consumers enhance the importance of a reliable performance and, thus, uniform coating structure. This structure is influenced by three preliminary attributes, which all act independently to form an integrated system: pi-e-plating procedures, the actual coating process, and post-plating treatments. Extensive studies have recently been conducted relating to the preplating procedures and immersion coating of copper tube by tin and the role of contamination in determining coating morphology, thickness and integrity. (ii) The ability of different preplating processes, degreasing and pickling, to clean the contaminated copper surface prior to deposition has been studied by contact angle determinations, residual oil measurements and potentiostatic polarization cycles. The influence of the preplating processes on the buildup of the immersion tin coatings and subsequent deposit structure has been studied by electron microscopy. Alkaline degreasers were found to effectively eliminate the organic soil from the surface, thus facilitating uniform coating nucleation and good adhesion properties. Pickling gave rise to a regular coating appearance throughout the structure. In addition, the applicability of contact angle measurements for studying the efficiency of cleaning treatments was also demonstated. (iii) The initiation and growth of immersion tin coatings from hydrochloric acid based and methanesulphonic acid based baths on the inner surface of copper tube has been investigated. The formation of immersion tin coating crystallites from hydrochloric acid based baths occurred semi-coherently with the copper substrate. Tin crystallites grew both in the vertical and horizontal directions yielding an equiaxial grain structure. The immersion tin deposit from the methanesulphonate based bath proceeded by the formation of tin nanocrystals. These nanocrystals transformed into columnar grains during the grain growth process. Differences in the coating formation characteristics between the two plating baths could be correlated with the microstructural properties of the final coatings, such as surface morphology, porosity and adhesion.

72

(iv) Further analyses have revealed differences in the unformity of the immersion tin coatings in the two plating solutions. The hydrochloric bath yielded non-uniform coatings on irregular or improperly cleaned substrates, since large size grains developed immediately after coating initiation. These large size grains were suggested to orientate to follow the contours of impurity particles or surface irregularities introducing misalignment in grain columns and, thus, non-uniformity into the coatings. In contrast, a methanesulphonic acid based bath was still able to produce uniform tin coatings on contaminated or rough surfaces, as the coating was proposed to accommodate to substrate surface irregularities by the build-up of a nanocrystalline zone at the early stages of tin coating deposition. Sulphur containing elements in the methanesulphonic acid plating bath were claimed to play the central role in the nanocrystalline layer formation. (v) A microstructural study has been carried out of the inhibition of immersion tin coatings due to substrate surface contamination. The formation of the immersion tin coating from the hydrochloric acid based bath on the inner surface of clean and contaminated copper tubes was studied. The mechanism of inhibition by a drawing lubricant layer was the focus of attention. The substrate surface contamination was found to influence both the coating nucleation and growth processes and the overall appearance of the immersion tin coating. A discontinuous, thin, nanocrystalline and irregular tin coating forms on a contaminated copper substrate in place of a continuous, regular tin coating of reasonable thickness, which builds up on a clean copper surface. However, the nucleation mechanism of the immersion tin deposit is equivalent on both surfaces. The oily contamination layer is, thus, only suggested to block the accessibizity of aqueous plating solution onto the surface, thereby hindering the coating nucleation at the areas of poor cleaning. Furthermore, no grain growth ws encountered in tin coatings deposited on the poorly cleaned copper.

a a

a
2.

0
The main focus of electroless plating work has been in the development even more effective corrosion resistant tin coatings for the interior of copper drinking water supply tubes than those described above. (i) Autocatalytic tin coatings are capable of increasing the thickness of the existing tin coatings and, therefore, of improving their properties. A two-step process has been developed which is composed of an immersion tin coating phase combined with an autocatalytic plating step, utilizing a bath containing sodium hydroxide, sodium citrate and stannous chloride. This autocatalytic step was accomplished using the disproportionation mechanism discussed previously (Section A). The development of the coatings proceeds by alternate grain nucleation and growth processes; grain growth advances until a completely compact layer of tin grains is formed, which is followed by a new nucleation and successive growth phase. A bath temperature of 80C was found to be optimal for the autocatalytic tin coating development; here, grain growth is favoured, introducing an even cating layer with a reasonable thickness.

a e a a e

a
73

(ii) Utilising the autocatalytic process described above yields improved corrosion performance in tin coated copper tubes due to a more efficient shielding ability. Studied by potentiodynamic polarization experiments in water exhibiting moderate aggressivity towards copper, the utilization of dense and continuous autocatalytic tin coatings was observed to shift the corrosion current density value of uncoated copper to less than one tenth of the original value and the corrosion potential by up to 350 mV in a negative direction. The magnitude of these effects, generated by the dual coating layer, is much greater than that observed for an immersion coating alone.

D) Applications in the Field of Power Sources

1.
Few applications relating to immersion plating have been reported in the field of power sources. One exception concerns the use of tin (or indium) as replacements for mercury based corrosion inhibitors for zinc in alkaline manganese batteries. The former metals can be plated onto the zinc spontaneously from the alkaline electrolyte via a simple immersion coating process. By contrast with the above, a significant number of publications have been produced relating to improvements in the performance of power sources using electroless tin plating technology. The power sources include batteries, photovoltaic cells and fuel cells. (i) In the field of lithium-ion batteries, carbonaceous materials are widely used as anode active materials for lithium-ion batteries and the background to their use, coupled with that of tin, has been recently been described in this review. Carbon can be lithiated to form LiC6 with a theoretical capacity of 372 mA h g-I, but carbon anodes usually deliver a reversible capacity of 280-320 mA h g-. The carbons can exist in various forms. The carbon anode materials used in lithium-ion batteries are categorized into three types: (1) hard carbon which does not graphitize at high temperature, (2) soft carbon which is changeable by heat treatment, and (3) graphite. Amongst these, the graphitized mesocarbon microbeads are the industry benchmark anode materials for lithium-ion batteries. These have stable lithium intercalation and deintercalation characteristics with a reversible capacity of 300 mA h g-I. Current research is focused upon developing either cheaper or higher performing alternatives.

2.

In order to increase the capacity of the anode, tin-based composite oxides and tin-based alloys have been developed. These new anode materials can deliver a lithium storage capacity exceeding by 2.5 times that of carbonaceous materials. The potentials for lithiation of the tin based alloys are higher than that of carbonaceous anodes, significantly reducing passivation of the lithium and improving the safety characteristics of the anodes. The amorphous tin based composite oxides have a first insertion capacity of 1030 mA h g- and a reversible capacity of 650 mA h g-. However, both the tin-based oxide anodes and tin-based alloys suffer from poor cyclability. This is mainly caused by the large volume changes in Li,Sn alloys.

74

0
The increase of the volume associated with the formation of different Li-Sn phases during the charging process (tin expands as much as 259% when alloying with lithium) and the reverse of this (contraction) during discharging, eventually leads to the disintegration of the anode and rapid capacity decay with cycling. This problem can be significantly alleviated by embedding active Sn, Sn-based oxides or tin-based alloys, in ductile graphite matrices.Ttin/graphite materials or composites have been developed as anode materials for lithium-ion batteries in which electroless tin deposition processes have been utilized in the initial production phase of the materials. Both tin coated graphite and tin coated mesocarbon microbeads have been investigated. (ii) BP Solar has been manufacturing the buried contact solar cell under the product name Saturn since 1992. A huge number of individual cells are required in this form of energy conversion. The company is currently investigating improved processes for the fabrication of the cells, including a more environmentally friendly method for the metallisation of the cell. These include copper plating and cyanide-free metal coating processes as capping layers on the copper to avoid tarnishing and improve solderability. In regard to the latter, various electroless silver and tin electroless coatings have been investigated as suitable candidates. It has been found that tin coatings proved to be particularly effective, passing all the applied tests, and therefore provide an alternative to the current cyanide-based coatings. The silver coatings, by contrast, were shown to be less suitable and failed several of the tests. (iii) The CO tolerance of the anode catalysts for low temperature polymer electrolyte membrane fueZ cells (PEMFC) can be markedly improved by combining Pt with a less noble metal component, allowing oxidation of the poisoning COad,species, This process involves surface reaction with OH species, electrosorbed onto oxophilic metal sites, at a lower potential compared to that for Pt alone. The latter reaction sequence is usually referred to as a blfunctional mechanism. This has stimulated enormous efforts (both experimentally and theoretically) to formulate novel PEMFC catalyst materials with an improved performance and the subject has recently been reviewed. A detailed categorisation of the literature has been undertaken. The most promising compositions for electrocatalytic applications are Ru, Os, Ir, Sn, Bi, MO,V, W, Re, etc, binary or ternary/quatemary combinations with Pt. These can be divided into two major groups with respect to catalyst preparatiordcomposition, i.e. (i) bimetallic alloys and (ii) surface-modified catalysts . The second group (ii) deals Pt surface modification by oxophilic metals. Three basic methods are involved here: (a) underpotential deposition and electrodeposition of monolayers or submonolayers, e.g. Sn on the Pt surface; (b) physicochemical deposition of modifying metal through an organometallic route, e.g. thermal decomposition of organyl complexes of non-noble metals on Pt, photolithography, ion implantation, or epitaxially grown overlayers under ultra high vacuum conditions; and (c) surface modification through spontaneous deposition.

a a

a a

75

Very recently, a detailed investigation has been undertaken of the surface modification of Pt by a spontaneous dip coating approach involving the generation of both tin oxy-species and tin metal, based on hydrolysis of a tin chloride complex and autocatalytic deposition of tin. The method consisted of (i) Pt immersion into SnC12/HC1 solution under open-circuit conditions and (ii) subsequent rinsing of the surface by pure water. The resulting tin modified Pt surfaces were characterized by atomic force microscopy, X-ray photoelectron microscopy and cyclic voltammetry. Two types of tin species, namely, tin oxidehydroxide species and metallic tin were identified at the Pt surface. The former were assumed to be derived as a result of Sn(I1) chloride complex hydrolysis, while the latter were most likely deposited spontaneously due to disproportionation of Sn(I1) to Sn(1V) and metallic tin, competing with the dissolution of tin in the strongly acid media. The modifyng tin species exhibited a satisfactory stability in 0.5 M H2S04 solution at potentials relevant tg low temperature fuel cell operating conditions, i.e. below 0.6 V vs. standard hydrogen. The effectiveness of the above treatments in enhancing the catalytic activity of Pt in direct methanolfuel cell applications has been assessed. The electrocatalytic activity of the spontaneously Sn-modified Pt was compared to that of a polycrystalline Pt electrode in the electrooxidation ofpre-adsorbed CO and the simple so-called C-1 molecules methanol, formic acid and formaldehyde. The spontaneously Sn-modified Pt catalyst exhibited a superior activity towards adsorbed CO oxidation and could thus be considered promising for polymer electrolyte fuel cell applications operating on COcontaminated hydrogen oxidation. Although the methanol oxidation rate was hardly changed on the Sn-modified Pt surface, compared to the Pt electrode, it was shown that the formic acid oxidation rate could be enhanced and that for formaldehyde could be dramatically increased. The latter was observed at the most negative potentials where anodic formaldehyde oxidation is normally completely suppressed on a pure Pt electrode. The results were discussed in terms of poisoning CO intermediate formation resulting from dehydrogenation of the organic molecules on Pt sites and oxidation of poisoning adsorbed CO species via the surface reaction with OH adsorbed on neighbouring Sn sites.

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7. References
1. Processes and Applications for Tin and Tin-Based Alloy Surface Coating Technologies, Stage 1, Electrolytic Deposition: Part 1, Electrodeposition and Electroplating o Tin; Part 2, Corrosion Resistant Coatings; Part 3, f Electrochemical Power Sources; and Part 4, Solders and Applications in Electronics; compiled for Tin Technology by L. M. Baugh and dated January, February, March and April, 2005, respectively. 2. Immersion Plating. S .Hirsch and C. Rosenstein, Metal Finishing (New Jersey), 93, no. 1A (1995), pp 415-419. 3. Electroless (autocatalytic) Plating. J. R. Henry, Metal Finishing (New Jersey), 102, no. 4A (2004) pp 355-366. 4. Deposition of Thin Tin Coatings on Aluminium Alloys. D. S. Stoychev, E. A. Stoyanova and S. Rashov, Surface Technology; 23 (1984) pp 127-141.
5. Kinetics o Anodic and Cathodic Processes during Immersion Treatment o f f

0
Aluminium in Stannate Solutions. D. Stoyev and E. Stoyanova, Bulletin of Electrochemistry 4, no.7 (1988) pp 673-678. 6. Electroless Sn-Ag Plating by Displacement Reaction. S. Arai, M. Kumagai, N. Kaneko and N. Shinohara, Electrochemistry, 70 no.5 (2002) pp 3 1 1-3 15.
7.

a a

Sn Deposition onto Cu and Alloy Layer Growth by a Contact Immersion Process. Y . Fujiwara, Thin Solid Films, 425 (2003) pp 121-126.

8. Electroless Tin Plating through Disproportionation. H. Koyano, M. Ichikawa and M. Kato, Surface Engineering International Conference, 18th-22"d October, 1988, ~~275-284. 9. Preparation o Ni-Sn Alloys by an Electroless -Deposition Method. H. f Shimauchi, S. Ozawa, K. Tamura and T. Osaka, J. Electrochem. Soc. 141 no. 6 (1994) pp 1471-1476.
10. Autocatalytic Deposition of Tin. M. E. Warwick and B. J. Shirley, Trans. Inst. Met. Finish, 58 (1980) pp 9-14.

11. Aqueous Plating Soluiions. G. Bokisa and W. Willis, Patent US 555421 1, September, 1996.
12. Aqueous Immersion Plating Bath and Method for Plating. G. Bokisa and W. Willis, Patent US 6063 172, May 2000. 13. An Investigation o the Recommended Immersion Tin Thickness for Lead-Free f Soldering. S. Lamrecht, Circuit World, 31, no. 2 (2005) pp15-21. 14. Improved Adhesion o Polymeric Materials to Metal Surfaces. D. L. Whitney, G. f S. Bokisa, C. V. Bishop, et al., Patent WO 02079542, October 2002.

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15. Process forproviding bond enhancement and an etch resist in the fabrication of printed circuit boards. D. McKenny, A . J. Demaso, K. A . Gosselin, et al., Patent US 6645549, November 2003. 16. Tin Whisker-Free Printed Circuit Board. G. Bokisa and C. V. Bishop, Patent US 2002064676, May 2002 and US 6361823, March 2002.
17. Immersion Tin: A Proven Final Finish for Printed Circuit Boards Providing Reliable Soldering and Marginal Formation of Tin- Whiskers. P. Meeh, Circuit World, 31, no. 1 (2004) pp 28-40.

18. Superior, Whisker-Reduced Immersion Tin Technology. S. Schroeder, Circuit World, 3 1, no. 4 (2005) pp 42-46. 19. Electroless Tin and Tin Alloy Plating Bath, Electroless Plating and Electronic Part Coated with Tin or Tin Alloy Film. S. Tsuji, T. Nishikawa and K. Tanaka, Patent JP 11061426, March 1999. 20. The New Immersion Tin Generation in Practical Operation-A Surface Finish Process Including the Worlds First Organic Metal. S . Schroder, Circuit World, 29, no.1 (2002) pp 10-13. 2 1. Substitution Type Electroless Tin-Silver Alloy Plating Solution. Y. Nishihama, S . Shuichi and Y. Tanabe, Patent JP 2000309876, November 2000. 21. Electroless Tin-Silver Alloy Plating Bath. S. Tsuji, T. Nishikawa and K. Tanaka, Patent JP 2002088481, March 2002. 22. Substitution Type Electroless Plating Bath for Tin, Silver and Tin-Silver Alloy. S. Arai, N. Kaneko, N. Shinohara, et al., Patent JP 2002266077, September 2002. 23. Plating Method. M. A . Preznik and D. L. Jacques, Patent JP 2003034875, February 2003. 24. Immersion Plating of Tin-Bismuth Solder. C. M. Melton, A . Growney and H. Fuerhaupter, Patent US 5435838, July 1995. 25. Electroless Tin-Bismuth Alloy Plating Bath. S. Tsuji, T. Nishikawa and K. Tanaka, Patent JP 2000087252, March 2000. 26. Immersion Plating and Plated Structures. E. Cooper, C. C. Goldsmith, S . Kilpatrick, et al., Patent US 2004219384, November 2004.

27. Method of Making Lead-Free Solder Paste with Improved Wetting and ShelfLife. Z. Mei, Patent US 2003059642, March 2003.
28. Pretreatment Process o Tin Lead Plating. R. Iantosca, Patent US 5296268, f March 1994.

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8. Acknowledgements The following have kindly given their consent to reproduce the figures in this report:Figs 1-3. Reproduced by permission of Elsevier.
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Figs. 4. Reproduced by permission of The Electrochemical Research Institute of India. Figs. 5-8. Reproduced by permission of TheElectrochemical Society of Japan. Figs. 9 & 10. Reproduced by permission of Elsevier Figs. 14-16. Reproduced by permission of The Electrochemical Society, Inc. Figs. 17-20. Reproduced by permission of The Institute of Metal Finishing. Figs. 21 & 22. Reproduced by permission of Emerald Publishing. Fig. 23 & 24. Reproduced by permission of Emerald Publishing.
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Fig. 25 & 26. Reproduced by permission of ASTM International. Figs. 27-34. Reproduced by permission of Elsevier. Figs. 35-38. Reproduced by permission of The Electrochemical Society Inc. Figs. 39 & 40. Reproduced by permission of Elsevier. Fig. 41- 43. Reproduced by permission of Springer Publications.

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