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 1 ELECTROLYTIC DEPOSITION

PART 4 ELECTRODEPOSITION AND ELECTROPLATING OF TIN ALLOYS SOLDERS AND APPLICATIONS IN ELECTRONICS

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

April 2005

CONTENTS

1.
2.

Introduction .......................................................................... Tin-Lead Alloys .....................................................................

2.1 Background..................................................................... 5 2.2 Fundamental Aspects of Tin-Lead Plating .................................. 7 2.3 Application of Pulse Plating and Reverse Pulse Plating .................. 8 to the Deposition of Sn-Pb Alloys 12 2.4 Effect of Agitation on Tin-Lead Alloy Deposition ....................... 3. Tin-Silver Alloys ................................................................... 3.1 3.2 3.3 3.4 3.5 3.6
4

13 12 13 17 22 30 33 35 35 36 37
37

Background .................................................................... Sn-Ag........................................................................... Sn-Ag vs . Sn-Pb ............................................................ Sn-Ag-Cu...................................................................... Sn-Ag vs . Sn-Ag-Cu ......................................................... Sn-Ag vs . Sn-Ag-Cu vs . Sn-Pb ............................................

Tin-Bismuth Alloys ................................................................ 4.1 Background .................................................................... 4.2 Sn-Bi ........................................................................... 4.3 Sn-Bi coated Sn-Ag ..........................................................

Tin-Copper Alloys 5.1 5.2 5.3 5.4 5.5 5.6

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

Background .................................................................... 37 Sn-Cu........................................................................... 38 Sn-Cu-Ag and Sn-Cu-Bi ..................................................... 39 Sn-Cu vs . Sn-Bi ................................................................ 39 Sn-Cu vs . Sn-Bi vs . Sn-Ag-Cu.............................................. 42 Sn-Cu vs . Sn-Ag vs; Sn-Ag-Cu............................................. 43 43 43 44 44

6.

Miscellaneous Alloys ............................................................... 6.1 Sn-In .............. ..;... ........................................................ 6.2 Sn-Zn........................................................................... 6.3 Sn-Zn vs . Sn-Bi ...............................................................

7.

Gold-Tin Alloys ........................................ 7.1 7.2 7.3 7.4 7.5 7.6

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

45

.Background.................................................................... Development of Electroplating Solutions ................................. Microstructure and Preferred Orientation ................................. Comparison of DC and PC Plating .......................................... Deposition of Multilayers using PC Plating ............................... Role of Processing Variables ................................................

45 46 47 48 53 57 58

Miscellaneous Applications in Electronics ....................................

8.1 Electrodeposition of Tin Needle-Like Structures ......................... 8.2 Electrodeposition of Sn-Se ..................................................... 8.3 Electrodeposition of Cu-Zn-Sn ........... :.................................

58 58 59
60

9. 10. 11

Extended Summary ................................................................

References...........................................................................

66
71

Acknowledgements

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

1. INTRODUCTION

The current review forms part of a series concerned with detailed analyses of recent progress in the electrodeposition and electroplating of tin and tin alloys. Earlier works [ 11 covered developments in the electroplating ofpure tin (Part l), corrosion resistant tin alloys (Part 2) and the use of electrodeposited tin alloys in electrochemical power sources (Part 3). Part 4 of the series focuses on the use of electrolytic deposition in the formation of solders and applications in electronics. The Council of the European Community is planning directives dealing with wastes from electronic components, which will involve a ban on lead. The date for the enforcement of this regulation was planned for 1" January 2004, but later revised to 1" July 2006. The primary driver of this technological change is recycling efforts in Europe, where materials containing lead may not be disposed of as 'scrap' in waste disposal sites. Legislation has also been passed that requires recycling of all components in an automobile at the end of its useful life [2]. In order to meet these regulations, solderable systems that do not contain lead must be applied. A considerable literature has therefore arisen in the last few years in which various lead-free solders and lead-free deposits have been fonnulated and tested. The current review is the concerned with a detailed analysis of those alloy systems that have been produced via electrodeposition and electroplating. The main requirements on lead-free deposits have been listed by Jordan [2]:1. Preserving the solderability of electrical and electronic components 2. Compatability with lead-free solder pastes 3. Plating conditions similar to those which are actually used for the deposition of tin-lead alloys 4. Availability and costs for the lead-free alternatives must not be prohibitive to a general application of the new systems

Other attributes include: good reflowability; low porosity; good corrosion resistance; and unlformity of alloy composition, thickness, smoothness, and appearance, over a wide current density range [3]. A large number of review articles have been written on the subject of lead-free solders and lead-free plating alloys [2-81. In components of electronics packaging, electrodes to be soldered are electroplated particularly to improve corrosion resistance and wettability. As lead-free plating alloys, Pd, Au, Sn, Sn-Zn, Sn-Bi and Sn-Ag have been proposed, where the latter two alloys correspond to compositions of lead-free solders. The solder alloys that have been proposed also include Sn-Cu, Sn-Ag-Cu, Sn-In and Au-Sn. The results fi-om extensive field tests involving several lead-fiee tin alloys for electronics applications have been reported by Jordan [91. A major challenge in the deposition of lead-free alloys is the large difference in the standard potential of the metals that have to be deposited with tin. The metals Bi, Ag and Cu, for example, have standard potentials that are more noble than tin. The relative position of the elements on the scale of electrochemical standard potentials is shown in Fig. 1.

-1000

-500

500

1000

E us. NHE [mV

Fig. 1. Relative position of standard potentials for tin and possible metals for codeposition [2].

It can be seen that, whereas the standard potentials of tin and lead differ by only a very small amount (20 mV), those between tin and the remaining metals differ significantly. As a consequence, although it is possible to plate any desired Sn-Pb alloy composition fairly easily, the difference in standard potentials causes severe problems in the case of the other alloys. These problems include: preferred deposition of the more noble metal in the low current density range and therefore a large variation in alloy composition in relation to current density; immersion plating of the more noble metal; and possible redox reactions between divalent tin and the more noble metal.
In order to make electrodeposition of the above alloys possible, it is necessary to reduce the difference in the standard potentials of the metals. A cornmon method involves the addition of compkxing agents to the electrolyte. Compounds have to be found which shift the potential of the more noble metal in the cathodic (or negative) direction as far as possible. Clearly, these agents also need to be selective and should not simultaneously shift the potential of tin itself, since this would simply maintain the effective nobility of the alloying metal.

2.

Tin-Lead Alloys

It is logical to commence this review with a discussion of tin-lead plating, since this is still an important process for the electronics industry. Although the development of lead-free alloys continues to be the main thrust in recent investigations, some work has therefore continued to be published concerning Sn-Pb alloys. These studies have the objective of obtaining a better understanding of the system. However, the results from this work can also have consequences for the plating of lead-free alloys, particularly if novel electrochemical techniques have been employed in the investigations. Furthermore, the lead-free replacement alloys will need to be equally effective and have similar properties to the lead containing alloys. The Sn-Pb system therefore represents a reference point from which the other systems will be judged in the future. The following is an outline of both technological and fundamental aspects of Sn-Pb plating.
2.1

Background

The background to the application of tin-lead alloys has been summarised by Carano [101-

Tin-lead alloys (10-40% by weight tin) are plated on wire to protect the base from oxidising and to enhance solderability; on printed circuit boards (60% tin) to act as an etch resist and preserve solderability; and on electrical contacts for solderability enhancement and corrosion protection. Tin-lead alloy compositions in the range 90-98% by weight tin are electroplated on semiconductor device leads to preserve solderability and eliminate potential spontaneous metallic whisker growth. Although the major uses for tin-lead alloy plating are for electronic applications, the alloy is also used as an overlay on bearings and as terne plate, which provides corrosion protection for steel. For these applications the tin content is less than 12% by weight. There are two basic electroplating processes currently available for plating tin-lead alloy deposits, acidfluoroborate and acid sulphonate. The former process is the more widely used, although the latter is receiving increased attention from the environmental standpoint. Both processes are claimed to be relatively easy to operate at 100% cathode and anode efficiency. The acidjluoroborate electrolyte must contain free fluoroboric acid to provide solution conductivity; boric acid to prevent breakdown of the fluoro boric acid into free fluoride (which would cause unwanted precipitation of lead as lead fluoride); tin fluoroborate (as a source of tin ions); lead fluoroborate (as a source of lead ions); and a suitable grain refiner. The simplest grain refiners, based on gelatin and glue, provide smooth, tight grained deposits. Proprietary additives are also available and provide certain advantages, such as stability and ease of control not possible with gelatin and glue formulations. The acid sulphonate electrolyte is based on alkanesulphonic acid; tin alkanesulphonate; lead alkanesulphonate; and an organic addition agent. The alkanesulphonic acid provides solution conductivity, while the tin and lead alkanesulphonates provide the metal ions. The organic addition agents provide the same function as their fluoroborate counterparts. In general, however, the organic addition agents employed in the fluoroborate processes are not compatible with the acid sulphonate processes. Typical chemical make-up and operating conditions for both the fluoroborate and sulphonate processes yielding deposits containing 60% tin are described by Carano [lO]. The exact composition of tin and lead in the deposit is influenced by:(a) ratio of metal ions in the solution (b) cathodic current density (c) type and concentration of addition agent The tin content in the deposit increases with an increase in the ratio of tin to total metal and with an increase in cathodic current density. Certain additives, such as wetting agents, glue, or peptone, will also raise the tin content in the deposit. In general, deposits produced from the tin-lead electrolyte are semi-bright to matte. However, with careful control of the electrolyte and the addition of aldehyde/amine

brightening additives, a bright, lustrous tin deposit can be obtained. Although the bright tin-lead coatings do not require flow-melting or fusing to cosmetically enhance the finish, the process requires tight control of these organic brighteners. The organic addition agents act as a controlled impurity in the tin-lead electrolyte. A certain percentage of the organic material is incorporated into the plated deposit. Excessive levels of the organic material can be detrimental, causing solderablity problems. Some military specifications call for only matte deposits, with the organic content to be as low as possible.

In the electronics industry, the preservation of solderability is the main reason that tin-lead electrodeposits are used, or their replacements will be used in the future. Printed wiring boards are refiowed, or fused, to enhance solderability and improve the cosmetics of the matte tin deposits. In this process the parts are first coated with a flux, which cleans and activates the tin-lead surface. Heat is then applied to the parts. The heat can be applied by a number of sources: hot vapour; hot oil; or infi-a-red. Temperatures above 400F cause the tin-lead deposit to melt, forming a true alloy more commonly known as solder. The composition of the deposit is critical for the reflow operation, with an ideal deposit content of 63% tin and 37% lead. Tin-lead plated copper wire can be brightened by drawing the wire through dies, by fusing or flow melting, or by one of the brightened tin-lead processes.
2.2

Fundamental Aspects of Tin-Lead Plating

There has been considerable interest in the electrodeposition kinetics and properties of Sn-Pb coatings due to their importance to the electronics industry. A summary of the pertaining literature has been provided recently by Liu and Pritzker [ 113. One of the first kinetic investigations was conducted by Cheng and Cheh [ 121 on the galvanostatic pulsed current (PC) plating of tin, lead and tin-lead alloys onto a rotating disc electrode in fluoroborate solutions. Assuming that Sn and Pb deposition occur independently of one another, these authors presented a model that predicted the observed current-potential behaviour reasonably well. This model was extended by Pesxco and Cheh [ 131 to incorporate 2-dimensional transport and migration effects and compared with experimental radial profiles of deposit content and total current for DC plating. Good agreement was obtained when the plating bath was additive-free. However, less than satisfactory results were obtained when the surfactant Triton X100 was present due to a significant increase in cathodic polarisation attributed to interactions between the organic and the metal ions. Tam [ 141 investigated Sn-Pb deposition onto a rotating disc electrode in fluoroborate solutions containing peptone and also reported evidence of substantial interactions between the metal ions and the adsorbed organic. Chen et al. [ 151 studied alloy electrodeposition from methane sulphonate acid solutions containing equi-molar Pb2+and Sn2+concentrations in the absence of organic additives and reported that the deposition of each metal occurs independently of the other in both kinetic and mass transfer controlled regions. In these solutions, the resulting alloy contained more Pb than Sn due to faster electrode kinetics and mass transfer.

DC plating in methane sulphonate baths was also studied by Kim et al. [ 161. They found that the Pb content in the alloys rose sharply to the desired 20 wt.% with increase in applied current density to approximately 3 A dm-2and thereafter remained unchanged at higher current. The addition of an organic grain refiner substantially increased the cathodic polarisation during deposition and led to a much finer-grained deposit. Recent studies on Sn-Pb deposition were conducted by Peterson and Ahlberg [ 17,181 on glassy carbon and polycrystalline gold electrodes in fluoroborate solutions in the absence of organic additives. They found that the alloy deposition rate is controlled by metal ion diffusion to the electrode surface with 3-dimensional growth of nuclei. 2.3 Application of Pulse Platin9 and Reverse Pulse Plating to the Deposition of Sn-Pb Alloys

Few pulse plating studies of the Sn-Pb system have been reported. In addition to the work of Cheng and Chey [ 121, discussed previously, Kim et al. [ 161 investigated pulse current (PC) plating in methane sulphonic acid solutions. Variation offrequency and duty cycle from 10 to 100 Hz and 10-80%, respectively, at an average current density of 10 A dm-2had little effect on deposit composition, yielding the same result achieved by DC plating. However, it affected the deposit morphology significantly, producing very fine grains at low frequency and duty cycle that became coarser as duty cycle and frequency increased. Doss [ 191 compared the application of DC and PC plating to fabricate Sn-Pb studs for use in magnetic recording disc heads and found PC plating to yield more uniform and smoother deposits. Until very recently, no studies on the use ofpulse reverse plating had been reported for the tin-lead system. Previous work on other systems, e.g. Ni-Fe and CO-Fe, had shown that the use of a pulse reverse (PR) mode can affect deposit composition differently from that a normal pulse (PC) mode [20-221. This situation has now been remedied by an extensive investigation involving the application of DC, PC and PR modes of electrolysis to produce Sn-Pb coatings in a fluoroborate solution with a Sn:Pb weight ratio of 4: 1 [ 111. The effects of pulsefrequency, duty cycle and cathodic pulse amplitude on deposit composition were discussed. The results from this work are summarised below. The tin-lead electroplating bath in this study consisted of Sn(BF4)2 (40 g Sn l-*), Pb(BF& (10 g Pb 1-),HBF4 (15 g 1-), peptone (5 g 1-) and gelatin (2 g 1-). A copper disc working electrode was employed having a 0.64 cm diameter and this was cut from pure copper (99%). Electrode preparation involved acid etching in 1M HNO3, rinsing in distilled water; ultrasonic cleaning in ethanol, rinsing in distilled water; and finally polishing with S i c abrasive paper and rinsing in distilled water. The DCplating experiments were conducted over a range of current densities between 0.5 and 20 A dm-2.Current densities above 20 A drn-2were not applied since this would have produced coarse deposits. Under DC conditions, the Pb content in the alloy rose from 8.2 to 18 wt.% as the current increased from 0.5 to 20 A dm-2(Fig. 2). The results indicated that Pb deposition was inhibited. At low current densities, the Pb:Sn weight ratio in the deposit was much lower than the 1:4 ratio in the electrolyte.

In the case of the pulse plating experiments, it was found that the effect of the pulse parameters on alloy composition differed dramatically depending on the mode of electrolysis being applied. Pulse frequencies in the range 20 Hz - 200 kHz, duty cycles in the range 50-90% and cathodic pulse amplitudes 1.9-15.0 A dm-2,were investigated. Composition was only mildly influenced by frequency and duty cycle in PC plating and did not vary significantly from that obtained by DC plating (cf. Figs. 2 and 3). By contrast, use of the PR mode dramatically altered composition depending on the pulse frequency, duty cycle and current amplitude, yielding alloys with PB content both well above and below that achievable by DC plating (Fig. 3). It can be seen that the lead content varied from 2.5% to 28% over the frequency range from 20 Hz to 200 kHz using a duty cycle set at 80% and an average current density of 3.78 A dm-2.At a frequency of 20 Hz, the proportion of lead in the resulting alloy was always lower than that in the solution, regardless of the other parameters. By contrast, the proportion of lead in the alloy almost always exceeded that in solution when a 20 HIz frequency was imposed.

20

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z 8
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1 1 1 1

0 0

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current density / A dm-*

Fig. 2. Effect of current density on the Sn-Pb deposit composition during DC plating onto a copper disc electrode rotating at 500 rpm [ 113.

32

24

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a
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Fig. 3. Effect of frequency on Sn-Pb deposit composition during pulse current (PC) and pulse reverse current (PR) plating at 3.78 .A dm-*average current and 80% duty cycle [ 111.

The deposition and dissolution of the two metals during pulse plating and the resulting alloy composition is closely related to changes in the potential of the copper disc throughout each pulse cycle. In order to gain some insight into this question, the input current signal and working electrode potential were continuously monitored with a digital oscilloscope throughout the pulse experiments. Figs. 4 and 5 illustrate the current and potential responses, respectively, for both PC and PR modes of plating. Although not perfect square-wave waveforms, the signals closely fitted the pre-set frequency, amplitude and duty cycle over each cycle. The pulse current densities in the PR plating experiments were maintained at 6.3 A dm-2for both the cathodic and anodic going pulses, giving the same average current density as that utilised in the PC experiments of 3.78 A dm-2.Fig. 5 shows that the response during cathodic polarisation was very rapid, enabling the potential to reach a steady state between -0.65 and -0.70V, regardless of frequency and pulse mode. However, the response was slower once the current was turned off (PC mode) or reversed in polarity (PR mode) and did not reach steady state values by the end of this portion of the pulse cycle. Thus, as the frequency was increased, this portion of the electrode response was truncated, causing a negative shift in the electrode potential during both PC and PR plating. This appeared to be a general phenomenon that was observed for a variety of pulse parameters. Using data of the kind shown in Fig. 5, Liu and Pritzer [ 113 proposed that the alloy composition is primarily affected by events occurring during the off-time of PC plating or the anodic pulses during PR plating. For example, the large range of compositions obtained by PR plating (Fig. 3) may be due to the relative rates of Sn and Pb dissolution during the anodic pulse depending on the precise electrode potential reached during the anodic pulse andor the duration of the anodic pulse. Less positive potentials and shorter anodic pulse times, which are favoured at high frequencies, tend to yield alloys with a higher Pb content because it was postulated that Sn would dissolve preferentially during the anodic pulse, thus enriching the alloy with Pb.

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The authors claimed that their results may be inportant in relation to reducing the amount of Pb in Sn-Pb alloys due to environmental concerns. In particular, the use of high frequency PR plating may allow a desired alloy composition to be obtained from a plating bath with a lower Pb content than is otherwise possible. The work of Liu and Pritzer [ 111 is important because it demonstrates that a more sensitive control over alloy composition is possible by the use of the PR mode of plating rather than by the more conventional PC or DC modes. 2.4 Effect of Agitation on Tin-Lead Alloy Deposition

Chen et al. [23] have studied the effect of agitation on Sn-Pb alloy electrodeposition within methane sulphonic acid solutions ciculated in a flow-through cell. The thickness and composition of the deposit formed under static conditions were investigated initially, then contrasted with the data obtained under a reflow system. It was found that when the electrolyte was stagnant, the high current area appeared on the edge region of the electrode surface where the lead deposition dominated, while the central region of the plate was the low current area that facilitated tin deposition. An increase in flow rate was shown to significantly improve the distribution of the alloy deposit, although the exact alloy composition was unchanged, being mainly controlled by current density. This in turn was shown to be controlled by mass transfer of active ions, so the flow pattern and circulation greatly affected the current distribution. It was also shown that mathematical modeling could accurately simulate the flow pattern within the cell with the assistance of appropriate flow 3D software.

3.

Tin - Silver Alloys

Background

3.1

Solders generally contain 2-4% silver. The melting point range is 210-280C. The melting point of a Sn-Ag alloy with a silver content of 3.5% is 221C. To further reduce the melting point, bismuth or bismuth and copper may be added [7]. The challenge in the Sn-Ag alloy deposition from an acidic electrolyte is the control of bath stability. Tin in its divalent form (as is necessary for electroplating from an acidic electrolyte) is a reducing chemical and is capable of reducing Ag' ions to colloidal silver. By careful use of complexing agents the difference in the standard potentials of tin and silver can be reduced to enable codeposition of the metals and also ensure bath stability. The presence of the complexing agent also prevents the precipitation of tin in the form of stannic oxide [2]. The application of Sn-Ag alloys in the electronics industry has been discussed recently by Kim and Ritzdorf [23]. Mounting is a critical step in manufacturing devices related to the semiconductor industry. As the electronic devices are miniaturised and the circuitry increases in complexity, flip-chip (FC) technology, which involves turning over the chip and then bonding the terminals directly to a wiring substrate, is used for interconnects instead of conventional mounting technology. Flip-chip interconnection of active components has become more and

12

more popular not only due to cost, but also to guarantee the performance of the integrated circuits (ICs). In addition, the invention of surface mount technology (SMT) for the assembly of passive components causes a dramatic reduction in packaging costs. Trying to combine FC technology with SMT and ball grid array (BGA) technology under the constraint of further miniaturisation and lowest cost resulted in the concept of wafer level packaging (WLP). This package is completed directly on the wafer and then singulated by dicing for the assembly in a FC fashion Sn-Ag based alloys are being developed particularly for use as lead-free solder bumps due to their desirable melting point, good creep resistance, shear strength, thermomechanical fatigue behaviour and reliability. The most cost effective method of producing fine geometry bumps cost effectively is by electrodeposition and thus electroplating technology is receiving much attention in WLP. 3.2 Sn-Ag

The formation of Sn-Ag alloy films using electroplating methods has been reported by several authors during the past few years. Recently, Arai et al. [24] have described how Sn-Ag alloy solder bumps for flip chip bonding can be formed by electroplating with the aid of photolithography. These authors also provide a bibliography of their earlier work and that of others. The compositions of the plating baths used in the investigation of Arai et al. are listed in Table 1. Sn-Ag plating baths using I(4P207 as a complexing agent for Sn and KI as a complexing agent for Ag were employed. Bath 1 did not contain any organic compounds, whereas baths 2-4 were based on formaldehyde (FA), polyethylene glycol 600 (average molecular weight 600, PEG 600), or both.

Table 1. Composition of Sn-Ag Electroplating Baths (mol dm-3) [24].

To characterise the deposition behaviour of the Sn-Ag alloy, current-potential curves obtained under potentiostatic or galvanostatic conditions were determined using pure copper or stainless steel substrates and subsequent film compositions were analysed. Current-potential curves for each plating bath are shown in Fig. 6. Silver deposition began at a potential of -0.60V in all baths. Codeposition of Sn and Ag occurred at potentials more negative than -0.9V. Curve (b), corresponding to bath 2, was almost identical to curve (a), indicating that addition of formaldehyde by itself had only an extremely small effect on the electrodeposition of Sn and Ag. Curve (c) shows the current-potential curve of bath 3, which differed in composition from bath 1 only by
13

the addition of 0.002M PEG 600, revealing that the electrodeposition of Sn was strongly inhibited by the presence of PEG 600. As a result, Sn-Ag codeposition was also strongly inhibited. Curve (d) shows the current-potential curve of bath 4, whi,ch contained both formaldehyde and PEG 600. Comparison with curve (c) reveals that the inhibitive effect of PEG 600 on the codeposition of Sn-Ag, was weakened by the addition of FA.

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Fig. 7 shows the relationship between current density and composition of the fabricated films. For all the different baths, the Ag content in the film decreased with increasing current density. The broken line in the figure shows the eutectic composition of th Sn-Ag alloy (Sn-3.8 atom % Ag). The Ag content of films fabricated using bath 3 were higher than films formed using the other baths. Near eutectic Sn-Ag films were obtained in the range of current densities from 0.5 to 1.0 A dm-2using baths 1,2 and 4, and from 1.O to 1.5 A dm-2for bath 3.
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14

Fig. 8 shows surface SEM images of the films deposited under galvanostatic conditions (1A dm-2,total electrical charge of 1200 C dm-2).

Fig. 8. Surface SEM images of Sn-Ag alloy films electrodeposited under galvanostatic conditions (1 A dm-2,total charge 1200 C dm-2)from (a) bath 1, (b) bath 2, (c) bath 3 and (d) bath 4 [24]. The size of grains in the films deposited using bath 1 ranged from several micrometers to 10 pm. A similar morphology was observed in the film developed from bath 2. The film obtained from bath 3 contained relatively small grains, 1-2 pm, whilst the fl obtained from bath 4 had a smooth morphology with the deposited im grains so small that their diameters could not be discerned from the SEM photographs. The galvanostatic morphologies were compared with those developed potentiostatically by applying potentials to coincide with a current density of 1 A dm-2,as taken from Fig. 6, and a total electrical charge of 1200 C dm'2. Almost identical morphologies to those shown in Fig. 8 were obtained. Solder bumps were fabricated on a copper substrate based on the previous results. Deposits obtained using baths 1 and 2 did not follow the resist pattern faithfblly and were powdery. In the case of bath 3, the generation of hydrogen gas was observed during deposition such that uniform deposition was difficult to obtain. Bumps of satisfactory and consistent quality could only be obtained from bath 4. Furthermore, it was also found necessary to apply a potentiostatic rather than a galvanostatic mode of plating as additional aid to quality. Fig. 9 shows SEM images of straight walled and mushroom bumps produced from bath 4 under potentiostatic conditions (-1.35V).

Fig. 9. SEM images of bumps obtained under potentiostatic conditions (-1.35V) using bath 4
~41.

Fujiwara and Enomoto [25-271 have outlined a method of Sn-Ag composite plating from tin electrolyte solutions with a suspension of silver nanoparticles. It was shown that a Sn-Ag alloy film with p SnAg3 eutectic structure could be obtained from an electrolyte consisting of pyrophosphoric acid and silver nitrate. It was claimed that the use of this novel bath would solve the problems in conventional Sn-Ag alloy plating baths, because the Ag ion and its complex are not present, but metallic silver nanoparticles are suspended in the bath. The existence of the particles has been demonstrated by UV visible spectroscopy and the effectiveness of solders produced by the method has also been examined [27]. A number of patents have recently been filed containing details of bath compositions or plating methods required for improved deposits of Sn-Ag alloys. Yanada and Tsujimoto [28] have describeda Sn-Ag electroplating bath containing (i) a stannous salt, (ii) a silver salt, (iii) one or two kinds of acids selected from the group consisting of sulphuric, phosphoric, phosphonic, hydrocarboxylic, alkanesulphonic or alkanolsulphonic acids, (iv) a non-ionic surfactant, and (v) one or more kinds of additives selected from the group consisting of a mercapto group containing aromatic compound, dioxy-aromatic compound and unsaturated carboxylic acid. Brown et al. [29] have discussed an electrolyte for depositing tin-rich Sn-Ag alloys upon a substrate. The electrolyte includes a base solution containing soluble tin and silver compounds; a tin chelating agent consisting of a polyhydroxy compound in an amount sufficient to complex the tin ions provided by the tin compound; and a silver chelating agent consisting of a hterocyclic compound in an amount sufficient to

16

complex the silver ions provided by the silver compound. Preferably, the tin and silver compounds are present relative amounts to enable deposits containing 85-99 wt.% Sn and about 0.5-15 wt.% Ag. A pulse plating has been technique has been patented by Masuda and Tanaka which is claimed to reduce the flex cracking characteristics of electrodeposited Sn-Ag films [30]. The method involves the use of a current waveform having a current passing .period of not less than 3 ms and not more than 500 ms and an off period not less than 1 ms and not more than 500 ms. The additional condition is that the off period be equal to or shorter than the current passing period. Steinius [3 11 has described a process for the deposition of Sn-Ag alloy from an acidic, cyanide-free electrolyte, containing silver ions, tin ions, together with a complexing agent. An additive consisting of an aromatic compound with an aldehyde group is also included. The combination is claimed to produce a smooth, matte to silky surface, which is easily soldered. 3.3 Sn-Ag vs. Sn-Pb

Packaging technology has progressed from the conventional wire and tape automated bonding to area array flip chip bonding, which is able to provide increased U 0 counts and improved electrical performance. To fabricate flip chip packages with high performance, many problems such as fine pitch, uniformity, electrical reliability, electrical reliability and production cost have to be considered. For bumping techniques, evaporation, screen printing, electroplating, laser bumping and stud bumping methods are used. The electroplating method, one of the low cost bumping techniques, not only provides flexibility with respect to bump size and pitch, but also high production throughput. Comparative studies are very useful in quantifying differences between alloy systems, since the electrolyte formulations and fabrication methods are often common and only variations in performance attributable to the alloy itself become evident. Hwang et al. [32] have investigated the fabrication process for Sn-Ag and Sn-Pb solder bumps by electroplating them to make fine pitch solder bumps. The Sn-Ag and Sn-Pb electroplating characteristics were compared with each other and an electroplated bumping process was described. After fabrication of the solder bumps, their morphology and shear strengths were examined. Preliminary experiments were performed on 15 x 10 mm bare Si-wafers to determine the optimum plating conditions for the plating solutions. The under bump metallurgy (UBM) consisted of 70 nm Cr deposited as an adhesion layer, 500 nm Cu as a wetting layer, 100 nm Ni as a diffusion layer and 50nm Au as an oxidation barrier. Two commercial plating solutions were used for the solder electroplating. The Sn-Ag plating solution contained Sn2+(25g/l), Ag (1.8 g/l) and the Sn-Pb plating solution contained Sn2+ g/l), Pb2+(1Og/l). Electroplating was performed between 25 and 28C using (20 d.c. electrolysis. The solution was stirred with a rotation speed of 230 rpm. The process flow diagram for solder bumping by electroplating is shown in Fig. 10. An important point to be considered in flip chip fabrication is the compatibility of the UBM system situated between the solder bump and the aluminium pad. The thin film

17

Cr/Cu/Ni/Au UBM was deposited by E-beam evaporation and a Ti layer was then deposited to act as a solder dam.
1. UBM Deposition (Cr/Cu/Ni/Au)
BM

5. Solder electroplating

2 Solder dam deposition (Ti)

6. PR strip

4. Solder dam etching

7. Solder reflow (hotplate, VOC-free flux)

Fig. 10. Schematic diagram of experimental procedure [32].

The thickness of the Ti layer was 20 nm. A 45 pm thick layer of a photoresist (PR) was patterned on the UBM layer to form plating moulds of 110 pm in diameter on a 250 pm pitch. The test die was 5 x 5 rmn with a total of 189 I/O pads. After the photolithography process, the Ti layer was etched from the bottom of the plating moulds before Sn-Ag and Sn-Pb were plated into the moulds at the optimum conditions obtained fiom the preliminary plating experiments. The PR was stripped after plating, leaving mushroom shaped solder bumps. The uniformity of the plating thickness was measured using an alpha step profiler. Then, the bumped Si-die was reflowed on a hot-plate with volatile organic compound (V0C)-free flux in ambient atmosphere. The reflow temperatures for the Sn-Ag and Sn-Pb were 250 and 210C, respectively. After reflow, ball-shaped eutectic solder bumps were obtained. The bump shape and uniformity were observed with scanning electron microscopy. Bump shear tests were performed to measure shear strength after reflow durations of 5, 10 and 30 s. In the shear test, the test height was 5 pm above the UBM and the shear tool travelled at a speed of 200 pm/s. The fracture modes were investigated after the shear test. Polarisation curves of Sn-Pb and Sn-Ag are presented in Fig. 11. Fig. 11(a) suggested that the Sn-Pb plating rate was constant from 4 to 5 A dm-2.In this figure in the region <A> it was claimed that oxygen reduction occurred. In the region <B> both tin and lead ions were plated and hydrogen was generated in region <C>. From this polarisation curve, a limiting current of 4 A dm-*could be discerned. However, a limiting current did not appear for Sn-Ag plating until hydrogen was generated, as shown in Fig. 11(b).

18

-0.4
t

-0.6
U 1

-0.8
-1.0

>
\

>

.2

-1.2 -1.4 -1.6

5
Q

-1.8
-2.0

Sn-Pb solution gold working scan rate 2 rnVlsec

&

-c0.01

reliability experiment
. . .

-2.2

. . .

. . - - . I

0.1

. . . .-....

10

. . . . . . . .'

100

current densitylAldrn'

".-0.4

-0.6

Z ' L .v)

-0.8
-1.0 -1.2 -1.4

-1.6
-1.8

Sn-Ag solution gold working scan rate 2 mV/sec

- 0

-2.0
-2.2

- 0

reliability experiment
0.1 1

. . . . . . . - . - - _ ' . . . . . . . .' '

0.01

. . . . . . . .'

10

. . . . . . . .'

100

current densitylNdm'

(b)

Fig. 11. Polarisation curves of Sn-Pb and Sn-Ag plating, (a) Sn-Pb (b) Sn-Ag [32]. Fig. 12 presents the composition of silver and lead in the Sn-Ag solder and Sn-Pb solder as a fbnction of current density. As the current density increased in the Sn-Pb plating, the lead content decreased to the eutectic composition at 4 A dm-2.Then, a near eutectic composition was maintained up to 7 A dm-2.However, in the case of the Sn-Ag plating, the composition of silver was uniform at 3-5 wt.% over the entire range of current densities.

t
s
'5

5040 .

.\

Sn-Ag (Ag%)

9
c .

30

6
w

: 20
10

Current density/A/dm2

Fig. 12. Composition of plated Sn-Pb and Sn-Ag solder with respect to current density [32].

19

SEM images of the Sn-Pb and Sn-Ag plated deposits at current densities of 2 and 7 A dm-*are shown in Fig. 13.

Fig. 13. Morphologies of deposited particles at different current densities, (a) Sn-Pb (2 A dm-2),(b) Sn-Pb (6 A dm-2),(c) Sn-Ag (2 A dm-2)and (d) Sn-Ag (6 A dm-2)[32].

For high productivity, a high current density is desirable provided the eutectic composition can be maintained. In this work, the following optimal plating conditions were obtained: stirring rate 240 rpm; plating temperature 27-28C; current density 6 A dm-2;and plating time 1 h in the case of Sn-Ag and 3 h for Sn-Pb. Sn-Pb mushroom-shaped bumps of 110 pm in diameter were fabricated by plating for 2 and 4 h at the optimal current density of 6 A dm-2.As the plating time increased, the height and the column size of the solder bumps increased. After the reflow process, the shape of each bump was changed as shown in Fig.14. Perfect hemispherical bumps were not formed in 2 h plating, Fig. 14(b). Therefore, the plating time is critical in the formation of ball-shaped bumps. Sn-Pb and Sn-Ag solder bumps were fabricated in the optimal condition as shown in Fig. 15. The heights of the Sn-Pb and Sn-Ag bumps were 80 f 10 pm and 80 k 15 pm, respectively. To estimate the shear strength of the bumps, bump shear tests were performed. It was found that the strength of both types of bumps increased initially for 5 or 10 s reflow times, but then decreased abruptly. This was attributed to the formation of intermetallic compounds between the solder and the UBM creating a weakness in the solder joint. Fig. 16 illustrates the typical fracture surfaces observed after the shear tests. Fracture occurred within the solder in the case a 5 s reflow time and at the

20

solder/UBM interface for 30 s reflow. This was interpreted in terms of a change from ductile to brittle fracture as the reflow time increased.

(b)

Fig. 14. Morphologies of Sn-Pb solder bumps before and after reflow, (a) 2 h plating and (b) 4 h plating [32].

.
(b)

Fig. 15. Shape of solder bumps plated under 'optimal' conditions, (a) Sn-Pb (6 A dm-2,3 h) and (b) Sn-Ag (6 A dm-*), 1 h) [32].

21

Fig. 16. Fracture modes of solder bumps after shear testing, (a) 5 s reflow, (b) 10 s reflow and (c) 30 s reflow [32].

3.4

Sn-Ag-Cu

Near-eutectic SnAgCu alloys are receiving a growing interest due to such merits as good melting characteristics, solderability and reliability [33, 341. To use these alloys for general purpose solders, the contents of silver and copper are limited to neareutectic compositions (3.4-4.1 wt.% Ag and 0.45-0.9 wt.% Cu) on account of the limited level of melting points for bumping applications [34]. SnAgCu alloys are being investigated as alternatives to lead-bearing alloys for solder bumps, but the mainstream method of formation has been limited to screen printing technology, because this is a low cost method for producing relatively large geometry bumps. However, this method has serious limitations as the size/pitch of solder bumps decreases. Furthermore, as the density of patterns and the complexity of circuitry
22

increase, electrodeposition becomes preferred as an alternative method to screen printing [351. Kim and Ritzdorf [36] have very recently developed a bath and process capable of producing dendrite-free, near-eutectic SnAgCu alloys for lead-free bumping applications. Within this study, several process conditions were tested using an alkaline bath and their influences were determined. Amongst these, cathodic polarisation tests of the new bath were conducted, together with surface morphology and film composition studies. Wafers for testing cathodic polarisation had the structure Si(substrate)/SiO*/TiN (40 nm)/Pt (50 nm). The platinum seed layer was sputter deposited. Wafers for characterising surface morphology, film composition and difhsion limited current density (LCD), had the structure of Si (substrate)/SiOz/Ta (25 nm)/Cu (100 nm)/Cu (5 pm). The thin copper layer was sputter deposited, whereas the thick layer was electrodeposited.

In order to mount the wafers in a conventional rotating disc electrode (RDE) with as little hydrodynamic disturbance as possible, a device was manufactured which was referred to as a modified rotating disc electrode (MRDE). This is illustrated in Fig. 17.

Binless steel

electrical contact &G JPIY

>It

wafer with seed layer

nonconductive paint

Fig. 17. Schematic drawing of the modified rotating disc elelctrode [36].

To use the MRDE, the wafer was sectioned into 1.5 x 1.5 cm pieces and a wafer piece was then mounted onto the MRDE. The result was that no conducting part except for the exposed wafer with a 1.2 cm diameter came into contact with the plating solution. Additional characterisation of the bath was perfonned using an EG&G platinum RDE having a 4 mm diameter.
To evaluate film morphologies, wafer segments with an area of 3.0 cm2 were used as a cathode. The deposition time for each current was adjusted to meet a target thickness of 10 pm. Tested process conditions including bath compositions are listed in Table 1. Each bath was composed of tin ions, silver ions, copper ions, and two

23

complexing agents. These were used to shift the reduction potentials of the noble metal ions (silver and copper) to more cathodic values by forrning ion complexes. Table 1. Summary of process conditions [36].

Temperature: 20, 30,40 and 50 "C. Agitation: 0, 100 and 200 rpm. pH: 7.5, 8.5 and 9.5.

A cyanide-free alkaline bath was developed for electrochemically depositing the ternary SnAgCu solder alloy. As the concentration of silver and copper in these alloys for bumping applications are very low (generally < 4.1 wt.% Ag and < 0.9 wt.% Cu) [34], the bath also contained small amounts of silver and copper. The baths did not show any precipitation or colour change for more than 6 months without applying current. Fig. 18 shows the results of polarisation experiments conducted with bath composition 6 at room temperature and pH 9.5 at an electrode rotation rate of 100 rpm. The initial part of the curve is gently sloping followed by a plateau, Fig. 18 (b). This corresponds to the potentials at which, primarily, the binary silver-copper alloys were deposited. It was deduced from these results that the first plateau is derived from the mass-transfer limitation of noble metal ions and that ternary alloys are obtained only when the current density is driven beyond this masstransfer limitation of noble metals. Driving the current density beyond this point causes the voltage to increase to a point where tin is codeposited, leading to ternary alloy deposition. At a potential of approximately -0.7 V, the curve begins to rise sharply until it reaches the potential where mass-limitation of tin ions occurs. This rise is related to the inclusion of tin in the deposit. Therefore, ternary alloys can be obtained at this potential. Another rise at about -1.5 V after the second plateau results from proton discharge (hydrogen gas evolution). After the polarisation studies were completed, electrodeposition runs were conducted at various current densities and under various experimental conditions. The morphological transitions of the ternary alloy occurred in four stages with increasing current density: dendritic growth (stage 1); suppression of dendrites (stage 2); nodular growth (stage 3); and columnar/dendritic growth (stage 4). Fig. 19 shows an approximated relationship between the polarisation curve shown in Fig. 18 and the surface morphology. The exact boundary between stages was not defined clearly due to the gradual change of morphology with increasing current density.

24

-0.17

-0.37

-0.57

-0.77

-0.97

-1.17

-1.37

-1.57

(a)

Cathodic Potential (Volts vs. SHE)

-0.17

-0.27

-0.37

-0.47

-0.57

-0.67

-0.77

(b)

Cathodic Potential (Volts vs. SHE)

Fig. 18. (a) Cathodic polarisation curve of SnAgCu bath showing two plateaus, one produced by the mass transfer limitation of noble metals and the other by that of tin, (b) enlarged section of the initial part of the polarisation curve. Bath 6, room temperature, 100 rpm and pH 9.5 [36].

Cathodic Potential (Volts vs. SHE)

Fig. 19. Approximate relationship,between polarisation curve and surface morphology [36].

25

The content of silver and copper, whose deposition potential was less cathodic than that of tin, tended to drop with increasing current density and is illustrated in Fig. 20. The abrupt drop in the content of noble metals between 10 and 20 mA cm-2was accompanied by a significant change in morphology. In the case of alloy deposition, the content of each metal in the deposit is proportional to the partial current induced by each discharge reaction. The absolute partial current due to the discharge of the noble metals was constant after the first plateau, but the relative partial current decreased with increasing applied current due to the increase of the partial current due to tin deposition. This result indicated that the SnAgCu alloy deposition with this kind of bath was a normal codeposition type.

10

20

30

40

50

60 70

80

90 100 110

Current Density (mA/ern2)

Fig. 20. The change of film composition with increasing current density. Bath 5 , 40C, 200 rpm and pH 9.5 [36].

Fig. 21 shows the effect of the process parameters on the morphology of the deposits. The surface morphology became increasingly dendrite-dominated at a fixed current density with increasing concentration of noble metals, bath temperature and agitation. The extension of stage 1 with increasing mass transfer was due to the increase in the noble metal limiting current density. Similarly, the effect of the other parameters could be explained by changes in the relative diffusion limited partial currents. Other recent work concerning the electrodeposition of SnAgCu solder alloys has been reperted by Fukuda et al. [37]. These authors investigated the electrodeposition of the eutectic Sn-3.5 wt .%Ag-0.75wt.%Cu alloy as a lead-free solder in an H2S04 plating bath containing polyoxyethylene lauryl ether [C I z H ~ ~ - O - ( C H ~ - C H ~ - O ) ~ - H ] and thiourea as additives. The plating of SnAgCu alloy films with a eutectic composition is difficult because the standard equilibrium potentials of Ag and Cu are significantly more positive than that of Sn, as discussed previously. Ag and Cu depositions must therefore be suppressed during electrolysis. Additives are also necessary to stabilise the plating bath and produce deposits having the required surface morphology. Both polyoxyethylene lauryl ether (POELE) and thiourea produced alloy films with a smooth surface appearance and homogeneous distribution. Thiourea adsorbed on Ag, Cu and Sn and suppressed the subsequent codeposition, while POELE adsorbed only on Sn, leading to the suppression of the subsequent Sn deposition. These effects resulted in the codeposition of the SnAgCu alloy with a eutectic composition and a

26

smooth surface. The melting point of the electrodeposited alloy was 2 16"C, thus satisfying the industrial temperature requirements for Pb-free solder.

(a)

Bath 1 (stage 2)

Bath 3 (stage 1)

Bath 4 (stage 1)

1OPm

10pm
m

(b) 20C (stage 2)

30C (stage 2)

40C (stage I )

50C (stage 1 )

(c)

Orpm (stage 2) 2OOrpm (stage 1) at 2.5mA/cm2

Orpm (stage 2) 200rpm (stage 1) at 5.0mA/cm2 1Opm

(d) pH 9.5 (stage 2)

pH 8.5 (stage 2)

PH 7.5 (stage 2 )

1Opm

Fig. 21. Effects of process parameters on the morphology of deposits at low current densities. (a) Effect of the concentration of noble metals: 2.5 mA cme2, bath 1, bath 3 and bath 4, at 3OoC, 0 rpm and pH 9.5. (b) Effect of bath temperature: 5.0 mA cm-*,bath 3, 0 rpm and pH 9.5. (c) Effect of agitation: 2.5 and 5.0 mA cm-2,bath 3, room temperature and pH 9.5. (d) Effect of pH: 2.5 mA cm-2,bath 3, room temperature and 0 rpm [36].

The basic bath composition and operating conditions were as follows: H2SO4, (2M); SnS04, (0.2M); AgN03, (0.01M); CuS04.5H20, (0.02M); thiourea, (0.004M); temperature, 20C; and current density, 2 A dm'2. A pure copper plate was used as the working electrode and this was degreased in an alkaline solution followed by a neutralising dip in 10% sulphuric acid. The electrodeposition was carried out up to a total charge of 6C in each process. The addition of thiourea was necessary for the stabilisation of the plating bath containing Ag', Cu2+and Sn2+ions, because Ag precipitation occurred if it was not present. Moreover, thiourea suppressed the dissolution of the Cu substrate as Cu2+ together with Ag deposition from Ag' (this corresponding to a redox Ag deposition

27

where Cu acts as a reductant). The effect of thiourea was attributed to its chelation with Cu2+and Ag+ [38, 391. The visible spectrum for the absorption of hydrated Cu2+ disappeared by complex formation with thiourea, as shown in Fig. 22.

600

800

1000

1100

Wavelength / nm Fig. 22. Absorption spectra of a bath consisting of 0.02M Cu2+and 0.2M thiourea: (a) 2M H2S04 + 0.2M Cu2+(pH<O.l), (b) 2M H2S04 + 0.2M Cu2++ 0.2M thiourea (pHCO.1) [37].

The Ag and Cu contents in the SnAgCu film deposited as a hnction of current density are shown in Fig. 23 and and polarisation curves for the individual components in the plating bath are shown in Fig. 24. The Ag content decreased to a constant value with increasing current density in the region below 5 A dm-2(Fig. 23), where the increase in current density caused the negative shift of electrode potential (Fig. 24). The high Ag content in the low current density region was due to the relatively noble equilibrium potential of Ag compared with those of Sn and Cu. The Cu content increased stepwise with current density in the regions from 0 to 0.5 A dm-2and fiom 2 to 3A dm-2.These changes were dependent upon those mirrored in the electrode potentials shown in Fig. 24. The electrochemical processes of Cu deposition changed from a charge transfer controlled process to a diffusion limited process in the low current region, whilst hydrogen evolution affected the diffusion process in the high current region. The Ag and Cu contents were about 3.5 and 0.75 wt. % (eutectic composition), respectively, at a current density of 2.0 A dm-2 and consequently this bath composition was chosen as the optimal condition for the alloy plating.

28

100

10

01 .

0.01
0

Current density f A d ~ n - ~

Fig. 23. Ag and Cu contents as a fimction of deposition current density in the plating bath [371.
-100
b)
C)

- - - - :Ag+

d)

-- : Sn2+ - - - : Sn2++Ag+~CCu2++Thioura

-10

-1

-0.1

0 0

-500
Potential / mV vs. Ag/AgCl

-1000

Fig. 24. Polarisation curves showing the current-potential relationships for individual components in the plating bath [37J .

Fig. 25 depicts SEM micrographs of the surfaces of the deposited Cu, Ag and Sn films, where only single component metal ions were present. The addition of thiourea resulted in surface smoothing in all solutions.These smoothing effects were attributed to the adsorption of the thiourea on the evolving Cu, Ag and Sn structures. However, the addition of POELE brought about smoothing only in the case of solutions containing Sn +. This suggested that POELE adsorbs only on depositing Sn.

I conclusion, Fukuda et al. claimed that their procedure could effectively generate n
the eutectic alloy composition with a satisfactory surface morphology. The X-ray pattern of the deposited film demonstrated that it consisted of P-phase Sn, Ag3Sn and Cu6Sns. These results were claimed to be in agreement with the phase diagram of the eutectic alloy.
29

3.5

Sn-Ag vs. Sn-An Cu

&m and Ritzdorf [23] have recently provided a detailed investigation of the electrodeposition of near-eutectic Sn-Ag solders for wafer-level packaging using a Shipley-Ronal EXP-700 Sn-Ag plating bath and some comparisons with the Sn-Ag-Cu system have been made. The approach was similar to that reported earlier by these authors for Sn-Ag-Cu [36], as described previously in section 3.3. Fundamental studies were undertaken to determine polarisation behaviour, morphological transitions and compositional changes. It was shown that the mass transfer of silver ions at low potentials drove the drastic change of morphology through four stages (dendrites, suppression of dendrites, facets and dendrites) and the content of silver in the deposit dropped with increasing current density.
No additive

With 0.004 M POELE

With 0.2 M Thiourea

Cu deposit

Ag deposit

Sn deposit

10 urn

Fig. 25. SEM micrographs of the surfaces of Cu, Ag and Sn films deposited in 2M H2S04, (a) 0.02M Cu2', (b) 0.01M Ag' and (c) 0.2M Sn2' [23].

The deposition mechanism of SnAg alloys with the above bath appeared to be very similar to that of SnAgCu alloy deposited with an alkaline bath due to similar

30

polarisation behaviour. Pattern plating results, including studs, mushrooms and stacks, could be summarised as fine-grained, having a high deposition rate (2-3 pdmin), good uniformity and good repeatablity. Two types of in situ stack plating, CdSnAg and Ni/SnAg, were successfully performed with no defects between two layers. Reflow tests conducted with near eutectic SnAg solders on copper studs exhibited spherical shapes with smooth surfaces, where the average melting point of whole bumps in a wafer was 223,7OC which is close to the melting point (221C) of the eutectic composition. Figs 26-29 show comparisons between polarisation curves, cornpositional changes, and morphological transitions and for the two alloy systems. Both baths exhibited a similar polarisation behaviour as can be seen from Figs. 26/27, where the mass transfer limitation of noble metals is observed at low potentials. The only difference was that the reduction potential of tin in the SnAgCu bath was more cathodic than in the SnAg bath because tin ions in the former bath were comdexed.
I

40

30 20

,e iz
.I(

2 10
0

0.30
,

0.20

0.10

0.00

-0.10

-0.20

-0.30

10

20

30

40

50

60

70

80 -

(4

Potential (Volts vs. SHE)

(a)
40

Current Density (rnA/cm2)

\
-0;30

-0.40

(b)

-0.50 -0.60 Potential (Volts vs. SHE)

-0.70
0
10

20

30

40

50

60

70

80

(b)

Current Density (rnA/cmZ)

Figs. 26/27. Comparison of the polarisation behaviour (Fig. 26, LHS figures) and alloy composition (Fig. 27, RHS figures) as a function of current density: (a) Sn-Ag and (b) Sn-Ag-Cu [23].

The morphological transitions occurred in four stages as shown in Fig. 28. However, the morphology of stage 3 was different between the two systems, resulting from the different types of supporting electrolyte and additives.

31

Stage-1

Stage-2

Stage-3

Stage4

low current densityN - 4

high current density

-2pm

Fig. 28. Comparison of morphological transitions with increasing current density: (a) Sn-Ag and (b) Sn-Ag-Cu [23].

In general, it could be concluded that the electrodeposition of near-eutectic SnAg solders is very similar to that the near-eutectic SnAgCu system from a mechanistic viewpoint.
Fig. 29 illustrates the results from reflow tests with the SnAg solder bumps consisting of a15 pm thick copper stud and a 38 pm thick solder mushroom. After reflow, sperical shapes with smooth surfaces were obtained. Similar results would be expected with a SnAgCu alloy.

solder
IMCs

Cu stud

Fig. 29. Reflown SnAg solder bumps: (a) original bump with Cu (15 pm)/SnAg (38 pm) stacks, (b) ion beam image of cross-section before UBM etch, (c) bump after UBM etch, (d-f) reflown bumps, (8) cross-section after reflow and (h) ion beam image showing the formation of intermetallic compounds around the copper stud and in the tin matrix [23].

32

3.6

Sn-Ag vs. Sn-Ag-Cu vs. Sn-Pb

Kim and Ritzdorf [40] have discussed the most widely considered solders for wafer level packaging. These include high lead Pb-Sn (Pb95-97S n 4 , eutectic Pb-Sn (Pb61.9 Pb38.1), eutectic Sn-Ag (Sn96.5Ag3.5), eutectic Sn-Cu (Sn99.3Cu0.7) and eutectic Sn-Ag-Cu (Sn95.5Ag3.9 cu0.6). The electrodeposition of these alloys is of considerable interest and is being actively researched. When considering the electrodeposition of metals or metal alloys, the local rate of the electrode reaction, which influences growth rate, surface morphology and shape evolution, depends not only upon charge transfer kinetics at the metal-electrolyte interface, but also on mass transport through the difhsion layer and current distribution in the electrolyte. For a given applied current (or voltage) the value of the local current density at the cathode may be influenced by mass-transport conditions and by the potential distribution in the bulk electrolyte, where a non uniform potential and concentation normally leads to a non uniform current distribution on the cathode. The influence of geometric factors, electrochemical factors and mass transport (diffusion and convection) on shape evolution within the cavity has been investigated by several authors researchers. Currently, extensive research is also being performed regarding electrical waveform mediation on the grounds that changing the waveform can influence the charging and discharging of the electrical double layer (capacitance effect), mass transfer by the formation of a duplex boundary layer, crystallisation mechanism, current distribution, and thusfilm properties [41-441. As far as research on the application of pulse waveforms is concerned, most studies have been conducted with rotating disc electrodes or small pieces of wafers. However, comparative experimental research regarding the effect of waveform on shape evolution or thickness distribution within the feature, pattern and workpiece, is limited. Very recently, however, Kim and Ritzdorf [40] have examined the effect of electrical mediation on through-mask deposition of solder bumps with 200 mm diameter wafers for wafer level packaging applications. The influence of varying duty cycle on deposit properties, including: shape evolution within the cavity; abnormal growth; surface morphology; alloy composition; and thickness distribution; was investigated with a variety of plating baths. The plating baths included: PbSn (high Pb); eutectic PbSn; eutectic SnAg; eutectic SnAgCu; and Cu. The plating baths and plating conditions were as follows: PbSn (Shipley-Ronal: Solderon baths 1 and 2, 35-65 mA cm-2);SnAg (Shipley-Ronal: EXP 0700, 60 mA cm-2);SnAgCu (Semitool: proprietary bath, 45 mA cm-2);and Cu ( Semitool: Proprietary baths, 200 mA cm-2).These baths produced plating rates in the range 2-4 pm mid'. The wafers had the structure Si(substrate)/Si02/TflVDCu/mask.The frequency for pulse plating was fixed at 100 Hz. The bath temperature was 30C, the flow rate 5-6 gallons per minute and the wafer rotation speed was 2060 rpm. The direction of wafer rotation was reversed every 30s during the deposition time to mitigate its influence on shape evolution. It was shown that the electrical mediated through-mask deposition of the solder bumps had many effects. With properly selected duty cycles, these included:

33

(i) (ii) (iii) (iv)

improved surface flatness and morphology when the shape ratio (thickness at cavity edge / thickness at cavity centre) with d.c. was <1 Suppressed probablity of abnormal growth (e.g. non-homogeneous growth such as large nodules) Reduced grain sizes resulting in smoother surfaces Modulated alloy composition at a given bath and process condition

.,

With decreasing duty cycle, the thickness distribution within the feature, pattern and workpiece also changed due to the increased influence of primary current distribution. The fraction of current flowing along the cavity edge, die edge and wafer edge also increased with decreasing duty cycle. As an example of these conclusions, Fig. 30 illustrates the effect of duty cycle on the surface morphology of lead-free solder bumps consisting of eutectic SnAg and eutectic SnAgCu alloys. The grain size and surface roughness was reduced with no outstanding change in growth habit. As a further example, Fig. 31 compares the effect of duty cycle on the composition of solder bumps consisting of near-eutectic SnAg and near-eutectic PbSn alloys.

- 5pm
(a)

lOO%(DC)

25%

(b)

lOO%(DC)

5 0%

25%

10%

-Opm 1

Fig. 30. Effect of duty cycle on the surface morphology of lead-free solder bumps, (a) eutectic SnAg; 60 rnA cm-2,5 gpm, 20 rpm and 30C, and (b) eutectic SnAgCu; 45 mA cm-*,5 gpm, 40 rpm and 30C [40].

With decreasing duty cycle, the content of silver in the near-eutectic SnAg alloy was decreased as shown in Fig.3 1(a). In an alloy bath which is of a normal codeposition type, the noble metal content in the deposit decreases with increasing current density. This is due to the increased partial current density of tin relative to silver with increasing peak current density. In eutectic PbSn deposition, the content of lead in alloys tended to increase with decreasing duty cycle as shown in Fig. 3 1(b). As the reduction potentials of lead and tin in this bath were similar, it was proposed that the change of difhsion flux of each component, due to the formation of thinner pulsating diffusion layers, caused the change of alloy composition with decreasing duty cycle.

34

6 3
(a)

! i

1
0% 25%

50%

75%

100%

125%

Duty Cycle (at 1OOHz)

v) C

n 40 pc
C ."

Fig. 3 1. Effect of duty cycle on the composition of solder bumps; (a) near-eutectic SnAg; 60 mA cm'2, 5 gpm, 20 rpm and 3OoC, and (b) near-eutectic PbSn; 65 mA cm-2,5 gpm, 20 rpm and 30C [40].

4.

Tin-Bismuth Alloys Background

4.1

Lee et al. [45] have very recently discussed the merits of various lead-free solders. These included Sn-3.5Ag, Sn-3.5Ag-0.7Cu, Sn-8.8211 and Sn-58Bi. To apply these solders in a commercial process, they should have physical and chemical properties corresponding to a eutectic Sn-Pb solder as follows: (i) (ii) (iii)
Melting temperature comparable to the Sn-Pb solder Wetting properties comparable to the Sn-Pb solder Thermomechanical reliability comparable to the Sn-Pb solder

Sn-3.5Ag (Tm:472 K) and Sn-0.7Cu (Tm:500 K) alloys have comparable wettability and thennomechanical reliability and are therefore considered to be possible candidates for applying the soldering process in electronics. However, these solders have higher melting points than the eutectic Sn-Pb solder (456 K). Their reflow process temperatures are therefore 30-40 K higher than the eutectic Sn-Pb solder. Higher process temperature causes a severe negative impact on component performance, such as thermal damage on the chip or printed circuit board and makes them difficult to apply in conventional processing devices. A high melting temperature is regarded as the biggest obstacle to replacement of eutectic Sn-Pb solders with Pb-free alternatives. Certain Sn-Bi alloys can have melting temperatures

35

comparable or lower than that of eutectic Sn-Pb, e.g. Sn-58Bi (Tm:41 1 K) and are accordingly receiving attention as Pb-free alternatives. The following is a summary of some of the recent developments.
4.2

Sn-Bi

Zang et al. [46] have discussed the problem of Sn-Bi plating. Although electroplating of Sn-Bi alloys has been known for many years, it was traditionally considered a difficult process. The major difficulty in plating Sn-Bi alloys arises from the large difference in standard deposition potential of tin and bismuth ions. The problem was traditionally solved by adding a complexing agent to change the electrodeposition reaction from simple metal ion reduction to reduction of a metal complex. The shift in the reduction potential provided by the complexing agent allows the deposition of two different metals to take place at the same potential over a wide range of current densities. Examples of these complexing agents are ligands such as EDTA, DTPA, polyamines and gluconates. Complexing usually allows very good control of the plating process and properties of the deposit. However, most of the known complexing agents are environmentally undesirable and some of them have been banned in many countries.

A different approach to deposition of tin alloys involves the utilisation of a metal-speczfic surfactant, which can significantly slow or even idubit deposition of one of the alloying elements in a certain potential range. The resulting formulation will be environmentally safe, provide good control of alloy composition and have a wide operating window. Until recently, all attempts to develop such chemistries had failed because of the strong immersion plating of bismuth on tin parts, which always takes place during the the electrodeposition process. The phenomenon of immersion plating is caused by the large difference in the deposition potentials of Bi and Sn when no complexing agent is present. As a result, the more noble metal (Bi) is deposited on the surface of the less noble metal (Sn) before, during and after electroplating. Zang et al. [46] have described an electroplating solution for the deposition of bright tin-bismuth solder alloy coatings in high speed electroplating applications. In order to provide good solderability, the bismuth content in the alloy should normally be between 0.5 and 5%. Typically, the solution comprises:(i) (ii) (iii) (iv) (iv) Methanesulphonic acid Tin and bismuth sulphonates (150 g/l and 10 g/l, respectively) Polyhydroxy benzene (antioxidant) Acrylic acid (grain refiner) A surfactant comprising one or more (and preferably a mixture) of:(a) polyethylene glycol-block-polypropyleneglycol with a molecular weight in the range 2,000 to 10,000 (b) polyethylene glycol-ran-polypropylene glycol with a molecular weight in the range 2,000 to 10,000 (c) ethy1ene diamine t etraki s (p olyethylene g1yc 01-block-p olypropy1ene glyc o1) t et ro1

36

The electroplating solution is maintained at a temperature in the range 18-45C and the current densities are typically between 100-300 ASF. The substrate is maintained in the solution under the above conditions foe a period of time sufficient to plate a coating of the desired thickness, normally in the range 3-6 pm. It was claimed that the alloy composition was stable in a wide operating window and was only slightly sensitive to the current density. An excellent solderability of the deposit was also claimed in experiments such as dip and look and in reflow tests. The major advantage of the proposed bath was the negligible immersion plating b f Bi on Sn, which can typically be left in solution for prolonged periods of time. The effects of plating parameters on the microstructure of Sn-Bi electrodeposits and the growth kinetics of intermetallic compounds at the CdSn-Bi interface has been studied by Suh et al. [48]. Alloy coatings of Sn-Bi were deposited on a Cu plate from an organic sulphonate bath using direct or pulsed currents. In addition, the effects of alloy composition on the formation kinetics of intermetallic compounds were examined. The addition of a grain refiner to the bath increased the cathodic polarisation and reduced the difference of the deposit potential between Sn and Bi. Thus, the Sn-Bi alloy could be electrodeposited with fine and rounded grains in the bath containing the additive. The Sn content in the deposits was increased with an increase of Sn content in the bath. The preferred deposition trend of Sn was stronger than that of Bi, because the deposition potential of the former was more positive in the presence of the additive. The Sn content in the deposits decreased with an increase in current density and the grains of the deposit became finer because of the increased cathodic overpotential. When the Sn-Bi alloy was electrodeposited using pulse current at 4 A dm-2peak current density, the Sn content in the deposit was increased with increasing pulse frequency and decreasing duty cycle. The morphology of the deposits also became finer with decreasing pulse frequency and increasing duty cycle. When the deposits were aged at 80C, the growth of an intermetallic compound layer (consisting of Cu3Sn and Cu6Sn~) exhibited a parabolic time dependence and the growth rate depended significantly on the composition of the Sn-Bi electrodeposits. The apparent activation energy for the growth of the intermetallic compound in the Sn-58Bi electrodeposit was 52.48 kJ mol-I, that in Sn-30Bi was 43.32 kJ mol-I, and that in Sn-1OBi was 41.35 kJ mol-I. 4.3 Sn-Bi coated Sn-Ag

The problem of finding low melting point solders to replace eutectic Sn-Pb has been discussed previously. One obstacle to the use of Sn-3.5Ag is its comparatively high melting point (Tm:494 K). Lee et al. [45] have investigated the use of Sn-Bi coated Sn-3.5Ag solders, where the Sn-Bi layer was applied as a melting point suppressant.

5 .
5.1

Tin-Copper Alloys
Background

Sn-Cu has been known to solder manufacturers as a lead-free alternative for a long time. The eutectic composition has a 0,7% copper content. Sn-Cu layers have excellent solderability and, in contrast to Sn-Ag deposits, tend not to tarnish [7].

37

The commercial codeposition of Sn and Cu is mainly known as bronze plating. In this process a high copper content alloy is formed. However, most of the known bronze plating chemistries cannot be used for high speed electrodeposition of the Sn-0.7Cu required by the electronics industry. The following discussion focuses upon recent work aimed at establishing viable plating systems for the solder alloy.

5.2

Sn-Cu

Oka et al. [48] have developed a plating bath which comprises a water-soluble tin salt, a water soluble copper salt, an inorganic acid and one or more compounds selected from thioamide compounds and thiol compounds as a bath stabiliser or complexing agent. Examples of these include thioamide compounds having 1-15 carbon atoms such as thiourea, dimethylthiourea, trimethyl thiourea, etc.; and thiol compounds having 2-8 carbon atoms such as mercaptoacetic acid (thioglycolic acid), mercaptosuccinic acid (thiomalic acid), and mercapto lactic acid. In addition, nonionic surface active agents may be incorporated into the bath formulation, e.g. polyoxyethylene compounds.

A Sn-Cu alloy plating solution capable of forming a bright plating film in a wide range of current densities has been discussed by Tamura [49]. The electroplating solution is a cyanide-free aqueous solution containing an organosulphonic acid, divalent tin and copper salts of the former acid, a dispersant and a brightener. The dispersant comprises at least two members selected from the group consisting of polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl ethers, and alkylene glycol alkyl ethers. The brightener comprises at least two members selected from the group consisting of aliphatic and aromatic aldehydes, aliphatic and aromatic ketones, and aliphatic carboxylic acids. Antioxidants may also be added for suppressing the oxidation of tin. These may include catechol, resorcin, hydroquinone, or pyrocatechol. Bright Sn-Cu alloys can typically have a high carbon content which leads to soldering problems. Therefore, matte or satin bright solder finishes are usually utilised when solderability is crucial. Satin bright finishes provide distinct advantages when compared to matte finishes. Specifically, the satin bright finish provides a smoother surface, greater cosmetic (visual) appeal and better solderability. Zhang et al. [50] have recently formulated an electroplating solution that produces a satin bright Sn-Cu alloy coating having a low organic (carbon) content at current densities as high as 200 ASF. The electroplating solution comprises sulphonic acid, a soluble tin compound (sulphonate), a soluble copper compound (sulphonate), a non-ionic surfactant, a satin brightener and an antioxidant.The preferred brightening additive, known as Satin Brightener P , is formed by the oxidation of aqueous 1-phenyl-3-parazolidinone. Alternative brighteners include aromatic and tertiary amines. The non-ionic surfactant improves the dispersibility and also ensures that the plated solder coatings adhere well to the underlying substrate. The preferred surfactant is polyoxyethylene-blockpolyoxypropylene with a molecular weight between 2000 and 10,000.Alternative nonionic surfactants include end-labeled polyethylene glycol. The preferred antioxidant is catichol. An excellent solderability of the tin-copper deposit was claimed in tests such as dip and look and reflow.

38

Fukuda et al. [5 11 have studied the mechanism and conditions for Sn-O.7Cu electrodeposition. Polyoxyethylenelauryl ether (POELE) was an important additive, producing a smooth surface with uniform component distribution. The melting point of the alloy was 227"C, thus satisfying the temperature requirements for Pb-fiee solders. It was found that POELE adsorbs selectively on the deposited Sn surface, then suppresses subsequent deposition of both Sn and Cu during electrodeposition. Luo et al. [52] have developed a high speed electroplating bath composition for Sn-Cu solders. The coatings were deposited on copper wire of O . 5 m diameter in sulphuric acid baths containing a Schiff base and an aldol condensation product. It was claimed that the Sn-(0.3%-0.6%)Cu coatings had good solderability and could be used to replace Sn-Pb solders. 5.3 Sn-Cu-Ag and Sn-Cu-Bi

Nishikawa et al. [53] have described plating bath compositions suitable for the deposition of Sn-Cu, Sn-Cu-Ag or Sn-Cu-Bi alloys. The baths are claimed to have a low dependence of plated coating composition on current density, a high stability and resistance to turbidity. A particular feature in all the compositions is the presence of a specific suZphur containing compound. A very large number of suitable compounds are listed and covered in this patent. 5.4 Sn-Cu vs. Sn-Bi

Zavarine et al. [541 have compared and contrasted the electroplating characteristics and properties of Sn-O.7Cu and Sn-2Bi alloys. These authors noted that the electroplating of these alloys is challenging because of the large differences in the reduction potentials of the individual elements and the difficulties resulting from immersion deposition and poor alloy control. To overcome these problems, metalspecific non-complexing organic additives were employed to significantly reduce or completely inhibit deposition of the alloying elements in a certain range of potentials. The electrochemical measurements were conducted in a conventional three-electrode cell. A 5 mm diameter copper rotating disc electrode served as a working electrode. Tin alloy coatings were also plated on a 50 pm copper or steel substrate using a rotating cylinder electrode. A typical plating bath of 0.5 dm-3contained 60 g dm-3Sn, 6 g dm-3Bi or 2 g dm-3 Cu and 150 g dm-3methanesulphonic acid. In order to obtain smooth deposits and a stable alloy composition, polyethylene glycol-based copolymers and aniline derivatives were added to the bath. These were described as additives A (wetting agent) and B (grain refiner). An anti oxidant was also present. Fig. 32 shows potentiodynamic cathodic polarisation curves for tin, copper and bismuth with no additives in the solution. As expected, the deposition of copper and bismuth commenced at 0 V. Since the tin concentration in the solution was relatively low, the current reached its diffusion controlled limit at -0.1 V. The increase in bismuth reduction current at -0.5 V was attributed to the onset of dendritic growth. Tin deposition commenced at -0.4 V and rapidly increased with potential. In the absence of any inhibition of either bismuth or copper at potentials positive of -0.4 V, electrodeposition of the alloys would be impractical, since

39

immersion plating of the noble metals would occur immediately after plating commenced.

5
40

1 - 4 0 g dm-3 Sn 2 - 10 g dm-s Bi 3 - 5 g dm-3 Cu 1509 dm3 MSA

30

0.1

0.0

-0.1

-0.2

-0.3

-0.4

-0.5

-0.6

Potential vs Ag/AgCI V

Fig. 32. Cathodic polarisation curves for the deposition of tin, copper and bismuth [54].

As an example of the effectiveness of the additives, Fig. 33 shows potentiodynamic cathodic polarisation curves for the reduction of tin and bismuth in the presence of the additive A, which is itself mixture of organic compounds. At a potential of -0.25 V, the bismuth current density sharply fell to 0.1 mA cm-2,apparently due to the adsorption of the additive on the electrode surface at this potential. Under such conditions, it was possible to prevent immersion plating almost completely. At potentails negative to -0.25 V, the bismuth current only increased slowly with potential, which was clearly beneficial for stable alloy formation at different current densities. The additive also had a strong effect on tin electrodeposition in the whole range of potentials, which is a necessary condition for the formation of a smooth deposit.

100

0 a
U

5
C

40 20
0
I I
I

c .

0.0

-0.8 Potential vs Ag/AgCI V

-0.4

-1.2

Fig. 33. Cathodic polarisation curves for deposition of tin and bismuth in the presence of additive A [54].

40

In order to achieve a good reflective surface, a grain refining additive B was introduced into the plating bath. This had little effect on the kinetics of tin electrodeposition .
Fig. 34 shows the effect of the additives on the immersion characteristics of the Sn-Bi plating bath. Two tin electrodes were immersed in the plating baths in the presence and absence of the additives. After 20 minutes in the solution without additives, Fig. 34(b), the electrode surface ws completely covered with a black layer of deposited bismuth. In the plating bath containing all the additives, however, the tin surface remained almost unaffected after 24 hours, Fig. 34(a). The Sn-Cu alloy was deposited using similar principles to those depicted for the Sn-Bi alloy in Figs. 33 and 34. Both alloys were characterised with regard to their appearance, ductility and solderability. The as-plated samples had a smooth appearance with grain size 1 pm. The melting temperature, in particular, is an important characteristic of the deposit and strongly depends upon the Cu and Bi content and phase composition. This is especially important for the Sn-Cu alloy, since at concentrations higher or lower than 0.7% Cu, the melting temperature increases sharply according to the phase diagram. Measurements demonstrated that the melting temperature of both alloys was less than that of tin, which is 232C. Both Sn2Bi and Sn0.7Cu alloys melted at 226C and exhibited good solderability in dip and look and reflow tests.

Fig. 34. Tin electrodes after immersion: (a) for 24 hours in solution with the developed additives; (b) for 30 min in the solution without additives [54].

The factors influencing the solderability of lead-free deposits have been investigated in some detail by Doyle et al. [ 5 5 ] . The solderability of five electrodeposits of various composition was determined using a wetting balance. Copper foils were plated with the following deposits using high speed methanesulphonic acid-based electroplating processes: (a) matte, 90/10 tin-lead; (b) matte, 100% tin; (c) matte, 99/1 tin-copper; (d) bright, 9911 tin copper; and (e) matte, 97/3 tin-bismuth. A full factorial matrix was tested utilising all electrodeposits, solder types, solder temperatures, flux types, and sample aging conditions. It was found that the solderability performance of all the as-

41

plated electrodeposits was comparable with tin-lead and tin-silver-copper solders at various solder temperature and flux types. By far, the greatest effect on solderability was aging. It was concluded that with correct choice of soldering parameters, any of the lead-free electrodeposits tested could be used as a suitable replacement for tin-lead solderable finishes . 5.5 Sn-Cu vs. Sn-Bi vs. Sn-ApCu

Fukuda et al. [56] have developed three new plating baths for the above alloys. These or POELE, as an contain polyoxyethylene laurylether C12H25-0-(CH2-CH2-O-)6H7 additive for the preparation of eutectic Sn-0.7Cu7Sn-3Bi and eutectic Sn-3.5Ag-0.75Cu films. The mechanisms of the effect of POELE in these electrodeposition systems have been described [5 7 3 81. The electrodeposited alloy films were obtained from sulphate baths and were homogeneous with respect to the constituents and exhibited a highly smooth surface. The melting points of electrodeposited Sn-Cu, Sn-Bi and Sn-Ag-Cu alloy films were 227,2 18 and 2 16 C, respectively, in agreement with the phase diagrams. A mechanism for the effect of POELE in the electrodeposition process was proposed in which POELE adsorbs onto deposited Sn surfaces at negative potentials, thereby suppressing subsequent deposition during electrolysis and providing a surface smoothing effect. Fig. 35 shows SEM micrographs of the surfaces of deposited Cu, Bi and Sn, from 2M H2S04 solutions at a current density of 2 A dm-2.The addition of 0.004M POELE resulted in a smoothing effect of the surface for Sn and to a lesser extent for Bi. However, smoothing was not observed for Cu. These results suggested that the strongest adsorption occurred on a tin surface.

\l(a)

Cu depositions I (b) Bi depositions I(c) Sn depositions

Without POELE

With 0.004 M POELE

10 fim

Fig. 35. Effects of POELE on Cu, Bi and Sn depositions on a copper electrode: (a) 2M H2SO4 + 0.02M Cu; (b) 2M H2S04+ 0.02M Bi3+;(c) 2M H2S04+ 0.2M Sn2 [56].

42

5.6

Sn-Cu vs, Sn-AP vs. Sn-Ag-Cu

Electroplating processes for lead-free solder bumps in flip chip packaging have been developed by Kiumi et al. [59] using Sn and the above alloys. The bumps were fabricated on 300 mm wafers with a multi-step plating process at higher deposition rates using thicker resist masks. The thickness of the photoresist used was in the range 50 to 120pm, the diameter of the pattern was in the range of 20 to 250p.111, and the electroplating rate was from 1 to 7.5pm mid' depending on the material deposited. The results showed that the processes could easily be applied to mass production and the bumps could be formed with well controlled geometry, composition and uniformity within 10% over the entire wafer. Jordan [601 has discussed the problem of lead-free coating of components. Several alloys containing tin were described, whereby a pure tin coating was considered to be ideal, except for the formation of whiskers, which must be avoided. The ways in which this could be achieved were described. The solderability of lead-free tin alloys was discussed along with a description of a test for solderability, especially for Sn-Cu and Sn-Ag alloys. It was concluded that whisker formation is prevalent in high gloss depositions. The addition of 1-3% Cu into a matte coating could eliminate whisker formation. It was also concluded that the title alloys are suitable alloys for lead-fiee soldering, whereby the exact percentage of either Ag or Cu (from 3.5 up to 10%) does not change the suitability of the ally significantly.

6.
6.1

Miscellaneous Alloys Sn-In

Sn-In alloys have been considered as replacements for Sn-Pb solders in the mounting of electronic components. Early work on the plating of these alloys involved the use of alkaline cyanide as an essential component. The alloy was had a low melting point with an indium content from 40 to 60%. More recent developments have been concerned with the formulation of cyanide-free Sn-In electroplating solutions capable of producing smooth films in a wide range of current densities. Tsunoda and Tamura [61] have proposed a weakly alkaline aqueous solution for Sn-In plating prepared by adding a tetravalent tin salt of metastannic acid; a trivalent indium salt of an organosulphonic acid; a chelating agent; and adjusting the pH of the solution to a value of 7 to 11 with a caustic alkali. As an example, one formulation is as follows: methanesulphonic acid (100 gA); potassium metastannate (27 g/1 as Sn); indium methane sulphonate (3 g/1 as In); gluconic acid (150 g/l); and KOH as a pH adjuster (PH 9). Plating is conducted at 2A for 5 mins. A non-toxic electrolyte with a pH of less than 7, enabling the use of soluble anodes in the Sn-In plating process, has been proposed by Zor'kina and Perelygin [62] using citric acid based electrolyte. It was shown that the most suitable coatings could be produced when the ratio of the sum of the concentration of metal ions in solution to the citric acid concentration was equal to 1:3 (mo1A).

43

6.2

Sn-Zn

Moon [63] has patented a series of bath compositions claimed to be effective in the plating of the above alloy, and in addition, those of Sn-Bi, Sn-Cu and Sn-Co. As an example, 1 litre of a Sn-Zn plating composition was prepared by dissolving the following ingredients in distilled water. Methanesulphonic acid (75 g/l); stannous methanesulphonate (190 gA); zinc sulphate (14 g/l); sodium gluconate (35 g/l); triethanolamine (3.7 g/l); ethoxylated nonyl phenol (0.03 g/l); formylhexahydrocarbazole (0.01 g/l); and ristomycin monosulphate (0.02 g/l). A lead fi-ame was plated in1 litre of the resulting Sn-Zn alloy plating composition at a current density of 1O dm-2to give an alloy plating layer having the composition Sn- 1O%Zn. A The plated film was tested in terms of its adhesiveness and solderability. In the former, a plated sample was baked at 400C for 2 minutes and then the appearance of the surface of the sample was examined with a magnifying glass. The presence of peeling, blistering and llfting marks were also assessed when the surface was scratched with a sharp tool, or in experiments with scotch tape. In the solderability test, a plated sample was mold-hardened at 175C for 3 minutes and then kept at the same temperature for 3 hours. The hardened substrate was maintained at 145C for 95 hours and then soldered in a flux (kester) for 3 seconds. The uniformity of the soldered part was observed by a microscope. An excellent adhesiveness and solderability was claimed for the Sn-Zn alloy. Different bath formulations were specified for the deposition of the Sn-Bi and the Sn-Cu alloys and the same tests were applied. An excellent performance was also claimed for these alloys. 6.3 Sn-Zn vs. Sn-Bi

Gurunathan et al. [641 have discussed the use of Sn-Zn and Sn-Bi alloys as lead-free solders and have compared and contrasted their plating characteristics with Sn in an experimental study. Both Sn-Zn eutectic (Sn-9Zn) and Sn-Bi eutectic (Sn-52 Bi) have an advantage of a comparatively low liquidus temperature of 199C and 138C, respectively. Although the Sn-Bi liquidus comes dangerously close to the circuit operating temperatures, it has good tensile strength and fatigue life. Various noneutectic compositions of these alloys are also being studied. In spite of difficulties like corrosivity and poor wetting (Sn-Zn) and embrittlement (Sn-Bi), either in eutectic composition or otherwise, both these alloys are considered to be contenders as replacements for lead containing solders. The above alloys were electrodeposited using an acidic bath with sulphate salts of Sn and Bi or chloride salts of Zn at a constant current within the range 10-21 mA cm-2. Sodium dodecyl sulphate was used as a finishing agent. The tin films were silver white, soft and exhibited a good conductivity. Observations of the films under an optical microscope revealed growth in the form of faceted grains. Good silvery Sn-Zn films were also obtained. Gurunathan et al. [64] discuss the physical and compositional properties of the as-deposited films of the above metal and alloys with respect to their deposition conditions. The reflow characteristics of the films were also discussed.

44

7.

Gold-Tin Alloys

During the past few years the selection of viable plating baths and processing conditions for the electrodeposition of suitable gold-tin alloy solders for application in the field of optoelectronic devices has been extensively researched by Ivey et al. [65-721. Sun and Ivey [73] and Okada et al. [74] have also patented plating baths. 7.1 Background

Sun and Ivey have discussed the background to the use of electrodeposited Au-Sn alloys in optoelectronic applications [77].
In electronic/optoelectronic packaging, chip bonding serves three major functions, i.e. mechanical support, heat dissipation and electrical connection. The choice of solder material for bonding is based on optimisation of a number of properties, including solderability, melting temperature, Youngs modulus (or stiffness), coefficient of thermal expansion, Poissons ratio, fatigue life,creep rate and corrosion resistance. In terms of melting temperature, solders are typically classified as either hard (high melting temperature) or soft (low melting temperature). The Pb-Sn system is an example of a soft solder, which is commonly used in electronic packaging. Hard solders, e.g. Au-Sn, are used for optoelectronic packaging. Au-20%Sn, which corresponds to the Au-rich eutectic composition, is the most common composition utilised. This solder has a relatively high melting point (280C), good creep behaviour and good corrosion resistance.

Traditionally, solder preforms, paste or deposited solder have been used to bond microelectronic and photonic devices. Deposited solder offers advantages over the other two processes, such as decreased oxide formation prior to bonding and more accurate control of the solder thickness and volume. The solder can be deposited using thin film technology, either vapour deposition or electron-beam deposition, using patterned photoresist or a shadow mask, or by electroplating. However, the electropzating method is particularly attractive because of its low cost and simplicity. It also avoids the considerable heating effects that may accompany other deposition methods, e.g. in electron beam evaporation techniques. Interest in codepositing Au-Sn alloys dates back several decades, but until recently only a few papers had been published. Information concerning codeposition has been mainly cofined to the patent literature, but even this often relates to cyanide containing plating baths. The main difficulties in coplating Au-Sn are two-fold. Firstly, it is difficult to control the electrodeposition process because not only must the two metals be codeposited, but their compositions must also be controlled. The second problem concerns the continual oxidation of the stannous tin to stannic tin at insoluble anodes. The Au-Sn alloy system has two eutectic points (Fig. 36), the first at 29.5 at.% Sn and 280C and the second at 93.7 at.% Sn and 217C. Even though the second eutectic point has a lower melting point and a much lower gold content (6.3%), it has been eliminated as a soldering material for three reasons. Firstly, the q phase (AudSn) is known to be brittle; secondly the electrical, mechanical and thermal properties of the

45

q phase are unknown; and thirdly there is a reversible transition between p-Sn (metallic) and a-Sn (semiconducting) between 13 and 20C [68].

GOO .

400 -

200

0-

-200

Au

At% Tin

Sn

Fig. 36. The Au-Sn phase diagram [68].

7.2

Development of Electroplating Solutions

Sun and Ivey [65] have shown that a relatively stable cyanide-free Au-Sn plating bath can be formulated. This is a weakly acidic system containing ammonium citrate, (NH4)3C6H507,as a buffering agent for hydrogen ions and Sn ions; ammonium citrate-sodium sulphite (Na2S03) as a mixed complexing agent for Au; and L-ascorbic acid (CsHgO6) as a Sn hydrolysis inhibitor; together with gold and tin chloride salts (KAuC14 and SnC12.2H20). Bath stability depends on the total gold and tin content, as well as additives and the way the solution is prepared and stored. Preliminary electroplating experiments with the developed electrolyte indicated that uniform, homogeneous deposits could be formed over a range of compositions, including the eutectic and near eutectic values. The effects of ammonium citrate, sulphite and AdSn concentration on the polarisation behaviour were studied on a cathode consisting of a piece of InP wafer metallised with a Ti adhesion layer and a 200 nm Au coating. In tin solutions, the addition of ammonium citrate changed the cathode open-cicuit potential and the hydrogen evolution potential to more negative values. The ammonium citrate concentration had very little effect on the polarisation behaviour of both Au and Sn solutions. Addition of sodium sulphite to gold solutions lowered the open-circuit potential substantially, although the concentration of sulphite had very little effect on the polarisation behaviour. For tin solutions, the addition of sulphite moved the opencircuit potential to higher values and increased the limiting current density, thereby enhancing Sn plating. The shape of the tin polarisation curve underwent a significant change with the addition of sulphite, from a single-wave to a two-wave process. This was believed to result f o m the interaction between sulphite and ammonium citrate. Gold and tin plating from a common solution appeared to be somewhat independent processes, with a current density of 1 to 4 mA cm-2being optimal. Causticity tests

46

showed that both InP and GaAs were essentially immune to the corrosive effects from the electrolyte. 7.3 Microstructure and Preferred Orientation

Doesburg and Ivey [66] have commented that in single metal electroplating, the microstructure produced is related to the current density or polarisation. At low current densities, the growth of existing grains is favoured, whilst at high current densities the formation of new grains is favoured. The microstructures formed from alloy plating solutions have not been studied as thoroughly. Doesburg and Ivey [66] have used the technique of pulsed plating to investigate the microstructure and preferred orientation of Au-Sn alloys when deposited from the KAuC14, SnC12.2H20, sodium sulphite and L-ascorbic acid plating bath described above. A series of electroplating tests at average current densities ranging from 1.2 to 3.6 mA cm-2were performed using the same substrates as those described above. The types of microstructures produced from this plating solution followed the trend observed for single metal electroplating. It was found that the preferred orientation in the deposits related not only to the microstructure produced, but also to the phase or phases present in the deposit. The microstructures had a columnar or FT (field oriented) structure which changed to a fine grained UD ( unorientated dispersion) structure similar to the structures proposed for a single metal plating system with medium to high inhibition. Preferred orientations were present in both the AuSSn and AuSn phases found in the deposits. For deposits containing only Aug Sn, the amount of preferred orientation reached a maximum at a current density of 1.4 mA cm-*and then decreased. For deposits only containing the AuSn phase, the amount of preferred orientation reached a maximum at a current density of 2.4 mA cm-2and then also decreased. The amount of preferred orientation was at a minimum when both AuSSn and AnSn were present in the deposit (2.0 mA cm-*)and when the current reached the limiting value (3.6 mA cm-2),as the structure changed to a UD structure. These results are summarised in Fig. 37.

12 .

16 .

2.0

2.4

2.8

32 .

36 .

Current Density (mA/cmz)

Fig. 37. Preferred orientation and tin content of the deposit vs. average current density [66].

47

7.4

Comparison of DC and PC Plating

Sun and Ivey have camed out a detailed microstructural comparison of direct current (DC) and pulse current (PC) methods for the codeposition of Au-Sn alloys [67]. Plating conditions, including current density and on7and off times were varied to optimise the process. It was shown that a range of alloy compositions can be deposited, including the eutectic and near eutectic compositions, with compositional and microstructural uniformity potentially suitable for microelectronic and optoelectronic applications. Deposit composition results for DC and PC plated samples (on period 2ms and off period 8ms) are shown in Fig. 38. The composition variations were similar for both types of plating. The Sn content initially increased with increasing average current density, reached a plateau and then decreased. Increasing the current density tended to favour plating of the less noble metal (Sn). If the current density was too high, however, hydrogen evolution became significant, decreasing the efficiency for alloy plating. From Fig. 38 it is clear that DC deposits obtained at the same current densities were consistently lower in Sn than PC deposits. A similar trend has been observed for other pulse plating systems, e.g. Au-CO and Au-Ni.

Sn Content in Deposit (at %)

50

PC

:
0 1
1.2
1.6
I

I
4.0

20 .

2.4

2.8

32 .

36 .

Average Current Density (mA/crn2)

Fig. 38. Deposit composition vs. average current density for DC plating and PC plating. The on and off times for PC plating were 2ms and Sms, respectively [67].

Representative microstructures for the deposition conditions represented in Fig. 38 are shown in Fig. 39.

48

2.0 mA/cm*

2.4 rnA/crn*

2.8 mA/cm2

Fig. 39. SEM secondary electron images for PC plated deposits (a-c) and DC plated deposits (d-f). The on and off times for PC plating were 2ms and Sms, respectively [67].

DC and PC deposits were similar for current densities in the 1.6-2.OmA cm-2 range, i.e. at low current densities. PC plating had no obvious influence on deposit microstructure. Both DC and PC deposits showed a tendency towards coarser microstructures at higher current densities, with the effect more pronounced for DC deposits. At a given average current density, the peak current density is considerably higher for PC plating, i.e. about 5 times that for DC plating (based on a duty cycle of 20%). The higher peak current density results in higher overpotentials and a j n e r deposit structure, because the rate of electron transfer in PC deposition to form adatoms is much faster than the diffusion rate of the adatoms across the surface to positions in the lattice, which favours nucleation. Grain refinement has been observed in other systems. If the current density is too high, the limiting value is exceeded, i.e. matal ions are capable of being consumed faster than they can amve at the cathode and the plating is under diffusion control, resulting in dendritic growth and a rough deposit surface.
Deposit composition results obtained at different on times, for a constant peak current density of 10 mA cm-2and off time of 8ms are plotted in Fig. 40.

49

Sn Content in Deposit (at %)

40

30

20

10

0 .

0.0

1.o

2.0

3.0

4.0

ON Time (ms)

Fig. 40. The effect of on time on the deposit composition at a constant peak current density of 10 rnA cm-*and off time of 8 ms [67].

The Sn content increased with increasing on time for short on times, reached a plateau and then decreased . The rising portion of the curve may be related to the transition time for Au plating. For on times longer than OSms, Au plating became diffusion controlled and Sn plating or hydrogen evolution began. As such, the Au transition time was 20.5ms. When the on time was increased to 2ms, both Au and Sn plating was likely to be diffusion controllred, giving rise to the plateau in the composition plot. Further increases in the on time lead to additional hydrogen evolution, which may have resulted in an increase in the local pH value and suppression of Sn plating.

SEM micrographs of deposits obtained at different on times are shown in Fig. 41. The lms on time sample had a much finer microstructure than the other deposits. This was due in part to its high Au content or low Sn content (16.7%) relative to the others, which had Sn levels greater than 33%. For the higher Sn content deposits, roughness increased with increasing on time. At longer on times the average current density increased leading to coarser deposits. At 4ms of on time, the microstructure approached that obtained from DC plating.
Cleaved cross-sections of the deposits in Fig. 41 are shown in Fig. 42. The lms on time sample exhibited ductile fracture, which was due to its high Au content. Deposits obtained at 2 and 3ms of on time were dense and uniform and adhered well to the substrate. The microstructures were very similar to solidified cast structures, with the initial deposit fine grained and subsequent grains growing in a columnar manner. The fractured surfaces of these two deposits were more characteristic of brittle fracture, due to the increased amount of AuSn; both deposits being hypereutectic in composition, i.e. 39 at.%Sn compared to the eutectic value of 30 at.%Sn. The 4 ms on time was very rough and its thickness varied from 1.4 to 8.9 pm, which was due to the high average current density of 3.3 mA cm-2,likely to be close to the limiting current density.

50

1 ms

2 rns

3 ms

4 ms

2 Pm
Fig. 41. SEM secondary electron images of deposits obtained at different on times, with a constant peak current density of 10 mA cm-2and an off time of 8 ms [67].

51

1 ms

2 ms

3ms

4 ms

Fig. 42. SEM of cleaved cross-section images of deposit obtained at different on times, with a constant peak current of 10 mA cm-*and an off time of 8 ms [67]. It was concluded that on times of 1-3 ms could produce suitable microstructures and reasonable plating rates of 0.7-1.7 pm per hr. Higher plating rates could be achieved by increasing the Au and Sn contents in the plating bath, which had the effect of increasing the limiting current density.

In addition to the investigations described above, experiments were also undertaken to establish the role of the off time, when the on time and the current density were held constant. With increasing off time, the Sn content in the deposits first increased and then remained constant. Short off times (3-4 ms) gave coarse grained microstructures, while longer off times (6-10 ms) gave consistently uniform microstructures.
Reproduciblity tests indicated that several 2 inch wafers ( N O ) could be electroplated with Au-Sn solder (- 39 at.%Sn) to a thickness of 3.5 pm.

52

7.5

Deposition of Multilayers using Pulse Plating,

Two separate Au-Sn compositions, containing 15 at.% Sn and 50 at.% Sn can be deposited under appropriate plating conditions, i.e. current density, pulse on-off time and duration. These compositions, according to the Aw-Sn phase diagram, correspond to AuSSn and AuSn, respectively. By using multiple current pulses and varying their duration, it is possible to deposit a composite solder structure with an*overall composition ranging from 15 to 50 at.% Sn, including the important eutectic composition [701.

An examination of the tin composition vs. current density plot in Fig. 43 revealed that there were two composition plateaus, one at current densities below 1.O mA cm-*and one at current densities above 2.0 mA cm-*.The first corresponded to a specific AuSn intermediate phase, disordered AugSn, while the second corresponded to the intermediate phase AuSn. Both phases are, in fact, the two phases which form during reflow of Au-30at.%Sn (Fig. 44). Phase identification was confirmed by XRD.

a si-

40.0 30.0 20.0 -

10.0 -

0.0
0.00

0.50

1.00

1.50

2.00

2.50

3.00

Current Density, mA/cm2

Fig. 43. Plot of Sn composition vs. plating current using pulsed current at an on time of 2ms and an off time of 8ms [70].

g2!
a ,

200

P
0

10

20 30 at oo Sn /

40

50

Fig. 44. Gold-rich portion of the Au-Sn phase diagram [70].

53

The behaviour exhibited in Fig. 43 can be explained by considering the metal ions in solution. Gold is more noble than tin. The standard electrode potentials for Au3 ions and Sn2+ions are 1.48 V and -0.138 V (vs. SHE), respectively. As such, Sn2+ions are not as easy to reduce as Au3+ions.Even in the presence of sodium sulphite as a complexing agent to bring the potentials of the two metals closer together, gold will remain more noble relative to tin and will tend to deposit more readily than tin. At lower current densities (4mA cm-2)or at lower applied overpotentials, gold, tending to reduce more easily than tin, will be in greater concentration on the wafer surface. Preferential gold reduction favours the formation of a gold-rich compound, such as AuSSn. As the current density is increased, the overpotential for both tin and gold increases together. At higher current densities, i.e. 2 to 3 mA cm-2,the reduction of gold ions reaches its limiting value and therefore occurs at a constant rate. Any increase in overpotential, however, increases the deposition rate of tin and since the deposition rate of gold is fixed, the SdAu concentration ratio on the wafer surface increases. As a result, Au5Sn is no longer the preferred phase for deposition. The next possible phase for deposition , apparent from the Au-Sn phase diagram in Fig. 44, is AuSn. The two-phase transition region depicted in Fig. 43 represents a condition intermediate to the two cases discussed above. Local variations in current density lead to local surface compositional variations, which may favour nucleation of one phase over the other. It is possible that local variations in microstructure, protrusions for example, may provide a sufficient local increase in overpotential causing AuSn to become the more favourable compound for deposition in those regions. In areas where the overpotential is not increased by the film morphology however, the ratio of ions reacting at the wafer surface will remain conducive for depositing AuSSn. This model accounts for the codeposition of AusSn and AuSn as well as the large amount of compositional scatter in the transition region. Based on the above results and analysis, it follows that overall deposit compositions ranging ftom 15 to 50 at.% Sn can be reproducibly achieved through the apprpriate integration of two current pulses corresponding to the respective plateaus in Fig. 43. The utilisation of two pulses, one below 1.O mA cm-2and one above 2.0 mA cm-2,is preferred over a single pulse corresponding to the desired deposit composition, because of improved process control, i.e. small current fluctuations will not alter the deposit composition. As an example, a slightly hypereutectic (-35 at.% Sn), 6 mm thick deposit was obtained by plating at current densities of O.8mA cm-2and 2.4 mA cm2 (Figs. 43a and 43b). The duty cycle for each pulse was maintained at 20% (2ms on and 8ms off) but the duration for plating of each phase was varied to yield the intended composition. The plating times for each layer in Fig. 45a corresponded to 20 min at 0.8 mA cm-2and 5 min at 2.4 mA cm12.These current densities were chosen to provide reasonable plating rates, while ensuring good composition and morphology control. The deposit shown in Fig. 45a was melted at 300C in a furnace with a forging gas (95% N2 + 5% H2) atmosphere to produce the eutectic microstructure shown in Fig. 45c.

54

.
4 -

.-Si

Fig. 45. Cross-section SEM secondary electron images of a multilayer deposit at (a) low and (b) higher magnification. A plan view SEM backscattered electron image of the deposit annealed at 300C is shown in (c) [70]. In additional work, Djurfors and Ivey [69] have camed out a detailed microstructural characterisation of the formation of the individual AuSSn and AuSn phases. This study revealed many differences between the formation mechanisms of the two. phases. AuSn film formation was shown to be a growth controlled process. A continuous dense layer was formed within 60s. The film growth mechanism is typical of the high current deposition mechanism described in electrocrystallisation theory with a dominant two-dimensional nucleation step. The resulting layer began with a layer of equiaxed particless that later transformed into a columnar structure due to the effects of preferred growth. At a current density of 2.4 mA cm-*,the film nucleated as AuSn and then continued to grow as this phase. The AuSn grain size was approximately 50-75 nm. The fine grain size is a result of the relatively high deposition current density and consequent nucleation rate. Fig. 46 depicts the film growth progression for the AuSn phase.

55

Fig. 46. Film growth progression for AuSn phase. Depositions conducted at 2.4 mA cm* using a pulsed current with an on time of 2 ms and an off time of 8 ms [69].

By contrast, Au5Sn formation was shown to be a nucleation controlled process. A continuous, dense layer formed within 600 s.The film formation mechanism was typical of a low current density deposit with a preponderance of a lateral growth mechanism resulting in a topographically smooth deposit. At 0.8 mA cm-2,the film nucleated and grew as the A q S n phase with a grain size of 200 nm. The grain size was significantly larger than that for the AuSn phase because of the lower current density used for the deposition. The low deposition current density also resulted in a relatively slow deposition rate when compared with the AuSn phase deposited at 2.4 mA cm-2.Fig. 47 depicts the film growth progression for the AuSSn phase.

56

Fig. 47. Fim growth progression for the AusSn phase. Depositions conducted at 0.8 mA cm-2 using a pulsed current with an on time of 2 ms and an off time of 8 ms [69].

7.6

Role of Processing Variables

Ivey et al. have studied the effect of various processing parameters on the electrodeposition characteristics . These include the role of solution stability, agitation and temperature [71] and the effect of sodium citrate concentration [72]. The useful lifetime of the plating bath described earlier (Section 7.1) was found to be about three days [71]. Deposit morphology could be improved by solution agitation, although too much agitation reduced the tin content and increased the surface

57

roughness in the deposit. Moreover, it was observed that increasing the solution temperature to above 35C was not beneficial, due to an increase in the oxidation rate of tin, which in turn reduced the amount of tin available for plating. However, both agitation and bath temperature appeared to be beneficial in terms of increasing plating rates. In studies to determine the effect of sodium citrate concentration [72], it was found that the transition current density for plating the two different gold-tin intermetallics, AuSSn and AuSn, was shifted to a lower current density at a lower citrate concentration.

8.
8.1

Miscellaneous Applications in Electronics Electrodeposition of Tin Needle-Like Structures

Electrodeposited needle-like structures have applications as novel cathodes in the field of vacuum microelectronics. Silicon and molybdenum are two of the most common field emission cathode materials. However, efficient field emission from an array of sharp tips using silicon and molybdenum depends largely on sophisticated microfabrication techniques. The electrodeposition of metallic dendrites could offer an alternative that is simple, scalable and inexpensive for field emitter fabrication. Rime et al. [75] have described techniques for the electrodeposition of arrays of needle-like Sn structures with tip radii -7 nm that can be used as electron emitters for field electron emission applications. Although these structures may be used as electron emitters, the low melting point of Sn precludes their use in practical devices. However, the authors claim that their unique preparation method could be used to investigate electrodeposited field emitter tips fiom higher melting point alloys. 8.2 Electrodeposition of Sn-Se for Solar Energy Applications

In the search for new semiconducting materials for efficient solar energy conversionthrough photo-electrochemical solar cells, metal chalcogenides with layered structures are increasingly studied. Among the many chalcogenides IV-VI semiconductors, SnS, SnSe, GeS and GeSe meet the required conditions. SnSe has a band gap of 1.0 eV and could prove to be an efficient material for solar energy conversion. However, little work has been conducted on the semiconducting and optical properties of electrodeposited SnSe thin films. Subramanian et al. [76] have investigated the electrical properties and optical absorption of SnSe films deposited onto tin oxide coated glass substrates.
The electrodeposition technique was used to obtain SnSe films fiom an aqueous solution containing stannous and selenite [Se03]*-ions. The redox reactions and polarisation curves of Sn and Se were studied to fix the pH (2.8) and potential values to get uniform deposition. Films were cathodically deposited at 55C. XRD studies showed an orthorhombic structure with a preferred orientation along the (2 10} and (402) directions. The as-deposited films were polycrystalline and showed improved

58

crystallinity and increased grain size on annealing at 200C for 30 min. All films exhibited p-type conductivity and an indirect band-gap of 1.05 eV. 8.3 Electrodeposition of Cu-Zn-Sn Alloy

Huber & Suher Ltd (UK) employ an alkaline cyanide plating bath (trade name SUCOPLATE) operated at 333 K for the electrodeposition of a bright, abrasion resistant Cu-Zn-Sn alloy for finishing electronic components. This plating bath falls into the classification of a highly complexed, high throwing power solution. However, the bath composition is not similar to those reported earlier for other Cu-Zn-Sn alloys and can lead to alloys with quite different compositions. In order to obtain further information on this problem, Picincu et al. [77] have undertaken a detailed analysis of the electrochemistry of the SUCOPLATE@ plating bath and have described the morphology and composition of the deposit formed in common operating conditions. The influence of the concentration of bath components on the electrochemistry of the system, alloy composition and deposit quality was examined in a later paper [78]. The plating bath consisted of: CuCN (9.1 g/l); Zn(CN)2 (5.4 gh); Na2Sn(OH)6 (5.7 g/l); Na2C03 (6.5 g/l); free NaCN (25 g/l); free NaOH (2.1 gA); and Copper Glo solution. The high quality chemicals were supplied by Huber & Suher Ltd (UK). Copper Glo solution is an electroplating additive supplied by Lea Ronal Ltd where the active ingredient is believed to be an aliphatic tertiary amine oxide with a long chain amide substitute. The substrate for electroplating was either brass (68% Cu, 32% Zn) or the brass covered with a silver strike. Using a combination of voltammetric and electron microscopic techniques, it was shown that a highly reflecting alloy composition in the range 47-5 1% Cu, 8-12% Zn and 38-43% Sn could be produced under a range of conditions. The rate of alloy deposition was proved to be partially limited by mass transport and partially by the kinetics of reactions in homogeneous solution [77]. The voltammetry, the deposit composition and the morphology were investigated as a function of the concentrations of the three metal ions, Cu(II), Zn(I1) and Sn(N) as well as the concentrations of cyanide, hydroxide, carbonate and Copper Glo additive (78). It was shown that all components combine to control the bath performance, although the trends in alloy composition and quality could be predicted from the known chemistry of the bath. It was also concluded that the deposition of tin has an important role in initiating the growth of alloy layers.

59

9.

Extended Summary

As in the case of the other topics reviewed in this series, the application of electrodeposited tin alloy solders in the field of electronics continues to receive much attention in the scientific and patent literature. The following is a summary some of the more important observations. A) Although the development of lead-fkee alloys continues to be the main thrust in recent investigations, some work has continued to be published concerning Sn-Pb alloys. These studies have the objective of obtaining a better understanding of the system. However, the results from this work can also have consequences for the plating of lead-free alloys, particularly if novel electrochemical techniques have been employed in the investigations. Until very recently, no studies on the use of pulse reverseplating had been reported for the tin-lead system. Previous work on other systems, e.g. Ni-Fe and CO-Fe, had shown that the use of a pulse reverse (PR) mode can affect deposit composition differently from that a normal pulse (PC) mode. This situation has now been remedied by an extensive investigation involving the application of DC, PC and PR modes of electrolysis to produce Sn-Pb coatings in a fluoroborate solution with a Sn:Pb weight ratio of 4:l. The effects of pulse frequency, duty cycle and cathodic pulse amplitude on deposit composition have been discussed The authors claim that their results may be important in relation to reducing the amount of Pb in Sn-Pb alloys due to environmental concerns. In particular, the use of high frequency PR plating may allow a desired alloy composition to be obtained from a plating bath with a lower Pb content than is othenvise possible. The work is important because it demonstrates that a more sensitive control over alloy composition is possible by the use of the PR mode of plating rather than by the more conventional PC or DC modes. Near eutectic Sn-3.8Ag based alloys are being developed particularly for use as lead-free solder bumps due to their desirable melting point, good creep resistance, shear strength, thermomechanical fatigue behaviour and reliability. The most cost effective method of producing fine geometry bumps cost effectively is by electrodeposition and thus electroplating technology is receiving much attention in wafer level packaging. Solder bumps of satisfactory and consistent quality can be obtained from a bath composition cosisting of: &P207; KI; Sn2P207; AgI; PEG; and HCHO. Interestingly, it was found necessary to apply a potentiostatic rather than a galvanostatic mode of plating as an aid to quality. A method of Sn-Ag composite plating has been devised from tin electrolyte solutions with a suspension of silver nanoparticles. It has been shown that a SnAg alloy film with p SnAg3 eutectic structure can be obtained from an electrolyte consisting of pyrophosphoric acid and silver nitrate. It was claimed that the use of this novel bath would solve the problems in conventional Sn-Ag alloy plating baths, because the Ag ion and its complex are not present, but metallic silver nanoparticles are suspended in the bath. The existence of the particles has been demonstrated by UV visible spectroscopy and the effectiveness of solders produced by the method has also been examined.

60

D) Comparative studies are very useful in quantifying differences between alloy systems, since the electrolyte formulations and fabrication methods are cornrnon and only variations in performance attributable to the alloy itself become evident. A recent study has compared Sn-Pb solder bumps of 130 pm diameter and 250 pm pitch made using an electroplating process with those of Sn-Ag. The shape and thickness of the solder bumps were compared. Bump shear testing was performed to measure the adhesion strength between the solder bumps and the under bump metallurgy. It was found that the Sn-Ag plating thickness was proportional to the current density, whilst the Sn-Pb thickness saturated above the limiting current value. The optimal conditions for solder bump fabrication were for found at 6 A dm-* for 3 h in the case of Sn-Pb bump plating and 6 A dm-* 1 h for Sn-Ag plating. The bump shear strength for Sn-Ag was found to be higher than that of Sn-Pb.
E) Near-eutectic Sn-Ag-Cu alloys are receiving a growing interest due to such merits as good melting characteristics, solderability and reliability. To use these alloys for general purpose solders, the contents of silver and copper are limited to neareutectic compositions (3.4-4.1 wt.% Ag and 0.45-0.9 wt.% Cu) on account of the limited level of melting points for bumping applications. SnAgCu alloys are being investigated as alternatives to lead-bearing alloys for solder bumps, but the mainstream method of formation has been limited to screen printing technology, because this is a low cost method for producing relatively large geometry bumps. However, this method has serious limitations as the size/pitch of solder bumps decreases. Furthermore, as the density of patterns and the complexity of circuitry increase, electrodeposition becomes preferred as an alternative method to screen printing. A plating bath and process capable of producing dendrite-free, neareutectic SnAgCu alloys for lead-free bumping applications has recently been devised. Within this study, several process conditions were tested using an alkaline bath and their influences were determined. Amongst these, cathodic polarisation tests of the new bath were conducted, together with surface morphology and film composition studies.
F) The effects of electrical mediation on through-mask deposition of solder bumps with 200 mm diameter wafers for wafer level packaging applications have been examined in detail. The influence of varying duty cycle on deposit properties, including: shape evolution within the cavity; abnormal growth; surface morphology; alloy composition; and thickness distribution; have been investigated with a variety of plating baths. The plating baths included: PbSn (high Pb); eutectic PbSn; eutectic SnAg; eutectic SnAgCu; and Cu. It was shown that the electrical mediated through-mask deposition of the solder bumps had many effects. With properly selected duty cycles, these included: (i) (ii) (iii) (iv) improved surface flatness and morphology when the shape ratio (thickness at cavity edge / thickness at cavity centre) with d.c. was <1 Suppressed probablity of abnormal growth (e.g. non-homogeneous growth such as large nodules) Reduced grain sizes resulting in smoother surfaces Modulated alloy composition at a given bath and process condition

61

An electroplating solution for the deposition of bright Sn-Bi solder alloy coatings

in high speed electroplating applications has been proposed. In order to provide good solderability, the bismuth content in the alloy should normally be between 0.5 and 5%. Typically, the solution comprises:(i) (ii) (iii) (iv) (iv) Methanesulphonic acid Tin and bismuth sulphonates (150 g/l and 10 g/l, respeetively) Polyhydroxy benzene (antioxidant) Acrylic acid (grain refiner) A surfactant comprising one or more (and preferably a mixture) of:(a) polyethylene glycol-block-polypropyleneglycol with a moleculanveight in the range 2,000 to 10,000 (b) polyethylene glycol-ran-polypropyleneglycol with a molecular weight in the range 2,000 to 10,000 (c) ethylene diamine tetrakis (polyethylene glycol-blockpolypropylene glycol) tetrol

The electroplating solution is maintained at a temperature in the range 18-45C and the current densities are typically between 100-300 ASF. The substrate is maintained in the solution under the above conditions for a period of time sufficient to plate a coating of the desired thickness, normally in the range 3-6 pm. It was claimed that the alloy composition was stable in a wide operating window and was only slightly sensitive to the current density. An excellent solderability of the deposit was also claimed in experiments such as dip and look and in reflow tests. The major advantage of the proposed bath was the negligible immersion plating of Bi on Sn, which can typically be left in solution for prolonged periods of time. The problem of finding low melting point solders to replace eutectic Sn-Pb has been discussed in the current review. One obstacle to the use of Sn-3.5Ag is its comparatively high melting point (Tm: 494 K). Investigations have taken place into the use of Sn-Bi coated Sn-3.5Ag solders, where the Sn-Bi layer was applied as a melting point suppressant. Sn-Cu has been known to solder manufacturers as a lead-fi-ee alternative for a long time. The eutectic composition has a 0,7% copper content. Sn-Cu layers have excellent solderability and, in contrast to Sn-Ag deposits, tend not to tarnish. Bright Sn-Cu alloys can typically have a high carbon content which leads to soldering problems. Therefore, matte or satin bright solder finishes are usually utilised when solderability is crucial. Satin bright finishes provide distinct advantages when compared to matte finishes. Specifically, the satin bright finish provides a smoother surface, greater cosmetic (visual) appeal and better solderability. An electroplating solution has recently been formulated that produces a satin bright Sn-Cu alloy coating having a low organic (carbon) content at current densities as high as 200 ASF. The electroplating solution comprises sulphonic acid, a soluble tin compound (sulphonate), a soluble copper compound (sulphonate), a non-ionic surfactant, a satin brightener and an antioxidant. The preferred brightening additive, known as Satin Brightener P, is formed by the Alternative brighteners include oxidation of aqueous 1-phenyl-3-parazolidinone.

62

aromatic and tertiary amines. The non-ionic surfactant improves the dispersibility and also ensures that the plated solder coatings adhere well to the underlying substrate. The preferred surfactant is polyoxyethylene-block-polyoxypropylene with a molecular weight between 2000 and 10,000. Alternative non-ionic surfactants include end-labeled polyethylene glycol. The preferred antioxidant is catichol. An excellent solderability of the tin-copper deposit was claimed in tests such as dip and look and reflow.

In a detailed comparative study, Sn-Cu and Sn-Bi electrodeposited alloys have been characterised with regard to their appearance, ductility and solderability. The as-plated samples had a smooth appearance with grain size 1 pm. The melting temperature, in particular, is an important characteristic of the deposit and strongly depends upon the Cu and Bi content and phase composition. This is especially important for the Sn-Cu alloy, since at concentrations higher or lower than 0.7% Cu, the melting temperature increases sharply according to the phase diagram. Measurements demonstrated that the melting temperature of both alloys was less than that of tin, which is 232C. Both Sn2Bi and SnO.7Cu alloys melted at 226C and exhibited good solderability in dip and look and reflow tests.

Further detailed comparisons have been made in regard to the characteristics of electrodeposited Sn-Cu, Sn-Bi and Sn-Ag-Cu alloys and three new plating baths have been developed. These contain polyoxyethylene laurylether C 12H25-0-(CH2CH2-0-)& or POELE, as an additive for the preparation of eutectic Sn-0.7Cu, Sn-3Bi and eutectic Sn-3.5Ag-0.75Cu films. The mechanisms of the effect of POELE in these electrodeposition systems have been described. The electrodeposited alloy films were obtained from sulphate baths and were homogeneous with respect to the constituents and exhibited a highly smooth surface. The melting points of electrodeposited Sn-Cu, Sn-Bi and Sn-Ag-Cu alloy films were 227, 218 and 216C, respectively, in agreement with the phase diagrams. A mechanism for the effect of POELE in the electrodeposition process was proposed in which POELE adsorbs onto deposited Sn surfaces at negative potentials, thereby suppressing subsequent deposition during electrolysis and providing -a surface smoothing effect. The addition of 0.004M POELE resulted in a smoothing effect of the surface for Sn and to a lesser extent for Bi. However, smoothing was not observed for Cu. These results suggested that the strongest adsorption occurred on a tin surface.

M) Sn-In alloys have been considered as replacements for Sn-Pb solders in the mounting of electronic components. Early work on the plating of these alloys involved the use of alkaline cyanide as an essential component. The alloy was had a low melting point with an indium content from 40 to 60%. More recent developments have been concerned with the forrnulation of cyanide-free Sn-In electroplating solutions capable of producing smooth films in a wide range of current densities. A recently proposed bath composition for Sn-In plating consists of a weakly alkaline aqueous solution prepared by adding a tetravalent tin salt of metastannic acid; a trivalent indium salt of an organosulphonic acid; a chelating agent; and adjusting the pH of the solution to a value of 7 to 11 with a caustic alkali

63

N) During the past few years the selection of viable plating baths and processing conditions for the electrodeposition of suitable Au-Sn alloy solders for application in the field of optoelectronic devices has been extensively researched. Au-20%Sn, which corresponds to the Au-rich eutectic composition, is the most common composition utilised. This solder has a relatively high melting point (28OoC), good creep behaviour and good corrosion resistance. It has been shown that a relatively stable cyanide-free Au-Sn plating bath can be formulated. This is a weakly acidic system containing ammonium citrate, (NH4)3C6H507, as a buffering agent for hydrogen ions and Sn ions; ammonium citrate-sodium sulphite (Na2SO3) as a mixed complexing agent for Au; and L-ascorbic acid (C6H806) as a Sn hydrolysis inhibitor; together with gold and tin chloride salts (KAuC14 and SnC12.2HzO). Bath stability depends on the total gold and tin content, as well as additives and the way the solution is prepared and stored. Electroplating experiments with the developed electrolyte have indicated that uniform, homogeneous deposits can be formed over a range of compositions, including the eutectic and near eutectic values. In a detailed series of investigations, the following electrodeposition characteristics have been thoroughly researched, including: the microstructure and preferred orientation of the deposits; a comparison between d.c. and a.c. plating methods; the deposition of multilayered alloys; and the role of bath temperature and bath agitation.

P) The foregoing analysis demonstrates that a basic understanding of the parameters controlling the electrodeposition of solders for applications in the field of electronics has continued to grow during the past few years and a considerable number of potentially acceptable lead-free alternative solders alloys now exist. However, despite the extensive nature of the electrochemical work, fewer investigations have attempted to compare and contrast the relative effectiveness of the proposed alloys, e.g. in solderability tests. In some cases, the differences in performance would appear to be quite small and more focused effort will be required in the fwture to positively identify the more viable candidates.

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11.

Acknowledgements

The following have kindly given their consent to reproduce the figures in this report:Fig. 1. Reproduced by permission of Elsevier. Figs. 2-5. Reproduced by permission of Springer Publications. Figs. 6-9. Reproduced by permission of The Electrochemical Society, Inc. Figs 10-16. Reproduced by permission of Emerald Publishing. Figs. 17-3 1. Reproduced by permission of The Electrochemical Society, Inc. Figs. 32-34. Reproduced by permission of The Institute of Metal Finishing. Fig. 35. Reproduced by permission of Elsevier. Fig. 36. Reproduced by permission The American Platers and Surface Finishers Association. Fig. 37. Reproduced by permission of Elsevier. Figs. 38-42. Reproduced by permission of Springer Publications. Figs. 43-45. Reproduced by permission The American Platers and Surface Finishers Association. Figs. 46 & 47. Reproduced by permission of Elsevier.

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