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Surface & Coatings Technology 187 (2004) 377 387 www.elsevier.

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Development of a sorbitol alkaline CuSn plating bath and chemical, physical and morphological characterization of CuSn films
G.A. Finazzi, E.M. de Oliveira, I.A. Carlos *
Departamento de Qumica, Universidade Federal de Sao Carlos, Via Washington Luiz, KM 235, CP 676, 13565-905, Sao Carlos-SP, Brazil Received 18 July 2003; accepted in revised form 20 January 2004 Available online 25 May 2004

Abstract A non-cyanide Cu Sn plating bath containing sorbitol as ligand has been developed, which has the advantage of low toxicity and relative ease of handling, in contrast to cyanide baths. The Cu Sn deposition voltammetric curve from this bath showed that the reduction process has the same characteristic features as copper deposition, which is controlled by mass transport, whereas the deposition of tin is controlled by activation. The hydrodynamic studies indicate that the Cu Sn deposition process is controlled by mass transport and that the diffusion coefficient of the Cu(II)/Sn(IV) complex species is 8.1 10 8 cm2 s 1. SEM analysis showed that the films obtained are smooth and cover the substrate totally, showing that sorbitol has brightening and leveling properties. EDS of Cu Sn films showed that the deposits have a maximum of f 3% of tin and that sorbitol was not incorporated in the deposit. It was observed that the Cu Sn electrodeposited films were golden when obtained voltammetrically from 0.6 to 1.6 V or chronoamperometrically at 1.4 V and a charge density of 2.55 C cm 2, from baths containing Cu(30) Sn(70) plus sorbitol at concentrations 0.15, 0.30 and 0.45 M, as well as Cu(70) Sn(30)/0.30 M sorbitol and Cu(70) Sn(30)/0.45 M sorbitol, even when the film Sn content was less than 10%. Bright reddish-colored films were obtained from baths containing Cu(50) Sn(50) plus sorbitol at concentrations 0.15, 0.30 and 0.45 M. X-ray spectra showed that probably a mixture of Cu and Cu3Sn alloy was deposited at various cathodic potentials. D 2004 Elsevier B.V. All rights reserved.
Keywords: Copper tin alloys; Sorbitol alkaline bath; Platinum substrate

1. Introduction Cu Sn alloys are materials that have good corrosion resistance, malleability, ductility and solderability. These alloys are used industrially for metal coating, with the aim of conferring corrosion protection and decorative properties to the substrate, and, therefore the proportions of Cu and Sn in the alloy are of fundamental importance in obtaining the desired characteristics [1]. Cu Sn deposition baths described in the literature have cyanide as a component, and are thus incompatible with modern standards, due to high toxicity, difficult handling and the need for costly industrial wastewater treatment for the correct disposal of cyanide in the environment. Thus, some more satisfactory alternative electrolytes have been sought for Cu Sn depo* Corresponding author. Tel.: +55-16-260-8208; fax: +55-16-260-8350. E-mail address: ivani@dq.ufscar.br (I.A. Carlos). 0257-8972/$ - see front matter D 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.surfcoat.2004.01.029

sition, for example, tartrate, pyrophosphate, oxalate, fluoborate and sulfate [1,2]. However, the electrolytes investigated have limitations, such as susceptibility to corrosion, low solubility of copper and tin, bath decomposition and the need for various additives [1 8]. The utilization of polyalcohols in baths for the deposition of metallic copper and copper alloys, nickel, lead, zinc and iron [9 27] has currently been under study in our laboratory. It has been observed that these polyalcohols improve the bath properties and result in high quality deposits. Also, polyalcohols inhibit the growth of tin crystals in tin autocatalytic deposition solution [28]. In this context we have developed an alternative Cu Sn plating bath that avoids the use of cyanide, containing sorbitol as a complexing agent. The work described here shows how sorbitol can modify the characteristics of Cu Sn electrodeposits and also the optimization of the new electrolytic solution for use in copper tin scrap recycling.

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2. Experimental details All chemicals were analytical grade. Double-distilled water was used throughout. The electrochemical experiments were performed in non-cyanide baths containing copper sulfate (CuSO4) and sodium stannate (Na2SnO3) in various concentrations: 0.06 M/0.14 M (Cu(30) Sn(70)); 0.10 M/0.10 M (Cu(50) Sn(50)); 0.14 M/0.06 M (Cu(70) Sn(30)); for each proportion of Cu(II)/Sn(IV), several concentrations of sorbitol and NaOH were studied: 0.15 M/3.15 M; 0.30 M/3.30 M; 0.45 M/3.45 M; 1.00 M/ 4.00 M. pH was measured and the values were f 12.7 in all the plating baths. A platinum disc (0.196 cm2); a platinum plate and a calomel electrode (0.1 M KCl) were employed as working, auxiliary and reference electrodes, respectively. Where indicated, the Pt disc electrode was replaced by Cu or Sn disc electrodes. Immediately before each experiment, the Pt working electrode was ground with 0.3 Am alumina, immersed in concentrated sulfuric

nitric acid solution, and then rinsed with deionized water, while the Cu and Sn disc electrodes were only ground with 0.3 Am alumina and rinsed. Potentiodynamic curves were recorded using a PARC electrochemical system consisting of a model 173 potentiostat/galvanostat, at a scanning rate of 10 mV s 1. All experiments were carried out at room temperature (25 jC). The Cu Sn films analyzed by SEM, EDS, X-ray diffraction (XRD) and AFM techniques were obtained chronoamperometrically from 0.6 V to 1.2, 1.3, 1.4 and 1.6 V at a charge density of 2.55 C cm 2. Scanning electron microscopy (SEM) photographs were taken with a Stereoscan 440 electron microscope (Leica) and energy-dispersive X-ray spectroscopy (EDS) readings were made with an eLX (Oxford). X-ray diffraction patterns were produced with filtered Co Ka radiation (1.78897 A), using a D5000 automatic diffractometer (Siemens) set at 40 kV and 20 mA. The diffraction experiments were in 2u scan mode (grazing incidence type

Fig. 1. Voltammetric curves from Cu(30) Sn(70) baths containing sorbitol at 0.15 M (); 0.30 M ( . ); 0.45 M (...) and 1.00 M (), for platinum substrate, at 10 mV s 1. Inset: Voltammetric curves for platinum (solid line), copper (dashed line) and tin (dotted line) substrates in sorbitol 0.30 M solution at 10 mV s 1. Potential values were referred to the calomel 0.1 M KCl electrode.

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Table 1 Variation of peak potential (Ep) and peak current density ( Jp) with sorbitol concentration. Potential values were referred to the calomel 0.1 M KCl electrode [Sorbitol]/M 0.15 0.30 0.45 1.00 Ep/V Cu(30) Sn(70) 1.28 1.21 1.22 1.21* Ep/V Cu(50) Sn(50) 1.23 1.20 1.20 1.21* Ep/V Cu(70) Sn(30) 1.26 1.21 1.22 1.22 Jp/mA cm 2 Cu(30) Sn(70) 3.65 4.90 3.55 1.75 Jp/mA cm 2 Cu(50) Sn(50) 6.45 6.40 6.30 2.60 Jp/mA cm 2 Cu(70) Sn(30) 8.50 9.50 9.50 4.50

* Half wave potential.

[29,30], with N fixed at 3j). Atomic force microscopy (AFM) images (tapping mode) were produced with a Nanoscope IIIA Multimode.

3. Results and discussion 3.1. Voltammetric studies of Cu Sn electrodeposition Fig. 1 shows voltammograms of Cu Sn electrodeposition on to a platinum stationary electrode from baths containing Cu(30) Sn(70) and different concentrations of sorbitol. The main features of the voltammograms are: in the cathodic scan, a wave (baths containing 0.15 M and 1.00 M sorbitol) and a peak (baths containing 0.30 and 0.45 M sorbitol) and, in the anodic scan, the occurrence of two dissolution peaks (aV and bV). To analyze the deposition voltammograms better, they are divided into regions: a, b, c, d. In region a, a limit current plateau can be seen only for the bath containing 0.15 M sorbitol. In region b, the deposition current density increases steeply, except for the bath containing 1.00 M sorbitol. Beyond this region, the deposition process reaches a current density limit value (region c), indicating that the deposition is controlled by diffusion. Immediately after this region, the current density increases again, due to the hydrogen evolution reaction occurring in parallel with the reduction reactions of ions Cu(II) and Sn(IV) (region d). Anodic peaks may represent the dissolution of Sn or of Sn-rich alloy (aV) and dissolution of Cu or of Cu-rich alloy (bV). The voltammograms of Cu Sn alloy deposition on platinum stationary electrode from baths containing Cu(50) Sn(50) and Cu(70) Sn(30) and various sorbitol concentrations show the same kinetic processes described in Fig. 1. The hydrogen evolution reaction region on platinum, copper and tin electrodes was investigated further and the cathodic voltammograms for these substrates do not show any current up to approximately 1.2, 1.4 and 1.5 V, respectively (inset of Fig. 1), suggesting that hydrogen evolution is not a significantly competitive reaction in the initial part of the deposition process. Moreover, the cathodic current density observed from 0.6 to 1.3 V in the copper electrode voltammogram can be attributed to copper oxide reduction [25,31]. Table 1 shows that the thermodynamics of Cu Sn deposition process is affected in the plating baths con-

taining 0.15 M sorbitol, since in these a shift of at least 30 mV in the negative direction is observed, for each copper/tin ratio. In the plating baths with 0.15 M sorbitol, there are fewer sorbitate anions than in the other plating baths (0.30 and 0.45 M), since the free sorbitate concentration decreases with decreasing sorbitol concentration in the plating bath. Probably, the stoichiometry of the Cu sorbitate complexes present in the baths with 0.15 M sorbitol is not only different for each Cu:Sn ratio (Cu(30) Sn(70); Cu(50) Sn(50); Cu(70) Sn(30)), but also different from the baths containing sorbitol concentrations higher than 0.15 M. Also, it can be inferred from the results of Table 1 that the most stable Cu sorbitate complexes are obtained in the baths containing 0.15 M sorbitol, since the peak potentials are more cathodic in these baths than in the others. The influence of several sorbitol concentrations on the Cu Sn deposition kinetics at various proportions of Cu(II) and Sn(IV) concentrations is also shown in Table 1. The Cu Sn deposition rate from the bath Cu(30) Sn(70)/0.30 M sorbitol is greater than that from the other baths containing Cu(30) Sn(70). In this case, a good stoichiometry exists between Cu2 + ions and sorbitate [25], which is in excess of 0.18 M. This sorbitol concentration also stabilizes stannate ions in solution and leads to an adequate electrolyte conductivity, which is not the case in plating baths containing higher sorbitol concentrations, due to the increased solution viscosity. The rate of deposition from the bath Cu(70) Sn(30)/0.15 M sorbitol is lower than that from baths Cu(70) Sn(30)/0.30 M sorbitol and Cu(70) Sn(30)/0.45 M sorbitol, implying that in this bath a poor stoichiometry exists between the ion-pair stannate/sorbitate. This leads to significant Sn(IV) precipitation, since stannate is not stabilized by sorbitate anions. Broggi [27] and Molenaar et al. [28] observed that hydroxystannite ions were stabilized by sorbitol. Thus, the results obtained in our study suggest that the sorbitate anion can also stabilize the stannate ion in solution. In the baths containing 1.00 M sorbitol, the current density is significantly reduced by the solution viscosity, which inhibits the reduction process. Moreover, the sorbitol concentrations of 0.45 and 1.00 M are not optimal because in these cases it was observed that the [Cu(II)/sorbitate] complexes are not stable with time and Cu(II) precipitates. As the deposition rate is a function of Cu(II) concentration, if Cu(II) ions precipitate the plating rate decreases with the aging of the solution.

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Table 2 EDS analysis of Cu and Sn contents of the deposits obtained chronoamperometrically from various Cu Sn plating baths at 1.4 V (referred to the calomel 0.1 M KCl electrode) and charge density of 2.55 C cm 2 Bath Cu(30) Sn(70)/sorbitol Cu(30) Sn(70)/sorbitol Cu(30) Sn(70)/sorbitol Cu(50) Sn(50)/sorbitol Cu(50) Sn(50)/sorbitol Cu(50) Sn(50)/sorbitol Cu(70) Sn(30)/sorbitol Cu(70) Sn(30)/sorbitol Cu(70) Sn(30)/sorbitol 0.15 0.30 0.45 0.15 0.30 0.45 0.15 0.30 0.45 M/3.15 M/3.30 M/3.45 M/3.15 M/3.30 M/3.45 M/3.15 M/3.30 M/3.45 M M M M M M M M M NaOH NaOH NaOH NaOH NaOH NaOH NaOH NaOH NaOH Cu (%) 99.1 96.7 98.0 > 99.9 99.7 99.4 98.7 >99.9 >99.9 Sn (%) 0.9 3.3 2.0 < 0.1 0.3 0.6 1.3 < 0.1 < 0.1

Also, Table 1 shows an increase of peak current density with Cu(II) concentration in deposition baths, indicating that the Cu Sn deposition kinetics are controlled by copper concentration.

It was observed that the color of the Cu Sn films was influenced strongly by the proportions of Cu(II)/Sn(IV) and, even more, by the presence of sorbitol in the plating bath. The color of the films obtained voltammetrically up to 1.6 V from Cu(50) Sn(50) plating baths was reddish, indicating that in these baths the Cu deposition is more pronounced than in the Cu(30) Sn(70) or Cu(70) Sn(30) baths. On the other hand, golden Cu Sn films were obtained voltammetrically up to 1.6 V from baths containing Cu(30) Sn(70) and various concentrations of sorbitol and from the baths with Cu(70) Sn(30)/0.30 M sorbitol and Cu(70) Sn(30)/0.45 M sorbitol. However, it can be observed in Table 2 that the content of copper in the films did not increase significantly with the ratio of Cu(II)/ Sn(IV) in the plating baths. Moreover, these films (Table 2) contain a much lower proportion of Sn than the golden Cu Sn films obtained from cyanide baths (10 15% Sn) [1]. Also, it was observed that reddish and golden Cu Sn films were very bright, corroborating previous studies in this laboratory on the effect of sorbitol on copper electro-

Fig. 2. Deposition voltammograms from Cu(30)/sorbitol 0.30 M (solid line); Sn(70)/sorbitol 0.30 M (dashed line) and Cu(30) Sn(70)/sorbitol 0.30 M (dotted line) on platinum substrate. Inset: Anodic scan from Sn(70)/sorbitol 0.30 M on platinum substrate. v = 10 mV s 1. Potential values were referred to the calomel 0.1 M KCl electrode.

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deposition [21,25], in which it was found that the copper films were golden or reddish, depending on the deposition conditions, and that sorbitol has brightening and leveling characteristics [21,25]. These results imply that the color of the film is mainly due to the presence of sorbitol in the plating baths, which influences the rate of deposition (Fig. 1) and the size of the Cu Sn crystallites and consequently the morphology of the films. The Cu Sn film colors obtained voltammetrically from 0.6 to 1.6 V correspond to those obtained chronoamperometrically at 1.4 V and a charge density of 2.55 C cm 2. 3.2. Electrochemical studies of the bath containing Cu(30) Sn(70)/0.30 M sorbitol Considering that the Cu Sn films obtained from the plating bath Cu(30) Sn(70) were always of a golden color, in contrast to the other concentrations of Cu(II) and Sn(IV) in the electrolytic solution, and that within this system the bath Cu(30) Sn(70)/0.30 M sorbitol showed higher deposition rates than the other baths, this composition was chosen for more detailed study. Fig. 2 shows the voltammograms from plating baths Cu(30), Sn(70) and Cu(30) Sn(70), all in the presence of 0.30 M sorbitol. It can be observed in this figure that copper(II) species deposits at f 1.2 V, which is much more negative than the equilibrium reduction potential of copper ( + 0.34 V) because in an alkaline plating bath

containing sorbitol, the latter reacts with OH to form sorbitate [25], which complexes Cu(II) ions and causes a shift in the deposition potential of copper toward more negative values. Also, it can be seen that Cu Sn deposition has an electrochemical behaviour similar to that of copper deposition, implying that the copper(II) species control the electrochemical process of Cu Sn deposition. Besides, it can be observed that Sn deposition is controlled by activation, at least up to 1.5 V (Fig. 2), at which potential hydrogen evolution on Sn begins (Fig. 1, inset). Hence, after 1.5 V the deposition current density of Sn on platinum substrate (Fig. 2) increases due to the hydrogen evolution reaction, parallel to Sn deposition. Analyzing the dissolution process of copper (solid line), two anodic peaks can be seen. The first ( 0.55 V) corresponds to dissolution of Cu to Cu+ and the second ( 0.30 V) to dissolution of Cu to Cu2 +. Comparing the Cu and the Cu Sn anodic voltammograms, it can be observed that peak aV (Fig. 2) probably refers either to dissolution of Cu to Cu+, or to dissolution of a copper tin alloy richer in Sn, because the Sn anodic peak potential ( 0.45 V, inset in Fig. 2) and the potential of peak aV ( 0.55 V) are not close. The anodic peak bV (Fig. 2) probably refers to the dissolution of copper and/or a copper-rich alloy, because the Cu anodic peak potential ( 0.30 V) and the potential of peak bV ( 0.25 V) are close. To characterize better the Cu Sn reduction process, the reverse-scan voltammetric technique was used. The reversescan voltammograms obtained from the Cu(30) Sn(70)/

Fig. 3. Reverse scan voltammograms obtained from Cu(30) Sn(70)/sorbitol 0.30 M. Scan direction reversed at (a) 1.1 V; (b) 1.2 V; (c) 1.5 V. v = 10 mV s 1. Potential values were referred to the calomel 0.1 M KCl electrode.

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0.30 M sorbitol bath may be observed in Fig. 3a, b and c. When the cathodic scan was reversed at a potential of 1.1 V (Fig. 3a), an increase in the cathodic current density was seen, suggesting that Cu Sn deposition occurs by nucleation [21,25,32]. At a potential of 1.25 V (Fig. 3b), it can be observed firstly that the current density decreases indicating that the deposition process is controlled by mass transport. Also, there are two cross-overs in the cathodic reverse scan, which corroborates the results of Fig. 3a. Finally, when the scan direction is reversed at 1.50 V (Fig. 3c), the current density decreases, showing that there is no second nucleation process. In all the anodic scans two anodic peaks can be seen, at 0.48 V and at 0.30 V, which increase, as the amount of the deposited metals increases, when the cathodic sweep is reversed at more and more negative potentials (Fig. 3a, b and c). Fig. 4a shows the Cu Sn deposition voltammograms, at different scan rates. It can be observed that the peak current density increases as the scan rate increases, suggesting that

the deposition process is controlled by mass transport. Fig. 4b shows that the peak current density ( jp) increases with v1/ 2 , but it is not quite proportional. This result suggests that the reduction process of Cu(II) and Sn(IV) is quasi-reversible in this region [33 35]. Fig. 4c shows that the peak potential (Ep) shifts negatively with increasing v, corroborating the results of Fig. 4b [33 35]. Fig. 5 shows Cu Sn deposition voltammetric curves with a rotating disk electrode at various rotation speeds. These studies show that the copper tin deposition process is strongly controlled by mass transport from the initial moments of the voltammetric process, as the deposition current densities increase with rotation speed increasing within the potential range chosen. Also, the rotating disk electrode limit current densities are greater than the stationary platinum electrode value, and the cathodic peak does not disappear completely with rotation, even at rotation speeds as high as 1000 rpm. The diffusion coefficient (D0) of the system was calculated from the rotating disc electrode

Fig. 4. (a) Deposition voltammograms of bath Cu(30) Sn(70)/0.30 M sorbitol, carried out at 1.0 ( . ); 2.0 (); 5.0 ( .. ); 10 (); 20 ( . ); 50 (...) and 100 mV s 1 ( .. ); (b) Graph of peak current vs. square root of scan rate; (c) Graph of peak potential vs. scan rate v. Potential values were referred to the calomel 0.1 M KCl electrode.

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expected, is smaller than either the copper sulfate D0, 9.8 10 6 cm2 s 1 [36], or the sodium stannite D0, 5.0 10 6 cm2 s 1 [37]. This is because [Cu(II)/sorbitate] [25] and [Sn(IV)/sorbitate] [27] complexes are greater in volume than [Cu(H2O)6]2 + and [HSnO2] ions, respectively, and consequently they have smaller diffusion rates. Moreover, stannate is stabilized by sorbitate anions, hindering its decomposition to SnO2 caused by absorption of carbon dioxide from the air [6,27]. The size of the stannate sorbitate complex is greater than that of the stannate ion, and consequently the former has lower mobility. Also, comparing the diffusion coefficients of the systems [Cu(II)/ sorbitate] [Sn(OH)6]2 , 8.1 10 8 cm2 s 1 and [Cu(II)/ sorbitate] [Zn(OH)4]2 , 1.2 10 6 cm2 s 1 [9], it can be seen that the species diffusion in the first system is much more hindered than in the second system, implying that the electroactive species volumes in the [Cu(II)/sorbitate] [Zn(OH)4]2 system are probably smaller than in the [Cu(II)/sorbitate] [Sn(OH)6]2 system.
Fig. 5. Deposition voltammograms of bath Cu(30) Sn(70)/0.30 M sorbitol, performed at rotation speeds of 0 (.-.-.); 60 (); 120 (); 240 (...); 480 ( . ) and 1000 rpm (__ __). v = 10 mV s 1. Potential values were referred to the calomel 0.1 M KCl electrode.

3.3. Scanning electronic microscopy Fig. 6a, b, c and d show SEM micrographs of Cu Sn films formed from the Cu(30) Sn(70)/0.30 M sorbitol plating bath at 1.2, 1.3, 1.4 and 1.6 V with a charge density of 2.55 C cm 2. Comparing these micrographs, it

studies. Assuming a kinematic viscosity of 0.01 cm2 s 1 and a roughness factor of approximately 2 (Pt substrate), the diffusion coefficient is 8.1 10 8 cm2 s 1. This value, as

Fig. 6. SEM micrographs of films obtained chronoamperometrically from Cu(30) Sn(70)/0.30 M sorbitol plating bath on platinum substrate at (a) 1.2 V; (b) 1.3 V; (c) 1.4 V; (d) 1.6 V. Charge density of 2.55 C cm 2; A = 0.196 cm2 (10 000 ). Potential values were referred to the calomel 0.1 M KCl electrode.

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can be observed that the Cu Sn films completely covered the substrates and had similar morphologies, exhibiting coalesced crystallites. It may be noted in the voltammograms of Cu Sn electrodeposition (Fig. 1) that at 1.2 V and 1.3 V the deposition process is controlled by mass transport and limit mass transport, respectively. Also, at 1.4 V and 1.6 V hydrogen evolution occurs, significantly, parallel to the Cu Sn deposition and probably contributes to smoothing of the Cu Sn films as could be seen in the case of Sn deposition [37]. These results imply that the more cathodic the deposition potential the smoother the Cu Sn film, since refining of the crystallites occurs. From the SEM results it can be concluded that sorbitol plating bath leads to better quality deposits than acid-tartrate solutions [8,38], since smooth and bright films without cracks were obtained.

3.4. AFM analysis AFM analysis was carried out on Cu Sn films obtained at 1.4 V and a charge density of 2.55 C cm 2 (Fig. 7a, b, c and d). It can be observed that the Cu Sn film completely covered the substrate and exhibited coalesced crystallites, corroborating the results of SEM analysis. In addition, the roughness mean square (RMS) factor was determined and its value was 43.090 nm. 3.5. Energy-dispersive X-ray spectroscopy (EDS) EDS analysis was performed on the Cu Sn films obtained from the Cu(30) Sn(70)/0.30 M sorbitol bath, at various deposition potentials and a charge density of 2.55 C cm 2, to determine the Cu and Sn contents and whether sorbitol had been incorporated (Table 3). It may be noted in

Fig. 7. AFM images of the Cu Sn films obtained at 1.4 V and a charge density of 2.55 C cm 2. (a) 2-D image; (b) 3-D relief image; (c) section relief of the Cu Sn film; (d) roughness analysis. Potential values were referred to the calomel 0.1 M KCl electrode.

G.A. Finazzi et al. / Surface & Coatings Technology 187 (2004) 377387 Table 3 EDS analysis of Cu and Sn contents of the deposits obtained from bath Cu(30) Sn(70)/sorbitol 0.30 M/3.30 M NaOH. Potential values were referred to the calomel 0.1 M KCl electrode Edeposition/V 1.2 1.3 1.4 1.6 Cu (%) >99.9 98.3 97.1 >99.9 Sn (%) < 0.1 1.7 2.9 < 0.1

385

Table 3 that Cu is deposited preferentially in the potential range 1.2 to 1.6 V, since Cu(II) species control the deposition process (Fig. 2). Also, comparing the Sn content in the films, it can be observed that the highest Sn content occurs in the deposits obtained at 1.4 V, because this potential is more favourable for Sn deposition than 1.2 V or 1.3 V and also there is less hydrogen evolution at 1.4 V than 1.6 V. It was observed that Cu Sn film is reddish coloured ( < 0.1% Sn) when obtained at 1.2 V, golden (1 3% Sn) at 1.3 V and 1.4 V and brown coloured ( < 0.1% Sn) at 1.6 V. These results are very promising because golden Cu Sn films were obtained with an Sn content in the range of 1 3%, while in the literature [1] Cu Sn films are golden only when Sn content is 10 15%. EDS did not show any carbon in the electrodeposit, indicating that sorbitol was not incorporated. 3.6. X-ray analysis of the Cu Sn deposits Fig. 8a, b and c show typical X-ray diffraction patterns of deposits obtained from the Cu(30) Sn(70)/0.30 M sorbitol plating bath, at different potentials and a charge density of 2.55 C cm 2. The observed crystallographic distances, d1(hkl) (at 1.2 V); d2(hkl) (at 1.3 V) and d3(hkl) (at 1.4 V) are compared with expected values (d exp ) described in JCPDS [39] in Table 4. It can be verified (Table 4) that some diffraction lines are easily assigned to dexp (Pt), dexp (Cu) and dexp (Cu3Sn). These results show that the peak at dobs = 2.26 can be attributed to Pt or SnO2. However, since the intensity of expected Pt peak (dexp) is 100% and dexp of the SnO2 is 16%, this peak is attributed to Pt. The peak at dobs = 1.95 can be attributed to Pt and the peak at dobs = 1.38 to Pt or Cu3Sn. The peaks at dobs = 2.09 and at dobs = 1.80 are attributed to copper since dexp(Cu) values are 2.0879 (I/Io = 100%) and 1.8079 (I/Io = 31%). The peaks at dobs = 2.09, 2.08, 1.38 and 1.26 are attributed to Cu3Sn, whose dexp are 2.0816 (I/ Io = 100%), 1.3811 (I/Io = 30%), and 1.2410 (I/Io = 40%). However, the peak at dobs = 1.38 could also be attributed to Pt (dexp = 1.3873, (I/Io = 31%)). It is possible that tin oxides were produced in the electrodeposition of the Cu Sn films, but it can be verified in Table 4 that only two lines for each oxide of tin (SnO, dexp = 1.80 (I/I o = 10%) and 1.389 (I/I o = 20%); SnO2, dexp = 2.26 (I/Io = 16%) and 1.38 (I/Io = 13%)) correspond

to dobs (Table 4). These expected diffraction lines of tin oxides have intensities lower than 30%, whereas expected diffraction lines for Cu and Cu3Sn have intensities over 30%, indicating that it is more probable that Cu and Cu3Sn are present in the films. Moreover, various diffraction lines of both SnO (e.g. dexp = 2.78 (I/Io = 100%) and dexp = 1.66 (I/Io = 82%)); and of SnO2 (dexp = 2.78 (I/Io = 80%) and dexp = 1.66 (I/Io = 50%)) with intensities higher than 10% are not present in the results (Fig. 8a, b and c), indicating that probably there is no tin oxide in the Cu Sn deposits obtained from the sorbitol alkaline plating bath. Also, EDS showed trace quantities of oxygen in these films, implying that tin oxides are either present in trace quantity or not present at all in these films.

Fig. 8. X-ray diffraction patterns of the deposits obtained from the Cu(30) Sn(70)/0.30 M sorbitol plating bath, on platinum substrate, with a deposition charge of 2.55 C cm 2, at (a) 1.2 V; (b) 1.3 V; (c) 1.4 V. A = 0.196 cm2. Three substances are identified: Pt, Cu, Cu3Sn [36]. Potential values were referred to the calomel 0.1 M KCl electrode.

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Table 4 Observed interplanar distances, d(hkl), of X-ray diffraction pattern of Cu Sn deposits obtained from the bath Cu(30) Sn(70)/0.30 M sorbitol at various potentials: 1.2 V (d1(hkl)); 1.3 V (d2(hkl)) and 1.4 V (d3(hkl)); deposition charge of 2.55 C cm 2. The expected values (dexp) are from JCPDS [39]: Pt, Cu, Cu3Sn, above 10% of relative intensity. Potential values were referred to the calomel 0.1 M KCl electrode d1(hkl) 2.26 2.09 2.08 1.95 1.80 1.38 1.26 d2(hkl) 2.26 2.09 2.08 1.95 1.81 1.39 1.27 d3(hkl) 2.26 2.09 2.08 1.95 1.81 1.39 dexp(Pt) 2.2650 2.0879 2.0816 1.9615 1.8079 1.3873 1.3811 1.2410 dexp(Cu) dexp(Cu3Sn) dexp(SnO) 1.8 1.382 dexp(SnO2) 2.2643 1.3849

dobs: d1(hkl); d2(hkl) and d3(hkl).

Therefore, the diffractograms of the deposits obtained from the bath containing Cu(30) Sn(70)/0.30 M sorbitol at 1.2 V probably indicated the occurrence of Cu3Sn and Cu (Fig. 7a; Table 4). Similar results were obtained from the films at 1.3 and 1.4 V. Considering the ratio of copper to tin in the Cu3Sn alloy, it can be asserted that the percentage of Sn in the mixture of pure copper and Cu3Sn in the film cannot exceed 38%. These results are compatible with Cu and Sn contents obtained by EDS analysis (Sn maximum content of the films is 2.9%).

also because it does not present any effluent discharge problem, since the system does not contain any toxic additive.

Acknowledgements Financial support from the Brazilian agency FAPESP (Proc. 01/01707-3) is gratefully acknowledged.

References 4. Conclusion Golden Cu Sn electrodeposits were successfully obtained voltammetrically from 0.6 to 1.6 V or chronoamperometrically at 1.4 V and a charge density of 2.55 C cm 2, from non-cyanide baths containing Cu(30) Sn(70) plus sorbitol concentrations 0.15, 0.30 and 0.45 M, as well as from the baths Cu(70) Sn(30)/0.30 M sorbitol and Cu(70) Sn(30)/0.45 M sorbitol. Bright reddish Cu Sn electrodeposits were successfully obtained under the same conditions from non-cyanide baths containing Cu(50) Sn(50) and various concentrations of sorbitol. The bath Cu(30) Sn(70) and 0.30 M of sorbitol showed good conductivity and viscosity, giving the highest deposition rate within the system Cu(30) Sn(70). The kinetic studies on this bath showed that copper(II) species control the electrochemical process of the Cu Sn deposition and that this reduction process is controlled by mass transport, with a diffusion coefficient of 8.1 10 8 cm2 s 1. SEM analysis showed that these baths lead to high quality films, which were smooth, bright and without cracks. EDS analysis showed that the golden Cu Sn films obtained at deposition potentials of 1.3 and 1.4 V and charge density of 2.55 C cm 2 have 1 3% Sn content, and that sorbitol is not incorporated in the deposit. The X-ray analysis of the deposits obtained from the bath containing Cu(30) Sn(70)/0.30 M sorbitol at 1.2, 1.3 and 1.4 V indicated the probable occurrence of Cu3Sn and Cu, corroborating the results of EDS analysis. This newly developed bath proved promising, not only for its high deposition rate and the good characteristics of the Cu Sn films, but
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