MA TE RI A L S CH A R A CT ER IZ A TI O N 6 8 (2 0 1 2) 2 2–3 2

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Influence of current density on microstructure of pulse

electrodeposited tin coatings

Ashutosh Sharmaa , Sumit Bhattacharyaa , Ranjan Sena , B.S.B. Reddya , H.-J. Fechtb ,
Karabi Dasa,⁎, Siddhartha Dasa
a
Department of Metallurgical and Materials Engineering, Indian Institute of Technology-Kharagpur, Kharagpur-721302, India
b
Institut für Mikro- und Nanomaterialien, Universität Ulm, D-89081 Ulm, Germany

AR TIC LE D ATA ABSTR ACT

Article history: Pulse electrodeposited tin coatings on copper substrate have been synthesized from an
Received 1 November 2011 aqueous solution containing sodium stannate (Na2SnO3.3H2O) and sodium hydroxide
Received in revised form (NaOH). The effect of current density on surface morphology of the deposits has been
12 January 2012 investigated. As deposited coatings are characterized by X-ray diffraction, scanning
Accepted 3 March 2012 electron microscopy, electron backscatter diffraction, and line profile analysis. The X-ray
diffraction analysis shows that the deposits consist of tetragonal (β-Sn) structure with mi-
Keywords: crocrystalline grains. The deposits plated at lower current density exhibit (110) texture
Coatings which decreases with increasing current densities. The effects of current density on Cu–
Pulse electrodeposition Sn diffusion and whisker growth of the electrodeposited tin coatings are also reported here.
Current density © 2012 Elsevier Inc. All rights reserved.
Diffusion

1. Introduction films. However, these surfactants should be added to the elec-

Pulse electrodeposited tin coating has been the subject of
research owing to its excellent solderability, and oxidation
and corrosion resistance in the microelectronic industry. Con-
ventional lead–tin plating is now being avoided due to its toxic
effect on the environment [1–3]. In general, two types of elec-
trolytes are used for tin electroplating, alkaline stannate
based electrolytes and acidic stannous sulfate or methyl
sulfonic acid based electrolytes [4–7]. Both these classes of
electrolytes are aqueous in nature.
Irregular, dendritic, or needle-like tin electrodeposits are
obtained from acidic electrolytes without organic additives.
To improve the surface finish, morphology, and adhesion of
the films during acidic tin plating, various organic chemicals
have been added in the past. These include surface active
agents [7–9], aliphatic and aromatic compounds [10,11]. Sever-
al authors have already used gelatine [12,13], gluconate [14],
thiourea [15], etc. to enhance the quality of the deposited
trolyte in optimum level, since an excess quantity may lead to
a poor wetting behavior of the deposit [16].
The alkaline electrolytes usually contain sodium or potas-
sium stannate and the corresponding alkali metal hydroxide.
They are non-corrosive in nature and free from organic addi-
tives [17]. The alkaline tin baths have a very high throwing
power and can be operated over a wide current density
range [4,5,17]. These electrolytes are also environment friend-
ly. However, in alkaline baths, tin exists in tetravalent state as
compared to divalent state in acidic baths, and this leads to
consumption of more electrical energy [17].
Compared to DC electrodeposition, pulse electrodeposition
can produce more diversified microstructures. One can vary
the operating parameters such as current density, pulse duty
cycle, and frequency during pulse electrodeposition [18–20].
Pulse electrodeposition has also been shown to produce
whisker resistant coatings under specific conditions [21].
Pulse electrodeposition can be used for the development of

⁎ Corresponding author. Tel.: +91 3222 283254, +91 9434016142 (M); fax: +91 3222 220 666, 255 303.
E-mail address: karabi@metal.iitkgp.ernet.in (K. Das).

1044-5803/$ – see front matter © 2012 Elsevier Inc. All rights reserved.
doi:10.1016/j.matchar.2012.03.002
 MA TE RI A L S CH A R A CT ER IZ A TI O N 6 8 (2 0 1 2) 2 2–3 2 23

Table 1 – Bath parameters for electrodeposition.

2. Experimental Methods
Experimental parameters Values

pH ~13 Pulse electrodeposition is carried out using an Autolab

Current density 0.1–0.5 A/cm2 PGSTAT 30 with a 10 A current booster. The measurements
Bath temperature 60 ± 1 °C under galvanostatic mode are made directly on the computer
Duration 30 min
using the Eco Chemie software module. All the current/poten-
Anode (99.8%) tin plate
Bath agitation (with magnetic stirrer) 300 rpm
tial values are referred to 3 M KCl Ag/AgCl electrode. The ca-
Ton a, Toff b 0.001 s, 0.01 s thodic current efficiency (CCE) is calculated in terms of ratio
of the metal deposited at the cathode to the theoretical
a
Time during which the current flows.
b
amount predicted from Faraday's laws given by equation:
Time during which no current flows.

Ma
CCEð% Þ ¼ 100 
simple Sn, Sn-alloy or composite lead-free solders [1,21]. The Mt
purpose of this investigation is to study the effects of current
density on microstructure, Cu–Sn diffusion and whisker where M a is the actual amount of metal deposited at the cath-
growth of the pulse electrodeposited tin coatings on copper ode and M t is the theoretical amount of metal calculated from
substrate. Faraday's laws [22]. The solution pH is stabilised to ~13 by

Fig. 1 – Scanning electron micrographs (SE mode) of tin deposited at different current densities at pH ~13.0 (a) 0.1, (b) 0.2, (c) 0.3,
(d) 0.4 and (e) 0.5 A/cm2.
24 MA TE RI A L S CH A R A CT ER IZ A TI O N 6 8 (2 0 1 2) 2 2–3 2
adding few drops of 30% glacial acetic acid and is measured by
the Sartorius professional meter PP-50.
Copper foils, 0.5 mm thick (Merck Specialties Pvt. Ltd, elec-
trolytic grade, 99.8%) with 6 cm2 surface area, is used as the
cathode. The copper foil is rinsed with 10% dilute H2SO4 to re-
move the inherent oxide layer and foreign impurities. Tin
metal plate (Merck Specialties Pvt. Ltd, electrolytic grade,
99.8%) of approximately 10 cm2 surface area is used as the
anode.
The chemicals used for bath preparation are of reagent
grade sodium stannate, Na2SnO3.3H2O (90 g/L) (Loba chemie,
99.9%) and sodium hydroxide, NaOH (15 g/L) (Loba chemie,
99.9%). The bath composition is based on the previous litera-
ture [23]. To prepare the plating solution, the sodium stannate
is dissolved in deionized water followed by the gradual addi-
tion of NaOH. The solution is stirred until the sodium salt is
fully dissolved. The experimental parameters used for electro-
deposition are shown in Table 1.
Pulse electrodeposited films are analyzed using a scanning
electron microscope (Carl Zeiss supra EVO-40) which is
equipped with an ultra thin window energy dispersive X-ray
detector and an X-ray diffractometer (Bruker's D8 Advance)
with a Co target (Kα1 wavelength of 0.179 nm). The micro-
Fig. 2 – (a) Thickness of tin coatings, and (b) cathodic current efficiency as a function of current density.
texture measurements are carried out using the technique of
electron backscatter diffraction (FEI Quanta 3D FEG) with a
step size of 30 nm and a beam current of 16 nA. The thickness
and surface roughness of the electrodeposits is measured by a
surface profilometer (Veeco DEKTAK). The tin whisker growth
is studied for the samples which are aged at room tempera-
ture for 1 year.
3. Results and Discussion
3.1. Surface Morphology
Fig. 1 shows the surface morphology of tin electrodeposited on
copper substrate at various current densities ranging from 0.1
to 0.5 A/cm2. With increasing current densities (e.g., 0.1–
0.3 A/cm2), smooth, uniform and compact electrodeposits
are obtained, while at higher current densities (e.g., 0.4–
0.5 A/cm2) the deposits are porous. This change in morphology
can be explained in the following way. At low current densities
the discharge of Sn ions occurs slowly, and hence the rate of
growth of nuclei exceeds the rate at which the new ones
form; the deposits obtained under these conditions should be
 MA TE RI A L S CH A R A CT ER IZ A TI O N 6 8 (2 0 1 2) 2 2–3 2
Table 2 – Variation of surface roughness of the tin
coatings with current density.
Current density (A/cm2) Roughness (μm)
0.1 0.17 ± 0.15
0.2 0.12 ± 0.14
0.3 0.26 ± 0.16
0.4 0.67 ± 0.18
0.5 0.92 ± 0.17
coarsely crystalline. As the current density is raised the rate of
formation of nuclei will be greater than the growth and the de-
posit will become finer-grained. This is related to the fact that
as the current density increases there is an increase in the
overpotential which promotes the nucleation process [24].
Hence, a compact and fine grained electrodeposit is obtained.
However when current density exceeds a critical value,
(0.3 A/cm2), a porous and non uniform microstructure de-
velops. This can be attributed to the very high overpotential,
which causes the Sn ions, from solution to move at a very
fast rate towards cathode. This may lead to a depletion of the
Sn ion concentration of the aqueous solution adjacent to the
cathode and the electrode surface gets polarized. In order to
overcome the concentration polarization, a greater change in
potential is required to maintain the current and thus, the sys-
tem enforces hydrogen ions to be discharged at a very high
rate. The hydrogen evolution competes with the metal deposi-
tion as the current density increases further. The hydrogen gas
evolution give rise to bubble formation that often gets incorpo-
rated in the crystal lattice resulting in porous and spongy
deposits [25,26]. The pores, as shown in the enclosed circle of
Fig. 1(d, e), are clearly visible in the films deposited at higher
current densities (e.g., 0.4–0.5 A/cm2).
3.2. Thickness
The effects of current density on thickness and current effi-
ciency of the electrodeposited films are shown in Fig. 2(a)
and (b). From Fig. 2(a), it is observed that there is an increase
in thickness up to current density of 0.3 A/cm2 and then
Fig. 3 – A typical X-ray diffraction pattern of Sn plated copper substrate at a current density of 0.3 A/cm2.
25
decreases with current density. This can be attributed to the
significant increase in hydrogen evolution beyond 0.3 A/cm2
resulting in a lowering of current efficiency as shown in
Fig. 2(b). The current efficiency increases initially up to
0.3 A/cm2 and then falls. Beyond 0.3 A/cm2, loss in current
efficiency is due to a rapid increase in hydrogen evolution
and hence metal (Sn) deposition is reduced [25–27].
3.3. Roughness
It is seen from Table 2 that the roughness values increase with
the increase in the current density. The mean roughness
values (Ra) obtained for the deposits produced at different cur-
rent densities are in the range 0.17–0.9 μm. It is found that the
deposits are quite smooth at the lower current densities
(0.1–0.3) A/cm2 due to the increasing current efficiency.
At higher current densities, (0.4–0.5) A/cm2, due to a
marked decrease in current efficiency, the hydrogen evolution
is prominent. More and more number of moles of hydrogen
gas may get adsorbed in the deposit. Thus, the porosity
increases resulting in an increase in the roughness of the
deposits [17,25,27].
3.4. X-ray Diffraction and Texture Analysis
3.4.1. X-ray Diffraction
The X-ray diffraction (XRD) measurements are conducted on
tin films electroplated at different current densities. A typical
pattern taken from the sample which is electroplated at
0.3 A/cm2 is shown in Fig. 3. The diffraction pattern shows
that the electroplated tin film has the tetragonal crystal struc-
ture (β-Sn). The crystallite sizes of the individual grains occur
in the micrometer range that is beyond the scope of Scherrer
formula (~200 nm). Therefore, it is measured using a scanning
electron microscope and it is in the range of 290–2100 nm.
Beside the indexed tetragonal (β-Sn) peaks, the rest of the
peaks, (111), (200), (220) and (311) reflections are from the
copper substrate. The Cu6Sn5 intermetallic compound has
not been detected by the XRD analysis in the as deposited
samples.
26 MA TE RI A L S CH A R A CT ER IZ A TI O N 6 8 (2 0 1 2) 2 2–3 2

3.4.2. Texture Analysis
Electron backscatter diffraction (EBSD) analysis has been
carried out in order to analyze the texture developed in the
deposited coatings. The preferred relative texture has been
interpreted in terms of inverse pole figure maps [28,29], as
shown in Fig. 4(a–e) and (f) shows the standard inverse pole
triangle for a body centered tetragonal crystal structure [30].
As seen from the color code maps, if the texture index is great-
er than 1, we consider it as a presence of texture [31].
Therefore, from the inverse pole figures (Fig. 4(a–e and f)) it
is found that a texture of (320) and (110) exists at a current
density of 0.1 A/cm2 and it changes to (321) at 0.2 A/cm2. A fur-
ther rise in the current density to 0.3 A/cm2, results in (212)
texture. Beyond 0.3 A/cm2, (112) comes into picture with an in-
herent (110) texture, while at 0.5 A/cm2 it changes to (310).
Strongest plane normal, as shown in the inverse pole figure
map (IPF), depends on the maximum (inverse pole figure
color code) IPF value, Fig. 4(a–e). The results of the texture
analysis have been summarized in Table 3.
From Table 3, it is observed that with an increasing current
density there is a change in texture. There are a number of
factors involved in electrodeposition that decides the film
texture, e.g., deposit composition, thickness, current density,
bath concentration, additives, and bath conditions (i.e., stir-
ring rate). Therefore, there is no straightforward explanation
for the texture evolution with current density in literature
[32–34]. However, it has been postulated in the past that the
surface energy anisotropy plays an important role in texture
evolution. The surface energy of the deposit depends on the
hydrogen adsorption ability of the different crystallographic

Fig. 4 – Continuous inverse pole figures of Sn plated Cu substrate at different current densities (a) 0.1, (b) 0.2, (c) 0.3, (d) 0.4 and
(e) 0.5 A/cm2, (f) The standard inverse pole triangle for a body centered tetragonal crystal structure[30].
 MA TE RI A L S CH A R A CT ER IZ A TI O N 6 8 (2 0 1 2) 2 2–3 2
Table 3 – Texture variations in electrodeposited tin
coatings with varying current density as observed from
inverse pole figure maps.
Current density Preferred β-Sn grain
(A/cm2) orientation (hkl)
0.1 320, 110
0.2 321
0.3 212
0.4 112, 110
0.5 310
planes [35–38]. The adsorbed hydrogen helps in lowering the
surface energy of the deposit. Huang, Zhou and Pan [37]
have found that adsorption of hydrogen in nickel electrode-
posits changes the texture from (111) to (100) to minimize
surface energy. A similar behavior is noticed for copper elec-
trodeposits where formation of (110) texture is attributed to
the lowest surface energy anisotropy [38,39]. Thus, it can be
concluded that the preferred orientation in the electrode-
posits depends on the surface energy anisotropy which gets
modified by changing the current density which is consistent
with the present investigation [36–40].
At lower current density the (110) texture is present which
has been reported to be whisker resistant orientation
[17,41–43]. Some authors have studied the effect of preferred
grain orientation on whisker growth propensity [44,45]. Gaylon
and his coworkers [44] have measured the stress in tin film
and correlated it with grain orientation and whisker growth.
The whisker resistant orientations other than (110) are
reported to be (210), (220), (320), and (420); whereas grain orien-
tations (112) and (321) are considered to be whisker prone [45].
Similar claims have been made by Schetty and Vickers where
(220) is a whisker resistant orientation [43]. Keith, Crossby
and Toben [42] have explained this on the basis that the depos-
it with a large proportion of narrow interplanar angles is more
prone to whisker growth. Therefore, the (110) orientation in
deposits is beneficial in preventing tin whiskers [41–45].
3.5. Diffusion of Cu in Sn and Whisker Formation
It has been reported in the literature that pure Sn and the
Sn-rich alloys react with copper substrate to form the inter-
metallic compounds like Cu6Sn5, Cu3Sn, etc.[46,47]. These in-
termetallic compounds generate internal compressive stress,
a root cause of whisker growth in the Sn plated coatings [46].
It is already known that a high current density produces the
internal stress in the plating [48]. Choi and Tu have reported
that whisker growth is faster on the SnCu finish compared
to the Sn finish [49,50].
In order to investigate the effect of current density on the
diffusion of Cu–Sn, the interface is examined by line profile
analysis, as shown in Fig. 5(a–e). A schematic view of the
cross section of the sample which is prepared by sandwiching
two samples is shown in Fig. 5(f). It is clear that the Cu–Sn
interface changes its shape with the current density. At
0.1 A/cm2 (Fig. 5(a)), there is almost no diffusion of Cu in Sn
layer. This may be correlated with the presence of whisker re-
sistant orientations (110) and (320) which introduce minimum
27
stress in tin film [45]. As the current density increases, there is
a possibility of some diffusion, Fig. 5(b–d). With a further in-
crease in current density to 0.5 A/cm2 (Fig. 5(e)), the Cu–Sn dif-
fusion at the interface approaches its peak. Beyond 0.1 A/cm2,
this (110) component decreases and the Cu–Sn diffusion is
likely to be enhanced at higher values of current densities.
This increase in Cu–Sn diffusion can be related to the change
in texture with current density as given in Table 3. The (110)
texture starts to decrease as the current density increases
from 0.1 to 0.3 A/cm2 and thus the diffusion is enhanced, but
no whisker growth is observed in the as deposited films
[41–44]. It is also observed that at a current density of
0.4 A/cm2, (112) orientation co-exists with (110) but there is
no decrease in diffusion. This might be due to the fact that
(112) orientation is stiffer than (110), and therefore, it is more
likely to enhance film stress and diffusion [44,45,51].
For the as deposited samples, it may be inferred that at room
temperature the Cu–Sn diffusion is related to the orientation of
the deposits which in turn depends on the plating current den-
sities. However, this is not sufficient to induce whisker in the
coatings. Therefore, the whisker growth is further examined
by ageing the samples at room temperature for a certain length
of time (e.g., 1 year). There is also a noteworthy point that we
have studied only Sn deposits plated from alkaline bath and
the results might differ from one bath to other.
3.6. Ageing Behavior
The ageing behavior at room temperature (~26 °C) for a period
of one year of the as deposited Sn films has been investigated.
Fig. 6 shows the whisker morphologies on tin deposits. It is
clear that the orientation plays an important role in the whis-
ker growth kinetics. The films plated at lower current density
0.1 and 0.2 A/cm2 (Fig. 6(a, b)) show minimum whisker growth.
The average length of the whiskers is 10 μm and nodular mor-
phology can also be observed. This can be explained in terms
of the inherent (110) orientation causing minimum stress in
the film.
It is observed from Fig. 6(c, d) that as the current density in-
creases (0.3–0.4 A/cm2), the nodular features or hillocks pre-
sent on the surface are minimized and whiskers develop.
This is due to the fact that (110) orientation becomes weak
and hence it can not resist whisker growth. The average length
of the whiskers increases from 24 μm to 120 μm as the current
density increases from 0.3 A/cm2 to 0.4 A/cm2 due to (112) tex-
ture. However, the film plated at 0.5 A/cm2 shows short length
whiskers of about 5–25 μm with a sufficient number of pores,
(Fig. 6(e). A typical high resolution image of a whisker is
shown in Fig. 6(f). It can be inferred that even though the diffu-
sion of Cu in Sn is high, the porosity plays an important role in
relieving the stress to restrict the whisker growth [52].
It has been already debated in the past that the compres-
sive stress is developed within a certain period of time,
when there is an excessive Cu–Sn diffusion at the interface
to form the intermetallic compounds [47–50]. The formation
of these compounds in aged samples is confirmed by the
XRD analysis of tin coatings. The XRD pattern of an aged sam-
ple (plated at 0.3 A/cm2, Fig. 7) shows the presence of only
Cu6Sn5 and no Cu3Sn or other compounds, since Cu3Sn exists
only at elevated temperatures [46]. Thus, it can be inferred
28 MA TE RI A L S CH A R A CT ER IZ A TI O N 6 8 (2 0 1 2) 2 2–3 2

Fig. 5 – Line scan profile of tin and copper at the Cu–Sn interface at different current densities (a) 0.1, (b) 0.2, (c) 0.3, (d) 0.4 and
(e) 0.5 A/cm2 and (f) schematic of the Cu–Sn interface used for line scan study.

that the growth of these Cu6Sn5 provides the driving force for
the spontaneous whisker formation. The chemical force that
drives this reaction is the formation energy of Cu6Sn5 interme-
tallics at room temperature as per the following reaction:
6Cu þ 5Sn→Cu6 Sn5
The heat of formation value of Cu6Sn5 is − 72 m eV/atom at
room temperature [53]. Since the heat of formation for Cu6Sn5
is negative, it is therefore energetically stable. Thus, it con-
tinues to grow within a certain period of time.
Fig. 8 shows a set of cross sectional scanning electron micro-
graphs of the Cu–Sn interface. The thickness of the coating is
around 3–5 μm. The deviation in thickness from the initial as
deposited value of the tin layer after ageing may be due to the
slow Sn consumption by the interfacial reaction resulting in
the formation of the Cu6Sn5 compounds and their coarsening
with time [54]. It is observed that with an increase in current
 MA TE RI A L S CH A R A CT ER IZ A TI O N 6 8 (2 0 1 2) 2 2–3 2 29

Fig. 6 – Scanning electron micrographs (SE mode) of 1 year aged tin deposits at different current densities (a) 0.1, (b) 0.2, (c) 0.3,
(d) 0.4, (e) 0.5 A/cm2 and (f) high resolution micrograph of a tin whisker.

density, voids and micro cracks are generated at the interface as

shown in Fig. 8(d, e). Rapid diffusion of Cu into Sn may cause va-
cancies in Cu. These vacancies coalesce to form voids. Some re-
searchers have attributed these voids to Kirkendall voids.
Others attributed the void formation to impurities in the Cu
layer of the Cu–Sn couple [46]. The rise in number of these
voids is presumably due to the consumption of copper substrate
by a gradual formation of Cu6Sn5 during ageing [47,55].

4. Conclusions

1. Pulse electrodeposited tin coatings (β-Sn, tetragonal) have

been synthesized successfully from a simple, non hazard-
ous electrolyte.
2. At lower current densities (0.1–0.3 A/cm2), the deposits are
smooth and uniform, but roughness and porosity increase
with the increase in current density. Initially the (110) tex-
ture is present in the coatings which decreases at higher
Fig. 7 – XRD pattern of the aged sample plated at 0.3 A/cm2. current density.
30 MA TE RI A L S CH A R A CT ER IZ A TI O N 6 8 (2 0 1 2) 2 2–3 2
Fig. 8 – Cu–Sn Cross sectional scanning electron micrographs of Cu–Sn interface at different current densities (a) 0.1, (b) 0.2,
(c) 0.3, (d) 0.4 and (e) 0.5 A/cm2.
3. As deposited films at low current densities show very little
diffusion of Cu across Cu–Sn interface and this can be pri-
marily attributed to the (110) texture of Sn films while at
higher current density, the diffusion is enhanced since
(110) texture is minimized.
4. The whisker growth during ageing is minimized in films
electroplated at low current density (0.1 and 0.2 A/cm2).
The whisker growth increases as the current density in-
creases and becomes maximum at 0.4 A/cm2. However,
when the current density increases to 0.5 A/cm2, the whis-
ker growth again decreases due to the presence of porosi-
ties which relieve the internal stress.
Acknowledgements
The authors are grateful to Professor Indradev Samajdar and
Mr. Lokendra Jain of the Indian Institute of Technology,
Bombay for their help with the EBSD work carried out at the
National Facility of Texture & OIM, a DST-IRPHA facility at
the IIT Bombay.
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