Effect of current density on morphology of

electroplated tin
A. Sharma, Y. J. Jang and J. P. Jung*
In this work, tin electroplating from acidic sulphate bath containing stannous sulphate, sulphuric
acid and a glycol type additive with a leveller has been studied on steel substrates. The effects of
plating current density on microstructural and morphological features are investigated. The
structural and morphological characteristics have been studied by X-ray diffraction (XRD), and
scanning electron microscopy (SEM). The XRD analysis confirms that the coatings produced by
sulphate bath consist of tetragonal (b-Sn) crystal structure. The grain size of the deposits
decreases up to a critical current density (y30 mA cm22), and then an increase in grain size is
noticed. The coating morphology turns irregular and porous at higher current densities (about 40–
50 mA cm22) due to the rapid increase in hydrogen evolution as depicted from the secondary
electron SEM images. Line profile analysis across the cross-section of the coatings further
confirms the absence of any constituent coming from the bath additives.
Keywords: Electrodeposition, Nucleation, Morphology, Tin, sulphate

Introduction sulphuric acid. In acidic baths, further addition of

organic chemicals known as additives is essential for a
Nowadays tin plating is the choice of material for smooth and bright finish. If the additives are absent in
protecting both ferrous and non-ferrous substrates. Tin these baths, dendritic and needle-like deposits with poor
plating provides an excellent resistance to corrosion and cathode coverage are produced. In the past, enormous
oxidation as well as improves the wettability of the amount of research has been done on tin plating from
substrate.1,2 Tin based coating has been known for more acidic baths involving various organic chemicals. The
than a century as it facilitates the solderability and use of additives not only provides a good surface finish
weldability of metallic components.3–5 Various plating but also improves the adhesion to the substrate. Various
baths are used for tin and tin based alloys ranging from organic additives such as wetting agents,6,9 branched
acidic to alkaline pH values in the literature.6–9 The carbon chain compounds,5,6 and aliphatic or aromatic
alkaline electrolytes involve high pH values and are chain products12,13 have been tried including gelatin, b-
mainly composed of sodium or potassium stannate salts. napthol, glycols and phenolphthalein.14,15 The prime
The supporting electrolyte for alkaline bath is sodium objective of using these additives in the plating bath is to
hydroxide or potassium hydroxide. The alkaline electro- improve the deposit quality. However, their excess
lytes are usually non-corrosive and do not require any addition in a plating bath may lead to a complicated
further addition of organic agents. The deposits are chemistry and uncontrolled deposition. This may give
highly smooth and are obtained at elevated temperatures. rise to poor or burnt deposits, or even no deposition at
At room temperature, the tin deposits obtained from all due to the severe passivation of the electrodes.
alkaline baths are spongy and powdery. This happens due Among the various additives added in the past, glycol
to the formation of a passive layer over anode, and based derivatives have been reported to provide an
imposes a further requirement of anode cleaning. easier tin reduction and uniform surface finish.15
Alkaline baths have limited applications in microelec- In this study, stannous sulphate bath containing the
tronic packaging due to their high pH (y14) which may glycol type additive in conjunction with an organic
damage the photoresist film of the electronic devices. One leveller is used for tin electroplating on steel substrates.
more drawback of alkaline baths is the requirement of The effect of plating current density upon the micro-
higher electric power due to the presence of tetravalent Sn structure and the surface morphology of tin coatings has
compared with other acidic baths in literature.8 been investigated. The change in morphology and grain
Another major category of the tin electroplating bath size of the coatings with increasing current densities is
is acidic in nature and mostly based on stannous also reported here.
sulphate salt. The supporting electrolyte is generally
Experimental
Department of Materials Science and Engineering, University of Seoul, Plating bath composition
Seoul 130-743, Korea The plating bath consists of the following chemicals:
*Corresponding author, email jpjung@uos.ac.kr stannous sulphate (SnSO4), sulphuric acid (H2SO4).

ß 2014 Institute of Materials, Minerals and Mining

Published by Maney on behalf of the Institute
Received 6 August 2014; accepted 23 November 2014
DOI 10.1179/1743294414Y.0000000427 Surface Engineering 2014 VOL 000 NO 000 1
Sharma et al. Effect of current density on morphology of electroplated tin

a without additive; b with additive

1 Cathodic polarisation curves obtained from tin sulphate bath

Glycol type organic additive and a leveller are also Research). Cathodic potential curves are obtained by
added to the plating bath. All the chemicals used in the plotting the steady state current for 10 min duration of
present study are of reagent grade (Sigma Aldrich, electrolysis against the applied potential. The cathodic
99?9%). The basic composition of the plating bath used current efficiency (CCE) is calculated, and reported as
is shown in Table 1. the ratio of the metal deposited at the cathode to the
theoretical amount of metal as predicted from Faraday’s
Plating bath preparation laws given by the equation
The plating baths are prepared using the stannous
sulphate and sulphuric acid in doubly distilled water. Mactual
CCE~ |100
The sulphate salt is first dissolved in distilled water Mtheoretical
followed by the gradual addition of H2SO4 due to the
where Mactual is the actual amount of metal deposited at
exothermic nature of the reaction. The solution is kept
the cathode and Mtheoretical is the theoretical amount of
on stirring for 24 h continuously until the tin salt gets
metal that can be deposited calculated from Faraday’s
fully dissolved. Finally the additives are added and kept
laws.9 The thickness of the coatings is measured with a
on stirring for complete homogenisation of the bath.
surface profilometer.
Substrate preparation
Microstructural characterisations
Stainless steel substrate, 1?0 mm thick (Merck Spe-
cialties Pvt. Ltd, electrolytic grade, 99?8%) with 1 cm2 Electroplated coatings are analysed using a scanning
surface area is used as the cathode. The cathode is electron microscope (Hitachi - 4300S) equipped with an
polished using 400–1600# SiC papers followed by 1 mm ultrathin window energy dispersive X-ray (EDS) detec-
diamond polishing. The stainless steel cathode is further tor. The structural characterisation is done by an
degreased in an ultrasonicator for 30 min, followed by X-ray diffractometer (Bruker’s D8 Discover) with a Cu
alcohol cleaning and drying in an open atmosphere. A target operating at 40 kV and 40 mA (Ka wavelength
platinum metal plate (Merck Specialties Pvt. Ltd, y0?154 nm).
electrolytic grade, 99?8%) approximately 1 cm2 surface
area is used as the anode, and a saturated calomel
electrode is utilised as a reference electrode.

Electrochemical investigations
Electrochemical experiments are performed using
EPP-400 pulse plating machine (Princeton Applied

Table 1 Plating bath composition

Compositions Values

Tin sulphate 50 g L21

Sulphuric acid 200 g L21
Thiourea 0.1 g L21
Additive (glycol derivative) 0.05 mL L21
Leveller 0.01 mL L21
pH 1.6
Current density 10–50 mA cm22
Temperature 25uC
Agitation Magnetic stirring@200 rev min21
2 X-ray diffraction pattern of Sn plated steel substrate

2 Surface Engineering 2014 VOL 000 NO 000

 Sharma et al. Effect of current density on morphology of electroplated tin

3 Effect of current density on a cathodic current efficiency and b thickness of tin coatings

Results and discussion The nucleation of tin begins at a higher cathodic

potential (about 20?55 V) in the presence of additives,
Polarisation measurements as shown in curve (b). In this case, the current density
The cathodic polarisation behaviour of tin on stainless increases slowly with cathodic potential and stabilises
steel substrate is shown in Fig. 1a and b. In the absence over a wide range of potential up to 20?78 V. The
of additive (curve a), the formation of Sn nuclei takes plateau region (20?55 to 20?78 V) corresponds to the
place at about 20?46 V. The current density rises with useful region for tin deposition. Beyond 20?78 V, there
further increase in cathodic potential, and becomes is a sudden increase in current density indicating setting
rapid after a potential of 20?57 V is reached. A rapid up of hydrogen evolution reaction. These observations
increase in current density with cathodic potential reveal that a large cathodic polarisation is associated
signifies a vigorous evolution of hydrogen gas over with the presence of additives. The glycol molecules in
metal deposition.16 Therefore, the deposition rate is the additives are likely to be adsorbed on the cathode as
poor in the absence of additive. well as freshly deposited tin surfaces. The adsorption of

4 Physical appearance of Sn plated steel substrate at different current densities

Surface Engineering 2014 VOL 000 NO 000 3

Sharma et al. Effect of current density on morphology of electroplated tin

5 Sn coating on steel substrate plated without additive at current density a 10, b 20, c 30, d 50 mA cm22, and with addi-
tive at current density e 10, f 20, g 30 and h 50 mA cm22

4 Surface Engineering 2014 VOL 000 NO 000

 Sharma et al. Effect of current density on morphology of electroplated tin

a without additives; b with additives

6 Spectrum (EDX) of tin plated stainless steel substrate

glycol molecules causes a partially blocked cathode current density of 30 mA cm22 can be ascribed to the
surface, and thus polarisation is enhanced. The deposi- lowering in CCE caused by the rapid increase in
tion of tin usually proceeds through various reduction hydrogen evolution.9
and oxidation steps. Tin ions usually form tin hydroxyl
complexes near the cathode, which get reduced and Physical appearance
plated at the cathode.9,16 It is clearly noticed that a well Figure 4 shows a series of photographs showing the
developed plateau region emerges in the presence of change in physical luster of the tin platings as a func-
additives (Fig. 1b), showing improved deposition rate tion of current density. It is noticed that a bright tin
and quality. coating can be obtained only at a current density of
30 mA cm22. At lower current densities y10 and
X-ray diffraction (XRD)
20 mA cm22, the deposit density is not uniform due to
The XRD pattern of the tin coating is shown in Fig. 2. the presence of lesser number of Sn ions. The deposition
There are various diffraction peaks in this diffraction rate increases gradually with an increase in current
pattern. All peaks are indexed to tetragonal tin (b-Sn)
crystal structure. X-ray diffraction analyses of other
coatings plated at different current densities show
similar crystal structure irrespective of the solution
composition and parameters.
Cathodic current efficiency (CCE) and thickness
The influence of current density on CCE and deposit
thickness is shown in Fig. 3a and b. It is observed that
the CCE increases to 84?8% at a current density
y30 mA cm22. The CCE decreases further when the
current density exceeds 30 mA cm22. This can be
explained in the following way. When the current
density is low, the probability of hydrogen evolution
reaction is negligible. The hydrogen evolution reaction is
an inherent process in electroplating. As the current
density exceeds 30 mA cm22, hydrogen evolution
becomes violent resulting in a reduced metal deposition.
This creates a lowering in CCE. The deposit thickness
increases initially up to 10?1 mm at 30 mA cm22, and 7 Effect of current density on grain size of tin deposits
then falls (Fig. 3b). Loss in deposit thickness beyond with and without additive

Surface Engineering 2014 VOL 000 NO 000 5

Sharma et al. Effect of current density on morphology of electroplated tin

8 a cross-sectional SEM of tin plated steel substrate, and b line scan profile across tin plated steel substrate

density up to 30 mA cm22. The coating appears quite The hydrogen evolution exceeds metal deposition at this
dark at 40 and 50 mA cm22. A dark coating usually stage causing bubbling near cathode or inside the
indicates poor cathode coverage or less deposition due deposits, and thus porous deposits are obtained.
to the evolution of hydrogen gas at the cathode.
Compositional analysis (EDS)
Microstructure (SEM) The EDS spectrum shows the elemental composition
Figure 5a–h shows the surface morphology of tin analysis of tin deposit on a steel cathode. In the absence
electroplated on steel substrate at various current of additives, the spectrum shows a prominent peak of
densities in the presence and absence of additives. The elemental Fe, several smaller peaks of Fe, Sn, and a
coatings plated at different current densities (i.e. 10, 20, small Cr peak (Fig. 6a). The Fe and Cr peaks are
30 and 50 mA cm22) in the absence of additives are noticed from the substrate material. It may be due to the
shown in Fig. 5a–d. The coatings plated at different fact that the coating thickness is not uniform due to
current densities (i.e. 10, 20, 30 and 50 mA cm22) in the poor cathode coverage. When the additives are added to
presence of additives are also presented (Fig. 5e–h). It is the bath, the deposit density is improved and thus
noticed that in the absence of additives, the coating several peaks of Sn are visible with a few tiny peaks of
density is very poor. The cathode coverage is non- Fe (Fig. 6b). The smaller peaks of Fe are noticed
uniform and big sized nodules/lumps of tin develop (i.e. because of the fact that the interaction volume of the
at 10 mA cm22). When the current density is increased electron beam is greater than the thickness of the
up to 30 mA cm22, the nodules are refined gradually. electroplated Sn film. These observations confirm that in
The cathode coverage increases due to the increase in the presence of additives, the deposit density and finish
deposition rate at higher current density. However, the is improved significantly.
cathode coverage falls beyond y30 mA cm22 due to the
evolution of hydrogen gas at the cathode. The steel Grain size
cathode becomes visible as indicated by arrows, and Figure 7 shows the effect of current density on the grain
grain refining action is lost (Fig. 5d). size of electroplated tin coatings. It is observed that
When the additives are added into the bath, the the in the presence of additives, the grain size is smaller.
morphology of the coatings is quite improved. The grain As already discussed, the additives refine the grain
size of deposits in the presence of additives is smaller as size by increasing the cathodic polarisation. The grain
shown in Fig. 5e–h. The additives usually refine the grain size of the deposits is lowest at a current density
size by increasing the cathodic polarisation, as already y30 mA cm22, for both without additives and in
discussed in the section on ‘Polarisation measurements’. the presence of additives. The grain size decreases from
Moreover, the grain size refinement also occurs on 350 to 240 nm in the presence of additives compared
increasing the current density from 10 to 30 mA cm22. to 600 to 300 nm in the absence of additives (Fig. 7). At
This can be correlated to a higher nucleation rate with an higher current densities, the nucleation rate is higher
increase in the current density.9–15 Deposits plated at as compared to the grain growth rate. The deposits
higher current density (.30 mA cm22) are irregular and obtained under these conditions should be fine grained.
coarse grained structure. This can be attributed to the fast However, the increase in grain size beyond 30 mA cm22
movement of Sn ions towards cathode which creates a can be attributed to the progressive increase in hydrogen
region devoid of Sn ions near the cathode. To fill this evolution. Consequently, the deposit density is reduced
depleted zone, hydrogen gas evolves at a very high rate. and grain size increases.9,15

6 Surface Engineering 2014 VOL 000 NO 000

 Sharma et al. Effect of current density on morphology of electroplated tin

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