Materials Letters 62 (2008) 44734475

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Materials Letters
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m a t l e t

A superelastic nanocrystalline CuSn alloy thin lm processed by electroplating

Motohiro Yuasa a,, Kota Kajikawa a, Masataka Hakamada b, Mamoru Mabuchi a
a

Department of Energy Science and Technology, Graduate School of Energy Science, Kyoto University, Yoshidahonmachi, Sakyo-ku, Kyoto 606-8501, Japan
Materials Research Institute for Sustainable Development, National Institute of Advanced Industrial Science and Technology, 2266-98 Anagahora, Shimoshidami, Moriyama,
Nagoya 463-8560, Japan

a r t i c l e

i n f o

Article history:
Received 10 July 2008
Accepted 8 August 2008
Available online 13 August 2008
Keywords:
Superelasticity
Electroplating
Nanocrystalline
Copper alloys
Hardness tests

a b s t r a c t
A nanocrystalline CuSn alloy lm was processed by electroplating, and the indentation tests and
microstructural observation were conducted on the electroplated CuSn alloy lm. The indentation tests at
room temperature showed that a large amount of strain was recovered on unloading for the electroplated
CuSn alloy lm, in contract, such a large reversible strain was not found in an electroplated pure Cu lm.
Thus, the electroplated CuSn alloy lm exhibited superelastic behavior. The grain size of the CuSn alloy
lm was 99 nm. In spite of the very small grain size, the austenite start and nish temperatures of the CuSn
alloy lm were relatively high. This is suggested to be related to the presence of the -Cu phase.
2008 Elsevier B.V. All rights reserved.

1. Introduction
Currently, shape memory alloys are used in various elds such as
aerospace, medicine and dentistry [1,2]. Recently, there is a growing
interest in micro-electromechanical systems and micro-total-analysis
systems. Thin lms of shape memory alloys are needed for use as
microactuator in the microsystems [35]. Until now, shape memory
NiTi alloy thin lms have been processed by sputtering method [6].
However, the cost of sputtered NiTi is very high.
The present paper shows that an as-electroplated CuSn alloy thin
lm exhibit superelasticity at room temperature. Electroplating is of
particular interest compared to sputtering because of its lower cost.
Besides, very small grain sizes of the order of nanometers can be
obtained by electroplating [7]. Hence, remarkable high materials
performances such as high strength [8] are expected in electroplated
thin lms. Superelasticity of shape memory alloys is the result of
martensitic transformation, and it is worthwhile to investigate the
relationship between martensitic transformation behavior and microstructural characteristics of the electroplated thin lm. In the present
paper, indentation tests and microstructural observation are conducted
on the as-electroplated CuSn alloy lm, and the results are compared
with those for the electroplated pure Cu lm showing no superelasticity.
2. Experimental
A CuSn alloy thin lm with a thickness of 50 m was processed by
electroplating. The electrolyte composition was CuSO 4 5H 2 O

Corresponding author. Tel.: +81 75 753 5421; fax: +81 75 753 5428.
E-mail address: yuasamotohiro@t03.mbox.media.kyoto-u.ac.jp (M. Yuasa).
0167-577X/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2008.08.008

(0.225 mol/l), SnSO4 (0.275 mol/l) and H2SO4 (1.0 mol/l). Cresolsulfonic acid (0.25 mol/l) was used as additive. The current density was
30 mA/cm2 with direct current. The lm was electroplated on an
amorphous Fe substrate plate. The bath temperature was maintained
at 293 K. For comparison, a pure Cu lm was processed by
electroplating. The electrolyte composition for the pure Cu lm was
CuSO45H2O (220 g/l) and H2SO4 (60 g/l). Gelatin (0.05 g/l) was used as
additive. The current density was 100 mA/cm2 with direct current. The
pure Cu lm was electroplated on an amorphous Fe substrate plate.
The bath temperature was maintained at 300 K.
Two kinds of indentation tests were carried out at room
temperature on the CuSn alloy and pure Cu lms. First, the
nanoindentation tests were performed by a Shimadzu DUH-W201
hardness tester. Using a sharp indenter such as a Vickers indenter,
high peak strain levels tend to be generated immediately below the
indenter and result in generation of a high density of dislocations,
even at low applied loads [1113]. Because the presence of a lot of
dislocations inhibits the formation of martensite within the parent
phase, superelasticity cannot be fully obtained by indentation tests
with a sharp indenter. Hence, a spherical diamond indenter
(r = 500 m) was used for investigating superelasticiy because of low
peak strain levels. The lm specimen was indented at a constant
loading rate of 13.24 mN/s. The load was held constant for 10 s at
100 mN for the CuSn alloy and 50 mN for the pure Cu, and then the
specimen was unloaded. Another indentation tests were carried out
with a Vickers indenter to investigate the hardness. Both the lm
specimens were indented at a constant loading rate of 2.64 mN/s to a
load of 50 mN. The indentation tests were carried out 10 times and the
average and standard deviation of hardness were measured.
The residual stress tends to occur during electroplating [9].
However, the load-displacement behavior during indentation with a

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M. Yuasa et al. / Materials Letters 62 (2008) 44734475

spherical indenter is hardly affected by the residual stress when

deformation is in a low plastic strain range or when plasticity is fully
developed [10]. In the present work, deformation during indentation
with a spherical indenter is in a low plastic strain range. Besides, both
the CuSn alloy and pure Cu lms were not bended when they had
been deposited. Therefore, it is suggested that there are little effects of
the residual stress on the lm.
Microstructure of the CuSn alloy and pure Cu lms was
investigated by transmission electron microscopy (TEM). The TEM
observation was carried out by a JEOL JEM-2010 at an operating
voltage of 100 kV. The specimens observed by TEM were thinned by a
dimple grinder and an Ar ion milling. Also, differential scanning
calorimetry (DSC) was performed on the CuSn alloy lm to examine
the transformation temperatures, using a SEIKO DSC120U instrument,
where the specimen weight was 23.8 mg. The specimen was cooled to
143 K by the liquid nitrogen, and then it was heated to 323 K at a
heating rate of 10 K/min.
3. Results and discussion
The load-displacement curves by the indentation tests with a spherical indenter are
shown in Fig. 1 for the CuSn alloy lm and in Fig. 2 for the pure Cu lm, respectively.
Note that the signicant difference between the two curves is the magnitude of
recoverable strain, although the maximum indenter depths for the two curves are
almost the same. For elastic-plastic solids, the reversible strain during unloading result
only from elastic deformation and irreversible strain resulting from plastic deformation
remains. In the pure Cu lm, the irreversible strain was very large. In the CuSn alloy
lm, however, a large amount of strain was recovered on unloading under the same
maximum indenter depth as that in the pure Cu lm. Because the maximum indenter
depth is 0.25 m, the maximum strain is 0.5%. This value is much larger than the strain
at the elastic limit, indicating that the large reversible strain on unloading for the CuSn
alloy lm is not mainly due to elastic deformation. Thus, the CuSn alloy lm exhibited
superelastic behavior. It is known that the superelasticity for the CuSn alloy is
attributed to the -CuSn phase, where martensitic transformation occurs [1417]. From
the hardness tests with a Vickers indenter, the hardness was 201 4 Hv for the CuSn
alloy lm and 171 3 Hv for the pure Cu lm, respectively. Therefore, the larger
hardness for the CuSn alloy lm is likely to be attributed to the presence of the -CuSn
phase.
A transmission electron micrograph of the CuSn alloy lm is shown in Fig. 3. The
grains of the CuSn alloy lm were very ne. From measurements with a lot of grains,
the average grain size was 99 nm for the CuSn alloy lm and 115 nm for the pure Cu
lm, respectively. It should be noted that the nanocrystalline CuSn alloy exhibiting
superelasticity was fabricated by electroplating. The TEM-EDX analysis revealed the
presence of the -Cu phase in the electroplated CuSn alloy lm. Therefore, the CuSn
alloy lm consisted of the -CuSn phase and the -Cu phase.
From the DSC experiments, an endothermal reaction due to martensitic
transformation was found in the CuSn alloy lm. The austenite start and nish
temperatures, As and Af, were 259.7 and 265.5 K, respectively. These temperatures for
the CuSn alloy lm are close to or a little higher than those in the previous studies

Fig. 1. The load-displacement curve by the indentation tests with a spherical indenter
for the as-electroplated CuSn alloy lm.

Fig. 2. The load-displacement curve by the indentation tests with a spherical indenter
for the as-electroplated pure Cu lm.

[14,15]. In the thermoelastic martensitic transformation, the free energy balance at one
instance of transformation, GP/M, can be given by [18]
P=M

GP=M Gch Eel Eir

where GP/M
ch is the chemical free energy change on parent to martensite transformation, Eel and Eir are the elastic strain energy and irreversible energy associated with the
friction of the motion of the parent/martensite interface, respectively. The free energy
balance affects the thermodynamical equilibrium temperature which is estimated from
the average of Ms and Af values [19]. It is known that the grain size affects the
martensitic transformation temperature [2023]. Guilemany et al. [21] noted that the
martensitic transformation temperature increases as the grain size decreases because
the interaction between martensite plates and grain boundaries increases the elastic
strain energy which facilitates the nucleation of new plates. On the other hand, Tong
et al. [22] suggested that the martensitic transformation temperature decreases with a
decrease in grain size because the grain boundaries serve as barrier of nucleation of the
transformation. Suzuki et al. [24] showed a signicant lowering of the transformation
temperatures in nanometer crystals compared to those in micrometer crystals because
the difference in transformation behavior between the nanometer crystals and the
micrometer crystals may be related to the transformation nucleation mechanisms.
However, the present work showed that although the electroplating CuSn alloy lm
consisted of the nanometer crystals, its' As and Af temperatures were close to those of
the CuSn alloy whose grain sizes were of the order of micrometers [14,15]. The CuSn
alloy lm consisted of the -CuSn phase and the -Cu phase. Therefore, it is suggested
that the / interfaces play no role as barrier of nucleation of the transformation,
resulting in no signicant lowering of the transformation temperatures, in spite of the
very small grain size, for the electroplated CuSn alloy lm.
For ingot metallurgy process, rapid quenching is needed to produce superelastic
CuSn alloy [1417] because the -CuSn phase is unstable at room temperature.

Fig. 3. A transmission electron micrograph of the as-electroplated CuSn alloy lm.

M. Yuasa et al. / Materials Letters 62 (2008) 44734475

However, the present work demonstrated that the as-electroplated CuSn alloy lm
exhibits superelasticity without any thermal treatments, indicating that the -CuSn
phase is in a metastable state in the as-electroplated CuSn alloy lm. This is because
electroplating tends to cause the nonequilibrium state. In addition, the transformation
temperatures may be controlled by varying the fraction of -Cu phase in the
electroplated CuSn alloy lm.

4. Conclusions
CuSn alloy and pure Cu thin lms were processed by electroplating, and indentation tests and microstructural observation were
conducted. The results are concluded as follows:
1. From the results of indentation tests at room temperature, a large
amount of strain was recovered on unloading in the CuSn alloy
lm, on the other hand, the irreversible strain was very large in the
pure Cu lm. Thus, the as-electroplated CuSn alloy lm exhibited
superelastic behavior.
2. The grain size of the CuSn alloy lm was 99 nm. In spite of the very
small grain size, the As and Af temperatures of the CuSn alloy lm
were relatively high. This is suggested to be related to the presence
of the -Cu phase.
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