Materials Letters 65 (2011) 416419

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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

Effect of temperature on the evolution of diffusivity, microstructure and hardness of

nanocrystalline nickel lms electrodeposited at low temperatures
C.K. Chung , W.T. Chang, C.F. Chen, M.W. Liao
Dep't of Mechanical Engineering, Center for Micro/Nano Science and Technology, National Cheng Kung University, Taiwan 701, ROC

a r t i c l e

i n f o

Article history:
Received 17 September 2010
Accepted 21 October 2010
Available online 28 October 2010
Keywords:
Electrodeposition
Nickel
Hardness
Atomic force microscopy
Diffusion coefcient

a b s t r a c t
Most nickel (Ni) lms galvanostatically electrodeposited at 4050 C exhibited low hardness about 4 GPa and
rough surface. In this article, we have investigated Ni electrodeposition at low temperatures of 520 C in
order to enhance the hardness and smoothness of lms and performed by potentiostatic mode instead of
galvanostatic mode to avoid the low-temperature precipitation of electrolyte agents. Effect of temperature on
the evolution of diffusion coefcient, deposition rate, morphology and hardness was studied. Electrodeposition at low temperature without hard-element addition can reduce diffusion rate and produce the negrain, smooth morphology and dense lm together with compressive residual stress to enhance hardness up
to 6.18 GPa at 5 C. The growth and hardening mechanism of low-temperature electrodeposited Ni were
further discussed in details.
2010 Elsevier B.V. All rights reserved.

1. Introduction
Nickel (Ni) electrodeposition has attracted great interest these
decades and become one popular surface treatment technology for
the coatings or microelectromechnical system (MEMS) application
[1]. High strength and good smoothness are both crucial issues in the
decorative or functional coatings [2]. Two kinds of methods are
commonly used to improve strength of coatings in electrodeposition:
one is performed by pulse voltage and the other is alloyed with hard
elements. Pulse electrodeposition produces ne grains in deposits to
enhance the hardness via HallPetch strengthening [3,4]. The
hardness can be improved from 3.90 GPa by direct-current electrodeposition to 4.87 GPa by pulse electrodeposition [3]. Hardness of codeposited nickelcobalt (NiCo) alloys can be enhanced to 8.72 GPa
by adding 22.53 at.% Co to Ni during electrodeposition [5]. Also, the
compressive residual stress of thin lms from ion bombardment or
thermal annealing can enhance hardness of coatings [6,7]. Electrodeposition performance at low electrolytic temperature generally has
unique properties of low diffusion coefcient, low nucleation rate and
low deposition rate [810]. However, some problem of electrolyte
agent precipitation at low temperature may occur in conventional
galvanostatic electrodeposition. In this article, we have investigated
the potentiostatic electrodeposition at low temperature to enhance
smoothness and hardness of deposits and to eliminate the precipitation problem. Temperature effect on the evolution of diffusion

coefcient, surface morphology and hardness of deposits was

correlated and discussed.
2. Experimental procedures
The Ni lms were electrodeposited on the thin Cr/Au-coated
silicon (Si) substrates at low temperatures of 520 C which were
controlled by a cooling system inside the isothermal container. The Cr/
Au-coated Si(100) wafers were used and diced into 0.5 cm 0.5 cm
chips. Then they were cleaned with acetone and isopropanol in an
ultrasonic bath for 15 min. The Ni was used as the anode, Cr/Aucoated Si as cathode and saturated calomel electrode as reference
electrode. Potentiostatic electrodeposition was employed at a constant voltage of 1 V by potentiostat (Jiehan5000, Taiwan) and
deposition duration was 30 min. The electrolytic composition consisted of nickel sulphamate 450 g/l, nickel chloride 4 g/l and boric acid
40 g/l. The initial pH of electrolyte was controlled at 3.8. The
morphology of deposits was measured by atomic force microscopy
(AFM, Nanosruf Mobile S, Swiss) at a scanning area of 10 10 m2.
Hardness of the deposits was measured by MTS Nano Indenter with
the continuous stiffness measurement (CSM) technique to obtain the
hardness as a function of depth. The hardness values were selected
from the 150200 nm less than 10% of lm thickness to avoid the
substrate effect on lm property.
3. Results and discussion

Corresponding author. Tel.: + 886 6 2757575x62111; fax: + 886 6 2352973.

E-mail address: ckchung@mail.ncku.edu.tw (C.K. Chung).
0167-577X/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2010.10.064

The chronoamperometry method is used for studying the diffusion

behavior of ions during Ni electrodeposition at various electrolytic
temperatures by recording the evolution of current with time. Fig. 1

C.K. Chung et al. / Materials Letters 65 (2011) 416419

(a) and (b) shows the current (I) vs. deposition time (t) curves and I
vs. t 1/2 curves, respectively, in chronoamperometry whose potential
is stepped up from open circuit to 1.3 V at which reduction of nickel
ions proceeds. The magnitude of current is linked to the diffusion
coefcient (D), bulk concentration (C0), surface area (A) of electrode
and time (t), and can be governed by Cottrell equation below [11].

it =

nFAD1=2 C0
1=2 t 1=2

where n is the number of electrons and F is the Faradic constant. The

current initially rises to a maximum peak current (Imax) at a specic
critical time (tmax). It corresponds to either growth of new phase or
the number of nuclei. Formation of each nickel nucleus has individual
diffusion zone and overlap of these zones results in a maximum
current at tmax which is characteristic of nucleation and growth. The
shifting of peaks to longer time at low temperature reveals that the
prolonged time is required for overlapping the localized diffusion
zones. It indicates that the nucleation and growth rates decrease at
low temperature [9,10]. The current does not decline much after
rising to peak. It is because nickel subsequent replenishment at
the electrode surface is high enough to compensate consumption
[12]. The diffusion coefcient can be obtained by substituting all
known parameters into the calculated slope of I t 1/2 curves i.e.
nFAD1=2 C

slope = 1=2 0 .
The values of calculated slopes (A s1/2) at 5, 10, 15 and 20 C are
0.0006, 0.0015, 0.0022 and 0.0024, respectively. Thus the
corresponding diffusion coefcients are 0.31 10 8, 0.77 10 8,
1.13 10 8 and 1.23 10 8 cm2/s, respectively, as listed in Table 1.
It decreases with decreasing electrolytic temperatures. The lower
diffusion coefcient at low temperature leads to the lower reduction
current. The estimated current densities at 5, 10, 15 and 20 C are
4.377 0.139, 6.629 0.323, 9.371 0.323 and 11.200 0.323 mA/
cm2, respectively. Reaction current in electrodeposition corresponds
to deposition rate. High current density leads to high deposition rate
as listed in Table 1. Low-temperature electrodeposition produces
relatively low deposition rate due to limited mass transfer and may
vary in characteristics of deposits.
Fig. 2(A) shows AFM images (a)(d) of the Ni lms at 5, 10, 15 and
20 C, respectively. The morphology of lm at low temperature is
smoother than that at high temperature. Smooth morphology of the
lm at 5 C (Fig. 2(A-a)) has compact clusters all over the scanning
area. Moreover, Fig. 2(A-bd) show rough morphologies with much
larger clusters arrangement. The average roughness of deposits at 5,
10, 15 and 20 C are 30.43, 66.17, 78.62 and 76.43 nm, respectively.
The lowest roughness is achieved at 5 C and it drastically increases at
1020 C due to high growth rate for large clusters. These Ni lms are
polycrystalline with three distinct diffraction peaks of Ni(111), (200)
and (220) planes in X-ray diffraction patterns which is similar to that

417

Table 1
Characteristics of Ni lms by electrodeposition at low temperatures of 520 C.
Temperature
(C)

Current
density
(mA/cm2)

Deposition
rate (m/min)

Diffusion
coefcient
(cm2/s, 10 8)

Hardness
(GPa)

5
10
15
20

4.377 0.139
6.629 0.323
9.371 0.323
11.200 0.323

0.087 0.017
0.147 0.029
0.170 0.034
0.223 0.045

0.31
0.77
1.13
1.23

6.18 0.46
5.30 0.33
4.21 0.55
4.01 0.40

by DC galvanostatic electrodeposition at 50 C [5]. The mean grain size

of the polycrystalline lms can be calculated from the well-known
Scherrer's Formula (t = B 0:9
cos b , where B represents full width at half
maximum (FWHM) of GIXRD patterns in radian, b is 2 of the peak in
radian, and is the wavelength of X-ray in Angstrom or nm). The
calculated mean grain sizes of Ni lms from the primary Ni(111) peak
at 5, 10, 15 and 20 C are about 23.4, 24.7, 24.9 and 25.4 nm, respectively, which decreases with decreasing temperature. It is consistent
with AFM result that the smaller grain size favors for smooth morphology. Fig. 2(B) shows the loaddisplacement curves of Ni lms at
temperatures of 520 C using CSM nanoindentation. The indentation
depth is xed at 1000 nm. Therefore the hard deposit with greater
ability against plastic deformation leads to higher imposed loading
than the soft one. The imposed loading at the maximum indented
depth at 5, 10, 15 and 20 C are 128.6 N, 102.3 N, 93.0 N and
90.2 N, respectively. It indicates that hardness of deposit can be
enhanced at lower temperature. The average hardnesses of deposits at
5, 10, 15 and 20 C are 6.18, 5.30, 4.21 and 4.01 GPa, respectively, as
listed in Table 1. Note that hardness of pure Ni lms is in the range of
3.904.87 GPa [1] and NiCo alloy lms are around 8.72 GPa [5]. It
indicates that hardness of Ni lms can be much enhanced by lowtemperature electrodeposition without hard-element addition. The
hardness enhancement is attributed to the thermal-induced compressive residual stress as well as dense microstructure. The dense
microstructure at low temperature (Fig. 2(A-a)) results from electrocrystallization with heterogeneous nucleation. It has lower defects to
enhance the resistance of plastic deformation for higher hardness
compared to that at high temperature.
Fig. 3(A) shows the schematic heterogeneous semi-spherical
nucleation with a wetting angle () at the cathode surface in liquid
electrolyte. The cathodenucleus (CN), nucleusliquid electrolyte
(NL), and cathodeliquid electrolyte (CL) interfacial energies are
represented by vectors. The surface tension force balance in the plane
of at surface can be expressed below:
CL = CN + NL cos :

The phase transformation i.e. liquid solution to solid phase will

occur when free energy change (G) has a negative value. Assume

Fig. 1. (A) The current (I) vs. deposition time (t) curves and (B) I vs. t 1/2 curves of electrodeposited Ni lms at 520 C by chronoamperometry method.

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C.K. Chung et al. / Materials Letters 65 (2011) 416419

Fig. 2. (A) AFM images and (B) loaddisplacement curves of Ni lms deposited at 520 C.

each nucleus has a mean radius r. The model of heterogeneous semispherical liquidsolid phase transformation can be modied from
homogeneous spherical one as shown in Fig. 3(B). The scheme
displays the free energy change of homogeneous spherical nucleation
vs. embryo/nucleus radius curves together with volume free energy
and surface free energy at both high and low temperatures, respectively, as well as the critical free energy change (G*) and the
critical nucleus radius (r*). The total free energy change (G) is equal
to the sum of two contributions of volume free energy and surface free
energy. In the case of heterogeneous semi-spherical nucleation (Fig. 3
(A)), the shape factor S() should be added and presented as [13]
G =



4 3
2
r Gv + 4r S:
3

The values of S() are approximately from 0.01 to 0.5 for angles of
30 to 90.
According to Eq. (3), G corresponding to the rst term (Gv is
negative) decreases with r3. And the second term of 4r2 is positive
and increases with r2. Thus, the total free energy change increases
rst, reaches a maximum (i.e. G* at r*) and then decreases. Both of
the critical radius (r*) and the activation free energy (G*) decrease
with decreasing temperature i.e. G*H N G*L and r*H N r*L. That is, more
nuclei are formed at low temperature [13]. The increased nuclei at low
temperature favor for the formation of ne-grain lm. Therefore, the
compact deposits with ne grains can be obtained at low temperature
and it is benecial for hardness enhancement.
Moreover, the compressive residual stress of lms from both the
internal microstructure and external thermal effect can also enhance

hardness of coatings. The internal residual stress induced by ne

grains is more compressive than that by coarse grains because of the
denser arrangement between atoms in lms. The other external
residual stress is from thermal stress which can be estimated by the
E

f
formula, th = 1
T, where Ef (300350 GPa from indentaf
tion data) and vf (~0.30) are the Young's modulus and Poisson's ratio
of lms, respectively. T and are the difference in temperature and
coefcient of thermal expansion (CTE) between the lms and substrate. The CTE of lms (Ni, 13 10 6 C 1) is higher than substrate
(Si, 2.6 10 6 C 1). Both the lm and substrate shrink at lowtemperature electrodeposition and expand from low temperature to
room temperature after deposition. The magnitude of Ni expansion is
higher than Si due to higher CTE and thus the lms are constrained
onto the substrate with a compressive residual stress. The calculated th is small, around 22 MPa (for 20 C) to 104 MPa (for 5 C).
Therefore, the dense-microstructure-induced internal residual stress
is much more important than external thermal stress. The residual
compressive stress tends to against the external loadings for
hardening. The compressive thermal stress from the dense microstructure at low temperature causes the higher hardness. Therefore,
low-temperature electrodeposition is favorable for enhancement of
Ni deposits hardness due to the smooth dense morphology and
compressive residual stress.

4. Conclusions
The characteristics and hardening of Ni lms in low-temperature
electrodeposition have been investigated. Chronoamperometry is

Fig. 3. (A) The schematic heterogeneous semi-spherical nucleation at the cathode surface within liquid electrolyte and (B) the schematic free energy change vs. embryo/nucleus
radius curves of homogeneous spherical nucleation at both high and low temperatures together with the critical free energy change (G*) and the critical nucleus radius (r*).

C.K. Chung et al. / Materials Letters 65 (2011) 416419

used for studying the diffusion coefcient. The diffusion coefcient,

reduction current and deposition rate decrease with decreasing temperature. Smooth and dense lms can be obtained at low temperature
of 5 C due to low deposition rate. The compressive residual stress is
generated in lms after low-temperature electrodeposition. Both
smooth dense morphology and compressive residual stress of deposit
at low-temperature electrodeposition enhance hardness up to
6.18 GPa at 5 C.

Acknowledgement
This work is partially sponsored by National Science Council under
contract No. 99-2221-E-006-032-MY3.

419

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