DOI: 10.

1021/cg9004888

Growth Kinetics of Nickel Crystals in Nanopores

Cuiyan Yu, Yanwu Xie,*, Tao Xu, Yan Chen, Xiaohong Li, Wei Li, Baoting Liu, and
Xiangyi Zhang*,

2009, Vol. 9
38403843

State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, 066004
Qinhuangdao, P. R. China, and College of Physics Science and Technology, Hebei University, 071002
Baoding, P. R. China
Received May 4, 2009; Revised Manuscript Received June 21, 2009

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ABSTRACT: The well-controlled synthesis of perfect and homogeneous nanowires requires a fundamental understanding of their
growth kinetics. In the present study, we succeeded in studying for the first time the growth kinetics of electrodeposited Ni crystals in
nanopores by employing the temperature-dependent rate constants yielded from deposition current-time curves. A small growth
-1
activation energy Ea = 0.25 ( 0.01 eV and prefactor t-1
are determined for the Ni crystals in 25 nm diameter pores, and
E,0 = 4.5 ( 0.3 s
they increase with the pore diameter following the Meyer-Neldel compensation rule. On the basis of these studies, the growth
mechanism of electrodeposited Ni nanowires has been revealed.
Crystal growth is one of the most intensively studied topics in
materials science and solid-state physics because many technological systems in the fields of information, communication, energy,
transportation, etc., depend on the availability of suitable crystals
with tailored properties.1 A substantial progress has been made in
the science and technology of crystal growth, and the basic
mechanisms of crystal nucleation and growth are now understood at atomic/molecular levels for bulk and thin film systems,
which enables a well-controlled synthesis of these materials.1-4
Recently, with the rapid development of nanotechnology, a great
deal of interest has been generated in the well-controlled synthesis
of nanocrystals at the nanoscale level in order to produce
nanostructured materials with excellent and tunable functional
properties.5-11 A profound understanding of the growth kinetics
(e.g., growth activation energy and prefactor) of crystals in
nanoscale spaces is crucial for yielding well-controlled perfect
and homogeneous nanowires, which are of particular importance
for fabricating nanodevices with excellent functional properties.
Previous studies on the growth mechanism of nanowires have
been dominantly focused on the thermodynamic processes and
the kinetic studies are limited and mostly focused on the growth of
nanowires yielded by the vapor-liquid-solid route, in particular
the growth of Si nanowires.8-10 Although the electrodeposition
technique has been proven to be one of the most successful
approaches to produce various nanowires with controlled length,
diameter, and growth orientiation,12,13 the growth kinetics and in
particular the microscopic growth mechanism of electrodeposited
crystals in nanopores is far less well understood. This is probably
due to the lack of an experimental technique in obtaining reliable
data on crystal growth in nanopores. More recently, the superlattice structured nanowires have been significantly employed to
study the growth mechanism of electrodeposited nanowires.14
Although in principle the growth rate of electrodeposited crystals
is proportional to the current because the total amount of
substance being converted is proportional to the amount of
charge, hydrogen evolution also consumes charge and makes
it difficult to identify the growth rate of deposited crystals
exclusively.15 Here, in the exemplary case of Ni crystals, we
demonstrate for the first time that the growth kinetics of electrodeposited crystals in nanopores can be experimentally determined
by employing the temperature-dependent rate constants yielded
from deposition current-time curves. This methodology can be
further extended to the study of growth kinetics of other metal
*Corresponding author. E-mail: xyzh66@ysu.edu.cn (X.Z.); xieyanwu@
ysu.edu.cn (Y.X.).
pubs.acs.org/crystal

Published on Web 07/09/2009

and semiconductor systems in nanopores and thus is of wide

interest.
In the present study, the Ni crystal was used as model system
because it is a simple and typical crystal with well-obtained
knowledge of growth processes at the macroscopic scale.
The deposition of Ni was performed in a homemade threeelectrode system that was placed in a temperature-controlled
chamber with a precision of ( 0.1 C, where the pure Ni plank
and a standard calomel electrode (SCE) were used as the counter
electrode and the reference electrode, respectively. The two-step
anodization technique was employed to prepare porous alumina
templates (PATs) with different pore diameters d 25, 40, and
160 nm and a thickness of 700, 600, and 500 nm, respectively. A
Cu film with a thickness of 100 nm was deposited on one side of
the PATs and served as the cathode electrode by employing a
thermal evaporation approach. The electrolyte was made of
1.3 M NiSO4 3 6H2O and 0.6 M H3BO3. Deposition experiments
were performed at a constant potential of -1.0 V (versus SCE) in
the temperature range from 273 to 288 K, and the current-time
curves were measured using a computer-controlled recording
system with a time resolution of 1
10-1 s. All deposition parameters used in the present study were experimentally determined
by considering the application of the present methodology and
the time needed to perform deposition experiments. The pore
diameter and thickness of PATs were determined using a XL
S-FEG scanning electron microscope (SEM). The microstructure
of deposited nanowires was studied by employing a Rigaku D/
max-2500 X-ray diffractometer (XRD) with Cu KR radiation and
a JEM-2010 transmission electron microscope (TEM). For TEM
studies, the PAT was fully dissolved using NaOH (0.5M) solution.
We want to point out here that the quality, uniformity, and
pretreatments of the pure Al sheets used in the present studies as
well as the two-step anodization process of PATs were strictly
controlled in order to eliminate the uncertainties affecting the
pore diameter and pore length of PATs. Moreover, the deposition
of Cu film, electrodeposition processes (in particular the deposition temperature), and the recording of current-time curves were
also strictly controlled so as to eliminate the effect of uncertainties
on the determination of characteristic time tE. For each deposition temperature, more than three repeatable measurements have
been performed to reduce the effects of experimental uncertainties.
At a given potential, under the pseudosteady-state conditions,
the deposition current is directly proportional to the area of the
electrodeposit.16 Therefore, the deposition process of crystals in
nanopores can be directly monitored from the current response.
As shown in Figure 1 (for T = 275.5 K), after the initial transient
r 2009 American Chemical Society

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Communication

Figure 1. Deposition current-time curves measured for electrodeposition of Ni into a porous alumina template (PAT) with 40 nm
diameter pores at a constant potential of -1.0 V at different
deposition temperatures. The insets indicate three stages of the
electrodeposition process (see text). The tE is the characteristic time
indicating the end of the growth process of Ni crystals in the
nanopores (stage I) and can be determined from the current-time
curves (see this figure, T = 275.5 K).

decrease of deposition current, the current-time curve of the

deposition of Ni into the PATs presents three distinct regions.
Region I corresponds to the growth of Ni crystals in nanopores
yielding Ni nanowires. A rapid increase in deposition area occurs
as the nanopores are completely filled with Ni crystals and the
electrodeposit begins to form hemispherical caps over the end of
each nanowire (region II), which leads to a continuous increase in
deposition current until these caps coalesce into a film, where the
deposition current presents a constant (region III). In region I,
after an initial transient decrease, the current-time curve presents
a horizontal line, indicating a more uniform growth rate of the Ni
crystals in nanopores. Obviously, the transition point between the
regions I and II, corresponding to which the deposition time is
defined as the characteristic time tE, indicates the end of the
growth process of Ni crystals in nanopores. The variation in the tE
with deposition temperature (see Figure 1) demonstrates a strong
temperature dependence of the growth of electrodeposited Ni
crystals in nanopores.
Given a template, the growth rate of Ni crystals in nanopores is
proportional to the reciprocal of the characteristic time tE. The tE
decreases with increasing deposition temperature T (see Figure 1),
demonstrating a thermal activation process for the growth of Ni
crystals in nanopores. Therefore, the temperature variation of the
rate constants t-1
E can yield direct kinetic information on the
growth of Ni nanowires. According to the Arrhenius equation


Ea
tE-1 tE-1
1
exp
,0
kB T
where Ea is the apparent growth activation energy, kB is the
Boltzmann constant, t-1
E,0 is the prefactor, and T is the deposition
temperature. Linear fits of eq 1 to the data in Figure 2 yield the
values of Ea = 0.25 ( 0.01, 0.70 ( 0.02, and 1.26 ( 0.02 eV and
8
19 -1
t-1
for
E,0 =4.5 ( 0.3, (9.0 ( 0.5)
10 , and (1.0 ( 0.1)
10 s
the growth of Ni crystals in 25, 40, and 160 nm diameter pores,
respectively. The Ea seems to have a linear reduction with the
inverse of the pore diameter 1/d (see the inset in Figure 2). To
confirm this conclusion, Ea data yielded in a wide pore diameter
range are required, which will be performed in the future.
We want to point out here that the initial transient decrease of
deposition current (see Figure 1) is a typical characteristic for
electrodepositing crystals into the nanopores of PATs as demonstrated in previous studies,16-19 which has been attributed to the
mass transport limitation17 or the creation of the diffusion
layer.18 Because this process lasts only a short time as compared

Crystal Growth and Design, Vol. 9, No. 9, 2009

3841

Figure 2. Deposition temperature dependence of the rate constant

t-1
E of Ni crystal growth into the PATs with different pore diameters.
Linear fits to these data according to eq 1 yield the activation energy
Ea and the prefactor t-1
E,0 for Ni crystal growth in the nanopores. The
temperature T0 at the crossover of three Arrhenius plots is the
isokinetic temperature.

Figure 3. Prefactor t-1

E,0 versus activation energy Ea for the growth
of electrodeposited Ni crystals in nanopores. The variation of Ea
with ln(t-1
E,0) follows the Meyer-Neldel compensation rule, from
which the excitation energy kBT0 = 23.9 meV for the Ni crystal
growth is yielded.

with crystal growth in nanopores, it has little influence on the

determination of the characteristic time tE and thus on the
determination of both the Ea and the t-1
E,0.
Usually, if a process in solids involves an activation energy Ea
that is much larger as compared with both the energies of
excitations (e.g., infrared vibrations or phonons) and kBT, a large
number of excitations must be collected for the process to take
place.20,21 By this simple idea, the Meyer-Neldel compensation rule (MNR), which indicates that the prefactor increases
exponentially with the activation energy, has been understood
well.20-24 In the present study, the variation of t-1
E,0 with Ea follows
the MNR (see Figure 3), demonstrating a multiexcitation mechanism for the growth of the Ni crystals in the nanopores.
20,21,23,24
According to the MNR the t-1
E,0 and Ea are given
ln tE-1
,0 C

Ea
kB T0

where C is a constant, the term kBT0 represents the typical energy

of excitations, and the T0 is the isokinetic temperature at which
various Arrhenhius plots cross. A linear fit of eq 2 to the data in
Figure 3 yields kBT0 =23.9 meV and thus T0 = 277 K, which is in

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3842

Yu et al.

Crystal Growth and Design, Vol. 9, No. 9, 2009

good agreement with that yielded from the crossover of the

Arrhenius plots in Figure 2.
Previous study25 show that the frequency distribution function
of the vibrations of Ni crystal has two main peaks, 1 = 5.8 THz
(h1/kB = 278 K, h is the Planck constant) and 2 = 8 THz (h2/
kB = 384 K). Our experimental temperatures are very close to
the excitation temperature of 1, and the phonon energy hv1 =
24 meV is in good agreement with the experimentally determined
excitation energy kBT0 = 23.9 meV. Moreover, a surface vibration with the phonon energy of 24 meV has also been experimentally observed on Ni surface.26 These results demonstrate that the
phonons of Ni lattice vibrations provide the energy necessary to
overcome the energy barrier Ea for the growth of Ni crystals in the
nanopores. The number n = Ea/h1 of phonons21,24 necessary for
Ni crystal growth in 25, 40, and 160 nm pores are calculated to be
10, 29, and 53, respectively.
To understand the activation energies Ea for the growth of Ni
crystals in nanopores, we need to consider fundamental electrodeposition processes: (1) mass transport of Ni2 in electrolyte
outside nanopores, (2) mass transport of Ni2 through electrolyte
inside nanopores to the surface of deposited Ni nuclei, (3) charge
transfer of Ni2 at crystal surface, forming Ni adatoms (Ni*), (4)
mass transport of Ni* on crystal surface, and (5) incorporation of
Ni* into crystal structure. As the processes are sequential, the
rate-limiting step is the slowest process with the energy barrier Ea.
The process (1) would not be the rate-limiting step because the
activation energy for the mass transport of Ni2 in water is 0.2
eV,27 much lower than our measured values (see Figure 2).
Previous studies show that the ability of mass transport of metal
ions in nanpores decreases with decreasing pore size,19 opposite to
the present experimental results, suggesting that process (2) is also
not the rate-limiting step. Charge transfer is not believed to be
the rate-limiting step for the growth of the Ni crystals in nanopores because an exchange current density in the order of 1

10-4 Acm-2 was experimentally determined at 278 K in the
present work (not shown here), several orders of magnitude
larger than those (1
10-10 to 1
10-6A cm-2)28-30 measured
in electrodeposited Ni in macroscale from the similar Ni/NiSO4
system, implying a very fast charge transfer for Ni crystal growth
in the nanopores. The energy barrier for process (5) is expected to
be small because no bonds will be broken.10 Therefore, the mass
transport of Ni* on crystal surface is the most likely mechanism to
limit the growth of the Ni crystals in the nanopores. This
conclusion is supported by above results that the phonons of Ni
lattice vibrations provide the energy necessary to overcome the
energy barrier Ea for the growth of Ni crystals in nanopores,
which is strongly relative to the mass transport of Ni* on crystal
surface. This is further strengthened by following discussions.
The Ni nanowires deposited in 25 nm diameter pores have a
single-crystal characteristic with a [110] growth direction (see
Figure 4a), a two-dimensional layer growth mechanism is, therefore, expected and the activation energy of mass diffusion should
be close to that of the intrinsic diffusion on the Ni (110) crystal
face. The activation energies of intrinsic Ni* self-diffusion on
(111), (100), and (110) faces are calculated to be 0.06, 0.68, and
0.39 eV, respectively.31 A value of Ea 0.31 eV for Ni* selfdiffusion on the (110) face was also experimentally determined.32
Taking into account that adatom interactions generally reduce
the Ea by tens of millielectronvolts,33 the measured value
Ea =0.25 eV in the present study is in satisfactory agreement with
the intrinsic self-diffusion activation energy on the Ni(110) face.
With increasing the pore diameter, the Ni nanowires gradually
change into a polycrystalline structure (see panels b and c in
Figure 4), indicating that the two-dimensional layer growth
behavior is violated. This makes the surface of deposited crystals
imperfect with kinks, steps, and terrace vacancies that can act as
sources or sinks for mobile adatoms, and thus causes the surface
mass diffusion deviate from the intrinsic diffusion and increases

Figure 4. XRD spectra of Ni nanowires electrodeposited into the

PATs with different pore diameters at a temperature of 278 K. The
nanowires deposited in 25 nm diameter pores show a single-crystal
characteristic, which is further confirmed by TEM and the selectedarea electron diffraction (ED) studies [see (a)], whereas those
deposited in 40 and 160 nm diameter pores show a polycrystalline
nature [see (b) and (c)]. Some ED points in the inset in (a) are
elongated, which is attributed to the existence of defects, e.g.,
dislocations and stacking faults in the deposited nanowire, and thus
leads to crystal imperfections.36,37

the Ea.34 This qualitatively explains our experimental results in

Figure 2. Moreover, an extrapolation of the Ea-1/d curve to the
unconfined situation (1/d = 0) yields Ea =1.44 eV (see the inset in
Figure 2). This value is comparable to that Ea = 0.87-1.69 eV
determined for the surface mass diffusion of bulk Ni.34,35
In summary, the present studies on the electrodeposited Ni
nanowires demonstrate that the growth kinetics of deposited
crystals in nanopores can be experimentally determined by
employing the temperature-dependent rate constants yielded
from deposition current-time curves. This technique is universal
and can be applied to other metal and semiconductor systems for
understanding their growth kinetics in nanopores and thus of
wide interest. Moreover, the present studies provide unique
insights into the microscopic growth mechanisms of electrodeposited Ni crystals in nanopores and therefore are of importance
for future studies of high-quality magnetic nanowires.
Acknowledgment. We are indebted to the NSFC (50525102,
50671090, 50871095, and 50821001) and the National Basic Research Program (2005CB724404) of China for financial support.

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