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CuO nanowire growth on Cu2O by in situ thermal

Cite this: CrystEngComm, 2013, 15,
oxidation in air
8559
Ang Li, Huaihe Song,* Jisheng Zhou, Xiaohong Chen and Siyuan Liu

Received 1st June 2013,
Accepted 30th August 2013
DOI: 10.1039/c3ce40985f
www.rsc.org/crystengcomm
CuO nanowires were synthesized by in situ thermal oxidation of Cu2O for the first time in the temperature range
of 300750 C in air. In this process, the effects of annealing temperature and growth time on the growth of CuO
nanowires were investigated by SEM, XRD, EDS mapping and line-scan profile measurements. We found that the
nucleation of CuO nanowires is a solid-state transformation process, and the nanowire length obeys a parabolic
law with annealing time. The nanowire growth shows a diffusion-controlled behavior. Based on the above-
mentioned study, the mechanism of the nucleation and growth of CuO nanowires from Cu2O is proposed.

1. Introduction have focused on the growth mechanism of oxide nanowires,

Metal oxide nanowires, especially transition metal oxides,
have attracted many attentions because of their unique prop-
erties and extensive applications in catalysis,1 semiconductor
devices,2,3 gas sensing,1,4 field emission5 and energy stor-
age.69 Further exploitation in practice needs pragmatic prep-
aration methods, so scientists have developed some synthesis
approaches, like vapor phase growth,10,11 wet-chemical method,9
electrochemical method,12,13 hydrothermal method,14 and ther-
mal oxidation method.1517 Among the various approaches, in
situ thermal oxidation is considered as a superior way because
it can generate not only nanowires with large-scale and
aligned patterns, but also controlled-morphology conveniently
and at low cost by just annealing the precursors in oxygen or
ambient atmosphere. The first report noticing the growth of
metal oxide nanowires was brought about by Tylecote18 when
he investigated the mechanism of copper oxidation at high
temperature in pure oxygen in 1952. However, studies focus-
ing on the growth of metal oxide nanowires might begin with
Jiang's19 work when they heated the copper grids in air to
obtain high-density aligned CuO nanowires. Since then, in situ
thermal oxidation has been used to synthesize oxide
nanowires from other metal elements, like zinc,17 iron,20 tung-
sten,21 cobalt16 and so on. It is necessary to point out techni-
cally that the in situ thermal oxidation here was carried out
below the melt point of the metal. Having an insight into the
mechanism of in situ thermal oxidation may help to obtain
optimal products for different applications. Many investigations
State Key Laboratory of Chemical Resource Engineering, Key Laboratory of
Carbon Fiber and Functional Polymers, Ministry of Education, Beijing University
of Chemical Technology, Beijing, 100029, PR China. E-mail: songhh@mail.buct.
edu.cn; Fax: +86 10 64434916; Tel: +86 10 64434916
Electronic supplementary information (ESI) available. See DOI: 10.1039/
c3ce40985f
especially CuO nanowires, the most representative ones. Sev-
eral typical models were proposed to discuss the growth
mechanism of CuO nanowires.19,2227 In these models, stress-
induced short-circuit diffusion with the most evidence is con-
sidered as the outstanding one. However, it is still unknown
whether the oxidation intermediate, the Cu2O layer, plays a
role in the growth of CuO nanowires, though Kaur et al.24 and
some other groups38 have conjectured that the existence of
Cu2O is of no use, only an inevitable phenomenon in the oxi-
dation of copper.
Here, we report a wholly new phenomenon that the CuO
nanowires can be synthesized by in situ thermal oxidation of
Cu2O in air. The novel precursor for preparing CuO nano-
wires will expand the types of starting materials of in situ
thermal oxidation. On the other hand, CuO nanowire growth
was observed on the oxidized Cu2O, indicating that the for-
mation of Cu2O is related to the growth of nanowires during
the in situ thermal oxidation of pure Cu; this will bring inspi-
ration to find an insight into the growth mechanism of metal
oxide nanowires.
2. Experimental
The pure Cu2O powder (metal basis purity of 99.9%, powder
size 10 m, Shanghai Qinxiang Chemical Co., Ltd.) was used
as starting material. The Cu2O powder was firstly compacted
to form discs under 15 MPa pressure, then placed in an alu-
mina boat (60 mm 30 mm 15 mm) and loaded in a box
furnace, and annealed at 300800 C for 6 h under air atmo-
sphere and ambient pressure. The heating rate was kept at
~10 C min1. The annealing time also varied in the time
span of 212 h to investigate the influences of annealing time
on the growth of CuO nanowires. The annealed samples were
characterized by scanning electron microscopy (FE-SEM;

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Hitachi S-4700), high-resolution transmission electron micros-
copy (HRTEM; JEOL JEM-3010F), energy-dispersive X-ray spec-
troscopy (EDS; attached to SEM), X-ray diffraction (XRD;
Rigaku D/max-2500B2+/PCX system with CuK = 1.5406 ,
2 = 590), and thermogravimetric analysis and differential
scanning calorimetry (TGA and DSC; Netzsch STA 449C).
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3. Results and discussion
Fig. 1a and b show the SEM images observed in different
areas of the same sample annealed at 600 C. Two types of
oxide substrates, the flat areas and the semi-cylindrical protu-
berances, can be seen in the SEM images. The nanowires in
the two areas are of almost the same appearance, but quite
different density with sparse nanowires growing at flat area,
while exuberant on the protuberance. The possible reason
why the growth density of CuO nanowires is so different in
the two areas will be given in the following discussions. In
Fig. 1c, the average length and diameter of CuO nanowires
are calculated and plotted as functions of growth time, and
the inset images correspond to the CuO nanowires growing
at 2, 4 and 6 h from left to right, respectively. It can be seen
from Fig. 1c that both length and diameter are positively
correlated with growth time before 6 h, after that the param-
eters change over into a flat trend, which is roughly in
accordance with the mass variation in the oxidation process
for Cu2O slices.
Fig. 2 shows the XRD pattern of a Cu2O slice annealed at
600 C for 6 h in air, whose value is quite in agreement with
the CuO standard spectrum (small blue blocks, PDF#80-
1916). Hence, we consider that Cu2O has been converted into
CuO completely and nanowires growing on the substrate are
composed of CuO with a monoclinic structure. The EDS spec-
trum of a selected area on a single nanowire is also
Fig. 1 SEM images of sample annealed at 600 C for 6 h taken from: (a) the flat
area, (b) the semi-cylindrical protuberance; (c) nanowire lengths and diameters as
functions of growth time (insets show the SEM images of CuO nanowires at the
pointed times).
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Fig. 2 XRD pattern of the Cu2O slice after oxidation at 600 C for 6 h in air (inset
shows the EDS spectrum of a selected area on a single nanowire in the
red rectangle).
performed, and the result shown as an inset in Fig. 2 shows
that Cu and O are the only elements on the selected nanowire
without any other impurities, and the atom number percent-
age of each element is 51.31% and 48.69% for Cu and O
respectively, which also indicates that the nanowires are of
CuO phase.
A further investigation of the structure and crystallography
of the as-grown nanowires was carried out by HRTEM. Fig. 3a
shows a single CuO nanowire peeled off from the substrate
by collodion, and we can see that the nanowire has smooth
surfaces and a uniform diameter of 170 nm or so. The
detailed information of the microstructure is illustrated in
the HRTEM image (Fig. 3b) and its fast Fourier transform
(FFT) pattern (Fig. 3c). It can be concluded that this nanowire
is monocrystalline CuO and its growth direction is along
[010]. In Fig. 3b, lattice fringes of two growth directions can
be observed clearly, their interplanar spacings are 3.175
and 2.765 , corresponding to the directions of [101] and
Fig. 3 (a) TEM image of a single CuO nanowire; (b) enlarged HRTEM image of the
selected area in TEM image and (c) the FFT pattern of image (b).
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[110], respectively. The FFT also shows that the interplanar
spacings in the directions of [020] and [111 ] are 1.690 and
2.535 , respectively, which are all in good agreement with
the data for monoclinic CuO.
Copper has two common thermodynamic oxides, CuO and
Cu2O, which can reciprocally transform in different tempera-
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nanowires formed on Cu2O by in situ thermal oxidation, and
in analogy to the mechanism of CuO nanowires growing
directly on pure copper, we propose that the nucleation of
CuO nanowires is a process of solid solution precipitation,
and the nanowire growth is driven by short-circuit diffusion.
To have a better understanding of the kinetics of nucle-

ture ranges in the presence of oxygen.28 Under standard
atmosphere, CuO in conditions above about 1000 C will
become unstable and decompose into Cu2O and oxygen, and
in the same atmosphere below 900 C, Cu2O will be oxidized
into CuO. The mechanism of the oxidation process of Cu2O
has been extensively studied.2931 The growth of the CuO layer
can be described as the following: at the oxygen/CuO inter-
face, the oxygen is first chemisorbed on the surface of the
oxide scale, then attracts an electron from the Cu2O lattice
site with an electron hole to emerge. And a fully ionized
oxygen will be embedded on the surface by reacting with an
Cu2+ ion to form a CuO molecule, accompanied by a Cu
cation vacancy and another electron hole being created.
Therefore, the reaction occurs at oxygen/CuO interface can be
represented as follows:32
1
O2 CuO 2h V2
Cu 1 activation energy for atomic migration per CuO molecule,
2 here ECuO = 46.652 kJ mol1, and its determination details are
ation of CuO nanowires, we performed a statistical analysis
on the growth densities of nanowires, as illustrated in
Fig. 4a. First, the nucleation densities of nanowires were
investigated by measuring the density of nanowires as a func-
tion of annealing temperatures (annealing times are all 6 h).
At this condition, the nucleation rate I, or the flux of embryos
at a certain time through unit area at critical size n*, can be
expressed as36,37
 
DG ECuO
I Z N exp a
3
kT
where * is the frequency factor, representing the frequency
of one more additional molecule entering a critical nucleus;
N is the number of nucleation sites per unit area; ECuO
a is the
a

Where h+ represents an electron hole with an effective posi-

tive charge and V2
Cu is a cation vacancy having a negative
charge of 2e. The Cu cation vacancies and the electron holes
forming at the oxygen/CuO interface diffuse inward across
the CuO layer, and are finally annihilated at the CuO/Cu2O
interface. A molecular Cu2O accepts a cation vacancy and an
electron hole and transforms into a CuO molecule, in accor-
dance with the reaction:30,32

Cu2 O 2h V2
Cu CuO 2

Then we can conclude that the CuO layer occurred at both

the oxygen/CuO and CuO/Cu2O interfaces growing at the
same growth rate,32 and the rate determining step of the
CuO formation is the outward diffusion of Cu2+ cations.
The growth of nanowires can usually be explained by a
vaporsolid (VS) or vaporliquidsolid (VLS) mechanism.
Compared with CuO, Cu2O possesses a lower melting point
(Cu2O 1232 C, CuO 1326 C), the growth of CuO nanowires
occurs in a relatively low temperature range, in which the
vapor pressure of the oxide is negligible (even at 800 C the
vapor pressure of CuO is just 1.15 104 mmHg).33,34 There-
fore it cannot be ascribed to these mechanisms. Recently,
many reports have been issued to discuss the growth mecha-
nism of CuO nanowires formed by the in situ oxidation of
pure copper. A series of mechanisms were proposed, of
which the stress-induced diffusion process supported by the
more experimental evidences was considered as the most
promising one.27,35 Though these newly founded mecha-
Fig. 4 (a) CuO nanowire density as a function of annealing temperature (blue
nisms can explain the nanowire growth, they do not give the hollow dots) and the fitting result with eqn (6) (dash line). (b) Square of the length
origin of the nanowires, i.e., the nucleation of the CuO of CuO nanowires for the sample oxidized at 600 C versus the annealing time
nanowires. In order to elucidate the mechanism of CuO (blue boxes) and the resulting fit with eqn (7) (red line).

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displayed in Fig. S1; k is the Boltzmann's constant and T is
the annealing temperature; Z is called the Zeldovich non-
equilibrium factor, which corrects, among other things, for
the fact that some nuclei with the critical size still decay to
smaller sizes, and is by definition36
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 1=2
1 2 G
Z j
2kT n2 nn
G is the free energy of forming a nucleus with a radius of r
containing n molecules, which can be expressed as37
G n 4r 2
It is the sum of two terms: the driving force of nucleation,
n, where is the free energy change associated with the
transformation reaction, and the surface energy 4r2, where
is the interfacial tension. As the annealing time is deter-
mined, the density of the nanowires is proportional to the
nucleation rate.38 Then we fit the density of nanowires PNW
as a function of temperature with the model of steady-state
nucleation on the basis of eqn (3)
 
T C T 1=2 

P NW exp T C T ECuO =kT
T a
TC is the critical temperature for the growth of CuO
nanowires, is a proportional constant. The details of the
derivation of eqn (6) see the ESI. As illustrated in Fig. 4a,
the density of the nanowires keeps increasing and reaches a
maximum value at ~650 C, then exhibits a sharp decline
from 650700 C; after 700 C, nanowires hardly ever form
even with prolonging the annealing times or raising the tem-
perature. It can be seen that the model can explain the exper-
imental data precisely, so we conclude that CuO nanowire
nucleation is determined by the process of solid solution pre-
cipitation under steady-state nucleation circumstances.
We also analyzed the growth data of the CuO nanowires.
As illustrated in Fig. 1c, the lengths of the nanowires arising
Fig. 5 (a) The electronic image of a single nanowire and its corresponding EDS mappings of (b) O and (c) Cu. (d) EDS line-scan profile for Cu (azure) and O (red) along the
yellow line on the nanowire (the same one as shown in (a)).
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at 600 C exhibit a parabolic trend in the kinetic period
from ~2 h to 6 h. In Fig. 4b, we plot the square of the
length of CuO nanowires for the sample oxidized at 600 C
versus the annealing time. The curve presents a quite near-
linear dependency, indicating that the CuO nanowire
growth is determined by the migration of Cu2+ ions, or dif-
fusion-controlled. The data in Fig. 4b can be fitted to the
4
parabolic kinetic equation:
L2 kt 7
Where L is the length of nanowires, t is the annealing time,
and k is the parabolic rate constant.
5
In order to set up an intuitive image on the diffusion of
the Cu cations and the distribution of each element involving
the nanowires growth, we also performed EDS mapping and
a line-scan profile, as illustrated in Fig. 5. In Fig. 5b and c,
the dispersions of Cu and O are revealed, in which the atom
number percentages are 51.31% and 48.69% respectively.
Moreover, as the nanowire is a single crystal with few defects
being observed, we speculate that the diffusion species are
the Cu2+ ions with a motion path of surface diffusion. The
data of the line-scan profile in Fig. 5d further confirm this
viewpoint. The copper element on the nanowire is detected
6 strongly at the root and the signal intensity gradually attenu-
ates from root to tip along the yellow line, so we conclude
that there exists a concentration gradient of Cu2+ ions with a
decrease towards the tip, while there is no noticeable varia-
tion of the signal intensity of oxygen. Another evidence of
surface diffusion of Cu2+ ions is that, in the TEM image
(Fig. S2) some inhomogeneous crystallinity can be observed
on the surface of the single crystal nanowire, we suspect that
at the end of the annealing process some of the surface-
diffusional Cu2+ ions could not move to the CuO nanowire
tip to incorporate onto the existing crystal of the nanowire,
but terminate halfway on the sidewall and precipitate with
the oxygen in air to form the inhomogeneous crystal on the
surface of the nanowires.
Now we discuss the aforementioned phenomenon that
CuO nanowires densities become so different in the flat areas
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Fig. 6 Schematic view of the mechanism for CuO nanowire growth on Cu2O.
and the semi-cylindrical protuberances. Since CuO and Cu2O
belong to different crystal systems and have different crystal
lattice parameters (CuO is monoclinic system with cell =
4.684 3.423 5.129 , = 99.54; Cu2O is cubic system
with a = 4.270 ), the lattice mismatch between the Cu2O
substrate and the CuO overlayer generates compressive stress
in the oxide scale. As the compressive stress together with
the thermal stress induced during the heating process accu-
mulates gradually, protuberances on the free surface of the
oxide layer is brought into being to release the stress. On the
other hand, the driving force from the stress also advances
the outward diffusion of Cu2+ ions besides the thermal diffu-
sion. The flux of the diffusion species caused by the stress-
induced motion can be expressed as39
CD
J 8
kT
Here C is the atomic concentration, is the atomic vol-
ume, D is the local diffusion coefficient, T is the absolute
temperature, and is the normal stress. Thus, we contend
that the gradient of the stress (including the compressive
stress and thermal stress) will have a strong effect on the out-
ward diffusion of Cu2+ ions. That's why the growth of
nanowires exhibits such a dense state on protuberances
which happen to be in a local region with higher stress. To
further investigate the stress effect on the growth of
nanowires in depth, we performed a contrast experiment by
annealing the Cu slice at 600 C for 6 h in air. The result
shows that the CuO nanowires growing on the Cu slice
appear to be denser and longer than the Cu2O precursor
(Fig. S3). The oxidation of pure copper will form two oxide
layers, Cu2O and CuO, and the stress generated from Cu/Cu2O
and Cu2O/CuO interfaces is much stronger than that from a
single Cu2O/CuO interface,27,35,40 so we deduce that the stress
strongly impacts on the density and the growth rate of CuO
nanowires, but not noticeably on the width.
Based on the experimental data and our analysis, the
growth mechanism of CuO nanowires from Cu2O could be
proposed as follows. At the beginning of the oxidation of
Cu2O, there are microamounts of CuO molecules dissolving
in the Cu2O lattice to form a solid solution (as displayed in
Fig. 6A). While the reaction is proceeding, the solute CuO
becomes saturated and starts to precipitate. The deposited
CuO molecules continue aggregating to form monoclinic
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crystal nuclei, which is in accordance with Fig. 6B. According
to the theory of crystallography, the critical nucleus of mono-
clinic crystalline structure usually presents a rhombic prism
shape, the ends of which are pointed,41 and nuclei with the
specific alignment would develop into nanowires following
the principle of precipitate growth of diffusional transforma-
tions in solids. As the sequential CuO film takes shape, the
growth of the nanowires is controlled by eqn (1) and (2). In
the growth stage of the nanowires, as the foregoing kinetics
of Cu2O oxidation describes, half of the generated CuO grows
out of eqn (2) and the other moiety is owing to eqn (1), with
the outward diffusion of Cu2+ ions occurring mainly through
grain-boundaries. Some of the Cu2+ ions migrating onto the
surface react with oxygen and incorporate into the CuO sub-
strate, while the remainders will keep on moving via surface
diffusion driven by the chemical potential gradient between
the substrate and the nanowire tip to support the growth of
nanowires (as shown in Fig. 6C).
4. Conclusion
In summary, CuO nanowires were obtained by heating com-
pressed Cu2O powder slices in air, and their growth mecha-
nism was also investigated. The effects of growth conditions
on the length, diameter and number density of CuO
nanowires were discussed. The growth mechanism of CuO
nanowires consists of two parts: (a) a nucleation and the
growth process before the continuous CuO layer formed can
be explained by the diffusional nucleation and the precipita-
tion phase growth of solid-state transformation theory; (b)
the growth of CuO nanowires on a continuous CuO scale is
due to the short-circuit diffusion of Cu2+ ions through grain-
boundaries in the CuO scale and on the surface of the
nanowires. Compressive stress plays a very important role on
the growth of CuO nanowires by influencing the diffusion
flux of Cu2+ ions.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (50972004 and 51272019).
Notes and references
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