Journal of Alloys and Compounds 454 (2008) 268–273

CuO nanowires synthesized by thermal oxidation route

J.T. Chen a , F. Zhang a , J. Wang a , G.A. Zhang a ,
B.B. Miao a , X.Y. Fan a , D. Yan a , P.X. Yan a,b,∗
a School of Physical Science & Technology, Lanzhou University, Lanzhou 730000, PR China
b State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics,

Chinese Academy of Sciences, Lanzhou 730000, PR China

Received 21 October 2006; received in revised form 5 December 2006; accepted 6 December 2006
Available online 19 March 2007

Abstract
CuO nanowires were prepared on the copper foil by thermal oxidation in air. The effect of annealing temperature and growth time on the
morphology of the nanowires is investigated. It is found that the annealing temperature and the growth time play an important role in the
morphology of CuO nanowires such as the density, the length and the diameter. The length and the density of nanowires increase with prolonging
growth time; but if the time is too long, CuO crystallite grains form instead of nanowires. Annealing copper foils at lower or higher temperature,
the density of nanowires is lower. For comparison, the Cu films on Si substrate deposited by direct current (dc) magnetron sputtering are oxidized,
but we do not find large-scale of nanowires. The possible mechanism is also discussed for the growth of CuO nanowires.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Thermal oxidation; CuO nanowires; Annealing temperature; Growth time

1. Introduction cations, many methods have been developed to prepare CuO

Since carbon nanotubes were discovered by Iijima [1], nanos-
tructure materials especially one and two dimensional (1D, 2D)
nanomaterials, such as nanowires [2,3], nanorods [4,5], nanorib-
bons [6,7] and nanosheets [8–10], have attracted more attentions.
Nanomaterials possess diminished dimensions, which leads to
diversely outstanding and surprising properties. Owing to their
unique and predictable applications, as nanoscaled building
blocks, they can fabricate the nanoscale electronic devices.
In recent years, cupric oxide (CuO) has been received exten-
sive investigations for its prospective applications in many fields.
CuO is a p-type semiconductor with a narrow band gap of 1.4 eV
[11], and is also an antiferromagnetic material with local mag-
netic moment per unit formula of 0.60 ␮B [12]. CuO has similar
properties with high-Tc superconducting cuprates but consists
of Cu–O bonding only, so it has been used as a basic mate-
rial in high-Tc superconductors [13,14]. It also can be used
potentially in gas sensors, solar cells, FE emitters, electronic
cathode materials and catalysts [15–19]. Based on these appli-
∗ Corresponding author. Tel.: +86 931 8912719; fax: +86 931 8913554.
E-mail address: pxyan@lzu.edu.cn (P.X. Yan).
with various morphologies. Li et al. synthesized nanodendrite-
like CuO via the hydrothermal route [20]. CuO nano-shuttle was
also prepared under surfactant assisted using the same method
[21]. CuO nanorods and nanoribbons were synthesized by wet
chemical methods [7]. In addition, the nanofibers of CuO were
prepared by thermal oxidation on Cu substrate but importing
the polycarbonate membrane template for initial deposition of
Cu nuclei [22]. Methods mentioned above cannot be departed
from complex chemical reactions or process. Thermal oxida-
tion under controlled conditions may assist the production of
catalysts, semiconductor devices, or functional oxide films [23].
The direct and simple thermal oxidation method was employed
to synthesize CuO nanowires and nanorods. Using this conve-
nient route, with no catalyst and template assisted, many research
teams prepared CuO nanowires successfully by oxidizing cop-
per foils under different conditions such as different annealing
temperatures, time or atmosphere [24–27].
In this paper, CuO nanowires were synthesized by heating Cu
foils in air. The aim of the present work is to investigate the effect
of the annealing temperature and the time on the growth of CuO
nanowires; and Cu films prepared by dc magnetron sputtering
were also oxidized for investigating the growth mechanism of
CuO nanowires.

0925-8388/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jallcom.2006.12.032
 J.T. Chen et al. / Journal of Alloys and Compounds 454 (2008) 268–273
2. Experimental details
CuO nanowires were synthesized on Cu foils by thermal oxidation in air
at the temperatures of 300, 400 and 500 ◦ C for different time (0.5, 1, 2, 4, 8
and 24 h). The experiment was carried out on the copper foils with purity of
99.96% and 0.2 mm in thickness. The target with same purity was used to pre-
pare Cu films on Si (1 0 0) substrate by dc magnetron sputtering. Before the
growth of CuO nanowires, the copper foil was cleaned in diluted H2 SO4 solu-
tion to remove the negative oxide and contaminations. Then the foil was washed
in distilled water and absolute alcohol under ultrasonic bath for 10 min, respec-
tively. After dried in air, the foil was loaded in an alumina boat and placed in
the muffle furnace. The temperature was monitored by the thermocouple near
to the foil or Cu films. In all experiments, the heating rate was ∼8 ◦ C/min. After
oxidized, the sample was cooled down to room temperature naturally. And then,
the black and fragile CuO layer was peeled off carefully for characterizations.
The morphology of the samples was investigated by field emission scanning
electron microscope (FE-SEM, Hitachi S-4800) operated at an accelerated volt-
age of 5 kV. The selected area electron diffraction (SAED) was carried out on
transmission electron microscopy (TEM, Hitachi H-600) operated at 100 kV.
The structures of the samples were characterized by X-ray diffraction (XRD,
D/Max-2400X, Rigaku Co., Japan) using Cu K␣ radiation (λ = 1.54056 Å) with
θ–2θ mode ranging from 10 to 80 ◦ C.
3. Results and discussions
CuO nanowires were grown on the Cu substrates by thermal
oxidation in air. At first, the samples were oxidized at 400 ◦ C in
air for different time of 0.5, 2, 4 and 8 h for studying the effect
of the time on the morphology as shown in Fig. 1. It can be seen
from Fig. 1a, a few nanowires with short length of ∼500 nm are
found in the sample annealed for 0.5 h and some protuberances
appear in the surface. The average diameter of the protuberances
is 1 ␮m. When the growth time is prolonged to 2 h (Fig. 1b), more
nanowires with length of 2–3 ␮m can be seen on the surface.
While prolonging the growth time to 4 or 8 h, the length of most
nanowires are in the range of 6–10 ␮m. Besides, the coverage
Fig. 1. The surface morphology evolution of the oxide films on the copper foils annealed thermally at 400 ◦ C in air. The growth time is: (a) 0.5 h, (b) 2 h, (c) 4 h and
(d) 8 h, respectively.
269
area of CuO nanowires on the Cu foils show remarkable devel-
opment, the nanowires become denser which can be observed in
Fig. 1d. We also find that a few nanowires with larger diameter at
the base grown on Cu foils. It could be concluded from Fig. 1a–d
that the growth time has an important influence on the length and
the density of nanowires, but no obvious effect on the diameter.
Whereas, Kumar et al. reported that the growth time had little
effect on the density of nanowires [25]. This may be attributed
to that the growth time that Kumar and co-workers chose was in
the optimal scale. Oxygen ambient for growing CuO nanowires
maybe extends the optimal time scale relatively.
In order to obtain an optimal annealing temperature to prepare
nanoscale CuO wires, the surface morphology of sample pre-
pared at different temperatures were also studied. Fig. 2 shows
the morphology of the samples obtained by annealing Cu foils
at 300 and 500 ◦ C in air for 8 or 24 h. It can be seen from Fig. 2a
that large grains formed on the surface of the sample prepared at
300 ◦ C and the size of diameter reaches to micrometer. No large-
scale of nanowires can be found. Via XRD analysis (can be seen
in Fig. 5), the oxide grains are cuprous oxide (Cu2 O). The inset
of Fig. 2a shows that Cu2 O grain is porous and grain boundaries
can be observed clearly. And there are a few nanowires on the
surface of Cu2 O grains. Fig. 2b shows the overview morphology
of the sample prepared at 500 ◦ C. On the surface of Cu foils, long
valley-like protuberance formed. It is obvious that nanowires
appear on the sidehill and the valley, no nanowires are found
on the hilltop. Fig. 2c shows high magnification morphology of
the valley. Nanowires do not have uniform length and diame-
ter. And the density is low. The maximum length and diameter
reaches ∼10 ␮m and ∼500 nm, respectively. And the diameter
of nanowires reduces gradually from its base to tip. Nanowires
are mostly extruded from the substrate perpendicularly or with
small angles. The higher magnification of nanowires (shown in
270 J.T. Chen et al. / Journal of Alloys and Compounds 454 (2008) 268–273

Fig. 2. The morphology of oxides prepared at different temperatures in air: (a) 300 ◦ C, 8 h; (b and c) 500 ◦ C, 8 h, they show morphology of overview and valley,
respectively; (d) 500 ◦ C, 24 h.

the inset of Fig. 2c) demonstrates that the nanowire is multi-
face with apparent edges. Otherwise, the appearance of product
obtained by heating Cu foil at 500 ◦ C for 24 h is investigated by
FE-SEM method which is shown in Fig. 2d. It is found that no
wires grown on the Cu foil except CuO crystallites.
The structure of the sample obtained by annealing the copper
foil at 500 ◦ C in air for 8 h is further studied by transmission
electron microscopy (TEM). It is shown in Fig. 3. It can be seen
that the single nanowire with diameter of about 300 nm shows
multi-face and the edges are clear. It is consistent with the image
shown in Fig. 2c. The d-spacing of nanowire calculated from
the corresponding SAED pattern (shown in Fig. 3) is indexed to
CuO phase. And the SAED pattern indicates that the nanowire
is monocrystalline with a monoclinic structure.
Fig. 4 shows the plane and cross-section views of the Cu films
and oxide of the Cu films. The Cu films with 1 ␮m in thickness
were oxidized at 400 ◦ C for 1 h in air. From Fig. 4a and b, we
find the film has obvious grain boundaries and column structure.
After oxidization, a few whiskers appeared on the oxide films,
and the column structure disappeared. It can be seen from Fig. 4c
and d.
XRD is a useful method to analyze the structure. The XRD
pattern is collected by θ–2θ mode which can collect the informa-
tion from the inside of materials. Fig. 5 shows the XRD patterns
of the Cu foil and the samples annealed in air for 8 h at 300, 400
and 500 ◦ C. The thickness of the oxide on the Cu foils does not
exceed the detection scale of the X-ray here. It can be seen from
Fig. 5, the Cu foil is polycrystalline with fcc structure and shows
the diffraction peaks (2 2 0), (1 1 1) and (2 0 0). After annealing,
the diffraction peak (2 0 0) becomes the strongest. This demon-
strates that the inner structure and preferred orientation of the
Cu foil changes. The growth of the grain which favoring to low

Fig. 3. Typical TEM image and SAED pattern of single CuO nanowire synthesized by annealing the copper foil at 500 ◦ C in air for 8 h.
 J.T. Chen et al. / Journal of Alloys and Compounds 454 (2008) 268–273 271

Fig. 4. The plane and cross-section views of the Cu films (a and b) and Cu films oxidized at 400 ◦ C for 1 h in air (c and d), respectively.

energy state occurred in the Cu foil coexisting with the oxida-
tion. The oxide is dominated by Cu2 O phase when annealed
at 300 ◦ C. As temperature increasing to 400 ◦ C or 500 ◦ C, the
mixture phase of Cu2 O and CuO appear, and the dominate phase
is CuO. The average crystalline aggregate sizes of oxides were
determined by Scherrer equation from the broadening of charac-
teristic diffraction lines. The sizes of Cu2 O aggregates are 14, 24
and 37 nm, respectively, for the samples annealed at 300, 400 and
500 ◦ C. It can be found that the Cu2 O aggregates increase with
the annealing temperatures. For CuO aggregates, the aggregate
sizes are 18, 29 and 27 nm, respectively, for the samples annealed
at 300, 400 and 500 ◦ C. Fig. 6 shows the XRD of the Cu film.
The Cu film has a preferred growth along the 1 1 1 direction.
The growth mechanism of CuO nanowires remains unclear
and needs to be further studied. The growth of the nanowires has
two famous mechanisms which are vapor–liquid–solid (VLS)
mechanism and vapor–solid (VS) mechanism [28,29]. In VLS
growth process, evidently, there is a catalyst (metal droplet) at
the tip of the nanowires, and the diameter of the nanowires deter-
mined by the size of the metal droplet is uniform from base to tip.
In our experiment, the metal catalyst droplet is not observed at
the tip of nanowires in FESEM or TEM images; and the diameter
of the nanowire is reduced from base to tip (shown in Fig. 2c).
Therefore, the VLS growth mechanism could be excluded. VS
growth process was introduced by researchers to explain the
growth of CuO nanowires [27,30]. In VS process, the key step
is the evaporation of the precursors in high temperature region
and followed by condensing and growing to nanowires in low

Fig. 5. XRD patterns of the copper foil and the copper foils annealed in air for
8 h at 300, 400 and 500 ◦ C. Fig. 6. XRD pattern of the Cu film prepared by dc magnetron sputtering.
272 J.T. Chen et al. / Journal of Alloys and Compounds 454 (2008) 268–273
temperature region. The melting point of Cu and Cu2 O are 1085
and 1243 ◦ C, respectively; the decomposition temperature of
CuO is 1124 ◦ C [31]. But the temperature in our experiment is
far less than the melting points mentioned above. Moreover, the
low and high temperature regions are difficult to distinguish.
Therefore, the VS growth is also not valid. In the viewpoint of
Milton O. Peach, the growth of whiskers occurs as a result of
diffusion along the core of the screw dislocation [32]. In addi-
tion, the Pd oxide hillocks were prepared by oxidizing the Pd
films [33]. The formation of the oxide hillocks leads to the relax-
ation of the internal stress, and the reaction-diffusion proceeds
under the internal stress [33,34]. The energy is stored in a film
or cold-worked metals by the internal stresses [35]. Kumar et
al. reported that the growth of CuO nanowires was the result
of the accumulation and relaxation of the stress in annealing
process [25]. During the annealing, the oxide forms and the
structure of the Cu foil changes. Due to lattice mismatch and
increasing in molecule volume (Cu < Cu2 O < CuO), the com-
press stress is induced in oxide layer. The protuberance on the
oxide layer is brought on to release the stress, and the diffu-
sion of atoms is driven by the compress stress besides thermal
diffusion. Meanwhile, accumulating larger stress needs higher
temperature and long time. At low temperature 300 ◦ C, porous
Cu2 O grains formed and had the ability to release the stress,
so no large-scale of nanowires appeared. Kaur et al. also found
that no nanowires grown by oxidizing the Cu2 O pellets directly
[26]. This explicates that Cu2 O is a reaction product which is
inevitable but unnecessary. If growth time was insufficient at
400 ◦ C, no sufficient stress or energy compelled to form extra
surface. But if the growth time was too long at 500 ◦ C, CuO crys-
tallites formed rather than nanowires owing to surface diffusion
of atoms (shown in Fig. 2d). Surface diffusion of the atoms has
the effect of smoothing the surface. And for modest growth time
at 500 ◦ C, the stress needed to form extra surface to minimize the
surface energy, so nanowires formed in the valley and the side-
hill, and the diameter was larger than that of nanowires obtained
at 400 ◦ C. The curvature at the top of the valley-like protuberance
was large, thus no required surface formed, namely, nanowires
were useless to grow (shown in Fig. 2b and c). The internal stress
not only determines the shape of nanowires but also determines
the growth region of nanowires. But we do not find large-scale
of nanowires on Cu films oxidation at 400 ◦ C for 1 h even deal-
ing with at low temperature or long time except nanocrystallites.
This is due to the relaxation of the internal stress via the diffusion
among the grain boundaries and column structure. Whereas the
internal stress in the Cu foil during the oxidation is released by
excluding the nanowires or protuberance from the foil. Further,
the substrate of the Cu film cannot supply Cu atoms continuously
or adequate energy as the driving force owing to the growth of
the Cu film along lowest energy plane; yet the Cu foils had the
preferred growth along higher energy plane even after the oxi-
dation. The surface energy of Cu (1 1 1) is lowest than other
surface such as Cu (1 0 0) and (1 1 0) [36]. A fewer nanowires
may be produced by the non-uniform or defects on the Cu film.
The oxidation of Cu film also confirms that the VS growth mech-
anism is not valid. We can conclude that growth process of CuO
nanowires is the combination of: (1) the accumulation and the
relaxation of the stress; (2) the formation of the extra surface;
(3) the diffusion along nanowires driven by internal stress; (4)
copper atoms provided continuously by the source of the Cu
substrate.
4. Conclusions
CuO nanowires on Cu foils were prepared by thermal oxi-
dation route in air. The annealing temperature and the growth
time have an evident influence on the morphology of nanowires.
The density and the length of the nanowires increase with
the growth time prolonging at 400 ◦ C. When the tempera-
ture is elevated to 500 ◦ C and the growth time is 8 h, the
density becomes low, and the growth region of nanowires
is distinct. Owing to larger internal stress, the diameter of
nanowires altered drastically. CuO crystallites formed instead of
nanowires when growth time is too long. But at lower tempera-
ture of 300 ◦ C, porous Cu2 O formed. Large-scale of nanowires
was synthesized at 400 ◦ C for 8 h. For oxidation of Cu film,
no large-scale of nanowires were found because the stress
released through the grain boundaries and column structure.
Through the diffusion of the atoms supplied by Cu substrate,
the growth of nanowires is driven by internal stress generated
in copper substrate and oxide layer during oxidation of Cu
foils.
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