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Preparation and characterization of copper oxide thin films deposited by

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Article  in  Journal of Physics D Applied Physics · December 2003

DOI: 10.1088/0022-3727/37/1/013

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INSTITUTE OF PHYSICS PUBLISHING JOURNAL OF PHYSICS D: APPLIED PHYSICS
J. Phys. D: Appl. Phys. 37 (2004) 81–85 PII: S0022-3727(04)69209-6

Preparation and characterization of

copper oxide thin films deposited by
filtered cathodic vacuum arc
Z H Gan1,3 , G Q Yu1 , B K Tay1 , C M Tan1 , Z W Zhao1
and Y Q Fu2
1
School of Electrical and Electronic Engineering, Nanyang Technological University,
Nanyang Avenue 639798, Singapore
2
School of Mechanical and Production Engineering, Nanyang Technological University,
Nanyang Avenue 639798, Singapore
E-mail: ezhgan@ntu.edu.sg

Received 19 September 2003

Published 10 December 2003
Online at stacks.iop.org/JPhysD/37/81 (DOI: 10.1088/0022-3727/37/1/013)

Abstract
Copper oxide thin films deposited on Si (100) by a filtered cathodic vacuum
arc with and without substrate bias have been studied by atomic force
microscopy, x-ray diffraction (XRD), x-ray photoelectron spectroscopy
(XPS) and Raman spectroscopy. The results show that the substrate bias
significantly affects the surface morphology, crystalline phases and texture.
In the film deposited without bias, two phases—cupric oxide (CuO) and
cuprous oxide (Cu2 O)—coexist as cross-evidenced by XRD, XPS and
Raman analyses, whereas CuO is dominant concurrent with CuO (020)
texture in the film deposited with bias. The film deposited with bias exhibits
a more uniform and clearer surface morphology although both kinds of films
are very smooth. Some explanations are given as well.

1. Introduction many new techniques have been proposed to synthesize the

Cupric oxide (CuO) and cuprous oxide (Cu2 O) are the two
main semiconductor phases of copper oxide with narrow band-
gap. It has been reported [1] that Cu2 O has a cubic crystal
structure and a direct band-gap of 2.2 eV, while CuO has
a monoclinic structure and an indirect band-gap of 1.4 eV.
They have attracted much interest due to their potential
applications in solar cells [2], magnetic devices [3] and
catalysis [4, 5] and because they have radiation properties
similar to those of an ideal black body. Another special
fundamental characteristic of CuO and Cu2 O is the satellite
structure on the high-energy side of valence and core levels in
their x-ray photoelectron spectra (XPS) [6]. It is the satellites
that provide important information on the electronic structure
of these transition metal oxides. Rakhshani [2] documented a
good review of the preparation, characterization and properties
of copper oxide, where the techniques included high- and low-
temperature oxidation, electro-deposition, anodic oxidation,
chemical oxidation and reactive sputtering. Since then,
3 Author to whom any correspondence should be addressed.
copper oxide thin films and nanoparticles, such as activated
reactive evaporation (ARE) [7], rapid liquid dehydration and
precipitation [8], one-step solid state reaction [9] and the
dip-coating technique [10].
Filtered cathodic vacuum arc (FCVA) deposition is
a common method to prepare oxide, nitride and metal
films, where various methods are employed to remove
macroparticles inherent to arc evaporation itself. This arc
source provides particles of high ionization rate and high ion
energy (50–150 eV) for condensation on substrate. By using
this technique, the resultant films can be obtained on a rather
low substrate temperature. This is favourable for temperature-
sensitive substrates such as plastic. Also thermal residual stress
in the film could be low compared to other high temperature
processes. On the other hand, the films usually adhere well due
to the induced ion mixing by the bombardment of energetic
particles. Recently, polycrystalline ZnO semiconductor thin
films [11] and dense tetrahedral amorphous carbon films with
high sp3 [12] produced by FCVA have been reported. However,
few studies have been conducted on the preparation and
properties of copper oxide films by this technique.

0022-3727/04/010081+05$30.00 © 2004 IOP Publishing Ltd Printed in the UK 81

Z H Gan et al

In this paper, we report on the preparation and (a)

characterization of copper oxide thin films synthesized
by FCVA. The thin films were investigated by atomic
force microscopy (AFM), x-ray diffraction (XRD), x-ray
photoelectron spectrum (XPS) and Raman spectroscopy. The
results show that the films could be pure cupric oxide or a
mixture of cuprous and cupric oxides.

2. Experimental details

The FCVA system has been described elsewhere [13]. In brief,

the system consists of three main components: a cathode target
and anode pair, a filtering duct, and a sample chamber. The
target arc is initiated by striking a graphite trigger to the target
surface, and the plasma produced is sustained due to a DC
voltage applied to the cathode–anode pair. The plasma is
then steered out through the filtering duct into the sample
chamber, where the ions impinge on the substrate and the
thin films form. The filtering duct is applied not only to (b)
eliminate the unwanted macroparticles but also the neutral
species from the plasma stream. A high purity Cu plate,
30 mm thick and 50 mm in diameter, was used as the cathode
source. The deposition chamber, roughly pumped by a rotary
pump, was evacuated to a base vacuum of ∼5 × 10−6 Torr
with a cryo-pump. Prior to deposition, the (100) n-type silicon
wafer was in situ sputtered for 5 min by an Ar ion beam at
∼800 eV and ∼200 mA. During deposition, the arc current was
set at 60 A. Simultaneously, a mixture of oxygen and argon
gas, with 100 sccm and 5 sccm, respectively, was admitted
into the cathode–anode region, where a small amount of Ar
gas greatly improved the stability of the arc, possibly due to
the fact that Ar plasma is easily ignited and sustained and
reduces somewhat the oxidation of the target. Accordingly, the
process pressure was ∼2 × 10−4 Torr. Two types of samples
were prepared: without bias (sample A) and with −100 V
(sample B), respectively. The films deposited were, both, of
the same thickness, around 120 nm. Figure 1. AFM surface morphologies of (a) sample A (no bias), and
The surface morphology and roughness of the thin (b) sample B (−100 eV bias), indicating a more uniform and clearer
morphology in the latter.
films were characterized by atomic force microscope (AFM,
Dimension 3000, Digital Instruments). The phase of the thin
films was identified by XRD (x-ray diffractometer, D5005, as disclosed by XRD analyses, in which it is found that the film
SIEMENS) using Cu Kα radiation (wavelength of 1.54 Å) at deposited with bias possesses smaller crystallites compared
40 kV and 40 mA with a thin film goniometer (Rigaku, Japan). to the film deposited without bias. The clearer morphology
The incident angle of the x-ray is 1˚. The chemical states of the is a result of the bias-enhanced sputtering, which removes
atomic species in the thin films were analysed by XPS (Kratos some particles bonded with each other weakly, as reported
AXIS spectrometer, UK) with the monochromatic Al Kα x-ray in [14, 15].
radiation. The microstructure of the films was examined by Glancing angle XRD patterns of the two samples are
Raman scattering using the 514.5 nm line of an Ar+ laser as shown in figure 2. As seen, both samples are of polycrystalline
the excitation source. structures. For sample A, there are three strong XRD peaks at
2θ = 35˚, 36.6˚ and 42.2˚, corresponding to the (−111) and
3. Results and discussion (002) crystal planes of CuO, (111) and (200) planes of Cu2 O,
respectively. The weak peak at 2θ = 38.3˚ corresponds to
The AFM images for samples A and B are shown in figure 1. the (111) and (200) planes of CuO crystal. Another wide and
The surface of the copper oxide thin films obtained by FCVA weak peak centred at 2θ = 55.4˚ is related to the contribution
is quite smooth, both of rms roughness less than 1 nm. This from the overlapping of the CuO (020) and (202) planes, as
atomic-scale smoothness is a natural feature of the FCVA, supported by the normal XRD analysis discussed below. This
i.e. high energy of depositing ions inducing high surface XRD pattern indicates that cupric and cuprous oxides coexist
mobility. It is observed that sample B deposited with −100 V in sample A. In contrast, for sample B, besides the occurrence
bias presents a more uniform and clearer morphology. This of the weak peak at 31.3˚, the peak at 35˚ greatly reduces
relatively uniform cluster is related to the film microstructure, in intensity whereas the peaks at 36.6˚ and 42.2˚ disappear.

82
 Preparation and characterization of copper oxide films

300 450

Cu2O
sample A 400 Cu2O sample A
250 CuO Cu O sample B CuO (111) (200) sample B
2
(-111) (111) 350 (-111)
(002) (002) CuO
(111)
Intensity (a. u.)

200 300
Cu2O (200)

Intensity
(200) 250
150 CuO CuO
(111) (020) 200 CuO
CuO (200) (202) CuO (020)
100 (110) 150 (110)

100
50
50

0 0
30 35 40 45 50 55 60 30 35 40 45 50 55 60
2θ (°) 2θ (°)

Figure 2. Glancing angle XRD patterns of samples A and B. It is Figure 3. Normal mode XRD patterns of samples A and B to
seen that cupric and cuprous oxides coexist in sample A, whereas characterize the texture of the samples. It is again observed that
sample B is composed of the pure CuO phase. CuO and Cu2 O coexist in sample A while CuO exists in sample B,
consistent with the glancing angle XRD results.
The other two weak peaks at 38.3˚ and 55.4˚ hardly change
in intensity. No obvious peak shift can be observed. It is
1600
interesting to note that all peaks are associated with CuO crystal CuO
planes for sample B, showing that the thin film deposited with sample A Cu2O
bias voltage is a pure monoclinic CuO phase or that the fraction 1400
sample B
of crystalline Cu2 O is so small that it cannot be detected. This
indicates the substrate bias can noticeably affect the phase 1200
Si
Intensity

composition of copper oxide films. The great reduction in

the peak at 35˚ is believed to be due to more defects existing in 1000
sample B, which are induced by bombardment of condensing CuO
ions with higher energy as compared with sample A. It is found 800
that the crystallite size in sample B is reduced as evidenced
by the peak widening and as reflected from the above AFM 600
images. The grain refinement effect induced by strong ion-
bombardment during deposition is often observed [16]. The 400
average crystallite size can be calculated using the Scherrer 200 300 400 500 600 700
equation [17]: Raman shift (cm )
-1

0.9λ
D= , Figure 4. Raman spectra of samples A and B, agreeing well with the
B cos θ
where λ is the x-ray wavelength, θ is the Bragg diffraction
angle, and B is the full-width at half-maximum (FWHM) of
the peak corresponding to θ. When calculated by using the
peak corresponding to the (002) plane of CuO, the resultant
grain sizes are 9.3 nm and 5.4 nm, respectively, for samples A
and B. Note that the FWHM of the peak is obtained by fitting
the XRD patterns and using the Grams/32 software, which is a
commercial software for a Renishaw Ramascope Spectrometer
(RENISHAW, Gloucestershire, UK).
The textures of samples A and B are characterized by
normal mode XRD spectra. As shown in figure 3, there
are four strong peaks, corresponding to the CuO (−111) and
(002), Cu2 O (111), CuO (111) and (200), and Cu2 O (200)
planes, and the weak peak belonging to CuO (110) plane in
sample A. However, for sample B, the peak corresponding to
the CuO (020) plane is prominent while other peaks are greatly
suppressed, denoting that CuO (020) preferential orientation
occurs. From the normal mode XRD spectra, it is again
observed that CuO and Cu2 O coexist in sample A while CuO
XRD results for sample composition identification. The broadening
of the Cu2 O profile in sample B may be attributed to the amorphous
characteristic of the phase which could not be detected by XRD.
exists in sample B, consistent with the glancing angle XRD
results.
Raman spectra of samples A and B are displayed in
figure 4. For sample A, three peaks located at around 300,
340, 600 cm−1 are observed. Both the strong peak at 300 cm−1
and the weak peak at 340 cm−1 are ascribed to CuO [18]. The
broad peak centred at 600 cm−1 is believed to be contributed by
several Cu2 O-related sub-peaks such as 570, 618 or 624 cm−1
[18, 19]. In contrast, for sample B, the CuO-related peaks at
300 and 340 cm−1 both become stronger. However, the broad
peak at 600 cm−1 associated with Cu2 O is largely suppressed
in intensity. It is well-known that the intensity of Raman
scattering is directly proportional to the number of scattering
centres present in the volume illuminated by the laser beam.
Thus, it is concluded that both CuO and Cu2 O exist in sample A
while CuO is dominant in sample B, agreeing with the result

83
Z H Gan et al
of XRD. We also note that the Cu2 O-related Raman peak does
not disappear completely for sample B whereas the Cu2 O
diffraction peak cannot be observed. This difference may
exist because Cu2 O does not crystallize or the amount of
crystalline Cu2 O is low so that it cannot be detected by XRD.
Another possible explanation is that Raman scattering is more
sensitive to copper oxide compared with XRD, as reported by
Gong et al [18].
A possible reason for the different phases of copper oxide
in the films with and without bias, could be that applying
substrate bias during deposition induces impact-stimulated
chemical composition variation in the resulting films. The
application of bias may lead to more incorporation of oxygen
into the films as in ion beam assisted deposition. In sample A
without substrate bias, CuO and Cu2 O form simultaneously.
However, by biasing the substrate, the extra-incorporated
oxygen with higher energy is supposed to lead to the formation
of CuO from Cu2 O, as indicated by the following reaction:
Cu2 O + O → 2CuO.
As a consequence, the amount of Cu2 O in sample B is greatly
reduced and almost undetectable by XRD as presented earlier.
As a result, the crystalline phase changes with substrate bias
correspondingly.
The survey spectra of XPS for both samples A and B are
presented in figure 5. The spectra are globally similar to each
other. The peaks corresponding to Cu 3d, 3p, 3s, 2p and Auger,
O 1s and Auger are obviously observed. C 1s peak is also
found, which is due to the exposure of the samples to air. No
argon is seen, indicating that no argon exists in the samples
or the argon content is lower than the detection limit. The
high-resolution spectra corresponding to Cu 2p and O 1s are
given in figures 6(a) and (b). They are plotted after correction
of charging effects using a binding energy of 284.8 eV as the
C 1s peak.
Figure 6(a) shows Cu 2p3/2 and 2p1/2 spectra. The
respective main peaks of Cu 2p3/2 for samples A and B lie
at 933.7 and 933.8 eV. These main peaks can be assigned to
Cu2+ ions, rather than Cu+ ions, which have a main peak at
20000 sample A
sample B
15000
Cu Auger
Intensity (a.u.)
10000
O 1s
5000
Cu 3p C 1s
Cu 3s
Cu 3d
0
0 200 400 600
Binding energy (eV)
Figure 5. XPS survey spectra of samples A and B. The spectra are
globally similar to each other. The peaks corresponding to Cu 3d,
3p, 3s, 2p and Auger, O 1s and Auger are obviously observed.
84
a lower binding energy of about 932.4 eV [20]. In addition
to the main peaks of Cu 2p3/2 , their satellite peaks are also
observed at higher binding energies. This satellite feature
observed in both samples is an indication of materials having a
partially filled d9 shell configuration in the ground state, such
as copper dihalides, metallic nickel, or CuO [20]. For Cu2 O
with a completely filled shell (d10 ), this satellite peak is absent
because screening via a charge transfer into the d states is not
allowed. Moreover, in both samples, the main peaks of 2p1/2
are located at a binding energy that is 20 eV higher than that
of their 2p3/2 main peaks. The similarity of the Cu2p XPS
spectra of samples A and B proves that these surfaces are both
dominated by CuO. However, as concluded from the XRD
analysis, Cu2 O exists in sample A. This difference is due to
the fact that XPS, unlike XRD, can only get the composition
information from surface rather than bulk. It is, therefore,
concluded that CuO and Cu2 O coexist in sample A in which
CuO is dominant on its surface, whereas only CuO is present
in sample B. This assumption is supported by the Raman
scattering analysis discussed earlier. Balamurugan et al [7]
also reported that Cu2 O nanoparticles were capped with a
surface layer of CuO, which stabilizes the more symmetric
cuprous oxide phase.
There are two components (one main peak S1 and one
satellite S2 ) in the O 1s spectra after curve decomposition is
performed for both samples A and B, as shown in figure 6(b).
The main peaks for both cases are located at 529.8 eV. The
FWHM of the main peak of sample A is about 1.0 eV, which
is slightly narrower than that of sample B (1.22 eV). Note
that both the FWHM are larger than that of single crystal
cupric oxide (0.8 eV), where the satellite component almost
disappears [21]. The energy of the satellites in samples A
and B are centred at approximately 1.6 eV and 2 eV higher
than their main peaks, respectively. The area ratios of S1 /S2
for samples A and B are about 1.41 and 0.65, respectively,
meaning that sample B presents a larger satellite component. It
is well-known that the main peak and satellites of O 1s spectra
correspond to different chemical states of the oxygen atoms
[22]. The main peak at lower binding energy is attributed to
the normal O2− , interacting with the copper atoms to form the
chemical Cu–O bond. The satellite is ascribed to the extra-
lattice oxygen [21], indicating non-stoichiometric nature of
O Auger the thin films. This result fits well with the differential FWHM
of the main peaks between our oxide thin films and the single
Cu 2p
crystal cupric oxide. Again, the more extra-lattice oxygen in
sample B, i.e. a lower S1 /S2 ratio, is attributed to the higher
incorporated oxygen resulting from substrate bias.
It is worth mentioning that thermal annealing would
change the composition/structure, and thus the properties, of
the copper oxide thin film [23, 24]. Therefore, it is necessary
and meaningful to further investigate how thermal annealing
affects the structure and properties of the present copper oxide
thin films.
4. Conclusions
800 1000
Copper oxide thin films have been deposited on Si (100)
by FCVA with and without substrate bias and investigated
by AFM, XRD, x-ray photoelectron spectroscopy (XPS) and
Raman spectroscopy. The results show that substrate bias

(a)
Figure 6. (a) Cu 2p and (b) O 1s XPS spectra of samples A and B, showing that the surfaces are both dominated by CuO. Note that the
Cu2 O phase in sample A as detected by XRD is covered by the surface CuO layer, which was also reported by Balamurugan et al [7]. The
difference between XPS and XRD is that XPS, unlike XRD, can only get the composition information from the surface rather than the bulk.
significantly affects the surface morphology, crystalline phases
and texture. In the film deposited without bias, two phases—
cupric oxide (CuO) and cuprous oxide (Cu2 O)—coexist,
whereas CuO is dominant concurrent with the CuO (020)
texture in the film deposited with bias. Also, XRD suggests that
the film prepared with bias has more defects compared to the
film prepared without bias. Substrate bias makes the deposited
film exhibit a more uniform and clearer surface morphology.
By comparing samples A and B, it is found that the bias applied
makes Cu2 O convert to CuO due to more incorporation of
oxygen, and also makes the film structure change partly from
crystalline to amorphous, as evidenced by XRD.
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