J Mater Sci: Mater Electron (2011) 22:1244–1247

DOI 10.1007/s10854-011-0294-0

Preparation of nanocrystalline Cu2O thin film by pulsed laser

deposition
Muslem F. Jawad • Raid A. Ismail •

Khaled Z. Yahea

Received: 20 October 2010 / Accepted: 6 January 2011 / Published online: 14 January 2011
Ó Springer Science+Business Media, LLC 2011

Abstract In this paper, the synthesis of nanocrystalline films, many methods, including sputtering [10], thermal
copper oxides Cu2O and CuO thin films on glass substrates oxidation [11], evaporation [12], molecular beam epitaxy
using a pulsed 532 nm Nd:YAG laser is presented. Depo- [13], and electrodeposition [14], have been used. However,
sition of films is achieved at two different substrate tem- there were few reports on the single-phase Cu2O and CuO
peratures. The influence of substrate temperature on the films grown by pulsed laser deposition (PLD) technique,
structural and optical properties of copper oxide films are which is widely used for the growth of oxide films because
discussed and analyzed. The X-ray diffraction (XRD) it allows for the stoichiometry of the synthesized material.
results show that the deposited films are crystalline in Recently, Ogale [15] studied the copper oxide films on Si,
nature. Films prepared at 300 °C substrate temperature MgO, and SiO2 substrates by PLD. Kikuchi [16] reported
were Cu2O and has (111) and (200) diffracted peaks, while electrical and structural properties of laser deposited Ni
films grown at 500 °C were CuO and has (111) and (020) doped Cu2O films. Despite the studies mentioned above,
planes. The morphology of deposited films were charac- the studies on the growth of copper oxide on glass sub-
terized by scanning electron microscope (SEM) and atomic strates by PLD are still insufficient. A more detailed study
force microscope (AFM). The optical energy gap of Cu2O need to be carried out to understand the structural and
and CuO films have been determined and found to be 2.04 optical properties of the films in different conditions by
and 1.35 eV respectively. PLD. In this work we report the fabrication and charac-
terization of nanostructured copper oxide thin films
deposited on glass substrates with the aid of PLD
1 Introduction technique.

In recent years, copper oxide thin films have attracted

much interest due to their potential applications for solar 2 Experimental procedure
cells and gas sensor [1–3]. Cuprous oxide (Cu2O) and
cupric oxide (CuO) are the two main semiconductor phases 2.1 Film preparation
of copper oxide with narrow band gap. It has been reported
that Cu2O is a cubic crystal structure and mostly p-type Crystalline Cu2O films were deposited on cleaned coring
semiconductor having a band gap of 2.0–2.6 eV [4–8], glass substrates using 10 Hz, 7 ns, Nd:YAG laser at
while CuO having the value of 1.3–2.1 eV [5–7, 9]. During 532 nm. The laser beam was focused on high purity Cu2O
the past years, in order to obtain high-quality copper oxide target using 5 cm positive lens.Laser fluence of 1.5 J/cm2
as used for in the ablation. The substrates were placed at
4 cm distance from Cu2O target. The chamber was kept at
vacuum pressure of 10-3 mbar. The Cu2O target was
M. F. Jawad
R. A. Ismail (&)
K. Z. Yahea
ablated from 10 to 100 pulses (10–20 min) to get single
Applied Science Department, University of Technology,
Baghdad, Iraq layer thin films. During the deposition the substrate tem-
e-mail: raidismail@yahoo.com peratures (Ts) were kept at 300 °C and 500 °C.

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2.2 Film characterization 100

90 Ts =500 C
80

Transmitance (%)
The structure of the grown films was determined by X-Ray Ts =300 C
70
diffraction (XRD) measurements (Philips PW 1050, k =
60
0.1542 nm) using Cu-ka source. Film transmission mea-
50
surement is performed at spectral range 400–900 nm using 40
UV–VIS-PV-8800 (Perkin Elemer Company) spectropho- 30
tometer. The surface morphology was examined by scan- 20
ning electron microscopy (SEM–JEOL 7000) and atomic 10
force microscopy (AFM-Digital Instruments NanoScope) 0
0 200 400 600 800 1000
working in tapping mode. hv (eV)

Fig. 2 UV-VIS transmittance spectra of the Cu2O and CuO

3 Results and discussion
This result indicates that the structure of the films can be
Figure 1a shows the XRD pattern of the Cu2O films controlled by adjusting the growth temperature.
deposited on glass substrate at 300 °C under an oxygen The UV–Vis optical properties in the range from 300 to
pressure of 0.1 mbar. The film is polycrystalline in nature 900 nm at various temperatures (300 °C and 500 °C)
and the diffracted peaks located at 2h = 32.7° and revealed that the transmittance depends stronger on the
2h = 36.7° are observed, which correspond to (111), (200) temperature as shown in Fig. 2. It was also found that the
of Cu2O phase, no other diffracted peaks are found in average transmittance of the Cu2O film exceeded 80% in
spectrum. The mean grain size (d) of the film was calcu- the visible and near-infrared region and the film was red
lated to be 23 nm using the Scherrer’s equation [11], and transparent. This indicates that Cu2O film can be used
d = 0.9k/BcoshB, where k the wavelength of X-ray radi- as a window material for solar cells applications. For all the
ation, B the full-width at half-maximum, and hB is the films analyzed, it is observed that the optical transmittance
diffraction angle. However, when the substrate temperature decreases slightly with increasing substrate temperature.
increased to 500 °C other peaks located at 2h = 38.5° and This is probably due to increasing the surface roughness
2h = 51.9° start to appear as shown in Fig. 1b, which which in turns increases the surface scattering of light. In
correspond to (020) and (111) planes of CuO structure. The fundamental absorption region, the optical absorption
grain size of the films increases from 23 to 42 nm as the coefficient (a) can be calculated from the transmittance
substrate temperature increased from 300 °C to 500 °C; data.
this is ascribed to the improvement of the film crystallinity. The plots of (ahm)2 versus hm shown in Fig. 3 are linear
indicating the presence of direct transition. The energy gap
of films at different temperatures are calculated from Fig. 3
and found to be 2 and 1.35 eV for 300 °C and 500 °C
respectively. The first value of energy gap belongs to Cu2O
film while the second belongs to CuO film; these results
agree well with reported data by [7].
Figure 4 displays the 3D AFM images of Cu2O films
formed at 300 °C and 500 °C. It is clear that the films
contain some islands with different triangular sizes top.
These elongated islands are formed at higher temperature
500 °C. The surface profile reveals that triangular-top
island formed at T = 300 °C has an average height of
10 nm (Fig. 4a), while the island with height of 30 nm was
observed at T = 500 °C. Furthermore, some of islands
have heights larger than their lateral size. AFM analysis
provided root mean square (RMS) roughness of the nano-
structured Cu2O film. The AFM measurements showed that
the values for RMS were 10 and 26 nm for Cu2O films
prepared at 300 °C and 500 °C respectively. The grain size
of Cu2O and CuO film deduced from AFM were 28 and
Fig. 1 XRD spectra of Cu2O and CuO films 35 nm respectively. The disagreement between the results

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Fig. 3 Plots of (ahm)2 verses a

photon energy (hm) of the Cu2O 6000 b 6000

and CuO thin films prepared at

αhν)2 (cm-1.eV)2

αhν)2 (cm-1.eV)2
5000 Ts=300 C 5000 Ts=500 C
substrate temperature a 300 °C
4000 4000
and b 500 °C
3000 3000

2000 2000

1000 1000

)
)
0 0
0 0.5 1 1.5 2 2.5 3 3.5 0 0.5 1 1.5 2 2.5
hv (eV) hv (eV)

Fig. 4 AFM 3D images of the

Cu2O and CuO thin films
prepared at substrate
temperature a 300 °C and
b 500 °C

Fig. 5 SEM images of the Cu2O and CuO thin films a 300 °C and b 500 °C

from the diffractograms and AFM images implies that the individual particles. Cu2O thin films have a quite uniform
diffraction peaks broadening are not just due to the grain and hole-free surface. At 300 °C the film has homogeneous
sizes. X-ray diffraction peaks are known to become broad surface morphology, with a wide size distribution of the
due to the existence of stress and defects in the crystal. particles from about 25 nm. With increasing substrate
Thus, we expect the nanocrystals of Cu2O formed in the temperature, the average size of aggregated particles
film to be in a stressed state with defects in the crystal. increases. When the substrate temperature reaches 500 °C,
It is possible here to emphasize that an average grain the particle size increases obviously. The increase of par-
observed by the AFM contains other smaller size crystal- ticle size is an indication that the higher substrate tem-
lites belonging to different orientations, as observed in the perature can induce more heat aggregation. Therefore, at
XRD [17]. Figure 5 reveals the SEM images of the Cu2O 500 °C the size of some aggregated particles is above
and CuO thin films deposited at substrate temperatures 50 nm as shown in the Fig. 5. The particle size obtained by
of 300 °C and 500 °C respectively. The films are highly XRD is differed from those obtained from SEM. The
dense and non-uniform, which makes easy to distinguish noticed grain sizes observed by SEM are larger than the

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J Mater Sci: Mater Electron (2011) 22:1244–1247 1247

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