Surface & Coatings Technology 205 (2010) S206–S209

Contents lists available at ScienceDirect

Surface & Coatings Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s u r f c o a t

Effect of Al content on electrical conductivity and transparency of P-type Cu-Al-O

thin film
Ping-Hung Hsieh a, Yang-Ming Lu b, Weng-Sing Hwang a,⁎, Jing-Jia Yeh a, Wei-Luen Jang a
a
Department of Materials Science and Engineering, National Cheng Kung University, Tainan, Taiwan
b
Department of Electrical Engineering, National University of Tainan, Tainan, Taiwan

a r t i c l e i n f o a b s t r a c t

Available online 3 August 2010 Copper aluminum oxide (Cu-Al-O) film was prepared by radio-frequency (RF) sputter method using a pure
metal Cu target and a mosaic target with different relation between Al and Cu at room temperature,
Keywords: respectively. The effects of Al content on crystal structure, electrical conductivity, and optical transmittance
Cu-Al-O thin film were studied. The composition of the film was adjusted by placing various numbers of Cu disks on the Al
p-type target surface. The Al concentration in the films were measured as 0, 4.2, 6.8, and 20.5 at.%, respectively. As
Mosaic target
the Al content in the deposited films increased, the crystal structure changed from CuO to amorphous CuAlO2
and the resistivity of the deposited films increased. The resistivity of Cu-Al-O films obtained in this study
ranged from 0.5 Ω-cm to 4.8 MΩ. The increased resistivity can be attributed to the incorporated Al3+ ions
substituting the Cu2+ ions, thus decreasing the hole concentration. The average optical transmittances in the
visible range (400–800 nm) of the deposited films were measured as 20.1%, 33%, 43.9%, and 73.9 % and the
related optical band gaps obtained from optical transmittances were 2.1, 2.6, 2.7, and 2.9 eV, respectively.
Crown Copyright © 2010 Published by Elsevier B.V. All rights reserved.

1. Introduction laser deposition [1,10], chemical vapor deposition [11,12], sputtering

Transparent conducting oxides (TCOs) have a wide range of
applications, such as optoelectronic devices [1,2], solar cells [3], gas
sensors [4], and p-n junctions [5]. For these applications, the p-n
junction requires a combination of n-type and p-type TCOs. N-type
TCOs such as zinc oxide (ZnO), tin dioxide (SnO2), and indium tin oxide
(ITO) have been extensively studied and they are widely applied as
transparent electrodes for liquid crystal displays (LED) [6], organic
light-emitting diodes (OLEDs) [6], flat panel display (FPD) [7], and solar
cells [7]. However, the p-type TCOs showed either low electrical
conductivity or low optical transmittance and needed further studies.
For example, the CuO and Cu2O are well-known p-type conductors with
an optical band gap of 1.5 and 2.1 eV [8,9], which is too low to be used in
TCO applications. Until recently, Kawazoe [1] incorporated Al into
copper oxide and synthesized a p-type CuAlO2 thin film. The
synthesized CuAlO2 thin film has a wide band gap of ~3.5 eV, an
electrical conductivity of 0.95 × 10− 1 Scm−1, and a carrier mobility of
10.4 cm2/V-s at room temperature [1], which is better than most other
p-type materials. This material gets much attention and more and more
studies have been done on p-type TCO materials in recent years. Also,
CuAlO2 film has been prepared using various techniques, such as pulsed
⁎ Corresponding author. No.1, University road, Tainan City, Taiwan ROC. Tel.: + 886 6
275 7575x62963; fax: + 886 6 2344393.
E-mail addresses: hann0613@hotmail.com (P.-H. Hsieh), ymlumit@yahoo.com.tw
(Y.-M. Lu), wshwang@mail.ncku.edu.tw (W.-S. Hwang), yohoho001@hotmail.com
(J.-J. Yeh), harmonic1124@hotmail.com (W.-L. Jang).
[13–15], and electron beam evaporation [16].
Among these techniques, the sputtering process is commonly
used for preparing films on various substrate materials as it allows
good control of the deposition film parameters. The physical
properties of the sputtered films mainly depend on deposition
parameters such as substrate temperature, sputtering power [17],
working pressure [18], and oxygen partial pressure [19]. However,
the effect of Al content on crystal structure and electrical
conductivity has seldom been studied.
In this study, Cu-Al-O films were deposited by radio-frequency
(RF) magnetron sputtering with various numbers of Cu disks on an Al
target surface. The aim of this work is to investigate the effects of Al
content on the crystal structure, chemical bonding, electrical
conductivity, and optical properties.
2. Experimental procedure
Cu-Al-O films were deposited on a Corning 1737 substrate by an RF
magnetron sputtering system. A pure copper target and a mosaic
target with different relations between Al and Cu were respectively
used to prepare the Cu-Al-O films. The distance between target and
substrate was kept at 6 cm. The composition of the deposited films
was adjusted by placing one, three, or six pieces of a Cu metal disk on
the Al target surface. The thickness and diameter of the Cu disks
were controlled to be 0.1 cm and 1 cm, respectively. Before
deposition, the chamber was pumped to an ultimate background
pressure of 6 × 10− 3 Pa. The sputtering working pressure was fixed

0257-8972/$ – see front matter. Crown Copyright © 2010 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2010.07.077
 P.-H. Hsieh et al. / Surface & Coatings Technology 205 (2010) S206–S209 S207

at 1.33 Pa. The pre-sputtering process ran for 10 minutes to clean the
target surface and to remove any possible contamination. The RF power
was set at 100 W and the oxygen partial pressure (O2/Ar+ O2) was kept
at 5%. A conventional stylus surface roughness detector (Alpha-step
200) was used to measure the film thickness. All the film thicknesses
were kept at an approximate value of 200 nm. The composition of
the deposited film was determined by wavelength-dispersive X-ray
(JXA-8500F Fe-EPMA). The crystal structures of the deposited films
were studied by X-ray diffraction (XRD, Rigaku D/MAX2500) with
monochromatic Cu-Kα radiation. The deposited film chemical
binding state was examined with X-ray photoelectron spectroscopy
(XPS, ULVAC-PHI, PHI 5000; VersaProbe). The resistivity and carrier
type of the films were measured using a four-point probe system
(Napson, RT-7) and Hall measurements (Lake Shore model 7604),
respectively. The optical transmittance measurements were performed
with a UV–Vis spectrophotometer (HMT: OOIBase32, MFS-630).

3. Results and discussion

3.1. Composition of Cu-Al-O thin films

The films were deposited by a pure copper target and a mosaic

target with different relations between Al and Cu, respectively. The
film composition is shown in Table 1. The deposited films were
named 0% Al, 4.2% Al, 6.8% Al, and 20.5% Al, respectively. The 0% Al
sample was prepared using a pure Cu target; the film composition
(at.%) was measured as Cu: O = 50.7:49.3. The 4.2% Al to 20.5% Al
samples were prepared using a mosaic target with different relations
between Al and Cu; the measured Cu/Al ratio decreased from 10.6 to
1.2 with decreasing number of pieces of the Cu disk on the Al target
top surface. The Cu disk occupied approximately 5% of the area on
the Al target top surface. The composition of the film deposited with
one piece of the Cu disk placed on the Al target is quite close to the
composition of the CuAlO2 phase. The number of Cu disks required to
obtain the stoichiometric composition of the CuAlO2 phase was
lower than expected. This result is due to the great difference
between the sputtering yields of Al and Cu materials. Generally, the
sputtering yield of an oxide target is lower than that of a metal target
because the former has strong chemical bonds. The Gibbs formation
energy [20] of Al2O3, which can be easily formed under low oxygen
pressure, is quite low as compared to that of CuO. The use of O2
atmosphere during sputtering may lead to the formation of an Al2O3
layer on the Al target surface, in which Cu is relatively inert.
Therefore, the difference in sputtering rates can be attributed to the
great difference between the activation formation energies of Al2O3
and CuO.
3.2. Structure properties of Cu-Al-O films
Fig. 1 shows the GIAXRD spectra of Cu-Al-O films with various
levels of Al content. For the 0% Al sample, the film was deposited
using a pure Cu target. According to the previous study [21], the
possible crystal structure of the film deposited in this condition may
be CuO or Cu2O. In this report, the crystal structure was studied by
determining the lattice constants of the XRD pattern. The calculated
lattice constants a, b, and c for monoclinic CuO were 0.466, 0.347,
and 0.599 nm, respectively. Also, the calculated lattice constants a, b,
Table 1
Composition (at. %) of Cu-Al-O films with various Al concentrations.
Sample name Cu (at. %) Al (at. %) O (at. %)
0% Al 50.7 0.0 49.3
4.2% Al 44.6 4.2 51.2
6.8% Al 42.8 6.8 50.4
20.5% Al 25.1 20.5 54.4
Fig. 1. GIAXRD spectra of Cu-Al-O films with various levels of Al content.
and c (a = b = c) for cubic Cu2O were 0.391 nm. Compare the
calculated lattice constants with the standard lattice constants of
CuO (JCPDS 74-1021) and Cu2O (JCPDS 77-0199), the crystal
structure of 0% Al sample can be identified as CuO. The result is
consistent with the composition data presented in Table 1. As Al
incorporated in the deposited film, the XRD peaks of 4.2% Al sample
shifts to a higher 2θ angle. As the Al content further increased, the
XRD peak of the 6.8% Al sample showed a wide diffusive peak, and
the 20.5% Al sample showed an amorphous structure which
indicates that the crystallinity of the deposited films decreased as
the Al content increased.
Generally, the shifts in XRD peaks could be attributed to the
substitution of ions with various sizes in a doping process [22–24].
Since the radius of Al3+ ion (0.53 Å [25]) is smaller than that of Cu2+
ion (0.73 Å [25]). The shift of XRD peaks of 4.2% Al sample can be
attributed to the smaller Al3+ ions substituting the Cu2+ ions. As Al
content further increased, the substitution effect increased, which
may distort the lattice and decrease the crystallinity of the film. In
this study, the XRD peaks correspond to Al2O3 phase and other
second phase were not found, which indicates that the incorporated
Al3+ might be uniformly distributed in the CuO crystalline. The XRD
peak of the 6.8% Al sample showed a wide diffusive peak, and the
20.5% Al sample show an amorphous structure which implies that
the crystallinity of deposited films decreased as the Al content
increased. Since the incorporated Al3+ distributed uniformly in the
CuO crystal, CuO crystallinity was distorted as Al incorporated in the
film. Therefore, the incorporated Al3+ ions were supposed to
substitute the Cu2+ site in the films. Also, the XRD pattern of the
20.5% Al sample shows a broad peak near 36° at the 2θ angle.
Accordingly [14,26], the XRD peak can be identified as amorphous
Cu/Al CuAlO2. Referring to the Al2O3-CuO phase diagrams [27], the CuAlO2
– phase should exist at temperatures above 1000 °C. The sputtering
10.6 process was conducted at room temperature; under these condi-
6.2 tions, the formation energy was too low to form a crystalline CuAlO2
1.2
structure.
S208 P.-H. Hsieh et al. / Surface & Coatings Technology 205 (2010) S206–S209
Fig. 2. XPS spectra of (a) Cu 2p spectrum of the 0% Al sample and (b) the 20.5% Al sample.
3.3. Chemical binding of Cu-Al-O film
XPS measurements were performed to evaluate the chemical
state of the Cu-Al-O film. Fig. 2 shows the XPS spectrum of Cu 2p1/2,
Cu 2p3/2, and the shake-up satellites of 0% Al and 20.5% Al. The
reported binding energies of Cu 2p3/2, Cu 2p1/2, and the shake-up
satellites are 933 eV, 953 eV, and 943 eV, respectively [28,29]. In this
study, the binding energies of Cu 2p3/2, Cu 2p1/2, and the shake-up
satellites were located at 932.2 eV, 952.1 eV, and 942.9 eV, respec-
tively. The existence of shake-up satellites in the 0% Al sample
implies the presence of Cu2+ [30,31] in the deposited film. In the
20.5% Al sample, no satellite peaks were detected, which suggests
that the incorporated Al substituted the Cu ions, and decreased the
number of Cu2+ ions in the film.
3.4. Cu-Al-O thin film electrical properties
Table 2 shows the resistivity of Cu-Al-O films with various Al
concentrations. The resistivity of the 0% Al sample was 0.5 Ω-cm. The
resistivity increases with increasing Al content. When the Al content
reached 6.8 at.%, the resistivity became undetectable. The electrical
conductivity measurement was performed using a multimeter (probe
distance of 1 mm). When Al content was increased to 20.5 at%, the
resistivity was too large to be detectable either by the four-point
probe system or the multimeter. The carrier concentrations of the 0%
Al and 4.2% Al samples were 6.77 × 1020 and 2.67 × 1018 cm-3,
respectively. The carrier mobilities of the 0% Al and 4.2% Al samples
were 5.90 × 10−2 and 2.64 × 10− 1 cm2/V-s, respectively. The 0% Al and
4.2% Al samples were confirmed to have p-type conductivity from Hall
measurements. When the Al content of the film was above 6.8 at.%,
the resistivity exceeded the detection limits of Hall measurement.
When Al is incorporated into the film, it effectively substitutes Cu
ions and distorts the lattice, as described in Section 3-2. The defect
equation of Al3+ substituted Cu2+ ions is shown as Eq. (1) [32]. The
substitution of Al3+ ions for Cu2+ ions will consume some native
holes. For p-type semiconductor, the decreased hole concentration
increases the electrical resistivity. Also, the incorporated Al3+ ions
were supposed to substitute the Cu2+ site in the films. Therefore, the
Table 2
Resistivity of Cu-Al-O films with various Al concentrations.
Sample Name Resistivity
0% Al 0.5 Ω-cm
4.2% Al 11.8 Ω-cm
6.8% Al Multimeter 4.8 MΩ
20.5% Al – 20.5% Al
Fig. 3. UV–Vis spectra of Cu-Al-O films with various levels of Al content.
reason for the resistivity increasing is the incorporation of Al3+
substituting Cu2+ ions.
• • x 1
Al2 O3 + 2h = 2AlCu + 2OO + =2 O2 ð1Þ
3.5. Cu-Al-O thin film optical properties
Fig. 3 shows the UV–Vis spectra of Cu-Al-O films with various
levels of Al content. All the film thicknesses were kept at an
approximate value of 200 nm. The transmittance of the 0% Al sample
was ~20.1% in the visible range. The transmittance of Cu-Al-O film
increased with increasing Al content. When the Al content reached
20.5 at.%, the average transmittance of the deposited film was 73.9%.
Table 3 shows the energy gap (Eg) varying with the Al content in
the Cu-Al-O films. The optical band gap of the Cu-Al-O films was
estimated from the intercept plot of the photon energy axis, which
assumes a transition using the relationship [19]:
 1 = n
αhν = A hν−Eg ð2Þ
where A is a constant, hν is the photon energy, Eg is the optical band
gap energy, and n depends on the type of transition (n = 2 and 1/2 for
direct and indirect transitions, respectively). According to previous
studies [14–17], the p-type CuAlO2 film has a direct band gap. The
relation of (αhν)2 vs. hν is plotted for the 20.5% Al sample in Fig. 4. The
optical band gap of the 0% Al sample was 2.1 eV. The optical band gap
increased with increasing Al content. When the Al content reached
20.5 at.%, the optical band gap was 2.9 eV. The obtained optical band
gap is higher than the reported values for CuO and Cu2O [8,9], and it is
very close to the optical band gap of CuAlO2 (2.9–3.5 eV) [14].
Although the composition is similar to that of the CuAlO2 phase, the
optical band gap is lower than that of CuAlO2 [1,14]. This result may be
due to the amorphous structure of the film.
Table 3
Energy gap (Eg) obtained from calculations of transparency for Cu-Al-O films with
various Al concentrations.
Sample Name Energy gap (eV)
0% Al 2.1
4.2% Al 2.6
6.8% Al 2.7
2.9
 P.-H. Hsieh et al. / Surface & Coatings Technology 205 (2010) S206–S209
Fig. 4. Optical absorption plot of the film with Al content of 20.5 at.%.
4. Conclusion
In this study, Cu-Al-O films were deposited using an RF magnetron
sputtering system at room temperature. The crystal structural,
chemical binding state, electrical conductivity, and optical properties
of the Cu-Al-O films were examined at various levels of Al content in
the films. The results can be summarized as follows.
A decrease of Cu disk on the Al target was found to increase Al
content in the deposited film. The composition of the film deposited
with one Cu disk placed on the Al target was similar to that of the
CuAlO2 phase, but its crystal structure was amorphous. This result
may be attributed to the insufficient energy for a perfect crystalline
structure during sputtering. The XRD and XPS results show that the
additional Al ions substituted the Cu ions; this substitution
decreased the crystallinity and electrical conductivity of the films.
The resistivity obtained in this study ranges from 0.5 Ω-cm to
4.8 MΩ depending on the concentration of Al. The transmittance of
Cu-Al-O film changed from 20.1% to 73.9% when Al content increased
from 0 to 20.5 at.%. The optical band gap was estimated to be in the
range of 2.1 to 2.9 eV. Due to the amorphous structure, the optical
band gap of the deposited film was lower than that previously
reported.
S209
Acknowledgments
The authors are grateful to the National Science Council and Ministry
of Economic Affairs in Taiwan for financially supporting this research
under grants NSC97-2221-E-006-006-MY3, NSC96-2221-E-024-021-MY3,
and 98-D0204-2.
References
[1] H. Kowazoe, M. Yasukawa, H. Hyodo, M. Kurita, H. Yanagi, H. Hosono, Nature 389
(1997) 939.
[2] G. Thomas, Nature 389 (1997) 907.
[3] J. Müller, B. Rech, J. Springer, M. Vanecek, Sol. Energy 77 (2004) 917.
[4] A.V. Tadeev, G. Delabouglise, M. Labeau, Mater. Sci. Eng. B57 (1998) 76.
[5] H. Yanagi, K. Ueda, H. Ohta, M. Orita, M. Hirano, H. Hosono, Solid State Commun.
121 (2002) 15.
[6] H. Hosono, Int. J. Appl. Ceram. Technol. 1 (2004) 106.
[7] H. Yanagi, S.I. Inoue, K. Ueda, H. Kawazoe, H. Hosono, J. Appl. Phys. 88 (2000) 7.
[8] B. Balamurugan, B.R. Mehta, Thin Solid Films 396 (2001) 90.
[9] A. Buljan, M. Liunell, E. Ruiz, P. Alemany, Chem. Mater. 13 (2) (2001) 338.
[10] M.N. Spallart, S.P. Pai, R. Pinto, Thin Solid Films 515 (2007) 8641.
[11] Y. Wang, H. Gong, Chem. Vap. Depos. 6 (2000) 285.
[12] J. Cai, H. Gonga, J. Appl. Phys. 98 (2005) 033707.
[13] A.N. Banerjee, C.K. Ghosh, K.K. Chattopadhyay, Sol. Energy Mater. Sol. Cells 89
(2005) 75.
[14] R.S. Yu, C.J. Lu, D.C. Tasi, S.C. Liang, F.S. Shieu, J. Electrochem. 154 (2007) H838.
[15] N. Tsuboi, Y. Itoh, J. Ogata, S. Kobayashi, H. Shimizu, K. Kato, F. Kaneko, Jpn. J. Appl.
Phys. 46 (2007) 351.
[16] D.S. Kim, S.J. Park, E.K. Jeong, H.K. Lee, S.Y. Choi, Thin Solid Films 515 (2007) 5103.
[17] A.S. Reddy, H.H. Park, G.M. Rao, S. uthanna, P.S. Reddy, J. Alloys Compd. 474 (2009)
401.
[18] G. Dong, M. Zhang, X. Zhao, Y. Li, H. Yan, J. Cryst. Growth 311 (2009) 1256.
[19] A.S. Reddy, P.S. Reddy, S. Uthanna, G.M. Rao, J. Mater. Sci., Mater. Electron. 17
(2006) 615.
[20] JANAF, Thermochemical Table, 3rd Edn, American Chemical Society and American
Institute of Physics for National Bureau of Standards, Midland USA, 1985.
[21] W.Y. Yang, W.G. Kim, S.W. Rhee, Thin Solid Films 517 (2008) 967.
[22] B. Chen, D. Yang, P.A. Charpentier, M. Zeman, Sol. Energy Mater. Sol. Cells 93
(2009) 1550.
[23] S.H. Jeong, B.N. Park, S.-B. Lee, J.–.H. Boo, Thin Solid Films 516 (2008) 5586.
[24] W.L. Jang, Y.M. Lu, W.S. Hwang, W.C. Chen, J. Eur. Ceram. Soc. 30 (2010) 503.
[25] L.H. Ahrens, Geochim. Cosmochim. Acta 2 (1982) 155.
[26] C. Bouzidi, H. Bouzouita, A. Timoumi, B. Rezig, Mater. Sci. Eng., B 118 (2005) 259.
[27] K.T. Jacob, C.B. Alcock, J. Am. Ceram. Soc. 58 (1975) 192.
[28] John F. Moulder, Handbook of X-ray Photoelectron Spectroscopy, Physical
Electronics, In, 1992.
[29] K. Tang, X. Wang, W. Yan, J. Yu, R. Xu, J. Membr. Sci. 286 (2006) 279.
[30] N.S. Mclntyre, S. Sunder, D.W. Shoesmith, F.W. Stanchell, J. Vac. Sci. Technol. 18
(1981) 714.
[31] J. Ghijsen, L.H. Tjeng, J. van Elp, H. Eskes, J. Westerink, G.A. Sawatzky, Phys. Rev., B
38 (1988) 11322.
[32] S.I. Suda, T. Aoyama, K. Kanamura, T. Umegaki, Jpn. J. Appl. Phys. 39 (2000) 3566.