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Effect of post-annealing on the properties of copper oxide thin films obtained

from the oxidation of evaporated metallic copper

Article  in  Applied Surface Science · April 2008

DOI: 10.1016/j.apsusc.2007.12.019

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Applied Surface Science 254 (2008) 3949–3954

www.elsevier.com/locate/apsusc

Effect of post-annealing on the properties of copper oxide thin films

obtained from the oxidation of evaporated metallic copper
V. Figueiredo a, E. Elangovan a,*, G. Gonçalves a, P. Barquinha a,
L. Pereira a, N. Franco b, E. Alves b, R. Martins a, E. Fortunato a
a
Materials Science Department, CENIMAT-I3N and CEMOP-UNINOVA, FCT-UNL, Campus de Caparica, 2829-516 Caparica, Portugal
b
LFI, Dep. Fı́sica, Instituto Tecnológico e Nuclear, EN10, 2686-953 Sacavém, Portugal
Received 23 October 2007; received in revised form 12 December 2007; accepted 14 December 2007
Available online 23 December 2007

Abstract
Thin films of copper oxide were obtained through thermal oxidation (100–450 8C) of evaporated metallic copper (Cu) films on glass substrates.
The X-ray diffraction (XRD) studies confirmed the cubic Cu phase of the as-deposited films. The films annealed at 100 8C showed mixed Cu–Cu2O
phase, whereas those annealed between 200 and 300 8C showed a single cubic Cu2O phase. A single monoclinic CuO phase was obtained from the
films annealed between 350 and 450 8C. The positive sign of the Hall coefficient confirmed the p-type conductivity in the films with Cu2O phase.
However, a relatively poor crystallinity of these films limited the p-type characteristics. The films with Cu and CuO phases show n-type
conductivity. The surface of the as-deposited is smooth (RMS roughness of 1.47 nm) and comprised of uniformly distributed grains (AFM and
SEM analysis). The post-annealing is found to be effective on the distribution of grains and their sizes. The poor transmittance of the as-deposited
films (<1%) is increased to a maximum of 80% (800 nm) on annealing at 200 8C. The direct allowed band gap is varied between 2.03 and
3.02 eV.
# 2008 Elsevier B.V. All rights reserved.

PACS : X-ray diffraction-crystal structure 61.10.N; Scanning electron-microscopy 61.16.B; Atomic force-microscopy-surface structure 61.16.C; Optical properties
78.66; Electron beam deposition 81.15.E

Keywords: X-ray diffraction; Physical vapor deposition processes; Copper oxide thin films; Oxides; Semiconducting materials

1. Introduction p-type semiconductor, conduction arises from the presence of

Oxides of copper are known to show p-type conductivity and
are attracting renewed interest as promising TCO materials in
the fabrication of a wide range of optoelectronic devices. Non-
toxic, economic and abundant availability and relatively simple
formation of oxide makes copper oxide as an interesting
material [1]. Two common forms of copper oxide are cuprous
oxide or cuprite (Cu2O) and cupric oxide or tenorite (CuO) [1].
Both the CuO (monoclinic) and Cu2O (cubic) are p-type
semiconductors with a band gap of 1.9–2.1 and 2.1–2.6 eV
respectively [2]. However, CuO is also reported to possess n-
type conductivity [3]. Cu2O is one of the oldest semiconducting
materials [4] which is useful in solar cell applications [5]. As a
* Corresponding author. Tel.: +351 212948562; fax: +351 212948558.
E-mail address: elam@fct.unl.pt (E. Elangovan).
0169-4332/$ – see front matter # 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2007.12.019
holes in the valence band (VB) due to doping/annealing [6].
Unlike the other oxides, the top states of VB in Cu2O are
derived from the fully occupied Cu 3d10 states which are not
localized (more mobile) when converted into holes [7].
Formation of Cu vacancy is an often stated mechanism for
the origin of p-type conductivity in Cu2O [6]. Stoichiometric
Cu2O is a well-studied material and first principles studies can
be found elsewhere [8]. CuO is also an interesting candidate in
the applications of solar energy converting devices, gas sensors
and superconducting devices [9]. A variety of deposition
techniques such as pulsed magnetron sputtering [1], electro
deposition [10,11], thermal oxidation [6], chemical deposition
[12], dc reactive sputtering [13], RF reactive sputtering [14],
ion beam sputtering [15], plasma evaporation [16], sol–gel [17],
molecular beam epitaxy [18] and chemical vapor deposition
[19] have been employed to study copper oxide films. As the
development of p-type transparent conducting oxide [20] is one
3950 V. Figueiredo et al. / Applied Surface Science 254 (2008) 3949–3954

of the key technologies for p–n junction-based oxide devices,

the research on copper oxide thin films has attracted the
researchers globally. The copper oxide films in the present
study were obtained through the conventional and inexpensive
thermal oxidation of evaporated metallic copper (Cu) films. The
physical properties of the films were studied in order to find the
possibility to use them in p–n junction based applications.

2. Experimental details

Thin films of Cu were deposited on microscopic glass

substrates (25 mm  25 mm  1 mm) by e-beam evaporating
the Cu pellets (CERAC; 99.999%). The distance between the
source and substrate was 25 cm. The thickness of the films
measured using profilometry was found to be 150 nm, which
is in agreement with the value obtained through quartz crystal
monitor mounted in the evaporation unit. The as-deposited Cu
films were post-annealed in a Barnstead Thermolyne F21130
tubular furnace, at temperatures ranging from 100 to 450 8C in
air for 30 min. The thickness of the as-deposited films is
increased by about 13–20%, to ranging 170–180 nm on
annealing due to the difference in lattice parameter of the Cu
and copper oxide phases. Similar results have been obtained
earlier by Matsumura et al. [21]. The as-deposited and post-
annealed films were characterized by X-ray diffraction (XRD),
Hall measurements, atomic force microscopy (AFM), scanning
electron microscopy (SEM) and UV–vis spectrophotometer. A
radiofrequency power generator (13.6 MHz) from Advanced
Energy (Model: RFX 2500) was used for sputtering the target.
The thickness of the films was measured using a surface
profilometer (Dektak3) with an accuracy of 20 nm. The
crystal structure of the films was confirmed using an X-ray Fig. 1. Comparison of XRD patterns of the copper oxide films as a function of
diffractometer (DMAX-III C from Rigaku; sealed tube, Cu Ka annealing temperature (symbol representations of the planes: (#) metallic Cu
radiation) in Bragg–Brentano geometry (u/2u coupled). Optical films, (b) Cu2O films and (~) CuO films).
transmittance was measured using a double-beam spectro-
photometer (Shimadzu UV-3100). The surface morphology (ICDD File: 05-0667; space group #224) was obtained along
was analyzed using scanning electron microscopy (Hitachi; with the other reflections from Cu phase. A single Cu2O phase
SU-70). The electrical parameters were estimated using a Hall was obtained for the films annealed at 200 and 250 8C, with a
measurements setup (BioRad HL5500 Hall system) with a strongest orientation along (1 1 1)b plane. When the annealing
permanent magnet of 5 kG in van der Pauw configuration. temperature is increased to 300 8C, the Cu2O phase transforms
Tapping mode AFM experiments were performed in a into copper(II) oxide (cupric oxide; CuO) phase. However, a
Multimode AFM microscope coupled to a Nanoscope IIIa small component of (1 1 1)b diffraction peak is retained that
Controller (Digital Instruments, Veeco). Commercially etched resulted in mixed Cu2O–CuO phase. A similar kind of mixed
silicon tips with a typical resonance frequency of ca. 300 kHz Cu2O–CuO phase for the films annealed at 300 8C is reported
D
were used as AFM probes. earlier [12]. The diffraction peaks of ð1 1 1Þ and (1 1 1)~ from
the monoclinic CuO phase were identified from the standard
3. Results and discussion data (ICDD File: 45-0937 and 48-1548; space group #15). A
further increase in annealing temperature (350 8C) leads to
It is perceptible that the XRD patterns obtained from the the formation of a single CuO phase, retaining the diffraction
D
films in the 2u ranging 30–608 (Fig. 1) are polycrystalline. The peaks of ð1 1 1Þ and (1 1 1)~. The conversion of Cu2O to CuO
diffraction peaks of (1 1 1)# and (2 0 0)# obtained from the as- during heating in the presence of oxygen is well known [22]. It
deposited films were matched with the standard Cubic Cu phase is earlier reported by Nair et al. [12] that the Cu2O phase
(ICDD File: 04-0836; space group #225). The reflection from convert into CuO phase when annealed at 350 8C, which
(1 1 1)# plane was found to be the strongest orientation. corroborate the present work. The composition of CuO is
Annealing at 100 8C partially oxidized the films to copper(I) maintained even for the annealing at 450 8C. It is also reported
oxide (cuprous oxide; Cu2O) which lead to the mixed Cu–Cu2O that at still higher temperature, CuO could revert to Cu2O [20],
phase. A diffraction peak from the (1 1 1)b plane of cubic Cu2O but however this possibility is not verified in the present work.
 V. Figueiredo et al. / Applied Surface Science 254 (2008) 3949–3954 3951

Table 1
XRD data of the copper oxide films as a function of annealing temperature
(symbol representations: (#) metallic Cu films, (b) Cu2O films and (~) CuO
films)
Annealing temperature (8C) Phase hkl 2u I/I0
#
RT Cu (1 1 1) 43.37 100
(2 0 0)# 50.70 14
100 Cu (1 1 1)# 43.37 100
(2 0 0)# 50.70 17
Cu2O (1 1 1)b 36.56 25
b
200 Cu2O (1 1 1) 36.56 100
250 Cu2O (1 1 1)b 36.56 100
300 Cu2O (1 1 1)b 36.56 73
D
Fig. 2. Variation of electrical properties of the copper oxide films as a function
CuO ð1 1 1Þ 35.70 64
of annealing temperature.
(1 1 1)~ 38.73 100
350 CuO D 35.70 73
ð1 1 1Þ to 300 8C. The r is then decreased slightly with increasing
(1 1 1)~ 38.73 100
annealing temperature by an order of magnitude to
400 CuO D
ð1 1 1Þ 38.73 100 3.1  101 V cm when annealed at 450 8C. The carrier
(1 1 1)~ 38.73 100 concentration (n) of the films (dominating metallic Cu phase)
450 CuO D 35.70 75 annealed at 100 8C decreased from 3.75  1022 cm3 by about
ð1 1 1Þ
(1 1 1)~ 38.73 100 six orders of magnitude to 3.69  1016 cm3 when annealed at
200 8C. The n is then gradually increased with increasing
annealing temperature to reach 7.19  1017 cm3 at 450 8C.
The obtained XRD peaks are in good agreement with the earlier The mobility (m) of the films annealed at 100 8C decreased
reports [9–14]. The XRD data are summarized in Table 1. unexpectedly from 6.11 to 1.56 cm2/V s for the increase in
The electrical properties were estimated from the Hall annealing temperature to 200 8C. The m then decreased
measurements in van der Pauw configuration. The type of gradually to 0.28 cm2/V s at 450 8C. The evident aspect of
conductivity was confirmed from the sign of Hall coefficient. electrical properties is that the films with Cu2O show p-type
The different electrical parameters are summarized in Table 2 conductivity. However, relatively poor crystallinity of these
along with a few optical data. The as-deposited and low films leads to reduced electrical characteristics. It may be
temperature (100 8C) annealed films showed n-type conduc- noteworthy that the Hall measurements were carried out again
tivity. The conductivity is changed to p-type for the films after about 7 months and the electrical properties are found to
annealed between 200 and 300 8C, where the Cu2O phase is be the same. This indicates that the deposited films have high
dominant. However, the conductivity is reverted to n-type for environment stability.
the further increase in annealing temperature to 350 8C, The surface microstructure of the films was analyzed by
where CuO phase is dominant. The variation in type of AFM. The surface of the as-deposited Cu films is very smooth
conductivity reveals that the films are p-type conducting when and the grains are distributed uniformly. The RMS roughness of
they crystallize in Cu2O phase. The variation of electrical these films is found to be 1.47 nm. The RMS roughness of the
properties is shown schematically in Fig. 2 as a function of films is increased to 11.78 nm on annealing at 100 8C,
annealing temperature. The bulk resistivity (r) of the films presumably due to the random distribution of the grains. The
annealed at 100 8C is increased from 2.73  105 to RMS roughness is increased to a maximum of 14.42 nm on
5.51  102 V cm for the increase in annealing temperature annealing at 200 8C but then decreased gradually to a value of

Table 2
Optical and electrical data of the copper oxide films as a function of annealing temperature
T (8C) t (mm) AVT (%) Band gap (eV) Carrier type Resistivity Mobility (cm2 V1 s1) Carrier concentration (cm3)
Rsh (V/&) r (V–cm)
RT 0.15 0.1 – n 0.29 3.51  106 18.30 9.72  10 22
100 0.15 5.1 2.70 n 1.82 2.73  10-5 6.11 3.75  10 22
200 0.17 65.6 3.02 p 6.37  106 108 1.56 3.69  10 16
250 0.17 49.4 2.57 p 1.48  107 251 1.27 1.95  10 16
300 0.17 38.0 2.85 p 3.24  107 551 0.21 5.45  10 16
350 0.18 44.4 2.03 n 1.07  107 192 0.26 1.25  10 17
400 0.18 43.0 2.79 n 3.22  106 58 0.22 4.98  10 17
450 0.18 36.4 2.80 n 1.73  106 31 0.28 7.19  10 17
T—annealing temperature; t—film thickness; AVT—average visible transmittance; Rsh—sheet resistivity; r—electrical resistivity.
3952 V. Figueiredo et al. / Applied Surface Science 254 (2008) 3949–3954

Fig. 3. AFM microstructures of the copper oxide films as a function of annealing temperature.

Fig. 4. SEM microstructures of the copper oxide films as a function of annealing temperature.
 V. Figueiredo et al. / Applied Surface Science 254 (2008) 3949–3954 3953

10.26 nm when annealed at 450 8C. The typical AFM

microstructures obtained from the as-deposited and those
annealed at 100, 250 and 450 8C films are shown in Fig. 3. The
surface of the as-deposited films is comprised of uniformly
distributed and tightly packed grains with the size ranging
10–20 nm. However, there appear few bigger grains with the
size as big as 40 nm. When the films are annealed at 100 8C,
the surface show randomly distributed cluster of grains.
Further, the grains vary in size between 10 and 30 nm with
few agglomerated grains as big as 60 nm on top of smaller
grains. There appear few drains throughout the surface of the
films. The drains seem to contain grains which are not
distinguishable presumably due to the technical limitation of
AFM. The drains are suppressed for the 250 8C annealing,
which probably suggest that the grains are distributed
uniformly due to the increased surface energy. The grains Fig. 5. Comparison of transmittance spectra of the copper oxide films as a
are cubical in shape and the size of the grains varies between 15 function of annealing temperature.
and 30 nm. The grains are held together by a uniformly
distributed bunches, which gives a cauliflower-like morphol-
ogy. There appear few agglomerated grains as big as 70 nm
on top of this morphology. The size of the grains increases to a
range 20–40 nm when the films are annealed at 450 8C, with
fewer agglomerated grains on the surface.
The typical microstructures of the films analyzed by SEM
are shown in Fig. 4. The surface of the as-deposited films is very
smooth and well packed with tiny grains. The films annealed at
100 8C comprise cubical shaped grains size of which varying
between 10 and 40 nm, on top of very fine grains. The size of
the grains is increased to ranging 40–90 nm when annealed at
250 8C. The grains are agglomerated and it is very hard to
identify the shape of the grains. The grains appear to grow as
stacking of layers and correspondingly the surface looks rough.
The stacking of grains as layers is clearly visible when the films
are annealed at 450 8C, which is akin to the etched surface. The
Fig. 6. Comparison of the a2 vs. hn plots of the copper oxide films as a function
size of grains decreased to a range 20–70 nm. of annealing temperature.
The transmittance spectra recorded in the wavelength
ranging 350–2500 nm are shown in Fig. 5 as a function of
annealing temperature. The as-deposited films showed poor oxide film is known to be a direct-allowed semiconductor, and
transmittance (<1%), which is understandable due to the high hence a graph is plotted (Fig. 6) with a2 versus photon energy
absorption of the metallic Cu. The transmittance is increased on (hn) as a function of annealing temperature. Intersect of the x-
annealing, and the transmittance of the films annealed at axis from the extrapolation of the linear portion of the curve to
200 8C is varying between 70 and 80%. The average visible a2 = 0 gives the value of Eg. The calculated direct-allowed Eg
transmittance (AVT) calculated in the wavelength ranging 600– estimated from the plot is varied ranging 2.03–3.02 eV. The
800 nm is varied between 50 and 66%. The minimum AVT obtained values are in agreement with the previous reports [2–
of 5 obtained for the films annealed at 100 8C is increased 6]. Due to the poor transmittance and undistinguishable
with increasing temperature to 66% at 200 8C. The AVT is absorption edge, the Eg of undoped films (metallic Cu) could
then decreased to 50% for the films annealed at 250 8C. The not be estimated. The Eg of the films annealed at 100 8C is
AVT of the films annealed at 300 8C is reduced to be around 2.70 eV, which is increased to 3.02 eV when annealed at 200 8C
40%. The transmittance data are summarized along with but then decreased significantly with the further increase in
electrical properties in Table 2. The optical absorption in the annealing temperature. The variation of Eg is oscillatory when
UV region is dominated by the optical band gap (Eg) of the correlated with the annealing temperature, which is quantita-
semiconductor that is related to the optical absorption tively presented in Table 2. To the best of authors’ knowledge
coefficient (a) and the incident photon energy (hn) by the the value of 3.02 eV obtained in the present study is the highest
relation a = (Eg  hn)n [23], where ‘n’ depends on the kind of reported Eg value for copper oxide thin films. A relatively low
optical transition that prevails. Specifically, n is 1/2, 3/2, 2 and 3 Eg value (2.03 eV) obtained for the films annealed at 350 8C
when the transition is direct-allowed, direct-forbidden, indir- may probably suggest that the films have structural defects
ect-allowed, and indirect-forbidden respectively. The copper which needs to be studied in detail.
3954 V. Figueiredo et al. / Applied Surface Science 254 (2008) 3949–3954
4. Conclusion
Thin films of copper oxide were obtained through oxidization
of the metallic Cu films deposited on glass substrates by e-beam
evaporation. It is demonstrated that the cubic Cu phase of the as-
deposited films changes into single cubic Cu2O phase for the
annealing between 200 and 300 8C, and whereas the films
annealed between 350 and 450 8C show a single monoclinic CuO
phase. The films with dominating Cu2O phase are p-type
conducting, but however, a relatively poor crystallinity of these
films limited the p-type characteristics. The films with Cu and
CuO phases show n-type conductivity. The surface of the as-
deposited films is smooth (RMS roughness of 1.47 nm) and is
comprised of uniformly distributed grains. The post-annealing is
found to be effective on the distribution of grains and their sizes.
The poor transmittance of the as-deposited films (<1%) is
increased to a maximum of 80% (800 nm) on annealing at
200 8C. The direct allowed band gap is varied between 2.03 and
3.02 eV. The p-type characteristics need to be improved to make
these films useful for applications like transparent p–n junction
based devices.
Acknowledgements
This work was partially funded by the Portuguese Science
Foundation (FCT-MCTES) through projects POCI/CTM/
55945 and POCI/CTM/55942 and by European contract
NMP3-CT-2006-032231 (Multiflexioxides project).
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