J Mater Sci: Mater Electron (2012) 23:1492–1499

DOI 10.1007/s10854-011-0616-2

Nanocrystalline CuO thin films: synthesis, microstructural

and optoelectronic properties
D. M. Jundale • P. B. Joshi • Shashwati Sen •

V. B. Patil

Received: 8 November 2011 / Accepted: 26 December 2011 / Published online: 4 January 2012
Ó Springer Science+Business Media, LLC 2012

Abstract Nanocrystalline copper oxide (CuO) thin films optoelectronic applications. The optical band gap energy
have been synthesized by a sol–gel method using cupric decreases (1.64–1.46 eV) with increasing annealing tem-
acetate Cu (CH3COO) as a precursor. The as prepared perature. It was observed that the crystallite size increases
powder was sintered at various temperatures in the range of with increasing annealing temperature. These modifications
(300–700 °C) and has been deposited onto a glass substrates influence the morphology, electrical and optical properties.
using spin coating technique. The structural, compositional,
morphological, electrical optical and gas sensing properties
of CuO thin films have been studied by X-ray diffraction, 1 Introduction
Scanning Electron Microscopy (SEM), Four Probe Resis-
tivity measurement and UV–visible spectrophotometer. The Cupric oxide (CuO, tenorite) has been reported to exhibit
variation in annealing temperature affected the film mor- p type [1–3] as well as n-type properties [4–6]. It is observed
phology and optoelectronic properties. X-ray diffraction that the CuO having a p type conductivity shows a band gap of
patterns of CuO films show that all the films are nanocrys- nearly 2.1 eV [1–3] whereas CuO showing n type conduc-
tallized in the monoclinic structure and present a random tivity is observed to show band gap between 1.3–1.5 eV [4–6].
orientation. The crystallite size increases with increasing It is speculated that the presence of oxygen deficiency which
annealing temperature (40–45 nm). The room temperature are unavoidable during the process of synthesis makes the
dc electrical conductivity was increased from 10-6 to 10-5 CuO to exhibit n type conductivity [4–6]. Cupric oxide has
(X cm)-1, after annealing due to the removal of H2O vapor been employed in heterogeneous catalysis for several envi-
which may resist conduction between CuO grain. The ther- ronmental processes as well as in the production of gas sensing
mopower measurement shows that CuO films were found of devices, owing to the conductivity changes induced by the
n-type, apparently suggesting the existence of oxygen reaction of gases with surface adsorbed oxygen [7]. Con-
vacancies in the structure. The electron carrier concentration versely, when combined with small noble metal particles,
(n) and mobility (l) of CuO films annealed at 400–700 °C copper (II) oxide displays high activity as optical gas sensor
were estimated to be of the order of 4.6–7.2 9 1019 cm-3 [8, 9]. In this context, an increasing attention is being devoted
and 3.7–5.4 9 10-5 cm2 V-1 s-1 respectively. It is to the preparation of nanosystems, owing to the synergy
observed that CuO thin film annealing at 700 °C after between their large surface area and high defect content that
deposition provide a smooth and flat texture suited for are expected to result in peculiar functional properties [10–
12]. In the preparation of such systems, stoichiometry and
phase composition represent a major concern. Further aspects,
D. M. Jundale  P. B. Joshi  V. B. Patil (&)
Materials Research Laboratory, School of Physical Sciences, such as crystallite size and distribution, can be suitably tai-
Solapur University, Solapur 413255, MS, India lored by a proper choice of the molecular precursors and of the
e-mail: drvbpatil@[Link] annealing conditions. Among the different chemical routes to
nanosystems, the sol–gel technique plays an outstanding role
S. Sen
Crystal Technology Section, Technical Physics Division, BARC, as a soft bottom-up approach to achieve a good control over
Mumbai, India film composition and microstructure.

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J Mater Sci: Mater Electron (2012) 23:1492–1499 1493

To the best of our knowledge, no work is available in the

Cupric Acetate + Methanol
literature on the sol–gel synthesis and characterization of n
type CuO-based nanosystems.
Owing to the discussion above the present paper reports
novel method of synthesis of n type CuO by sol gel route Stirring at 60 oC for 1 hr
annealed between 300 and 700 °C and investigate their
compositional, structural, optical and electrical transport
properties. After cooling at RT
Cyan Powder
2 Experimental details

Nanostructured CuO have been synthesized by a sol–gel

method using cupric acetate Cu(CH3COO)H2O as a source of Sinter powder at 300-700 oC for 1 hr in air
Cu. In a typical experiment; 2.5096 gm of cupric acetate was
added to 20 mL of methanol and stirred vigorously at 60 °C
for 1 h, leading to the formation of cyan powder. The as
prepared powder was sintered at various temperatures ranging Nanocrystalline CuO powder
from 300 to 700 °C with a fixed annealing time of 1 h in an
ambient air to obtain CuO with different crystallite sizes. The
nanocrystalline CuO powder was further dissolved in m-cresol
and solution was continuously stirred for 11 h at room tem- CuO powder + m cresol
perature and filtered. The filtered solution was deposited on to
a glass substrate by a single wafer spin processor (APEX
Instruments, Kolkata, Model SCU 2007). After setting the
Spin coat the solution on the glass
substrate on the substrate holder of the spin coater, the coating substrate at 3000 rpm for 40 sec.
solution (approximately 0.2 mL) was dropped and spin-cas-
ted at 3,000 RPM for 40 s in an air and dried on a hot plate at
100 °C for 10 min. Figure 1 shows the flow chart for the sol
gel synthesis of the CuO films prepared by using the spin- Heat treatment at 100 oC for 10 min in air.
coating technique. The structural properties of the films were
investigated by means of X-ray diffraction (XRD) (Philips
PW-3710, Holland) using Cu Ka radiation (k = 1.5406 Å).
The compositional analysis of nanocrystalline CuO thin film CuO films
annealed at 700 °C was conducted using the EDAX facility on
the scanning electron microscope. The surface morphology of Fig. 1 Flow diagram for CuO films prepared from the sol–gel
process using the spin- coating technique
the films was examined by using scanning electron micros-
copy (SEM) (Model: JEOL-JSM-6360, Japan), operated at Cu ðCH3 COOÞ2 : H2 O þ CH3  OH
20 kV. The room temperature dc electrical conductivity ! CuðOHÞ2 þ 2CH3 COOCH3 þ H2 O
measurements were performed using four probe technique.
The optical absorption spectra of the CuO thin films were Since to improve crystallinity and remove hydroxide phase,
measured using a double-beam spectrophotometer Shimadzu powders were annealed for 1 h pure CuO is formed after
UV-140 over range of 200–1,000 nm. The thickness of the air annealing by following mechanism:
Airannealing
film was measured by using weight difference method and Cu ðOHÞ2 # þ2CH3 COOCH3 ! CuO þ H2 O "
Oxidation
Dektak profilometer.
Thin films of annealed CuO powder is prepared in m-cresol
and deposited on glass substrate as discussed in Sect. 2.
3 Results and discussion
Thickness was calculated by weight difference method
using formula:
3.1 CuO film formation mechanism and thickness
t ¼ m=Aq ð1Þ
measurement
where t is film thickness of the film; m is actual mass
The mechanism of CuO film formation by the sol gel spin deposited onto substrate; A is area of the film and is the
coating method can be enlightened as follows: density of nanocrystalline copper oxide (6.31 g/cm3).

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1494 J Mater Sci: Mater Electron (2012) 23:1492–1499

Table 1 - Effect of annealing on CuO thin film properties

Sr. no Annealing Crystallite Size, Thickness Energygap, Activation Carrier (n) concentration, Mobility(l) cm2,
temperature oC nm (from XRD) lm Eg eV energy, Ear, eV V-1 s-1 9 10-5
91019 cm-3
HT LT

1. 300 40.10 0.910 1.64 0.010 0.0012 4.60 3.70

2. 400 41.55 0.864 1.59 0.016 0.0010 5.75 3.98
3. 500 43.20 0.820 1.54 0.023 0.009 6.20 4.53
4. 600 46.80 0.781 1.51 0.040 0.026 6.80 5.20
5. 700 50.67 0.547 1.46 0.110 0.077 7.20 5.40

on the annealing temperature. It increases as the annealing

o
(a) 300 C temperature increases. The lattice constants calculated
(002)

(111)

o
(b) 400 C
o
from the present data are a = 4.6890, b = 3.4250 and
(c) 500 C
o
(d) 600 C c = 5.1324 Å respectively. The average CuO thin film
o
(e) 700 C particle sizes were calculated using the full width at half
maximum (FWHM) of (111) peak from the Debye Scher-
Intensity (a.u)

er’s formula and were presented in Table 1. The calculated

(200)

values of the crystallite size ranged between 40 and 50 nm.

(112)

(113)

It was observed that crystallite size increased with

(004)
(110)

(221)
(202)

(e) increasing annealing temperature, which can be understood

(202)

(311)
(220)

(023)

(d) by considering the merging process induced from thermal

(c) annealing. For CuO nanoparticles, there are many dangling
(b)
bonds related to the copper of oxygen defects at the grain
(a)
boundaries. As a result, these defects are favorable to the
20 30 40 50 60 70 80 merging process to form larger CuO grains while increas-
2θ (degree) ing the annealing temperature. The FWHM of (111) plane
Fig. 2 X ray diffraction patterns of CuO films annealed at different
of CuO thin film with various annealing temperatures is
temperatures (300–700 °C) also compared. As the annealing temperature increases
from 300 to 700 °C, the FWHM value exhibits a tendency
to decrease, which can be attributed to the coalescences of
It was observed that increasing the annealing tempera- grains at higher annealing temperature [14]. As a result; it
ture resulted in a decrease in film thickness from 0.901 lm implies that the crystallinity of the CuO thin films is
(300 °C annealing) to 0.546 lm (700 °C annealing). The improved at higher annealing temperatures. Other workers
CuO thin film thickness is also confirmed by using Dektak [15, 16] have also observed the improvement in crystal-
profilometer and is presented in Table 1. linity of the CuO thin films with the increase of annealing
temperature. These may be due to high annealing temper-
3.2 Structural properties ature providing energy to crystallites gaining enough
energy to orient in proper equilibrium sites, resulting in the
Figure 2 shows X-ray diffraction patterns of CuO thin films improvement of crystallinity and degree of orientation of
annealed at different temperatures viz, 300, 400, 500, 600, the CuO films.
and 700 °C. Below 400 °C annealing temperature, small The crystallite size (D) is calculated using equation as
peaks were observed and the film shows a poor crystal- follows [17]:
linity. Four different reflections along (110), (002), (111),
D ¼ 0:9k=bcosh ð2Þ
and (202) are prominently seen when the films annealed at
300–700 °C, which corresponds to characteristics of the where, b is the half width of diffraction peak measured in
CuO monoclinic phase [JCPD No.80-1917]. It is concluded radians. The calculation of crystallite size from XRD is a
that all the films were polycrystalline with a monoclinic quantitative approach which is widely accepted and used in
structure and a random orientation, which generally occurs scientific community [18–20]. The average crystallite size
in the growth of CuO thin films [13]. The degree of c-axis calculated and it was about 40–50 nm revealed a fine
orientation of the CuO thin films was strongly dependent nanocrystalline grain structure.

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J Mater Sci: Mater Electron (2012) 23:1492–1499 1495

which may resist conduction between CuO grains. Similar

type of increase in electrical conductivity has been
observed by Pawar et al. for sol gel derived TiO2 [21]. It is
observed (Fig. 5) that the conductivity of film was
increased with increase in annealed temperature, which
indicates a semiconducting electrical behavior of the CuO
thin films. The activation energies were calculated using
the relation:
r ¼ ro expðEa =kTÞ ð3Þ
where, r is the conductivity at temperature T, ro is a
constant, k is the Boltzmann constant, T is the absolute
temperature and Ea is the activation energy. The activation
energy represents the location of trap levels below the
conduction band. From Fig. 5, activation energy (Ea) was
Fig. 3 EDAX spectra of CuO thin film annealed at 700 °C increases from 0.010 to 0.11 eV, when film annealed from
300 to 700 °C indicating no significant change.

3.3 Compositional analysis 3.5.2 Thermoelectric power measurement

Figure 3 shows EDAX spectra of nanocrystalline CuO thin The thermo-emf of CuO films annealed between 300 and
film annealed at 700 °C. The EDAX analysis revealed the 700 °C was measured as a function of temperature in the
presence of copper and oxygen and other elements from the temperature range 300–500 K. The polarity of the ther-
glass substrates. The gold traces arise from the gold coat- mally generated voltage at the hot end was positive, indi-
ings applied to enhance the SEM imaging. cating that the CuO films are of n-type [22]. The variation
of the thermo-emf (DV) with temperature is shown in
3.4 Morphological analysis Fig. 6. The thermo-emf increases with increasing temper-
ature. The thermo-electric power (TEP) was used to eval-
The two-dimensional high magnification surface mor- uate the carrier mobility (l) and carrier concentration
phologies of CuO thin films were carried out using SEM (n) using the relation
images are shown in Fig. 4. SEM micrograph reveals the h i
 3=2
formation of particles with different shapes and sizes, it TEP ¼  k=e A þ lnf2 2p mc kT =nh3 g ð4Þ
seems appropriate to consider that the particles which
appear in SEM images are, in fact, grain agglomerates, where A is a thermoelectric factor (2 for copper oxide), n is
which get fragmented with rise in annealing temperature. electron density, h is Plank’s constant, m*c is the effective
The films annealed at 300–600 °C shows, larger particles/ mass of the electron.
grain agglomerates as compared to films annealed at higher After substitution of various constants Eq. (4) simplifies
temperatures. However, morphological features of the films to [23]:
annealed at 700 °C, appeared most uniform. The randomly
Log n ¼ 3=2 log T  0:005TEP þ 15:719 ð5Þ
oriented morphology with slight increase in crystallite size
(40–50 nm) has been observed after annealing. The electron density (n) was calculated using the above
equation and was in the order of 1019cm-3 for films
3.5 Electrical transport studies annealed at 300–700 °C. The mobility (l) of the charge
carriers is determined from the relation:
3.5.1 Electrical conductivity measurement
l ¼ r=ne ð6Þ
The four-point probe method of dc electrical conductivity where n is electron density and r is conductivity. The
measurement was used to study the variation of electrical variation of log n and log l as a function of temperature for
conductivity of the film with annealing temperature. The CuO film annealed at 700 °C is shown in Fig. 7. It is
variation of log r with reciprocal of the temperature observed that electron density (n) and mobility (l) increases
(1,000/T) is depicted in Fig. 5. After annealing, room with temperature. The electron carrier concentration (n) and
temperature electrical conductivity was increased from mobility (l) of CuO films annealed at 300–700 °C were
10-6 to 10-5 (X cm)-1, due to the removal of H2O vapor estimated to be of the order of 4.6–7.2 9 1019 cm-3 and

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1496 J Mater Sci: Mater Electron (2012) 23:1492–1499

Fig. 4 SEM images of CuO

thin films anneled at a 300 °C
b 400 °C c 500 °C d 600 °C
and e 700 °C

3.7–5.4 9 10-5 cm2 V-1 s-1 respectively. The temperature 3.6 Optical studies
variation of carrier mobility suggests that there is a con-
siderable amount of scattering mechanism due to the inter- The variation of optical absorbance (at) of the CuO film is
grain barrier potential [24–27]. This carrier scattering is shown in Fig. 9. This spectrum reveals that as-deposited
temperature dependent, and therefore it is related to the CuO film has low absorbance in the visible region, which is
carrier mobility (l) and intergranular potential (Ub) [24–27]. the characteristic of CuO. The absorbance was ‘‘red shif-
ted’’ after annealing, which may be due to the water
l ¼ lo expðUb =kTÞ ð7Þ removal after annealing. The theory of optical absorption
gives the relationship between the absorption coefficient a
where all the terms have their usual meanings. Intergran-
and the photon energy hm for direct allowed transition:
ular potential (scattering potential) is therefore calculated  1=2
hm  Eg
from the log lT1/2 versus 1,000/T variation (Fig. 8) as a¼ ð8Þ
suggested by Micocci et al. [28] and its values is in hm
between 0.35 and 0.48 eV for CuO film annealed at The equation gives the band gap energy Eg, when straight
400–700 °C. portion of (ahm)1/2 versus hm plot is extrapolated to the

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J Mater Sci: Mater Electron (2012) 23:1492–1499 1497

-3.2
(e) (a) o
(a) 300 C
o
-3 o
-3.6 (a) 300 C (b) 400 C
o (b) o
(b) 400 C (c) 500 C
o o
-4.0 (d) (c) 500 C (c) (d) 600 C
o
(d) 600 C -4 (d) o
(e) 700 C
(c)
o
-4.4 (b) (e) 700 C (e)

1/2
log μ T
log σ

-4.8 (a) -5

-5.2
-6
-5.6

-6.0
-7
-6.4

1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 2.0 2.2 2.4 2.6 2.8 3.0 3.2
-1
1000/T (K )
-1 1000/T (K )

Fig. 5 Arrhenius plot of dc log conductivity vs. 1,000/T of CuO thin Fig. 8 Plot of log lT1/2 vs. 1,000/T
film annealed at different temperatures (300–700 °C)
3.0
o
(a) 300 C
o
(b) 400 C
2.5 o
(c) 500 C
o
10 (a) (d) 600 C
o
(b) 2.0 (e) 700 C
Absorbance (αt)

(c) (e)
Thermo-emf ( mV/ K)

8
o

1.5 (d)
(d)

(e) (c)
6
1.0 (b)

(a)
4 0.5
o
(a) 300 C
o
(b) 400 C
o
(c) 500 C 0.0
2 o
(d) 600 C
o
(e) 700 C
400 600 800 1000

0
Wavelength (nm)
300 350 400 450 500
o Fig. 9 Variation of absorbance (at) (a absorption coefficient, t thick-
Temperature ( K)
ness) with wavelength (k) of CuO thin film annealed at different
Fig. 6 The variation of thermo-emf with temperature for of CuO thin temperatures (300–700 °C)
film annealed at different temperatures (300–700 °C)

point a = 0. Figure 10 shows plot of (ahm) 2 versus hm for

-2.6 the CuO thin film. From the Fig, the Eg value is found to
19.90
decrease from 1.64 to 1.46 eV with increasing annealing
-2.8 temperature from 300 to 700 °C. The decrease in Eg
19.85
indicates an improvement of the quality of the film due to
-3.0 19.80 the annealing out of the structural defects. This is in
log n
log μ

agreement with the experimental results of XRD analysis.

-3.2 19.75 According to XRD results, the mean grain size increased
with increased annealing temperature. As grain size
19.70
-3.4 increased, the grain boundary density of a film decreased,
19.65 subsequently, the scattering of carriers at grain boundaries
-3.6 decreased [29]. A continuous increase of optical constants
2.0 2.2 2.4 2.6 2.8 3.0 3.2
-1
and also a shift in absorption edge to a higher wavelength
1000/T (K )
with increasing annealing temperature may be attributed to
Fig. 7 Variation of log n and log l as a function of temperature for the improvement in the crystalline quality of the films
CuO thin films annealed at 700 °C along with reduction in porosity.

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1498 J Mater Sci: Mater Electron (2012) 23:1492–1499

5.0x10
14
(e)
The electron carrier concentration (n) and mobility (l) of
4.5x10
14 o
(a)300 C (d) CuO films annealed at 300–700 °C were estimated to be of
o (c)
4.0x10
14
(b)400 C
o
(c)500 C (b) the order of 4.6–7.2 9 1019 cm-3 and 3.7–5.4 9 10-5 cm2
14
o
(d)600 C (a) V-1 s-1 respectively. Optical absorption studies showed
(αhυ) (cm eV )

3.5x10 o
2

(e)700 C
14
low-absorbance in visible region with band gap 1.64 eV
3.0x10
which was decreased to 1.46 eV after annealing. This has
-2

14
2.5x10
been attributed to the decrease in defect levels. The p-type
2

14
2.0x10 electrical conductivity is confirmed from thermo-emf
14
1.5x10 measurement with no appreciable change in thermoelectric
14
1.0x10 power after annealing.
13
5.0x10
0.0
Acknowledgments Authors (VBP) are grateful to DAE-BRNS, for
0.5 1.0 1.5 2.0 2.5 3.0 financial support through the scheme no.2010/37P/45/BRNS/1442.
Band gap (eV)

Fig. 10 Plot of (aht)2 versus band gap (eV) of CuO thin films for
different annealing temperatures (300–700 °C) References

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