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Journal of Alloys and Compounds 610 (2014) 250257

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Journal of Alloys and Compounds


journal homepage: www.elsevier.com/locate/jalcom

Study of copper doping effects on structural, optical


and electrical properties of sprayed ZnO thin lms
A. Mhamdi a,, R. Mimouni a, A. Amlouk a, M. Amlouk a, S. Belgacem a,b
a
b

Unit de physique des dispositifs semi-conducteurs, Tunis EL MANAR University, 2092 Tunis, Tunisia
College of Sciences and Art at ArRass, Qassim University, PO Box 53, 51921, Saudi Arabia

a r t i c l e

i n f o

Article history:
Received 27 February 2014
Received in revised form 1 April 2014
Accepted 1 April 2014
Available online 13 April 2014
Keywords:
Thin lms
Cu doped ZnO
Structure
Optical constants
Dielectric properties
Impedance spectroscopy

a b s t r a c t
Copper-doped zinc oxide thin lms (ZnO:Cu) at different percentages (13%) were deposited on glass
substrates using a chemical spray technique. The effect of Cu concentration on the structural, morphology
and optical properties of the ZnO:Cu thin lms were investigated. XRD analysis revealed that all lms
consist of single phase ZnO and were well crystallised in wrtzite phase with the crystallites preferentially oriented towards (0 0 2) direction parallel to c-axis. The Film surface was analyzed by contact
atomic force microscopy (AFM) in order to understand the effect of the doping on the surface structure.
Doping by copper resulted in a slight decrease in the optical band gap energy of the lms and a noticeably
change in optical constants. From the spectroscopy impedance analysis we investigated the frequency
relaxation phenomenon and the circuit equivalent circuit of such thin layers. Finally, all results have been
discussed in terms of the copper doping concentration.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Zinc oxide ZnO is an n-type semiconductor. The n-type semiconductor behaviour is originated by the ionization of excess zinc
atoms at interstitial positions and the oxygen vacancies [1]. Also,
one of the efcient ways of improving the properties of ZnO lms
is the addition of certain dopants. Transition metal elements have
been successfully employed as dopants in ZnO such as V, Ni, Mn
and Cu. In particular, the group IB transition element, copper with
similar ionic radius to that of Zn2+ ion and electronic shell structure, has many physical and chemical properties similar to those
of Zn [2]. Zinc oxide is a very promising for optoelectronic applications in UV region, especially as TCO in solar cells, gas sensors and
acoustic devices (LEDs) [36]. This paper deals with the synthesis
of microcrystalline Cu-doped ZnO thin lms an appropriate at
low substrate temperature by simple and inexpensive spray pyrolysis technique. The structural and optical properties of ZnO thin
lms are studied as a function of copper doping concentration.
In the same way, this work reported the electrical of impedance
spectroscopy measurements to model the microstructure of such
oxide lms in terms of Cu content and determine the activation
energy evolution with doping.

Corresponding author. Tel.: +216 97797763.


E-mail address: mhaammar@gmail.com (A. Mhamdi).
http://dx.doi.org/10.1016/j.jallcom.2014.04.007
0925-8388/ 2014 Elsevier B.V. All rights reserved.

This study aims to use these CZO thin lms in sensitivity applications. It is reported that this type of doping may be of interest to
change native n-type of ZnO to p-type character as reported by
Chung et al. [7]. Moreover, this behavior leads indeed to some
interesting change in electrical properties especially the resistivity
of such lms. Thus, Cu doped element can in principle reinforce
ZnO lms as gas sensors as reported by Gong et al. [8] for the
sensitivity of CZO regarding CO toxic gas at 6 ppm. That is why
we focus our study to reach more information on structural and
electrical investigations by means of conductivity measurements
at various temperatures of CZO sprayed lms.

2. Experimental details
ZnO thin lms were deposited onto glass substrate at 460 C by the chemical
spray technique [9,10]. Undoped ZnO thin lms were prepared using zinc acetate
(C4H6O4Zn, 2H2O) dissolved in isopropyl alcohol to obtain a starting solution with
a 102 mol/l concentration. Consecutively and under similar experimental conditions, copper-doped (ZnO:Cu) thin lms solution have been prepared by adding
hydrated copper chloride anhydrous (CuCl2, 99.9% purity) to the precursor solution
while maintaining acidity level at 4.7 acetic acid. In the different elaborated
samples, the ratio in the starting solution between Cu and Zn ([Cu]/[Zn]) elements
varies from 1% to 3%. X-ray diffraction data of Cu doped ZnO lms were performed
by a copper-source
diffractometer (Analytical X Pert PROMPD) with the wavelength
0
k = 1.54056
A. Morphological aspects and surface topography of the lms were
examined by atomic force microscopy (AFM) (Park Scientic Instrument) in contact
mode. The optical measurements in the UVVisible range were carried out using a
Shimadzu UV 3100 double-beam spectrophotometer within 3001800 nm
wavelength range. Finally, the electrical measurements of real and imaginary

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A. Mhamdi et al. / Journal of Alloys and Compounds 610 (2014) 250257

Table 2
The interplanar spacing dhkl and the lattice constants a and c values of the sprayed
ZnO:Cu thin lms.

(002)
ZnO:Cu 3%

(002)

Interplanar spacing
(0 0 2)
dhkl ()
(1 0 1)
a ()
c ()

Intensity (a.u)

ZnO:Cu 2%

c
a

(002)

undoped
(101)
30 31 32 33 34 35 36 37 38 39 40

2 ()
Fig. 1. X-ray diffraction spectra conned to the range h = [15, 20].

components of impedance parameters (Z0 and Z00 ) were made over a wide range of
temperature 618708 K and frequency 10 Hz13 MHz by means of a HewlettPackard HP 4192 impedance analyzer. The conguration for electrical measurements
was performed using two-electrodes which were applied on the two extremities
of the sample using silver paste.

3.1. Structural properties


Fig. 1 shows the XRD patterns of CZO thin lms of d = 0.2 lm
thickness prepared at different Cu doping concentrations: 13%.
For the undoped ZnO, it can be seen that thin lm is polycrystalline
with several strong diffraction peaks located at 2h = 34.46 and
36.30 corresponding respectively to (0 0 2) and (1 0 1) directions
of ZnO in hexagonal wurtzite structure. For further clarication
and comparison we have included in Fig. 1 all spectra with limited
angles range over the constructive diffraction of X-rays. In all lms
(undoped and Cu doped) the crystallites have preferential c-axis
orientation along (0 0 2) direction perpendicular to the plane of
the glass substrate, this is indicated by the values of the orientation
degree of the (0 0 2) line given in Table 1. Furthermore, no phases
corresponding to Cu oxides were detected, which indicate that
copper ions occupy substitutional positions and did not change
the hexagonal wurtzite structure in CZO lms. Also, the orientation
degree of the peak representing (0 0 2) plane was lower in the ZnO

Table 1
The constructive diffraction angle and the orientation degree II002
values of the sprayed
101
Cu doped ZnO thin lms.

I 002
I101

2.60

2.60

2.60

2.59

2.59

2.48

2.47

2.47

2.47

3.25
5.20
1.60

3.24
5.20
1.60

3.24
5.19
1.60

5.19

3.25
5.19
1.59

lm than in all ZnO:Cu lms. By increasing the Copper doping concentration, the reected intensity at (0 0 2) plane appears to
increases at 2% at the expense of those at 1% and 3%. This indicates
that dopant incorporation affects the crystallinity of the lms, possibly because copper ion Cu+ has slightly greater ionic radius
(0.096 nm) than Zn2+ (0.074 nm). In addition, the position of
(0 0 2) peak shifted slightly (0.05) from 2h = 34.46 in undoped
ZnO lm to higher angles as Cu content increases (2h = 34.51 for
CZO 3%).
From these spectra, we calculated the interplanar spacing dhkl of
the crystalline planes families (hkl) using Braggs law. We found
that the results shown in Table 2 are largely matched with standard data [11]. In the same way, by using the relationship of dhkl
for the hexagonal system and inclusion of Miller indices for the
two crystallines planes (0 0 2) and (1 0 1), we deduced the appropriate lattice constants a and c as follows:

1
dhkl r

 2
4 h2 k2 hk
c2
2
3
a

3. Results and discussion

Orientation degree

Experiment: Cu content Cu/Zn (%)

ZnO:Cu 1%

(002)

Constructive diffraction
angle 2h ()
(0 0 2)
(1 0 1)

Results JCPDS
(pure powder
ZnO)

8
d002 q1 2c
>
>
>
22
>
<
c2
1
d101 r
>
 
>
>
>
4 12 12
:
3 a2
c2

Experiment: Cu content
Cu/Zn (%)
0

34.43
36.24

34.46
36.30

34.47
36.31

34.51

34.51
36.25

0.56

3.43

2.53

12.67

3.75

(
)

c 2d002
2cd101
a p
2

3c2 d101

We note that the parameter c decreases from 5.200 in the


undoped ZnO to 5.192 in ZnO:Cu 3% lms, Table 2. This decrease
in c lattice parameter may be due to a possibly substitution of Zn2+
by Cu ions. Indeed, if most Cu atoms replace Zn, (0 0 2) peak position of ZnO:Cu moves to a slightly high angle as compared to that
of undoped ZnO because the ionic radius of Cu+ has a greater ionic
radius than does Zn2+. This result is also reported by Drmosh et al.
on ZnO:Cu prepared using pulsed laser deposition [12].
On the other hand, the values of full width at half maximum
(FWHM) for (0 0 2) diffraction peak for CZO lms were carried
out and used in order to estimate the mean grain size by the
DebyeScherrers formula [13]:

Results JCPDS
(pure powder
ZnO)

Kk
bcos h

where K = 0.9 and b is its FWHM. The results is reported in Table 3


where it can be seen that the doping ZnO:Cu 2% exhibits the best
crystallinity with D = 48.97 nm. A broadening in X-rayon peak with
increasing copper concentration is especially observed at 3% of Cu
content beyond which the disorder appears. Similar results were
obtained elsewhere [14].

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A. Mhamdi et al. / Journal of Alloys and Compounds 610 (2014) 250257

Table 3
The grain size D and the roughness values of the sprayed Cu doped ZnO thin lms.
Cu content Cu/Zn (%)

FWHM b(002) ()
The grain size D (nm)
Roughness RMS (nm)

0.12
69.37
14.69

0.17
48.97
25.49

0.10
83.25
18.68

0.17
48.97
22.35

Cu-doped ZnO lms the lower value corresponding to the doping


2%, so that there is a compromise between the improvement of
the crystallinity and the surface roughness. However a slightly tormented surface is quite favorable for the use of such component
type in the photovoltaic conversion eld.

3.3. Optical study


3.2. Surface morphology
An atomic force microscope (AFM) was used to measure the
surface roughness of the lms over a 2 lm  2 lm area in contact
mode. The three-dimensional (3D) images of AFM micrographs are
shown in Fig. 2 where we note that all lm surfaces are rough. The
perturbed surfaces are probably due to very small droplets of
the aerosol spray of started liquid solution which is vaporized on
the substrates for growing germs giving rise microcrystallites. In
fact the thin layers are distinguished by rounded clusters separated
by the depressions that can be interpreted as crystallized zones
limited by grain joints. We observe also nanoncrystallites on these
clusters whose density decreases especially at 2% Cu content. This
observation is in agreement with those found by X-ray diffraction
analysis.
We note a root-mean square (RMS) of average surface
roughness 14.5 < dRMS < 25.2 nm in thin layers, In particular, for

3.3.1. Optical band-gap


In order to correlate the optical behavior of lms with results
obtained from X-ray and AFM analysis, the optical transmittance
and reectance measurements of undoped and doped ZnO thin
lms were made in the wavelength range of 3001800 nm using
UVVis spectroscopy, Fig. 3. These lms show a high transparency
within the visible range with an average transmittance lying
between 80% and 90%. This suggests that these lms indicate a
good optical quality due to low scattering or absorption losses.
The reectance decreases while the transmittance increases,
depending on the Cu doping.
From Fig. 3, it is clear that all the samples have sharp absorption
edges in the wavelength region between 360 and 400 nm. This suggests that the optical band gap has shifted toward the blue region
with incorporation of Cu. These blue shifts may be caused by a
change of c lattice parameter in ZnO matrix due to doping. An analysis of the optical band-gap energy Eg of the thin lms has been

ZnO undoped

ZnO :Cu 1%

ZnO :Cu 2%

ZnO :Cu 3%

Fig. 2. AFM 3D micrographs of sprayed ZnO:Cu thin lms. (x: 0.5 lm/div; z = 200 nm/div).

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A. Mhamdi et al. / Journal of Alloys and Compounds 610 (2014) 250257

100

Table 4
Calculated values of the optical band gap Eg of the sprayed Cu doped ZnO thin lms.
Cu content Cu/Zn (%)

80
Eg (eV)

T%

60

R%

ZnO pur
ZnO:Cu 1%
ZnO:Cu 2%
ZnO:Cu 3%

40

20

400

600

800

1000

1200

1400

1600

1800

Wave length (nm)


Fig. 3. Transmission and reection spectra of doped sprayed ZnO:Cu thin lms.

made using the optical absorption coefcient a given in mean


absorption domain by the approximate formula [15]:

1  R2
T

1
d

a Ln

!
4

As shown in Fig. 4, the (ahm)2 plots with the photon energy hm


axis are linear in mean absorption range indicating that the electronic transitions are direct. From the intersection of these linear
parts slope, the optical band gap Eg values were deduced to according the following relation [16]:
2

ahm Ahm  Eg

in which A is a constant characteristic of the semiconductor. The


obtained Eg values are given in Table 3 where it can be seen that
the value of Eg decrease with Cu doping 2%. In fact, theoretical calculations based on the density functional theory (DFT) show well that
the band gap is narrowed by Cu doping in ZnO [17] (see Table 4).
3.3.2. Refractive index and extinction coefcient
The refractive index and the extinction coefcient of lms have
been obtained by tting from the transmittance and reectance
spectra of ZnO:Cu thin lms in the spectral domain varying from
300 to 1800 nm. For these calculations, we have used the method
of Belgacem et al. based on the Muller numerical method of resolution of non-linear equations [15].
13

5x10

13

3.28

3.27

3.26

3.25

The calculated variation of refractive index varying with the


phonon energy for all lms is shown in Fig. 5. For a given doping,
we note a decrease of the refractive index values with the wavelength in the range [1.95; 2.67] whereas the extinction coefcient
of lms is characterized by an increase but remains relatively low
in the domain [0.015; 0.095], Fig. 5. In fact, the slight increase in
the values of k at the long wavelengths is due to the contribution
of the absorption of the free carriers which is much stronger in
the doped layers. In addition, the great values of k in the fundamental absorption region (low wavelength k < 4 lm) are due to
the intrinsic absorption for the higher energy gap. In the visible,
the low value of k implies that these layers are transparent as
showed in the transmission spectra.
We also observe a dependence on wavelength of the refractive
index and the extinction coefcient with the doping concentration.
This phenomenon can be explained on the basis of the contribution
from both lattice parameter change and the presence of defaults in
the prepared lms. In particular, we note a decrease in the extinction coefcient when Cu content increases, which may be due to
the increase in the average crystallite size in the ZnO lms after
Cu doping and a decrease in the surface roughness effect as shown
in Fig. 2.
3.3.3. Dielectric constant
From the refractive index and the extinction coefcient results,
we have analyzed the real and imaginary parts of complex dielectric constant e(x) of pure and doped ZnO with copper at different
concentrations using the following relations:

ek nk  ikk2 e1 k  ie2 k

e1 k nk2  kk2

e2 k 2nkkk

For all samples, it is found that in infrared range the dispersion of


e1 is linear function of the square of the wavelength k2 while the
absorption e2 is linear with k3, Fig. 6. This behavior is in good agreement with the classical theory of the dielectric constant which
expressed by the following system in the near infrared (xs  1) [15]:
0,7

-1

ZnO pur : Eg=3.28 eV


ZnO:Cu 1%: Eg=3.24 eV
ZnO:Cu 2%: Eg=3.16 eV
ZnO:Cu 3%: Eg=3.18 eV

13

3x10

2,7

0,6

2,6

0,5

2,5
2,4

0,4

13

2x10

2,3

( )2 (eV.cm )

4x10

0,3

2,2
2,1

0,2
13

1x10

2,0

0,1
0
2,0

1,9

0,0
2,2

2,4

2,6

2,8

3,0

3,2

3,4

h (eV)
Fig. 4. Variation of the absorption (ahm)2 as a function of the light energy hm of
sprayed ZnO:Cu thin lms.

200

400

600

800

1,8
1000 1200 1400 1600 1800

Wave length (nm)


Fig. 5. Refractive index n(k) and extinction coefcient k(k) of ZnO doped Cu thin
lms.

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A. Mhamdi et al. / Journal of Alloys and Compounds 610 (2014) 250257

where e1 is the dielectric constant at high frequencies, xp the pulsation plasma and the relaxation s time.
The extrapolation of the curve of e1 at low wavelengths provides the dielectric constant e1 which shows a decrease from
5.22 to 4.52, Table 5. We note the same variation of the plasma
pulse xp with doping deduced from the slope of the same curves.
In particular, the different values of xp correspond to the wavelengths k higher than 1.8 lm, this explains the non decay of the
transmission in the area of relative transparency to visible.
From the slope of the linear dependence of the e2(k3) and the
knowledge of xp we have determined the relaxation time s
whose the values are gathered in Table 5. In the same table we
introduced the values of the free carrier concentration to effective
mass ratio mN which is calculated from the following well-known
equations:

Table 5
Calculated values of e1, xp and other constants.

ZnO undoped
ZnO:Cu 1%
ZnO:Cu 2%
ZnO:Cu 3%

s (1014 s)

N
m

5.22
4.71
4.47
4.09

5.95
4.25
4.67
3.13

7.79
0.73
1.01
0.34

6.38
2.95
3.37
1.39

(1047 g1 cm3)

e1 x2p 2
k
4p2 c2

e1 x2p 3
k
8p3 c3 s

10

0,6

10
9

0,4

ZnO pur
ZnO:Cu 1%
ZnO:Cu 2%
ZnO:Cu 3%

0,5

ZnO pur
ZnO:Cu 1%
ZnO:Cu 2%
ZnO:Cu 3%

0,3
0,2

4
0,1

3
2
0,0

0,0
0

5,0x10 1,0x10 1,5x10 2,0x10 2,5x10 3,0x10 3,5x10


2
2

1x10

(nm )

2x10

3x10

4x10

5x10

3(nm3 )

Fig. 6. Variation of the real and imaginary parts e1 and e2 of dielectric constant of sprayed Cu doped ZnO as a function of k2 and k3 respectively.

600

400
T=628 K
T=638 K
T=648 K
T=658 K
T=668 K
T=678 K
T=688 K
T=698 K
T=708 K

400
300

CuZN 1%

ZnO undoped

T=638 K
T=648 K
T=658 K
T=668 K
T=678 K
T=688 K
T=698 K
T=708 K

300

Z'' (Kohm)

Z'' (Kohm)

500

200

200

100
100
0

10

12

14

16

18

10

12

Ln ()

16

18

600

500
400

T=618 K
T=628 K
T=638 K
T=648 K
T=658 K
T=668 K
T=678 K

CuZNO 3%

T=618 K
T=628 K
T=638 K
T=648 K
T=658 K
T=668 K
T=678 K

CuZNO 2%

600

500

300
200

400
300
200
100

100
0

14

Ln ()

700

Z'' (Kohm)

e2 

xp (1014 rad s1)

Z'' (Kohm)

e1  e1 

e1

10

12

14

Ln ()

16

18

10

12

14

Ln ()

Fig. 7. Angular frequency dependence of Z00 of sprayed ZnO:Cu thin lms at different temperatures.

16

18

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A. Mhamdi et al. / Journal of Alloys and Compounds 610 (2014) 250257

ZnO undoped
ZnO:Cu 1%
ZnO:Cu 2%
ZnO:Cu 3%
fit ZnO undoped
fit ZnO:Cu 1%
fit ZnO:Cu 2%
fit ZnO:Cu 3%

16,0
15,6

Ln ( m )

15,2
14,8
14,4
14,0

When k decrease away from the region of the near infrared, we


remark a deviation from the evolution of two parts of the dielectric
constant under the classical theory particularly the quadratic law
of e1. This difference arises from the fact that this region need to
be involved in the relationships (9) and (10) the relaxation time
s which depends on the conduction mechanism of carriers in
the optical and acoustic phonons, lattice defects and ionized
impurities.
3.4. Complex impedance analysis

13,6
13,2
1,40

1,44

1,48

1,52

1,56

1,60

-1

1000/T (K )
Fig. 8. Temperature dependence of angular frequency relaxation of sprayed ZnO:Cu
thin lms for different doping.

Table 6
Calculated values of activation energy Ea.

Ea

xm xo eKT

Cu content Cu/Zn (%)

Ea (eV)

0
1
2
3

0.87 0.008
0.65 0.045
0.90 0.034
0.71 0.028

Ne2
eo e1 m

11

where eo is the vacuum dielectric constant.

400

600
T=628 K
T=638 K
T=648 K
T=658 K
T=668 K
T=678 K
T=688 K
T=698 K
T=708 K

500
400
300
200

CZO 1%

350

T=638 K
T=648 K
T=658 K
T=668 K
T=678 K
T=688 K

300

Z'' (Kohm)

ZnO undoped

Z'' (Kohm)

12

where xo is a constant and Ea is the thermal activation energy of the


carriers charge. In this case, Ea represents the difference between
the trap level and the conduction band. As shown in Fig. 8, the


expression of Lnxm f 1000
leads to a linear function, in good
T
agreement with expression Eq. (12). The calculated values of the
activation energy vary slightly around the value 0.78 eV with a
slight increase for 2% Cu content, Table 6. A similar frequency
dependence of relaxation time in Fe-doped ZnO thin lms has been
observed by Hassan et al. [19].

250
200
150
100

100
0

50
0

200

400

600

800

1000 1200 1400

400

600

(a)

(b)

800

1000

600
T=618 K
T=628 K
T=638 K
T=648 K
T=658 K
T=668 K
T=678 K

CZO 2%

500

Z'' (Kohm)

200

Z' (kohm)

600

400
300
200

T=618 K
T=628 K
T=638 K
T=648 K
T=658 K
T=668 K
T=678 K

CZO 3%

500
400
300
200
100

100
0

Z' (kohm)

Z'' (Kohm)

x2p

3.4.1. Impedance analysis


The ColeCole plots of imaginary part Z00 with frequency for CZO
at different working temperatures are plotted in Fig. 7. It is still
remarkable that the imaginary part Z00 increases with frequency
reaching a maximum peak Z 00max at the relaxation frequency xm
after what it decreases as the temperature increases. Moreover,
the position of the relaxation peak shifts towards higher frequencies with increasing temperature while Z 00max values decrease.
In fact, the angular relaxation frequency obeys to the wellknown Arrhenius law [18]:

200

400

600

800

1000 1200 1400

200

400

600

800

Z' (kohm)

Z' (kohm)

(c)

(d)

1000 1200 1400

Fig. 9. Complex impedance spectra of sprayed ZnO:Cu thin lms at different temperatures.

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A. Mhamdi et al. / Journal of Alloys and Compounds 610 (2014) 250257

1,2

ZnO undoped
ZnO:Cu 1%
ZnO:Cu 2%
ZnO:Cu 3%

R (Mohm)

1,0

R (Mohm)

T=638 K
T=648 K
T=658 K
T=668 K
T=678 K

1,0

0,8
0,6

0,5

0,4
0,2
620

640

660

680

700

0,0

720

T (K)

Cu content Cu/Zn (%)

(a)

(b)
4,0
3,5
3,0

C (pF)

2,5

ZnO undoped
ZnO:Cu 1%
ZnO:Cu 2%
ZnO:Cu 3%

2,0
1,5
1,0
0,5
0,0

620

640

660

680

700

720

T (K)

(c)
Fig. 10. The variation of the capacitance and parallel resistance of sprayed ZnO:Cu thin lms at different temperatures.

400

400

ZnO undoped
ZnO:Cu 1%
ZnO:Cu 2%
ZnO:Cu 3%

350

250

300

Z" (Kohm)

Z" (Kohm)

300

200
150

250
200
150

100

100

50

50

0
0

200

400

600

800

Z' (Kohm)
Fig. 11. Complex impedance spectra of sprayed ZnO:Cu thin lms at T = 648 K.

3.4.2. The equivalent ac circuit


The Nyquist plots for CZO with working temperature are displayed in Fig. 9. The plots drawn between imaginary Z00 and real
parts Z0 of the impedance show semicircular arcs whose their
radius decreases with increase in temperature. The proper interpretation of the given impedance spectra allowed us to determine
the equivalent ac circuit of this polycrystalline CZO thin lm
deposited on glass substrate composed by a parallel resistor R

ZnO:Cu 2%
Fit curve ZnO:Cu 2%

350

0
0

200

400

600

Z' (Kohm)
Fig. 12. The complex impedance spectra theoretical and experimental of ZnO:Cu 2%
at T = 648 K.

and capacitor C network connected. This parallel circuit RC represents the contribution of the grain boundaries delineating the oriented columnar microcrystallites along c-axis.
The experimental values of the above parameters were found as
follow: the capacitance was determined from the associated frequency at the maximum data point Z 00max of the curve on the real
axis (Fig. 10), the second intercept gave the value of resistance R.

A. Mhamdi et al. / Journal of Alloys and Compounds 610 (2014) 250257

It was noted that R value decreased dramatically with the composition as shown in Fig. 10. Essentially, it appears from this study
that the low value of R corresponds to the doping of 2% indicating
the homogeneity of the layer. We observe this clearly in Fig. 11
where the Nyquist plots were compared for the various percentages of doping at the same temperature T = 648 K.
To check the validity of this approach, we have introduced the
experimental values of R and C in the known relationships of the
real and imaginary parts of parallel circuit RC complex impedance
and calculated the theoretical variation of Z00 (Z0 ) which shows a
good agreement with experiment for example as illustrated in
Fig. 11 at 2% doping. These observations are consistent with the
results of XRD (see Fig. 12).

electromagnetic radiation. Finally the behaviour of the spectra of


the components of the dielectric constant needs more investigations particularly in infra-red region but we can consider beforehand that this result is quite encouraging since a costless and
simple used depositing technique.
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4. Conclusion
We have investigated the structural and the optical properties
of Cu-doped ZnO thin lms deposited by the spray pyrolysis technique. It has been found that these properties depend mainly on
the Copper-to-Zinc ratio. All lms were crystallized in the hexagonal wurtzite structure with preferential c-axis orientation along
(0 0 2) direction which is quite dominant especially for 2% Cu
content. On the other hand, the optical study showed that the
deposited lms have a relatively high absorption coefcient
(a P 104 cm1) and exhibit a direct transition gap. The results
obtained by impedance measurements of sprayed ZnO thin lms
are discussed in terms of the copper content and it found that they
conrm those obtained by XRD particularly the structure type. The
same again this study has provided us the electro-optical parameters consistent with the results of structure and interesting for the
use of such materials as a window of light in solar cells and sensors

257

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