Beruflich Dokumente
Kultur Dokumente
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.
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
251
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.
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
Orientation degree
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
Results JCPDS
(pure powder
ZnO)
Kk
bcos h
252
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
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).
253
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
1 R2
T
1
d
a Ln
!
4
ahm Ahm Eg
5x10
13
3.28
3.27
3.26
3.25
ek nk ikk2 e1 k ie2 k
e1 k nk2 kk2
e2 k 2nkkk
-1
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
254
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
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
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
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
255
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
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
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
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
250
200
150
100
100
0
50
0
200
400
600
800
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
200
400
600
800
200
400
600
800
Z' (kohm)
Z' (kohm)
(c)
(d)
Fig. 9. Complex impedance spectra of sprayed ZnO:Cu thin lms at different temperatures.
256
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)
(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.
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.
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).
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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