Optik 125 (2014) 58645868

Contents lists available at ScienceDirect

Optik
journal homepage: www.elsevier.de/ijleo

The crystalline structure, conductivity and optical properties of

Co-doped ZnO thin lms
Said Benramache a,b, , Boubaker Benhaoua b , Okba Belahssen a,c
a
b
c

Material Sciences Department, Faculty of Science, University of Biskra, Biskra 07000, Algeria
VTRS Laboratory, Institute of Technology, University of El-Oued, El-Oued 39000, Algeria
Mechanics Department, Faculty of Technology, University of Tbessa, Tbessa 12000, Algeria

a r t i c l e

i n f o

Article history:
Received 23 October 2013
Accepted 31 May 2014
Keywords:
ZnO
Thin lm
Semiconductor doping
Ultrasonic spray technique.

a b s t r a c t
Transparent conductive Co-doped ZnO thin lms were deposited by ultrasonic spray technique. Conditions of preparation have been optimized to get good quality. A set of cobalt (Co)-doped ZnO (between
0 and 3 wt%) thin lms were grown on glass substrate at 350 C. The thin lms were annealed at 500 C
for improvement of the physical properties. Nanocrystalline lms with hexagonal wurtzite structure and
a strong (0 0 2) preferred orientation were obtained. The maximum value of grain size G = 63.99 nm is
attained with undoped ZnO lm. The optical transmissions spectra showed that both the undoped and
doped ZnO lms have transparency within the visible wavelength region. The band gap energy decreased
after doping from 3.367 to 3.319 eV when Co concentration increased from 0 to 2 wt% with slight increase
of electrical conductivity of the lms from 7.71 to 8.33 ( cm)1 . The best estimated structure, optical
and electrical results are achieved in Co-doped ZnO lm with 2 wt%.
2014 Elsevier GmbH. All rights reserved.

1. Introduction
Wide band gap IIVI semiconductors have attracted the interest of many research groups during the past few years due to the
possibility of their applications in light-emitting diodes (LEDs) and
laser diodes. Among the IIVI semiconductors, ZnO is an important optoelectronic device material for use in the violet and blue
regions because of its wide band gap (3.37 eV) and large exciton
binding energy (60 meV) [1,2]. ZnO thin lms are promising candidates for applications in short-wavelength light-emitting devices,
lasers, eld emission devices, solar cells and sensors [3,4].
ZnO thin lms can be produced by several techniques such
as reactive evaporation, molecular beam epitaxy (MBE), magnetron sputtering technique, pulsed laser deposition (PLD), solgel
technique, chemical vapour deposition, electrochemical deposition
[57] and spray pyrolysis [8]. Among those techniques that have
been reported to prepare thin lms of ZnO, we will focus more particularly in this paper on the spray ultrasonic technique which is a
low cost and suitable method for large-scale production. It offers
several advantages in producing nanocrystalline thin lms, such as,
a simple deposition on glass substrate with a large range of temperatures, easy control of the lm thickness and ne and porous

microstructure with relatively homogeneous composition. Moreover, it is possible to alter the mechanical, electrical, optical and
magnetic properties of ZnO nanostructures with doping. There are
several reports on ZnO nanostructures doped with different elements, such as Al, Mn, Na, Mg, Ni, Ag [913].
The cobalt-doped ZnO thin lms (ZnO:Co) have various
applications such as transparent conductive; ferromagnetism;
semiconductors; piezoelectric and solar cells; the lms have low
resistivity, good optical gap energy at low temperature and good
transparency in the visible region [14]. Due to its high conductivity,
good transparency and lower cost, the lms are considered to be
an utmost important material.
In this paper, we have prepared Co-doped ZnO thin lms on
microscope glass substrate through ultrasonic spray technique. The
solution was sprayed on substrate at 350 C, and their thin lms
were annealed at a temperature of 500 C to improve their physical
properties. The effect of the Co concentrations on the ZnO lms has
been studied, in order to nd optimum Co doping concentration
which gives highly semiconducting properties of Co-doped ZnO
thin lms.
2. Experimental procedure
2.1. Preparation of spray solution

Corresponding author at: University of Biskra, Material Sciences Department,

Faculty of Science, Biskra, Algeria. Tel.: +213 779276135.
E-mail address: saidzno2006@gmail.com (S. Benramache).
http://dx.doi.org/10.1016/j.ijleo.2014.07.055
0030-4026/ 2014 Elsevier GmbH. All rights reserved.

ZnO solution was prepared by dissolving 0.1 M Zn(CH3 COO)2 ,

2H2 O in the solvent containing equal volume of absolute ethanol

S. Benramache et al. / Optik 125 (2014) 58645868

5865

solution of 99.995% purity and bi-distilled water, then we have

added drops of HCl solution as a stabilizer, the mixture solution
was stirred at 50 C for 120 min to yield a clear and transparent
solution.
ZnO:Co solutions were prepared by adding to the precedent
solution a cobalt chloride, 4-methoxyethanol with ratio of Co/Zn
lying in the range of 13 wt%. The solution became clear and homogeneous after stirring for 120 min at 5070 C.
2.2. Deposition of thin lms
The resulting solutions were sprayed on the heated glass substrates by ultrasonic nebulizer system (Sonics) which transforms
the liquid to a stream formed with uniform and ne droplets of
35 m average diameter (given by the manufacturer). The depositions were performed at 350 C as substrate temperature and 2 min
as time of deposition; then the thin lms were annealed at 500 C,
during 120 min period, for improvement of the physical properties
[15].
The substrate was R217102 glass in a size of
1 cm 1 cm 0.1 cm, prior to pumping; the substrates (R217102
glass) were cleaned with alcohol in an ultrasonic bath and blow
dried with dry nitrogen gas.

Fig. 1. X-ray diffraction spectra of undoped ZnO lm and Co-doped ZnO lms at
different concentrations.

2.3. Characterization
Crystallographic and phase structures of the thin lms were
determined by X-ray diffraction (XRD, Bruker AXS-8D) with CuK
radiation ( = 0.1541 nm) at scanning range between 2 = 25 and
55 . The optical properties of the deposited lms were measured in
the range of 300800 nm using an ultravioletvisible spectrophotometer (UV, Lambda 35); whereas, the electrical conductivity of
the lms was measured in a coplanar structure obtained after evaporation of four golden stripes on the surface of deposited lms. All
spectra were measured at room temperature (RT) in air.
3. Results and discussion
Fig. 2. Variation of TC (1 0 0), TC (0 0 2), TC (1 0 1) and TC (1 0 2) with doping level in
ZnO:Co thin lms.

3.1. The crystalline structure Co-doped ZnO thin lms

The X-ray diffraction patterns of undoped and Co-doped ZnO
thin lms, deposited on glass substrates at 350 C are presented
in Fig. 1. As can be seen, the diffraction peaks at 2 = 31.8 , 34.5 ,
36.4 and 47.5 correspond to the (1 0 0), (0 0 2), (1 0 1) and (1 0 2)
planes, respectively. Whereas the Co-doped ZnO thin lms with
1 and 3 wt% have only preferential (0 0 2) orientation. The lm
doped at 2 wt% has higher and sharper diffraction peak indicating
an improvement in (0 0 2) peak intensity compared to the undoped
ZnO thin lm and the lms doped at 1 and 3 wt%. The deposited
lms exhibit nanocrystalline structure with hexagonal wurtzite
structure from the spectra [16,17]. This indicates that all lms have
preferential c-axis orientation along the (0 0 2) plane [18]. One can
see that the high intensities directions were affected by the different degree of substitution of Zn2+ ions by Co2+ ions. The result
indicates that the doping level of the lms improved the structural
properties. In order to conrm this remark, one can go for the calculation of the texture coefcient TC(h k l). The later can be calculated
from the Xray data using the well-known formula of the intensity
peaks corresponding to the (1 0 0), (0 0 2), (1 0 1) and (1 0 2) planes
[5]:
TC(h k l) =

I(h k l)/I0 (h k l)
N 1

I(h k l)/I0 (h k l)

(1)

where I(h k l) is the measured relative intensity of (h k l) plane,

I0 (h k l) is the standard intensity of the plane (h k l) taken from the

JCPDS data, N is the reection number and n is the number of diffraction peaks. The variations of TC(h k l) values for four major peaks of
the thin lms are presented in Fig. 2.
We can also observe that the texture coefcient of (0 0 2) peak is
the highest one conforming that all lms having preferential c-axis
orientation along the (0 0 2) plane as it was mentioned in the above
paragraph. The texture coefcient of (1 0 0), (1 0 1) and (1 0 2) planes
of the Co-doped ZnO thin lms for 1 and 3 wt% are approached near
zero. The enhanced crystalline quality of Co-doped ZnO thin lms
was obtained with 2 wt%. With the increase of Co concentration,
the intensity of (0 0 2) peak was increased, whereas the full widthat-half-maximum (FWHM) is decreased as it was shown in Table 1;
this remark is similar to the previously reported one in the litera-

Table 1
Bragg angle 2, the interplanar spacing d0 0 2 , the full width at half-maximum FWHM,
the crystallite size G, lattice parameters c and the residual stress  for ZnO:Co thin
lms were measured as a function of doping level.
Doping level
(wt.%)

2 ( )

d (A)

FWHM ( )

G (nm)

c (nm)

 (GPa)

0
1
2
3

34.54
34.49
34.54
34.55

2.59470
2.59834
2.59470
2.59397

0.13
0.28
0.14
0.26

63.99
29.61
59.42
31.88

5.18939
5.19668
5.18939
5.18793

1.436
0.805
1.436
1.562

5866

S. Benramache et al. / Optik 125 (2014) 58645868

Fig. 3. The variation of crystallite size, the FWHM and the residual stress of undoped
and Co-doped ZnO thin lms with doping level.
Fig. 4. Transmission spectra of Co-doped ZnO thin lms as a function of cobalt
concentration Co/Zn: (a) 0, (b) 1, (c) 2 and (d) 3 wt%.

tures [19,20]. The average crystallite size of the lms from the XRD
was calculated using the Scherers equation [21]:
D=

0.9
.
cos 

(2)

where D is the crystallite size,  is the X-ray wavelength

is the full width at half-maximum (FWHM), and
( = 1.5406 A),
 is Bragg angle of (0 0 2) peak.
According to the hexagonal symmetry of the ZnO structure, the
lattice constant can be calculated by the following formula [22]:


dh k l =

l2
4 h2 + hk + k2
+ 2
2
3
a
c

1/2
.

(3)

where a, c are the lattice parameters, (h, k, l) are the Miller indices
of the planes and dh k l is the interplanar spacing.
Additional information on structural properties can be obtained
from the residual stress measurements calculated by the following
formula [23].
 = 450

c0 c
.
c

(4)

where  in (GPa) is the mean stress, c and c0 are the lattices

constant of the ZnO thin lm and the bulk material (standard
c0 = 0.5206 nm). The calculated data of average mean stress  is
summarized in Table 1.
In Fig. 3 we have reported the variation of the crystallite size,
the full width-at-half-maximum (FWHM) and the residual stress
as a function of doping level. As it can be seen, the variation of crystallite size is opposite to the full width-at-half-maximum (FWHM).
From 0 to 1 wt% Co doping levels the crystallite size decreases from
63.99 to 29.61 nm (see Table 1) then increases to reach 59.42 nm
as maximum value of 2 wt% and decreases further than the doping
level increase. The values of residual stress decreases with increasing of cobalt concentration from 0 to 1 wt% then increases with
3 wt% whereas the lattice parameter of the lms decreases indicating that the stress is done along the c-axis. The increase in the
crystallite size reveals the enhancement of the crystallinity under
c-axis orientation of ZnO thin lms.
3.2. The optical properties of Co-doped ZnO thin lms
Fig. 4 shows the optical transmission spectra of undoped and Codoped ZnO as a function of doping level. As can be seen, a region
of strong transparency is located between 400800 nm; the value
of the average transmission is about 7095%, then decreases in
the region of the absorption edge, in the layers (360400 nm) the
decrease is due to the transition between the valence band and the
conduction band revealing the onset fundamental absorption. At
naked eye, we are noting that the doping effect was clearly observed
in the layer quality; hence the smoothness and homogeneity of the

Fig. 5. The typical variation of (Ahv)2 vs. photon energy hv for undoped ZnO thin
lm. The inset shows the drawn of ln A as a function of photon energy (hv) for
deducing Urbach energy.

layers reached an optimal state for the elaborated doped lm with

2 wt%.
In order to investigate the effect of Co concentration on ZnO:Co
lms further, the optical band gap energy (Eg ) was measured from
the transmission spectra using the following relations [24]:
A = d = ln T,

(5)

(Ah) = C(h Eg ),

(6)

where A is the absorbance, d is the lm thickness; T is the transmission spectra of thin lms; is the absorption coefcient values; C
is a constant, h is the photon energy and Eg the band gap energy
of the semiconductor. As it was shown in (Fig. 5) a typical variation of (Ah)2 as a function of photon energy (h) of undoped ZnO
thin lm, the optical band gap was determined by extrapolation
of the linear region to (Ah)2 = 0 [25]. Besides, we have used the
Urbach energy (Table 2), which is related to the disorder in the lm
network and expressed as [15]:
A = A0 exp

 h 
Eu

(7)

Table 2
The band gap energy Eg , the Urbach energy Eu and electrical conductivity  for
ZnO:Co thin lms were measured as a function of doping level.
Doping level (wt%)

Eg (eV)

Eu (meV)

 ( cm)

0
1
2
3

3.367
3.278
3.319
3.295

085
267
040
166

7.71
7.19
8.33
7.86

S. Benramache et al. / Optik 125 (2014) 58645868

5867

substitutional sites of Zn2+ , as a result the carrier density increases.

Moreover, the decrease of the electrical conductivity with increasing of the doping level may be explained by a segregated part of
cobalt atoms into the grain boundaries which acts in increasing of
the potential barriers, this interpretation is consistent with similar
results obtained elsewhere [2631].
4. Conclusions

Fig. 6. The variation of optical band gap and Urbach energy of undoped and Codoped ZnO thin lms with doping level.

where A0 is a constant and Eu is the Urbach energy, the latter

decreased with increasing the band gap indicating the decrease of
defects in the elaborated lms as shown in (Table 2).
Fig. 5 shows a plot of absorbance (Ah)2 vs. photon energy (h)
for undoped ZnO thin lms. The linear dependence of A on h at
higher photon energies indicates that the lms are essentially direct
transition n-type semiconductors. Extrapolation of linear portion of
the graph to the energy axis at A = 0 in the range between 360 and
380 nm giving the band gap energy Eg . The inset show the drawn
of ln A as a function of photon energy (hv) for deducing the Urbach
energy Eu . The determined values of Eg and Eu are shown in Table 2.
In Fig. 6 we have reported the variation of band gap (Eg ) for
the elaborated lms as a function of the doping level. It could be
noticed that the band gap energy of the lms decrease from 3.367 to
3.278 eV with increasing Co doping from 0 to 1 wt%, then increase
to 3.319 eV for 2 wt%. This variation in band gap with the cobalt
concentration may be explained in terms of MossBurstein effect
(band values should increase with Co concentration, but Eg value
decreasing with doping of 3 wt%). This may be explained by the
increasing of the crystallite size (see Fig. 3). As can be seen in Fig. 6,
a minimum Urbach energy was reached with Co-doped ZnO thin
lms at 2 wt%, which means that this doping level (2 wt%) leads to
a less disorder; we have as consequence large band gap and vice
versa as it was expressed in the literatures [15,26,27].
3.3. The electrical conductivity of Co-doped ZnO thin lms
Fig. 7 shows the variation of electrical conductivity  of undoped
and Co-doped ZnO lms as a function of doping level. As can be seen,
the conductivity decreases from 7.71 to 7.19 ( cm)1 when the
Co concentration increases from 0 to 1 wt% then increase to reach
8.33 ( cm)1 for 2 wt% doping level. The slight variation (increase)
in the conductivity of the lms has been explained by displacement
of electrons [28] which are coming from the ions Co2+ donors in the

Fig. 7. Electrical conductivity  of undoped and Co-doped ZnO thin lms as a function of cobalt concentrations.

In conclusion, highly transparent conductive Co-doped ZnO thin

lms have been deposited on glass substrate by ultrasonic spray
at a substrate temperature of 350 C. The structural, optical and
electrical properties were investigated; these properties of thin
lms were improved by annealing temperature at 500 C. All the
lms are nanocrystalline-hexagonal structure wurtzite and with
strong (0 0 2) orientation; the maximum value of crystallite size
G = 63.99 nm is attained with undoped ZnO lm. The value of the
average transmission is about 7095% in the visible region. The
band gap energy decreased from Eg = 3.367 to 3.319 eV for undoped
and Co-doped ZnO thin lms at 2 wt%. The electrical conductivity of
the lms increased from 7.71 to 8.33 ( cm)1 . Improved Co-doped
ZnO lms are achieved with 2 wt% as amount of Co doping level.
Acknowledgments
This work was supported in part by the National Project
Research (PNR) and VTRS laboratory of El-Oued University, Algeria.
X-ray diffraction data in this work were acquired with an instrument supported by the University of Biskra. We thank Prof. S.
Rahman and B. Gasmi (Biskra Universty) for the assistance in XRD
data acquisition.
References
[1] S. Benramache, O. Belahssen, A. Arif, A. Guettaf, A correlation for crystallite size of undoped ZnO thin lm with the band gap energyprecursor
molaritysubstrate temperature, Optik 125 (2014) 13031306.
[2] S. Zhao, L. Yang, Y. Zhou, K. Zhao, Fast photovoltaic characteristic of silver
nano-cluster doped ZnO thin lms induced by 1.064 m pulsed laser, Optik
122 (2011) 960962.
[3] J. Ramesh, G. Pasupathi, R. Mariappan, V. Senthil Kumar, V. Ponnuswamy, Structural and optical properties of Ni doped ZnO thin lms using solgel dip coating
technique, Optik 124 (2013) 20232027.
[4] S. Benramache, A. Rahal, B. Benhaoua, The effects of solvent nature on spraydeposited ZnO thin lm prepared from Zn (CH3COO)2, 2H2O, Optik 125 (2014)
663666.
[5] S. Benramache, B. Benhaoua, N. Khechai, F. Chabane, Elaboration and characterization of ZnO thin lms, Matr. Tech. 100 (2012) 573580.
[6] S. Rahmane, M.A. Djouadi, M.S. Aida, N. Barreau, B. Abdallah, N. Hadj Zoubir,
Power and pressure effects upon magnetron sputtered aluminum-doped ZnO
lms properties, Thin Solid Films 519 (2010) 510.
[7] F. Chouikh, Y. Beggah, M.S. Aida, Optical and electrical properties of Bi-doped
ZnO thin lms deposited by ultrasonic spray pyrolysis, J. Mater. Sci. 22 (2011)
499505.
[8] S. Jongthammanurak, M. Witana, T. Cheawkul, C. Thanachayanont, The effects
of carrier gas and substrate temperature on ZnO lms prepared by ultrasonic
spray pyrolysis, Mater. Sci. Semicond. Process. 16 (2013) 625632.
[9] C. Ton-That, M. Foley, M.R. Phillips, T. Tsuzuki, Z. Smith, Correlation between
the structural and optical properties of Mn-doped ZnO nanoparticles, J. Alloys
Compd. 522 (2012) 114117.
[10] Y. Lu, X. Zhang, J. Huang, et al., Investigation on antireection coatings for
Al:ZnO in silicon thin-lm solar cells, Optik 124 (2013) 33923395.
[11] J. Lv, K. Huang, X. Chen, et al., Effect of preheating temperatures on microstructure and optical properties of Na-doped ZnO thin lms by solgel process,
Superlattices Microstruct. 49 (2011) 477486.
[12] H. Benzarouk, A. Drici, M. Mekhnache, et al., Effect of different dopant elements
(Al, Mg and Ni) on microstructural, optical and electrochemical properties of
ZnO thin lms deposited by spray pyrolysis (SP), Superlattices Microstruct. 52
(2012) 594604.
[13] F. Xian, K. Miao, X. Bai, Y. Ji, F. Chen, X. Li, Characteriaction of Ag-doped ZnO
thin lm synthesized by solgel method and its using in thin lm solar cells,
Optik 125 (2014) 18161820.
[14] C.B. Fitzgerald, M. Venkatesan, J.G. Lunney, L.S. Dorneles, J.M.D. Coey, Cobaltdoped ZnO: a room temperature dilute magnetic semiconductor, Appl. Surf.
Sci. 247 (2005) 493496.

5868

S. Benramache et al. / Optik 125 (2014) 58645868

[15] S. Benramache, B. Benhaoua, Inuence of annealing temperature on structural

and optical properties of ZnO: in thin lms prepared by ultrasonic spray technique, Superlattices Microstruct. 52 (2012) 10621070.
[16] S. Benramache, B. Benhaoua, F. Chabane, A. Guettaf, A comparative study on
the nanocrystalline ZnO thin lms prepared by ultrasonic spray and solgel
method, Optik 124 (2013) 32213224.
[17] S. Benramache, B. Benhaoua, F. Chabane, F.Z. Lemadi, Inuence of growth time
on crystalline structure, conductivity and optical properties of ZnO thin lms,
J. Semicond. 34 (2013) 02300123004.
[18] A. Mhamdi, A. Boukhachem, M. Madani, H. Lachheb, K. Boubaker, A. Amlouk,
M. Amlouk, Study of vanadium doping effects on structural, opto-thermal and
optical properties of sprayed ZnO semiconductor layers, Optik 124 (2013)
37643770.
[19] L. Xu, X. Li, Y. Chena, F. Xu, Structural and optical properties of ZnO thin lms
prepared by solgel method with different thickness, Appl. Surf. Sci. 257 (2011)
40314037.
[20] A. Kalaivanan, S. Perumal, N.N. Pillai, K.R. Murali, Characteristics of GZO thin
lms deposited by solgel dip coating, Mater. Sci. Semicond. Process. 14 (2011)
9496.
[21] P. Lv, L. Lin, W. Zheng, M. Zheng, F. Lai, Photosensitivity of ZnO/Cu2 O thin lm
heterojunction, Optik 124 (2013) 26542657.
[22] M. Mazhdi, J. Saydi, M. Karimi, J. Seidi, F. Mazhdi, A study on optical, photoluminescence and thermoluminescence properties of ZnO- and Mn-doped ZnO
nanocrystalline particles, Optik 124 (2013) 41284133.

[23] A.J. Hashim, M.S. Jaafar, J. Alaa, N.M. Ghazai, Ahmed, Fabrication and characterization of ZnO thin lm using solgel method, Optik 124 (2013) 491492.
[24] S. Benramache, B. Benhaoua, Inuence of substrate temperature and cobalt
concentration on structural and optical properties of ZnO thin lms prepared
by ultrasonic spray technique, Superlattices Microstruct. 52 (2012) 807815.
[25] N. Karak, P.K. Samanta, T.K. Kundu, Green photoluminescence from highly oriented ZnO thin lm for photovoltaic application, Optik 124 (2014) 62276230.
[26] S. Benramache, B. Benhaoua, F. Chabane, Effect of substrate temperature on the
stability of transparent conducting cobalt-doped ZnO thin lms, J. Semicond.
33 (2012) 09300193004.
[27] A. Hafdallah, F. Yanineb, M.S. Aida, N. Attaf, In doped ZnO thin lms, J. Alloys
Compd. 509 (2011) 72677270.
[28] H. Gomez, A. Maldonado, M. de la, L. Olvera, D.R. Acosta, Gallium-doped ZnO
thin lms deposited by chemical spray, Sol. Energy Mater. Sol. Cells 87 (2005)
107116.
[29] A. Mosbah, M.S. Aida, Inuence of deposition temperature on structural, optical
and electrical properties of sputtered Al-doped ZnO thin lms, J. Alloys Compd.
515 (2012) 149153.
[30] M.A. Lucio-Lpez, M.A. Luna-Arias, A. Maldonado, M. de la, L. Olvera, D.R. Acosta,
Preparation of conducting and transparent indium-doped ZnO thin lms by
chemical spray, Sol. Energy Mater. Sol. Cells 90 (2006) 733741.
[31] A. Rahal, S. Benramache, B. Benhaoua, Preparation of n-type semiconductor
SnO2 thin lms, J. Semicond. 34 (2013) 08300183011.