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Journal of Alloys and Compounds 657 (2016) 296e301

Contents lists available at ScienceDirect

Journal of Alloys and Compounds


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

Fabrication and characterization of optical and electrical properties of


AleTi Co-doped ZnO nano-structured thin lm
Akbar Davoodi a, Mohammad Tajally a, Omid Mirzaee a, Akbar Eshaghi b, *
a
b

Faculty of Materials Science and Engineering, Semnan University, Semnan, Iran


Faculty of Materials Science and Engineering, Maleke Ashtar University of Technology, Shahinshahr, Esfahan, Iran

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 3 August 2015
Received in revised form
5 October 2015
Accepted 13 October 2015
Available online 23 October 2015

Al and Ti Co-doped zinc oxide (ATZO) nano-structured thin lms with 1 at % Al and 0.1 at % Ti were
deposited on glass substrate via solegel technique. X-ray diffraction (XRD) analysis, eld emission
scanning electron microscopy (FESEM) and atomic force microscopy (AFM) methods were used to
investigate the structure, morphology and surface roughness of the thin lms. The optical properties
were investigated by spectroscopic ellipsometry (SE) and UV-VIS spectrophotometer. The resistivity
measurement was performed using a LCR-meter. XRD analysis conrmed the zinc oxide hexagonal
wurtzite structure for the thin lms. It was found that Ti doping reduces the roughness and grain size
values to 8.2 nm and 50 nm, respectively. The optical band gap energy was concluded to be 3.23 eV for
ZnO lm and it increases to 3.26 eV for ATZO lms. Refractive index decreased upon Ti doping as a
consequence of increase in charge carrier concentration. All the thin lms exhibit high transmittance
over 85% in the visible wavelength region. Ti replacement causes to decrease in resistivity and minimum
resistivity value of 13  106 Ucm was measured for ATZO thin lm.
2015 Elsevier B.V. All rights reserved.

Keywords:
Nanostructured materials
Thin lms
Solegel processes
Optical properties

1. Introduction
Vast eld of applications due to tunable properties are responsible for growing attraction of ZnO-based compounds. As a promising transparent conductor or semiconductor category of
materials, it can be employed in thin lm transistors (TFT), solar
cells, light emitting diodes (LED) and at panel displays [1]. Hexagonal wurtzite ZnO is a natural n-type semiconductor with direct
wide band gap of 3.37 eV and large exciton binding energy of
60 meV. It has protable properties of high transmittance, high
chemical stability, non-toxicity and low cost, but, it is highly
resistive unfortunately [2]. The substitution of several cations such
as Cu2 [3], Co2 [4], Ni2 [5], Mn2 [6], Al3 [7], Ga3 [8], In3 [9],
Sn4 [10] and V5 [11] have been widely investigated in order to
improve the electrical and optical properties of ZnO. Progressing
investigations move to use of Al3 as one of the most promising
substitutes [12] along with other cations, for example Al3eCu2
[13], Al3eNi2 [14], Al3eIn3 [15], Al3eGa3 [16], and
Al3eSn4 [17]. It have been previously claimed that replacement
of Zn2 with Ti4 enhances the properties of ZnO thin lms and Ti4

* Corresponding author. Tel.: 98 3145912574; fax: 98 3145228530.


E-mail address: Eshaghi.akbar@gmail.com (A. Eshaghi).
http://dx.doi.org/10.1016/j.jallcom.2015.10.107
0925-8388/ 2015 Elsevier B.V. All rights reserved.

can act as an effective n-type donor to generate free charge carriers


[18]. Thin lms of AleTi Co-doped ZnO have been manufactured by
radio frequency magnetron sputtering with the composition of 97%
ZnO 1.5% Al2O3 1.5 TiO2 (wt %) [19]. Based on our knowledge
there is not a comprehensive scientic reports of solegel derived
AleTi Co-doped ZnO thin lm at concentration of 1 at % Al and 0.1 at
% Ti. In the present study, the AleTi Co-doped ZnO thin lm has
been grown on glass substrate by a solegel method. The inuence
of AleTi Co-doping on the optical, electrical and structural properties of the samples were investigated.
2. Experimental details
Utilizing solegel method, AleTi Co-doped ZnO thin lms were
deposited on glass substrate by a dip-coating technique. Before
deposition, the substrates were carefully pre-cleaned by detergent
solution and then were successively cleaned with acetone, ethanol
and de-ionized water. High purity materials all from Merck company included zinc acetate dehydrate (Zn (CH3COO)2.2H2O,
purity  99.5%), aluminum nitrate nonahydrate (Al (NO3)3$9H2O,
purity  98.5%) and titanium tetra-n-butoxide (C16H36O4Ti,
purity  98%) were used as the starting materials in synthesis of the
samples. 2-methoxyethanol (C3H8O2, purity  99.5%) and

A. Davoodi et al. / Journal of Alloys and Compounds 657 (2016) 296e301

diethanolamine (C4H11NO2, purity  99%) were used as a solvent


and a stabilizer, respectively. Zinc acetate dehydrate was rst dissolved in a mixture of 2-methoxyethanol and diethanolamine solution to obtain a uniform precursor solution of ZnO. The molar
ratio of diethanolamine to zinc acetate dehydrate was maintained
at 1.0 and the concentration of zinc acetate was 0.5 M. Aluminum
nitrate nonahydrate was then added in order to obtain a precursor
solution of Al doped-ZnO (AZO). The concentration of aluminum
nitrate nonahydrate in the solution was adjusted to achieve doped
ZnO with 1 at % of Al ([Al/Zn] 1 at %). Finally for preparation of Al
and Ti Co-doped zinc oxide (ATZO) precursor solution, titanium
tetra-n-butoxide solution was added to AZO precursor solution at
concentration of 0.1 at % Ti ([Ti/Zn] 0.1 at %). Each solution was
stirred using a magnet stirrer at 70  C for 2 h, after which a
transparent and homogenous solution was obtained. The solutions
were subsequently aged for 24 h at room temperature before
deposition. ZnO, AZO and AleTi Co-doped ZnO thin lms were
deposited by dip-coating method on the glass substrates. After
being deposited, the lms was dried at 300  C for 15 min, with a
heating rate of 3  C/min, in an oven to evaporate solvents and
remove organic residuals. The procedures from coating to drying
were repeated ve times for each sample. The samples were then
annealed in ambient atmosphere at 550  C for 2 h. X-ray diffraction
(XRD) analysis was performed using a PHILIPS PW3040 diffractometer with Cu Ka radiation (l 1.5405 ) to investigate the
crystal structure of the thin lms. Counts were collected from 30 to
70 with scan step of 0.05 and scan speed of 5 /min. The
morphology and roughness of the thin lms were observed by eld
emission scanning electron microscopy (FE-SEM, HITACHI S-4160,
operating at maximum accelerating voltage of 30 kV) and atomic
force microscope (AFM, Bruker nanos 1.1, contact mode with precision of 0.1 nm). The optical transmittance measurements were
performed by an Avantes spectrophotometer in the wavelength
range of 300e900 nm at room temperature in air. Spectroscopic
ellipsometry is well known, because of its accuracy and nondestructiveness, by which it is possible to measure the change in
the polarization state of the light reected from the surface and
subsequently utilizing a tting dispersion model to derive the
refractive index and extinction coefcient values [20]. It is also
possible to measure the thickness of the thin lms. Horiba Uvisel
Yvon spectroscopic ellipsometer was used with incident angle of
70 . The spectral wavelength range was from 250 to 900 nm with a
step of 5 nm. Cauchy model as an appropriate model for AleTi Co-

doped ZnO thin lms was used to extract the optical constants of
the samples. The resistivity measurement was performed using a
LCR-meter (Hameg, programmable LCR-bridge HM8118).

3. Results and discussions


Fig. 1a shows X-ray diffraction pattern of the ATZO thin lm
deposited at room temperature. As it can be seen, the results are in
good agreement with standard data from JCPDS (Joint committee
on powder diffraction standards) card number 89e1397 [21], which
is provided in Fig. 1b. The observed (100), (002), (101), (102), (110),
(103) and (112) peaks in XRD patterns shows that the lm has a
random orientation. It is obvious that the synthesized lm is single
phase and there is no evidence of secondary peaks.
The surface morphology of the thin lms was characterized by
FE-SEM. Fig. 2aec shows the typical FE-SEM micrographs of the
ZnO, AZO and ATZO thin lms. An image analyzer was used to estimate the mean grain size of the samples, which are illustrated in
Fig. 3. The mean grain size of ZnO, AZO and ATZO thin lms were
59, 55 and 50 nm, respectively. It was found that the mean grain
size of samples decreased upon doping with Al and Ti. The ATZO
thin lm exhibits smaller grain sizes with more uniform distribution than those of the ZnO and AZO thin lms. This size difference
may be attributed to the stress arising from the difference between
the ionic radius of zinc and dopant elements; in addition, incorporation of the dopant elements into the ZnO structure may tend to
create more nucleation centers [22]. The cross-sectional FE-SEM
image of the ATZO thin lm is shown in Fig. 2d. As can be seen, the
surface is uniform and compact with a typical dense columnar
structure, thus implying good crystallinity of the sample. The
measured thickness of the ATZO thin lm was about 200 nm, which
is in accordance with ellipsometry results. Supplementary discussion about the thickness of the thin lms is provided in ellipsometry results section.
Energy dispersive X-ray (EDX) analysis was carried out to
identify elements present on the thin lms. The EDX spectra of thin
lms are illustrated in Fig. 4. Fig. 4 shows the presence of Zn, Al, Ti
along with oxygen in the ATZO thin lm.
Fig. 5 presents the typical 3D AFM images of the ZnO, AZO and
ATZO thin lms. The corresponding root mean square (RMS)
roughnesses of the samples are given in Fig. 3. The results clearly
indicate that RMS roughness and grain size of the thin lms has
affected by the addition of Al and Ti substitutes. RMS roughness of
the ZnO, AZO and ATZO thin lms were found to be 11.7, 9.4 and
8.2 nm, respectively. The decrease in roughness could be described
as a consequence of a reduction in grain size with more compact
and uniform surface morphology [23], which is in good accordance
with FE- SEM results.
The room temperature transmittance spectra as a function of
wavelength for ZnO, AZO and ATZO thin lms is shown in Fig. 6a.
The average transmittance values in the visible range are presented
in Table 1. The samples are revealed to be transparent in the visible
optical region and the average transmittance of the ZnO, AZO and
ATZO thin lms were found to be about 85%. The absorption coefcient for a direct band gap semiconductor is calculated using the
relation,

Fig. 1. X-ray diffraction pattern of the ATZO thin lm (a) and JCPDS card number
89e1397 (b).

297

 
1
1
ln
d
T

(1)

where d is the thickness of the lm and T is the optical transmittance [24]. The optical band gap (Eg) of thin lms was estimated
using Tauc model [21],

298

A. Davoodi et al. / Journal of Alloys and Compounds 657 (2016) 296e301

Fig. 2. FE-SEM micrographs of the ZnO (a), AZO (b), ATZO thin lms (c) and the cross-sectional image of the ATZO thin lm (d).

doped with Ti, which leads to the energy band broadening effect
[19].
Ellipsometric analysis was performed using Cauchy model
considering a roughness layer on the top of the thin lms. Ellipsometric data were simulated with a 3 layer model: air/roughness
layer/thin lm. Following relations were used to determination of
refractive index and extinction coefcient of the lms,

nl An

Bn
l2

Cn
l4



 
1
1

kl Ak exp Bk 1:24
l
Ck

Fig. 3. Surface roughness and grain size of the ZnO, AZO and ATZO thin lms.

ahn2 Ahn  Eg

(2)

where hn is the photon energy and A is constant. The variations of


(ahn) 2 versus the photon energy (hn) in the absorption region are
plotted in Fig. 6b. Extrapolating the linear portion to a 0 gives the
Eg value (Table 1). Eg value for ZnO, AZO and ATZO thin lms equals
to 3.23, 3.24 and 3.26 eV, respectively. It was concluded that optical
band gap of the ATZO thin lm is broader than AZO thin lm and Ti
doping led to increase in optical band gap energy. This widening of
the optical band gap is generally attributed to the Burstein-Moss
shift and it results from the lling of the electronic states near
the bottom of the conduction bands. As a consequence, the Fermi
level was lifted into the conduction band when the thin lms were

(3)

(4)

where An, Bn and Cn are the Cauchy coefcients, Ak is the absorption


amplitude, Bk is the broadening and Ck is the absorption band edge
xed at the lowest wavelength of measured data [25]. The variation
of the refractive index as a function of wavelength for ZnO, AZO and
ATZO thin lms is presented in Fig. 7a. For all the thin lms, it is
obvious that the refractive index increases initially in the wavelength range from 250 to 350 nm and then decreases in the
wavelength range from 350 to 900 nm. It can be attributed to the
increase and decrease of optical absorption in the wavelength range
from 300 to 350 nm and the wavelength range from 350 to 900 nm,
respectively [20]. As can be seen the refractive index values of the
AZO and ATZO thin lms are lower than those of the ZnO thin lm.
Decrease of the refractive index may be as a result of the increase of
the carrier concentration [26]. It was mentioned previously that Ti
can act as an effective n-type donor to generate free charge carriers
[18], as Al can act the same way. Accordingly, charge carrier concentration of the thin lms increases via replacement of Zn with Al
and Ti substitutes. The reduction in the refractive index due to
replacement of Zn with Al and Ti substitutes is consistent with
other works [20,27]. The variation of extinction coefcient as a
function of wavelength for ZnO, AZO and ATZO thin lms is shown
in Fig. 7b. The reduction of extinction coefcient with wavelength is

A. Davoodi et al. / Journal of Alloys and Compounds 657 (2016) 296e301

299

Fig. 4. EDAX spectra of the (a) ZnO, (b) AZO and (c) ATZO thin lms.

due to little absorption in range of 400e900 nm. The lm thicknesses obtained by FESEM were also checked by ellipsometry
method and rather similar results were obtained (Table 1). The
thicknesses of the ZnO, AZO and ATZO thin lms are in the range of
220e224 nm.
Results of resistivity measurement for ZnO, AZO and ATZO thin
lms are indicated in Table 1. It was concluded that replacement of
Zn with Al and Ti substitutes cause to decrease of resistivity. When

Al is introduced into the sample, the Al atom could be ionized into


Al3 and be replaced in Zn2 site [7], according to the following
equation:

1
1
0
Al O /AlZn  O
O O2 e
2 2 3
4

(5)

where, AlZn  stands for Al ion sitting on a Zn lattice site with

300

A. Davoodi et al. / Journal of Alloys and Compounds 657 (2016) 296e301

Fig. 5. AFM micrographs of the ZnO, AZO and ATZO thin lms.

Fig. 6. Optical transmittance spectra (a) and estimation of Eg by plots of (ahn)2 against hn for ZnO, AZO and ATZO thin lms (b).

singular positive charge and O


O is oxygen ion sitting on oxygen
lattice site with neutral charge. A free electron is produced from
one zinc atom replacement. In addition, ATZO thin lm shows a
lower value of resistivity, as compared to AZO thin lm. As can be
seen, ATZO thin lm has the minimum resistivity value of 13  106
Ucm. This shows that the decrease in Zn concentration along with
addition of Ti can reduce the resistivity of the lm. This is because
of the fact that Ti atom can submit an electron more than Al atom,
which cause to increase in the number of charge carriers, based on
the following equation:

TiO2 /TiZn  O
O

1
O 2e0
2 2

(6)

Table 1
Transmittance, optical band gap, thickness and resistivity of the ZnO, AZO and ATZO
thin lms.

ZnO
AZO
ATZO

Transmittance (%)

Eg (eV)

Thickness (nm)

Resistivity (106 Ucm)

86
85
86

3.23
3.24
3.26

220
224
221

900
48
13

where, TiZn  stands for Ti ion sitting on a Zn lattice site with double
positive charge. Accordingly, decrease in resistivity can be attributed to increase in charge carrier concentration [7,18].

4. Conclusion
Using a solegel technique, ZnO, AZO and ATZO nano-structured
thin lms were deposited on glass substrate. The effects of Al and Ti
Co-doping on structural, electrical, and optical properties of the
thin lms have been investigated. XRD analysis conrmed the zinc
oxide hexagonal wurtzite structure. The results clearly indicate that
RMS roughness and grain size of the thin lms has affected by the
addition of Al and Ti substitutes. The mean grain size and RMS
roughness values of ATZO were 50 and 8.2 nm, respectively. The
samples are revealed to be transparent in the visible optical region
and the average transmittance of the thin lms were found to be
about 85%. Eg value for ZnO, AZO and ATZO thin lms equals to
3.23, 3.24 and 3.26 eV, respectively. Replacement of Zn with Al and
Ti substitutes cause to decrease in refractive index. It was observed
that addition of Ti can reduce the resistivity of the thin lm. Minimum resistivity value of 13  106 Ucm was measured for ATZO thin
lm.

A. Davoodi et al. / Journal of Alloys and Compounds 657 (2016) 296e301

301

Fig. 7. Refractive index (a) and extinction coefcient (b) as a function of the wavelength for ZnO, AZO and ATZO thin lms.

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