Beruflich Dokumente
Kultur Dokumente
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
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).
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
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)
(3)
(4)
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
1
1
0
Al O /AlZn O
O O2 e
2 2 3
4
(5)
300
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).
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)
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.
301
Fig. 7. Refractive index (a) and extinction coefcient (b) as a function of the wavelength for ZnO, AZO and ATZO thin lms.
References
[1] P. Chand, A. Gaur, A. Kumar, U.K. Gaur, Structural, morphological and optical
study of Li doped ZnO thin lms on Si (100) substrate deposited by pulsed
laser deposition, Ceram. Int. 40 (2014) 11915e11923.
[2] A. Eshaghi, M. Hajkarimi, Optical and electrical properties of aluminum zinc
oxide (AZO) nanostructured thin lm deposited on polycarbonate substrate,
Optik Int. J. Light Electron Opt. 125 (2014) 5746e5749.
[3] C. Xia, F. Wang, C. Hu, Theoretical and experimental studies on electronic
structure and optical properties of Cu-doped ZnO, J. Alloys Compd. 589 (2014)
604e608.
[4] L. El Mir, Z.B. Ayadi, H. Rahmouni, J. El Ghoul, K. Djessas, H. von Bardeleben,
Elaboration and characterization of Co doped, conductive ZnO thin lms
deposited by radio-frequency magnetron sputtering at room temperature,
Thin Solid Films 517 (2009) 6007e6011.
, J. Savkova
, P. Nov
sek, P. Sutta,
[5] R. Siddheswaran, M. Netrvalova
ak, J. O
cena
J. Kova
c, R. Jayavel, Reactive magnetron sputtering of Ni doped ZnO thin lm:
investigation of optical, structural, mechanical and magnetic properties,
J. Alloys Compd. 636 (2015) 85e92.
[6] R. Mimouni, O. Kamoun, A. Yumak, A. Mhamdi, K. Boubaker, P. Petkova,
M. Amlouk, Effect of Mn content on structural, optical, opto-thermal and
electrical properties of ZnO: Mn sprayed thin lms compounds, J. Alloys
Compd. 645 (2015) 100e111.
[7] X. Zi-qiang, D. Hong, L. Yan, C. Hang, Al-doping effects on structure, electrical
and optical properties of c-axis-orientated ZnO: Al thin lms, Mater. Sci.
Semicond. Process. 9 (2006) 132e135.
[8] R. Ajimsha, A.K. Das, P. Misra, M. Joshi, L. Kukreja, R. Kumar, T. Sharma, S. Oak,
Observation of low resistivity and high mobility in Ga doped ZnO thin lms
grown by buffer assisted pulsed laser deposition, J. Alloys Compd. 638 (2015)
55e58.
[9] L. El Mir, Z.B. Ayadi, M. Saadoun, K. Djessas, H. Von Bardeleben, S. Alaya,
Preparation and characterization of n-type conductive (Al, Co) Co-doped ZnO
thin lms deposited by sputtering from aerogel nanopowders, Appl. Surf. Sci.
254 (2007) 570e573.
[10] N. Chahmat, T. Souier, A. Mokri, M. Bououdina, M. Aida, M. Ghers, Structure,
microstructure and optical properties of Sn-doped ZnO thin lms, J. Alloys
Compd. 593 (2014) 148e153.
[11] L. El Mir, F. Ghribi, M. Hajiri, Z.B. Ayadi, K. Djessas, M. Cubukcu, H. von Bardeleben, Multifunctional ZnO: V thin lms deposited by rf-magnetron sputtering from aerogel nanopowder target material, Thin Solid Films 519 (2011)
5787e5791.
[12] J. Liu, W. Zhang, D. Song, Q. Ma, L. Zhang, H. Zhang, X. Ma, H. Song,
Comparative study of the sintering process and thin lm sputtering of AZO,
GZO and AGZO ceramics targets, Ceram. Int. 40 (2014) 12905e12915.