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Progress in Natural
Science
Materials International
Progress in Natural Science: Materials International 25 (2015) 1221
www.elsevier.com/locate/pnsmi
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Original Research
Pulsed laser deposited Al-doped ZnO thin lms for optical applications
Gurpreet Kaurn, Anirban Mitra, K.L. Yadav
High Power laser Lab, Department of Physics, Indian Institute of Technology Roorkee, Roorkee 247667, Uttarakhand, India
Received 29 June 2014; accepted 1 December 2014
Available online 21 February 2015
Abstract
Highly transparent and conducting Al-doped ZnO (Al:ZnO) thin lms were grown on glass substrates using pulsed laser deposition technique.
The profound effect of lm thickness on the structural, optical and electrical properties of Al:ZnO thin lms was observed. The X-ray diffraction
depicts c-axis, plane (002) oriented thin lms with hexagonal wurtzite crystal structure. Al-doping in ZnO introduces a compressive stress in the
lms which increase with the lm thickness. AFM images reveal the columnar grain formation with low surface roughness. The versatile optical
properties of Al:ZnO thin lms are important for applications such as transparent electromagnetic interference (EMI) shielding materials and solar
cells. The obtained optical band gap (3.23.08 eV) was found to be less than pure ZnO (3.37 eV) lms. The lowering in the band gap in Al:ZnO
thin lms could be attributed to band edge bending phenomena. The photoluminescence spectra gives sharp visible emission peaks, enables Al:
ZnO thin lms for light emitting devices (LEDs) applications. The currentvoltage (IV) measurements show the ohmic behavior of the lms
with resistivity () 10 3 cm.
& 2015 Chinese Materials Research Society. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Keywords: Al:ZnO thin lms; Transparent conducting oxide (TCO); Pulsed Laser Deposition (PLD); Optical properties; Photoluminescence (PL)
1. Introduction
Transparent conducting oxides are promising materials in
the class of optoelectronic devices due to their potential
applications in gas sensors, piezoelectric transducers, light
emitting devices and in solar cells [1]. Transparent oxide ZnO
is a n-type semiconductor, has a direct band gap of 33.37 eV
and with a large exciton binding energy of 60 meV, more than
the thermal energy at room temperature [2]. ZnO is widely
used because of its properties, nontoxic, less expensive and
abundantly available on earth, chemically and thermally stable
[1,3]. There are quite similarities between the optical properties
and band structures of ZnO and GaN [4]. Both GaN and ZnO
are direct wide band gap (Eg 4 3 eV) semiconductors, transparent in the visible region, having wurtzite crystal structures,
comparable lattice constants, with nearly same c/a lattice
constant ratios [5]. Both of the semiconductors owe defect
n
http://dx.doi.org/10.1016/j.pnsc.2015.01.012
1002-0071/& 2015 Chinese Materials Research Society. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
13
Nd-YAG Laser
355 nm
150 mJ/pulse
10 Hz
800020,000 in steps of 4000
Al:ZnO-target
Oxygen (99.9% purity)
2.67 Pa
Glass
350 1C
35 mm
14
The optical properties transmittance, absorbance and reectance for these thin lms were observed by JASCO Model V650 spectrophotometer. The optical band gap was calculated
from the Tauc's plot (h)2 versus h. The photoluminescence
(PL) properties of the thin lms were observed by SHIMADZU-RF-5301PC, spectrouorophotometer. The current
voltage (IV) characteristics within voltage sweep of 01 V,
using four point probe method were observed at room
temperature using Keithley 2636A dual channel Source major
unit sealed in the Black Box and provided with a probe station.
To study IV characteristics, Ag top electrodes were deposited
on the thin lms using a shadow mask.
equation [3]:
n
d
1
2 sin
Here n is the order of diffraction and taken as 1, is the
wavelength of X-rays used 0.154 nm, for Cu K target and
is the Bragg diffraction angle of the peak (002). For the
hexagonal lattice, lattice spacing d is given by the following
relation [18]:
1
4 h2 hk k2
l2
2
2
2
2
3
a
c
d
where h, k and l are the Miller indices of the plane, a and c are
the lattice constant for the hexagonal unit cell. Using Eq. (2)
values for the lattice constants a and c are calculated. A
slight increase in the lattice constants for Al:ZnO thin lms are
due to the incorporation of Al3 ions in the interstitial
positions [1]. The change in lattice spacing, d with the
thickness of lms implies a strain occurs between atomic
planes. Strain, in the thin lms along c-axis can be calculated
using the equation [18]:
cf ilm cbulk
3
cbulk
Here cbulk is the unstrained lattice parameter measured for
bulk ZnO and its value is 0.521939 nm. This strain in the thin
lms is caused by the combined effect of thickness and Aldoping in ZnO. Stress in thin lms can be obtained using the
biaxial strain model [18]:
f ilm 232:8 GPa
Fig. 1. XRD pattern describing the excellent crystallinity and c-axis oriented
thin lms of different thickness, from A 487 nm to D 964 nm deposited via
PLD. The intensity and width of the peak is changed signicantly with the lm
thickness.
15
Table 2
Calculations from XRD analysis of thin lms: Lattice spacing, lattice constants, strain, stress, crystallite size and degree of texture for plane (002). As the thickness
increases from sample A to D, the lattice parameters are changed which inuence the stress in the lms.
Sample Lattice spacing, d (nm) Lattice constant, a (nm) Lattice constant, c (nm) Strain () Stress (GPa) FWHM () Crystallite size (nm) Degree of texture
A
B
C
D
0.2663
0.2661
0.2651
0.2646
0.3361
0.3359
0.3339
0.3326
0.5326
0.5322
0.5302
0.5292
0.0205
0.0197
0.0158
0.0139
4.7729
4.5946
3.6757
3.2475
0.4794
0.5402
0.6201
0.6372
17.12
15.21
13.24
12.88
0.8311
0.8121
0.9851
0.7882
Fig. 2. AFM images describing the surface morphology for the Al:ZnO thin lms. The grain distribution and the surface roughness are inuenced by the sample
thickness, from A 487 nm to D 964 nm.
Table 3
Grain size of the thin lms calculated from AFM and FESEM analysis,
Average and Root mean square (rms) roughness calculated from AFM
analysis.
Sample
AFM
Grain size (nm)
A
B
C
D
22.706
20.834
17.925
15.005
FESEM
Roughness (nm)
Average
rms
2.7827
2.1989
1.6752
1.1768
2.9885
2.2422
1.7419
1.2587
20
16.67
12.5
10
observed grains had small diameter and the average grain size
varied from 23 nm to 15 nm with the change in lm thickness.
The surface morphology of the thin lms was highly
16
Fig. 3. Grain formation observed from FESEM analysis describes the changes evaluated, decrease in grain size with the increase in lm thickness.
17
Fig. 4. Energy dispersive analysis of X-rays, EDAX analysis to describe the atomic and weight composition of thin lms.
6n2
n4 3:25n2 2:25
1
1
ln
t
T
10
18
Fig. 5. The crystal formation in the thin lms as viewed under transmission electron microscopy (TEM).
11
19
(110)
(002)
(100)
Fig. 7. The optical transmittance versus wavelength plots for the Al:ZnO thin
lms at room temperature. The fringe pattern is permuted when the thickness
of the lm is changed from A 487 nm to D 964 nm.
Table 4
Calculations for thin lm thickness and optical refractive index, from the fringe
pattern observed in optical transmittance versus wavelength plot, band gap
values calculated from (h)2 versus h plot and resistivity values calculated
from room temperature IV plots.
Sample Refractive
Index, n
Thickness, t
(nm)
Band gap
(eV)
Resistivity
( cm)
A
B
C
D
487.5
632.5
789.1
964.5
3.2
3.11
3.12
3.08
0.59 10 3
1.24 10 3
1.42 10 3
2.28 10 3
1.7323
1.8074
1.7569
1.7768
Fig. 8. The optical absorbance versus wavelength plots for Al:ZnO thin lm
samples. As the lm thickness is increased from A 487 nm to D 964 nm, a
red shift in absorption spectra is observed.
Fig. 9. The optical reectance versus wavelength plots for Al:ZnO thin lm
samples.
from deep donor levels to the valence band [19]. For Al-doped
ZnO, Al ions exist in the form of Al3 and Zn ions in the form
of Zn2 , Al ions will consume the residual O ions and results in
decreasing the concentration of interstitial oxygen in the Al:ZnO
layers. It has been observed that, Al doping leads to the
reduction of concentration of oxygen vacancies according to
3OXo . Al-doping facilitates
the reaction: Al2O3 V-2AlZn
the non radiative transition rate, in regard to the localization of
the Al impurity states [30]. Visible photoluminescence peaks
enable Al:ZnO thin lms for optoelectronic device applications
such as LEDs.
3.6. Electrical properties
Room temperature current versus voltage (IV) characteristics of thin lms are shown in Fig. 13. The enhanced
conduction in these lms is due to the Al-doping, which
creates donor impurities via the formation Al3 ions in the
crystal and the resulting Al:ZnO n-type semiconductor. The
20
Fig. 10. Plots of (h)2 versus h describing band gap for the semiconducting
Al:ZnO thin lms. The decrease in band gap is observed with the increases in
lm thickness from A 487 nm to D 964 nm.
Fig. 12. Schematic layout of various energy states correspond to Photoluminescence emission peaks.
Fig. 13. Plot describing currentvoltage (IV) curves for the semiconducting
Al:ZnO thin lms at room temperature. The resistivity increases with the
increase in lm thickness from A 487 nm to D 964 nm.
12
ln 2 I
4. Conclusions
Al:ZnO thin lms of varying thickness were successfully
deposited on glass substrates. The deposited thin lms are
single phased with preferential growth in (002) plane, along c-
21
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