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Abstract
This paper reports on the structural and optical properties of Al doped ZnO nanoparticles prepared through a solgel method. Different atomic
ratio's of Al were doped into ZnO ranging from 1 at% to 6 at%. X-ray diffraction (XRD) and FE-SEM results showed that the average crystallite
size of ZnO nanoparticles decreased with increasing Al concentration. A compressive strain induced in ZnO with Al doping was calculated using
WH plot analysis. The band gap increased monotonously as Al concentration was increased from 1 at% to 6 at%. ZnO nanocrystals showed an
emission peak positioned at 396 nm. The intensity of this peak decreases with Al doping for all concentrations. The decrease of the intensity of
396 nm emission peak is due to the worsening of the crystal quality due to Al doping. In addition to this, another peak at 437 nm is developed
with Al doping and it is speculated to be due to the zinc interstitial defects.
& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Keywords: C. Optical properties; Al doped ZnO nanoparticles; Solgel method; X-ray diffraction
1. Introduction
Zinc oxide (ZnO) is one of the IIVI group compound
semiconductors which crystallize in wurtzite structure belonging
to the space group P63mc. It has characteristics of high transparency in visible range, good light trapping, low resistivity, nontoxicity, natural abundance, etc. which are important properties of
optoelectronic and piezoelectric materials [1,2]. It has a direct band
gap of 3.37 eV with a large exciton binding energy of 60 meV
which ensures stable exciton emission even at room temperature.
These unique properties make ZnO an important optoelectronic
material due to its strong quantum connement effects in experimentally suitable conditions. Iskandar [3] reported that, some
nanoparticles (NPs) exhibited unique optical properties with a
range of refractive indeces, high transparency, novel photoluminescence and plasmon resonance, etc. These can nd potential
applications such as catalysts, drug carriers, sensors, pigments,
magnetic and optical materials and also in bio imaging, etc. [3].
For obtaining desired optical properties, preparation of ZnO
nanoparticles (NPs) of different nanostructures such as 1D (Wires,
n
http://dx.doi.org/10.1016/j.ceramint.2014.04.057
0272-8842/& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
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arc lamp of 450 W was used as the excitation light source to record
the emission spectra of samples.
3. Results and discussion
3.1. XRD analysis
The XRD patterns of ZnO nanoparticles doped with different
Al concentrations are shown in Fig. 1. The diffraction peaks
corresponding to planes (100), (002), (101), (102), (110), (103),
(112), and (201) conrmed the hexagonal wurtzite structure of
ZnO nanoparticles [12]. No other secondary phase of oxides
of Al or metallic Al was observed, indicating that Al is present in
X-ray in an amorphous state [13]. The continuous increase in
broadening of the XRD signals with increasing concentrations of
Al indicates that the crystallite size of nanoparticles decreases
[14,1]. The average crystallite size (davg) of the prepared samples
was estimated from the width of diffraction peaks in the XRD
spectrum using the Scherrer's equation [15].
0:9
1
cos
q
where 2FWHM 20 is the peak broadening after removing
the instrumental broadening, (FWHM) is the full width at half
maximum and 0 is the correction factor (0.007 rad). The average
crystallite size calculated using Debye Scherrer's formula, in case
of undoped sample is 32 nm, whereas for Al doped samples
of AZO1, AZO2, AZO3, AZO4 and AZO6, they were 23 nm,
16 nm, 13 nm, 12 nm and 8 nm, respectively. By increasing doping concentrations, the intensity of peaks monotonously decreased
with simultaneous increase in the FWHM. This indicates that the
crystallinity deteriorated with increasing doping concentrations.
With reference to the pristine ZnO peak, there is a slight shift
observed in Al doped ZnO peak positions to higher angles may be
because of incorporation of Al induced shift in the diffraction peak
position to higher angles due to smaller atomic radii of Al. Since
there is a difference in the ionic radii of the Zn2 (0.60 ) and
Al3 (0.39 ), incorporation of Al ions in ZnO lattice probably
dxrd
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Fig. 3 shows the typical SEM micrographs of ZnO nanoparticles prepared with different nominal Al concentrations. The
formation of the polyhedral morphology with uniform grains of
all samples which are in the range of 100500 nm size is clear
from the micrographs. The average grain sizes of all samples
were determined by counting sufciently large number of grains
for ensuring the accuracy. The average grain size of undoped and
doped samples estimated is below 100 nm. The grain sizes of
samples were reduced up to 2 at% of Al concentration and then
grain sizes increased for the other concentrations. The decrease in
the average grain size with Al doping can be attributed as the
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Fig. 3. Typical SEM micro graphs of (a) undoped (b) AZO1 (c) AZO2 (d) AZO3 (e) AZO4 and (f) AZO6 nano structures.
Fig. 4. FTIR spectrum of Al doped ZnO; (a) pristine ZnO sample, (b) AZO1,
(c) AZO2, (d) AZO3 (e) AZO4, and (f) AZO6.
Photoluminescence (PL) investigations are important to characterize a variety of material's parameters. The PL emission
yields information on life time of excited states, identication of
surface interface and impurity levels and intrinsic and extrinsic
defects [28]. In PL spectra of ZnO, typically there are emission
bands in the ultraviolet (UV) and visible (green, yellow, blue, and
violet) regions. The ultraviolet emission is usually considered
as the characteristic emission of ZnO, and is attributed to the
band edge transition or the exciton recombination. For the green
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Fig. 5. (a). The UVvis spectra of Undoped and Al doped ZnO samples. (b). The individual absorption peaks of all the samples. (c). The h2 vs h Tauc plots
and the band gap energy estimation for undoped and Al doped ZnO nano particles.
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4. Conclusions
The AZO NPs were successfully synthesized by the solgel
method with PVA as chelating agent. The effect of Al doping on
the structural as well as optical properties were studied. The XRD
patterns conrmed the formation of hexagonal wurtzite structure of
ZnO. In addition, XRD results indicates that the crystallite size as
well as the intensity of ZnO was inuenced by Al doping. The
average crystallite size of the samples decreased with increasing Al
doping. The strain evaluated from WH plot analysis exhibited an
overall increase with Al doping concentration. This induced strain
is reected in the emission peaks also. The blue shift observed
from UVvis absorption spectrum with increase of Al doping,
conrmed the quantum size connement effects. It is also observed
from the absorption peaks that peaks got broadened with increasing
Al concentration. This can be explained as, the doping of Al
induces defect levels with which, the transition from valence band
to these defect levels broadened absorption peaks. There is an
overall increase in the band gap of all the doped samples thereby
exhibiting increased quantum size connement effect with increase
of Al doping. From the emission peaks, it became clear that, the
intensity of the emission peaks monotonously decreased with Al
doping, which was also observed in the XRD and absorption
peaks. This can be attributed to defects which are generated with
Al doping. Hence there is an extra emission peak generated at
437 nm with Al doping in emission peaks. Thus the feasibility of
Al incorporation into ZnO implies the ability to control the
crystallinity as well as tailoring of the band gap.
Fig. 6. (a). Room temperature PL spectrum of undoped and Al doped ZnO
nanoparticles. (b). Gaussian deconvolution of the PL spectrum of ZnO nano
particles containing 6 at. % of Al.
Acknowledgment
The authors are greatly thankful to MHRD, Govt. of India for
the nancial support through Institute fellowship for Ph.D.
program. The authors wish to thank Mr. Rajasegaran E, Indian
Institute of Sciences Bangalore (IISc) for helping in FE-SEM
measurements and authors would also like to thank Mr. Y.B
Ravishankar (University of Hyderabad) for his help in XRD
measurements.
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