Article

DOI: 10.1557/jmr.2018.506
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A structural, morphological, linear, and nonlinear optical

spectroscopic studies of nanostructured Al-doped ZnO
thin films: An effect of Al concentrations
Mohd Arif1, Mohd Shkir2 , Salem AlFaify2, Vanga Ganesh2, Amit Sanger3, Hamed Algarni2,
Paula M. Vilarinho4, Arun Singh1,a)
1
Advanced Electronic & Nanomaterials Laboratory, Department of Physics, Jamia Millia Islamia, New Delhi 110025, India
2
Advanced Functional Materials and Optoelectronic Laboratory (AFMOL), Department of Physics, College of Science, King Khalid University, Abha
61413, Saudi Arabia
3
School of Materials Science, Ulsan National Institute of Science and Technology, Ulsan 44919, South Korea
4
Department of Materials and Ceramic Engineering, University of Aveiro, Aveiro 3810-193, Portugal
a)
Address all correspondence to this author. e-mail: arunsingh07@gmail.com
Received: 20 October 2018; accepted: 3 December 2018

Sol–gel spin coating is applied to fabricate the pure and different concentrations of aluminum (Al)-doped ZnO
films on high-quality silicon substrates. All films are showing high crystallinity in X-ray diffraction study, and
lattice constants were obtained using PowderX software. The value of crystallite size was found in range of
20–40 nm. EDX/SEM mapping was performed for 2 wt% Al-doped ZnO film, which shows the presence of Al and
its homogeneous distribution in the film. SEM investigation shows nanorods morphology all over the surface of
films, and the dimension of nanorods is found to increase with Al doping. The E(g)dire. values were estimate in
range of 3.25–3.29 eV for all films. Linear refractive index was found in range of 1.5–2.75. The v1 value is found
in range of 0.13–1.4 for all films. The v3 values are found in range of 0.0053 × 10−10 to 6.24 × 10−10 esu for
pure and doped films. The n2 values were also estimated. These studies clearly showed that the properties of
ZnO have been enriched by Al doping, and hence doped films are more appropriate for optoelectronic
applications.

Introduction reported that a nonstoichiometric composition of the ZnO

Significant research efforts have been dedicated to transparent
conductive oxide (TCO) thin films of metal oxide material with
increased attention in the area of emerging electronic devices
such as photovoltaic devices, transparent electronic displays,
photodiodes, and chemoresistive gas sensors [1, 2, 3, 4]. Since
past few years, in the field of different metal oxide and
conducting thin films, zinc oxide (ZnO) has been considered
structure with zinc interstitials delivers a virtuous environment
for many dopants and enhances the nonlinear optical proper-
ties [11]. Additionally, the properties of ZnO thin films can be
dramatically enhanced by doping with suitable ions of metal
such as tin, manganese, gallium, indium, aluminum, and cobalt
[12, 13, 14, 15, 16, 17]. It has been observed that AZO films not
only have high optical transparency and virtuous electrical
j Journal of Materials Research j www.mrs.org/jmr

conductivity in the visible region (380–800 nm), but also offers

as a promising candidate for technological applications such
as photovoltaic cells [5] and spintronics [6]. It is a recognized
n-type inorganic semiconductor material from II–VI group [7]
with broad energy gap and exciton energy, i.e., 3.37 eV and
60 MeV, respectively. Zinc oxide exists in several forms such as
nanowires, nanoflowers, and nanosheets [8, 9, 10]. Pure ZnO
thin films offers wide range of applications owing to their
stability and low resistivity. However, in the literature, it is
good thermal, chemical, and mechanical stability. Numerous
reports are available from the literature review for the fabrica-
tion of pure and doped ZnO films, which involves methods
such as pulse laser deposition [18], dc sputtering [19], chemical
vapor deposition [20], hydrothermal [21], spray pyrolysis
[22, 23], and sol–gel method [24]. Among all, sol–gel
spin-coated method has been used to fabricate AZO thin films
because of its simplicity and low cost. The pure and aluminum

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Figure 1: (a) XRD patterns and (b) variation of crystallite size with Al doping.

(Al)-doped ZnO films were earlier examined intensively for TABLE I: Calculated lattice constant, D, and d values for pure and Al-doped
ZnO films.
core characteristics; however, some rare investigations associated
with linear and nonlinear optical parameters are present [25]. Samples a 5 b (Å) c (Å) V (Å)3 D (nm) d (1/nm)2
Sofiani et al. report the third-order nonlinear (TONLO) studies JCPDS# 36-1451 3.2498 5.2066 47.6200 ... ...
on cerium-, fluorine-, erbium-, aluminum-, and tin-doped ZnO PZO 3.2497 5.2054 47.6081 20.132 0.0025
1 wt% AZO 3.2495 5.2064 47.6100 22.345 0.0020
films [26]. Nagaraja et al. studied TONLO of ZnO with Mn
2 wt% AZO 3.2514 5.2120 47.7165 25.278 0.0016
doping, using Z-scan experiment [27]. All the work on nonlinear 3 wt% AZO 3.2529 5.2065 47.7113 28.122 0.0013
properties has been done on different substrates but not on
silicon (Si). Hence, in the current study, high-quality thin films
of pure and Al-doped ZnO with different molar concentrations
(1, 2, and 3 wt%) were designed on Si(100) substrate by spin
coating, and its detailed linear and nonlinear properties were
studied. Several important properties of fabricated thin films
such as structural, morphological, optical, and nonlinear optical
such as: lattice constant, crystallite size, dislocation density, direct
and indirect band gap, refractive index and nonlinear, were
investigated and conferred in their corresponding sections.

Results and discussion

Structural analysis
The X-ray diffraction (XRD) spectra for AZO thin films, spin-
coated on Si(100) substrate can be seen in Fig. 1(a). It is observed Figure 2: Raman spectra of pure and Al-doped (1–3 wt%) ZnO films.
that all the thin films have XRD peaks analogous to (100), (002),
(101), (102), (110), and (103) planes. However, it is found that the
intensity is high for (201) plane from others for 2 wt% AZO films. the previous report by Benramache et al. [14]. The dislocation
The indexed diffraction peaks of the XRD patterns correspond to density (d) of films can be estimated by [34, 35, 36] d 5 1/D2. This
hexagonal wurtzite ZnO structure, which is in harmony with is a measure of film quality. Here, ZnO and AZO films possess
j Journal of Materials Research j www.mrs.org/jmr

JCPDS: 36-1451. The XRD analysis confirms the polycrystalline

nature of the AZO thin films. Scherer’s formula [28, 29, 30] was
used to determine the crystallite size of the films (Table I) from the
width of XRD peaks [31, 32, 33], D ¼ b0:9k cos h, where (b) is FWHM
(radians) and k is wavelength (1.5406 Å). In the present study,
large crystallite size is seen for 3 wt% Al in ZnO material owed to
effect of doping on crystallinity enhancement. Figure 1(b) shows
the crystallite size increasing with the increase in concentration of
aluminum doping (i.e., 1, 2, and 3 wt%), which is quite similar to
dislocation density in the range of 2.5  103 to 1.3  103 nm2,
which might be the indication that Al incorporation in ZnO
reduced the defects. Such results have previously been reported for
Sn-, Al-, Co-, In-doped ZnO [13, 14].
FT Raman analysis
From Raman spectra of ZnO and AZO films depicted in Fig. 2,
here it is describing the shifting of Raman spectra with

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Figure 3: EDX elemental mapping micrographs for 2 wt% Al-doped ZnO film.
Figure 4: SEM images of (a) pure, (b) 1 wt% Al, (c) 2 wt% Al, and (d) 3 wt%
Al-doped ZnO thin film.
intensity. It is visible from the figure that the Raman modes
positioned at ;302 6 5, 521 6 3, 620 6 4, and 960 6 3 cm1
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are assigned to Si substrate on which the films are deposited.
Moreover, Raman modes positioned at ;436 6 2 cm1 are
ascribed to E2 (high), which is a key vibration of ZnO wurtzite
phase; however, it shows some shift toward lower wavenumber
compared to bulk ZnO (i.e., 443 cm1). Such a shift is might be
owing to low-dimensional nanorods formation in ZnO and
AZO in the current work. Another Raman mode positioned
at ;580 6 3 cm1 is ascribed to A1 (LO) and E1 (LO) mode of
vibration, which is asymmetric vibration mode that may have
arisen from short and lofty wavenumbers contributions. The
other low-intensity Raman modes observed at ;370 6 4,
416 6 5, and 548 6 3 cm1 are assigned to transverse and
second-order modes of vibrations. The key vibration mode is
found to have ;7 6 2 cm1 shifting in wavenumber toward
the lower side, which may be due to small particle size and also
the possibility of development of stress in films. This verifies
that ZnO and AZO films possess more favorable epitaxial
growth with Si substrate. The currently observed vibrational
modes are well matched with previous reports [37, 38].
j Journal of Materials Research j www.mrs.org/jmr
EDX/elemental mapping and SEM analyses
Figure 3 shows the EDX spectrum along with elemental mapping
images for 2 wt% Al-doped ZnO films. Figure clearly showed that
the Al has been doped homogeneously in ZnO matrix throughout
the films. Figures 4(a)–4(d) show the SEM images of pure, 1 to
3 wt% Al-doped ZnO films. From Fig. 4(a), it is observed that the
films contain very low size grains, which are maybe guessed as
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Figure 5: (a) Diffused reflectance spectra, (b, c) direct and indirect band gap, and (d) linear refractive index of pure and Al-doped ZnO films.
nanorods morphology. However, with 1 wt% Al doping, the
nanorods morphology [see Fig. 4(b)] is very clear, which is
growing more and more at higher concentration doping of Al
[see Figs. 4(c) and 4(d)]. The diameter of nanorods for pure ZnO
[Fig. 4(a)] is maybe ,5 nm; however, the average dimension is in
the range of 30–50 nm. These dimensions in case of 1 wt% and 25
AZO films are increased [Fig. 4(b)], and hence the diameter is also
affected; however, at 3 wt% Al doping, the dimension becomes
almost constant and showing well-defined nanorods, which are
homogeneously distributed throughout the film surface.
Linear optical properties
A study of electronic structure in reference to the optical
properties is vital when non-centrosymmetric semiconductor
materials, such as ZnO, are involved [39, 40]. The application
of linear optical characteristics in modern optoelectronic
devices has gained them much importance and well-
discussed [41, 42, 43, 44, 45]; the current study presents
a systematic calculation of the parameters such as diffused
reflectance, linear and nonlinear susceptibilities, nonlinear
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refractive index, and various other parameters using standard
relations.
Figure 5(a) displayed DR spectra of ZnO and Al-doped
ZnO films in 200–1800 nm range. It is visible from the figure
that all films show reasonable transmittance with the edge of
absorption at ;400 nm for ZnO and ;1000 nm for Si
substrate. Measured data were used to determine the energy
gap by Kubelka–Munk theory. Kubelka–Munk equation [46] is
Þ2
given by F ðRÞ ¼ ð1R 2R ; here F(R) is a function of Kubelka–
Munk and R indicates to reflectance of films. The coefficient of
absorption in terms of F(R) is a ¼ absorbance
t ¼ FðtRÞ; here the
symbols are of standard meanings and t is thickness of the
j Journal of Materials Research j www.mrs.org/jmr
films. Energy

1r band gap can be obtained using
1
ðahmÞr ¼ F ðRtÞhm ¼ A hm  Eg ; here the symbols are of
standard meanings [47, 48]. The band gap of AZO films was
computed for direct and indirect allowed transition values of
r (r 5 1/2 and 2) and plotted as hm versus [F(R)hm/t]1/r in
Figs. 5(b) and 5(c). The value of direct energy gap, E(g)dire., is
obtained to be in range of 3.25–3.29 eV and is alike to previous
reports [13, 14, 49]. Value of indirect energy gap, E(g)indire., is
obtained to be in range of 3.05–3.14 eV. Values of E(g)dire. and
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Figure 6: Plots of variation of (a) v1, (b) v3, and (c) n2 with energy for ZnO and AZO films.
E(g)indire. are increasing with doping of 1 and 2 wt% and are
higher in comparison to pure material. But the band gap value
for 3 wt% doping is found to be slightly less than the other
doping concentrations, however still higher than pure ZnO.
The reason for this may be attributed to the increased thickness
of the film at higher doping concentration, which leads to
reduced bad gap value. Such doping concentration effect on
energy gap broadening may be explained through Burstein
Moss shift [50]. It can be seen in figure that there is another
energy gap ;1.1 eV, which attributes due to Si substrate. The
refractive index, n, of all filmsrffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
was also calculated using the
1þR
4R 
following relation [51]: n ¼ 1R þ ð1RÞ2 . Figure 5(d)
displayed calculated n values for all films and its value is in
range of 1.5–2.75. This clearly shows that Al doping in ZnO
increases its refractive index.
Nonlinear susceptibility and refractive index
analyses
To understand the nonlinear behavior of fabricated films and
see the effect of Al doping on these properties, we have
determined several constraints, as it is essential to investigate
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the linear and third-order nonlinear susceptibilities and non-
linear refractive index of all films for various nonlinear device
applications [52, 53, 54].
Polarizability (p) in terms of nonlinear polarizability (PNL)
is expressed as [55] p 5 v1E 1 PNL; here PNL 5 v2E2 1 v3E3;
here v1, v2, and v3 are linear, second-order, and third-order
nonlinear optical susceptibilities. In similar manner, n(k) is
n(k) 5 n0(k) 1 n2(E2); here, n(k) is expressed as n0 (k)  n2
(k), n(k) 5 n0(k), and (E2) is defined as mean square value of
electric field and n2 is known as nonlinear refractive index. The
values of v1 and v3 are determined using the equations [56, 57,
2
58, 59], v1 ¼
n04p1and v3 5 A(v1)4; from these equation, we
2 4
have v3 ¼ A n04p1 , where A is a constant and its values is 1.7
 1010 esu [60]. The calculated values of v1 and v3 are plotted
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in Figs. 6(a) and 6(b). As can be seen from figure that the value
of v1 is found to be higher at 0.64 eV energy viz. ;0.94 for pure
and 1.38 for 3 wt% Al-doped ZnO; however, in energy range of
0.68–1 eV, its value is found almost equal to 0.61 for pure ZnO
and 0.75 for 1 wt% Al-doped ZnO films. After 1.15 eV energy,
the value of v1 is found to be in range of ;0.13–0.51 for ZnO
and AZO films. Figure 6(b) displayed the plot for v3 values and
found to have similar behavior as of v1. Its value is found in the
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range of 0.0053  1010 to 1.3  1010 for pure films and
0.004  1010 to 6.24  1010 for doped films. These values are
found to be comparable with previous theoretical and exper-
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imental reports [25, 26, 27].
The value of n2 is obtained using the equation [61],
3
n2 ¼ 12pv
n0 , and displayed in Fig. 6(c). From figure, it can be
observed that the value of n2 is found to be higher at 0.64 eV
energy viz. ;1.37  109 for pure ZnO and 5.49  109 for
3 wt% Al-doped ZnO; however, in energy range of 0.68–1 eV, its
value is found almost equal to 3.1  1010 for pure ZnO and 7.1
 1010 for doped ZnO films. After 1.15 eV energy, the value of
n2 is found to be ;2.1  1013 for pure and doped ZnO films.
Such variation in these values is may be due to all three factors
such as Si substrate, Al doping, and thickness of films. Also, it
may be due to light interaction, which generates polarization
higher in such specific wavelength region [13, 54, 62]. Hence, all
above characteristics of ZnO are enhanced by Al doping and
found to be comparable with earlier reports on ZnO films [63].
Conclusions
Fabrication of good quality pure and 1 wt%, 2 wt%, and 3 wt% Al-
doped ZnO films was achieved by spin-coating process on silicon
(Si) substrates, which were subsequently annealed at 600 °C. High
crystallinity of fabricated films was confirmed from XRD patterns.
Lattice constants were found to be varied with Al doping in ZnO;
however, no major change was observed, which confirms the single
phase. Scherer equation is used to calculate crystallite size and
found in a range of 20–40 nm. Presence of Al and its homogeneous
distribution throughout the film was approved by EDX and EDX
elemental mapping analysis. Nanorods-like morphology was con-
firmed by SEM investigation. The dimension of nanorods is
increased with increasing Al doping concentration and leads to
best nanorods morphology. The direct and indirect band gap are
calculated in the range of 3.25–3.29 eV and 3.05–3.12 eV,
respectively, for pure and doped films. The linear refractive index
is determined and found in a range of 1.5–2.75. The value of v1 is
estimated in range of 0.12–0.94 for pure and 0.13–1.4 for doped
ZnO films. The v3 values are estimated in range of 0.0053  1010
to 1.3  1010 for pure and 0.004  1010 to 6.24  1010 for
doped ZnO films. The n2 values are found in range of 0.0009 
109 to 1.4 109 for pure and 0.0008  109 to 5.4  109
for doped ZnO films. Such enhanced results for doped ZnO films
make them suitable for optical and nonlinear devices.
Experimental procedure
The synthesis procedure of sol–gel spin-coating method used
for depositing pure and Al-doped (1–3 wt%) ZnO thin films is
described in an earlier reported work [64]. In summary, for the
fabrication of thin films, zinc acetate dihydrate (Zn(CH3COO)
22H2O, 97%; Merck, Mumbai, India), 2-methoxy ethanol,
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(CH3O(CH2)2OH, 97%; Merck), aluminum chloride dihydrate
(AlCl3 2H2O 97%; Merck), and monoethanolamine (MEA)
((HOCH2CH2) NH2, 97%; Merck) were used without further
purification, as the source, solvent, dopant, and stabilizer,
respectively. In the initial phase, 2.173 gm of Zn(CH3COO)
22H2O was liquefied in 20 mL 2-methoxy ethanol at a constant
temperature of 60 °C and was stirred for 1 h using a magnetic
stirrer to prepare a 0.5 M homogeneous precursor solution.
Also, 0.5 mL of monoethanolamine was added as a stabilizer to
the resultant solution during continuous stirring for the
equivalent time and temperature. Analogous procedure was
implemented to fabricate the other three solutions for Al
doping with the desired amount of dopant, which was added
in different molar ratios of 1 wt%, 2 wt%, and 3 wt%. As-
synthesized solutions of ZnO and AZO were stored in the
shaded area for ;48 h for suitable gel formation. After
preparing all the chosen solutions, thin films were fabricated
on Si(100) via spin coating.
Earlier to deposition, Si(100) substrates, 1  1 cm2 in size,
were cleaned in ultrasonic cleaner by placing the substrate in
a warm acetone bath for 10 min and in methanol for 5 min,
followed by drying with oxygen blower. Sols of ZnO with 0, 1, 2,
and 3 wt% Al doping was spin coated on the substrates at
a rotation speed of 3000 rpm for 30 s to form thin films, which
were then heated at 300 °C for 10 min and then permitted to
cool down to RT. The method of coating and successive drying
was repeated for 10 times to obtain the desired thickness of the
film sample. Finally, the thin films were exposed to annealing at
600 °C for 2 h and cooled down to room temperature by using
a programmable muffle furnace. The average thickness of ZnO
and AZO thin films measured over thickness monitor is found
to be 250 nm. The fabricated pure and AZO films were exposed
to X-ray diffraction (XRD) analysis (Shimadzu Lab-X, XRD-
600 40 kV, 30 mA; Kyoto, Japan) using Cu Ka radiation of
wavelength 1.54056 Å with constant scanning rate 2°/min. The
vibrational modes of the films were studied from the FT Raman
spectra obtained via DXR FT Raman spectrometer over the
range of 3500–500 cm1. The elemental composition, mor-
phology, and microstructure were examined by SEM/EDX
(SEM, JSM 6360 LA, JEOL, Ltd., Tokyo, Japan). Diffused
reflectance (DR) measurement was done using UV-3600
(Shimadzu UV-Vis-NIR spectrophotometer, Kyoto, Japan)
j Journal of Materials Research j www.mrs.org/jmr
over 190–1800 nm wavelength region.
Acknowledgment
The authors are grateful to Department of Science and
Technology Ministry of Science and Technology & University
Grants Commission, Government of India for the financial
support. A.S. would like to thank the Department of Science &
Technology, Ministry of Science & Technology, Govt. of India
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for the award of Young Scientist and BOYCAST Fellowship.
The authors from KKU would like to express their appreciation
to the Deanship of Scientific Research at the King Khalid
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University for funding this work through Research Groups
Program under Grant No. R.G.P. 2/10/39. Authors are also
thankful to Prof. I.S. Yahia, KKU, KSA for help in OC.
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