Ceramics International 43 (2017) 3562–3568

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Effect of structural defects, surface roughness on sensing properties of Al MARK

doped ZnO thin films deposited by chemical spray pyrolysis technique
Manjeet Kumara,d, Bikmramjeet Singhb, Pankaj Yadavc, Vishwa Bhattc, Manoj Kumarc,
⁎ ⁎
Kulwinder Singhb, A.C. Abhyankara, Akshay Kumarb, , Ju-Hyung Yund,
a
Department of Materials Engineering, Defence Institute of Advanced Technology, Girinagar, Pune 411025, India
b
Department of Nanotechnology, Sri Guru Granth Sahib World University, Fatehgarh Sahib 140407, Punjab, India
c
School of Technology, Pandit Deendayal Petroleum University, Gandhinagar 382007, India
d
Department of Electrical Engineering, Incheon National University, Incheon 406772, South Korea

A R T I C L E I N F O A BS T RAC T

Keywords: In this article, the gas sensing properties of Al-doped ZnO thin films have been reported where the
ZnO nanocrystalline ZnO based thin films were well deposited by a simple and inexpensive ‘chemical spray pyrolysis
Thin films (CSP)’ technique. Films have been found to be uniform, pinhole free and well adherent to the substrate. The
Gas sensor morphology, structures, and surface roughness of the deposited Al-doped ZnO thin films were studied by
Spray pyrolysis
various types of characterization techniques. In addition, the authors have observed that the sensor response
and selectivity towards CO gas is improved by the Al doping at a low operating temperature. XRD results
showed that the obtained films are nanocrystalline in nature with hexagonal wurtzite phase. Further, the
annealed films were used for detection of CO in the air and maximum response was observed at 175 °C. The
improvement in sensor response of Al-doped ZnO thin films to CO gas attributed to the defect chemistry,
crystallite size and surface roughness.

1. Introduction standing the sensing properties and their working mechanism.

However, the detrimental and less exposed surface area of ZnO
Metal oxides (MOs) have gained a considerable research interest nanostructure should be controlled during the synthesis process to
due to its low cost and simple processing steps and high potential for enhance the sensing capability. Thus, to synthesize and analyse the
the electronic and optoelectronic applications [1–5]. The progress in sensing behaviour of the doped ZnO nanostructure and to further
the field of utilizing MOs for gas sensing application was highlighted by understand the insights of sensing mechanism is one of the aims of the
the high sensing capabilities of MOs and their physical properties such present studies.
as electrical transport, magnetic, optical response, thermal conductivity The doped and un-doped nanostructures of the ZnO thin films have
and superconductivity [6–13]. The MOs semiconductor materials have been synthesized by several methods such as radio frequency magne-
been extensively studied in gas sensing applications due to their ease of tron sputtering [26,27], atomic layer deposition (ALD) [28], metal-
detection both oxidizing and reducing gases. Among various MOs organic chemical vapor deposition (MOCVD) [29,30], solution growth
semiconductors, ZnO is a direct, wide band gap (Eg=3.37 eV at room [31–34], thermal evaporation [35], sol gel [36], hydrothermal process
temperature) and most promising multifunctional material because of [37,38], spin coating [39] etc. The common feature between the
its abundance in nature, less expensive and has high exciton binding mentioned techniques is the requirement of sophisticated and con-
energy of 60 meV, which makes the exciton state stable even at room trolled environment that leads to an increase in cost and complications
temperature [14,15]. Additionally, its biodegradable and biocompatible in the process. However, a non-vacuum based chemical spray pyrolysis
properties also make it a suitable candidate for various applications (CSP) process, a non-vacuum process, is more convenient, along with
[16–24]. least expensive and suitable for large area of deposition [40]. One of the
ZnO based electronic devices such as gas sensors are predicted to be advantages of this technique regarding doping of samples is that it is
a high performer and enable the new functions [25]. Moreover, the very easy to dope the samples of any element whose salt can be
optimized doped ZnO thin film possesses a huge potential for under- dissolved in the spray solution. The growing global concern for

⁎
Corresponding authors.
E-mail addresses: akshaykumar.tiet@gmail.com (A. Kumar), juhyungyun@inu.ac.kr (J.-H. Yun).

http://dx.doi.org/10.1016/j.ceramint.2016.11.191
Received 22 September 2016; Received in revised form 8 November 2016; Accepted 27 November 2016
Available online 28 November 2016
0272-8842/ © 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
M. Kumar et al. Ceramics International 43 (2017) 3562–3568

environmental safety, pollution, and its influences have stimulated the

attention of the research community in the developing field of gas
sensor. CO is widely produced in transportations and industrial
appliances and it is hazardous in nature as well as its leakage detection
is also an important issue. The applications of the MOs for gas sensing
has been widely studied. However, the deposition of nanocrystalline
thin films of Al-doped ZnO and their morphological and structural
effect on gas sensing properties are rarely found in the literature.
In the present study, we report the synthesis of ZnO and Al-doped
ZnO based thin films by a simple and inexpensive method, i.e. CSP and
it is characterized to evaluate its gas sensing properties. Structure,
surface morphology and micro-structure of the films were investigated
by X-ray diffraction (XRD), atomic force microscopy (AFM) and field-
emission scanning electron microscopy (FESEM), techniques respec-
tively. The sensor responses of pure and Al-doped ZnO films were
studied for CO, NH3, and ethanol gasses. The effect of operating Fig. 1. XRD pattern of (a) Pure, (b) 3% Al-doped, (c) 5% Al-doped ZnO thin films.
temperature on sensor response of deposited films towards CO
exposure is discussed. Scherer's formula was employed to estimate the crystallite sizes of
the pure and Al doped ZnO thin films, and is given by,
2. Experimental method
kλ
D=
Pure and Al-doped ZnO thin films on a glass substrate were β cos θ (1)
deposited using CSP technique. Zn(CH3COO)2·2H2O (≥98%) and
where constant k is 0.9, wavelength λ of the X-Ray is 1.5045 Ǻ, β is the
AlCl3·6H2O (99%) was used as source materials for the deposition of
Full Width at Half Maxima (FWHM) (in radians) of the diffraction
thin films. Glass substrates were cleaned with ultrapure DI water, then
peak. The average crystallite size of pure and Al (3 and 5 wt%) doped
washed with acetone and lastly by ethanol, using an ultrasonic cleaner.
ZnO films was found to be 16(3),13(4) and 8(2) nm, respectively.
0.1 M precursors were dissolved in an appropriate amount of ethanol.
The role of the Al doping on the crystalline structure of the ZnO was
Al doping concentration varied from 0 to 5 wt%. The homogeneous-
also studied and observed a shift in the diffraction peak positions on an
mixing was done using an ultra-sonication bath for 15 min. The
increase in aluminum doping concentration of ZnO lattice. Al3+
resulting solution was sprayed onto the glass substrate by using an
incorporation in ZnO lattice causes for an increase in lattice constant
atomizer. Compressed air was let into the gas inlet after passing
(shown in Table 1) due to the difference between their ionic radii as
through the dust filter where the compressed air and solution flow
Al3+(53 pm) and Zn2+(74 pm), which in turn leads to a shift of the
rate are maintained at 50 psi and 4 ml/min. The deposition tempera-
diffraction peaks at smaller diffraction angles [42].
ture for the thin films was maintained at 450 °C. The distance between
Further, the defect chemistry of these deposited films was studied
the substrate and atomizer was kept constant at 15 cm for all
from the XRD patterns. Variations of Δd/d with Nelson–Riley factor
depositions. After deposition, pure and Al-doped ZnO thin films were
(NRF) [43] for ZnO films with different Al concentrations is shown in
sintered at 500 °C for 4 h.
the Fig. 2. The standard data for d-spacing values of ZnO were taken
from JCPDS file no. 36-1451. It is observed that with an increase in
3. Characterization
aluminum concentration of the films, ‘scattered-ness’ of Δd/d values
increase. It infers the introduction of stacking faults with the incor-
The crystallographic studies of the as-deposited pure and Al-doped
poration of different concentration of aluminum in ZnO thin films [43].
ZnO thin films were carried out using Bruker AXS, Germany (Model D8
Qualitatively, the scattered-ness of Δd/d values indicate the density of
Advanced) diffractometer in the scanning range of 20–80° (2θ) using
stacking faults present in the samples [43]. It can, therefore, be
Cu Kα radiations with wavelength of 1.5045 Ǻ. Surface topography of
inferred that aluminum incorporation leads to an increase in the
these films was studied by atomic force microscopy (AFM) using the
stacking fault density of the ZnO films with an increase in the lattice
Asylum Research. The morphology of deposited thin films was
parameter. The effect of these enhanced stacking defects in gas sensor
examined by field-emission scanning electron microscopy (FE-SEM,
performance has been discussed at the end of this section.
Hitachi, S-4200). Gas sensing experiments were performed with an
The morphology and microstructure of the surface of the thin films
indigenously built gas sensing setup [40] at an operating temperature
with different doping concentrations were investigated by the tapping-
100–300 °C at a relative humidity of 18–34%. Silver paste was applied
mode AFM. Atomic force micrographs of the ZnO films are shown in
to ensure good ohmic contacts with the films and the area of the films
Fig. 3(a)–(c) for pure and different Al concentrations. The surface
were defined (0.25 cm2) for gas sensing measurement of the films. The
morphologies for different doping concentrations of the films appear to
change in resistance of the films was measured as a function of time
be dense; the topography images almost do not show any changes and
under exposure of chemical inputs through a computer interfaced
reveal good quality films. The relatively smooth surface was clearly
EXTECH MultiMaster™ 560A True RMS digital multimeter.
seen for pure ZnO; in contrast, an increasing in Al (3 and 5 wt%)
amount to ZnO lattice appeared with a relatively high surface rough-
4. Results and discussion
ness. The 5 wt% Al-doped ZnO films, displayed that the smaller
particles agglomerated and made larger globules particles as compares
Fig. 1 depicts the XRD patterns of pure and Al (3 and 5 wt%) doped
ZnO thin films. The obtained diffraction pattern of pure and Al doped
Table 1
ZnO samples are indexed to the hexagonal crystal structure of ZnO with Lattice parameters for pure and doped (3% and 5% Al) ZnO.
space group P63mc (JCPDS card file 36-1451). From the shown XRD
pattern in Fig. 1, it is clearly observed that the peak intensity decreases Lattice parameters (JCPDS-36-1451) Pure ZnO 3% Al-ZnO 5% Al-ZnO
with the Al incorporation in ZnO lattice and width has become broader
a (Å) 3.249 3.2507 3.2576 3.2745
validating small grain formation. Analogous behaviour has been earlier c (Å) 5.206 5.2053 5.2212 5.2048
reported by H Kim et al. [41].

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M. Kumar et al. Ceramics International 43 (2017) 3562–3568

Fig. 4(a)–(c) shows the SEM micrographs of pure and different Al

concentrations doped ZnO thin films under the same magnification.
The micrograph clearly indicates the modulation in the average grain
size with an increase in Al doping. Fig. 4(a)–(c) shows that the films are
uniform, and grains are approximately spherical in nature. Both the
XRD pattern and the FESEM micrographs conclude that the addition
of Al in ZnO lattice restricts the growth of grains. The average grain size
observed in case of the pure ZnO film was about 100 nm and found to
decrease ~70 and ~50 nm for 3 and 5 wt% Al-doped ZnO.
The estimated crystallite sizes using Scherer's formula and from
FESEM micrographs for pure and Al (3 and 5 wt%) doped ZnO films
are not comparable with each other, it may be due to the existence of
amorphous phase around the grains. The film thicknesses were
measured using the FESEM in a cross sectional view shown in
Fig. 4d and thickness was found to be ~200 nm.
Fig. 5(a) and (b) displays the sensing response to CO gas concen-
trations for Al (3 and 5 wt%) doped ZnO films. The gas sensitivity is
Fig. 2. Plot of Δd/d vs Nelson–Riley factor (NRF) for the deposited ZnO films. defined as follows:

Ra
to another. Therefore, these results further approve the shape distor- S= Rg (2)
tion of crystallites in Al-doped ZnO films attributed to more stacking
defects present in the samples. Root mean square (RMS) roughness of
where Ra and Rg are the resistance of the samples in presence of air
films with 0%, 3% and 5% Al content are 10, 12 and 15 nm,
and gas atmosphere respectively.
respectively. These results are similar to other reports related to the
Fig. 5(a) and (b) shows the response of 3 and 5 wt% Al-ZnO sensors
surface roughness studies by AFM [43,44].
for CO at various amounts of concentrations. Fig. 5(c) shows the CO

Fig. 3. AFM images of (a) Pure, (b) 3% Al-doped, (c) 5% Al-doped ZnO thin films.

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Fig. 4. SEM images of (a) Pure, (b) 3% Al-doped, (c) 5% Al-doped, (d) Cross-sectional view, ZnO films.

gas concentrations versus the sensor response at optimum operating 100 ppm of CO at 175 °C.
temperature. It has been observed that the 5 wt% Al-ZnO sensor The sensing mechanism of Al doped ZnO doped sensor in air and in
exhibited the maximum sensitivity to CO as compared to another. the tested gas can be understood by the energy band diagram as shown
The sensor response increases with CO concentration up to 100 ppm in the Fig. 6(a) and (b). It is seen that by 5 wt% Al doping in the ZnO
and sensor response saturated beyond 100 ppm of CO gas exposure. leads to a good response to CO and the changes in the defect in the ZnO
The saturation in the sensor response beyond 100 ppm of CO gas crystal is observed due to substitution of Al3+ ions instead of Zn2+ ions
attributed to limited reaction sites existing on the film surface. The in the ZnO lattice. It is known that the oxygen vacancies are the most
temperature-dependent sensor response of Al doped ZnO thin films common defects observed in the semiconducting metal oxides [44,45].
was studied in the temperature range of 100–300 °C to find out the In case of ZnO, oxygen vacancies are present in three different charge
optimum operating temperature for CO sensing. Fig. 5(d) elucidate the states: V˙O (neutral charge vacancy of oxygen), V˙O and Vö [46,47]. As
sensor responses as a function of temperature for pure and Al doped (3 the ionic radius of Al3+ is smaller than that of the Zn2+ ions, it is easy to
and 5 wt%) ZnO thin films. The sensor response of 5 wt% Al doped ZnO substitute Al3+ ions in place of Zn2+ ions, but it is necessary to maintain
thin films is excellent at 175 °C but saturated beyond 175 °C for all gas the electrical neutrality by compensating the valence charge of the Zn
concentration, whereas pure ZnO thin films showed sensor response at site by releasing the electrons. Hence, the enhanced response is
higher operating temperature ~275 °C. The cross sensitivity behaviour observed by increasing the concentration of free electrons which
of pure and Al doped (3 and 5 wt%) ZnO thin films have been studied reduces the resistance of the oxide. This can be expressed by the
for different chemical inputs (NH3, C2H5OH and CO) respectively. The equation given as:
results are summarized in Fig. 5(e) which reveals that 5 wt% Al-doped
Al2O3(s)⟹2Al•Zn + 3O×0 + 2e−
ZnO thin films are highly selective towards CO as compared to NH3 and ZnO (3)
C2H5OH. The repeatability of 5 wt% Al doped ZnO sensor towards CO •
where Al Zn is an Al ion sitting on the zinc lattice site with a positive
at 175 °C was investigated for 120 days shows in Fig. 5(f). It is found
charge and O0 is oxygen ion sitting on an oxygen lattice site with a
that 5 wt% Al doped ZnO sensor shows the good stability and
neutral charge. When the as prepared sample is kept under the air
repeatability at the end of 3rd and 4th month, which is ~96–98%
exposure, the electrons are captured by the oxygen in air from the
w.r.t first measurement. Hence, stability and repeatability results
sample to form oxygen ions this leads to increase in resistance of the
suggest that the 5 wt% Al doped ZnO sensor can be used for long
sensor material by creation of Schottkey barrier as shown in Eq. (4).
operating cycles which is very good for practical applications.
It is inferred that Al incorporation in ZnO leads to an increase in 1
O2 + e− ↔ O−.
stacking fault density. It is confirmed that Al-doped ZnO has more 2 (4)
defects (in the form of oxygen vacancy) than pure ZnO. Therefore, − −
CO(g) + O → CO2 + e . (5)
results show that the surface chemistry of ZnO thin films has been
modified in Al-doped ZnO. Hence, by increasing the stacking fault Similarly, when the sample is kept under the exposure of CO, the
defects, leading to an improvement of the gas sensing performance. electrons are liberated by O- ions into the conduction band of the
Accordingly, we can conclude that the defect chemistry plays a sample and CO2 is formed and an increase the electron concentration
significant role in the sensor performance. The sensing mechanism is and, therefore, reduce in the electrical resistance as shown in Eq. (5).
governed by defects in the form of oxygen vacancies on the film surface Hence, the basic characteristic in enhancing the sensor performance is
which modify the electronic properties of ZnO. It has been demon- associated with the defects (i.e. nonstoichiometry) formation and
strated that, when CO gas exposed among all the sensors, 5 wt% Al modifications of electronic and chemical properties due to the syner-
doped ZnO sensor exhibit maximum sensor response (Sr=4.6), for gistic effects between the dopant and host material. Therefore, the

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Fig. 5. (a) and (b) Sensing response to CO gas concentrations for Al 3 and 5 wt% doped ZnO films, respectively (c) Sensor response vs CO concentration, (d) Sensor response vs
Temperature, (e) Selectivity of pure and doped (3% and 5% Al) towards CO, ethanol, and ammonia at 175 °C (all gas concentrations were 400 ppm) (f) The stability of long-term sensor
response of the 5 wt% Al doped ZnO sensor.

sensing mechanism which is explained by above mentioned reactions is also be noted here from the present study that the 5 wt% Al doped
systematically illustrated in Fig. 6(a) and (b). Hence, it is projected that sensor significantly improved the CO sensing at lower operating
Al doped ZnO will have a remarkable sensor response towards CO temperature at 175 °C with faster response (recovery) time ~1–2 s
detection and this is in good agreement with the measured sensor (~15–20 s).
response of Al doped ZnO thin films. In order to summarize the enhanced gas sensor response of 5 wt%
In Table 2, the CO sensing response of the 5 wt% Al doped ZnO Al doped ZnO thin films towards CO, three major factors are
based sensors are compared with those of the previous reports [48– responsible (i) more stacking fault, defect present in the sample, (ii)
54]. Table 2 shows sensor response, operating temperatures, response high surface roughness value and (iii) high surface to volume ratio. Due
and recovery times of some CO sensors. Although, sensor response of to more stacking fault defects, many unsaturated bonds are present in
ZnO based sensors are good, but operating response-recovery time is the sample which can act as better sites for adsorption of CO gas. The
very slow and operating temperatures are also very high. But, it must calculated crystallite sizes ~16(3), 13(4), 8(2) nm for pure Al-doped

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Fig. 6. Sensing mechanisms of the Al-doped ZnO-based sensor to CO: (a) in air and (b) in the tested gas.

Table 2
Comparison of the CO sensing capability of 5 wt% Al doped ZnO thin film sensor deposited by spray pyrolysis in this study to those of the previous reports.

Analyte Gas Materials Used Deposition technique Operating Temperature Sensor Response Time Recovery Time Reference
(°C) Response (s) (s)

CO and CO2 Sr and Ni-ZnO Printing 250 5 15 < 90 48

CO Co-ZnO Electro-deposition 350 1.3 49
CO Pt/ZnO Spin-coating 300 7 40 310 50
CO Mg:ZnO Drop casting 350 5.5 51
CO In-ZnO Screen printing 300 4.8 52
CO and NO2 ZnO Sol-gel and electro- 300 1.1 53
spinning
CO Cu-ZnO Co-sputtering 350 ~5.5 54
CO Al-ZnO Spray Pyrolysis 175 4.6 ~1–2 ~15–20 This work

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