Physica B 527 (2017) 7–15

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Physica B
journal homepage: www.elsevier.com/locate/physb

Synthesis of ZnO thin film by sol-gel spin coating technique for H2S gas MARK
sensing application
⁎
Amol R. Nimbalkara,b, Maruti G. Patila,b,
a
JJT University, Jhunjhunu, Rajasthan 333001, India
b
Department of Physics, Dattajirao Kadam Arts, Science and Commerce College, Ichalkaranji, Maharashtra 416115, India

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

Keywords: In this present work, zinc oxide (ZnO) thin film synthesized by a simple sol-gel spin coating technique. The
H2S gas sensor structural, morphology, compositional, microstructural, optical, electrical and gas sensing properties of the film
ZnO thin film were studied by using XRD, FESEM, EDS, XPS, HRTEM, Raman, FTIR and UV–vis techniques. The ZnO thin
Sol-gel film shows hexagonal wurtzite structure with a porous structured morphology. Gas sensing performance of
Selectivity
synthesized ZnO thin film was tested initially for H2S gas at different operating temperatures as well as
Reproducibility
concentrations. The maximum gas response is achieved towards H2S gas at 300 °C operating temperature, at
Stability
100 ppm gas concentration as compared to other gases like CH3OH, Cl2, NH3, LPG, CH3COCH3, and C2H5OH
with a good stability.

1. Introduction been synthesized with different synthesis techniques [13–16]. Some of

Zinc oxide is a multifunctional material in II–VI semiconductor
group and having a broad energy band gap (3.37 eV), large exciton
binding energy of 60 meV at room temperature [1] and been an active
area of research because of their unique properties like nontoxic,
inexpensive, high thermal, chemically stability at room temperature
make it attractive for potential use in different fields like solar cells, UV
detectors [1,2], chemical and biological gas sensors [3], piezoelectric
devices [4,5] etc.
Gas sensors have been used for the detection of toxic and harmful
environmental pollutant gases such as Cl2, H2S, NH3, CH3OH, CO, and
LPG, etc. and for the prevention of hazardous gas leaks, which comes
from the many industrial processes and vehicles [6,7]. There are
numbers of types of gas sensors that have been used to detect various
toxic gases like catalytic gas sensors, infrared gas sensors, semicon-
ductor gas sensors, etc. [8,9]. However, gas sensors based on metal
oxides that are playing a crucial role in the detection of toxic pollutants.
The two types of metal oxide material gas sensors that have been used
are p-type such as nickel oxide and cobalt oxide or n-type such as tin
dioxide, titanium oxide, iron oxide and zinc oxide, the working of metal
oxide sensor was based on a change in their electrical resistance, in the
absence and presence of various test gas. [10–12].
Zinc oxide (ZnO) was leading material in gas sensing because a
large variety of nanostructures in form of nanoparticles, nanotubes,
nanowires, nanobelts, nanopores, nanorods or nanotetrapods have
them are pulsed laser deposition, spray pyrolysis, hydrothermal
method, chemical vapor deposition, electrochemical deposition, and
the sol–gel method [17–19]. In this present work, sol–gel spin coating
technique is preferred because of the deposition of the film at a low,
high purity, homogeneous, large area film at relatively low tempera-
tures and easily controls the film thickness by changing the number of
spin coating and pre-annealing cycles [20]. In this present work, we
fabricate ZnO thin film by the sol–gel spin coating technique to study
the H2S gas sensing properties of ZnO thin film.
2. Experimental details
2.1. Synthesis of ZnO thin film
The ZnO thin film was synthesized by the sol-gel spin coating
technique onto a glass substrate using zinc acetate dihydrate
[Zn(CH3COO)22H2O]. The precursor solution (0.2 M) was prepared
by dissolving required amount of zinc acetate (99.99%, A.R. Grade
Thomas Baker) in absolute ethanol and m-cresol (99.99%, A.R. Grade,
Merck) and stirred at 70 °C for 90 min, leading to the formation of a
clear and homogeneous solution. The solution was deposited onto a
pre-cleaned glass substrate by a single wafer spin coater (APEX
Instruments, Model spin NXG-P1). During synthesis process, few trails
were made and the experimental conditions such as the rpm of the spin
coater, time duration, a number of spin coating cycles and annealing

⁎
Corresponding author at: JJT University, Jhunjhunu, Rajasthan 333001, India.
E-mail address: marutipatil1956@gmail.com (M.G. Patil).

http://dx.doi.org/10.1016/j.physb.2017.09.112
Received 26 July 2017; Received in revised form 26 September 2017; Accepted 27 September 2017
Available online 28 September 2017
0921-4526/ © 2017 Elsevier B.V. All rights reserved.
A.R. Nimbalkar, M.G. Patil
temperature were changed to achieve well size and thickness control.
After setting the substrate on the substrate holder of the spin coater,
the prepared solution (~ 0.5 ml) was dropped and accelerated at
300 rpm for 10 s and then spin-coated at 2000 rpm for 30 s in an air
and dried on a hot plate at 200 °C for 5 min to remove the organic
elements, the above procedure repeated 10 times. The prepared film
was annealed at 600 °C for 60 min in an air to obtain nanocrystalline
ZnO thin film.
2.2. Characterization of ZnO thin film
The structural properties of the film were investigated by X-ray
diffraction (XRD) (Bruker D2 phaser) using filtered Cu Kα radiation
(1.54056 Å). Morphological study of the film was carried out using field
emission scanning electron microscopy (Zeiss Ultra 55 FE-SEM with
Oxford EDX system). X-ray photoelectron spectroscopy (XPSPHI 5000
Versa Probe II USA) analysis was used to investigate the surface
composition and valence states of the material. High-resolution
transmission electron microscopy (HRTEM) and selected area electron
diffraction (SAED) images were obtained to study the microstructure of
ZnO thin film using Tecnai G2 F30, FEI. Raman spectra were measured
by Raman spectroscopy with an excitation wavelength of 532 nm.
Fourier-transform infrared spectroscopy (FTIR) measurement of the
thin film was performed to identify presence zinc species using FT/IR-
4600 Jasco, Japan. The optical absorption and transmission spectra of
ZnO thin film were obtained using UV–vis–NIR V-770 Jasco, Japan in
the 300–800 nm wavelength range. The thickness of ZnO thin film was
measured by using Bruker Dektakxt profilometer and is found to be
193 nm.
The gas sensing properties of ZnO thin film prepared by a sol-gel
spin coating technique, measured at 300 °C operating temperature. To
investigate the H2S gas response of ZnO film, the resistance of the films
was measured at 300 °C, in the air and in presence of test gas using
Keithley electrometer (6514). The gas response (Rs) was calculated
using (Ra/Rg) for H2S gas, where Ra is the resistance in air and Rg in
the presence of test gas of ZnO thin film.
3. Results and discussion
3.1. Structural analysis
Fig. 1 shows the X-ray diffraction pattern of ZnO thin film grown by
sol-gel spin coating technique and annealed at temperature 600 °C for
60 min. The result shows that all diffraction peaks have been matched
well with standard diffraction pattern data of ZnO (JCPDS card No. 01-
079-0205) with hexagonal wurtzite crystal structure and it shows main
(002)
Intensity (a.u.)
JCPDS Card: 01-079-0205
(101)
(100)
(102)
(110)
20 30 40 50
Angle (2θ)
Fig. 1. X-ray diffraction pattern of ZnO thin film.
Physica B 527 (2017) 7–15
significant peaks viz. (1 0 0), (0 0 2), (1 0 1), (1 0 2), (1 1 0), (1 0 3), (1
1 2) and (0 0 4) [21]. The highest intensity of peak (002) is oriented
along predominant (0 0 2) plane with hexagonal crystal structure. The
crystallite size of ZnO thin film was determined by using Scherrer
formula [22]:
0.9λ
D=
β cos θ (1)
where, D is crystallite size, λ is the of X- ray wavelength of Cu-Kα line, β
is the Full width at half maximum (FWHM) of the peaks, θ is the Bragg
angle and the average crystallite size of ZnO thin film is found to be
34 nm [23]. The lattice constants a and c were calculated by the
following relation [24]:
1 4 ⎛ h2 + hk + k 2 ⎞ l2
= ⎜ ⎟+ 2
d(hkl ) 3⎝ a2 ⎠ c (2)
where, d is the interplanar spacing and h, k, l are crystal Miller indices
respectively. The lattice constants calculated from the present XRD
data are a = 3.2478 Å and c = 5.2053 Å (a = 3.2417 Å and c = 5.1876 Å
for JCPDS card No. 01-079-0205).
3.2. Surface morphological and compositional analysis
Fig. 2 shows the field emission scanning electron microscopy
(FESEM) images and EDX spectrum of ZnO thin film. From the 2-D
high magnification micrographs (a1 and a2) shows randomly distrib-
uted spherical nanocrystallites with different sizes separated by voids.
The thin film is continuous and made up of a closely packed spherical
porous structure of ZnO nanocrystallites, such kind of spherical porous
morphology is good for gas sensing application [25]. Average ZnO
nanocrystallites size calculated from FESEM analysis is found to be
37 nm, it is closer to crystallite size calculated from XRD analysis.
The energy-dispersive X-ray (EDX) spectrometry measurement was
carried out to analyze the existence of zinc (Zn) and oxygen (O)
elements in the ZnO thin film. Fig. 2(b) shows the EDX spectra of ZnO
thin film grown by a sol-gel spin coating technique. The calculated
atomic percentage is tabulated in the table and shown in the inset of
Fig. 2(b). The peak of Zn and O can be clearly observed in the EDX
spectrum and it shows a purity phase of ZnO thin film. The absence of
other elements in the EDX spectrum reveals the phase purity of the
ZnO thin film, and the film possesses good stoichiometry in agreement
with the chemical composition of the ZnO nanocrystallites [26].
3.3. X-ray photoelectron spectroscopy studies
The surface elemental analysis of has been investigated using the X-
rays photoelectron spectroscopy (XPS). Fig. 3(a) shows the XPS survey
spectrum of ZnO thin film with wide energy scan revealed the presence
of zinc (Zn), oxygen (O) and carbon (C) elements in the film indicates
the purity of ZnO thin film by a sol-gel spin coating technique. The
detected elements and their relevant concentration are comparatively
equal to EDX analysis. The binding energy 284.16 eV of C 1s is usually
used as charge reference in the spectrum [27]. Fig. 3(b) shows narrow
scan XPS spectra of ZnO thin film for Zn 2p doublet whose binding
energies are 1043.74 and 1020.68 eV for Zn 2p1/2 and Zn 2p3/2
respectively. The spin–orbit splitting of 23.06 eV for Zn 2p3/2 and Zn
2p1/2 which confirms the presence of Zn atoms are in the oxidized
(103)
(004)
state, which is well with the earlier reports [28]. The O 1s binding
(112)
energy peak shows in Fig. 3(c), peak at the binding energies (BE) of
529.57 eV can be attributed to the oxidized metal ions in the
60 70 80 90
nanocrystallites, namely O–Zn in the ZnO lattice [29]. All the binding
energy positions of the elements present in various structures of ZnO
thin film are listed in Table 1.
8
A.R. Nimbalkar, M.G. Patil
Fig. 2. (a1 and a2) High-magnification FESEM images and EDX spectrum of ZnO thin film.
3.4. Micro-structural, Raman and FTIR analysis
The high-resolution transmission electron microcopy (HRTEM)
was carried out to study the microstructure of the ZnO thin film
annealed at 600 °C. Fig. 4(a) and (b) shows the TEM image of the ZnO
nanocrystallites. TEM image shows a fairly spherical porous structure
with 30–35 nm in size and aggregated with small crystallites of around
15–20 nm. The spherical porous structure of the thin film increases
surface area for gas adsorption. Fig. 4(c) reveals the HRTEM image of
the ZnO thin film, which shows well-defined lattice fringes with the
lattice spacing of 0.26 nm, in agreement with the ‘d’ spacing value of
the (002) planes of the wurtzite ZnO nanocrystallites. It shows that the
nanocrystallites grow along the c-axis. Inset of Fig. 4(c) shows selected
area electron diffraction (SAED) pattern, the bright diffraction spots
confirming the high crystallinity of thin film with wurtzite structure and
these spots arranged in rings also reveals the presence of well-defined
nanocrystallites in ZnO thin film. The nanocrystallites size distribution
as shown in Fig. 4(d). The average particle size of 106 nanoparticles
measured from the TEM image is found to be 30.5 nm with a standard
deviation of ± 7.8 nm (~ 25%) [30].
Raman measurements provide information about the material
quality, the phase, and purity in order to understand transport
properties and phonon interaction with the free carriers, which
determine the device performances [24]. Raman studies were also
carried out on the ZnO thin film to investigate the presence of the ZnO,
shown in Fig. 5.
The peak at 419 cm−1 is due to the presence of vibrational E2 (high)
phonon mode and corresponds to nanocrystalline wurtzite hexagonal
phase of ZnO. The peak of E2(high) − E2(low) mode at 314.9 cm−1 and B2
(silent) mode at 563.6 cm−1 are due to the Zn–O bond [31]. The
Raman spectrum shows the good quality of the hexagonal wurtzite
crystal structure in the ZnO thin film.
Fourier transform infrared (FTIR) spectroscopy was carried out to
investigate the functional groups attached with ZnO. The FTIR spectra
of ZnO thin film Fig. 6 shows a small peak at 904 cm−1 and 469 cm−1
9
Physica B 527 (2017) 7–15
for the stretching mode of a Zn–O bond. The peaks at 1390 cm−1 and
1123 cm−1 correspond to the C–O stretching vibration and unreacted
acetate ligand left after reaction. The small peak at 2342 cm−1 is due to
the stretching vibration for CO2 [32,33]. The peaks in the range 2925–
2856 cm−1 correspond to asymmetric C–H stretching [34]. The broad
peak at 3444 cm−1 is pointing to stretching of O-H vibration in the ZnO
thin film. Thus the formation of ZnO wurtzite structure in the film is
confirmed by FTIR spectra.
3.5. Optical properties
The optical absorbance and transmission spectra of ZnO thin film in
the wavelength region of 300–800 nm are shown in Fig. 7. The ZnO
thin film is highly absorbing in the UV region and highly transparent in
the visible region. The absorption band is observed in the UV region at
~ 370 nm because of the transition of electrons from valence band to
conduction band. The ZnO thin film show high transmittance (~ 90%)
in the visible region. The energy gap is calculated from the equation,
αhν = A(hν − Eg)n (3)
where, α is the absorption coefficient, ‘A’ is a constant, ‘hν’ is the
incident photon energy, Eg is the energy difference between the top of
the valence band and the bottom of the conduction band, n = 1/2 for
direct transition and n = 2 for indirect transition [35]. The band gap of
ZnO thin film has been calculated using the plot of (αhν)2 versus
photon energy (hν) as shown in the inset of Fig. 7. The direct band gap
of the synthesized ZnO thin film was determined by extrapolating the
linear part of the plot to zero absorption coefficient and is about
3.17 eV.
3.6. Electrical conductivity analysis
The DC conductivity of ZnO thin film was measured using two
probe method in the 27–300 °C temperature range, Fig. 8 shows the
curve of DC conductivity as a function of temperature. It is observed
A.R. Nimbalkar, M.G. Patil Physica B 527 (2017) 7–15

Fig. 3. (a) Wide survey X-ray photo-electron spectrum, (b) Zn 2p spectrum, and (c) O 1s spectrum of ZnO thin film.

Table 1 temperature is increased, with increasing temperature, more charge

The binding energy positions of the element present in different structures of zinc oxide. carriers overcome the activation energy barrier and these carriers
participate in the electrical conduction [38].
Sr. no. Chemical Observed Standard Height FWHM Area at%
species binding binding counts
energy energy
(eV) (eV)
3.7. Gas sensing performance
1 C 1s 284.16 284.6 2365 1.5372 4719 19.3
2 Zn 2p1/2 1043.74 1044.70 15,244 1.9933 35,353 17.7 3.7.1. Temperature dependent gas response
3 Zn 2p3/2 1020.68 1021.40 33,100 1.8297 68,232 29.3 The gas sensing properties of the ZnO thin film toward H2S are
4 Zn 3s 137.73 139.40 6440 3.1694 8055 1.4
investigated as a function of gas concentration and different operating
5 O 1s 529.57 530.21 10,054 2.5692 26,733 40.8
temperature. To determine the optimum operating temperature of the
sensor, H2S gas with known concentration (100 ppm) was injected into
that the conductivity of the film increases with temperature, the room the gas chamber at different operating temperatures (100 °C to 400 °C)
temperature dc conductivity is found to be 2.65 × 10−7 S/cm and after and the gas response, response/recovery times was calculated. Fig. 9
heating is increased to 4.42 × 10−4 S/cm at 300 °C. This suggests that clearly shows that, the H2S gas response with different operating
the thermally activated conductivity behavior of ZnO thin film [36]. temperatures (100 °C to 400 °C) for ZnO sensor at known concentra-
Inset of Fig. 8 shows the plot of ln σ versus 1000/T, which indicates the tion (100 ppm). The sensor shows a maximum gas response at 300 °C
electrical conductivity increases with the temperature. From the slope operating temperature towards H2S which is considered as optimized
of the ln σ versus 1000/T curve, activation energy was calculated using temperature. The resistance of ZnO thin film does not recover to its
the relation [37]: baseline value within the given interval of time. At lower operating
temperature adsorption and desorption reactions are slow and it
σ = σo exp (−Ea / kT ) (4) increases with increase in operating temperature. Fig. 9 also shows
that the gas response increases up to 300 °C and decreases at higher
where Ea is the activation energy, T is the temperature, k is the operating temperature because of the thermal energy assists the
Boltzmann constant and σo is the constant of proportionality. The chemical reactions involved in sensing mechanism and overcomes
activation energy of an electrical conduction is found be 0.45 eV. This the respective activation energy barriers [39]. Therefore further
activation energy value suggests that the activation of electrons is dependence of H2S gas response of ZnO thin film for different gas
excited thermally from donor levels to the conduction band, as the concentration at 300 °C operating temperature was studied.

10
A.R. Nimbalkar, M.G. Patil Physica B 527 (2017) 7–15

Fig. 4. (a) TEM, (b) HRTEM, (c) SAED pattern, and (d) particle size distribution of ZnO thin film.

E2 (high)
419
Raman Intensity (a.u.)

1123
Transmittance

A2 (silent) 904
563.6

(high) (low)
E2 - E2
1390
2342
314.9

2856
2925
3444

469

200 300 400 500 600 700 800

4000 3500 3000 2500 2000 1500 1000 500
-1 -1
Raman shift (cm ) Wavenumber (cm )
Fig. 5. Raman spectra of ZnO thin film. Fig. 6. FTIR spectra of ZnO thin film.

3.7.2. Effect of various H2S concentration on gas response
To study the lowest gas concentration detection limit, we investi-
gate the gas response of ZnO sensor for different concentrations of (5–
100 ppm) H2S gas. The change in the sensor resistance as a function of
time is recorded at 300 °C operating temperature. It was found that,
after H2S exposure, the sensor resistance decreases from the baseline
(air resistance) to a minimum resistance within few seconds and then
increases slowly and came to baseline resistance after fresh air is
passing through the test chamber. This decrease in the resistance of
ZnO sensor with H2S gas is due to the interactions between the H2S gas
molecules and the surface of the ZnO thin film. Fig. 10 shows the
response of the ZnO thin film versus time upon exposure to 5–100 ppm
of H2S at 300 °C. Fig. 10 shows the gas response is gradually increased
from 1.1 to 3.2 with increasing the H2S gas concentration. For higher
H2S concentrations (> 5 ppm), the sensor shows a similar behavior.
The maximum gas response is observed for 100 ppm H2S because of
the porous structured morphology of ZnO thin film. The porous surface
of the film facilitate gas diffusion in the film and chemisorption of

11
A.R. Nimbalkar, M.G. Patil Physica B 527 (2017) 7–15

100
3.3

100 ppm
1.0 90
3.0
80

Gas Response (Ra/Rg)

0.8

Transmittance (%)
70 2.7

50 ppm
Absorbance

0.6 60 2.4

40 ppm
50
2.1

30 ppm
20 ppm
0.4 40
1.8

10 ppm
30
0.2 1.5

5 ppm
20
1.2
0.0 10

0 0.9
400 450 500 550 600 650 700 750 800 0 200 400 600 800 1000 1200 1400 1600
Wavelength (nm) Time (S)
Fig. 7. Optical absorption spectra and transmittance spectra of ZnO thin film. Inset Fig. 10. Dynamic response of ZnO sensor for various concentrations of H2S gas.
shows the plots of (αhv)2 vs hν.

5.0x10 3.3

3.0
4.0x10
Gas Response Ra/Rg
2.7
Conductivity (S/cm)

2.4
3.0x10
σ

2.1

2.0x10 1.8

1.5
1.0x10
1.2

0.9
0.0
0 10 20 30 40 50 60 70 80 90 100 110

300 350 400 450 500 550 600

Gas Concentration (ppm)
Temperature (K) Fig. 11. Response of ZnO sensor for different concentration of H2S gas.

Fig. 8. DC conductivity and the variation of lnσ with 1000/T of ZnO thin film.
sensing response depends on the surface states and the oxygen
3.50 adsorption amounts on the material surface [40]. The relationship
H2S concentration = 100 ppm
o
between gas response and H2S concentrations (5–100 ppm) for the
3.25 300 C
o
ZnO sensor showed in Fig. 11.
3.00 350 C
o
Gas Response (Ra/Rg)

400 C 3.7.3. Gas sensing mechanism

2.75
o
The gas sensing mechanism of the ZnO thin film sensor is mainly
2.50 250 C
based on a change in the electrical resistance or conductance due to the
o
2.25 200 C oxygen adsorption and reactions of the gases adsorbed on the sensor
surface. The sensor operating temperature also affects the properties of
2.00 the materials and leading to a difference in the sensitivity of the sensor.
o
150 C Metal oxides mostly sense gases at higher operating temperatures. For
1.75
o
100 C the gas sensing investigation, the sample was heated in air at the
1.50
desired operating temperature. This thermal treatment creates oxygen
1.25 species on the sensor surface which play an important role in the gas
sensing phenomena shown in Fig. 12(a). The oxygen absorbed depends
1.00
on mainly on the type of materials and their reduction or oxidation
0 100 200 300 400 500 reaction with the gas. The oxygen adsorbed on the sensor surface
Time (S) undergoes the following reactions [8]:
Fig. 9. H2S gas response of ZnO thin film with different operating temperature for fixed O2 ↔ O2 (5)
(gas) (ads)
concentration of 100 ppm.

oxygen and gas on the film surface, which would result in an O2 (ads) + e− ↔ O2− (ads) (6)
enhancement in gas sensing properties, because the sensing mechan-
ism of the ZnO belongs to the surface controlled type and the change of
O2 (ads) + e− ↔ 2O− (ads) (7)

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A.R. Nimbalkar, M.G. Patil Physica B 527 (2017) 7–15

Fig. 12. Schematic diagram of the proposed mechanism of ZnO sensor (a) when interact with oxygen in air and (b) when interact with H2S gas.

O−(ads) + e− ↔O2− (ads) (8) 210

28
− −
where O is the oxygen adsorption, e are electrons. It is well known 200
that in metal oxide semiconductors, oxygen ions (O−) work as an Responce Time
190
acceptor at the surface of the film. When the reactive gas is adsorbed on
Response Time (s)
24

Recovery Time (s)

the surface of a sensor, this may lead to changes in the resistance value 180
of the sensing layer of the gas sensor. However, this change in
resistance is correlated with the concentration of the gases [8]. The
20 Recovery Time 170
H2S sensing mechanism of ZnO thin film could be explained as follows:
160
H2S is a reducing gas, when the samples exposed to H2S at the higher 16
temperature, they remove the adsorbed oxygen, restore electrons to the 150
conduction band and decrease the resistance of the semiconductor, the
process of the reaction can be described as follows [41]: 12 140

H2S (g) + 2O−(ads) → H2(g) + SO2(g) + 2e− (9) 130

8
This interaction between H2S and oxygen ions (O−) on ZnO surface 120
re-injects the electrons into the conduction band, which leads to 0 10 20 30 40 50 60 70 80 90 100 110
increase in conductivity with reference to baseline shown in Gas Concentration (ppm)
Fig. 12(b) [41]. Fig. 13. Variation of response and recovery time of ZnO sensor with H2S concentration.

3.7.4. Response and recovery times of ZnO sensor

3.3
The response and recovery time of the ZnO sensor were determined
by measuring the change in electrical response with time at different 3.0
concentrations of H2S. The response/recovery times are defined as the
Gas Response (Ra/Rg)

time required for absorption and desorption of the oxygen on, or from 2.7
the sensor surface to reach the saturation or to reduce the resistance
2.4
back to the baseline resistance, for ZnO sensor, the response and
recovery times are defined as the times required for a sensor to reach
2.1
90% of its full response/recovery ability with respect to baseline
resistance when the gas is turned on or off [8]. Fig. 13 shows the 1.8
variation of response and recovery times with different concentration
(5–100 ppm) of H2S gas at 300 °C. It is observed that, the gas response 1.5
of the ZnO sensor is fast but it takes more time for recovery, the
1.2
response time decreases from 28 to 10 s and the recovery time
increases from 127 to 198 s as the H2S gas concentration increases 0.9
(5–100 ppm). This may be due to gas diffusion in the sensor and 0 200 400 600 800 1000 1200
chemisorption of oxygen on the grain and it takes a longer time to Time (s)
completely desorption the gas.
Fig. 14. Reproducibility of ZnO sensor to 100 ppm of H2S gas.

3.7.5. Reproducibility and stability study of ZnO sensor
To investigate the reproducibility of ZnO sensor, the H2S gas
sensing test was repeating four times at 100 ppm gas concentration
and at 300 °C operating temperature, shown in Fig. 14. It is revealed
that the gas response of the ZnO sensor towards H2S is exactly constant
confirming the reproducibility of the sensor. In order to check the
stability of the ZnO sensor at 100 ppm concentration of H2S gas and at
operating temperature of 300 °C, the gas response of the film was
measured for 90 days at an interval of 10 days and the result is shown

13
A.R. Nimbalkar, M.G. Patil Physica B 527 (2017) 7–15

where Sa is the responses of a sensor towards target gas and Sb is the

3.3
responses of a sensor towards interfering gas. Table 2 represents the
3.0 calculated selectivity coefficient (K) of ZnO sensor. It is observed that
the ZnO thin film showed maximum response towards H2S (3.2) as
2.7 compared to CH3OH, Cl2, NH3, LPG, CH3COCH3, and C2H5OH at
Response(Ra/Rg)

Stability= 59% 300 °C operating temperature and more selective towards H2S than
2.4
other gases.
2.1
4. Conclusions
1.8
ZnO thin film based H2S sensor has been successfully developed by
1.5
a sol-gel spin coating technique. The formation of the ZnO is confirmed
1.2
by the XRD and XPS analysis. Microstructural analysis shows uniform
and porous structured morphology of ZnO thin film, which is good for
0.9 gas sensing application. From electrical DC conductivity, the ZnO film
shows the thermally activated conductivity behavior. The ZnO thin film
0 10 20 30 40 50 60 70 80 90 100
is sensitive as well as fast in responding to H2S gas against the other
Time (Days) interfering gases. The porous structured morphology of the ZnO film
Fig. 15. Stability study of ZnO sensor. improves the H2S gas sensing performance at 300 °C, the sensor shows
the highest gas response of 3.2 with 59% of stability for exposure of
100 ppm of H2S gas. The H2S gas sensing properties like selectivity,
Gas Concentration = 100 ppm
C H5OH
2 o response time, recovery time, reproducibility and stability study
Operating temperature = 300 C indicates that the ZnO thin film can stand as good sensor for detection
CH COCH
3 3
of H2S gas.

LPG Acknowledgements
Gases

NH
3
The authors are thankful to the center of Excellence in Nano-
electronics (CEN) at Indian Institute of technology, Bombay under
H S
2 Indian Nanoelectronics User Program (INUP) for providing character-
ization facility. We are also thankful to Dr. K. Nageswari for her
Cl constant encouragement and support.
2
The authors are also thankful to Dr. V. B. Patil, Functional
CH3OH Materials Research Laboratory, School of Physical Sciences, Solapur
University, Solapur for providing gas sensing facility.
0.0 0.4 0.8 1.2 1.6 2.0 2.4 2.8 3.2
Appendix A. Supplementary material
Gas Response
Fig. 16. Selectivity studies of ZnO thin film for different gases at 300 °C for 100 ppm gas Supplementary data associated with this article can be found in the
concentration. online version at doi:10.1016/j.physb.2017.09.112.

Table 2
Selectivity coefficient of ZnO thin film towards 100 ppm H2S at 300 °C operating
temperature.
Gases CH3OH Cl2 NH3
Selectivity coefficient (K) 8.8 2.6 32
in Fig. 15. From the figure, it is seen that the gas response dropped
initially and after 40 days remains constant with 59% stability. This
decrease in the gas response with the number of days can be attributed
to the formation of layer oxides/moisture [39]. Thus, it can be
concluded that the sensor with high response, high selectivity and
low response/recovery times based on ZnO thin film can stand as good
sensor for detection of H2S gas.
3.7.6. Selectivity of ZnO sensor
The selectivity of ZnO thin film carried out at 300 °C and at fixed
100 ppm concentration of different gases viz. H2S, CH3OH, Cl2, NH3,
LPG, CH3COCH3, and C2H5OH. Fig. 16 clearly shows the ZnO thin film
was quite sensitive and higher response towards H2S among various
oxidizing and reducing gases. Here, the selectivity of ZnO thin film
sensor measured in terms of selectivity coefficient (K) of a target gas
with respect to interfering gas is calculated using the equation:
K = Sa / Sb
References
[1] S.I. Inamdar, V.V. Ganbavle, K.Y. Rajpure, Superlattices Microstruct. 76 (2014)
LPG CH3COCH3 C2H5OH 253–263.
[2] M.A. Boukadhaba, W. Chebil, A. Fouzri, V. Sallet, A. Lusson, G. Amiri, C. Vilar,
M. Oumezzine, Superlattices Microstruct. 94 (2016) 158–177.
6.9 29.0 21.3
[3] C.S. Prajapati, P.P. Sahay, Appl. Surf. Sci. 2582 (2012) 823–2828.
[4] Cheng-Liang Hsua, Kuan-Chao Chen, Tsung-Ying Tsai, Ting-Jen Hsueh, Sens.
Actuators B 182 (2013) 190–196.
[5] Alex M. Ma, Manisha Gupta, Fatema Rezwana Chowdhury, Mei Shen, Kyle Bothe,
Karthik Shankar, Ying Tsui, Douglas W. Barlage, Solid-State Electron. 76 (2012)
104–108.
[6] Bhagaban Behera, Sudhir Chandra, Sens. Actuators B 229 (2016) 414–424.
[7] Anjali Sharma, Monika Tomar, Vinay Gupta, Sens. Actuators B 176 (2013)
875–883.
[8] K. Arshak, I. Gaidan, Mater. Sci. Eng. B 118 (2005) 44–49.
[9] Sergiu T. Shishiyanu, Teodor S. Shishiyanu, Oleg I. Lupan, Sens. Actuators B 107
(2005) 379–386.
[10] Kourosh Kalantar-zadeh, Jian Zhen Ou, Torben Daeneke, Arnan Mitchell,
Takayoshi Sasaki, Michael S. Fuhrer, Appl. Mater. Today 5 (2016) 73–89.
[11] Asaf Rotbart, C.K. Yao, Nam Ha, Michael D. Chrisp, Jane G. Muir, Peter R. Gibson,
Kourosh Kalantar-zadeh, Jian Zhen Ou, Sens. Actuators B 238 (2017) 754–764.
[12] Xiao Liu, Sitian Cheng, Hong Liu, Sha Hu, Daqiang Zhang, Huansheng Ning,
Sensors 12 (2012) 9635–9665.
[13] K.L. Foo, M. Kashif, U. Hashim, Wei-Wen Liu, Ceram. Int. 40 (2014) 753–761.
[14] Sunandan Baruah, Joydeep Dutta, Sci. Technol. Adv. Mater. 10 (2009) 013001.
[15] Lin Xu, Ruiqing Xing, Jian Song, Wen Xu, Hongwei Song, J. Mater. Chem. C 1
(2013) 2174.
[16] Shouli Bai, Song Chen, Yangbo Zhao, Teng Guo, Ruixian Luo, Dianqing Li,
Aifan Chen, J. Mater. Chem. A 2 (2014) 16697.
[17] M. Vishwasa, K. Narasimha Rao, A.R. Phani, K.V. Arjuna Gowda,
(10)

14
A.R. Nimbalkar, M.G. Patil Physica B 527 (2017) 7–15

R.P.S. Chakradhar, Solid State Commun. 152 (2012) 324–327. Abbas Shirmardi Dezaki, Phys. E: Low-Dimens. Syst. Nanostruct. 79 (2016)
[18] Michael Breedon, Mohammad Bagher Rahmani, Sayyed-Hossein Keshmiri, 113–118.
Wojtek Wlodarski, Kourosh Kalantar-zadeh, Mater. Lett. 64 (2010) 291–294. [30] Yo-Sep Min, Il Ha Lee, Young Hee Lee, Cheol Seong Hwang, Cryst. Eng. Commun.
[19] J. Yu, S.J. Ippolito, W. Wlodarski, M. Strano, K. Kalantar-zadeh, Nanotechnology 13 (2011) 3451.
21 (2010) 265502 (8pp). [31] Ahmad Hossein Adl, Piyush Kar, Samira Farsinezhad, Himani Sharma,
[20] Chien-Yie Tsay, Kai-Shiung Fan, Sih-Han Chen, Chia-Hao Tsai, J. Alloy. Compd. Karthik Shankar, RSC Adv. 5 (2015) 87007.
495 (2010) 126–130. [32] A. Dhanalakshmi, A. Palanimurugan, B. Natarajan, Carbohydr. Polym. 168 (2017)
[21] Sumayya Inamdar, Vinayak Ganbavle, Shahin Shaikh, Kesu Rajpure, Phys. Status 191–200.
Solidi A (2015) 1–9. http://dx.doi.org/10.1002/pssa.201431850. [33] R.K. Sonker, B.C. Yadav, A. Sharma, M. Tomar, V. Gupta, RSC Adv. 61 (2016).
[22] Amol R. Nimbalkar, Maruti G. Patil, Mater. Sci. Semicond. Process. 71 (2017) http://dx.doi.org/10.1039/C6RA07103A.
332–341. [34] Rajni Sharma, Firoz Alam, A.K. Sharma, V. Dutta, S.K. Dhawan, J. Mater. Chem. C
[23] Premalatha Ariyakkani, Suganya Lakshmikanthan, Sundaresan Balakrishnan, J. 5 (2014) 8142.
Alloy. Compd. 695 (2017) 3467–3475. [35] Amit Kumar Chawla, Davinder Kaur, Ramesh Chandra, Opt. Mater. 29 (2007)
[24] O. Lupan, T. Pauporte', L. Chow, B. Viana, F. Pelle', L.K. Ono, B. Roldan Cuenya, 995–998.
H. Heinrich, Appl. Surf. Sci. 256 (2010) 1895–1907. [36] Syed Khasim, Omar A. Al-Hartomy, RSC Adv. 4 (2014) 39844.
[25] Trilochan Sahoo, Myoung Kim, Mi-Hee Lee, Lee-Woon Jang, Ju-Won Jeon, Joon [37] Yasin Sahin, Sadullah Öztürk, Necmettin Kılınc, Arif Kösemen, Mustafa Erkovan,
Seop Kwak, In-Yong Ko, In-Hwan Lee, J. Alloy. Compd. 491 (2010) 308–313. Zafer Ziya Öztürk, Appl. Surf. Sci. 303 (2014) 90–96.
[26] S.T. Navale, V.V. Jadhav, K.K. Tehare, R.U.R. Sagar, C.S. Biswas, M. Galluzzi, [38] Yasemin Caglar, Müjdat Caglar, Saliha Ilican, Microstruct. Curr. Appl. Phys. 12
W. Liang, V.B. Patil, R.S. Mane, F.J. Stadler, Sens. Actuators B 238 (2017) (2012) 963–968.
1102–1110. [39] V.V. Ganbavle, M.A. Patil, H.P. Deshmukh, K.Y. Rajpure, J. Anal. Appl. Pyrolysis
[27] Prabhakar Rai, Yun-Su Kim, Hyeon-Min Song, Min-Kyung Song, Yeon-Tae Yu, 107 (2014) 233–241.
Sens. Actuators B 165 (2012) 133–142. [40] Shouli Bai, Chuanzhen Sun, Teng Guo, Ruixian Luo, Yuan Lin, Aifan Chen,
[28] Leong G. Mar, Peter Y. Timbrell, Robert N. Lamb, Thin Solid Films 223 (1993) Lina Sun, Jingbo Zhang, Electrochim. Acta 90 (2013) 530–534.
341–347. [41] K.G. Girija, K. Somasundaram, Anita Topkar, R.K. Vatsa, J. Alloy. Compd. 684
[29] Abdolhossein Saa'edi, Ramin Yousefi, Farid Jamali-Sheini, Ali Khorsand Zak, (2016) 15–20.
Mohsen Cheraghizade, M.R. Mahmoudiand, Mohammad Amin Baghchesara,

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