Superlattices and Microstructures 143 (2020) 106547

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Superlattices and Microstructures

journal homepage: www.elsevier.com/locate/superlattices

A SILAR fabrication of nanostructured ZnO thin films and their

characterizations for gas sensing applications: An effect of
Ag concentration
K. Radhi Devi a, G. Selvan b, *, M. Karunakaran c, K. Kasirajan c, Mohd Shkir d, e,
S. AlFaify e
a
PG and Research Department of Physics, Sethupathy Govt. Arts College, Ramanathapuram, India
b
Department of Physics, Thanthai Hans Roever College, Perambalur, India
c
PG and Research Department of Physics, Alagappa Govt Arts College, Karaikudi, 630003, India
d
Research Center for Advanced Materials Science (RCAMS), King Khalid University, Abha, 61413, Saudi Arabia
e
Advanced Functional Materials and Optoelectronics Laboratory (AFMOL), Department of Physics, College of Science, King Khalid University, Abha,
61413, Saudi Arabia

A R T I C L E I N F O A B S T R A C T

Keywords: Gas sensing device development is a key field of research in the recent scenario, Hence, in this
ZnO:Ag work, facile fabrication of ZnO films with diverse content of Ag was accomplished as a vapor
SILAR sensor using a cost-effective successive ionic layer adsorption and reaction (SILAR) process. X-ray
Thin films
diffraction (XRD) analysis provides evidence about the good crystalline nature of grown ZnO: Ag
X-ray diffraction
Optical properties
films and crystallite size was decreased from 38 to 27 nm with Ag content increased from 0 to 5
vapor sensor wt.%. Scanning electron microscope (SEM) analysis revealed the remarkable modification in
morphology from nanograins (undoped) to nanorods (5 wt.% Ag). Energy dispersive analysis of X-
rays (EDX) supports the Zn, O, and Ag content present in the final film. The prepared Ag-doped
ZnO films exhibited good optical nature and an improvement in the energy gap from 3.04 to 3.29
eV was noticed. The responsivity, response and recovery time of ammonia vapor sensor were
remarkably enhanced to 8260 %, 27 s, and 7 s respectively, for the 5 wt.% Ag doped ZnO
nanofilm. The responsivity of 5 wt.% Ag doped film was 15 times that of undoped ZnO film. These
results make low cost grown Ag-doped ZnO nanorod a good candidate for high quality vapor
sensor.

1. Introduction

There is continuous emission of hazardous gases, toxins, and biomolecules due to rapid technological and industrial developments.
Therefore, sensing of such undesirable environmental polluting gases has become an important research in recent years. Significant
quantities of gases related to ammonia, nitrogen, and carbon oxides are continuously accumulated in the air by various industries and
transportation, that have the worst influence on the atmosphere in innumerable ways [1]. Among these gases, the ammonia (NH3) is
increasing continuously in the atmosphere [2,3], which may lead to major health issues in humans through different routes [4].
Therefore, the detection and monitoring of NH3 gas are of high importance for both resource exploitation and human health. In recent

* Corresponding author.
E-mail address: selvan96@redifmail.com (G. Selvan).

https://doi.org/10.1016/j.spmi.2020.106547
Received 17 February 2020; Received in revised form 15 April 2020; Accepted 27 April 2020
Available online 30 April 2020
0749-6036/© 2020 Elsevier Ltd. All rights reserved.
K.R. Devi et al. Superlattices and Microstructures 143 (2020) 106547

decade’s number of semiconductor (MOS) sensors has been fabricated to detect and monitor the NH3 which includes ZnO, SnO2, WO3,
In2O3 and a few perovskite-type materials [5]. Among various metal oxide semiconductors, ZnO, a wide-band gap semiconductor,
recently proven as an outstanding applications in the field of photocatalysis [6–8], LED [9], memory [10], magnetic [11] and
photo-detector [12]. Typically, the sensor activity of MOS is based on structure, morphology, grain size, and surface area of sensing
materials [13]. In past literature, several actions/research has been done for improving the sensing ability of sensors. Sensors based on
ZnO were broadly investigated through experimental/theoretically routes for understanding the relationships among sensitivity and
structure [14]. Dong et al. documented that the nanosized ZnO is more sensitive compared to normal ZnO [15]. Though, ammonia
sensor based on ZnO exhibited decent response at higher temperatures only, where an easy reaction among thermally energy generated
surface electron carriers and oxygen atoms in air occurs that results in the formation of huge numbers of O species and as an output a
sensor with good response developed [16]. Moreover, at low functioning temperatures, the case is opposite to higher one and ZnO gas
sensing retort is saturated at low temperature and when treated to large content causing decreased rejoinder, regaining, and steadiness
of the sensor. To get rid of such issues and improving the response of the sensor devices at low working temperatures numerous efforts
were done like: development of p-n junction, doping of noble transition metals/metal oxides, and UV radiance [17]. The sensor
characteristics of seldom used metal oxides can also be altered by adding a small amount of other materials [18]. Platinum and
Palladium are well-known noble metals, which can enhance the sensitivity of any oxide material against reducing gases [19]. Other
noble metals were also utilized to improve the sensitivity of metal oxide semiconductors [20]. It is believed that in the catalysts of
sensor chemisorbed oxygen species are increased by enhanced chemisorption process creating more reaction centers for reducing gas
molecules. Silver (Agþ) is one of the noble metal which is used as doping content widely used that eases the acceleration of chemical
rejoinder, catalytic action/oxidation [21]. Besides, it is also the finest candidates owing to good solubility, greater ionic size, and
lowest orbital energy. Henceforth, Ag-doped ZnO (Ag: ZnO) films can advance the sensing retort/repossession/retort time in gas
sensors. N. L. Tarwal et al. synthesized Ag: ZnO/glass films, which exhibited an improved gas-sensing performance compared to the
ZnO sample. They also showed that the 15% Ag-doped ZnO sample showed uppermost sensitivity (85 %) at 225 � C [22]. Jing Ding
et al. showed that the hybrid Ag–ZnO significantly enhanced the retort/choosiness to ethanol sensing. Further, hybrid exhibited
retort-repossession features, decent replicability, and steadiness, demonstrating their auspicious usages as gas-sensors [23]. Hadeethi
et al. reported that hydrothermal synthesized Ag–ZnO nanoneedles unveiled quickly to retort with lowest response/repossession times
towards acetone gas [24]. Nevertheless, more enhancements in the sensing of harmful gasses at low-temperature is essential.
Based on the literature survey, no reports are available for RT sensing of ammonia using nanorods shaped ZnO: Ag. In the present
work, ZnO: Ag nanorods with various doping Ag concentrations are prepared by the modified SILAR procedure for the first time. SILAR
technique has many advantages such as a cost-effective, easy to be controlled coating cycle, solution concentration, PH, solution,
dopant concentration and morphology [25,26]. The structure-morphology and optical behaviors of the prepared films are investigated
and discussed. Finally, the sensing performance of ZnO: Ag nanorods have been investigated under the different ammonia vapor
concentrations. The vapor sensor study shows excellent performance with a responsivity of 8260 % and lowest response and recovery
time of 27 s and 7 s for 5 wt.% Ag-doped ZnO nanorod shaped film.

2. Investigational particulars

2.1. Constituents and solvents

Zinc sulfate [ZnSO4], Sodium Hydroxide [NaOH] and dopant precursor Silver nitrate [AgNO3.] were procured from Sigma-Aldrich/
Alfa Aeser. Distilled water was used throughout the process.

2.2. Film deposition

Before the deposition, the substrate cleaning was done using chromic acid tailed by cleaning by acetone. Then these substrates were
hanged in a solution bath of 0.1 M ZnSO4, 0.2 M NaOH over 90 � C, and attained sodium zincate at ~9 pH. After 10 s the substrate was
removed and washed in hotwater for 10 s. Similar procedure has been taken place for ~80 cycles to achieve pristine ZnO films and the
reaction is as follows [25]:
ZnSO4 þ 2 NaOH → Na2 ZnO2 þ H2 SO4 (1)

Na2 ZnO2 þ H2 O → ZnO þ 2 NaOH (2)

Ag-doped ZnO thin films were prepared by adding diverse content of silver nitrate as Ag source (i.e. 1, 3, and 5 wt.%) in the sodium
zincate bath. Finally, the deposited films were dried out in air and annealing at 400 � C for ~2 h was carried out.

2.3. Characterization tools

Structure of ZnO:Ag films was studied by X-ray diffraction using Bruker (D8 Advance Eco XRD) diffractometer using CuKα (λ ¼
1.5406 nm) radiation. EVO18 CARL ZEISS SEM was used to analyze morphology of films. PL was measured at λexc ¼ 380 nm using
Varian Carry Eclipse Photoluminescence Spectrometer. An Ocean Optics HR 2000 optical fiber-based spectrophotometer is employed
to record the optical nature of ZnO:Ag films over 300–800 nm wavelength region. A Mitutoyo SJ-301 Stylus profilometer was used to
find the films thickness. The measured thickness values are found to decrease as ∽ 950, 850, 800, and 750 nm for the raise of Ag

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K.R. Devi et al. Superlattices and Microstructures 143 (2020) 106547

content as 0, 1, 3, and 5 wt.% respectively. A vapor sensing camper is interfaced with source meter (Keithley 2450, USA) and a PC.

3. Result and discussion

3.1. Structural analysis

Patterns of XRD for prepared ZnO: Ag films are revealed in Fig. 1. Observed XRD peaks were connected to the lattice planes (1 0 0),
(0 0 2), (1 0 1), (1 0 2), (110), (1 0 3), (1 1 2) and (2 0 1) according to JCPDS card No. 36–1451 [27]. The deposited samples are
polycrystalline in nature with a ZnO hexagonal system. There is no secondary silver phase indicating complex integration of the
additives into the ZnO lattice. The intensity of peak (0 0 2) gradually decreases in the XRD pattern, whereas the intensity of peak (1 0 0)
increases as the concentration of Ag increases, indicating the film growth along (110) orientation. The same trend was reported
recently by Bekkari et al. [28].
The crystallite size of all the films deposited is measured using the well-known equation of Debye-Scherrer [29–31].
0:9λ
D¼ (3)
βcosθ

here D is crystallite size , and the peak position is at a maximum half-intensity. The determined D values were 38, 34, 30, and 27 nm for
the 0, 1, 3, and 5 wt. % increases in Ag doping concentration. The decrease in crystallite size is owing to a decrease in the rate of growth
of ZnO films by adding Agþ into the host lattice sites. The defects like strain (ε) and dislocation density (δ) for the ZnO: Ag was
evaluated using the relations [29,32,33].
β cot θ
ε¼ (4)
4

1
δ¼ (5)
D2

and the number of crystallites (nc) as [34]:

t
nc ¼ (6)
D3

where, t is the thickness and calculated values of ZnO: Ag films for micro-strain (ε) and dislocation density (δ) are given in Table 1.

Fig. 1. X-ray diffraction pattern of ZnO:Ag thin films with different Ag doping concentrations.

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K.R. Devi et al. Superlattices and Microstructures 143 (2020) 106547

Tabulated values disclosed that there is increase in ε, δ and N values for increase in Ag concentration is attributed to the enhancement
in amounts of defects which is favor for more vapor sensing. The volume of unit cell ‘V’ and the lattice constraints ‘a’ and ‘c’ of grown
hexagonal phase films are calculated by Ref. [35]:

v ¼ a2 cðsin60o Þ (7)
� � � 2�
1 4 h2 þ hk þ k2 l
¼ þ 2 (8)
d2 3 d2 c

here, hkl and d stand for common meaning. Variation in estimated values of ‘a’ and ‘c’ and ‘V’ for ZnO:Ag films is publicized in Fig. 2,
lattice constant values and cell volume increases by increasing the Ag concentration. This may be owing to the incorporation of Agþ of
high ionic radii of viz. 1.26 Å into ZnO lattice (Zn2þ ¼0.74 Å ) at substitutional sites [36].

3.2. Morphological and elemental analysis

The surface morphology of the Ag-doped ZnO (0, 1, 3 and 5 wt %) films was characterized by SEM and presented in Fig. 3(a–d).
ZnO–Ag (0 wt.%) film shows nanograins. When the Ag doping level increases from 0 to 1 wt. %, the spherical-shaped grains turn in to
quasi-spherical and agglomerated morphology. The ZnO–Ag (3 wt. %) film shows a densely packed grain that is homogeneous and
distributed evenly throughout the structure. In the case of 5 wt. % ZnO:Ag film, the particles are joined to form a nano rod-shaped
grains and some voids appear due to the inclusion of Ag in Zn sites that might stimulate the variations. Similar nano-rod shaped
grains were reported recently by Fang Lu et al. [36], Belchiolina Beatriz Fonseca et al. [37] and Oleg Lupan et al. [38] for ZnO:Ag.
Fig. 4 represents the EDX of ZnO: Ag (5 wt. %) thin film. As expected, the elements Ag, Zn, and O are present in the spectrum. Other
unknown peaks are observed in the spectrum due to glass substrates.

3.3. Photoluminescence analysis

Fig. 5 shows the room temperature PL emission spectrum (between 400 and 600 nm region) of different concentrations ZnO: Ag
films using a 380 nm wavelength of excitation. The emission range consists of 407, 420, 459,486, 519, and 540 nm emission peaks.
Because of Zn interstitials, the high violet emission peak at 407 nm occurs. Bands at 420, 459, and 486 nm are related to blue emission,
whereas the band for green emission is at 519 nm. Visible emission band is associated with an intrinsic defect in ZnO, that includes VZn,
Vo, Zni, Oi and replacement of O at Zn (OZn) [39–41]. Numerous ZnO’s PL emission property studies showed an advanced UV/green
emission level relative to blue one [42]. The violet emission at 407 nm is likely due to Zni and VZn’s radiative defects connected to
trapping at the interface at boundaries of ZnO grain. The bands at 420 and 459 nm are likely due to 2 levels of defects, like: Zni to VB or
from bottom of CB to Oi transitions [42]. The transition amongst Vo and Vi can be traced to the emission level of 486 nm [43]. The
bands at 519 and 540 nm are attributed to electron recombination through photo-excited hole in VB in a single ionized oxygen va­
cancy. The peak intensity of the doped films are increases compared to pure ZnO. Such changes occur as a result of the Agþ ions dopant
replaced to Zn2þ. Thus the doping will enhance the various defects centers in ZnO: Ag thin films which will promote the vapor sensing
due to its number of active sites.

3.4. UV–vis analysis

Fig. 6(a) illustrates the usual transmission (T) spectrum of ZnO:Ag films. The value of T of films increased on growing Ag doping
concentration. Good structural homogeneity and crystallinity are associated with high transparency [44]. The following relationship
[45,46] estimated the relationship among coefficient of absorption (α) and energy of photon (hυ) for the direct bandgap:
�1=2
ahv ¼ A hv Eg (9)

Emblematic plots (αhν)2 vs. hν are shown in Fig. 6 (b). With an increase in Ag content, the optical bandgap decreases. The obtained
optical bandgap values are in the range of 3.04 eV–3.29 eV. The improvement in film density and size of grain increase is another
possibility for the rise in doped film bandgap. But band gap of ZnO nano-rods smaller than its bulk value of 3.37 eV due to its less grain
size [47]. SILAR method is, therefore, useful for tuning the optical bandgap of the thin films.

Table 1
Film thickness, structural parameters and bandgap of prepared ZnO:Ag thin films.
Ag Film Crystallite size Dislocation density (�1015) Strain Number of crystallites Bandgap
Concentration (wt. Thickness (nm) lines.m 2 (�10 3) (�1016 m 2) (eV)
%) (nm)

0 950 38 0.6919 3.05 1.73 3.04

1 850 34 0.8877 3.46 2.25 3.12
3 800 30 1.1482 3.94 3.11 3.22
5 750 27 1.3352 4.27 3.66 3.29

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K.R. Devi et al. Superlattices and Microstructures 143 (2020) 106547

Fig. 2. Lattice paramerers of ZnO:Ag thin films with different Ag doping concentrations.

Fig. 3. SEM images of ZnO:Ag thin films with different Ag doping concentrations.

3.5. Gas sensor analysis

In demand to examine gas sensing property of the prepared films, contacts were made on top of the films using silver paste [48,49].
The scematic of ammonia gas sensing set up used is shown in Fig. 7. A vapor producing metal tube is connected to gas sensing cavity
interfaced with H-R electrometer (Keithley 2450, USA) and a PC. After loading the sample atmosphere air is allowed to the sample to

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K.R. Devi et al. Superlattices and Microstructures 143 (2020) 106547

Fig. 4. EDX image of ZnO:Ag thin films with different Ag doping concentrations.

Fig. 5. Photoluminescence spectrum of ZnO:Ag thin films.

measure the air resistance. Then a particular amount of liquid ammonia was taken in a metal tube attached inside the chamber. Now
the ammonia vapor is ejected from a metal tube when the appropriate heat is applied to the tube. The ammonia vapor is ejected
throughout the chamber. Then, suddenly a change of resistance with respect to base-line was noticed showing the sensing property of
the device, as shown in Fig. 8(a and b). The gas sensing responsivity (S) of the devices was calculated from the sensor resistance in
air/sensor resistance in gas (Ra/Rg). Furthermore, time of response and recovery [50] were intended through resistance and time plot,
where the time to reach 90 % and 10 % percent resistance of original baseline resistance was considered to calculate response/recovery
times . The gas sensing retort and retrieval state of the device is revealed in Fig. 8 (a) w.r.t. Ag doping content. The observed response
times of 57, 42, 31, and 27 s, recovery times of 13, 10, 8 and 7 s. The 5 wt.% of Ag -doped device showed quick response time compared
to other devices. While decreasing the response time for increased Ag doping concentration, the recovery time is also decreased, for
higher Ag concentration. The responsivity of the films increased as 541, 930, 1570 and 8260 % as an increase in Ag concentration. The
increase of responsivity attributes to distribution of more nano-rods with voids at higher Ag concentration. A comparison of the sensing
performance of ZnO nanorods with other NH3 sensors reported in literature is provided in Table 2.
Fig. 8(b) shows ammonia gas sensing effect of 5 wt.% ZnO:Ag film at diverse ammonium gas concentrations (100 ppm–200 ppm). It
clearly shows a variation of low resistance depending on gas concentration showing very low resistance for high concentration (200
ppm); it indicates the concentration -dependent response of the device. And also observed that response between 100 and 200 ppm is
not much varied owing to the saturation state of ammonia vapor even at 100 ppm. Ammonia gas sensing ability of various metal-doped
ZnO thin films are compared with this work. Ravichandran et al. [51] showed 760-120 s and 42- 10 s as response and recovery times,
respectively for10 ppm 100 ppm NH3 gas, which is 50 % and 80 % higher response and recovery time values compare with our work.
Krishnan et al. [52] reported NH3 gas-sensing performance with higher sensitivity performance of Ba doped ZnO nano-films at 250 � C
○

by using 600 ppm concentration. Compared to this report, our device exhibited a better report even for 100 ppm at RT. Manivasaham
et al. [53] reported response and recovery times of 67 and 13 s for 2 % Cr doped ZnO thin film for 200 ppm ammonia vapor which are

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K.R. Devi et al. Superlattices and Microstructures 143 (2020) 106547

Fig. 6. (a) Transmittance and (b) Band gap spectra of ZnO:Ag thin films with different Ag doping concentrations.

Fig. 7. Schematic diagram of ammonia gas sensing setup.

higher than our device. Ganesh Kumar Mani et al. [54] noticed time of response/recovery ~ 46/14 s for 750 ppm NH3 for Ni:ZnO film
and response and recovery times are not saturated even at 1000 ppm of ammonia for Ni doped film our case that is saturated around
200 ppm. Mhlongo et al. [55] reported ammonia gas sensing studies of Pd loaded ZnO nano-particles showing the lowest response and

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K.R. Devi et al. Superlattices and Microstructures 143 (2020) 106547

Fig. 8. (a) Response time (tres) and recovery time (trec) of ZnO:Ag (5%) thin film deposited on glass substrate with exposure and removal of NH3 gas
of 25 ppm concentration. (b) Gas response of ZnO:Ag (5 wt.%) thin film deposited on glass substrate with exposure and removal of NH3 gas.

Table 2
Comparison of the sensing performance of ZnO nanorods with other NH3 sensors reported in literature.
S. Material Method Operating Concentration Responsivity Response time Recovery time Ref.
No temperature (� C) (ppm) % (s) (s)

1. ZnO Nebulizer spray RT 200 – 60 7 51

pyrolysis
2. ZnO:Ba Nebulizer spray 250 600 17.9 52
pyrolysis
3. ZnO:Cr Nebulizer spray RT 200 – 67 13 53
pyrolysis
4. ZnO:Ni Spray pyrolysis RT 750 235 46 14 54
5. ZnO:Pd Chemical 350 40 150 21 79 55
precipitation
6. ZnO Chemical RT 0.5 99 2 3 56
precipitation
7. ZnO precipitation 250 3 80 3 5 57
8. ZnO:Ag(5w. SILAR RT 100 8260 27 7 Present
%) Work

recovery time of 21 and 79 s for 0.5 % Pd doped ZnO at 40 ppm. This lesser recovery and response times may be due to the high surface
area and porous nature consequent increase in O adsorption. Naila ZUBAIR et al. [56] response/recovery time of 2/3 s for the lowest
ammonia concentration of 5 � 10 6 for ZnO due to uniformly synthesized nanoparticles. Srinivasulu Kanaparthi et al. [57] investi­
gated 2D ZnO nanoflakes based ammonia sensing and reported response/recovery time of 3/5 s at 250 � C towards 3 ppm ammonia.
This is low values compared with our results due to the low ppm of ammonia. This present study of ZnO: Ag films showed better
response and recovery times compared to other reported values of ZnO thin films (see Table 2).

3.6. Sensing nature

Graphic illustration of ZnO:Ag vapo-r sensing is revealed in Fig. 9. The response of sensing is estimated through electrical con­
ductivity measurement upon revelation under numerous gases with a reference line set. Once the oxide film is bare to atmospheric air,
the O atoms adsorbed on film surface snares to CB electrons which leads to enhance the resistance of the surface. When the plummeting
type gas intermingles to oxygen adsorbed then electrons ejected back to surface. So the electrical conductivity of the material
increased.
The sensing representation towards vapor of ammonia is:

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K.R. Devi et al. Superlattices and Microstructures 143 (2020) 106547

Fig. 9. NH3 sensing mechanism towards (a) ZnO and (b) ZnO:Ag (5 wt.%) thin film.

O2ðatm ​ osphereÞ þ eðZnO ​ surfaceÞ → O2ðZnO ​ surfaceÞ (10)

4NH3 þ 3O2 ðadÞ → 2N2 þ 6H2 O þ 6e (11)

In pristine ZnO, O atoms adsorbed on surface lead in generating of O2 and O by grabbing the electrons from CB of the material,
creating a depletion layer and thus forming high resistance and related resistance (Ra) is acknowledged as a resistance of baseline. Once
ammonia gas is released, it interacts to O present on ZnO thin film surface reducing the surface depletion layer resistance (Rg) and
height of the potential barrier. Whereas, in Ag (5 wt.%) doped ZnO film, the responsivity for ammonia sensing is more due to the
reduction in the intergranular contact resistance of nanorod than nanoparticles resulted in the decreased height of the potential
barrier. Hence, more electrons are inoculated once NH3 react to O. Consequently, Rg lessened more for ZnO:Ag than pristine film.
Hence, silver-ZnO films are better sensitive against ammonia.

4. Conclusion

Herein, we have achieved the successful deposition and development of ZnO:Ag films-based sensor for ammonia gas by a cost-
effective SILAR method with different silver concentrations (0, 1, 3, and 5 wt.%). The films were noticed to be grown along (002)
plane and the system is monophasic hexagonal ZnO. Morphological studies confirmed the presence of nanoparticles which are con­
verted to nanorods when doped with Ag. The Ag existence along with Zn and O was confirmed by EDX. PL study shows a systematic
enhancement in emission intensity of ZnO when doped with Ag, which indicates more defects in Ag-doped ZnO films. RT sensing of
ammonia was observed for all coated films. Among all ZnO:Ag sensors, 5 wt.% silver doped ZnO film showed higher responsivity. Thus,
it is concluded that the sensor of ZnO:Ag film is a good contender for sensing of ammonia at RT.

Author contribution

All scientists who meet authorship criteria are listed as authors, and all authors certify that they have participated sufficiently in the
work to take public responsibility for the content, including participation in the concept, design, analysis, writing, or revision of the
manuscript.

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K.R. Devi et al. Superlattices and Microstructures 143 (2020) 106547

Declaration of competing interest

The authors declare that they have no conflict of interest.

Acknowledgments

The authors would like to express their gratitude to RCAMS at King Khalid University, Saudi Arabia for sanctioning grant (RCAMS/
KKU/005/20).

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