VOL. 7, NO.

2, FEBRUARY 2023 2000104

Sensor materials

Development of a Reliable Zinc Oxide Thin-Film-Based Ammonia Gas Sensor

Jitesh Agrawal , Mayoorika Shukla, and Vipul Singh
Molecular and Nanoelectronics Research Group, Department of Electrical Engineering, IIT Indore, Indore 453552, India

Manuscript received 26 October 2022; revised 26 December 2022; accepted 7 January 2023. Date of publication 10 January 2023; date of current version
27 January 2023.

Abstract—In this work, a simple ZnO thin-film-based ammonia gas sensor fabricated via a straightforward and cost-
effective sol-gel technique has been demonstrated. The as-prepared device was found to be extremely sensitive toward
ammonia gas and has shown a high response of 13.5% at concentrations as low as 10 ppm at an optimal temperature of
180 °C (much lower than the threshold value of 25 ppm). The device response was observed to be linear up to 70 ppm
ammonia concentration with a response of 51% corresponding to it. The simplicity, repeatability, low production cost, and
high efficiency have made the device a potential candidate for various future applications, especially in industries where
ammonia sensing is critical.

Index Terms—Sensor materials, ammonia, gas sensor, sol–gel technique, zinc oxide.

I. INTRODUCTION
In recent years, sensors and electronics related to it have been
explored exhaustively and applied to the areas such as triboelec-
tric nanogenerator-based sensor systems [1], motion monitoring and
human-machine interface, etc. [2], biosensors [3], and gas sensors
[4]. However, it has been a challenge to fabricate a gas sensor for
the selective detection of toxic gases at low concentrations with high
sensitivity.
Recently, ammonia gas sensing has gained a lot of attention from the
research community due to its wide applications in different industries
such as plastic, fertilizers, chemical, refrigerators, pesticides, etc.
Detection of ammonia beyond a certain threshold, i.e., 25 ppm has been
crucial for human health. Moreover, it may cause fire and explosions
in industries where either it has been used as a precursor or emitted as
an intermediate or end by-product [5].
A variety of metal oxides such as TiO2 , SnO2 , WO3 , NiO, CuO,
ZnO, etc., have been used to develop high-sensitivity ammonia gas
sensors. Amongst different types of metal oxide semiconductors, ZnO
has emerged as the most suitable material for fabrication of the same
owing to its high thermal and chemical stability, electron mobility, and
tunable aspect ratio of nanostructures and electronic energy states. In
addition to this, the piezoelectric property of ZnO has resulted in the
design and fabrication of innovative self-powered sensing devices [6].
Further, ZnO thin films and nanostructures can be synthesized on a
large scale via sol-gel techniques at a comparatively lower temperature,
making the process simple and cost-effective [7].
In the past, efforts have been made toward the improvement of
the gas sensor figure of merits. In this regard, Zhu et al. [8] have
used pristine ZnO nanorods and nanosheets, Kanaparthi et al. [9]
have synthesized ZnO nanoflakes, Wang et al. [10] have used Pt-
loaded ZnO nanosheets, Wang et al. [11] have uniformly dispersed Ag
nanoparticles over ZnO Nanoparticles for gas sensing applications.
Further, doped ZnO has also been employed for the same such as
Namgung et al. [12] have doped Al in ZnO nanorods, whereas Tsai
Associate Editor: J. Gardner.
Corresponding author: Vipul Singh (E-mail: vipul@iiti.ac.in)
This work was supported by Indian Space Research Organisation (ISRO), under
the ISRO RESPOND Scheme under Grant ISRO/RES/3/849/19-20.
Digital Object Identifier 10.1109/LSENS.2023.3235890
et al. [13] utilized Ag-doped ZnO nanoflowers and Devi et al. [5]
has used strontium-doped ZnO thin films. Moreover, various ZnO
nanocomposites have also been developed namely ZnO-MWCNT and
ZnO-CuO core hollow cubes for obtaining better gas sensor response
[14], [15]. Noteworthily, the most common approach used to develop a
ZnO-based gas sensor is to use pre-synthesized ZnO nanostructures to
prepare a paste or slurry by mixing them with some binder e.g., ethanol,
ethyl cellulose, and terpineol [16]. Which, in turn, was coated on the
substrate to obtain a ZnO thin film with a high aspect ratio. However,
the major disadvantage of such a process has been observed to be the
nonuniform film with poor adhesion over the substrate [17]. Further,
the use of such binder leads to poor electrical contact between both the
interfaces, i.e., ZnO/electrode and between nanostructures themselves.
Also, it blocks the gas molecules to reach active sites, which adversely
affects the performance of device [18]. Therefore, using ZnO thin
film directly grown on the substrate could significantly improve the
device sensing response. Henceforth, in this work, we have developed a
ZnO thin film-based ammonia gas sensor. A relatively straightforward
and single-step sol-gel technique has been utilized to obtain ZnO thin
film and a simple device structure. It has been observed to exhibit
a better response in comparison to some of the recently published
works, which have followed complex device structure and synthesis
techniques.
II. EXPERIMENTAL WORK
Pre-cut glass samples of 1.5 cm × 1.5 cm were ultrasonically
cleaned in acetone, isopropanol, and DI (deionized) water for 10 min
each. Thereafter, the precursor solution has been prepared by mixing
equimolar (3M) zinc acetate and ethanolamine in 2-methoxy ethanol
followed by stirring at 350 rpm for 6 h. Then the precursor solution
was spin-coated over the cleaned glass substrates at 3000 rpm for 30
s and annealed at 240 ˚C for 5 min for better crystallinity. Then the
Pt interdigitated electrodes (IDEs) of 500 µm channel length were
deposited using DC sputtering techniques at 60 W DC power.
The photoluminescence (PL) analysis of the samples was performed
using DongwooOptron DM 500 I, equipped with a 325 nm continuous
wave He-Cd (excitation wavelength 325 nm) and a photomultiplier
tube (PMT) detector. UV-VIS-NIR Perkin-Elmer Lambda 750 has
been used to obtain the absorption spectra of the samples. To record

2475-1472 © 2023 IEEE. Personal use is permitted, but republication/redistribution requires IEEE permission.
See https://www.ieee.org/publications/rights/index.html for more information.

Authorized licensed use limited to: Universiti Tunku Abdul Rahman. Downloaded on June 14,2023 at 06:00:55 UTC from IEEE Xplore. Restrictions apply.
2000104
Fig. 1. Optical characterization of the samples. (a) UV-Vis spec-
troscopy; inset shows absorption spectra in the visible region. (b) PL
spectroscopy analysis.
Fig. 2. (a) Device schematic. (b) Optimization of the temperature to
maximize the gas sensing response.
the gas sensing response of the fabricated device, the Keithley 2612A
source meter unit has been used. Aalborg DPC17 mass flow controller
was used to regulate the gas flow while purging the air-gas mixture
in the sensing chamber. The airflow was maintained at 2 Kg/cm2
throughout the gas-sensing characterization process.
III. RESULTS AND DISCUSSION
The absorption spectra of the ZnO thin film sample have been
shown in Fig. 1(a). High and sharp band edge absorbance in the near
UV region, which corresponds to the band-to-band transition in ZnO
has been observed which corresponds to the better crystallinity of
the sample. Further, there was considerable absorption in the visible
region [shown in the inset of Fig. 1(a)], which indicates the presence
of mid-gap energy states, e.g., singly and doubly charged oxygen
vacancies.
Fig. 1(b) shows the PL spectra of the sample. An intense and sharp
emission peak, centered at 380 nm, known as near band emission
(NBE) of ZnO, signifies the high crystallinity of the as-prepared ZnO
thin film. Further, a broad emission peak in the visible region was
observed which could be attributed to the deep energy levels, i.e.,
charged and neutral oxygen vacancies, present in the sample. It was
evident from the Absorption and PL spectroscopy that the sample
consists of a large number of oxygen vacancies-related defect states.
These vacancies act as preferential sites for the absorption of oxygen
molecules which may lead to improvement in the efficiency of the
gas-sensing device [19].
Fig. 2(a) shows the device schematic of the as-prepared gas sensor.
The typical time-dependent response recovery behavior of the gas
sensor has been recorded at 10 V of applied bias. The sensing response
is calculated as S = ((Ra-Rg)/Ra)×100%, where Ra and Rg are the
resistance of the device in zero air and zero air-ammonia mixture,
respectively. The device response depends significantly on the sensing
temperature, as the increase in temperature leads to the desorption of
the oxygen gas molecules from the active layer surface, whereas the
Authorized licensed use limited to: Universiti Tunku Abdul Rahman. Downloaded on June 14,2023 at 06:00:55 UTC from IEEE Xplore. Restrictions apply.
VOL. 7, NO. 2, FEBRUARY 2023
Fig. 3. (a) Time-dependent response recovery behavior of as-
fabricated gas sensor. (b) Gas sensor response to different ammonia
gas concentrations.
Fig. 4. A schematic of change in the depletion region of ZnO thin film
after purging the ammonia in the gas sensing chamber.
decrease in temperature leads to the adsorption of the gas molecules.
Therefore, it is highly desirable to optimize the sensing temperature
so that the gas adsorption–desorption equilibrium can be established.
Fig. 2(b) shows the ammonia sensing response as a function of tem-
perature ranging from 80 to 280 °C. It has been observed that the gas
sensing response has increased with the increase in temperature to
180 °C. However, further increasing the temperature has resulted in a
significant reduction in the response. Therefore, 180 °C temperature,
where the maximum response has been achieved was considered for
further characterization.
Fig. 3(a) shows the typical response recovery behavior of the gas
sensor, i.e., change in the resistance of ZnO for varied ammonia
concentrations. The device was found to be highly sensitive to am-
monia even at concentrations as small as 10 ppm. Furthermore, the
device response was observed to increase linearly with the ammonia
concentration as shown in Fig. 3(b). The gas sensor response has
increased from 13.5% to 51% with the increase in concentration from
10 to 70 ppm. In addition to this, it was observed to be highly linear
in this range.
Fig. 4 explains the gas sensing mechanisms of the ZnO thin film-
based device: As the oxygen molecules come in the vicinity of ZnO,
they would get adsorbed over the surface. These adsorbed oxygen
molecules capture the free electron from the ZnO surface and form
O− ions (1) which lead to increase in the resistance of the ZnO thin
film. Thus, a depletion region is formed over the surface and hence
the resistance of the ZnO thin film increases significantly. Further,
as the ammonia-air mixture is injected into the chamber, the ammonia
molecules react with O− ions resulting in the formation of N2 and H2 O.
Also, the electrons captured by the adsorbed oxygen were released
back into ZnO, which thereby restores the resistance of the film (2).
The chemical reactions involved in the NH3 sensing can be ex-
plained as follows [20]:
O2 (ads) + 2e− ↔ 2O−
(ads) (1)
2NH3 + 3O−
(ads) ↔ N2 + 3H2 O + 3e . −
(2)
 VOL. 7, NO. 2, FEBRUARY 2023
Fig. 5. (a) Device stability analysis. (b) Device sensing response for
ammonia and CO gases at 50 ppm.
Table 1. Comparison With Previously Reported Work
The device repeatability is essential for its reliability, as it should
reproduce the same output every time for the same amount of input.
Therefore, 30 ppm of NH3 has been repeatedly purged in the sensing
chamber and the response recovery behavior was recorded to check the
repeatability of device. As shown in Fig. 5(a), the response of device
was very stable at 27.1% response for 30 ppm of NH3 concentration.
The response time of the device was 112 s. Further, in order to verify
the device selectivity, another reducing gas, e.g., carbon monoxide
has been tested as shown in Fig. 5(b), at 50 ppm concentration and
the sensing response was recorded. It was observed that the device
response for ammonia was 40.6%, whereas for carbon monoxide it
was just 22.7%. Therefore, the device was clearly observed to be
∼179% more sensitive to the ammonia gas than CO. Moreover, the
obtained results were compared with the previously reported works
in Table 1. The present study was found to be comparable with the
recently published works.
IV. CONCLUSION
In this work, simple, cost-effective, and highly sensitive ammo-
nia gas sensor has been fabricated. The device has demonstrated a
significantly high response of 13.6% even at just 10 ppm ammonia
concentration. Additionally, the device response has been observed to
exhibit linear behavior for a large range of ammonia concentrations.
Authorized licensed use limited to: Universiti Tunku Abdul Rahman. Downloaded on June 14,2023 at 06:00:55 UTC from IEEE Xplore. Restrictions apply.
2000104
Therefore, the proposed device could be a potential candidate for
future applications where a lower concentration of ammonia sensing
is required.
ACKNOWLEDGMENT
Jitesh Agrawal is thankful to SIC, IIT Indore for Providing the Required Research
Facility and J. A. and V. S. are also thankful to Indian Space Research Organisation
(ISRO) for providing the financial support under the ISRO RESPOND Scheme (Project
No.: ISRO/RES/3/849/19-20).
REFERENCES
[1] D. Wang et al., “Ethylene chlorotrifluoroethylene/hydrogel-based liquid-solid tri-
boelectric nanogenerator driven self-powered mxene-based sensor system for ma-
rine environmental monitoring,” Nano Energy, vol. 100, 2022, Art. no. 107509,
doi: 10010.1016/j.nanoen.2022.107509.
[2] H. Zhang, D. Zhang, B. Zhang, D. Wang, and M. Tang, “Wearable pressure sensor
array with layer-by-layer assembled MXene nanosheets/Ag nanoflowers for motion
monitoring and human-machine interfaces,” ACS Appl. Mater. Interfaces, vol. 14,
no. 43, pp. 48907–48916, 2022, doi: 10.1021/acsami.2c14863.
[3] M. Adeel, M. M. Rahman, I. Caligiuri, V. Canzonieri, F. Rizzolio, and S. Daniele,
“Recent advances of electrochemical and optical enzyme-free glucose sensors
operating at physiological conditions,” Biosens. Bioelectron., vol. 165, 2020,
Art. no. 112331, doi: 10.1016/j.bios.2020.112331.
[4] D. Wang et al., “Multifunctional poly(vinyl alcohol)/Ag nanofibers-based
triboelectric nanogenerator for self-powered mxene/tungsten oxide nanohy-
brid NO2 gas sensor,” Nano Energy, vol. 89, 2021, Art. no. 106410,
doi: 8910.1016/j.nanoen.2021.106410.
[5] K. R. Devi, G. Selvan, M. Karunakaran, I. L. P. Raj, V. Ganesh, and S. AlFaify,
“Enhanced room temperature ammonia gas sensing properties of strontium doped
ZnO thin films by cost-effective SILAR method,” Mater. Sci. Semicond. Process.,
vol. 119, 2020, Art. no. 105117, doi: 11910.1016/j.mssp.2020.105117.
[6] D. Zhang et al., “Diversiform sensors and sensing systems driven by triboelec-
tric and piezoelectric nanogenerators,” Coordination Chem. Rev., vol. 427, 2021,
Art. no. 213597, doi: 42710.1016/j.ccr.2020.213597.
[7] J. Agrawal, T. Dixit, I. A. Palani, and V. Singh, “Highly visible-blind
ZnO photodetector by customizing nanostructures with controlled defects,”
IEEE Photon. Technol. Lett., vol. 32, no. 22, pp. 1439–1442, Nov. 2020,
doi: 10.1109/lpt.2020.3031732.
[8] L. Zhu, W. Zeng, and Y. Li, “New insight into gas sensing property of
ZnO nanorods and nanosheets,” Mater. Lett., vol. 228, pp. 331–333, 2018,
doi: 10.1016/j.matlet.2018.06.049.
[9] S. Kanaparthi and S. G. Singh, “Highly sensitive and ultra-fast responsive ammonia
gas sensor based on 2D ZnO nanoflakes,” Mater. Sci. Energy Technol., vol. 3,
pp. 91–96, 2020, doi: 10.1016/j.mset.2019.10.010.
[10] Y. Wang, X. N. Meng, and J. L. Cao, “Rapid detection of low concentration CO
using Pt-loaded ZnO nanosheets,” J. Hazard Mater., vol. 381, 2020, Art. no. 120944,
doi: 10.1016/j.jhazmat.2019.120944.
[11] S. Wang et al., “Fabrication of ZnO nanoparticles modified by uniformly dispersed
Ag nanoparticles: Enhancement of gas sensing performance,” ACS Omega, vol. 5,
no. 10, pp. 5209–5218, 2020, doi: 10.1021/acsomega.9b04243.
[12] G. Namgung, Q. T. H. Ta, W. Yang, and J. S. Noh, “Diffusion-driven al-doping
of ZnO nanorods and stretchable gas sensors made of doped ZnO nanorods/Ag
nanowires bilayers,” ACS Appl. Mater. Interfaces, vol. 11, no. 1, pp. 1411–1419,
2019, doi: 10.1021/acsami.8b17336.
[13] Y. T. Tsai et al., “High sensitivity of NO gas sensors based on novel Ag-doped ZnO
nanoflowers enhanced with a UV light-emitting diode,” ACS Omega, vol. 3, no. 10,
pp. 13798–13807, 2018, doi: 10.1021/acsomega.8b01882.
[14] L. Vatandoust, A. Habibi, H. Naghshara, and S. Mohammadi Aref, “Fabrication of
ZnO-MWCNT nanocomposite sensor and investigation of its ammonia gas sensing
properties at room temperature,” Synthetic Met., vol. 273, 2021, Art. no. 116710,
doi: 27310.1016/j.synthmet.2021.116710.
[15] J. E. Lee, C. K. Lim, H. J. Park, H. Song, S. Y. Choi, and D. S. Lee, “ZnO-CuO
core-hollow cube nanostructures for highly sensitive acetone gas sensors at the
ppb level,” ACS Appl. Mater. Interfaces, vol. 12, no. 31, pp. 35688–35697, 2020,
doi: 10.1021/acsami.0c08593.
[16] R. Sankar Ganesh et al., “Sensitivity enhancement of ammonia gas sensor based on
Ag/ZnO flower and nanoellipsoids at low temperature,” Sensors Actuators B: Chem.,
vol. 255, pp. 672–683, 2018, doi: 10.1016/j.snb.2017.08.015.
[17] M. Jiao et al., “Comparison of NO2 gas-sensing properties of three dif-
ferent ZnO nanostructures synthesized by on-chip low-temperature hydrother-
mal growth,” J. Electron. Mater., vol. 47, no. 1, pp. 785–793, 2017,
doi: 10.1007/s11664-017-5829-6.
2000104
[18] R. Ahmad, S. M. Majhi, X. Zhang, T. M. Swager, and K. N. Salama, “Recent progress
and perspectives of gas sensors based on vertically oriented ZnO nanomaterials,” Adv.
Colloid Interface Sci., vol. 270, pp. 1–27, 2019, doi: 10.1016/j.cis.2019.05.006.
[19] Z. Li et al., “Plasma-induced oxygen vacancies enabled ultrathin ZnO films for
highly sensitive detection of triethylamine,” J. Hazard Mater., vol. 415, 2021,
Art. no. 125757, doi: 10.1016/j.jhazmat.2021.125757.
[20] M. Poloju, N. Jayababu, and M. V. R. Reddy, “Improved gas sensing performance
of Al doped ZnO/CuO nanocomposite based ammonia gas sensor,” Mater. Sci. Eng.,
B, vol. 227, pp. 61–67, 2018, doi: 10.1016/j.mseb.2017.10.012.
[21] J. Wang, S. Fan, Y. Xia, C. Yang, and S. Komarneni, “Room-temperature gas
sensors based on ZnO nanorod/Au hybrids: Visible-light-modulated dual selec-
tivity to NO2 and NH3,” J. Hazard Mater., vol. 381, 2020, Art. no. 120919,
doi: 10.1016/j.jhazmat.2019.120919.
Authorized licensed use limited to: Universiti Tunku Abdul Rahman. Downloaded on June 14,2023 at 06:00:55 UTC from IEEE Xplore. Restrictions apply.
VOL. 7, NO. 2, FEBRUARY 2023
[22] Y. Tu et al., “Ammonia gas sensor response of a vertical zinc oxide nanorod-gold
junction diode at room temperature,” ACS Sens., vol. 5, no. 11, pp. 3568–3575, 2020,
doi: 10.1021/acssensors.0c01769.
[23] D. Wang, D. Zhang, Y. Yang, Q. Mi, J. Zhang, and L. Yu, “Mul-
tifunctional latex/polytetrafluoroethylene-based triboelectric nanogenerator for
self-powered organ-like mxene/metal-organic framework-derived CuO nanohy-
brid ammonia sensor,” ACS Nano, vol. 15, no. 2, pp. 2911–2919, 2021,
doi: 10.1021/acsnano.0c09015.
[24] X. Wang, L. Gong, D. Zhang, X. Fan, Y. Jin, and L. Guo, “Room tempera-
ture ammonia gas sensor based on polyaniline/copper ferrite binary nanocom-
posites,” Sensors Actuators B, Chem., vol. 322, 2020, Art. no. 128615,
doi: 32210.1016/j.snb.2020.128615.