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Materials Today: Proceedings 17 (2019) 976–981 www.materialstoday.com/proceedings

RAMM 2018

Performance of zinc oxide particles as liquid ethanol sensor

H.A. Hamid1,2, Z. Lockman1, T. Hattori3, K. A. Razak1,4 *

1
School of Materials and Mineral Resources Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang,
Malaysia
2Faculty of Applied Sciences, Universiti Teknologi MARA, 13500 Permatang Pauh, Penang, Malaysia
3
Department of Electrical and Electronic Engineering, Faculty of Engineering, Toyohashi University of Technology, 1-1 Hibarigaoka,
Tempakucho, Toyohashi-shi, Aichi 441-8580, Japan
4
NanoBiotechnology Research & Innovation (NanoBRI), INFORMM, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia

Abstract

In this work an electrode for detection of ethanol has been developed using zinc oxide (ZnO) particles grown by
annealing process with zinc oxide seeds. Zinc oxide particles were grown on an indium tin oxide (ITO) substrate
and accumulated in globular shapes. The morphology and crystallinity of the ZnO/ITO were determined by field
emission scanning electron microscopy (FESEM) and X-ray diffractometer (XRD). The diameter of particles was
~50 to 58 nm. The ZnO/ITO electrode was used to detect ethanol in liquid in the range of 7-25 mM by using three
electrodes cyclic voltammetry (CV) system in 1M potassium hydroxide (KOH) electrolyte solution. The ZnO/ITO
electrode shows high sensitivity of 8.14 µAmM-1.cm-2, with detection limit of 2.4 mM and linear correlation
coefficient of 0.9682. Therefore, ZnO/ITO electrode has an excellent potential as the ethanol sensor in liquid.

© 2019 Elsevier Ltd. All rights reserved.

Selection and peer-review under responsibility of the scientific committee of the 6th International Conference on Recent Advances in Materials,
Minerals & Environment (RAMM) 2018.

Keywords: Zinc oxide particles; ethanol sensor; cyclic voltammetry.

* Corresponding author. Tel.: +6043822638; fax: +6043822768.

E-mail address: khairunisak@usm.my

2214-7853 © 2019 Elsevier Ltd. All rights reserved.

Selection and peer-review under responsibility of the scientific committee of the 6th International Conference on Recent Advances in Materials,
Minerals & Environment (RAMM) 2018.
 H.A. Hamid et al. / Materials Today: Proceedings 17 (2019) 976–981 977

1. Introduction

Ethanol is a volatile organic compound that is highly toxic and carcinogenic and may have long term impacts on
human health as well as the ecosystem. Ethanol is colorless, volatile, highly flammable liquid that has mild and
pleasant odor. Ethanol consists of hydroxyl group that makes ethanol a sub-structure of the water molecule and can
mix well with other solvents and water. High exposure to ethanol can increase the risk of cancer in the upper
respiratory and digestive system, as well as affecting liver damage and possibility of breast cancer for women.
Therefore, early detection is crucial for environment protection purposes.
In order to sense and analyze ethanol existence in the environment, numerous tools and methods have been used
diversely such as high performance liquid chromatography [1], mass spectroscopy [2] and UV-visible
spectrophotometer [3]. These instruments are not-portable, costly, complicated handling execution and cannot be
categorized as low cost sensors. Therefore, it is important to develop portable and cheap electrode with high
sensitivity for ethanol detection in liquid phase. Metal oxide semiconductors have attracted significant interest
owing to their potential uses in accurate, sensitive and reliable detector for ethanol detection. ZnO has advantages of
wide band gap, stable morphological structure and inexpensive [4]. Bairui et al. reported on an amperometric
ethanol detection using silicon nanowires covered with co-deposited palladium-nickel (Pd-Ni/SiNWs) as their
working electrode [5]. On the other hand, Ileana et al. reported on ethanol detection using palladium nanoparticles in
alkaline media using cyclic voltammetry [6]. Tavakolian et al. reported on ethanol detection using cyclic
voltammetry using palladium-zinc oxide nanoparticles as their working electrode [4]. Electrochemical sensor is
chosen owing to its portability, simple experimental preparation, low cost, stable and accurate.
In this work, a simple method was used to prepare ZnO particles, which undergo short time drying in an oven
followed by annealing process. The method is relatively inexpensive, ease supervision and works at low annealing
temperature. To the best of our knowledge, limited evidence can be acquired on using undoped ZnO particles for the
detection of ethanol in liquid phase using a modest and reliable cyclic voltammetry (CV) technique. The ZnO
particles offer a low-cost and portable electrode that could be exploited in environmental monitoring.

2. Experimental methods

In this work, the 2x1 cm indium tin oxide (ITO) electrodes with sheet resistance of 10 Ω/sq were used as
substrates. The ITO substrates were immersed for 20 minutes in the mixed solution of ammonium hydroxide
(NH4OH), hydrogen peroxide (H2O2) and distilled water in a ratio of 1:4:20 and heated at 60 °C. ITO electrodes
were rinsed with distilled water and immersed again in 2-propanol before dried in an oven. Sol-gel technique was
used to prepare zinc oxide seeds by dissolving zinc acetate dehydrate in 15 mL methanol. The mixture was stirred
vigorously for 20 minutes at 60 °C. Then, 15 mL ethanolamine was added into the mixture under constant stirring
for 2 hours. The mixture was aged at room temperature for 24 hours. The ZnO seeds layer was drop casted on an
ITO electrode and dried in an oven for 20 minutes at 150 °C. This process was repeated three times. The coated ITO
electrodes were placed in a furnace for 2 hours at 500 °C for annealing process. The morphology of ZnO particles
was examined using Field Emission Scanning Electron Microscopy (FESEM) (Zeiss SUPRA 35VP at 5 kV). The
ZnO seeds phase was analyzed using X-Ray Diffractometer (P8Advan-Bruker) with Cu Kα radiation (λ=1.54 Å) in
the range of 20-65°, with a step size of 0.02°. The electrochemical measurement was performed using a three
electrode system (Metrohm Autolab) at room temperature where the ZnO/ITO acted as the working electrode. An
Ag/Cl was used as the reference electrode and platinum as the auxiliary electrode. 1M KOH was used and kept
constant at 25 mL during the experiment. The effect of ethanol concentration ranging from 7 to 25 mM of the
ZnO/ITO electrode in ethanol was studied.
978 H.A. Hamid et al. / Materials Today: Proceedings 17 (2019) 976–981

3. Results and discussion

FESEM image of ZnO particles is shown in Fig. 1. The morphology of the grown ZnO particles is densely
packed, homogeneous and uniformly distributed on the electrode. The diameter of each ZnO particle formed is ~450
nm. Each ZnO particle contains nano-grains with average diameter of ~52 nm as shown in Fig. 1 (inset).

Fig. 1 SEM image of ZnO particles on electrode after annealing for 2 hr at 500 °C. Inset is an enlarge image of the particle composed of nano-
grains.

The crystallinity nature of ZnO/ITO electrode was further analyzed by XRD as presented in Fig. 2. All
reflections peaks could be indexed to hexagonal wurtzite structure ZnO, which is in good agreement with the
literature (ICDD card No.00-036-1451) [7]. From the XRD result, the ZnO particles are highly crystalline. The
strong intensity of (002) peak demonstrated the growth of ZnO is in the c-axis direction [8]. There is no impurity
phase was detected from XRD analysis.

Fig. 2 XRD pattern of ZnO particles.

Fig. 3 shows the cyclic voltammetry (CV) current response of ZnO/ITO electrode in the absence and presence of
7 mM ethanol in 1.0 M KOH. The sweep rate was 50 mV/s in the potential range -1.0 to 0.5 V. As shown in Fig. 3,
there is no obvious peak detected in the absence of ethanol signifying no redox reaction occurred. On the other hand,
 H.A. Hamid et al. / Materials Today: Proceedings 17 (2019) 976–981 979

the oxidation peak is clearly observed in the presence of ethanol. The appearance of peak after addition of ethanolis
due to increase of current value compared to without ethanol, which suggests the good electro-catalytic oxidation
happens on the surface of the ZnO/ITO electrode. Similar finding was observed by the other researchers [9].
Moreover, ZnO/ITO electrode shows excellent electron transfer activities due to its spherical structures which has
high surface area and excellent adsorption capability towards the ethanol analytes as observed in Fig. 3.

Fig. 3 Cyclic voltammetry of ZnO/ITO electrode in the absence and presence of ethanol in 1.0 M KOH at scan rate of 50 mV/s.

Fig. 4 (a) presents the CV curves of the ZnO/ITO electrode with different ethanol concentration ranging from 7
to 25 mM. From the figure, it can be seen that the current peaks increased with increasing ethanol concentration.
The current increases remarkably due to the adsorption of ethanol molecules on the surface of ZnO/ITO electrode.
Fig. 4 (b) displays the calibration plot of the ZnO/ITO electrode with good linearity of current with respect of
ethanol concentration. The sensitivity, limit of detection and linear dynamic range calculated from the slope are 8.14
µAmM-1.cm-2, 2.4 mM and 0.9682, respectively. The comparison of ethanol detection using various electrode is
tabulated in Table 1.

Fig. 4 Cyclic voltammetry of ZnO/ITO electrode at different ethanol concentration ranging from 7 to 25 mM and (b) calibration plot of anodic
peak.
980 H.A. Hamid et al. / Materials Today: Proceedings 17 (2019) 976–981

Table 1. A comparison of various working electrodes in ethanol sensing.

Working electrode Limit of detection Linear dynamic range Reference
Pd-Ni/ SiNWs 6 µM 3.4 mM-17.1 M [4]
PdNPs/GCE 1.1 mM 6.25 mM-50 mM [5]
Pd-ZnO/CPE 20.3 µM 1.99 mM-3.35 M [6]
ZnONPs/ITO 2.4 mM 7-25 mM This work

Fig. 5 presents the schematic illustration for the sensing mechanism of the ZnO/ITO electrode. ZnO, as a typical
n-type metal oxide semiconductor involves in the surface-controlled conductivity to detect analytes. When ZnO/ITO
electrode is exposed to air as shown in Fig. 5 (a), oxygen molecules are adsorbed on the surface of ZnO/ITO
electrode and then attract electrons from the conduction band of ZnO to form oxygen negative ions species such as
O2-, O- or O2 [10]. These oxygen species could increase the depletion layer on the surface of ZnO/ITO electrode,
thus decrease the conductivity of the ZnO/ITO electrode. Fig. 5 (b) demonstrates the ZnO/ITO electrode sensor after
exposure to ethanol analyse. The oxygen species on surface of ZnO/ITO electrode reacts with the ethanol molecules
and discharge electrons back to the conduction band of ZnO/ITO electrode as revealed by Fig. 5 (c). As a result, the
depletion layer becomes thin and the ZnO/ITO electrode resistance decreases [4]. Therefore, ZnO particles can be
used competently for a high performance of liquid ethanol sensing.

(a) (b) (c)

Fig. 5 Sensing mechanism of ZnO/ITO electrode with ethanol analytes before and after ethanol injection.

4. Conclusion

In this work, ZnO/ITO electrode was successfully fabricated for the ethanol sensor application by using simple
annealing process. The morphology of ZnO particles were confirmed by SEM and showed each particles were in
diameter of ~50 nm which aggregated together to form sub-micron particles ZnO. The ZnO particles modified ITO
electrodes were used for the detection of ethanol in liquid phase using simple and reliable cyclic voltammetry
technique. The analytical performances of the ZnO/ITO electrode exhibited sensitivity of 8.14 µAmM-1cm-2,
detection limit of 2.4 mM and linear correlation coefficient of 0.9682. The produced ZnO particles could be used as
an effective ethanol sensor for environmental sensor.
 H.A. Hamid et al. / Materials Today: Proceedings 17 (2019) 976–981 981

Acknowledgements

The authors appreciate the technical supports from the School of Materials and Mineral Resources and Institute
for Research in Molecular Medicine (INFORMM), Universiti Sains Malaysia. This research was funded by a RU
top down grant 1001/Pbahan/870049 and Bridging Fund 304/PBahan/6316181.

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