Insan Akademika

Publications
INTERNATIONAL JOURNAL
OF BASIC AND APPLIED SCIENCE
P-ISSN: 2301-4458
E-ISSN: 2301-8038

Vol. 01, No. 01
July 2012
www.insikapub.com


14
Synthesis of Liquefied Petroleum Gas (LPG) Sensor based on Nanostructure
Zinc Oxide using Chemical Bath Deposition (CBD) Methods

Muhammad Iqbal
1,2
, Brian Yuliarto
2
, Nugraha
2


1
Research and Community Service Institute, Sekolah Tinggi Teknologi Garut
Jl. Mayor Syamsu No. 1, Garut Indonesia
m.iqbal@tf.itb.ac.id

2
Engineering Physics Research Group, Institut Teknologi Bandung
Jl. Ganesha No. 8, Bandung-Indonesia


Key words Abstract

Zinc Oxide;
Porous Thin Layer;
Liquefied Petroleum Gas;
Chemical Bath Deposition

Porous thin layer of zinc oxide have been made using chemical bath deposition
method with the precursor of zinc nitrate tetrahydrate on a substrate of alumina
(Al
2
O
3
). The morphology of the formed layer has the form of sheet structure and
flowerlike structure. ZnO layers showed the lack of oxygen. Conductivity sensors
varies with changes in operating temperature, the higher the operating
temperature, the higher the conductivity. The best performance shown by the
sensors with 100% solvent composition of water (sheet structure) at a temperature
of 200
o
C with a sensitivity of 44.83%, 80 seconds response time and 90 seconds
recovery time. The sensor is able to detect the presence of LPG and also can
measure the concentration of LPG.

2012 Insan Akademika All Rights Reserved



1 Introduction

Metal oxide semiconductors that featured on the optical and electrical properties, have been widely used as
an electrochemical device, such as chemical sensors (Hashimoto, et. al., 2005], photocatalyst (Yuliarto, et.
al., 2006), and dye-sensitized solar cell (Gratzel, 2003). One use of metal oxide semiconductor materials as
chemical sensors is to sense and to detect the presence of harmful gases, among others, carbon monoxide,
VOCs, and Liquefied Petroleum Gas (LPG). As we know, gas is a chemical compound consisting of the
elements and can react with other elements. In particular, it has learned that certain gases can react with the
nanostructure metal oxide semiconductor sensitive layer. This fact is what makes nanostructure metal oxide
semiconductor sensitive layer used as the gas sensor or detector. Gas sensors made from metal oxide
semiconductors are good for detecting hazardous gases such as SnO
2
, ZnO, TiO
2
, and MoO
3
. Types of
semiconductor sensors are highly sensitive, economical, has a fast response, and low energy consumption
(Elmer, et. al., 2007)

Utilization of metal oxide semiconductor as an electrochemical device, must have a porous structure. Recent
research has shown that the sensitivity of the sensor can be improved if the use of sensors that have a
mesoporous or nanoporous structure. Layer with a porous structure will have a specific surface area large
enough to improve the process of electrochemical reactions take place at the contact area between the oxide
Iqbal, et. al. International Journal of Basic and Applied Science,
Vol 01, No. 01, July 2012, pp. 14-21

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material with a reagent substance. Materials with pore size or even smaller micro can support a more
effective mass transfer.

The development of material processing techniques in the early years, allows us to get the shape in the form
of metal oxide semiconductor thin films with nanometer-sized pores. Has been learned from previous studies
that a thin layer of porous metal oxide semiconductor can be made using the Chemical Bath Deposition
(CBD) (Wu, et. al., 2008) CBD is a simpler method and less expensive than its predecessor with some
methods such as Chemical Vapor Deposition (CVD), one-step soft solution, spray pyrolisis, and anodization.
CBD method is done by simply immersing the substrate into a solution of aqueous metal salt which are
controlled by temperature condition, pH and duration of immersion (Wang and Xie, 2006).

Meanwhile, the metal oxide semiconductor materials are widely used for the fabrication of gas sensors is
zinc oxide (ZnO). This is due to ZnO is n-type semiconductor which has some very good electrical
properties for use as sensors, such as having a high mobility of conduction electrons, is stable to chemical
treatment and heat treatment, conductivity varies with the concentration of adsorbed gases and contains no
toxins (Wu, et. al., 2008; Wang and Xie, 2006)


2 Experiment

To prepare ZnO, CBD solution was synthesized from zinc nitrate tetrahydrate and the dissolving of urea in
the DI water. Zinc nitrate tetrahydrate and aqua DM + ethanol was dissolved at room temperature and stirred
using a magnetic stirrer for 30 minutes. Urea is added to the solution and stirred for 30 minutes to produce a
homogeneous solution. Alumina substrate has been cleaned up soaked and placed in a standing position on a
clear solution. Substrates were immersed in clear CBD solution, kept in the urnace at a temperature of 60
o
C
for 24 hr. Substrates have been deposited are removed from the place of immersion and washed using
acetone to stop the growth of crystals. Then the films were rinsed in DI water several times and dried at 60
o
C
for one hour in air atmosphere. A transformation into zinc oxide was conducted by calcination of the films at
300
o
C in air atmosphere for 30 minute with 20
o
C/minute heat rate (Ariyanto, et. al., 2009).

The resulting nanostructure ZnO film is confirmed using several materials characterization tools including
Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS), and X-Ray Diffraction
(XRD). Morphology of the nanostructure ZnO is known by Scanning Electron Microscopy measurement.
Purity of nanostruscture ZnO formed on the substrate was analyzed by Energy Dispersive Spectroscopy
measurements and crystalline phase of ZnO was analyzed by X-Ray Diffractometer using Philips Analytical
X-Ray. Diffraction patterns obtained with Cu radiation ( = 1.54060 ) through generator voltage of 40 kV
and current 25 mA. Tool set in step scan mode with 0.02 2 step size and 0.5 seconds step time in the range
20
o
-90
o
2 degree.


3 Result and Discussion

The Fig. 1 and Fig. 2 shows the results of XRD and EDS measurements on samples of the sensor which is
made from solvent with composition 100% of water. From XRD results, indicated that the zincite crystalline
phase was successfully formed and not indicated of another formation crystalline phase. Intensity of a
significant peak occurs at certain angles and this is in accordance with the standards of the Joint Committee
on Powder Diffraction Standards (JCPDS).


International Journal of Basic and Applied Science,
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Iqbal, et. al.

16 Insan Akademika Publications


Figure 1. X-Ray Diffraction patterns of nanostructure ZnO




Figure 2. Energy Dispersive Spectroscopy spectrum of nanostructure ZnO


The Fig. 2 shows EDS spectrum measurements of nanostructure ZnO. From the spectrum, can be seen that
there are no elements in the sample other than that of Zn and O. Table 1 shows the results of quantitative
analysis performed by EDS instrument. From the table can be known mass and atomic percentage of Zn and
O. Comparison of the percentage of Zn and O atoms are not exactly 1:1, but 1:0.996. This shows that the
ZnO layer is formed, there are lattice defects such as oxygen vacancy.


Table 1. EDS quantitative analysis result

Elements Mass% Atom%
O 19.60 49.90
Zn 80.40 50.10
Total 100.00 100.00


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Figure 3. Surface morphology of two sensors, (a) sheet structure and (b) flowerlike structure, (c) porous
of nanostructure ZnO


Fig. 3 shows the micrograph of the surface morphology of the sensors which synthesized with 100% water
and 75% water + 25% ethanol solvent composition. Sensors with 100% water solvent composition, grain
could be sheet-shaped structure. While the sensor is at 75% water + 25% ethanol solvent composition, which
formed a flowerlike morphological structure.

The LPG-sensing mechanism of the nanostrucure ZnO may be explained as follows. The adsorption of
atmospheric oxygen on the film surface forms ionic species such as O
2

and O

which acquire electrons from

the conduction band (Sahay and Nath, 2008). The reaction kinetics is as follows:

O
2
(gas) O
2
(ads)
O
2
(ads) + e
-
O
2
-
(ads)
O
2
-
(ads) + e
-
2O
-
(ads)

International Journal of Basic and Applied Science,
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Iqbal, et. al.

18 Insan Akademika Publications

Although the reaction mechanism for LPG is quite complex and proceeds through several intermediates
which are yet to be fully understood, but the overall reaction of LPG molecules with adsorbed oxygen
species may be explained as follows:

C
n
H
2n+2
+ 2O
-
H
2
O + C
n
H
2n
:O + e
-

C
n
H
2n
: O + O
-
CO
2
+H
2
O + e
-


Here, C
n
H
2n+2
represents CH
4
, C
3
H
8
, C
4
H
10
, etc. while C
n
H
2n
:O represents partially oxidized intermediates on
the ZnO surface. Thus, during oxidation LPG liberates electrons into the conduction band, thereby
decreasing the resistance of the film upon exposure to LPG (Sahay and Nath, 2008)

The Fig. 4 shows the relationship between the resistance (ohms) and time (seconds). This figure is one
example that shows the typical dynamic characteristics of the dynamic response of sensors in this study. The
Fig. 4 shows that the exposure of LPG gas yield change in resistivity indicate that the sensor has sensitivity
for LPG gas. The resistivity decrease as the exposure of LP gas and back to the initial line when the LP gas is
stopped. This phenomenon indicate that the nanostructure of ZnO absorp the LP gas and desorp very well.



Figure 4. Typical dynamic response of nanostructure ZnO


The Fig. 5 shows the gradient of conductivity of the sensor sheet structure and flowerlike structure. From the
figure could be seen that the higher operating temperature, the higher the conductivity sensor. Differences in
conductivity sensors increased along with the higher operating temperatures. With increasing temperature the
concentration of electrons in the conduction band will increase because electrons originating from lattice
defects (for ZnO are oxygen vacancies) are thermally excited into the conduction band. This phenomenon
can be explained by the equation:

n
c
= (N
c
N

)
12
. c
j-
E
g
kT
[
....(1)

where n
e
is the electron charge carrier concentration and energy gap E
g
is the width of the gap energy, k
Boltzmann constant, and T the absolute temperature sensor in Kelvin. While N
c
and N
v
are the effective
density of conduction band energy level and the valence band. From equation (1) above is known that higher
operating temperatures will cause the increase of charge carrier so that the conductivity will increase.
Conductivity sensors appear higher sheet structure due to the dense morphology of the surface layer, as
shown in Fig. 3(a).

If we analyze performance based on the morphology formed in each solvent composition, the performance of
the detection sensor to the shape of sheet structure would be better because the grains look more densely. In
other words, as shown by Fig. 3(a), a closer linkage of the grains making it easier for electron transfer from
one grain to another grain. Meanwhile, as shown by Fig. 3(b), grains on the morphology of flowerlike
structure, look relatively less densely.
Iqbal, et. al. International Journal of Basic and Applied Science,
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Figure 5. Conductivity of sensors


The Table 2 shows differences in response time and recovery time from a variety of sensor. From the table it
can be seen that the operating temperature has an influence on the sensor response time. Response time and
recovery time become faster at the higher operating temperatures.


Table 2. Response time and recovery time of sensors

Sensors Operating Temperature Response Time (secs) Recovery Time (secs)
Sheet structure
100
o
C 120 150-160
150
o
C 110 140
200
o
C 80 100
250
o
C 80 90
Flowerlike structure
100
o
C 110 140
150
o
C 110 130
200
o
C 90 90
250
o
C 90 90


The sensitivity of sensors is calculated using convensional formula of sensitivity (Eq. 1) as LPG possesses
the properties of reducing gas.


...(1)


where R
a
is the resistance of the sensor in air and R
g
is that upon exposure to LPG.

The comparison of sensitivity as a function of operating temperature has also been studied. The sensitivity
for all sensors increase as the increasing of operating temperature from 100
o
C until 250
o
C. The significance
increasing happened when the operating temperature increase from 100
o
C to 200
o
C. The optimum sensitivity
of sensors is happened at the sheet structure sensor operated at 250
o
C. This phenomenon shows that the
% 100

=
a
g a
R
R R
y Sensitivit
International Journal of Basic and Applied Science,
Vol 01, No. 01, July 2012, pp. 14-21
Iqbal, et. al.

20 Insan Akademika Publications

higher temperature make the surface structure of materials being open so that it can receive the LP gas better
than that is lower temperature. From the Fig. 6 could be seen that the higher operating temperature, the
higher sensitivity sensor.



Figure 6. Comparison of sensitivity at 100
o
C, 150
o
C, 200
o
C and 250
o
C operating temperatures.


The sensitivity for different concentration of LP gas also has been investigated. The sensor received different
concentration at 200 ppm, 400 ppm and 800 ppm. The resistivity change in different value for those
concentrations indicate that the sensors has different sensitivity for different concentration of LP gas. The
different sensitvity will make the sensor can be used as the concentration detection instruments.



Figure 7. Comparison of sensitivity at 200 ppm, 400 ppm and 800 ppm concentration of LPG



Iqbal, et. al. International Journal of Basic and Applied Science,
Vol 01, No. 01, July 2012, pp. 14-21

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4 Conclusions

Electrochemical sensors made from nanostructure zinc oxide has been successfully synthesized by chemical
bath deposition with zinc nitrate tetrahydrate precursors. Studies on the effect of solution composition on the
morphology of the sensitive layer indicates that the sensor sheet structures (100% water solvent composition)
has a higher sensitivity than the sensor flowerlike structures (solvent composition of 75% water + 25%
ethanol).

The sensor sheet structures has a maximum sensitivity of 44.83% at a temperature of 200
o
c and 800 ppm lpg
levels. While the sensor flowerlike structures has a maximum sensitivity of 37.02% at the same temperature
and level of LPG. Furthermore, the sensor sheet structures has the smallest response time of 80 seconds and
the smallest recovery time of 90 seconds at a temperature of 250
o
c. While sensor flowerlike structure has the
smallest response time of 90 seconds and the smallest recovery time of 90 seconds at a temperature of 200
o
c
and 250
o
c. LPG sensor can be used not only to detect the presence of LPG, but also can be used to measure
the concentration.


Acknowledgments

The work was financially supported by the Ministry of National Education, Republic of Indonesia, National
Strategic Research Grant (Hibah Strategis Nasional) which is gratefully acknowledged. The paper has been
presented at The 3
rd
Nanoscience and Nanotechnology Symposium Bandung, Indonesia, 16
th
June 2010,
Intitut Teknologi Bandung.


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