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Archives of Applied Science Research, 2011, 3 (4):256-264
(http://scholarsresearchlibrary.com/archive.html)

ISSN 0975-508X
CODEN (USA) AASRC9

Investigation on the Sol-Gel Synthesis, Structural, Optical and Gas

sensing Properties of Zinc Oxide Nanoparticles
A. Muthuvinayagama, Boben Thomasb, P. Dennis Christyc, R. Jerald Vijaya, T. Manovah
Davidd, and P. Sagayaraja*
a
Department of Physics, Loyola College, Chennai
b
Department of Physics, Mar Athanasius College, Kothamangalam, Kerala
c
Department of Physics, GKM College of Engineering, Chennai
d
Department of Chemistry, Hindustan University, Chennai
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ABSTRACT

Zinc Oxide (ZnO) nanoparticles have been synthesized adopting sol-gel process. The structure of
the obtained product is confirmed by the powder XRD analysis. The influence of size effect on
the optical properties of ZnO nanoparticles is examined using optical absorption spectrum. The
morphology, size and structure of the as prepared ZnO nanoparticles are investigated using
SEM and TEM analyses. In addition, LPG sensing properties is also investigated.

Keywords: Metal Oxide, Semiconductor nanoparticle, ZnO, SEM, TEM, LPG.

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INTRODUCTION

Semiconductor nanocrystals have received much attention because of their special properties in
comparison with those of bulk materials. In particular, Zinc oxide (ZnO) is an important group
II-VI semiconductor with a wide band gap (3.37 eV) and a large exciton binding energy of 60
meV at room temperature [1]. ZnO is an attractive material because of its unique properties,
such as optical transparency, electric conductivity, piezoelectricity and near-UV emission [2].
Nanoparticles of metal oxides are synthesized through different chemical routes. Chemical
methods, such as sol-gel, template growth, and hydrothermal methods, have been proved to be
attractive due to the low growth temperature and easy operation, promising scale-up fabrication
[3]. These wet chemical techniques are usually simple, economical, and versatile, and proved to
be very effective for large scale production [4]. The sol–gel route for obtaining ZnO presents
several advantages over the other techniques. It offers admirable homogeneity, the freedom to

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use both inorganic and organic precursors, potential to fabricate films on large area substrates,
and above all, environmental friendly [5].

Although ZnO is one of the earliest materials developed as a gas sensing material, because of
high operating temperature (around 400 ◦C to 500 ◦C) and poor selectivity, until recently it has
been less popular compared to SnO2. In recent years, several studies are carried out to improve
the performance of ZnO sensors in order to increase the selectivity and to lower the operating
temperature [6]. Most of the attempts are towards the use of ZnO nanoparticles to improve the
sensitivity or with additives for selective sensing of H2, H2S or NH3 gas. These are mostly based
on thin films, which require specific instrumentation as well as high temperature treatment. On
the other hand, thick film sensors are more versatile and amenable for largescale production.
There are some reports on thick film sensors with highly calcined samples [7] and a few on the
sensing of ethanol at an operating temperature of 332 0C. There is hardly any report on liquefied
petroleum gas (LPG) sensors based on ZnO. With the aim of developing a sensor to detect LPG
at comparatively low temperature, an attempt is made to synthesize nanoparticles of ZnO and
study their gas sensing characteristics.

In the present work, ZnO nanoparticles were prepared by employing a cost effective sol-gel
technique. The as-prepared sample was characterized by powder XRD, UV, SEM and TEM
analyses and the results are discussed. The sensitivity of the zinc oxide nanoparticles was
measured as a function of temperature as well as the concentration of the exposed gas.

MATERIALS AND METHODS

2.1 Precursors
Zinc chloride (Merck) is the chemical compound with the formula ZnCl2. It is used as a
precursor in preparing semiconducting zinc oxide nanoparticle in wet chemical methods.
Ammonium hydroxide (NH4OH, Merck) reagent is used in the experiment along with nitric acid
(HNO3, Merck).

2.2 Synthesis of ZnO nanoparticle

All the reagents were purchased from Merck Chemicals and used without further purification. In
a typical synthesis process, 0.05M ZnCl2 was dissolved in a mixed solvent of water (50 ml) and
hydrochloric acid of 0.05M (50 ml) under magnetic stirring. The presence of nitric acid helps to
improve the solubility. The pH of the solution was adjusted to 5.5 using NH4OH. After stirring
for several minutes, the as-prepared white precipitate was separated by centrifugation and
washed with Milli-Q water and ethanol for several times. The obtained product was annealed at
800 oC for 3 hours.

RESULTS AND DISCUSSION

3.1 Powder XRD Analysis

The X-ray diffraction (XRD) pattern of ZnO nanoparticles was obtained on a Philips PW 1730
X-ray diffractometer using CuKα (l=1.5461 nm) radiation. The crystallite size was calculated
from X-ray line broadening analysis by Scherrer formula. Figure 1 shows the X-ray diffraction
pattern of the as-prepared ZnO nanopowder synthesis via sol-gel method. The XRD diffraction

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analysis gives peaks for ZnO nanopowder which are conveniently indexed to the hexagonal
(Wurtzite structure) structure in comparison with the collected data from the standard JCPDS
(PDF NO 80-0075) data. From the XRD pattern of the sample, it is clearly evident that ZnO
particles exhibit good crystalline features. No relevant diffraction peak corresponding to impurity
atoms is observed. Though the broadening of peaks is not significant, the particle size
measurement gives the evidence for the confinement of ZnO crystallites with average size of 12
nm. The Bragg’s peaks indexed at (100), (002), (101), (102), (110) and (103), (112) and (201)
are analogous to bulk hexagonal structure. Lu et al 2008 reported the size of the crystallites of
average size 20.4 nm using a one-step mechanochemical method [1]. Thus, the synthesis
procedure adopted in this work show good control over the size of the nanoparticle.

Fig. 1 Powder X-ray diffraction pattern of ZnO

3.2 UV-Vis Absorption Spectral Analysis

The UV–Vis absorption spectrum was recorded in the region 200 to 800 nm using CARY 5E
spectrophotometer (Fig. 2). The optical study was performed to evaluate the potentially useful
optical qualities of the nanoparticles. The energy gap is found to be 4.12 eV, which higher than
the bulk ZnO material by 0.85 eV. The blue shift in the excitonic absorption clearly indicates the
quantum confinement property of nanoparticles. In the quantum confinement range, the band gap
of the particles increases, resulting in the shift of the absorption edge to lower wavelength as the
particle size decrease.

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4
Absorption (a.u)

0
200 300 400 500 600 700 800
Wave Length (nm)

Fig. 2 UV-Vis absorption spectrum of ZnO nanoparticles

3.3 Scanning Electron Microscopy

The SEM images were recorded using JEOL JSM 6310 scanning electron microscope. As the
surface to volume ratio is the dominant factor in nanostructured materials, probing the materials
surface features is the prerequisite for many important applications. Figure 3 shows the SEM
micrograph of ZnO nanoparticles prepared with mixed solvent of water-nitric acid. The image
indicates nearly spherical structures. They reveal the formation of nanocrystalline materials and
show the randomly oriented aggregates of nanoparticles with variable sizes. Zinc oxide
nanoparticles are prone to aggregate due to the large surface area and high surface energy.

Fig. 3 SEM micrograph of ZnO nanoparticles

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3.4 Transmission Electron Microscopy
M
The identification of particle morphology and the particles size measurements were conducted
using transmission electron microscopy (JEOL JEM 3010). The morphology of ZnO particle was
examined from TEM images and it is shown in Figure 4. The average particles sizes of ZnO
nanoparticles are estimated to be 10-12 nm. The TEM image further revealsreveal the formation of
nanostructure having different orientations and aggregates of particles with different shapes. The
ZnO nanoparticles achieved here are nearly spherical with some faceting. The larger particles
size is just be aggregates of small particles. The particles appear mostly in coalesced condition
but with moderate level of agglomeration.

Fig. 4 TEM image of ZnO nanoparticles

3.5 LPG Gas Sensing Properties

It is well known that the response of the metal oxide semiconductor sensors is mainly determined
by the interactions between a target gas and the surface of the sensors. Due to the greater surface
area of nanostructured
ostructured materials, its interaction with the adsorbed gases is stronger, leading to
higher gas response.

High surface-to-volume
volume ratio (available due to nanocrystalline nature) allows gas to interact with
larger surface area giving ultra large gas response. The characteristics of gas sensors are strongly
influenced by the properties of the sensing material. Many different metal oxides,
oxides namely zinc
oxide (ZnO), tin oxide (SnO2), titanium dioxide (TiO2) are currently being investigated for their
applications as gas sensors [8].
[8]. ZnO is a popular material for solid state gas sensors and has been
employed invarious forms such as sintered pellets, thick films, thin films and hetero junctions
[9].. Undoped and doped ZnO thin films were investigated by many rresearchers
esearchers for gas sensing
toxic and combustible gases [10].
[10]. There are still many critical limitations of commercial sensors
sensor
based on thin film semiconductor
semiconductor metal oxides such as high operating temperatures and poor
selectivity [11]. Various methods like spray s pyrolysis, sol–gel,
gel, electro
electro-spinning and
hydrothermal method are being used for the synthesis of zinc oxide nanostructures [12]. In our
work, we report the development of highly sensitive ZnO nanoparticles based gas sensor for
LPG detection. Gas-sensingng mechanism of ZnO-based
ZnO based sensors belongs to the surface
surface-controlled

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type, that is, the resistance change is controlled by the species and amount of chemisorbed
oxygen on the surface. However, for LPG, the reaction mechanism is quite complex and
proceeds through several intermediate steps, which are not yet fully understood. At an operating
temperature, in the absence of a target gas, oxygen gets adsorbed on the surface of the sensor and
it extracts electrons from the conduction band of the sensor material, which can be explained by
the following reactions[13-14]:

O2(gas) O2(ads) (1)

−
O2(ads) +e O2(ads)− (2)
O2(ads)− +e− 2O(ads)− (3)

Thus, the equilibration of the chemisorption process results in stabilization of surface resistance.
Any process that disturbs this equilibrium gives rise to changes in the conductance of the
semiconductors (Dayan et al 1998). It is well known that LPG consists of CH4, C3H8, C4H10, etc.,
and in these molecules the reducing hydrogen species are bound to carbon atoms. Therefore,
LPG dissociates less easily into reactive reducing components on the zinc oxide surface. The
overall reaction of LPG molecules with adsorbed oxygen can be explained as follows [15]:

CnH2n+2 +2O− H2O + CnH2n–O + e− (4)

Where, CnH2n+2 represents the CH4, C3H8 and C4H10.

60

58
500 ppm
1000 ppm
56 1500 ppm
2000 ppm
54
Sensitivity (%)

52

50

48

46

44

42

40
180 200 220 240 260 280 300 320 340 360
o
Temperature ( C)

Figure 5 (a): Sensitivity as a function of operating temperature for ZnO nanoparticle

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70

o
350 C
65 o
300 C
o
250 C
o
60 200 C
Sensitivity (%)

55

50

45

400 600 800 1000 1200 1400 1600 1800 2000 2200

LPG concentration (ppm)

Figure 5 (b): Relationship between sensitivity and LPG concentration

The as-prepared ZnO nanopowder was mixed thoroughly with the binder polyvinyl alcohol
(PVA) with the help of a mortar and pestle then cold pressed using a dye of 1 cm diameter in a
hydraulic press with an applied pressure of 4 tons/mm2. The thickness of the pellet was kept as
1.5 mm. Sintering of the pellet was done at 300 oC for one hour to provide physical strength and
electrical properties by the reaction of the pellet components and partly by O2 in the air ambient
furnace. In addition, the moisture content is also removed completely. Later the pellet was taken
out of the furnace and allowed for natural cooling for about an hour before using it as a sensor.
Then ohmic contact was made to form the sensing element with the help of highly pure silver
paste. The gas sensing study was carried out in a static gas chamber to sense LPG in air ambient.
The sensor was kept directly on a heater in the gas chamber and the temperature was varied. The
temperature of the sensor was monitored by the chromel-alumel thermocouple which was kept in
contact with the sensor. A known volume of the LPG was introduced into the gas chamber
prefilled with air and it was maintained at atmospheric pressure. Before exposing to the LPG, the
sensor was allowed to establish equilibrium inside the gas chamber for about one hour at
operating temperature. The experiment was repeated several times to measure the sensitivity as a
function of the operating temperature.

The electrical resistance of the sensor was measured employing a model 2400 Keithley
electrometer before and after exposing it to the LPG. The exposure time of the gas was
maintained as 10 min for all the measurements. In the case of ZnO nanoparticle based sensor, the
response time was found to vary between 50 to 60 seconds and the corresponding recovery time
was around 4 to 5 minutes. To investigate the gas sensing properties of ZnO nanoparticles, the
fabricated sensor was tested at different temperatures ranging from 200 to 350 oC in steps of 50

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o
C to optimize working temperature. The sensitivity was measured with LPG at concentrations of
500, 1000, 1500, 2000 ppm.

The Figure 5 (a) shows that the sensitivity as a function of operating temperature for ZnO
nanoparticles with LPG. The gas response increases with an increase in the operating
temperature and attains a maximum at around 250 oC, followed by a decrease in the sensitivity
with further increase in the operating temperature. The bell shaped distribution of gas response
against the operating temperature indicates that optimum performance is achieved at 250 oC for
LPG. The formation of bell shaped response of the sensor is identical to those reported for SnO2
based sensor for LPG [16-17]. Interestingly, the observed optimum temperature of 250 oC is
almost the same with varying concentration of LPG. The dependence of the sensitivity of the
ZnO nanoparticle on the LPG concentration at different operating temperature is shown in Figure
5 (b), which suggests the linear response of sensitivity with the increasing concentration of LPG.

CONCLUSION

Synthesis of ZnO nanostructures has been achieved using a single- step and low cost sol-gel
process. The powder XRD pattern confirmed the structure of the obtained product. The optical
absorption spectrum indicated a significant blue shift in the excitonic absorption for the ZnO
nanoparticles when compared to bulk counterpart. TEM images show the formation of spherical
particles of size between 10-12 nm. The sol-gel route employed in this work is simple, cost
effective and free of pollution and therefore, the technique can be extended to prepare many
other important semiconducting metal oxide nanoparticles. The gas sensing results reveal that
ZnO has remarkable LPG sensing characteristics which make them promising material for high
sensitive detection of toxic and combustible gases for practical application.

Acknowledgement
The authors wish to thank the UGC for financial assistance through Major Research project (F.
No. 38-128/2009 (SR) dated 19th Dec 2009) at Mar Athanasius College, Kothamangalam,
Kerala.

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