Effect of pH on the structural, optical and gas sensing

properties of SnO2 nanostructures

Gurpreet Singh1, a),Aman1,b), Amit1,c) and Ravi Chand Singh1, d)

1
Department of Physics, Chandigarh University, Gharuan, Mohali
2
Department of Physics, Guru Nanak Dev University, Amritsar, India
a)Corresponding author: gurpreetnano21@gmail.com
b)amankajal721@gmail.com
c)amitphour721@gmail.com
d)ravichand.singh@gmail.com
Abstract - In this paper, we study effect of pH on the structural, optical and liquid petroleum
gas (LPG) sensing properties of SnO2 nanostructures. SnO2 samples with varying pH (8, 9 and
10) have been prepared by using co-precipitation method. The synthesized samples were
characterized using various techniques such as X-ray diffraction (XRD), field emission scanning
electron microscopy (FESEM) and photoluminescence spectroscopy (PL). XRD investigation
revealed tetragonal rutile structure of SnO2 nanoparticles. Excitingly, crystallite size has been
reduced with increase in pH of solution which is ascribed to creation of huge number of
nucleation sites created just at the time of nanoparticles synthesis. FESEM results showed
spherical morphology of SnO2 nanostructures. PL results indicated that defect concentration
rises with increase in pH of solution. The thick films sensors fabricated from power samples
exhibited enhanced sensor response towards LPG gas. It has been observed that sensor response
towards LPG increases with increase in pH of SnO2. The enhanced sensor response towards
LPG is attributed to the reduced crystallite size and large number of defects present such as
oxygen vacancies in SnO2. The oxygen vacancies enhance the adsorption of gas on the surface
of SnO2 sensor. Moreover, in the present work an attempt is made to enhance the surface active
sites on the surface of SnO2 for the adsorption of LPG.

Introduction –
As due to science and technology there has been lot of innovation and
which has made our lives much easier by providing ample facilities to us but side by side there is
a dark side means due to industrialization and urbanization pollution has reached next level, so to
monitor, control the amount of various toxic gases present in our environment gas sensor are
widely used in day to day life. Here SnO2 ( n type semiconductor) based gas sensor is used
because of its interesting properties like low cost , high sensitivity , fast recovery time and
response , long lifespan etc. and as here we are dealing with SnO2 nanostructures so due to their
large surface to volume ratio our efficiency and response of gas sensor reaches next stage .
Although there are various methods to increase the sensitivity of gas sensor like doping, adding
additives, sensor geometry but here in this report we are dealing with the effect of pH on the
structural, optical and gas sensing properties of SnO2 nanostructures which is synthesized by
chemical method.
 Experimental-
In synthesis of SnO2 nanoparticles we have adopted a simple co-precipitation method
using chemicals. Initially we took 0.2M solution of Sncl 4.5H2O was prepared in
distilled water into which we added ammonium hydroxide solution drop wise, while
stirring continuously up to time the pH 9 is reached. It leads to formation of white
precipitates which then were filtered, dried and finally claimed at 500 0C. For XRD
analysis of synthesized nanoparticles Shimadzu 7000 diffractometer system at
diffraction angles ranging from 20 to 80 degrees is used. Photoluminescence (PL)
spectra of powder samples have been analyzed by Perkin Elmer L855 fluorescence
spectrometer. FESEM (Field Emission Scanning Electron Microscope) has been done
with Zeiss SUPRA 55.

Results and discussion –

Figure.1 represents XRD pattern of SnO2 nanoparticles with different pH. All
diffraction peaks of nanoparticles correspond to rutile type tetragonal structure of
SnO2. The crystallite size has been calculated using following relation:
D=0.9/cos
Where  is wavelength of incident X- rays,  is the full width at half maximum,
 Is the Bragg’s angle
Table 1.1 clearly represents the crystallite size decrease with the increase in pH from 8
to 10 which indicates that pH inhibits the growth of SnO2. As the size decreases the
surface area in case of nanoparticle will increase so selectivity, sensitivity, reactivity
will improve due to more adoption of oxygen in the vacancies. It can also be seen from
intensity of XRD peaks decreases with increase in the pH concentration which is
attributed to large number of defects.
 Fig. 1 represents patterns at pH 8,9,10

Sample Crystallite size (nm)

PH 8 9.3

PH 9 3.93

PH 10 3.17

Table 1.1 showing crystallite size decreasing with increasing pH

Figure.2 of FESEM (Field Emission Scanning Electron Microscopy) reveals spherical
morphology of SnO2 nanoparticles and the size of nanoparticles decreases with the
increase in pH from 8 to 10. It has also been confirmed by previous XRD analysis that
crystallite size decreases and here it is confirmed that size is spherical and it decreases
with the increase in pH concentration which leads to size increase of SnO2
nanoparticles due to which sensor response or we can say reactivity, vacancies,
selectivity, sensitivity increase of gas sensor and it will be maximum at pH10.

pH 8
pH9
pH 10

Figure.2 representing FESEM analysis of SnO2 nanoparticles at pH 8,9,10 respectively

Optical studies such as photoluminescence(Figure.3) provide information of energy

band gap or you can say structural defects induced by the impurities present in the
metal oxide semiconductor nanostructures. If band gap will be large then there is poor
conduction or we can say high resistance, here in case of pH 8 to 10 band gap increases
so resistance in air increase and in case of LPG gas resistance will be low and we will
get better sensor response. Below Figure.3 represents with increase in pH from 8 to 10
more defects are induced so, if defects will be more adsorption of oxygen will be more
and due to which the gas selectivity, sensitivity, sensing response of the gas sensor
increases.

Figure.3 Represents the Photoluminiscence spectra of SnO2 nanoparticles

Figure.4 shows the graph of sensor response vs operating temperature and it is clear from graph
that sensor response at operating temperature (3000C) is maximum .

Figure.4 Sensor response vs operating temperature

Conclusion-
SnO2 nanoparticles has been successfully prepared by chemical co-precipitation method and its
XRD analysis reveals rutile type tetragonal structure, crystallite size decreases and low peaks
show large number of defects . FESEM revels the spherical morphology of nanoparticles and
decrease in size of nanoparticle as we go from pH 8 to 10. Photoluminiscence reveals large band
gap and large number of defects. All these studies have shown increase in efficiency of the gas
sensor response due to decrease in crystal size, spherical shape, large number of defects and that
all was to be shown in this report.

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