2015 IEEE Student Conference on Research and Development (SCOReD)

Effect of Sn Dopant Concentration on Structural

and Electrical Properties of ZnO Nanostructures
Based Methane Gas Sensor
1*
A.K. Shafura, 1M. Hannas, 1N.D. Md. Sin, 1Uzer M, 1M.H. Mamat, 3A. Shuhaimi, 4Salman A.H. Alrokayan, 4Haseeb
A. Khan and 1,2,4**M. Rusop
1
NANO-ElecTronic Center (NET), Faculty of Electrical Engineering, Universiti Teknologi MARA (UiTM), 40450
Shah Alam, Malaysia
2
NANO-SciTech Center (NST), Institute of Science, Universiti Teknologi MARA (UiTM), 40450 Shah Alam,
Malaysia
3
Low Dimensional Materials Research Centre (LDMRC), Department of Physics, Faculty of Science, University of
Malaya, 50603 Kuala Lumpur, Malaysia
4
Research Chair for Biomedical Applications of Nanomaterials, Department of Biochemistry, College of Science,
King Saud University, Riyadh 11451, Saudi Arabia
Email: *shafura@ymail.com, **nanouitm@gmail.com

Abstract—Zinc oxide (ZnO) nanostructures had successfully
prepared using sol-gel immersion method. The tin (Sn) dopant
concentration was varied between 0.4 to 2.0 at.%. The surface
topography and electrical properties of the ZnO nanostructures
were studied using atomic force microscopy (AFM) and current-
voltage (IV) measurement. The highest conductivity of 1.68 × 10-2
Scm-1 was obtained by 2.0 at.% sample. The Sn-doped ZnO
sample is notably shortens the response time and recovery time
with better sensitivity towards methane gas.
Keywords—zinc oxide; Sn dopant concentration; immersion
method; methane gas sensor
I. INTRODUCTION
There has been extensive study on metal oxide
semiconductor based gas sensor, such as TiO2 [1], SnO2 [2]
and ect. Among n-type semiconducting materials, zinc oxide
(ZnO)-based thin films attracted considerable attention due to
their unique properties for use in gas sensor applications. It
has been found that the gas sensing properties are strongly
dependent on the surface properties of the sensing materials
[3-5]. The high electrical conductivity can be achieved by
added n-type dopant. K.J. Chen et al. reported Sn dopant
contribute to increase the conductivity of the ZnO films [6].
Methane gas (CH4) is a colorless, highly volatile, odorless and
flammable gas. Therefore the monitoring of CH4 from
escaping into the atmosphere is crucial since its involve public
health and environment [3].
Several deposition techniques has been applied to grow
ZnO nanostructures, such as chemical vapor deposition (CVD)
[7], physical vapour deposition (PVD) [8], spray pyrolysis [9]
and sol-gel process [10]. Comparing to other deposition
techniques sol-gel technique has not required expensive and
complicated equipment. It has advantage of being easy to be
coated on the desired shape and area [11]. There have been
few ZnO-based methane sensors reported so far [4, 12].
In this paper, we prepared the ZnO nanostructures at
different Sn dopant concentration using sol-gel immersion
method. We also measured the gas sensing properties for the
optimized sample.
II. EXPERIMENTAL
A. Deposition method
The ZnO template layer films were prepared using sol-gel
spin-coating technique [13]. The nanostructured ZnO were
grown on seed layer-coated glass substrate using sol-gel
immersion method. The solutions of 0.08 M were prepared
using zinc acetate dehydrate and dissolved in
hexamethylenetetramine (HMT, C6H12N4, 99% Sigma-
Aldrich) and deionized (DI) water. The molar ratio of HMT to
zinc acetate was fixed at 1. The tin (IV) chloride pentahydrate
(SnCl45H2O, 98% Sigma-Aldrich) were added as a dopant
source by increasing the dopant concentrations ranging
between 0.4 to 2.0 at.%. Then each resultant solution was
sonicated at 50 oC for 30 min using an ultrasonic water bath
(Hwasin Technology Powersonic 405, 40 kHz). The solution
was magnetically stirred and aged for 3 h at room temperature.
The template layer-coated glass substrate had been placed at
the bottom of a Schott bottle before the aged solution was
poured into the bottle. The immersion process was done in a
waterbath at 95 oC. After 1 h, the substrates were withdrawn
from the solution, thoroughly rinsed with DI water and dried
at 150 oC for 10 min. The substrates were annealed at 500 oC
for 1 h.

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 2015 IEEE Student Conference on Research and Development (SCOReD)

B. Gold electrode coating process

In order to inspect the conductivity of nanostuctured ZnO,
gold (Au) was deposited on top of the sample as an ohmic
electrode. 60 nm Au was deposited with the use of a physical
mask using thermal evaporator (ULVAC, VCP 1100) in a
vacuum environment.

C. Gas testing setup

In order to inspect the sensing properties of nanostructured
ZnO, pure (99.995%) methane gas and nitrogen in desired
proportions were allowed to flow into the chamber through a
mass flow meter (AALBORG, GFC 17) to keep the mass flow
rate and thus the methane gas concentration remained constant
(i.e. 5 % of CH4) throughout the test. The operation
temperature was fixed at 150 oC. The current-voltage (IV) was
supplied using Keithley 2400.

D. Characterization method
The structural properties were characterized using atomic
force microscopy (AFM, Park System). The electrical and
CH4 gas sensing properties were measured using two point
probe current-voltage (I-V) measurement (Keithley 2400).

III. RESULT AND DISCUSSION

A. Surface Topology Fig. 1. AFM topography images of (a) undoped, (b) 0.4 at.%, (c) 0.8 at.%,
(d) 1.0 at.% and (e) 2.0 at.% Sn doped ZnO films.
The AFM images of the ZnO nanostructures that prepared
at different dopant concentration were studied. Figs. 1 and 2
show the AFM 3D and watershed images of the ZnO
nanostructures scanned over an area of 5 × 5 µm2,
respectively. It can be seen from Fig. 1 that hexagonally facet
structures dominating the surface morphology and the particle
size become slightly larger as dopant concentration were
increased. It is clear from Fig. 2 that the number of grain
boundaries decreased as the doping concentration increased.
The result suggests that the electron movement increased as
the dopant concentration was increased. Table 1 present value
of the surface root mean square (RMS) roughness and total
grain boundaries obtained from the ZnO nanostructures films.
It can be observed that surface roughness increases as the
doping concentration increased. These rough surface
properties give a good potential in gas sensing applications
[14].

B. Electrical properties
In order to study the effect of dopant concentration on the
electrical properties of ZnO nanostuctures, gold (Au) was
deposited on top of the sample as an ohmic electrode. Fig. 4
showed the IV curve of the films. The highest conductive
sample was obtained by 2.0 at.% doped sample and least
conductive was obtained by undoped sample. Fig. 5 and Table
2 showed the conductivity calculated for each sample using
formula (1),
Fig. 2. AFM watershed analysis of (a) undoped, (b) 0.4 at., (c) 0.8 at., (d) 1.0
1 I l at.% and (e) 2.0 at.% Sn doped ZnO films.
   (1)
 V A

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 2015 IEEE Student Conference on Research and Development (SCOReD)

Fig. 3. The total number of grain boundaries calculated at different Sn dopant Fig. 5. The conductivity of ZnO nanostructures films at different Sn dopant
concentration. concentration.

TABLE I. NUMERICAL ANALYSIS OF AFM 3D IMAGE TABLE II. THE CONDUCTIVITY OF ZNO NANOSTRUCTURES THIN FILMS
AT DIFFERENT SN DOPANT CONCENTRATION
Dopant RMS Roughness, Rq Total grain
concentration (nm) boundary (N) Dopant concentration (at.%) Conductivity (Scm-1)
(at.%)
0 84 153 0 0.14 × 10-2

0.4 90 148 0.4 1.13 × 10-2

0.8 93 140 0.8 1.31 × 10-2

1.0 1.45 × 10-2
1.0 95 132
2.0 1.68 × 10-2
2.0 104 124

where, V is voltage, I is current, l is distance between contact

and A is area of contact. It is notable that the Sn dopant
improve electrical conductivity of the films which due to the
increase of the electrons concentration caused by tin ions
substituting the Zn2+ ions. The result also in close agreement
with AFM watershed analysis. The increase in dopant
concentration decreased the number of grain boundaries. The
high number of grain boundaries may behave as barriers
towards the electron movement which causes high electrical
resistivity. K.J. Chen et al. also reported that Sn dopant
concentration improved the electrical conductivity of the ZnO
films [6].

C. CH4 gas sensing properties

Fig. 6 showed a reduction of sensor resistance ratio
(Rgas/Rair) with time for undoped and Sn doped ZnO based
methane gas sensor (i.e. 2.0 at.%). The ration is less than one
Fig. 4. IV curve of ZnO nanostructures films at different Sn dopant
for reducing gases, since the resistance will decreases as in a
concentration. reducing environment. The response time and recovery time
are generally defined as the time taken to reach 90 % of its
total changed value (Rair-Rgas) [4]. From the Table III, the
response time of Sn doped ZnO sample is shortened from 80 s

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 2015 IEEE Student Conference on Research and Development (SCOReD)

methane gas sensor shows better response compared to

undoped sample.

Acknowledgment
This work was financially supported by LRGS grant (600-
RMI/LRGS 5/3 (3/2013)), Institute of Research Management
& Innovation (IRMI), Universiti Teknologi MARA (UiTM).
Also this work was partly supported by the Research Chair for
Biomedical Applications of Nanomaterials, Deanship of
Scientific Research, King Saud University, Riyadh, Saudi
Arabia. Author would like to thank to NANO-SciTech Centre,
UiTM for equipment facilities.

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