Manganese doped Zinc Oxide thin film Hydrogen gas sensor at reduced operating temperature.
Anjali Chatterjee, Partha Bhattacharjee, P.kumbakar and Nirmal Kumar Roy
Central Mechanical Research Institute , Central Mechanical Research institute, National Institute of Technology and
National Institute of Technology
Mahatma Gandhi Avenue, Durgapur, India-713209
anj12chat@yahoo.com, partha_cmeri@yahoo.com, nitdgpkumbhakar@yahoo.com and roy_nk2003@yahoo.co.in
Abstract
During the past few decades, semiconductor metal oxide
(SMO) gas sensors have become a prime technology in
several domestic, commercial, and industrial gas sensing. The
semiconductor properties of zinc oxide along with its dopant
remain to be trapped fully in its application as gas sensor. With
the advent of nanotechnology, miniaturization and high
sensitivity happens to be a key issue in sensor fabrication. Most
of the SMO gas sensors fabricated by nanotechnology process
operate at high temperature. This paper gives a new insight to
hydrogen gas sensor characteristics, by reducing the operating
temperature of hydrogen (H2) sensor, fabricated from the nano
particle of manganese doped zinic oxide(ZnO), synthesized by
chemical precipitation method.
Discussion 1 Introduction
Much has been said about hydrogen being the fuel of the
future due to its abundance and its non-polluting combustion
products. Currently, there is a great deal of interest in
hydrogen fuel cell technology. Widespread production,
distribution and use of hydrogen will require many
innovations and investments to be made in efficient and
environmentally-acceptable production systems,
transportation systems, storage systems and detection
devices. There is a need for fast response when the gas is
explosive and hazardous type, hence while designing H2 gas
sensor this parameter has to be considered. In the power
system, oil filled power transformers are the key equipment.
Most of the faults occurring inside the transformers contents
Hydrogen gas as a major constituent. Hence timely detection
of a change in concentration of dissolved hydrogen can
prevent many catastrophic failures. There are a number of
commercially available techniques currently used for the
detection of H2 gas dissolved in transformer oil. They are
based on gas chromatography and are costly. Application of
nanotechnology in the fabrication of semiconductor metal
oxides sensor for the detection of H2 in the transformer oil is
new in this field.
During the past few decades, semiconductor metal oxide
(SMO) gas sensors have become a prime technology in
several domestic, commercial, and industrial gas sensing
systems. These sensors are based on electrochemical
behavior, catalytic combustion, or resistance modulation of
SMO [1]. Among the available sensors, the SMO gas sensor
devices have several unique advantages such as low cost,
small size, measurement simplicity, durability, ease of
fabrication, and low detection limits in parts per million (ppm
levels).With the advent of nanotechnology, high performance
and miniaturization of sensor happen to be a key issue. Since
978-1-4577-0624-0/11/$26.00 ©2011 IEEE
the gas sensing mechanism is a surface reaction, use of nano
structured materials is expected to improve gas sensing
characteristics. Micro-structure of metal oxide films/pellets has
a direct influence on the sensitivity, selectivity, recovery and
response time for a particular gas. Considerable amount of
research have been done using tin-dioxide(SnO2), tungsten
oxide(WO3), titanium dioxide( TiO2) and gallium
oxide(Ga2O3) as metal oxide sensors as H2 sensors. Gas
sensors made from these materials have the desirable property
that their resistance depends strongly on the adsorption of
certain gases and their optimum working temperature are
350°C, 700°C and 280°C respectively. Their high operating
temperature makes them unsuitable for many applications like
in the coal mines and fire hazard places. Although both n-
type and p-type semiconductors are known to function as
sensors, the n-type semiconductors have more often been
utilized because the p-type oxides are relatively unstable to
the exchange of lattice oxygen with air.
Now the focus is on nano-sized ZnO which has the potential
that remains to be tapped fully in its application as gas sensor.
This semiconductor is attracting tremendous attention due to
its interesting properties such as wide band gap of 3.37eV at
room temperature, high chemical stability, low dielectric
constant, large electrochemical coupling coefficient and high
luminous transmittance [2]. Y.Ma et.al.[3], have discussed the
sensitivity of ZnO and the effect of size of the nano grains on
it. The effect of doping with palladium and platinum has been
studied at length but dopants like iron, calcium and
manganese have yet to be investigated fully. P.K.Basu
et.al.[4], in their work reduced the methane sensing
temperature by modifying the nanocrystalline ZnO thin
film, this was achieved by incorporating Pd dopant. ZnO can
detect hydrogen, LPG, methane and carbon monoxide[5]. The
existing semiconductor gas sensors have response time around
twenty seconds while the sensors manufactured from nano-
particles of metal oxide have response time in microseconds.
However most of hydrogen-sensitive sensors made up of
SMO materials have high operating temperature, which is
becoming an obstacle in its application in different areas.
This paper gives a new insight to sensor characteristics, by
reducing the operating temperature of hydrogen sensor,
fabricated from the nano particle of manganese doped ZnO,
synthesized by chemical precipitation method. Surface
characterization was done with a scanning electron microscopy
(SEM) and atomic force microscope (AFM) readings have
been employed to study their physical characteristics.
Discussion 2 Working principle of the sensor
We can broadly classify the sensor functioning into two
main category, one as a receptor and the other as a transducer
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[6]. The former involves the recognition of a target gas
through a gas-solid interface which induces an electronic
change of the oxide surface, while the latter is based on the
transduction of the surface phenomenon into an electrical
resistance change of the sensor. When a sensor is heated to a
high temperature in the absence of oxygen, free electrons
easily flow through the grain boundaries of the SMO film.
When there is an interaction of atmospheric oxygen with the
SMO surface, charged oxygen species are generated, which
extract the electrons from the semi-conductor material,
leading to the change in the carrier density and reduction in
conduction. The n and p type sensor material reacts differently
when exposed to different gases. For reducing gases such as
H2S and NH3 the conductivity increases for n-type materials
(as SnO2 and ZnO) and reduces for p-type materials (as Te).
The effect of oxidizing gases is opposite to that of reducing
gases. Upon interacting with an oxidizing or reducing gas,
absorbed oxygen concentration reduces and the trapped
electrons are released, lowering the potential barrier and thus
reducing the electrical resistance. In this manner, the sensors
act as variable resistors whose value is a function of gas
concentration. The change in conductivity is a measure of gas
concentration.
In order to get better performance, the system is initially
purge with nitrogen gas. It is observed that intra-granular
Schottky barriers are formed when the samples are exposed
in air, prior to its exposure to hydrogen gas .The depletion of
free electrons near the grain surfaces results from the reaction
of adsorbed surface oxygen to form O-[4]. When the sensor is
exposed to inert gas like nitrogen, oxygen impurities occur at
minimal levels of parts-per-million in the ambient nitrogen/
H2 gas stream. Consequently, the Schottky barrier height may
reasonably be expected to remain constant throughout the
sensing measurements, as the nitrogen background is inert
with respect to the oxide. The n-type sensor, therefore, may
be viewed as a medium consisting of two regions having a
wide variation in its conductivity, in which electrical
conduction is modulated by changing the volume fraction of
the highly conducting granular interior, through reaction with
an adsorbed gas. Rella,et al.[7] had shown that when the
grain size of SnO2 was below 10nm, it had good response to
NO2 and CO. Ferroni et al.[8] showed good response to NO2
by solid solutions of TiO2 and WO3 when their grain size
were 60nm. Ansari S.G et al.[9] have shown SnO2
nanoparticle of the range 20nm when used as a hydrogen
sensor was ten times more sensitive than the sensors using 25
– 40nm particle size. However it is seen that excessive
decrease in the particle size leads to instability in the
structure[10].
Discussion 3 Experimental Setup
As illustrated in Fig1, the sensor array mainly consists
of a target gas, a flow meter unit, a testing chamber, a DC
power supply, a stop watch, heater, thermocouple along with
the temperature controller and multimeter which uses 2x4
wire method to measure the resistance. LabVIEW based
software is mainly used to control all testing parameters and
measurements during the experiment. For sensor study high
purity (99.9%) hydrogen and nitrogen gas is used. Effort is
given to reduce the power consumption, weight and overall
dimension as well as simplifying the whole procedure. To
attain this goal ZnO (doped with 1% by weight of manganese
as well as undoped samples) were selected as the sensor
material having the grain size of approximately 20nm. A thin
layers of nano-particles of ZnO is deposited on the surface of
glass substrate, by chemical deposition techniques. The .
Figure 1: Experimental set up for the measurement of gas
concentration by sensors fabricated from nano-particles of
ZnO.
test chamber was designed in the shape of conical flask and
the sensor was placed on the top. The ohmic contact was
established by using silver conductive paste. Heater element
consisting of nickel chromium wire is placed below the
substrate to generate temperature as high as 400°C. To
monitor the temperature rise of the sensor material, a
thermocouple is placed on the surface of the film In our
work, the sensor is tested for gas sensing in the following
sequence. The temperature of the sensor is controlled by
varying the current flow through the heater and measured
with an accuracy of ± 1°C, using a temperature controller.
Initially a stream of nitrogen, used as carrier, is continuously
passed through the flask. After purging with nitrogen,
hydrogen is allowed to flow inside the chamber through a
flow meter valve. The flow rate is maintained constant and
variation in concentration of the gases was obtained by
adjusting the time of flow. The electrical characteristics of
the sensor are observed by changing its temperature from
room temperature to 300°C in air (ambient) and this
response is considered as a reference response for the
calculation of sensitivity. After injecting the test gas, all the
valves are closed to avoid hydrogen leakage during the
experiment. Then the resistance of the sensor is measured by
changing the sensor temperature in an ambience of air and the
injected gas separately. After completing the temperature scan,
the gas is leaked out; injecting fresh gas into the chamber
carries out the other cycles. Experiments were performed to
see the effect of varying concentration of hydrogen, at
different temperature on the sensitivity of the sensor. In
presence of the target gas at a fixed temperature the value of
the resistance decreases. The sensor resistance increases as
soon as the gas is removed from the sensor environment.
Throughout the experiment, the air pressure is equal to that
of atmosphere. The sensitivity of the sensor S was calculated
using the following mathematical expression
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 S = Rg / Ra (1)
Discussion 3 Results and discussion
(I) Film characterization
Fig 2 (a) shows the AFM image of ZnO nanoparticle
deposited in more than one layer on a glass substrate. It can
be seen that the particles are not distributed evenly and very
few individual particles were seen. The grain sizes are about
20 nm and they tend to agglomerate into large entities. This
acts as a limiting factor in enhancing the sensitivity of the
sensor. AFM image of some sections shows, that the lateral
growth amongst the grains have occurred, which results in a
rapid decrease in porosity.
( a) (b)
Figure 2: (a) AFM image of Mn doped ZnO thin film.
(b) XRD image of ZnO.
Unclear picture (fig 3a) is observed in such places within the
sample, which indicates the presences of moisture; the
particles couldn’t be observed distinctly. Reason for
absorption of moisture can be traced back to the sample
synthesis process; the acid is not removed totally which led to
the sample to have a tendency to absorb moisture. Fig 3b
shows dust particles in the form of bright bead like spots. This
could be due to sample handling problem or exposure of the
sample to the atmosphere. The pore size was found to be
53nm on the thin film.
(a) (b)
Figure 3: (a) Moisture laden sample of thin film of doped
ZnO under AFM. (b) Dust particles visible in the ZnO
sample.
When the sensor is stored for some time, a longer preheating
period is required to stabilize the sensor before usage. The
environmental humidity also acts as a limiting factor for good
response, as the water absorbed on the surface prevents the
free electron movement. Micro-structural characterization was
carried out by using scanning electron microscopy ( model no
S 3000n Hitachi ,Japan). The SEM micrograph (fig. 4) shows
a very roughness surface, which increases the effective film
surface exposed to the gas, which is important since the
sensitivity phenomena occurs essential at the thin film
surface.
(a) (b)
Figure 4: (a) & (b) Scanning electron micrographs showing
the ZnO surface topography.
(II) Electrical characteristics of ZnO film
Two samples of same thickness of ZnO film were taken,
where one was doped with manganese and the other was
without doping. The effect of doping on electrical
characteristics was studied by varying the temperature of the
thin film in presence of normal air. Fig 5 shows variation of
resistance with temperature for doped and undoped ZnO thin
film in air. The characteristic curves in fig 5 shows that there
is a decrease of resistance with the increase of temperature,
which indicates the n-type semiconductor behavior of ZnO.
The plot can be divided into two portions (i)exponential fall
region and (ii)saturation region. As the temperature of the thin
film increases, the electrons acquire enough energy and cross
the barrier at grain boundaries [11]. It is clearly visible that
the drop of resistance against temperature, in case of doped
ZnO is much sharper and it takes place at a much lower
temperature. Moreover, the exponentially dropped portion is
much longer and the saturation region comes at a much lower
resistance. To summarize, the doped ZnO shows much more
of semiconductor property at a very reasonable temperature
[12].
Figure 5: Drop in resistance of the sensor with rise of
temperature for Mn doped and undoped ZnO thin film
samples in air.
(III) Gas sensing characteristics
At low temperature there is no change in resistance, even
if the concentraion of the gas is increased. This shows the
available energy is not enough to carry out the reactions on
the surface. Variation in temperature is done from room
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temperature to 300°C, but only a part within the temperature
range from 180 to 270 °C is shown in fig 6 because in this
range sensitivity of the sensor is maximum.
Figure 6: Variation of reisistance at different temperature
for different concentration of hydrogen for ZnO thin film
sample.
(IV) Optimum operating temperature
One of the most important disadvantages of semiconductor
sensors is their high operating temperature (200-500ºC). For
this reason experiments were conducted to see the effect of
the operation temperature on the manganese doped ZnO
film’s, with an aim to optimize the operating temperature to
the lowest possible value. The increase in the operation
temperature leads to an enhancement of the film sensitivity
only upto a certain extent and then it starts falling. We
observe in fig 7 that the steep increase and decrease of
sensitivity occurs within a short temperature range. We notice
that the ideal operation temperature for hydrogen is around
190°C. Sensitivity value is directly proportional to the
concentration of hydrogen. Hence it can be seen that the
sensing properties of ZnO film has improved by doping it
with manganese, by reducing its optimum temperature.
Figure 7: Sensor sensitivity obtained at different
temperature for various concentration of hydrogen gas.
(V) Response time of the sensor
This work also involves study of the response time of the
sensor, so that we can determine its preheating time and the
time period after which the sensor output would quantify the
target gas. Fig 8 demonstrates typical behavior of the sensor
with the variation of heater temperature when exposed to
hydrogen gas and later removing the sensor from the gas
environment and reducing the heater voltage to zero. In this
Figure 8: The response and restore time recorded by the
sensor during the activation and deactivation of heater
voltage.
experiment, the heater wattage is gradually increased from 22
watts to 35 watts and then maintained constant at the optimum
operating temperature (nearly 190ºC as concluded in section
IV), for short time (20 seconds). Then the sensor is removed
from the test chamber and the heater voltage is removed, its
conductance will return back to its original value within a
very short time. It can be seen from Fig 8 that the recovery
time is shorter than the time of response, a characteristic of a
good sensor. The change in conductivity at the optimum
temperature is directly related to the amount of gas present,
resulting in a quantitative determination of its concentration.
(VI) Sensitivity Characteristics
Fig 9 represents typical sensitivity characteristics of a
hydrogen sensor, where all data have been gathered from fig
6. With the help of this curve one can quantify the
concentration of hydrogen gas present in parts per million
(ppm), maintaining the sensor temperature at 190°C
Figure 9: Sensor sensitivity observed for different
concentration of hydrogen (in ppm) maintaining the
temperature constant at 190°C.
Conclusions
The investigations have shown that thin film of ZnO
responds to the change in temperature after reaching 120°C .
The sensor has fast response and recovery time, a
characteristic of a good sensor. The result reveals that
manganese doped ZnO thin film sensor has maximum
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sensitivity to hydrogen at nearly 190°C. Doped ZnO exhibited
more sensitivity than the undoped samples. Hence it is more
appropriate to incorporate a catalyst metal (Mn) into the
structure, because the chemical reaction between the reducing
gas and the metal oxide surface increases, which leads to a
reduction process on the sensor surface and consequently
decreases the surface electrical resistance. Selection of
manganese dopant to ZnO has proven to be an advantage,
since it has lowered the existing operating temperature of
hydrogen sensor form 200°C to 190°C without sacrificing the
sensitivity.
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