Journal of ELECTRONIC MATERIALS

DOI: 10.1007/s11664-014-3253-8
Ó 2014 TMS

Nanostructured ZnO Films for Room Temperature Ammonia

Sensing

DHIVYA PONNUSAMY1 and SRIDHARAN MADANAGURUSAMY1,2

1.—Functional Nanomaterials & Device Lab, Centre for Nanotechnology & Advanced Biomate-
rials and School of Electrical & Electronics Engineering, SASTRA University, Thanjavur 613 401,
India. 2.—e-mail: m.sridharan@ece.sastra.edu

Zinc oxide (ZnO) thin films have been deposited by a reactive dc magnetron
sputtering technique onto a thoroughly cleaned glass substrate at room tem-
perature. X-ray diffraction revealed that the deposited film was polycrystal-
line in nature. The field emission scanning electron micrograph (FE-SEM)
showed the uniform formation of a rugby ball-shaped ZnO nanostructure.
Energy dispersive x-ray analysis (EDX) confirmed that the film was stoichi-
ometric and the direct band gap of the film, determined using UV–Vis spec-
troscopy, was 3.29 eV. The ZnO nanostructured film exhibited better sensing
towards ammonia (NH3) at room temperature (30°C). The fabricated ZnO
film based sensor was capable of detecting NH3 at as low as 5 ppm, and its
parameters, such as response, selectivity, stability, and response/recovery
time, were also investigated.

Key words: Zinc oxide, thin film, sputtering, sensor, ammonia

INTRODUCTION detection of highly selective gas/vapours, but the

techniques are limited by cost, bulk, and instrument
NH3 is one of the mostly widely produced chemi-
complexity, and are unsuitable for real-time moni-
cals in the world.1 It has extensive applications
toring. Thus, researchers are focussing on the
including the production of explosives, fertilizers
development of low cost, small size, and highly
and the coolant in refrigerants. NH3 is toxic to
portable sensors which can be used in real-time
humans at low ppm levels, the threshold limit of
monitoring.5 Metal oxides are a well-known mate-
NH3 concentration in air for humans being 25 ppm.2
rial for gas sensing applications because of their low
The natural NH3 level in the atmosphere is in ppb
cost, high sensitivity, fast response/recovery time,
range. The presence of a high concentration of NH3
portability, and real-time operation.6 ZnO is an
in the atmosphere is potentially harmful to humans,
interesting material due to its properties, such as
causing irritation of the skin, eyes, and respiratory
being an n-type semiconductor with wide band
system, and can also be fatal.3 So there is an urgent
(>3 eV), while it has good stability, is non-toxic, and
need for the development of cheap, reliable, and
has good optical and electrical properties,7 and so
highly sensitive NH3 sensors. NH3 sensors find
finds many applications in solar cells,8 light-emit-
several applications in areas such as leak detection
ting diodes, field effect transistors, transparent
in air-conditioning systems, breath analysis for
electrodes,9 ultraviolet photosensors,10 gas sen-
medical diagnosis, and exhaust emissions of auto-
sors11,12 etc. Many deposition techniques have been
mobiles.4
employed to synthesize ZnO thin films such as spray
A number of techniques such as gas chromatog-
pyrolysis,13 pulsed laser deposition,14 metal–organic
raphy and mass spectrometry, as well as infra-red
chemical vapour deposition,15 direct current (dc)
and UV–Vis spectroscopy, are available for the
and radio frequency magnetron sputtering,16,17 and
thermal evaporation.18 Among these techniques, dc
reactive magnetron sputtering is advantageous due
(Received February 25, 2014; accepted May 14, 2014) to uniform large area deposition, good adherence of
 Dhivya Ponnusamy and Sridharan Madanagurusamy

films with underlying substrate, easy control of film
properties with tuning in sputtering parameters,
high purity, etc.
Several researchers have attempted to detect NH3
using ZnO nanostructures19–21 with high sensitivity
and better selectivity. The sensors developed by them
were operating at high operating temperatures (which
required a separate controlled heater assembly to
operate the sensing device), which in turn led to high
cost and maintenance of the sensor. Also, the opera-
tion of the sensor at high temperature caused changes
in the material properties, and decreases in sensor life
time, selectivity, and reproducibility, and reductions
in fast response/recovery time, and long-term stabil-
ity.22 Hence, to bring down the operating temperature,
various metal dopants such as indium,23 ruthenium,24
nickel,25 and chromium oxide26 and polymers such as
polyaniline27 have also been introduced in ZnO films.
In addition, to obtain significant sensor response,
noble metals like platinum28 and palladium29,30 have
been added to the ZnO base material which increased
the cost of the sensor and limited the development for
large applicability. The available NH3 sensor reports
19–30
and the various sensitivities, response/recovery
times, operating temperatures, and detection limits
are shown in Table I.
The present work aims to fabricate a low-cost NH3
sensor using nanostructured ZnO films which will
have high sensitivity, selectivity, and a lower oper-
ating temperature. ZnO films were deposited over
glass substrates using a reactive dc magnetron
sputtering technique and their structural, morpho-
logical, optical, and NH3-sensing properties have
been investigated. The performance of NH3 sensing
of the fabricated ZnO sensor was tested at room
temperature (in ambient air) by varying the NH3
concentration from 5 to 100 ppm.
Film Deposition
ZnO thin films were deposited by dc reactive
magnetron sputtering onto thoroughly cleaned glass
substrates of 2 9 2 cm2. The glass substrates were
cleaned by the conventional cleaning procedure.31
The glass substrates were loaded into the deposition
chamber. Using the combination of an oil diffusion
pump and rotary mechanical pump, the deposition
chamber was evacuated to a base pressure of
2 9 105 mbar. A zinc target (purity 99.99%) of
50.8 mm diameter and 3.2 mm thickness was used
as the cathode. Before depositing the films, the
target was pre-sputtered in an argon atmosphere
for 20 min to remove contamination on the target
surface. High purity argon was used as the sput-
tering gas and high purity oxygen was used as the
reactive gas. High purity argon (15 sccm) and oxy-
gen (4 sccm) gases were introduced inside the vac-
uum chamber using mass flow controllers. The
working pressure inside the deposition chamber
during deposition was maintained as 4.2 9 103
mbar. The target to substrate distance and the
cathode power were maintained as 5 cm and 40 W,
respectively. The deposition was carried out at room
temperature for 15 min, and the thickness was
measured at 150 nm as measured by the stylus
probe method. The interdigitated electrodes used for
the NH3 sensors were fabricated by thermally
evaporating aluminium (99.99%) onto the glass
substrates of size 2 9 2 cm2 using a shadow mask
with a thickness of 300 nm. The ZnO film was
deposited over the interdigitated electrode in an
area of 1 9 1 cm2. The detailed description of the
electrode fabrication and the gas sensing setup is
available elsewhere.32
The structural properties of the film was exam-
ined with x-ray diffraction (XRD) (Bruker D8
Advance) using CuKa radiation (k = 1. 5406 Å) in
the 2h range of 20–80°. The surface morphology of
the film was studied by FE-SEM (JEOL JSM 6701
F) with 3-kV electron beam power and at a working
distance of 7 mm) in the secondary electron
imaging mode. The elemental composition of the
film was evaluated by energy dispersive x-rays
(EDAX) attached to the FE-SEM. Film thickness

Table I. State-of-the-art of ZnO-based NH3 sensors

Operating Sensor Detection
temperature Response Recovery response range
Sensor. no. Sensor material (°C) time (s) time (s) (S) (ppm) Reference

1 ZnO 300 35 35 0.68 100 19

2 ZnO nanorods 300 180 180 80.6 10–1000 20
3 ZnO 50 – – 24.8 200 21
4 In-ZnO 300 40 100 0.8 1–10 23
5 Surface ruthenated ZnO 250 18 960 386 1000 24
6 Ni-ZnO 190 35 120 9 200–850 25
7 Cr2O3-ZnO RT 25 75 13.7 100–300 26
8 CSA doped polyaniline ZnO RT 22 418 28.11 10–100 27
9 Pd-sensitized flower like ZnO 210 20 60 81.8 5–100 28
10 Pd-ZnO RT 4 – 60 80.6 29
11 Pt nanoparticle sensitized 300 100 100 36 5–1000 30
with ZnO nanowire
Nanostructured ZnO Films for Room Temperature Ammonia Sensing

was measured by the stylus probe method (Mitutoyo

SJ 301). The optical property was investigated using
a UV–Vis spectrophotometer in the wavelength
region of 400–800 nm.

Sensing Set-Up
NH3 sensing studies of the fabricated sensor with
ZnO film as the active layer were performed using a
custom-built sensing setup. It is made up of a glass
chamber which has a volume of l L. The sensing
studies were carried out by a two-probe instrument
(TPX-01, SES instrument). The schematic repre-
sentation of the sensing setup was reported in our
previous work.33 Prior to sensing measurements,
the sensor was stabilized for 30 min in ambient air
in order to obtain a stable baseline resistance value.
Once the stable baseline resistance was reached, Fig. 1. XRD pattern of ZnO film.
NH3 vapour (5–100 ppm) was injected into the gas
testing chamber and corresponding changes in the
resistance value were recorded. The gas sensing
ball-like structure with a size of around 40 nm. In
properties were evaluated by gas response (S) and is
some regions, the structures were aggregated,
given in Eq. 1
forming a larger cluster of about 80–100 nm. The
S ¼ Ra =Rg ; (1) rugby ball-shaped nanostructure formation is
clearly indicated by the arrows in the micrograph.
where Ra and Rg were the resistance of the sensor in The deposited ZnO film was porous in nature, which
air and in the gas analyte, respectively.34,35 is highly desirable for a gas-sensing application.
The EDAX spectrum of the ZnO film is shown in
RESULTS AND DISCUSSION Fig. 2c. The peaks in the EDAX spectrum show the
Structural Properties presence of the Zn and O elements. The deposited
film contained 54.37% of zinc and 45.63% of oxygen.
The XRD pattern of ZnO films deposited at 40 W The unindexed peaks were pertaining to the gold
for 15 min (thickness 150 nm) is shown in Fig. 1. which was coated over the sample in order to
The film was polycrystalline in nature with a pre- increase its conductivity.
ferred orientation along (002) plane and a hexago-
nal wurtzite structure (JCPDS file No 05-0664). The Optical Properties
peak at 34.2° corresponds to the diffraction from the
(002) plane of ZnO. This indicates that the film has The optical absorbance spectrum of the ZnO film
a strong c-axis orientation perpendicular to the recorded in the wavelength range 200–800 nm is
substrate. Two other peaks were also observed at shown in Fig. 3. The optical band gap value of the
2h = 36.28° and 63.50°, which corresponded to the film was calculated using the fundamental absorp-
(101) and (103) planes, respectively.36 No other tion energy which corresponds to the electron exci-
peaks were observed which indicates that the tation from the valence band to the conduction
deposited film is of high purity. The grain size was band. Band gap energy mainly depends on the
calculated for the predominant orientated plane absorption co-efficient and the photon energy given
(002) by using Debye Scherer’s relationship37: by the relation38:

Kk ðahmÞ1=n ¼ Aðhm  Eg Þ; (3)

Dð002Þ ¼ ; (2)
bð002Þ cos h
where D(002) is the mean grain size of the (002)-
oriented grains, K is the crystallite-shape fac-
tor, k is the wavelength of the x-rays, b(002) is the
full-width at half-maximum of the XRD peak, and
h is the Bragg angle. The determined grain size of
the ZnO film was around 38 nm.
Surface Morphology
FE-SEM micrographs of the ZnO film is shown in
Fig. 2a, b which shows a fairly smooth and uniform
coating of the ZnO film. This film exhibits a rugby
where a is the absorption co-efficient, hm is the
photon energy, and A is the constant exponent
corresponding to the type of transition which occur
in the material where n = 1/2, 2, 3/2 and 3 it is
corresponding to the allowed indirect, direct, for-
bidden indirect, and forbidden direct. The Tauc
plot is used for calculating the direct band gap by
taking n = 2 and plotting the graph between (ahm)2
on the Y-axis and photon energy (hm) on the X-axis
and extrapolating the linear portion of the graph
onto the X-axis. The intercept gives the value of
the direct band gap as 3.29 eV39 which is shown in
Fig. 3.

Fig. 2. FE-SEM micrograph with (a) low magnification and (b) higher magnification shows the rugby ball-like formation (indicated by arrow); inset
shows rugby ball; (c) EDX spectrum of ZnO film.
Fig. 3. Tauc’s direct band gap of ZnO film.
NH3 Sensing Properties
NH3 sensing studies of the fabricated sensor with
ZnO film as the active layer were carried out at
room temperature (30°C) in ambient air. The sens-
ing mechanism of the n-type semiconductor sensor
is that, when exposed to a NH3 concentration, a
reaction occurs between the absorbed oxygen spe-
cies and NH3, which causes the electrons to recom-
bine with holes in the lattice site which results in a
decrease in resistance.40 The kinetics representa-
tion of the interaction of the surface absorbed
Dhivya Ponnusamy and Sridharan Madanagurusamy
oxygen species and the NH3 vapour is given by
relations 4 and 541
O2 ðadsÞ þ e ! O
2 ðadsÞ; (4)
4NH3 þ 3½O 
2 ðadsÞ  ! 2N2 þ 6H2 O þ 3e : (5)
Figure 4 shows the transient response of sensor
with ZnO film as the active layer was exposed to
different NH3 concentration between 5 ppm and
100 ppm. The baseline resistance of the ZnO film
could recover to its initial value for each concen-
tration, which evidently indicates the good revers-
ibility of the NH3 sensor.42 The sensing response as
a function of NH3 concentration from 5 ppm to
100 ppm is shown in Fig. 5. It can be observed that
the sensor response increases as the concentration
increases. The excellent sensing performance at
room temperature is due to the rugby ball-shaped
nanostructure formation with high porosity. The
rugby ball-shaped nanostructures with smaller
grain size provided a high surface to volume ratio
which gave large numbers of surface active sites for
interaction with NH3 and the adsorbed oxygen
species. The presence of the porosity increased the
diffusion of the gas molecules into the film which led
to the excellent performance at room temperature.43
The repeatability of the sensor was also studied by
Nanostructured ZnO Films for Room Temperature Ammonia Sensing

Fig. 7. Response and recovery time curves of ZnO films towards

Fig. 4. Transient response of ZnO film over various NH3 various NH3 concentrations.
concentrations.

Fig. 8. Stability test of ZnO-based NH3 over the period of 10 days.

Fig. 5. NH3 response plot of ZnO film.

Fig. 9. Selectivity of ZnO-based NH3 sensor.

was observed. This indicates that the ZnO NH3

Fig. 6. Resistance variation of ZnO over 5 ppm of NH3 in three
cycles.
allowing 5 ppm of NH3 in three cycles as shown in
Fig. 6. The change in resistance measured during
cycles I, II, and III are almost identical and no drift
sensor has very good repeatability.
For an effective sensor, a fast response/recovery
time is needed for the rapid detection of NH3. The
response/recovery time is defined as the time
required by the sensor to reach 90% of its saturation
and 10% of the baseline before and after switching
off the target analyte.5 The response/recovery time

of the sensor was calculated for different NH3 con-
centrationa and is shown in Fig. 7. The response
time was found to be 92–110 s and the recovery
time was about 111–113 s. The response time was
relatively faster than the recovery time due to the
lower desorption rate of NH3 at room temperature.
The stability (Fig. 8) of the NH3 sensor was studied
over the period of 10 days (in time intervals of 2 days).
The stability study was carried out by exposing 5 ppm
of NH3 over a period of 10 days. During this period, the
sensor was highly stable except that on the 10th day
some drift was observed, which could be due to the
interference of humidity. The selectivity is the major
concern in quantifying gas-sensing performance,
which is defined as the ability of the sensor to distin-
guish a particular analyte from a collection of ana-
lytes. The selectivity was studied by exposing 100 ppm
of different interfering vapours such as acetone, eth-
anol, and methanol. The comparison of the sensing
responses towards each target vapour is shown in
Fig. 9. The response (S) was about 304, 112, 50 ,and 75
for NH3, acetone, methanol, and ethanol, respectively.
It is apparent that the selectivity experiment of the
nanostructured ZnO film shows an excellent response
towards NH3 (at room temperature) which is better
than the responses exhibited by the ZnO film towards
NH3 reported in the literature.
CONCLUSION
ZnO thin films have been deposited by reactive dc
magnetron sputtering onto thoroughly cleaned glass
substrates. XRD revealed that the deposited film
was polycrystalline in nature with a preferential
orientation along the (002) plane. The rugby ball-
like nanostructure with a size of around 40 nm of the
ZnO films were evidenced by FE-SEM. Enhanced
NH3 sensing properties were observed in the con-
centration range of 5–100 ppm at room temperature.
The developed ZnO NH3 sensor had better response/
recovery time, sensitivity, stability, and repeatabil-
ity, which are desirable for fast and continuous
detection of NH3 for various practical applications.
ACKNOWLEDGEMENTS
The authors thank DRDO, Govt. India for the
financial support and SASTRA University for pro-
viding the instrumental facilities.
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