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CERAMICS
INTERNATIONAL
Ceramics International 40 (2014) 13115–13122
www.elsevier.com/locate/ceramint

CO2 gas sensing properties of DC reactive magnetron

sputtered ZnO thin film
Padmanathan Karthick Kannana, Ramiah Saraswathia,n, John Bosco Balaguru Rayappanb
a
Department of Materials Science, School of Chemistry, Madurai Kamaraj University, Madurai 625021, Tamil Nadu, India
b
School of Electrical & Electronics Engineering and Centre for Nanotechnology & Advanced Biomaterials, SASTRA University, Thanjavur 613401, Tamil Nadu,
India
Received 4 April 2014; received in revised form 5 May 2014; accepted 5 May 2014
Available online 16 May 2014

Abstract

Nanostructured ZnO thin films were deposited on glass substrates using a DC reactive magnetron sputtering technique. Thin films of three
different thicknesses viz 40, 100 and 300 nm were prepared and subsequently annealed at 450 1C. The structural, topographical, and optical
characteristics of all the three annealed films were studied using X-ray diffractometer (XRD), Atomic Force Microscope (AFM) UV–visible and
photoluminescence spectrophotometers. The carbon dioxide (CO2) gas sensing behavior of these films was investigated in detail in the
concentration range of 500–10,000 ppm. The sensing performance was optimized with respect to the ZnO film thickness as well as the operating
temperature. ZnO film with 40 nm thickness showed better response characteristics at the operating temperature of 300 1C than that of thicker
ZnO films. A maximum sensitivity (%) of 1.13 with a response and recovery time of 20 s was observed towards 1000 ppm of CO2.
& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: CO2 gas sensor; Zinc oxide; DC reactive magnetron sputtering; Thin film sensor

1. Introduction Nanomaterials are widely used for the fabrication of gas

Carbon dioxide (CO2) is a principal gas among other
greenhouse gases and its increased emission into atmosphere
leads to the phenomenon, global warming [1]. Hence, it is very
important to detect and control CO2 gas concentration in
environment. In addition to environment quality monitoring,
detection of CO2 gas plays a crucial role in many other fields
such as in food packaging, agricultural and biotechnological
processes, air-conditioning and exhaust systems [2,3]. Many of
the commercially available CO2 sensors are based on a non-
dispersive infrared absorption (ND-IR) technique [4]. However,
major limitations of the ND-IR sensors are their bulkiness and
higher cost [5]. Chemiresistive sensors can be a feasible
alternative to ND-IR sensors due to their simple construction,
portability, high sensitivity and cost effectiveness [6–8].
n
Corresponding author. Tel.: þ91 452 2458247; fax: þ 91 452 2459181.
E-mail address: drrsaraswathi@gmail.com (R. Saraswathi).
sensors because of their enhanced surface area and hence the
increased adsorption of gas molecules. The increased sorption
of gas molecules promotes the kinetics of the surface processes
relevant to gas sensing [9]. Various nanostructured materials
have been proposed as sensing elements to develop chemir-
esistive type CO2 sensors. Metal oxides and mixed metal
oxides have always been the choice for CO2 sensor materials
[10–17] although a few reports exist on conducting polymers,
carbon nanotubes and graphene [18–22].
Nanostructured ZnO is a promising material in gas sensor
applications because of its high chemical sensitivity and
stability towards gaseous species, ease of preparation with
varied morphologies, non-toxicity and low cost [23,24].
Recently, many reports have appeared in the literature on the
use of nanostructured ZnO material of varied morphologies for
the detection of several gases including NO2, LPG, CO, H2S,
H2 and NH3 [25–30]. Also, ZnO has been reported to be one of
the most promising materials for detecting volatile organic
compounds such as ethanol, acetone, formaldehyde, benzene

http://dx.doi.org/10.1016/j.ceramint.2014.05.011
0272-8842/& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
13116 P.K. Kannan et al. / Ceramics International 40 (2014) 13115–13122
and toluene [31–35]. However, to the best of our knowledge,
except for one brief study [36], ZnO remains to be exploited
for CO2 detection.
DC reactive magnetron sputtered ZnO thin films have been
widely used for the fabrication of gas sensors, solar cells and
optoelectronic applications [37–40]. DC reactive magnetron
sputtering has its specific advantages for film growth such as
easy control for the preferred crystalline orientation, good
interfacial adhesion to the substrate and the high packing
density of the grown film [41]. Herein, we report the
development of a chemiresistive sensor using DC reactive
magnetron sputtered ZnO thin films for the detection of CO2
gas. In order to reduce the intrinsic defects and improve
crystallinity the sputtered ZnO films were annealed at 450 1C
in air atmosphere [42]. The annealed films were systematically
characterized by XRD, FTIR, UV–visible and photolumines-
cence techniques. The gas sensing properties of the sputtered
ZnO films towards CO2 gas were studied in detail in the
concentration range of 500–10,000 ppm. The sensing response
was optimized with respect to film's thickness and operating
temperature to obtain the calibration plot and other parameters.
2. Experimental details
A planar magnetron DC sputtering unit coupled with a
digital thickness monitor (Hind High Vacuum Company,
model-12” MSPT, India) was used for the deposition of ZnO
thin films of three different thicknesses viz 40, 100 and 300 nm
on glass substrates of 1 cm  0.5 cm dimension. Commercial
zinc metal of 99.99% purity with 2 in diameter and 0.125 in
thickness (Kurt J. Lesker Company, USA) was used as the
sputtering target. Microscopic glass substrates with a thickness
of 1.35 mm were used to deposit films after deft cleaning with
acetone and ethanol. High purity argon and oxygen gases were
used as the sputtering and reactive gases, respectively. A flow
rate of 10 sccm was maintained using built-in mass flow
controllers for both argon and oxygen gases. A base pressure
of 8  10  6 mbar was created inside the chamber before
deposition and the sputtering pressure was kept at 1  10  6
mbar during the deposition process. The distance between the
substrate and target was maintained at 10 cm. The discharge
current was fixed at 0.12 A which resulted in a discharge
voltage value of 300 V. The substrate temperature was main-
tained at 300 1C to improve the crystallinity of the film [43].
Finally, the deposited ZnO films were annealed at 450 1C for
3 h in air atmosphere. Annealed ZnO thin films of 40, 100 and
300 nm thicknesses will be henceforth denoted as S1, S2 and
S3, respectively.
X-ray diffraction (XRD) patterns of the film S1, S2, and S3
were obtained using a Shimadzu X-ray diffractometer (Model
6000) (Cu Kα; λ¼ 0.1542 nm). FTIR spectra of the ZnO thin
films deposited on the silicon substrates (Chemplast Sanmar)
were recorded using a Shimadzu (8400 S) spectrometer.An
atomic force microscope (APE Research Model A100 SGS)
was used to examine the surface topography of the films. The
molecular program software “Gwyddion” was used for particle
size and roughness analysis. Absorbance spectra were obtained
using a JASCO (V-550) double beam spectrophotometer.
Photoluminescence spectra were recorded using a
Fluoromax-4 spectrofluorometer (Horiba Jobin Yvon) at an
excitation wavelength of 325 nm.
A two-probe technique was employed for measuring the
resistance of ZnO thin films in the presence and absence of
target gas. The electrical contacts were made on the film
surface 0.2 cm apart using two thin copper wires and con-
ductive silver paste (Siltech, Bangalore, India). An indigenous
gas sensor testing system equipped with a stainless steel
chamber was used for sensing studies. A schematic of the
experimental arrangement used for the gas sensing measure-
ment is shown in Fig. 1. High purity N2 and CO2 gases were
used as the reference and target gases, respectively. These two
gases were injected into the chamber through mass flow
controllers.
The fabricated sensing element was placed on the heater
placed inside the testing chamber and a PID controller
controlled the temperature of the heater. Gas sensor measure-
ments were made in the operating temperature in the range of
30–400 1C. The sensor was first stabilized at N2 atmosphere to
obtain the base line resistance. Various concentrations of CO2
were injected into the chamber and the changes in the
resistance with reference to the base line were measured. Prior
to every measurement, the test chamber was purged with N2 to
remove previous traces of CO2 gas. The sensor response
towards CO2 was studied in the concentration range of 500–
10,000 ppm at the optimum operating temperature. The
sensitivity S (%) towards CO2 gas was calculated by using
the relation given in Eq. (1) [44]
 
RCO2  RN2
Sð%Þ ¼  100 ð1Þ
RCO2
where RCO2 is the resistance of the sensor at different CO2
concentrations and RN2 is the baseline resistance in the
nitrogen atmosphere. The resistance of thin film samples was
measured with the help of a Keithley electrometer (Model
6517A).
3. Results and discussion
Formation of ZnO thin films on the silicon substrates [45]
was confirmed using FTIR spectra. Since glass substrate has
strong absorption in the IR region, silicon substrate was used
to deposit ZnO film for FTIR study [46]. Fig. 2 shows the
FTIR spectra of S1, S2 and S3 samples coated on Si substrates.
Band observed at about 405 cm  1confirmed the stretching
vibration of Zn–O bond. The two additional bands observed at
611 cm  1 and 1100 cm  1 in all the three spectra can be
ascribed to Si–Si and Si–O–Si bonds, respectively. The Si–O–
Si bond might be due to the surface oxidation of Si during
annealing [47].
The XRD patterns of all the three films are shown in Fig. 3.
The diffraction peak observed at 2θ E 341 corresponding to
(002) plane for S1, S2 and S3 samples confirmed the formation
of films with hexagonal wurtzite structure [48]. These results
indicated that the films were preferentially oriented along the
 P.K. Kannan et al. / Ceramics International 40 (2014) 13115–13122 13117

Fig. 1. Schematic of the experimental setup used for CO2 sensor measurements.

Fig. 3. XRD patterns of ZnO films (a) S1 (b) S2 and (c) S3.

The estimated values of lattice constants along with the

Fig. 2. FTIR spectra of ZnO films (a) S1 (b) S2 and (c) S3.
c-axis perpendicular to the substrate surface. The preferential
orientation may be attributed to the development of compres-
sive stress in the film during annealing which in-turn lead to
the elongation of the unit cell towards (002) plane [49].
The stress (δ) and strain (εz) values can be calculated using
the formula Eq. (2) [50],
δ ¼  453:6  109  εz
where εz ¼ ((C  C0)/C0) in which C0 (5.206 Å) is the c-axis
lattice constant of the strain-free powder sample and C is the
observed c-axis lattice constant.
stress and strain (%) values are shown in Table 1. It was found
that all the three films showed positive stress (or negative
strain) suggesting that compressive stress was operative in
these films. Also, the stress and strain values were found to
decrease as the film thickness increased which might be due to
the film relaxation. XRD patterns of the films showed a linear
increase in the intensity of the peak corresponding to the (002)
plane. This implied that the crystallinity varied in the order viz
S3 4S2 4 S1. FWHM was found to be larger for the S1 film
than that of S2 and S3 films indicating the smaller grain size of
ð2Þ S1. The calculated particle's size using Debye Scherrer's
equation is shown in Table 1 [51].
AFM was used to analyze the particle size as well as the
surface roughness of ZnO films. Fig. 4 shows the AFM images
13118 P.K. Kannan et al. / Ceramics International 40 (2014) 13115–13122

Table 1
XRD characterization data of ZnO films.

Sample (nm) Stress  109 (N/m2) Strain (%) Intensity (counts) FWHM (θ) Particle size (nm)

S1 (40) 3.22 0.71 84 0.3936 22

S2 (100) 2.09 0.46 204 0.3444 25
S3 (300) 1.83 0.39 789 0.3444 25

Fig. 4. 2D and 3D AFM images of ZnO films S1 (a and b) S2 (c and d) S3 (e and f).

Table 2 of S1, S2 and S3 films. The estimated values of the particle

AFM characterization data of annealed ZnO films. size and surface roughness are shown in Table 2. It can be
Sample (nm) Particle size (nm) Roughness value (nm) observed that as the film thickness increased, the particle size
was increased and the surface roughness was decreased. The
S1 (40) 290 10.9 particle size values derived from AFM were 290, 380 and
S2 (100) 380 6.33 400 nm for S1, S2 and S3 films, respectively, which are much
S3 (300) 400 3.65
higher than those calculated from XRD pattern. Particle size
 P.K. Kannan et al. / Ceramics International 40 (2014) 13115–13122 13119

measured using AFM might be that of coalesced grains formed The measurements were performed at 50 1C intervals between
by the migration of grain boundaries during the annealing 150 and 400 1C.
process [52,53] while film growth alone was responsible for Fig. 6 shows a plot of sensitivity against temperature for S1,
the changes in FWHM values measured by XRD [54]. S2 and S3 films. It can be observed that all the three films
Fig. 5(A) shows the room temperature UV–visible spectra of showed a similar trend with respect to the effect of operating
the samples S1, S2 and S3 with absorption maxima at about temperature. The sensitivity was found to increase in the
355 7 1 nm . These values were very close to the data reported temperature range of 150–300 1C and decreased thereafter.
for annealed ZnO samples prepared by other methods such as Fig. 6 also indicates that all the three films exhibited maximum
chemical reduction and precipitation methods [55,56]. sensitivity at the same temperature of 300 1C. However the
The photoluminescence spectra for S1, S2 and S3 samples most significant observation was that among the three films, S1
showed a strong emission peak at 405, 410 and 425 nm, showed the maximum sensitivity in the entire temperature
respectively (Fig. 5(B)). This was found to be in contrast with range considered for this investigation.
that of as-deposited ZnO samples in which a strong UV The increase in S (%) value with increase in operating
emission was observed at about 350 nm and a broad defect temperature can be attributed to the following phenomenon:
related to deep level emission in the visible region was metal oxides like ZnO are known to have surface adsorbed
observed at 480 nm [57–59]. The red-shift of the UV emission oxygen ion species like O2 , O  and O2  whose stability
peak from 350 to 405 nm and above can be ascribed to the depends on the operating temperature [8]. At temperatures
influence of size effect on the energy level of confined between 100 and 300 1C, it was most likely that O  ions were
excitons. In other words, this result implied that the average adsorbed on the surface of the ZnO film. When the operating
particle size was increased as a result of aggregation caused by
annealing. The emission peak in the visible region is known to
be associated with a number of defects such as zinc vacancy,
oxygen vacancy, interstitial zinc, interstitial oxygen and
antisite oxygen [60,61]. The absence of deep level emission
in the visible region in the photoluminescence spectra of the
three annealed samples S1, S2 and S3 indicated that the
annealing process greatly eliminated such defects in
these films.
The sensitivity or response towards target gas is much
dependent on the operating temperature of the sensor [62]. The
operating temperature of a gas sensor is usually the tempera-
ture corresponding to maximum sensitivity [63]. The adsorp-
tion of gases is directly related to the temperature at the surface
of the sensing layer and it plays a vital role on the electrical
response of semiconductor based sensors [64]. In order to
optimize the operating temperature, the sensitivity of the
three annealed ZnO films towards CO2 gas was measured
as a function of temperature maintaining a constant gas Fig. 6. Sensitivity as a function of operating temperature for the samples S1,
atmosphere. The CO2 concentration was fixed at 1000 ppm. S2 and S3 towards 1000 ppm of CO2.

Fig. 5. (A) UV–visible and (B) Photoluminescence spectra of ZnO films (a) S1 (b) S2 and (c) S3.
13120 P.K. Kannan et al. / Ceramics International 40 (2014) 13115–13122

temperature was increased from 150 to 300 1C, the amount of

CO2 gas adsorption on the ZnO surface gradually increased
and in-turn increased the sensitivity. However, at temperatures
above 300 1C, progressive desorption of the surface adsorbed
oxygen ion species might have occurred and decreased the
sensitivity value. The increase in resistance value of the ZnO
film in the presence of CO2 at 300 1C can be explained on the
basis of a space charge layers model. Accordingly, when the
ZnO film was exposed to CO2 gas, the adsorbed O  ions
reacted with the CO2 gas and extracted the electrons from the
conduction band of the n-type ZnO film (Eqs. 3 and 4). As a
result, the concentration of electrons on the surface of ZnO
film was decreased and the film resistance was found to
increase. Among the three samples, S1 showed the maximum
value of S (%) towards 1000 ppm of CO2. It might be likely
that the adsorption and diffusion of CO2 molecules were rather
Fig. 8. Calibration plot in the CO2 concentration range in the of 2000–
rapid at the thinner S1 sample compared to S2 and S3. 10,000 ppm. Inset shows a plot of sensitivity S (%) against concentration of
CO2ðgÞ þ e  -CO2ðadsorbedÞ

ð3Þ CO2 gas.

 
CO2ðadsorbedÞ þ OðadsorbedÞ þ 2e  -COðgÞ þ 2O2ðadsorbedÞ

ð4Þ
It can be observed that sample S1 attained 90% of response
at 20, 18 and 16 s for 1000, 5000 and 10,000 ppm of CO2,
respectively with corresponding recovery time values of 20, 34
and 40 s.
Fig. 7 shows the dynamic response of S1 towards 1000,
5000 and 10,000 ppm of CO2 gas at 300 1C. It can be observed
that upon exposure to CO2, the increased resistance of the ZnO
film confirmed its n-type semiconducting behavior [65]. When
the CO2 gas was introduced, the resistance of the film
increased with time and reached a steady state within a few
seconds. At this point, CO2 gas flow was turned off and N2 gas
was introduced into the test chamber. The sensor resistance
value was found to decrease rapidly and reach the baseline
value and in-turn revealed the good recovery characteristics of
the sensor.
The sensitivity S (%) was calculated for S1 film as a
function of CO2 in the concentration range of 500–
10,000 ppm. The response data obtained for four independent
set of measurements showed an RSD value of 1.78% and
0.21% at 1000 and 10,000 ppm of CO2, respectively, which in-
turn confirmed the good repeatability of the sensor. From this
response trend it was clear that the sensitivity increased rapidly
below 2000 ppm and thereafter the response was found to be
slow and steady (Inset of Fig. 8). A linear calibration can be
obtained in the CO2 concentration range of 2000–10,000 ppm
(Fig. 8), which can be expressed by Eq. (5)
S ð%Þ ¼ 3  10  4 ½CO2  þ 1:29 ð5Þ
In order to ascertain the reproducibility of the sensor, the
device response was measured in the presence of 1000 and
10,000 ppm of CO2 at an operating temperature of 300 1C for
five samples of S1 film prepared under identical deposition
conditions. The observed sensitivity indicated a good reprodu-
cibility of the developed sensor with RSD values of 1.04% and
0.28% for 1000 and 10,000 ppm of CO2, respectively.

4. Conclusions

A chemiresistive-type CO2 gas sensor was developed using

Fig. 7. Dynamic response of S1 towards 1000, 5000 and 10,000 ppm of CO2
at 300 1C.
DC reactive sputtered ZnO thin film. For this purpose, CO2 gas
sensing properties of sputter coated ZnO films with three
different thicknesses viz 40, 100 and 300 nm were studied. The
influence of annealing at 450 1C for 3 h on the ZnO film
crystallinity with a preferred c-axis orientation as well as the
reduction of strain in the films was observed. Grain size was
increased with increase in film thickness and also upon
annealing. The optimized operating temperature for the better
sensing response was found to be 300 1C. Among the three
films, the film with 40 nm thickness showed a better response
in the entire temperature range of investigation. The developed
CO2 sensor showed a maximum sensitivity (%) of 1.13 with an
equal response and recovery time of 20 s at 1000 ppm of CO2.
 P.K. Kannan et al. / Ceramics International 40 (2014) 13115–13122
Acknowledgments
Financial support from University Grants Commission, New
Delhi, Government of India under the University with Poten-
tial for Excellence Scheme is gratefully acknowledged.
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