J Mater Sci: Mater Electron (2017) 28:11473–11481

DOI 10.1007/s10854-017-6943-1

Effect of thickness on the physical properties and gas sensing

application: anatase titanium dioxide nanofilms by automated
nebulizer spray pyrolysis (ANSP)
V. Gopala Krishnan1,2 · A. Purushothaman2 · P. Elango1

Received: 20 February 2017 / Accepted: 10 April 2017 / Published online: 17 April 2017
© Springer Science+Business Media New York 2017

Abstract In this work, effects of thickness towards vol- problems such as the greenhouse effect and the ozone
ume proportion of T ­ iO2 nanofilms were deposited on a hole. These problems are related to the release of pollut-
glass substrate at 500 °C by using ANSP method. The opti- ant gasses in the atmosphere, therefore their exposure and
cal profilometer shows the coated films thicknesses were demolitions are the hot global priority. As mentioned in the
increased (186, 234, 311, 397 and 433 nm) by increasing literature, the semiconducting metal oxide of solid-state
the volume proportion. Based on the thickness, The XRD ­(SnO2, ­TiO2, ZnO) gas sensors is widely preferred due to
reveals a polycrystalline tetragonal anatase phase with a sequence of specific advantages [1]. Particularly, n-type
decreased particle sizes. The topographical study (AFM) of metal oxide semiconductor of titanium dioxide (­ TiO2) is an
3D surface view shows the incremented average roughness effective material for the different new applications such as
­(Ra) values. The surface morphological variations with solar cell [2], purifier of environmental pollutants [3], pho-
decremented particle size were examined by FESEM. The tocatalysis [4], gas sensors [5], corrosion-protection [6] and
maximum transmittance ~78.5% (λ = 612.8 nm) is obtained microelectronics [7, 8] applications, due to its properties of
to 186 nm thickness and further increment of thickness non-toxicity in aqua, reasonable cost, powerful oxidation
shows the decremented value of transmittance with an potential and high chemical inertness ­TiO2 is an attractive
absorption edge shifted from lower to higher wavelength material owing to their notable ability to change the electri-
(blue shift) and the calculated band gap value Eg = 3.65– cal resistance (conductance) in response to oxidizing and
3.26 eV. The gas sensing performances of films was studied reducing gasses, and the electronic structure of T ­ iO2 and
by using a various sensing parameters, obviously ­C2H6O its consequences as far as the gas sensing performance is
gas shows highest response ­(Sm = 13% as 397 nm) at 300 °C concerned immensely.
for 150 ppm gas concentration against other gasses (­NH3, TiO2 defined with three polymorphic forms such as
­CH4O, ­C3H8O and C ­ 3H6O). anatase, brookite, and rutile. The Rutile (­D4h,14P42/mnm,
symmetry) and anatase (­D4h,19I41/amd, symmetry) make
a tetragonal phase and they were developed commercially,
1 Introduction but the orthorhombic phase of brookite (Pcab, lower sym-
metry) is very difficult to prepare but naturally present in a
The improvement of nanoscience and nanotechnology plays solitary crystal form. Brookite and anatase may be turned
an effective role to reduce several global environmental to rutile phase by the subject of higher temperature, usu-
ally at ~750 to ~1000 °C respectively [9]. A rutile phase
is usually the dominant phase in T ­ iO2, but some work has
* P. Elango been synthesizing an anatase phase because of their impor-
yuvagopal@yahoo.in
tance in practical engineering applications in sensors [10].
1
Department of Physics, Government Arts College, The fabrication of the anatase and rutile phases strongly
Coimbatore 641018, India depends on the temperature and deposition method [11].
2
Department of Physics, Sree Sakthi Engineering College, Attentively many techniques are used to prepare the stabi-
Coimbatore 641104, India lized anatase ­TiO2 thin films namely, sol–gel [12], chemical

13
Vol.:(0123456789)
11474 J Mater Sci: Mater Electron (2017) 28:11473–11481

vapor deposition [13], pulsed laser deposition [14], electro- Table 1  Optimized spray parameter for T
­ iO2 nanofilms with thick-
chemical [15], RF-magnetron sputtering and spray pyroly- ness variation
sis deposition [16]. Among them, the spray pyrolysis is Particulars Parameter
one of the significant methods which are may effectively
Spray type Nebulizer
opened new routes to nanotechnology. This process impor-
Air blast Atomizer
tantly has a very safety, less expensive, no need in vacuum
Carrier gas pressure 30 Pa
arrangement and sustaining homogeneity in large area of
Solution flow rate 0.10 ml/min
film coating [17] behaviors.
Distance from substrate to spray 5 cm
Significantly, the effect of thickness plays an important
nozzle
role in controlling the phase stability and film properties,
Substrate type Glass
which is one of the critical parameters to achieve a desired
Solvent Ethanol and acetyle acetone
structural and functional property [18]. As our knowledge,
Precursor Titanium isopropoxide
only a few works have been studied by using acetylac-
Concentration 0.1 mol/l
etone stabilized Ti-alkoxide precursors, whereas the phase
Deposition variation 2.50, 5.00, 7.50, 10.00, 12.50 ml
stability was not maintained on their works also [19–21].
Deposition temperature 500 °C
Particularly no systematic study of structural and optical
characterization of the anatase phase T ­ iO2 films deposited
by spray pyrolysis technique from the source of acetylac-
etone stabilized Ti-isopropoxide have been performed. Pre-
dominantly, the automated nebulizer sprayed anatase phase
stabilized and gas sensing performances of ­TiO2 film have
not been studied so far. The aim of this work is to deposit
­TiO2 nanofilms on preheated glass substrate at 500 °C with
different volume proportions by the method of automated
nebulizer spray pyrolysis and exemplify the effect thickness
on structural, optical, topography, morphological and gas
sensing performance of ­TiO2 nanofilms.

2 Experimental details

TiO2 nanofilms array with nominal volume proportions

(x) of 2.5, 5.0, 7.5, 10.0 and 12.5 ml is taken and prepared
by using automated nebulizer spray pyrolysis technique
(ANSP) in an air atmosphere. The experimental setup, Fig. 1  XRD study on various thickness of ­TiO2 nanofilms
procedure and advantages of ANSP were explained [9]
elsewhere and the observed basic parameters were men- (AFM, Model-Nanoscope E) and field emission scanning
tioned in Table 1. The primary stock solution was pre- electron microscopy (FESEM, Quanta-250 FEG) apply-
pared with 0.1 M/l of titanium tetra-isopropoxide (TTIP) ing an operating voltage 30.0 kV. An optical study of the
[Ti[OCH(CH3)2]4] dissolved in 50 ml mixed solution of films was done by Ultra Violet–Visible–Near Infrared
ethanol (EtOH) (­C2H5OH) solvent with acetylacetone (UV–Vis–NIR) spectrophotometer (Model JASCO-V-500)
(AcAc) ­[CH3COCH2COCH3] stabilizer in the ratio of in the range from 250 to 980 nm and thickness of the films
(4:1) and stirred for 15 min by using magnetic stirrer. The was determined by using surface profilometer (SJ-301
obtained transparent pale yellow solution with different Mitutoyo). Finally, the gas sensing performances were
above mentioned volume proportions was sprayed on the studied by LCR meter (GW Instek LCR-821).
ultrasonically cleaned glass substrate at 500 °C.
Various volume proportions of coated films may bring
into being a various thickness of the films and their charac- 3 Results and discussion
terization is analyzed by the following study. The structural
properties of T­ iO2 films were entirely studied by X-ray dif- XRD study of thickness varied (186, 234, 311, 397,
fraction (Bruker D8 advance X-ray diffractometer) with 433 nm) nanofilms of ­TiO2 are shown in Fig. 1. The coated
Cu Kα radiation (λ = 0.15418 nm). Surface morphology films were generally polycrystalline with stabilized anatase
of the films was characterized via atomic force microscope form of tetragonal phase with prominent diffraction peaks

13
J Mater Sci: Mater Electron (2017) 28:11473–11481 11475

at 2θ° = 25.51, 38.31, 48.66 and 55.44° corresponding to the films is increased with respect to thickness. This vari-
(101), (112), (200) and (105) reflection planes were well ation shows the fine correspondence with crystalline size
fitted with standard JCPDS data, card no. 89-4921. Mean- and d-spacing value of XRD study. Figure 2f–j shows the
time, this film was not detected other two remaining phases surface morphological characterisation of T ­ iO2 nanofilms
(brookite, rutile) because the preparation method and raw and it is analysed by using field emission scanning electron
materials were maintain the phase stability [22]. The crys- microscope (FESEM). The smaller thickness of the coated
tallite size ‘D’ is calculated using Scherrer formula [23], films (186 nm) depicts the spherical shape structures and
for the thickness of 234, 311, 397, 433 nm shows the micro
0.9 × 𝜆
D= (1) spherical structures. The observed particle sizes were
(𝛽 × cos 𝜃)
decreased by increase in thickness, which is in good agree-
n𝜆 ment with structural and topography study.
d= (2) The optical transmittance spectra of T
­ iO2 nanofilms over
(2 sin 𝜃)
the spectral range of 250 nm to 980 nm are shown in Fig. 3.
where D is the crystalline size, λ is the wavelength of
The oscillating nature of average transmittance is enhanced
X-rays, β is the broadening of diffraction line measured
up to 78.4% (at λ = 616 nm) for the coated film of 186 nm
at half its maximum intensity in radius, d is interplanner
thickness. The transmittance values of all coated films
spacing value and θ is the angle of diffraction. The average
were decreased by increase in thickness. This decrement is
crystallite size and d-spacing value were found to decrease
caused by the fundamental absorption of light may increase
with increase in thickness and their intensity of ­TiO2 films
the quality of defect less films immensely [26]. The UV
varied with respect to thickness. The lattice constants deter-
region of sharp absorption edges was shift from shorter to
mined from the present data are a = 3.788 and c = 9.549 Å.
longer wavelength (Blue-shift) due to the thickness (186,
The dislocation density and microstrain were calculated by
234, 311, 397, 433 nm) variations, since the improvement
using equations (3) and (4) for ­TiO2 films [9].
in crystal quality of the films along with a reduction in
1 porosity [27]. The band gap energy was calculated by using
𝛿= (3)
D2 the Tauc’s relation [28].

𝜆 𝛽
𝜀= − (4) 𝛼(h𝜈) = A(h𝜈 − Eg )1∕2 (5)
D sin 𝜃 tan 𝜃
The variation of dislocation density and microstrain where ­Eg is the optical band gap of the sample and A is
with different thickness of ­TiO2 was listed in Table 2. It has constant. Optical band gap ­(Eg) energy of ­TiO2 film is car-
been confirmed that the calculated average crystalline size, ried out by extrapolating linear region spectrum (αhν)2 ver-
d-spacing value, lattice parameter, dislocation density and sus (hν) as shown in Fig. 4. The obtained band gap energy
microstrain of the obtained films values corresponded to (Eg = 3.26–3.65) is decreased from higher to lower with
that of the bulk T
­ iO2 anatase phase structure [24]. respect to increasing thickness because of an improvement
Atomic force microscope (AFM) allows us to get micro- in film quality may reduce the structural defect. The stand-
scopic information on the surface structure and to plot ard band gap energy of anatase phase T ­ iO2 is 3.20 eV is
topographies representing the surface relief. This tech- finely coinciding with a coated thickness of 397 nm, hence
nique offers digital images which allow quantitative meas- the film was currently matched with XRD study.
urements of surface features, such as root mean square
roughness ­Rq, or average roughness ­Ra, and the analysis of 3.1 Gas sensing behavior of T
­ iO2 nanofilms
images from different perspectives, including three-dimen-
sional simulation. The topography view of 2 µm × 2 µm The schematic diagram of the gas sensor setup was repre-
sized three-dimensional AFM images of T ­ iO2 nanofilms sented in Fig. 5. As we can be seen, the cylindrical stainless
with different thickness (186, 234, 311, 397, 433 nm) is steel testing chamber inbuilt with a nichrome-heating ele-
shown in Fig. 2a–e. In sample with the lowest thickness, ment and a chromel–alumel thermocouple is fixed at bot-
particles rather are isolated from each other (Fig. 2a, b) tom of the testing chamber and it is well connected with
while in Fig. 2c–e are continually in distribution these a temperature controller for adjusting the temperature (~up
changes in surface morphology might lead to degradation to 500 °C). The sensing measurements were proceeded by
in the crystalline quality of the film [25]. This suggests a static process: a specified amount of the test gas such as
that the particles seen at the surface of the film are clus- ­C2H6O, ­NH3, ­CH4O, ­C3H8O, and C ­ 3H6O was injected into
ters of crystallites. The AFM analyses of average rough- a testing chamber and mixed with air. A mass flow control-
ness parameters were listed in Table 2. It can be seen from ler (MFCs) was used to control the concentration of the test
the figure, the surface roughness and coating thickness of gasses. The sensor films were electrically connected to a

13
 11476

13
Table 2  Obtained values of structural parameters, average roughness and coating thickness of the ­TiO2 films
Volume Peak position FWHM value (h k l) “D” partical size “δ” dislocation “ε” strain “d spacing” Stacking fault Average Thickness (nm)
(ml) 2θ (deg) (deg) Value (nm) ×1014 ­(linmet−2) ×104 ­(lin−2met−4) value roughness
x10−10 m (nm)
h k l

2.50 25.930 0.1673 1 0 1 50.94 3.854 7.114 3.436 0.088 1.781 186
38.313 0.2007 0 0 4 43.80 5.212 8.272 2.349 0.086
48.621 0.2676 2 0 0 34.05 8.624 10.641 1.873 0.101
54.364 0.8029 1 0 5 11.63 73.973 31.164 1.688 0.283
5.00 25.832 0.1673 1 0 1 50.93 3.856 7.115 3.449 0.088 2.061 234
38.454 0.4015 0 0 4 21.90 20.841 16.542 2.341 0.172
48.130 0.2676 2 0 0 33.99 8.657 10.661 1.891 0.101
54.400 0.4015 1 0 5 23.25 18.492 15.581 1.687 0.142
7.50 25.703 0.2007 1 0 1 42.44 5.552 8.538 3.466 0.106 2.683 311
38.459 0.3346 0 0 4 26.28 14.474 13.785 2.341 0.143
48.458 0.3346 2 0 0 27.22 13.501 13.314 1.879 0.126
54.153 0.5353 1 0 5 17.42 32.943 20.797 1.694 0.189
10.00 25.387 0.2676 1 0 1 31.81 9.883 11.391 3.508 0.143 2.815 397
37.872 0.2342 0 0 4 37.49 7.116 9.666 2.376 0.101
48.146 0.4725 2 0 0 19.25 26.988 18.824 1.890 0.179
53.153 0.4015 1 0 5 23.13 18.697 15.668 1.723 0.144
12.50 25.197 0.2007 1 0 1 42.40 5.563 8.546 3.534 0.107 3.104 433
37.912 0.4684 0 0 4 18.75 28.458 19.329 2.373 0.202
48.082 0.3346 2 0 0 27.18 13.541 13.333 1.892 0.127
53.225 0.6022 1 0 5 15.42 42.035 23.492 1.721 0.215
J Mater Sci: Mater Electron (2017) 28:11473–11481
J Mater Sci: Mater Electron (2017) 28:11473–11481 11477

Fig. 2  a–j Topography view of

AFM and surface morphology
of FESEM for ­TiO2 thin films

13
11478 J Mater Sci: Mater Electron (2017) 28:11473–11481

two-probe setup for measure the resistance variation (GW

Instek LCR-821) and hence calculate the sensing response.
The gas sensitivity response (S) factor of ­TiO2 nanofilms
was calculated by using the relation of resistance in the air
­(Rair) and resistance in reducing gasses ­(Rgas), which was
expressed as [29].

Rair − Rgas ΔR R
S= = ∼ air (6)
Rgas Rgas Rgas
Based on that, various parameters such as crystallite
size, film thickness, porosity, amount and nature of dopant,
catalysts and surface states are known to be important in
enhance the gas sensitivity of the sensors element [30]. The
main emphasis of this letter is to study the chemiresistors
(metal oxide) gas sensing surface phenomenon of adsorbed
Fig. 3  Variation of transmittance as a function of wavelength for oxygen and different gases ­(CH3OH, ­NH3, ­C3H8O, ­C2H6O
­TiO2 nanofilms and ­C3H6O) with various parameters of sensitivity, selec-
tivity, response and recovery times with respect to the
function of temperature (°C) and gas concentration (ppm)
of pure titanium oxide nanofilms were prepared by using
automated nebulizer spray pyrolysis method. The sensing
nature of pure T ­ iO2 films significantly relates with operat-
ing temperature [31]. Accordingly, the gas sensing response
behaviour of various coated thickness (186, 234 nm, 311,
397, 433 nm) of ­TiO2 nanofilms were represented with a
function of temperature (50–350 °C) at an constant gas
concentration (150 ppm) of ­C2H6O reducing gas is shown
in Fig. 6(left). As we can be seen, the gas response of all
the films increased with respect to operating temperature,
the sensor element (­TiO2) of the various coated thickness
of the films reaches the maximum gas response (­Sm = 13%
as 397 nm) at ­300○C and then falls with further increase
Fig. 4  Plot of (αhν) 2 versus hν for T
­ iO2 films sprayed at 773 K in operating temperature is due to the mechanism of gas
adsorption and desorption of chemiresistors (metal oxide)
[1]. Similarly, Fig. 6(right) denote the various reducing
COMPUTER gas sensing response of 397 nm thickness of T ­ iO2 with a
GW INSTEK LCR-821
function of temperature (50–350 °C) at a constant gas con-
12.3456 kΩ centration (150 ppm). Among the various reducing gas,
the ­C2H6O reducing gas reveals the highest gas response
­(Sm = 13%) may be due to the surface phenomenon of
adsorbed oxygen, nanocrystalline nature of films and
higher surface to volume ratio [32].
The dependence of sensitivity towards different thick-
AIR INLET AIR OUTLET ness of (186, 234, 311, 397, 433 nm) ­TiO2 on the ­C2H6O
SUBSTRATE
gas concentration at an operating temperature of 3­ 00○C
is shown in Fig. 7(left). It is observed that the sensitivity
GAS PRESSURE
vvCONTROLLER (MFCs) THERMO COUPLE
TEMP. increases linearly as the C ­ 2H6O concentration increases
CONTROL from 30 to 150 ppm and then decreases with further
increase in the ­C2H6O gas concentration. The linear rela-
CARRIER GAS tionship between the sensitivity and the C ­ 2H6O gas con-
centration at low concentrations may be attributed to the
availability of a sufficient number of sensing sites on the
Fig. 5  Schematic diagram of gas sensor setup

13
J Mater Sci: Mater Electron (2017) 28:11473–11481 11479

film to act upon the ­C2H6O. The lower and higher gas con- Figure 7(right) shows the various reducing gas response to
centration involves a lower and higher surface coverage of 397 nm thickness of ­TiO2 films at 300 °C operating tem-
gas molecules, resulting in a lower and higher surface reac- perature for different gas concentration. Which is shows the
tion between the surface adsorbed oxygen species and the ­C2H6O gas exposes highest sensitivity response when com-
gas molecules. Further increase in gas concentration the pared with other reducing gasses.
surface reaction will be gradual and reached saturation of Figure 8(left) shows the sensitivity response to different
the surface coverage of gas molecules. Thus, the maximum thickness (186, 234, 311, 397, 433 nm) of various reduc-
sensitivity was obtained at an operating temperature of ing gasses at 300 °C operating temperature with constant
­300○C for the exposure of 150 ppm of C­ 2H6O reducing gas. gas concentration (150 ppm). Among all gasses, the ­C2H6O

Fig. 6  Sensitivity response of

ethanol gas with the function of
temperature for various coated
thickness, sensitivity response
to 397 nm thickness with an
functions of temperature (right)

Fig. 7  Sensitivity response of

ethanol gas with the func-
tion of gas concentration for
various coated thickness (left),
sensitivity response to 397 nm
thickness with an functions of
gas concentration (right)

Fig. 8  Sensitivity response of

various gases with the function
of coated thickness (left side),
sensitivity response and recov-
ery time to 397 nm coated film
of ­TiO2 (right side)

13
11480 J Mater Sci: Mater Electron (2017) 28:11473–11481

gas reveals the high sensitivity response for the respective higher operating temperature, as the oxygen adsorbents are
parameter. The effective of these sensors is very fast as it desorbed from the surface of the sensor [35]. In addition,
can be observed; that the gas response and gas recovery at a higher temperature, the carrier concentration increases
times are defined as the times of conductance takes to reach due to intrinsic thermal excitation and the Debye length
90% of (­Rf–R0) when the gas is introduced and to recover decreases. This may be one of the reasons for decreases gas
30% of (­Rf–R0) when the flux of the air is restored. Fig- sensitivity at higher temperature [36].
ure 8(right) says the response and recovery time for ­C2H6O
are about 20 and 90 s respectively. The quick response
­C2H6O gas may due to faster oxidation, which shows 4 Conclusion
their good sensing ability and their time to the sensitivity
response of the sensor element has approximately constant Based on the structural, compositional, topography, surface
in every cycle, which is indicating the repeatability of the morphology, optical and gas sensing performance of our
sensor. samples were emerge out the following points: (i) different
thickness of the ­TiO2 films were examined by using opti-
3.2 Gas sensing mechanism cal profilometer and the obtained thickness are 186, 234,
311, 397, 433 nm with respect to volume proportion (ii) all
The fast response and quick recovery of ­C2H6O reducing samples exhibits a polycrystalline anatase phase of tetrago-
gas having a most important feature of the present inves- nal structure with strong plane orientation (101), and the
tigation are high gas response, high selectivity to against observed crystalline size were decreased with increase in
other gasses ­ (NH3, ­CH4O, ­C3H8O, and ­ C3H6O). The thickness. (iii) AFM shown the average roughness value
enhanced response could be attributed to nanocrystalline were increased by increase the thickness and the morpho-
nature of the films. It is known that the high sensitivity logical behavior of micro spherical structure with reduced
performances were sustained with a metal oxide, which particle sizes as revealed in the study of FESEM. (iv). The
absorbs oxygen species of O ­ −2, ­O− or O
­ 2− from the sur- optical transmittance values were decreased with an blue
rounding and also control the increment of conductivity shift of absorption edge; the band values were decreased
due to electron capture by oxidizing gas [33] were as, with increase in thickness due to the improvement of
O2 (gas) + e− → O2 (ads)− defect-free quality films was determined by optical meas-
(7)
urement. (v). Finally, the gas sensing performance of ­TiO2
O2 (ads)− + e− → 2O(ads)− (8) nanofilms shows their sensitivity response (%) with respect
The presence of chemically adsorbed oxygen could to operating temperature, coated thickness and gas con-
cause electron depletion in the thin film surface and be centration of various gasses. The reducing gas of ­C2H6O
building up of Schottky surface barrier; consequently, the exhibits a greatest sensitivity response (S = 13%) against
electrical conduction of thin film decreased to a minimum. other gasses at 300 °C for 150 ppm of gas concentration.
When a surface of the material exposed to the reducing gas,
Acknowledgements One of the authors (V. Gopala Krishnan)
the interaction with the chemisorbed oxygen can take place gratefully acknowledges to Dr. T. Shripathi, Dr. U. P. Deshpande
in a various way. Here, the maximum sensitivity of surface and Er. Mohan Gangrade from the UGC—DAE CSR, Indore Centre,
reactions can be written to the reducing gas of ethanol as Khandwa Road, India for their scientific advice and for providing the
the follows [34]: necessary laboratory facilities such XPS and AFM measurements for
carry out this investigation.
C2 H5 OH + O2 → CH3 CHO + H2 O (9)

CH3 CHO + O− (ads) → CO2 + H2 O + e− (10)

References
with this reaction, many electrons could be released to
a thin film surface. This could make the Schottky sur- 1. D. Mardare, N. Iftimie, D. Luca, J. Non-Cryst. Solids 354, 4396–
face barrier decrease; with the depletion layer thinner; 4400 (2008)
consequently, the electrical conductance of the thin film 2. I. Vaiciulis, M. Girtan, et al., Proc. Rom. Acad. Seri. A 13(4),
335–342 (2012)
increases. More gas would be absorbed by the thin film sur- 3. H. Ichiura, T. Kitaoka, H. Tanaka, Chemosphere 50(1), 79–83
face; thus, the gas sensitivity was enhanced. An increase in (2003)
operating temperature causes oxidation of a large number 4. M.O. Abou-Helal, W.T. Seeber, Appl. Surf. Sci. 195, 53 (2002)
of ­C2H6O molecules, thus producing a very large number 5. N.E. Stankova, I.G. Dimitrov, et al., Appl. Surf. Sci. 254, 1268
(2007)
of electrons. Therefore, conductivity increases largely. This 6. I. Poulios, P. Spathis, et al., J. Environ. Sci. Health. A, 34(7),
is the reason why the gas sensitivity increases with oper- 1455–1471 (1999)
ating temperature. However, the sensitivity decreases at 7. G.P. Burns, J. Appl. Phys. 65, 2095 (1989)

13
J Mater Sci: Mater Electron (2017) 28:11473–11481 11481

8. H.G. Choi, S. Yong, D.K. Kim, Kor. J. Mater. Res. 22(7), 352– 23. B.D. Cullity, Elements of X-ray Diffraction, 2nd edn. (Addison-
357 (2012) Wesley Publishing Company Inc, Toronto, 1978)
9. V. Gopala Krishnan, P. Elango, et al., Optik-Int. Light Electron 24. S.K. Joung, T. Amemiya, et al., Chem. Eur. J. 12, 5526–5534
Optics 127, 11102–11110 (2016) (2006)
10. H. Tang, K. Prasad, et al., Sens. Actuators B Chem. 26–27(1–3), 25. M.A. Martynez, C. Guillen, J. Herrero, J. Appl. Surf. Sci. 136, 8
71–75 (1995) (1998)
11. K.L. Choy, B. Su, J. Mater. Sci. Lett. 18, 943–945 (1999) 26. D. Mardare, M. Tasca, M. Delibas, et al, J. Appl. Surf. Sci. 156,
12. M. Bockmeyer, B. Herbig, et al., Thin Solid Film 517, 1596– 200–206 (2000)
1600 (2009) 27. N.M. Ganesan, T.S. Senthil, et al., Int. J. Chem. Tech. Res. 6(5),
13. N. Rausch, E.P. Burte, J. Electrochem. Soc. 140(1), 145–149 3078–3082 (2014)
(1993) 28. K.Y. Rajpure, C.D. Lokhande, et al., Mater. Res. Bull. 34, 1079–
14. J-C Orlianges, et al., J. Appl. Surf. Sci. 263, 111–114 (2012) 1087 (1999)
15. M. Bouaicha, N. Ghrairi, Nanoscale Res. Lett. 7, 357 (2012) 29. A.A. Haidrya, J. Puskelova, et al., Appl. Surf. Sci. 259, 270–275
16. A.I. Martinez, et al., J. Phys. 16(22), S2335–S2344 (2004) (2012)
17. R. Mariappan, V. Ponnuswamy, et al., Mater. Sci. Semicond. 30. C.H. Han, D.W. Hong, et al., Sens Actuators B Chem. 128, 320–
Process. 16, 1328–1335 (2013) 325 (2007)
18. L. Wei, O. Caiwen, P. Huang, et al., Int. J. Electrochem. Sci. 8, 31. L.A. Patil, D.N. Suryawanshi, et al., Bull. Mater. Sci. 37(3), 425–
8213–8226 (2013) 432 (2014)
19. I. Oja, A. Mere, M. Krunks, et al., Thin Solid Film 515, 674–677 32. C. Garzella, E. Comini, et al., Sens Actuators B Chem. 68, 189–
(2006) 196 (2000)
20. F.D. Duminica, F. Maury, et al., Thin Solid Film 515, 7732–7739 33. P. Shailesh, C. Manik, et al., J. Sensor Technol. 1, 9–16 (2011)
(2007) 34. M.R. Vaezi, S.K. Sadrnezhaad, Mater. Sci. Eng. B 140, 73–80
21. H. Zabova, V. Cirkva, J. Chem. Technol. Biotechnol. 84, 1624– (2007)
1630 (2009) 35. H. Windichamann, P. Mark, J. Electrochem. Soc. 126(4), 627–
22. W. Niu, G. Wang, et al., Int. J. Electrochem. Sci. 10, 2613–2620 633 (1979)
(2015) 36. J. Mizsei, Sens Actuators B Chem. 23, 173–176 (1995)

13