Sensors & Actuators: A.

Physical 369 (2024) 115181

Contents lists available at ScienceDirect

Sensors and Actuators: A. Physical

journal homepage: www.journals.elsevier.com/sensors-and-actuators-a-physical

TiO2-ZnO Composite thin films fabricated by Sol-Gel spin coating for room
temperature impedometric acetone sensing
Muthukumar Murugesan , S.R. Meher *
Department of Physics, School of Advanced Sciences, Vellore Institute of Technology, Vellore 632014, India

A R T I C L E I N F O A B S T R A C T

Keywords: Metal oxide semiconductor based volatile organic compounds (VOCs) sensors lack room temperature operation
Metal oxides and have a poor limit of detection. In this work, TiO2-ZnO composite thin film based acetone sensors with room
Semiconductors temperature (29 ± 2 ◦ C) operation and good sensor response have been fabricated by sol-gel based spin coating.
Thin films
The thin films based on the single-phase TiO2 and ZnO together with their composites have been evaluated for
TiO2-ZnO
Sol-gel spin coating
their structural and surface morphological properties through X-ray diffraction and field emission scanning
Acetone sensing electron microscopy respectively. The surface chemical state of the thin films surface has been analyzed through
the X-ray photoelectron spectroscopy. The optical properties of the single-phase as well as the composite phase
thin films were studied by optical absorption spectroscopy. The acetone sensing characteristics of these thin films
based sensors were evaluated through impedance spectroscopy. The composite thin films were found to exhibit
the maximum sensor response of 93.83% with a detection threshold of 3 ppm for acetone.

1. Introduction at various concentrations which can be helpful towards the diagnosis of

Human exhaled breath contains many volatile organic compounds
(VOCs) owing to metabolism and the alteration of the same can be an
indication of various pathological disorders. Due to the rapid advance­
ment of analytical techniques, the VOC concentration in exhaled breath
can act as a biomarker (BM) for several disease diagnoses. The acetone
concentration in healthy subjects ranges from 300–900 ppb whereas the
same rises to 1800 ppb (or 1.8 ppm) for patients suffering from diabetes
mellitus [1]. Therefore, a compact acetone sensor with a low detection
threshold that can operate under ambient conditions can be helpful for
the early diagnosis and control of diabetes mellitus.
Chemiresistive sensors based on metal-oxide-semiconductors (MOS)
offer trustworthy solutions to detect acetone in contrast to other sensing
techniques. Due to their exceptional chemical and physical features,
easily tuneable physicochemical traits, straightforward sensing pro­
cedures, ease of manufacture, and cost-effectiveness, MOSs are very
reliable for practical applications. Because of their excellent chemical
stability, quick reaction to target gas conditions, and other character­
istics, practical obstacles during acetone sensing can be addressed [2].
The development of MOS-based acetone sensors has been the subject of
many published studies [3,4]. Materials like SnO2 [5], ZnO [6], TiO2
[7], In2O3 [8], Fe3O4 [9], and WO3 [10] are useful for detecting acetone
diabetes.
Among these MOS, titanium dioxide (TiO2) with a wide band gap of
3.2 eV is particularly sensitive to acetone. The acetone sensing by TiO2 is
mostly attributed to the presence of native oxygen vacancies and anti-
site defects, which establish n-type conductivity in it [11]. The elec­
trical conductivity of TiO2 changes because of the change in its electron
concentration upon exposure to acetone. As per the literature, Navale
et al. [12] have developed a TiO2 mesoporous sensor with an enhanced
detection threshold of 500 ppb for acetone at an operating temperature
of 270 ◦ C. Meanwhile, the TiO2 nanotube-based sensor developed by
Bindra et al. [13] could detect various VOCs, including acetone, at room
temperature, although its detection threshold was greater than 100
ppm. The major practical problems associated with the single-phase
TiO2 based acetone sensors is their high operating temperature or
poor detection threshold at room temperature [14,15]. Numerous
studies have been conducted to modify the single-phase TiO2 in terms of
doping [16], metal-insulator-semiconductor (MIS) device approach [17]
and molecular imprinting [18] to overcome the above issues.
Another promising approach that has received a lot of attention in
the recent past to enhance the VOC sensing characteristics is the com­
bination of two different MOS to form heterojunction composites. There
are large number of active sites at the heterojunction interface due to the

* Corresponding author.
E-mail address: samirmeher@gmail.com (S.R. Meher).

https://doi.org/10.1016/j.sna.2024.115181
Received 10 November 2023; Received in revised form 21 January 2024; Accepted 12 February 2024
Available online 13 February 2024
0924-4247/© 2024 Elsevier B.V. All rights reserved.
M. Murugesan and S.R. Meher
lattice mismatch. Meanwhile, the difference in Fermi levels of the two
MOS in the composite would result in the establishment of a potential
barrier at their interfaces which is a key factor for enhancing the sensing
property of the heterojunction-based sensors [19]. The composite
MOS-based acetone sensors are reported to be more sensitive than
single-phase materials and have improved detection threshold [20]. The
composites of TiO2 - ZnO [21], TiO2 - SnO2 [22], TiO2 – reduced Gra­
phene Oxide (rGO) [20], and Graphene Oxide (GO)- TiO2 [23] are re­
ported to have good response with better detection threshold at lower
working temperatures. Among these heterojunctions, the composites of
TiO2 with ZnO have got potential features for enhancing the acetone
sensing characteristics. This is due to the wide band gap (~3.3 eV) and
n-type conductivity of ZnO which is identical to that of TiO2. The n – n
type TiO2 – ZnO heterojunction facilitates easy electron transfer be­
tween the semiconductors which in turn results in fast change in the
resistance upon exposure to the target gas. Feng et al. [24] have fabri­
cated acetone sensors based on the TiO2 @B-TiO2 @ZnO core-shell
heterojunction. They have reported an improved acetone detection
threshold of 170 ppb at 275 ◦ C which primarily has been attributed to
the narrower band gap (~1.54 eV) of black TiO2 (B-TiO2) due to Ti+3
self-doping in TiO2. Recently, Krishna et al. [25] developed a ZnO/TiO2
nanocomposites-based sensor that is capable of detecting acetone at
room temperature with a response of 179% and a low detection limit of
100 ppb, which emphasizes the potential of the sensor for diabetes ap­
plications due to its synergy.
The sensors based on nanostructured materials can significantly
enhance the sensor response as well as reduce the operating tempera­
tures. But they suffer from several issues such as repeatability and reli­
ability for practical usage. The thin film-based sensors are more robust
and are commercially viable [26]. As per the current status, there are no
reports on TiO2 thin film-based acetone sensors operating at room
temperature with an appreciable low-level detection threshold. In the
present investigation, we have prepared the thin films of single-phase
TiO2, ZnO and their composites by sol-gel based spin coating. The
impedometric room temperature (29 ± 2 ◦ C) sensing characteristics of
the fabricated sensors based on these thin films were evaluated in the
range 10 – 70 ppm.
2. Experimental methods
2.1. Thin film deposition
Sol-gel spin coating was used to coat the single-phase as well as the
composite thin films of TiO2 and ZnO. The films were deposited on
cleaned soda-lime glass substrates of size 25 mm × 25 mm. The glass
substrates were heated for 5 min at a temperature of 400 ◦ C and sub­
sequently cleaned with Cedepol soap solution to remove any kind of
organic contaminants. After 15 min of ultrasonic treatment with
ethanol, the substrates were treated with deionized water. The purpose
of this process was to clean the substrates for any kind of residual con­
taminants. Finally, the substrates were flushed with dry N2 before being
spin coated. Titanium (IV) isopropoxide (C12H28O4Ti) and zinc acetate
dihydrate (Zn(CH3COO)2.2 H2O) were the metalorganic precursors for
TiO2 and ZnO respectively. The 0.1 M of precursor salt for TiO2 was
dissolved in ethanol (CH2CH3OH), which served as the solvent. Under
constant stirring, a few drops of water to initiate the hydrolysis process
and a few drops of concentrated nitric acid (HNO3) to prevent precipi­
tation were added to the solution. To acquire a transparent homoge­
neous solution, the solution was stirred for 5 h. The obtained solution
was aged for 24 h before being spin coated. Similarly, for ZnO the Zn
precursor with a molar concentration of 0.3 M was added to 2-methox­
yethanol (CH3OCH2CH2OH) solvent. An equimolar concentration of
monoethanolamine (NH2CH2CH2OH) was used as the sol-stabilizer. The
resultant solution was stirred at room temperature for 5 h to obtain a
transparent homogeneous solution. The sol was kept for 48 h before
being used for spin coating. After the gelation, 12 layers of the solution
2
Sensors and Actuators: A. Physical 369 (2024) 115181
Table 1
The layer sequence of spin-coated single-phase (TiO2 and ZnO) and composite
(TiO2 – ZnO) thin films.
S. No TiO2 ZnO TiO2 - ZnO
1 T Z T
2 T Z T
3 T Z Z
4 T Z Z
5 T Z Z
6 T Z T
7 T Z T
8 T Z Z
9 T Z Z
10 T Z Z
11 T Z T
12 T Z T
Note: denote the TiO2 – T; denote the ZnO – Z.
were spin-coated on cleaned glass substrates at a spinning speed of 3000
rpm for 30 s with a ramping up for 5 s. After coating each layer, the films
were pre-heated at 250 ◦ C in air ambience for 3 min. For the deposition
of TiO2 – ZnO composite thin films, the molar concentrations for Ti and
Zn precursors were kept the same whereas the layer sequence was
changed. The sequence for various layers of deposition to obtain single-
phase TiO2, composite TiO2 – ZnO and single-phase ZnO is given in
Table 1. Finally, all the films were subjected to post-deposition
annealing of 500 ◦ C for 1 h in air ambience. Using spectroscopic
ellipsometry, the thickness of single-phase TiO2, ZnO and their com­
posite thin films were determined to be 297.5 nm, 272.4 nm, and 219.6
nm, respectively.
2.2. Thin film characterization
The phase and crystalline properties of the deposited thin films were
studied by the PANalytical X′Pert Pro X-ray diffractometer using a Cu Kα
radiation of wavelength 1.540 Å. The X-ray tube was operated at 35 kV
voltage and 30 mA current. The optical transmittance of the thin films
was measured using a JASCO V570 double-beam spectrophotometer in
the wavelength range of 300 – 2500 nm. Spectroscopic ellipsometry (J.
A. Wollam - Alpha SE) technique was used to determine the thickness of
the films. The surface morphology, grain size distribution and elemental
analysis were studied using the FEI Quanta 250 FEG field emission
scanning electron microscopy (FESEM). Further, the surface topography
and roughness were examined using the Nanosurf Easyscan 2 atomic
force microscope (AFM) (Model: 23–06-154). The chemical composition
and oxidation state of the sample surface were studied using the X-ray
photoelectron spectrometer (Model: PHI 5000 Versa Probe III) equipped
with Al Kα X-ray source of energy 1486.6 eV.
2.3. Sensor fabrication and measurements
To fabricate the acetone sensors, Ni electrodes were coated through
thermal evaporation in an interdigitated configuration on the deposited
single-phase and composite thin films by thermal evaporation. The work
function of Ni (5.01 eV) is ideal for forming Ohmic contacts with n-type
wide band gap semiconductors such as TiO2 and ZnO. The typical di­
mensions for the interdigitated configurations are depicted in Fig. 1. The
Ni electrode was thermally evaporated from a basket-shaped W filament
at a deposition rate of 5 Å/s onto the masked surface of the thin films.
The deposition rate was monitored in-situ using a quartz crystal monitor
and the final thickness of the electrodes was ~200 nm. After the depo­
sition of the electrodes, two-point electrical contacts were made using
Cu wires with the help of Ag paste on top of the electrodes. Finally, the
sensors were dried using a hotplate for 10 min at 200 ◦ C. To study the
acetone sensing performance, we fabricated the single-phase and com­
posite sensors for various acetone concentrations at room temperature
(29 ± 2 ◦ C). Gas sensing measurements in this study were conducted
M. Murugesan and S.R. Meher Sensors and Actuators: A. Physical 369 (2024) 115181

Fig. 1. (Colour online) Schematic of (a) Cross-sectional view of the proposed sensors (b) Top view of the electrode geometry.

impedance measurements with respect to different frequencies at

varying acetone concentrations, the sensors were initially placed in the
sensing chamber under ambient conditions. Then, the chamber was
sealed and filled with N2 gas at a flow rate of 10 sccm through a mass
flow controller. The primary purpose of N2 gas is to maintain a constant
baseline impedance for all sensors and to minimize interference from
other gases inside the sensing chamber. After 1 min, the flow of N2 gas
was stopped with the help of a gate valve. At that time, the N2 atmo­
spheric baseline sensor impedance was recorded for reference. During
acetone sensing, acetone vapor was collected from the bubbler system
and injected into the sensing chamber, where the concentration was
controlled using a needle valve. In parallel, the concentration was
monitored with the help of a VOC detector. For each concentration, once
the steady state was reached, the sensor impedance was continuously
monitored with respect to different frequencies. After the measurement
was completed, the sensing chamber was evacuated using a vacuum
pump. For the sensor response time measurement, initially, the sensor
impedance was recorded at a constant frequency of 100 Hz in the N2
atmosphere. The sensor impedance was then monitored for impedance
variations after 70 ppm of acetone was added to the chamber. For re­
covery time measurements, the sensing chamber was opened to expose it
to air, and then the sensors started to retain their original state with their
corresponding impedance values at room temperature.

3. Results and discussion

3.1. Structural, morphological and compositional studies of thin films

Fig. 2. (Colour online) XRD patterns for the single-phase (TiO2 and ZnO) and
composite (TiO2 – ZnO) thin films. The X-ray diffraction (XRD) patterns for the single-phase TiO2 and
ZnO thin films together with the TiO2 – ZnO mixed layer thin films are
using a homemade stainless steel chamber and commercially available shown in Fig. 2. All the deposited films are found to exhibit the poly­
high-purity VOCs. The sensing setup consists of a stainless steel chamber crystalline nature. The Bragg peaks for single-phase TiO2 thin films are
(350 mL) interconnected with a VOC concentration detector (Tiger XT observed at 25.28◦ , 37.8◦ , 48.04◦ , 53.8◦ and 55.06◦ corresponding to the
handheld detector), a conical flask with a bubbler system, and a PC (101), (004), (200), (105) and (211) lattice planes respectively (Fig. 2a).
interfaced with (Hioki: LCR HiTESTER 3532–50) LCR meter. By inter­ This confirms the tetragonal crystal structure of TiO2 in the anatase
facing the measuring instrument to the computer system through the phase (JCPDS: 21–1272). The growth is along the (101) lattice plane.
National Instruments software LabVIEW, the impedance data were ac­ The single-phase ZnO thin films crystallize in the hexagonal wurtzite
quired for the proposed sensors. The impedance (Z) and the phase angle structure (Fig. 2b). The corresponding lattice planes of (100), (002),
(Φ) were recorded in the frequency range of 100 Hz to 5 MHz. For (101) and (110) are confirmed from the respective diffraction peaks
centered at 31.7◦ , 34.4◦ , 36.2◦ and 56.4◦ (JCPDS: 36–1451). The pref­
Table 2 erential growth is along the c-axis [27]. On the other hand, for the mixed
Preferential orientation, FWHM and average crystallite size obtained from XRD layer films, the diffraction peaks corresponding to both anatase TiO2 and
for single-phase (TiO2 and ZnO) and composite (TiO2 – ZnO) thin films. wurtzite ZnO are observed which confirms their composite nature
Thin film Plane Peak FWHM Crystallite Size (Fig. 2c). For these composite films, the preferential growth for the ZnO
Orientation Position (nm) crystallites is along the a-axis whereas the crystallites corresponding to
(degree) (002), (101) and (110) orientations are absent. All the diffraction peaks
TiO2 (101) 25.28 0.2079 39.12 for anatase TiO2 are observed with a reduction in the intensity. The
ZnO (002) 34.45 0.1662 50.05 average crystallite size (D) was calculated by using the Debye-Scherrer
TiO2 – ZnO TiO2 – (101) 25.28 0.3116 26.09 formula given as:
ZnO – (100) 31.86 0.2818 29.24

3
M. Murugesan and S.R. Meher Sensors and Actuators: A. Physical 369 (2024) 115181

Fig. 3. (Colour online) High resolution XPS spectra for (a) Ti-2p (b) O-1s orbitals for the single-phase TiO2 thin films.

Fig. 4. (Colour online) High resolution XPS spectra for (a) Ti-2p (b) Zn-2p (c) O-1s orbitals for the composite thin films (d) Single and composite phase comparison of
Ti-2p orbitals.

4
M. Murugesan and S.R. Meher
Fig. 5. (Colour online) Valence band (VB) spectra for Single-phase TiO2
thin film.
0.9λ
D=
β cos θ
Here, λ is the wavelength of the X-ray, θ is the peak center and β is the
full width at half maximum (FWHM) corrected by the instrumental
broadening parameter determined from the monocrystalline Si diffrac­
tion line. The spherical crystallites are assumed for all the films. The
FWHM and the corresponding average crystallite size for all the films are
given in Table 2. A decrease in the crystallite size is observed for the
composite films compared to the single-phase films.
The chemical state and elemental composition of Ti, Zn and O atoms
at the film surface were characterized by X-ray photoelectron spec­
troscopy (XPS). Being a surface-sensitive technique with a penetration
depth limit of ~10 nm, all the films were sputter etched for 2 min using
Ar ions to remove the chemically adsorbed impurity atoms from the
surface. The XPS spectra were calibrated with respect to the adventitious
C 1 s peak corresponding to 284.6 eV. XPS PEAKFIT software was used
to deconvolute the high-resolution core-level spectra of Ti 2p, Zn 2p, and
Fig. 6. (Colour online) Planar view FESEM micrograph of (a) TiO2 (b) ZnO, and (c) TiO2 - ZnO thin films.
Sensors and Actuators: A. Physical 369 (2024) 115181
O 1 s peaks through Voigt profile with Shirley background correction.
The peak-to-peak distance and peak area ratio constraints were applied
during the deconvolution of peaks [28]. The high-resolution XPS spectra
for Ti 2p and O 1 s orbitals for the single-phase TiO2 thin films are shown
in Fig. 3. The signature peaks corresponding to Ti 2p3/2 and 2p1/2 are
observed at 458.51 eV and 464.25 eV respectively [29]. The peak po­
sitions and the spin-orbit energy difference of 5.74 eV confirms the + 4
oxidation state of Ti [30]. The high-resolution O 1 s spectra shows the
high-intensity peak centered at 529.80 eV corresponding to the lattice
oxygen (OL). The low-intensity peak at 531.34 eV is associated with the
O- adsorbed species at the oxygen vacancy (OV) sites [31,32]. The peaks
corresponding to Ti 2p3/2 and Ti 2p1/2 for the composite thin film are
observed at 458.45 eV and 464.22 eV, respectively (Fig. 4a). For the
composite thin films, the peaks corresponding to Ti 2p3/2 and 2p1/2
states shift slightly towards lower binding energy as compared to the
single-phase TiO2 (Fig. 4a). The Zn2+ chemical state is confirmed from
the XPS peaks located at 1021.71 eV and 1044.83 eV corresponding to
2p3/2 and 2p1/2 states [33] (Fig. 4b). The peak area ratio is subjected to
constraints specified by the (2J +1) condition. This condition is based on
the total angular momentum quantum number (J), which is equal to the
sum of orbital angular momentum (l), and the spin quantum number
(s = ±12). Accordingly, the peak area ratio of (Ti or Zn 2p1/2) and (Ti or
Zn 2p3/2) is 12 [34,35]. The increase in the relative intensity of the peak
(1) corresponding to OV signifies the formation of a greater number of ox­
ygen vacancy sites in the composite thin films (Fig. 4c). For the com­
posite thin films, the peaks corresponding to Ti 2p3/2 and 2p1/2 states
shift slightly towards lower binding energy as compared to the
single-phase TiO2 shown in inset of (Fig. 4d). The partial electron
transfer from ZnO to TiO2 causes the shift of the Ti 2p states towards
lower binding energy due to increase in the electron concentration [36].
The absence of any other chemical oxidation states of Zn or Ti suggests
that no other ternary phases were formed during the deposition.
The valence band maximum (VBM) relative to Fermi energy level
was determined from the valence band spectra through a linear
extrapolation of its lower energy region. The same has been depicted for
single phase TiO2 thin films in Fig. 5. The valence band spectra between
1.0 to 9.0 eV contains two peaks centered at 3.02 eV and 5.0 eV for the π
(non-bonding) and σ (bonding) O 2p orbitals, respectively. The corre­
sponding VBM is found to be 1.28 eV from the linear extrapolation. The
intensity of the σ orbital is higher than that of the π orbital which is
5
M. Murugesan and S.R. Meher
Fig. 7. (Colour online) AFM images (2 µm × 2 µm) of (a) TiO2 (b) ZnO (c) TiO2 - ZnO thin films with roughness.
Fig. 8. (Colour online) UV–Vis-NIR transmittance spectra for single-phase and
composite films. The Inset image shows the absorption edge.
consistent with the literature [28]. For the composite thin films in the
absence of any well-defined VBM, it was not possible to accurately
determine the same from the valence band spectroscopy.
The FESEM micrographs for the single-phase TiO2 and ZnO thin films
and the TiO2 – ZnO composite thin films are shown in Fig. 6. The TiO2
surface is free of any cracks with randomly distributed spherical grains
(Fig. 6a). The typical grain size ranges from 25 – 35 nm. Fig. 6b depicts
the morphology of single-phase ZnO thin films, which reveals that the
irregularly connected grains are distributed across the surface with
random agglomerated particles on top of the grains. In the case of
composite TiO2 – ZnO thin films, we observe an uneven distribution of
TiO2 and ZnO grains like a plum-pudding type morphology (Fig. 6c). The
ZnO grains appear to be diffused into the TiO2 layer because of the post-
deposition annealing.
Atomic force microscopy (AFM) in contact mode was used to
examine the morphology and surface roughness of the single-phase and
6
Sensors and Actuators: A. Physical 369 (2024) 115181
composite thin films. The AFM micrographs with a scan area of 2 µm
× 2 µm are shown in Fig. 7. The root mean square (RMS) roughness for
single-phase TiO2 films is found to be 12.16 nm with a random distri­
bution of the grains. This is in accordance with the FESEM results. The
ZnO thin films are found to be much smoother with an RMS roughness of
5.99 nm. The composite films exhibit a slightly higher RMS roughness of
23.16 nm. Both ZnO and the composite films are found to have hillock
shape domains. According to these results, the composite thin films have
distinct features with rough surface which can be attributed to the lattice
mismatch and the internal strain developed in them. Moreover, higher
surface roughness results in an increase in the number of surface reactive
sites which plays an essential role in the sensing of analytes [37].
3.2. Optical properties
The transmittance spectra for the deposited thin films in the wave­
length region 300 – 2500 nm are shown in Fig. 8. The TiO2 thin films are
found to have higher transmittance (> 80%) than the ZnO thin films in
the visible region. In the near-infrared (NIR) region, both the films
exhibit ~80 – 85% transparency. The oscillations corresponding to the
characteristic thin film interference indicates good optical quality of the
deposited thin films with a thickness of few 100 s of nm. The ultraviolet
(UV) absorption corresponding to the band edge is well-defined for the
single-phase films. In contrast, a broad absorption edge is observed for
the composite thin films signifying the presence of band tail states. The
band gap corresponding to the single-phase TiO2 and ZnO were deter­
mined through Tauc’s plot method Fig. 9. The band gap type (direct/
indirect) of TiO2 is debatable in the literature. But majority of the
experimental reports suggest an indirect band gap for anatase. In the
present study also, we have assumed the indirect band transition in TiO2
and have calculated the band gap value of 3.10 eV. On the other hand,
ZnO is a well-known direct band gap semiconductor and the calculated
band gap value is 3.22 eV. Because of the presence of broad absorption
edge, the parabolic band approximation is invalid for the composite thin
films. Therefore, the corresponding band gap cannot be determined
from the optical absorption.
3.3. Acetone sensing performance
The room temperature (29 ± 2 ◦ C) acetone sensing performance was
M. Murugesan and S.R. Meher
Fig. 9. (Colour online) The plot of (a) (αhν)1/2 versus hν for indirect bandgap for TiO2 (b) (αhν)2 versus hν for direct bandgap for ZnO thin films.
Fig. 10. (Colour online) Impedance vs acetone concentration of proposed
sensors at 100 Hz. The inset image shows the single-phase sensors impedance
changes in the kΩ range.
examined for the single-phase TiO2 and ZnO thin film sensors and TiO2 –
ZnO composite thin film sensors by observing its change in the imped­
ance with respect to the N2 baseline for various acetone concentrations.
Fig. 10 shows the variation in the impedance at 100 Hz for different
sensors exposed to acetone concentrations ranging from 10 – 70 ppm.
The lower frequency of 100 Hz has been chosen to ensure space charge
redistribution [38]. Upon exposure to acetone, we observe a significant
change in the impedance for the TiO2 – ZnO composite sensors
compared to the single-phase TiO2 and ZnO based sensors. The com­
posite sensors have a higher baseline impedance (2.55 MΩ @100 Hz)
due to the electron transfer from ZnO to TiO2 establishing a high space
charge region. In addition, the higher concentration of oxygen vacancies
in the composite thin films is favorable for chemisorbed O- ions on the
sensor surface. These observations are in good agreement with the XPS
spectra which suggest relatively large number of OV related active sites
at the surface. This leads to an improvement in the acetone sensing
performance for the composite sensors than the single-phase TiO2 and
ZnO based sensors. A change in the impedance from 2.55 MΩ to
7
Sensors and Actuators: A. Physical 369 (2024) 115181
Fig. 11. (Colour online) Sensor response of single-phase (TiO2 or ZnO) and
composite (TiO2-ZnO) sensors at 100 Hz.
157.7 kΩ is observed for the composite thin films when exposed to
70 ppm acetone. Together with this an improvement in the detection
threshold from 10 ppm to 3 ppm is observed for the composite sensors
compared to the single-phase ones. Acetone sensors with extreme
detection threshold of 20 ppb and 170 ppb have been reported in the
literature [22,24]. But these sensors require higher temperatures to
achieve this detection threshold. A potential acetone sensor for the early
diagnosis of diabetes requires lower detection threshold together with
room temperature operation [25]. In this context, the detection
threshold of 3 ppm is a significant improvement towards acetone
sensing.
The relative sensor response (%) is defined as the ratio between the
change in impedance upon exposure to acetone and the N2 baseline
impedance. The following expression was used to calculate the same.
ZN2 − Zg
SensorResponse(%) = × 100 (2)
ZN2
Here, ZN2 and Zg denotes the impedance of the sensor at N2 baseline
and various acetone concentrations. The sensor response (%) for all the
M. Murugesan and S.R. Meher
Fig. 12. (Colour online) Response and recovery plot (a) TiO2 (b) ZnO (c) TiO2 - ZnO sensors at 100 Hz.
acetone sensors under investigation are depicted in Fig. 11. The com­
posite thin film based sensors exhibit the highest sensor response of
93.83% compared to single-phase TiO2 (40.3%) and ZnO (52.41%) for
70 ppm acetone. The response for 3 ppm acetone concentration is found
to be 3.95% for the composite sensors. The higher surface roughness and
more OV sites are the significant reasons for the increased sensor
response exhibited by the TiO2 – ZnO composite thin film based sensors
[39,40]. Together with this, the contact potentials associated with
localized states at the heterojunction interface can easily trap and pro­
mote the reaction with acetone molecules which in turn affects the
impedance of the composite sensors [41].
In addition to the sensor response, the response and recovery times
are crucial parameters for evaluating the merit of a sensor. In the present
case, the response time is defined as the time required to lose 90% of its
impedance measured at 100 Hz when the acetone concentration is
increased from 0 to 70 ppm. The same is called as the recovery time
when the concentration is decreased. The dynamic response and re­
covery times of all the proposed sensors are illustrated in Fig. 12. We
have recorded three complete cycles of the response and recovery with
good repeatability. The estimated response time for the composite sen­
sors is 42 s whereas it is found to be 51 s and 130 s for the single-phase
TiO2 and ZnO based sensors respectively. With further increase of
acetone concentration beyond 70 ppm, the sensing behaviour starts to
saturate for the composite sensors resulting in a recovery time of 149 s
for the composite sensors. The recovery time observed for the single-
8
Sensors and Actuators: A. Physical 369 (2024) 115181
phase TiO2 and ZnO based sensors are 53 s and 165 s respectively.
The room temperature acetone sensors based on single-phase TiO2 is
found to have faster response and recovery times but poor sensor
response.
The bulk and surface contribution of the sensing material upon
exposure to acetone was evaluated through electrochemical impedance
spectroscopy (EIS). A sinusoidal peak-to-peak voltage of 1 V with fre­
quency varying from 100 Hz to 5 MHz was applied to all the sensors
resulting in a sinusoidal current. The obtained electrical impedance
Z(ω) = Z′(ω) +iZ′ (ω) was analysed for different sensors through the
Cole-Cole plots. Fig. 13 shows the Cole-Cole plots for the proposed
sensors for acetone concentrations ranging from 10 to 70 ppm. The
single-phase TiO2 and ZnO-based sensors exhibit an elongated semi­
circle with a small tail towards the lower frequency. For the TiO2 – ZnO
based composite sensors, a perfect semicircle is observed without any
tail-like features at lower frequency. For all the sensors, the higher
intercept on the X-axis is found to be shifting towards lower values with
an increase of acetone concentration. This is due to the release of the
trapped electrons because of the interaction between acetone molecules
and chemisorbed oxygen species on the active sites of the sensor surface
[42]. The shift of this intercept towards lower values is the highest for
the composite thin film based sensors. This is attributed to the higher
surface roughness and a greater number of oxygen vacancy sites as
validated by AFM and XPS investigations. The Col-Cole plots were fitted
with the relevant equivalent circuit using the EISSA software [26]. In the
M. Murugesan and S.R. Meher
Fig. 13. (Colour online) Cole-Cole plot of (a) TiO2 (b) ZnO (c) TiO2 - ZnO sensors and the inset referred to fitted equivalent circuit.
frequency dependent system, a typical equivalent circuit for EIS consists
of constant phase element (CPE), contact resistance (RC), grain boundary
resistance (RGB) and Warburg element (W). The impedance corre­
sponding to the constant phase element is given by ZCPE = Q(i21πf)n . Here A
is a real parameter, f is the frequency and the index n varies from 0 to 1.
For n = 0, the CPE behaves as a pure resistor and for n = 1, it behaves as
a pure capacitor. In the present study, the CPE describes the capacitance
between the sensor surface and the electrode. RC represents the resis­
tance at the interface between the electrode and the sensing layer. The
grain boundary resistance RGB varies due to the conduction variation
between the grains. The Warburg impedance (W) appears as a straight
line with a semicircle in the lower frequency region, which is due to the
diffusion of ions or electron transfer at the sensor/electrode interface
[43]. The corresponding equivalent circuit is provided in the inset of the
Cole-Cole plots. The CPE is connected in parallel to the RGB and W. The
variation in the fitted values of RGB and C with respect to the acetone
concentration for all the proposed sensors is shown in Fig. 14. A
remarkable change in the RGB is observed for the composite sensors
when compared with the single-phase ones. This is primarily attributed
to the increased electron densities at the grain boundaries because of the
trapped chemisorbed electrons. This enhances the grain boundary con­
ductivity with increase in the acetone concentration [42]. Similarly, a
9
Sensors and Actuators: A. Physical 369 (2024) 115181
significant increase in capacitance (C) is also observed for the TiO2 –
ZnO composite thin film-based sensors with acetone concentration. This
is due to the change in the dielectric properties of the material because
of the increase in the surface electron concentration caused by acetone
molecules. The Bode plot analysis shows the maximum impedance
changes between 100 Hz and 50 kHz for the single phase TiO2 and ZnO
thin films (Fig. 15). A relatively larger change in the impedance is
observed between 100 Hz and 5 kHz for the composite thin film based
sensors. At lower frequencies, the polarization of the chemisorbed
acetone molecules in composite sensors increases which leads to a
decrease in the impedance.
In order to check the selectivity of the proposed sensors, several
other VOCs such as ethanol, isopropyl alcohol, acetophenone, methanol
and 2-methoxy ethanol at 70 ppm concentrations were studied. The
corresponding sensors response to these VOCs are shown in Fig. 16. All
the proposed sensors were found to have higher response towards
acetone than other VOCs studied. The composite sensors have a response
which is 2.32 and 1.79 times higher than that of single-phase TiO2 and
ZnO respectively. In particular, the response of the composite sensors
towards acetone (93.83%) is significantly higher than the other VOCs.
The composite sensors exhibit the sensor response of 39.92%, 13.4%,
25%, 21.5%, and 43.81% for acetophenone, 2-methoxy ethanol,
ethanol, methanol, and isopropyl alcohol, respectively. Among these,
M. Murugesan and S.R. Meher
Fig. 14. (Colour online) Calculated (a) Grain boundary resistance (RGB) and (b) C – capacitance of the sensors at different acetone concentrations.
isopropyl alcohol has moderate response, which is 0.46 times lower than
the sensor response to acetone. Moreover, 2-methoxy ethanol exhibits a
very poor response to the composite sensor.
When the analyte VOC (acetone) interacts with the surface of the
sensor, which operates at room temperature (29 ± 2 ◦ C), humidity is
one of the main elements impacting the performance of the sensor [44].
Therefore, the baseline impedance of the TiO2-ZnO composite sensor
with respect to various relative humidity (RH) percentages and its
associated sensor response for 70 ppm of acetone were examined. As per
the report [26,45], we created and maintained constant relative hu­
midity levels of 12%, 32%, 54%, 75%, and 90% using a saturated so­
lution of potassium hydroxide (KOH), magnesium chloride (MgCl2),
magnesium nitrate (MgNO3), sodium chloride (NaCl), and sodium car­
bonate (Na2CO3), respectively. The percentage of RH was then contin­
uously monitored using a DHT11 temperature and humidity sensor
interfaced with the Arduino-UNO IDE. Fig. 17a depicts the change in
sensor impedance as a function of RH (%). The baseline impedance of
the composite sensor decreased at a higher RH%, which is due to the
Grotthuss chain reaction, as a result of the adsorption of water molecules
on the sensor surface [26]. The sensor response of the composite thin
films towards 70 ppm of acetone at different RH% has been shown in
Fig. 17b. At 90% RH, the sensor response dropped from 93.83% to
76.61%, due to the physisorbed and chemisorbed water molecules on
the surface of the composite sensor, which limit the interaction of the
acetone molecule with the active sites of the sensor [46]. That is the
main cause of the sensor response being reduced at 90% relative
humidity.
3.4. Acetone sensing mechanism
The grain boundary model [47,48] is widely accepted for the sensing
of VOCs by metal oxides. It involves the adsorption and desorption of gas
molecules on the sensor surface which in turn alters its conductivity. The
acetone sensing mechanism for single-phase TiO2 and ZnO thin films is
explained in Fig. 18 which is adopted from Xu et al. [49]. Since both
these materials are n-type semiconductors, we have outlined the basic
mechanism of acetone sensing by n-type single-phase metal oxide. When
an n-type metal oxide (TiO2 or ZnO) is exposed to air, atmospheric ox­
ygen molecules get adsorbed on the sensors surface. These chemisorbed
10
Sensors and Actuators: A. Physical 369 (2024) 115181
oxygen molecules capture an electron from the conduction band of the
n-type metal oxide and form a chemisorbed anion through a dangling
bond. Different oxygen species (O-2, O- and O2-) are involved in the
chemisorption depending on the temperature of the environment [50].
The depletion region formed between the grains causes an increase in
the impedance and the concentration of free electrons at the surface is
decreased by the adsorbed oxygen molecules. When the sensor surface is
exposed to acetone, it interacts with the chemisorbed anions according
to the following equations [51]:
CH3 COCH 3(gas) +4O−2(ads) →3H2 O(vap) +3CO2(gas) +4e− (return to sensor)
(3)
CH3 COCH3(gas) + 8O−(ads) →3H2 O(vap) −
+ 3CO2(gas) + 8e (return to sensor)
(4)
CH3 COCH 3(gas) +8O2−(ads) →3H2 O(vap) +3CO2(ads) +16e− (return to sensor)
(5)
Acetone adsorption causes an increase in electrical conductivity
because of the return of the trapped electrons to the sensor surface. This
leads to a drop in the overall impedance. For room temperature sensing,
O−2 is the most dominant species involved in the chemisorption and
hence the sensing in the present study takes place through Eq. 3.
In composite sensors, an additional band offset is created between
the grains of TiO2 and ZnO. The band offset type depends on the posi­
tions of the conduction band minimum (CBM) and valence band
maximum (VBM) of TiO2 and ZnO. The positions of CBM and VBM of
TiO2 and ZnO were calculated by the Mulliken electronegativity formula
[52]. However, this method ignores the lattice mismatch and the
structural factors of the semiconductors. The approximate positions of
the VBM (EVB) and CBM (ECB) can be expressed as,
EVB = X − Ee + 0.5Eg (6)
ECB = EVB − Eg (7)
Here, X is the electronegativity of TiO2 or ZnO (5.82 eV and 5.78 eV
[53] respectively), Ee is the energy of free electrons at the hydrogen scale
(= 4.5 eV vs. SHE) and Eg is the band gap of the semiconductor. The
positions of the CBM for TiO2 and ZnO were calculated to be − 0.23 eV
M. Murugesan and S.R. Meher Sensors and Actuators: A. Physical 369 (2024) 115181

Fig. 15. (Colour online) Bode plots of (a) TiO2 (b) ZnO and (c) TiO2 - ZnO sensors as a function of frequency.

and − 0.33 eV respectively. The corresponding positions for the VBM

were found to be 2.87 eV and 2.89 eV respectively. Based on these
values, the TiO2 – ZnO heterojunction exhibits type – I band offset as
shown in Fig. 19. This is in accordance with our XPS results for Ti-2p
associated peaks in composite thin films which showed a slight shift
towards lower binding energy values. In order to equilibrate the Fermi
energy, the electron transfer takes place from the CB of ZnO to the CB of
TiO2 because the position of the former is more negative than the latter.
As a result, electrons accumulate on the TiO2 side facilitating a larger
concentration of active sites at the interface. The charge redistribution
close to the heterojunction interface caused by the type-I band offset
significantly widens the depletion region. In addition to this, more
electrons are trapped at the heterojunction interface due to oxygen
adsorption. The increased thickness of the depletion region leads to an
increase in the impedance of the sensor. Upon exposure to acetone, the
chemisorbed oxygen readily interacts with it and the excess electrons
return to the sensor surface. This results in the narrowing of the deple­
tion region and hence a decrease in the impedance.
Table 3 summarizes the performance of the proposed sensors in
comparison with the TiO2 based sensors reported in the literature.
Fig. 16. (Colour online) Selectivity plot for the proposed sensors with
Compared to the other reports, the TiO2 – ZnO composite thin film based
various VOCs. sensors exhibit a better detection threshold of 3 ppm under room tem­
perature operations. The acetone sensors reported by Bhowmik et al.
[54] have a higher relative response of 178.6% at 150 ◦ C compared to

11
M. Murugesan and S.R. Meher Sensors and Actuators: A. Physical 369 (2024) 115181

Fig. 17. (Colour online) (a) Different percentage of RH vs composite sensor impedance (b) Sensor response to 70 ppm acetone at different RH% of the compos­
ite sensor.

Fig. 18. (Colour online) Schematic diagram of the single-phase (TiO2 or ZnO) acetone sensing mechanism.

Fig. 19. (Colour online) Schematic diagram of the TiO2-ZnO heterojunction acetone sensing mechanism.

12
M. Murugesan and S.R. Meher Sensors and Actuators: A. Physical 369 (2024) 115181

Table 3
Comparison of acetone sensing performance of existing TiO2 based sensors with the proposed TiO2 – ZnO composite thin film based sensors.
Material Fabrication technique Acetone Sensor Response/ Operating Limit of Ref.
concentration response Recovery time Temperature detection
(ppm)a; (ppb)b (s) ( ◦ C) (ppm/ppb)

TiO2 – ZnO Sol-gel spin coating technique 70a 93.83a 42/149 Room 3 ppm This
Thin films temperature work
(29 ◦ C ± 2)
TiO2/ SiO2 Dip coating technique 500a 178.6a 42.11/44.05 150 500 ppm [54]
Thin films
Pd/TiO2/Si Dip coating 50a 33a 7/20 200 0.5 ppm [17]
Thin films technique
a b
TiO2 Hydrothermal method 250 33.72 46/24 330 10 ppm [55]
flower-like
Nanomaterials
W – doped Hydrothermal method 500a 173.6b 14/9 240 5 ppm [56]
Nanoporous TiO2
TiO2/SnO2 Pulsed Laser deposition method 100a 301.5b 15/57 300 0.02 ppm [22]
Thin films
a a
GO/TiO2 Sol-gel technique 200 18.6 80/- Room 100 ppm [23]
Nanocomposites temperature
TiO2 @B-TiO2 @ZnO CVD method followed by 100a 80.45b 5/26 275 170 ppb [24]
NPs coprecipitation technique
TiO2/ZnO Co-precipitation method 100b 179a 13/11 Room 100 ppb [25]
Nanocomposite temperature
a a
TiO2/RGO Hummers method followed by 100 81.24 10/23 Room 20 ppm [20]
Nanocomposites Ultrasonication temperature

a Ra − Rg Ra
Note: denote the sensor response = × 100(%); b denote the sensor response =
Ra Rg

the TiO2 – ZnO composite sensors proposed in the present study. How­
ever, the major advantage of the proposed sensors is their room tem­
perature operation which is ideal for the easy diagnosis of diabetes
mellitus. However, the proposed sensors have moderate response time
and slow recovery time compared to the other acetone sensors which
need to be improved.
4. Conclusions
editing. Murugesan Muthukumar: Data curation, Investigation,
Methodology, Writing – original draft.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.

The thin films of single-phase TiO2 and ZnO and their composites
were coated on glass substrates by the commercially viable sol-gel spin
coating. XRD reveals the anatase and wurtzite phase for TiO2 and ZnO
respectively. The occurrence of diffraction peaks corresponding to both
anatase and wurtzite confirmed the composite nature of TiO2 – ZnO
mixed layer films. The formation of heterojunction between TiO2 and
ZnO grains is confirmed from the shift of the Ti-2p XPS peak towards
lower binding energies compared to the single-phase ones. XPS also
reveals the presence of more oxygen vacancy sites in composite thin
films than the single phase films. The fabricated sensors based on these
thin films were studied for their impedometric sensing performance
towards various VOCs. The composite sensors exhibit superior selec­
tivity towards acetone than other VOCs studied. They exhibit an
improved LOD of 3 ppm for acetone and a maximum sensor response of
93.83% for 70 ppm acetone when compared with single-phase of TiO2
and ZnO thin film based sensors. The higher acetone sensing perfor­
mance of TiO2 – ZnO composite thin film based sensors are attributed to
the higher surface roughness and the presence of greater number of
oxygen vacancies. In addition, the composite sensors have better
response time of 42 s compared to the single-phase TiO2 or ZnO based
sensors. The room temperature operability of the proposed acetone
sensors makes them ideal for the easy diagnosis of diabetes mellitus.
However, the slow recovery time of 149 s for the composite thin film
based acetone sensors need improvement through the aid of possible
functional materials.
CRediT authorship contribution statement
Data availability
Data will be made available on request.
Acknowledgment
The authors would like to acknowledge Department of Science and
Technology (DST), New Delhi, India for providing the financial support
through FIST (Fund for Improvement of S&T Infrastructure in Higher
Education Institution) project [no. SR/FST/ETI-015/2011]. The authors
also would like to acknowledge Vellore Institute of Technology, Vellore,
India for providing the financial support through VIT SEED GRANT
(RGEMS) [SG20230043]. The authors would also like to acknowledge
Prof. Zachariah C. Alex for useful discussions and suggestions.
References
[1] V. Saasa, T. Malwela, M. Beukes, M. Mokgotho, C.P. Liu, B. Mwakikunga, Sensing
technologies for detection of acetone in human breath for diabetes diagnosis and
monitoring, Diagnostics 8 (2018) 1–17, https://doi.org/10.3390/
diagnostics8020012.
[2] N. Goel, K. Kunal, A. Kushwaha, M. Kumar, Metal oxide semiconductors for gas
sensing, Eng. Rep. (2022) 1–22, https://doi.org/10.1002/eng2.12604.
[3] M. Ahmadipour, A.L. Pang, M.R. Ardani, S.Y. Pung, P.C. Ooi, A.A. Hamzah, M.F.M.
R. Wee, M.A.S.M. Haniff, C.F. Dee, E. Mahmoudi, A. Arsad, M.Z. Ahmad, U. Pal, K.
M. Chahrour, S.A. Haddadi, Detection of breath acetone by semiconductor metal
oxide nanostructures-based gas sensors: a review, Mater. Sci. Semicond. Process.
149 (2022) 106897, https://doi.org/10.1016/j.mssp.2022.106897.
[4] V. Amiri, H. Roshan, A. Mirzaei, G. Neri, A.I. Ayesh, Nanostructured metal oxide-
based acetone gas sensors: a Review, Sensors 20 (2020) 1–25, https://doi.org/
10.3390/s20113096.

Meher Samir Ranjan: Supervision, Validation, Writing – review &

13
M. Murugesan and S.R. Meher
[5] H.J. Cho, S.J. Choi, N.H. Kim, I.D. Kim, Porosity controlled 3D SnO2 spheres via
electrostatic spray: selective acetone sensors, Sens. Actuators B: Chem. 304 (2020)
127350, https://doi.org/10.1016/j.snb.2019.127350.
[6] Q. Jia, H. Ji, Y. Zhang, Y. Chen, X. Sun, Z. Jin, Rapid and selective detection of
acetone using hierarchical ZnO gas sensor for hazardous odor markers application,
J. Hazard. Mater. 276 (2014) 262–270, https://doi.org/10.1016/j.
jhazmat.2014.05.044.
[7] N. Chen, Y. Li, D. Deng, X. Liu, X. Xing, X. Xiao, Y. Wang, Acetone sensing
performances based on nanoporous TiO2 synthesized by a facile hydrothermal
method, Sens. Actuators B: Chem. 238 (2017) 491–500, https://doi.org/10.1016/j.
snb.2016.07.094.
[8] F. Chen, M. Yang, X. Wang, Y. Song, L. Guo, N. Xie, X. Kou, X. Xu, Y. Sun, G. Lu,
Template-free synthesis of cubic-rhombohedral-In2O3 flower for ppb level acetone
detection, Sens. Actuators B: Chem. 290 (2019) 459–466, https://doi.org/
10.1016/j.snb.2019.04.013.
[9] Q. Zhai, B. Du, R. Feng, W. Xu, Q. Wei, A highly sensitive gas sensor based on Pd-
doped Fe3O4 nanoparticles for volatile organic compounds detection, Anal.
Methods 6 (2014) 886–892, https://doi.org/10.1039/c3ay41867g.
[10] S. Wei, S. Li, R. Wei, S. Liu, W. Du, Different morphologies of WO3 and their
exposed facets-dependent acetone sensing properties, Sens. Actuators B: Chem. 329
(2021) 129188, https://doi.org/10.1016/j.snb.2020.129188.
[11] X. Tian, X. Cui, T. Lai, J. Ren, Z. Yang, M. Xiao, B. Wang, X. Xiao, Y. Wang, Gas
sensors based on TiO2 nanostructured materials for the detection of hazardous
gases: a review, Nano Mater. Sci. 3 (2021) 390–403, https://doi.org/10.1016/j.
nanoms.2021.05.011.
[12] W. Ge, S. Jiao, Z. Chang, X. He, Y. Li, Ultrafast response and high selectivity toward
acetone vapor using hierarchical structured TiO2 nanosheets, ACS Appl. Mater.
Interfaces 12 (2020) 13200–13207, https://doi.org/10.1021/acsami.9b23181.
[13] S.T. Navale, Z.B. Yang, C. Liu, P.J. Cao, V.B. Patil, N.S. Ramgir, R.S. Mane, F.
J. Stadler, Enhanced acetone sensing properties of titanium dioxide nanoparticles
with a sub-ppm detection limit, Sens. Actuators B: Chem. 255 (2018) 1701–1710,
https://doi.org/10.1016/j.snb.2017.08.186.
[14] D. Zhao, X. Zhang, W. Wang, L. Sui, X. Bai, H. Song, C. Guo, Y. Xu, X. Cheng,
S. Gao, L. Huo, Ultra-small TiO2 nanocubes with highly active (0 0 1) facet for
acetone fast detection and diagnosis of diabetes, Microchem. J. 184 (2023) 108122
https://doi.org/10.1016/j.microc.2022.108122.
[15] P. Bindra, A. Hazra, Selective detection of organic vapors using TiO2 nanotubes
based single sensor at room temperature, Sens. Actuators B: Chem. 290 (2019)
684–690, https://doi.org/10.1016/j.snb.2019.03.115.
[16] Z. Feng, L. Zhang, W. Chen, Z. Peng, Y. Li, A strategy for supportless sensors:
fluorine doped TiO2 nanosheets directly grown onto Ti foam enabling highly
sensitive detection toward acetone, Sens. Actuators B: Chem. 322 (2020) 128633
https://doi.org/10.1016/j.snb.2020.128633.
[17] B. Bhowmik, A. Hazra, K. Dutta, P. Bhattacharyya, Nanocrystalline p-TiO2 based
MIS device for efficient acetone detection, 2014-Decem, Proc. IEEE Sens. (2014)
293–296, https://doi.org/10.1109/ICSENS.2014.6984991.
[18] W. Yang, H. Shen, J. Ge, B. Xu, Improving TiO2 gas sensing selectivity to acetone
and other gases via a molecular imprinting method, Nanotechnology 32 (2021)
155503, https://doi.org/10.1088/1361-6528/abd818.
[19] S. Yang, G. Lei, H. Xu, Z. Lan, Z. Wang, H. Gu, Metal oxide based heterojunctions
for gas sensors: a review, Nanomaterials 11 (2021) 1–26, https://doi.org/10.3390/
nano11041026.
[20] M. Daneshnazar, B. Jaleh, M. Eslamipanah, R.S. Varma, Optical and gas sensing
properties of TiO2/RGO for methanol, ethanol, and acetone vapors, Inorg. Chem.
Commun. 145 (2022) 110014, https://doi.org/10.1016/j.inoche.2022.110014.
[21] M.M. Hashemi, A. Nikfarjam, H. Hajghassem, N. Salehifar, Hierarchical dense
array of ZnO nanowires spatially grown on ZnO/TiO2 nanofibers and their
Ultraviolet activated gas sensing properties, J. Phys. Chem. C. 124 (2020)
322–335, https://doi.org/10.1021/acs.jpcc.9b07207.
[22] B. Sharma, A. Sharma, J.H. Myung, Highly selective detection of acetone by TiO2-
SnO2 heterostructures for environmental biomarkers of diabetes, Sens. Actuators B:
Chem. 349 (2021) 130733, https://doi.org/10.1016/j.snb.2021.130733.
[23] V. Kumar, R. Madan, D. Mohan, Sol–gel derived GO/TiO2 nanocomposites for room
temperature acetone gas sensing application, J. Mater. Sci. Mater. Electron. 33
(2022) 7655–7667, https://doi.org/10.1007/s10854-022-07914-6.
[24] Y. Feng, W. Yang, Y. Li, H. Shen, The effect of near-surface electron trapping layer
on the acetone sensing performance of black TiO2 capped with ZnO,
Nanotechnology 33 (2022) 275712, https://doi.org/10.1088/1361-6528/ac5aea.
[25] K.G. Krishna, S.R. Parne, P. Nagaraju, Facile synthesis and enhanced sensing
properties of ZnO/TiO2 nanocomposite at room temperature, Mater. Sci. Eng. B.
297 (2023) 116734, https://doi.org/10.1016/j.mseb.2023.11673.
[26] M. Velumani, S.R. Meher, Z.C. Alex, Composite metal oxide thin film based
impedometric humidity sensors, Sens. Actuators B: Chem. 301 (2019) 127084,
https://doi.org/10.1016/j.snb.2019.127084.
[27] R.S. Gaikwad, G.R. Patil, B.N. Pawar, R.S. Mane, S.H. Han, Liquefied petroleum gas
sensing properties of sprayed nanocrystalline zinc oxide thin films, Sens. Actuators
A: Phys. 189 (2013) 339–343, https://doi.org/10.1016/j.sna.2012.10.005.
[28] M. Perez-Gonzalez, S.A. Tomas, J. Santoyo-Salazar, M. Morales-Luna, Enhanced
photocatalytic activity of TiO2-ZnO thin films deposited by dc reactive magnetron
sputtering, Ceram. Int. 43 (2017) 8831–8838, https://doi.org/10.1016/j.
ceramint.2017.04.016.
[29] B. Bharti, S. Kumar, H.N. Lee, R. Kumar, Formation of oxygen vacancies and Ti3+
state in TiO2 thin film and enhanced optical properties by air plasma treatment,
Sci. Rep. 6 (1) (2016) 12, https://doi.org/10.1038/srep32355.
[30] U. Diebold, T.E. Madey, TiO2 by XPS, Surf. Sci. Spectra 4 (1996) 227–231, https://
doi.org/10.1116/1.1247794.
14
Sensors and Actuators: A. Physical 369 (2024) 115181
[31] A. Lakshmanan, Z.C. Alex, S.R. Meher, Cu2O thin films grown by magnetron
sputtering as solar cell absorber layers, Mater. Sci. Semicond. Process. 148 (2022)
106818, https://doi.org/10.1016/j.mssp.2022.106818.
[32] A. Sahai, N. Goswami, Probing the dominance of interstitial oxygen defects in ZnO
nanoparticles through structural and optical characterizations, Ceram. Int. 40
(2014) 14569–14578, https://doi.org/10.1016/j.ceramint.2014.06.041.
[33] M.M. Alam, A.M. Asiri, M.T. Uddin, M.A. Islam, M.M. Rahman, Wet-chemically
prepared low-dimensional ZnO/Al2O3/Cr2O3 nanoparticles for xanthine sensor
development using an electrochemical method, RSC Adv. 8 (2018) 12562–12572,
https://doi.org/10.1039/c8ra01734d.
[34] P. Van der Heide. X-Ray Photoelectron Spectroscopy: An Introduction to Principles
and Practices, 1st ed..,, John Wiley & Sons, Inc, Hoboken, New Jersey, 2011.
[35] M. Perez-Gonzalez, S.A. Tomas, Surface chemistry of TiO2-ZnO thin films doped
with Ag. Its role on the photocatalytic degradation of methylene blue, Catal. Today
360 (2021) 129–137, https://doi.org/10.1016/j.cattod.2019.08.009.
[36] Y. Li, H. Yang, J. Tian, X. Hu, H. Cui, Synthesis of In2O3 nanoparticle/TiO2
nanobelt heterostructures for near room temperature ethanol sensing, RSC Adv. 7
(2017) 11503–11509, https://doi.org/10.1039/c7ra00011a.
[37] Y. Dessie, S. Tadesse, R. Eswaramoorthy, Surface roughness and electrochemical
performance properties of biosynthesized α-MnO2/NiO-based polyaniline ternary
composites as efficient catalysts in microbial fuel cells, J. Nanomater 3 (2021)
1–21, https://doi.org/10.1155/2021/7475902.
[38] A.A. Ward, State Art. Dielectr. Mater. Adv. Appl. (2015) 1–70.
[39] M. Kumar, B. Singh, P. Yadav, V. Bhatt, M. Kumar, K. Singh, A.C. Abhyankar,
A. Kumar, J.H. Yun, Effect of structural defects, surface roughness on sensing
properties of Al doped ZnO thin films deposited by chemical spray pyrolysis
technique, Ceram. Int. 43 (2017) 3562–3568, https://doi.org/10.1016/j.
ceramint.2016.11.191.
[40] E. Ciftyurek, Z. Li, K. Schierbaum, Adsorbed oxygen ions and oxygen vacancies:
their concentration and distribution in metal oxide chemical sensors and
influencing role in sensitivity and sensing mechanisms, Sensors 23 (2023) 1–30,
https://doi.org/10.3390/s23010029.
[41] A.J.T. Naik, I.P. Parkin, R. Binions, Gas sensing studies of an n-n heterojunction
metal oxide semiconductor sensor array based on WO3 and ZnO composites, Proc.
IEEE Sens. (2013), https://doi.org/10.1109/ICSENS.2013.6688509.
[42] M.I. Ikim, G.N. Gerasimov, V.F. Gromov, O.J. Ilegbusi, L.I. Trakhtenberg,
Synthesis, structural and sensor properties of nanosized mixed oxides based on
In2O3 particles, Int. J. Mol. Sci. 24 (2023) 1–23, https://doi.org/10.3390/
ijms24021570.
[43] M. Velumani, S.R. Meher, Z.C. Alex, Impedometric humidity sensing characteristics
of SnO2 thin films and SnO2–ZnO composite thin films grown by magnetron
sputtering, J. Mater. Sci. Mater. Electron. 29 (2018) 3999–4010, https://doi.org/
10.1007/s10854-017-8342-z.
[44] G.K. Mani, J.B.B. Rayappan, A highly selective room temperature ammonia sensor
using spray deposited zinc oxide thin film, Sens. Actuators B: Chem. 183 (2013)
459–466, https://doi.org/10.1016/j.snb.2013.03.132.
[45] L. Greenspan, Humidity fixed points of binary saturated aqueous solutions, J. Res.
Natl. Bur. Stand. A. Phys. Chem. 81A (1977) 89–96, https://doi.org/10.6028/
jres.081A.011.
[46] X. Chen, J. Hu, P. Chen, M. Yin, F. Meng, Y. Zhang, UV-light assisted NO2 gas
sensor based on WS2/PbS heterostructures with full recoverability and reliable
anti-humidity ability, Sens. Actuators B: Chem. 339 (2021) 129902 https://doi.
org/10.1016/j.snb.2021.129902.
[47] N.A. Isaac, I. Pikaar, G. Biskos, Metal oxide semiconducting nanomaterials for air
quality gas sensors: operating principles, performance, and synthesis techniques,
Microchim. Acta 189 (2022) 1–22, https://doi.org/10.1007/s00604-022-05254-0.
[48] A. Dey, Semiconductor metal oxide gas sensors: a review, Mater. Sci. Eng. B. 229
(2018) 206–217, https://doi.org/10.1016/j.mseb.2017.12.036.
[49] H. Xu, J. Xu, H. Li, W. Zhang, Y. Zhang, Z. Zhai, Highly sensitive ethanol and
acetone gas sensors with reduced working temperature based on Sr-doped BiFeO3
nanomaterial, J. Mater. Res. Technol. 17 (2022) 1955–1963, https://doi.org/
10.1016/j.jmrt.2022.01.137.
[50] H.J. Kim, J.H. Lee, Highly sensitive and selective gas sensors using p-type oxide
semiconductors: overview, Sens. Actuators B: Chem. 192 (2014) 607–627, https://
doi.org/10.1016/j.snb.2013.11.005.
[51] C. Li, P.G. Choi, K. Kim, Y. Masuda, High performance acetone gas sensor based on
ultrathin porous NiO nanosheet, Sens. Actuators B: Chem. 367 (2022) 132143,
https://doi.org/10.1016/j.snb.2022.132143.
[52] C. Chen, W. Bi, W. Yuan, L. Li, Hydrothermal synthesis of the CuWO4/ZnO
composites with enhanced photocatalytic performance, ACS Ome 5 (2020)
13185–13195, https://doi.org/10.1021/acsomega.0c01220.
[53] N. Bai, X. Liu, Z. Li, X. Ke, K. Zhang, Q. Wu, High-efficiency TiO2/ZnO
nanocomposite photocatalysts by sol-gel and hydrothermal methods, J. Solgel Sci.
Technol. 99 (2021) 92–100, https://doi.org/10.1007/s10971-021-05552-8.
[54] B. Bhowmik, K. Dutta, N. Banerjee, A. Hazra, P. Bhattacharyya, Low temperature
acetone sensor based on Sol-gel grown nano TiO2 thin film, IEEE Int. Conf. Emerg.
Trends Comput. Commun. Nanotechnology, ICE-CCN 2013, 2013, pp. 553–557,
https://doi.org/10.1109/ICE-CCN.2013.6528561.
[55] W. Yang, Q. Ou, X. Yan, L. Liu, S. Liu, H. Chen, Y. Liu, High sensing performance
toward acetone vapor using TiO2 Flower-Like nanomaterials, Nanoscale Res. Lett.
17 (1) (2022) 9, https://doi.org/10.1186/s11671-022-03721-4.
[56] L. Wang, X. Xing, N. Chen, R. Zhao, Z. Wang, T. Zou, Z. Wang, Y. Wang, W-doped
nanoporous TiO2 for high performances sensing material toward acetone gas,
J. Nanostruct. 10 (2020) 148–156, https://doi.org/10.22052/JNS.2020.01.016.
M. Murugesan and S.R. Meher Sensors and Actuators: A. Physical 369 (2024) 115181

Muthukumar M received his M.Phil. Degree from Alagappa University, Karaikudi, India, S. R. Meher currently working as an Associate Professor in the Department of Physics,
in 2020. He is pursuing his Ph.D. in the Department of Physics, School of Advanced Sci­ School of Advanced Sciences, VIT – Vellore, India. His current research interests include
ences VIT – Vellore, India. His research interests include the development of thin film and thin film and nanostructured Semiconductors for gas sensing, optoelectronic and self-
nanostructure based sensors for Volatile Organic Compound (VOC) sensing applications. cleaning smart window applications.

15