Nanotechnology

PAPER • OPEN ACCESS You may also like

- Improved Gas Sensing Performance of
Effect of temperature and humidity on the sensing ALD AZO 3-D Coated ZnO Nanorods
P. Lin, X. Chen, K. Zhang et al.
performance of TiO2 nanowire-based ethanol - MoS2 FET fabrication using adhesion
lithography and their application to
vapor sensors chemical sensors
Takahiko Ban, Masaki Ogura and Shin-ichi
Yamamoto
To cite this article: Mostafa Shooshtari et al 2021 Nanotechnology 32 325501
- The sensitivity enhancement of TiO2-
based VOCs sensor decorated by gold at
room temperature
Mostafa Shooshtari, Sten Vollebregt, Yas
Vaseghi et al.
View the article online for updates and enhancements.

This content was downloaded from IP address 110.54.182.73 on 11/12/2023 at 10:20

 Nanotechnology

Nanotechnology 32 (2021) 325501 (13pp) https://doi.org/10.1088/1361-6528/abfd54

Effect of temperature and humidity on the

sensing performance of TiO2 nanowire-
based ethanol vapor sensors
Mostafa Shooshtari1 , Alireza Salehi1 and Sten Vollebregt2
1
Department of Electrical Engineering, K N Toosi University of Technology, Tehran, Iran
2
Department of Microelectronics, Delft University of Technology, Delft, The Netherland

E-mail: s.vollebregt@tudelft.nl

Received 19 January 2021, revised 30 March 2021

Accepted for publication 29 April 2021
Published 17 May 2021

Abstract
In this paper, we study the influence of two key factors, temperature, and humidity, on gas
sensors based on titanium dioxide nanowires synthesized at 4 different temperatures and with
different morphology. The samples’ structure are investigated using SEM, XRD and FTIR
analysis. The effects of humidity and temperature are studied by measuring the resistance and
gas response when exposed to ethanol. At room temperature, we observed a 15% sensitivity
response to 100 ppm of ethanol vapor and by increasing the operating temperature up to 180 °C,
the response is enhanced by two orders of magnitude. The best operating temperature for the
highest gas response is found to be around 180 °C. Also, it was observed that every nanowire
morphology has its own optimum operating temperature. The resistance of sensors is increased
at higher Relative Humidity (RH). Besides, the response to ethanol vapor experiences a gradual
increase when the RH rises from 10% to 60%. On the other hand, from 60% to 90% RH the gas
response decreases gradually due to different mechanisms of interaction of the TiO2 with H2O
and ethanol molecules.
Supplementary material for this article is available online

Keywords: titanium dioxide, ethanol, vapor sensor, humidity, cross-sensitivity

(Some figures may appear in colour only in the online journal)

1. Introduction nanowire (NW-TiO2) can be prepared by several methods [9],

as will be discussed in more detail in the next section.
Titanium dioxide (TiO2) is an important metal oxide semi- NW-TiO2 based gas sensors have received great attention
conductor (MOS) that is desirable for many applications, such due to their excellent sensing property to alcohol vapors such
as pigment [1], solar cells [2], optical waveguides [3], filters as butanol, ethanol and acetone [10, 11]. The finite carrier
[4], and gas sensors [5]. Researchers present their properties density and high surface-to-volume ratio are possible causes
via quantum confinement and surface effect by reducing the for the observed high sensitivity [12]. In general, TiO2 gas
size of TiO2 crystals to nanoscale dimensions [6, 7]. Con- sensors can mainly detect a gas because of the change in the
trolling the morphology of TiO2 crystals in nanostructures, electrical signal caused by the adsorption and reaction of the
such as nanowires and nanoparticles, can also affect its gas molecules on absorption sites on the surface. The change
electrical properties such as sheet resistance [8]. TiO2 in the electrical property is the consequence of charge transfer
between the sensing layer and the gas molecules [5, 13].
The gas sensing mechanism of metal-oxide gas sensors is
Original content from this work may be used under the terms
related to the absorption sites and the number of oxygen
of the Creative Commons Attribution 4.0 licence. Any
further distribution of this work must maintain attribution to the author(s) and atoms on the surface [13, 14]. Besides the analyte of interest,
the title of the work, journal citation and DOI. water vapor is normally present in the ambient environment

0957-4484/21/325501+13$33.00 1 © 2021 The Author(s). Published by IOP Publishing Ltd Printed in the UK
Nanotechnology 32 (2021) 325501 M Shooshtari et al

Figure 1. Schematic diagram of the measurement system.

[15]. Similar to reducing gases, water vapor is known to solution-liquid-solid [29], arc discharge [28], vapor-liquid-
increase the conductance of semiconductor gas sensors [16]. solid [30], and the hydrothermal method [31] have been
The water molecule can affect both the gas-absorbing surface developed. Among these, the hydrothermal method is well-
and the number of surface oxygen atoms. known because it is a simple, controllable, safe, inexpensive,
On the other hand, increasing the operating temperature and novel approach. Also, hydrothermal synthesis does not
is a method often used to increase the sensitivity in metal- require any physical template or catalyst materials that may
oxide gas sensors while the temperature can also help reduce cause contamination.
the sensitivity to water. Despite its attractive features such as In this study, the growth of TiO2 nanowires is performed
a higher sensitivity, this may lead to an unrepeatable gas using 0.3 molar titanium isopropoxide mixed with 0.1 molar
response [17]. ethanolamine in a magnetic stirrer for two hours. Next, 10
In this paper, the effects of temperature and humidity on molar sodium hydroxide (NaOH) is added to the mixture and
the gas response of NW-TiO2 based ethanol gas sensors are kept on the magnetic stirrer for an extra hour. Then, the
investigated. A possible explanation of the observed temp- solution is held at a temperature between 120 °C and 180 °C
erature and humidity effects are given, and the mechanism of for 20 h. We define four samples A, B, C and D and expose
interaction of the TiO2 with H2O and ethanol molecules is them at temperatures of 120 °C, 140 °C, 160 °C, and 180 °C,
proposed. Based on the obtained results, optimal growth and respectively. This temperature range is required to form
testing conditions of gas sensing to reduce the effect of structures with different degrees of porosity. After this period,
humidity and temperature are discussed. the solution is cooled down to room temperature. The
obtained sediment is centrifuged and washed several times
with distilled water and placed at 60 °C to dry for 24 h. Dried
sediment is collected and added to a 0.1 molar hydrochloric
2. Experimental
acid (HCl) solution for one hour. The white colored sediment
is collected by centrifugation and washed several times again
2.1. NW-TiO2 growth
with distilled water and ethanol (C2H6O) and dried at 100 °C
A MOS sensor’s sensitivity can be increased by using for one hour. Finally, nanowire titanium dioxide is obtained
materials with nanostructures. To reduce the dimension of by baking the sediment at 500 °C in the air for an extra hour.
TiO2 from three to zero, several methods have been proposed
[18–21]. Recently, one-dimensional nanostructures such as
2.2. Fabrication of devices for the measurements
NW-TiO2, have attracted much interest owing to their high
surface-to-volume ratio and relatively easy and rapid synth- Figure 1 shows the schematic diagram of the measurement
esis for gas sensing [22–25]. To prepare the NW-TiO2 for gas system. The test set-up consists of a glass test chamber for
sensors, many techniques such as chemical vapor deposition sensors, two separate pipelines for entry and exit of water
(CVD) [26], microwave heating [27], laser ablation[28], vapor and gas, and the electrical measurement equipment to

2
Nanotechnology 32 (2021) 325501 M Shooshtari et al

Figure 2. SEM images of the samples obtained at different temperatures: (a) sample A (120 °C), (b) sample B (140 °C), (c) sample C
(160 °C), (d) sample D (180 °C).

acquire the electrical signals from the sensors. To measure The sensitivity factor of the NW-TiO2 sensor is obtained
conductivity via the 4-point probes method, a Keithley 238 using the measured current and voltage shown in figure 1.
source measure unit is used. The resistance R of the sample in air and when exposed to the
Relative humidity (RH) and temperatures inside the test gas is measured. The response factor of the sensors is then
chamber are monitored during all experiments. A Samwon expressed by:
commercial humidity meter is also used to measure ambient Ra
humidity. The amount of humidity required for calibration is Response = , (1 )
Rg
generated by a commercial ultrasonic humidifier JR model
JRG. A 1.6 MHz oscillator with 100 V output voltage is where Ra is the resistance of the sensor measured in air at
designed for the humidifier. A silica gel is used to reduce the room temperature and Rg is the resistance of the sensor in the
moisture content. The measurement operation is not carried presence of the test gas.
out until the pump has worked for 12 h to obtain a stable RH The sensors response were obtained at the presence of
in the test chamber. To ensure that the operating temperature ethanol vapor at different concentrations which were provided
of the sensor remains unchanged, the resulting chip is placed by evaporating an exact amount of liquid ethanol, which was
on a micro-heater. This micro-heater provides a tuneable measured by a micro sampler, into the air chamber. A 5-litre
temperature varying from room temperature up to 450 °C by air-filled glass container is utilized as the controlled atmos-
applying a DC voltage. A thermocouple type S is placed on phere chamber. Ethanol (Merck/ 1.00983.1000) vapor is used
the sensor surface to measure the temperature. as analyte. The evaporation of these liquids produces different

3
Nanotechnology 32 (2021) 325501 M Shooshtari et al

Figure 3. X-ray diffraction (XRD) pattern of synthesized structures for NW-TiO2 samples obtained at different treatment temperatures:
(a) sample A (120 °C), (b) sample B (140 °C), (c) sample C (160 °C), (d) sample D (180 °C). A(XXX) is Anatase (XXX).

Table 1. XRD Data of NW-TiO2 samples. x-ray diffractometry (XRD, Inel, EQUINOX3000) and
FWHM d-spacing
Fourier-transform infrared (FTIR, JASCO, 460 Plus)
Sample 2θ (Radian) βcosθ A (nm) (Å) spectroscopy. Before SEM observation, the samples are
coated with a 10 nm layer of gold using a sputter coater to
Sample A 25° 0.002058 0.00200 69 3.6 minimize the charging effect on the sample surface. In the
48° 0.001988 0.00181 77 1.9
XRD equipment monochromatic optic Kα1 or Kα1/2 are
Sample B 25° 0.001945 0.00189 73 3.6
48° 0.001867 0.00170 82 1.9 used (λ=0.154 05 nm, at 40 kV and 25 mA).
Sample C 25° 0.001972 0.00182 72 3.6 Figures 2(a)–(d) shows the titania nanowires formed in
48° 0.001913 0.00174 80 1.9 each sample. The manufacture nanowires are 10–20 micro-
Sample D 25° 0.001919 0.00187 74 3.6 meter in length and 30–60 nanometer in diameter. The
48° 0.001867 0.00170 82 1.9 nanowires have a higher surface area than the other crystalline
structures [32]. We note that the hydrothermal method of
synthesis applied to the NW-TiO2 samples provides condi-
ethanol concentration levels, from 5 to 100 ppm, in the closed tions for controlling the size of the nanowires through con-
chamber. trolling the synthesis temperature.
According to the SEM images, NW-TiO2 samples are
successfully fabricated by the applied hydrothermal method.
As can be seen, the NW-TiO2 are porous and clean with no
3. Result and discussion
apparent contamination attached to the wires. In addition,
some nanowires seem to be wider than others. This small size
3.1. Characterization
difference is attributed to the preparation process of the SEM
The structure and phase identification of NW-TiO2 samples sample where the Au coating can fuse NW which are adja-
are investigated with scanning electron microscopy (SEM), cent. This also prevents us from accurately determining the

4
Nanotechnology 32 (2021) 325501 M Shooshtari et al

Figure 4. Fourier-transform infrared (FTIR) spectra of synthesized structures for NW-TiO2 samples obtained at different treatment
temperatures: (a) sample A (120 °C), (b) sample B (140 °C), (c) sample C (160 °C), (d) sample D (180 °C).

Figure 5. Response profiles of ethanol vapor sensors based on NW-TiO2 samples upon exposure to different concentrations of ethanol vapor
at room temperature.

5
Nanotechnology 32 (2021) 325501 M Shooshtari et al

Figure 6. Schematic representation of (a) porous sensing layers with (b) energy bands.

diameter. As is clear from figure 2, the increase in temperature As shown in figure 3, all nanowire samples show
has led to an increase in porosity as well as an increase in the only the anatase phases. In addition, the figure shows that
length of the nanowires. the absence of spurious diffractions is a criterion to indicate
XRD is used to investigate the crystal structure of the crystallographic purity. Two peaks are considered for the
nanowires. The XRD pattern specifies the phases and sizes of study and using the Debye-Scherer formula (equation 2)
the crystalline materials, thus determines the ratio of the the grain size is calculated for the peaks. The peaks in the
anatase phase to the other phases in the NW-TiO2. Figure 3 XRD pattern at 2θ=25° (101) and 2θ=48° (200) indicated
presents the XRD pattern of the synthesized samples where the presence of the anatase phase. All peaks suggest that the
the peaks of anatase are well recognized. prepared samples are in a hexagonal structure [33, 34]. The

6
Nanotechnology 32 (2021) 325501 M Shooshtari et al

Figure 7. Responses of a resistive NW-TiO2 gas sensor Versus operating temperature at different concentration of ethanol. (a) sample A
(120 °C), (b) sample B (140 °C), (c) sample C (160 °C), (d) sample D (180 °C).

Table 2. Recovery and response time of NW-TiO2 samples under 100 ppm ethanol vapor.

Sample Temp (°C) Response time (s) Recovery time (s) Sample Temp (°C) Response time (s) Recovery time (s)
Sample A 25 330 800 Sample C 25 300 540
150 120 220 150 90 135
300 32 44 300 18 24
450 29 43 450 16 21
Sample B 25 330 560 Sample D 25 310 400
150 80 115 150 74 88
300 26 30 300 18 22
450 24 29 450 13 19

pattern matches well with the standard JCPDS files #21- From figure 3, considering the peak FWHM, the average
12729 [35]. The particle diameter A is given by particle size is calculated by using the Debye-Scherer form-
ula. Table 1 shows the d-spacing (Inter-planar spacing
l
A = 0.9 , (2 ) between atoms) calculated using Bragg’s Law:
b cos q
nl = 2d sin q , (3 )
where λ is the wavelength of x-ray applied in XRD char-
acterization (λ=0.15405 nm), β is the Full Width at Half where, n is the reflection order, which is a positive small
Maximum (FWHM) and θ is the diffraction angle. integer (number of crystal plates). We considered n to be one.

7
Nanotechnology 32 (2021) 325501 M Shooshtari et al

Figure 8. Dependence of the resistance of NW-TiO2 gas sensor on temperature during the temperature modulation in synthetic air and when
exposed to 10 ppm ethanol: (a) sample A (120 °C), (b) sample B (140 °C), (c) sample C (160 °C), (d) sample D (180 °C).

As can be seen from table 1, the increase in the treatment analyzers [38]. The variation of the sensor performance con-
temperature did not cause significant changes in the XRD results. cerning the concentration of ethanol vapor is depicted in figure 5,
The FTIR studies on the NW-TiO2 samples show the where the response of all four sensors increases almost linearly
characteristics of a high purity product formed with the least with the concentration. In addition, among the studied NW-TiO2
amount of impurities, as bands related to C−H and C−O samples, sample D exhibits the best performance in ethanol vapor
which are typical contaminants are not observed. Figure 4 detection.
shows a sequence of FTIR spectra for NW-TiO2 samples in Four different factors play roles in determining the electrical
the wavelengths varying between 500 and 4000 cm−1. All of properties of gas sensing in NW-TiO2 sensors: bulk resistance,
the obtained vibrational bands are similar to those observed in surface effects, grain boundaries and the contact between the
the literature [36, 37]. Almost the same spectrum is observed grain interface and the electrode [39–42]. As shown in
for the four samples. It is found that TiO2 nanowires with the figure 6(a) we can model each factor with a series resistor. The
characteristic peaks at 690 and 1620 cm−1 are assigned to the gas molecules on the surface of TiO2 based on the chemical or
Ti–O–O and Ti–O–Ti stretching vibrations, respectively. The physical adsorption/desorption can change these resistances due
bond –OH observed at 3440 cm−1 indicates hydrogen to the change in charge carrier concentration. The change in
bonding which could originate from the HCl. oxygen vacancy levels in the presence of ethanol molecules
occurs in all four resistance regions. A larger porosity and higher
adsorption sites can increase the sensitivity of the samples.
3.2. Gas response
Therefore, sample D shows a larger sensitivity. The oxygen
The gas test measurements are carried out at room temperature molecules in the air are adsorbed on the grain surface. Due to the
by recording the dynamic changes in the electrical resistance, porous structure of the NW-TiO2, the oxygen molecules gra-
which happens when the sample is exposed to various con- dually diffuse and they eventually cover all the grains. The
centrations (5–100 ppm) of ethanol vapor in dry air. These oxygen molecules remove the electrons from the grains during
concentrations are below the detection limit imposed on breath the adsorption. As shown in figure 6(b) loss of electrons may

8
Nanotechnology 32 (2021) 325501 M Shooshtari et al

Figure 9. Relative humidity versus dc resistance plots at room temperature.

form an electron depletion layer as well as a potential barrier operating temperature for titanium dioxide gas sensors is thus
between grains. important and its value is unchanged for various concentrations of
It is shown in many studies (e.g., [43]) that the amount of gas. However, each structure of the TiO2 gas sensor has an
oxygen vacancies in the TiO2 at room temperature is not suf- optimal operating temperature. The optimum temperature for
ficient for gas sensing. However, in the samples described here, TiO2 gas sensors at temperatures above 220 °C is reported in [46].
due to the presence of a very large volume to surface ratio, As shown in figure 7, the highest response is observed in the
there is a lot of surface oxygen with dangling bonds, which can four NW-TiO2 sensors at temperatures below 200 °C. Sample D
be absorbed by ethanol molecules and extracted from the TiO2. with the largest number of adsorption-desorption sites provides
As shown in equation (4) this process can lead to the release of its maximum response at the lowest temperature. This may
electrons in titanium dioxide and thus, a change in the Fermi happen because the nanowire becomes closer to the thickness of
level. When NW-TiO2 is exposed to ethanol vapor, the oxya- the depletion region [47]. A larger response arises from the
nions react with the ethanol molecules and deliver a large space-charge layer due to oxygen adsorption that penetrates
number of electrons to the grains. As shown in figure 6(b) these deeper into the nanowires. This is because when the nanowires
additional carriers reduce the distance between the Fermi level are close to twice the thickness of the depletion layer, the whole
and the conduction band and therefore, increase the con- particle can be depleted of carriers through surface interactions,
ductivity of the sample. The change in oxygen vacancy and which leads to an increase of the sensing properties.
electron distribution can also reduce the barrier between the The oxygen molecules in the air environment are che-
grain boundaries and the semiconductor metal barrier. misorbed in the forms of O− −
2 , O and O
2−
[48]. At a constant
C 2 H 6O + 6TiO2  2CO2 + 3H2 O + 6TiO+ + 6e-. (4) temperature there is a chemical equilibrium between different
oxygen molecules on the surface of TiO2 and the oxygen
molecule in the air:
O2 « O2- « O- « O2 - « O2. (5 )
3.3. The effect of temperature

At a low operating temperature, a relatively low sensitivity can be At low temperatures, reactions with the gas molecules
expected because the gas molecules do not have sufficient ther- occur only at the surface, while at high temperatures bulk
mal energy to react with the surface adsorbed oxygen species. reactions between point defects in the TiO2 lattice have a
Hence, most researchers present an optimized working temper- larger contribution. The reduction in the response of gas
ature for TiO2 gas sensors [24, 44, 45]. Selecting an optimum sensor above ~200 °C is likely due to the difficulty in ethanol

9
Nanotechnology 32 (2021) 325501 M Shooshtari et al

Figure 10. The long-term stability of NW-TiO2 sensors, measured at 1V at various. RH levels: (a) sample A (120 °C), (b) sample B (140 °C),
(c) sample C (160 °C), (d) sample D (180 °C) at room temperature.

gas adsorption, therefore, an optimum operating temperature chemisorption of a gas molecule is high which indicates that
should be considered to enhance the response. the ratio of the O− and O2− species to the O− 2 species is
The response and recovery times of our samples are greatly increased. These two species are dominant at higher
decreased significantly with increasing temperature. These temperatures and frozen at the surface due to the fast temp-
times do not follow a regular pattern as with the optimum erature change. They are also much more reactive with the
response. As can be seen from table 2 they decrease with gas and as a result the ethanol gas response is increased [49].
increasing temperature and then stay unchanged from Based on table 2, since the sensors have a different
about 300 °C. response and recovery time at each temperature, there exists a
Figure 8 shows the typical temperature dependencies of hysteresis curve when measuring the resistance. As the
the actual resistance of the sensors realized with the four temperature increases, the response and recovery time
nanowire structures during continuous exposure to the test gas become shorter and closer to each other. As can be seen from
or ambient environment. One can easily observe the qualita- figure 8, sample A has the largest hysteresis.
tive difference between the response of gases and the ambient
air. Moreover, a large change in resistance occurs, which is
3.4. The effect of humidity
due to the increased temperature. As it is clear from the figure,
increasing the temperature constantly reduces the resistance The measured resistance for all samples is shown as a func-
of the sample but in the presence of the gas, the change in tion of RH at room temperature in figure 9. It can be seen
resistance is also due to the interaction with the gas mole- from the logarithmic scale over the range of 10%–90% RH
cules. Therefore, in the diagram in the presence of gas in that the resistance of all nanowire samples decreases strongly
figure 8 (red), the resistance changes become non-linear after with increasing humidity and that the resistance of the sam-
the optimum temperature. At the optimum temperature, the ples varies exponentially with RH, showing a very high

10
Nanotechnology 32 (2021) 325501 M Shooshtari et al

Figure 11. The variation of the response and the sensitivity of NW-TiO2 sensors as a function of Relative Humidity (RH) during the exposure
to 20 ppm ethanol at optimal operating temperature.

sensitivity. Between the four different samples, only minor conductance increases with RH and the process is rever-
differences are observed, with the exception of sample A at sible [14].
high humidity. The increase in the conductance of TiO2 by increasing
The stability of NW-TiO2 sensors is investigated in dif- the RH can be described as a sequence of dissociation and
ferent relative humidity’s (RH). The sensing results are reduction [50]. There are two types of OH groups; a rooted
obtained at room temperature (25 °C) every day for two times, OH with an oxygen lattice and one bounded one with a
while kept in 10% RH, 30% RH, 70% RH and 90% RH, titanium lattice:
respectively. Figure 10 shows the effect of long-term stability. H2 O + TiO2 « {(TiO - OH) + OH} + (Vo+ + e-). (6)
The sensor impedance has no apparent deviation for samples
The reaction constitutes the homolytic dissociation of
B, C and D over time. The resistance variation is less than 3%
H2O and the reaction of the neutral H atom with the lattice
at each humidity region, during the time interval of 30 days.
oxygen. In addition to ionizing the lattice, the reaction
Sample A showed changes of about 50% for 90% humidity.
releases the electron as a donor to the rooted OH group.
After the stability test, the gas sensor response of the samples The change in the gas sensitivity due to the presence of
was re-examined. The same response curve was obtained for water molecules on the surface of titanium oxide can be the
each experiment under different conditions, see also figure S1 result of two factors. Firstly, free carrier changes and inter-
(available online at stacks.iop.org/NANO/32/325501/ action between both the hydroxyl group and the hydrogen
mmedia). The repeatability of the response showed that atom originating from the water molecule with a gas molecule
there is no serious sensing poisoning and that the sensors group. Secondly, co-adsorption of water on the adsorption of
were fully recoverable. another adsorbate could play a role as an electron accep-
To investigate the effect of humidity on the response of tor [51].
the fabricated sensors, ethanol vapor sensing is applied in the Consequently, H2O molecules provide the necessary
test chamber during a change in relative humidity. Figure 11 conditions for oxygen adsorption, electrons, and oxygen
shows the response as a function of the applied RH to vacancies. Water absorption can then accelerate the absorp-
NW-TiO2 samples when exposed to 20 ppm ethanol vapor. tion of oxygen. Thus, due to the surface distribution and
Here, the optimum operating temperature from figure 7 for coverage of hydroxyl groups and the presence of oxygen
each sample was applied. The effect of humidity on the species, an enhancement or reduction effect of RH may
conductance of metal oxide semiconductors is accepted as the happen on the conductance in the response to ethanol. As it is

11
Nanotechnology 32 (2021) 325501 M Shooshtari et al

clear in figure 11 there are fewer hydroxyl groups and oxygen ORCID iDs
on the surface of nanowires at low relative humidity, which
leads to a weak response of the sensors. Mostafa Shooshtari https://orcid.org/0000-0003-
When humidity increases to about 60% RH, the change 1292-0683
in the hydroxyl groups is smaller than that of oxygen on the Sten Vollebregt https://orcid.org/0000-0001-6012-6180
surface. Therefore, it continues to increase the response.
When the humidity is too high, the hydroxyl groups OH cover
almost the surface and limit the oxygen adsorption. Now,
according to equations (4) and (6), the absorption of water References
and ethanol increases electron carriers. Therefore, in high
humidity, the number of electrons released due to water [1] Karlsson M C et al 2012 Characterisation of silicon, zirconium
molecule absorption is considerably high such that the effect and aluminium coated titanium dioxide pigments recovered
of electrons due to the absorption of ethanol gas is less from paint waste Dyes Pigm. 162 145–52
[2] Aboulouard A et al 2020 Dye sensitized solar cells based on
observed. titanium dioxide nanoparticles synthesized by flame spray
The effect of relative humidity and temperature on the pyrolysis and hydrothermal sol−gel methods: a comparative
selectivity of fabricated gas sensors was examined for some study on photovoltaic performances J. Mater. Res. Technol.
gases such as other volatile organic compounds and ammonia 9 1569–77
[3] Klestova A, Cheplagin N, Keller K, Slabov V,
but no meaningful relationship between selectivity of fabri- Zaretskaya G and Vinogradov A V 2019 Inkjet printing of
cated sensor and these two parameter changes has been optical waveguides for single‐mode operation Adv. Opt.
observed. Mater. 7 1801113
[4] Schneider S L and Lim H W 2019 A review of inorganic UV
filters zinc oxide and titanium dioxide Photodermatol.,
Photoimmunol. Photomed. 35 442–6
[5] Rzaij J M and Abass A M 2020 Review on: TiO2 thin film as a
4. Conclusion metal oxide gas sensor J. Chem. Rev. 2 114–21
[6] Xue X et al 2012 Raman investigation of nanosized TiO2:
We studied the effects of humidity and temperature on the effect of crystallite size and quantum confinement J. Phys.
response of titanium dioxide nanowire to ethanol vapor. We Chem. C 116 8792–7
[7] Hmiel A and Xue Y 2012 Quantum confinement and surface
employed the growth of TiO2 nanowires via the hydrothermal relaxation effects in rutile TiO2 nanowires Phys. Rev. B 85
method as a simple and low-cost fabrication method. In the 235461
growth process of titanium dioxide, four different treatment [8] Shen S et al 2018 Titanium dioxide nanostructures for
temperatures were used to obtain different morphologies of photoelectrochemical applications Prog. Mater Sci. 98
299–385
nanowires. Gas sensing results showed that the sample with [9] Chen X and Selloni A 2014 Introduction: titanium dioxide
high porosity and longer wire length was more sensitive to (TiO2) nanomaterials Chemical reviews 114 9281–2
ethanol vapor than other samples. The ethanol vapor sensing [10] Taha S et al 2020 Titanium dioxide nanostructure based
characteristics as a function of temperature were investigated. alcohol vapor sensor AIP Conf. Proc. p 020195
[11] Hazra A, Dutta K, Bhowmik B, Chattopadhyay P and
We found that by increasing the treatment temperature in the
Bhattacharyya P 2014 Room temperature alcohol sensing by
growth process the maximum sensitivity shifts towards a oxygen vacancy controlled TiO2 nanotube array Appl. Phys.
lower operating temperature. Lett. 105 081604
In the case that both gas and water molecules are pre- [12] Dey A 2018 Semiconductor metal oxide gas sensors: a review
sented simultaneously in the test chamber, low humidity Mater. Sci. Eng. B 229 206–17
[13] Ji H, Zeng W and Li Y 2019 Gas sensing mechanisms of metal
increased the sensitivity to ethanol. In contrast, at high oxide semiconductors: a focus review Nanoscale 11
humidity we observed competitive sorption and reduction of 22664–84
the ethanol sensing response of the sensors. Thus far in the [14] Wang C, Yin L, Zhang L, Xiang D and Gao R 2010 Metal
study, we showed that the influence of humidity and temp- oxide gas sensors: sensitivity and influencing factors Sensors
10 2088–106
erature on the sensor response can be evaluated by the [15] Shooshtari M, Salehi A and Vollebregt S 2021 Effect of
morphology of the nanowires that can be changed in the humidity on gas sensing performance of carbon nanotube
growth process. Future studies will focus on the synthesis and gas sensors operated room temperature IEEE Sens. J. 21
the use of highly hydrophobic TiO2 that sorb alcohols vapor 5763–70
more selectively than water to improve the sensor insensi- [16] Gaman V, Anisimov O, Maksimova N, Sergeichenko N,
Sevast’yanov E Y and Chernikov E 2008 The effect of water
tivity to humidity. vapor on the electrical properties and sensitivity of thin-film
gas sensors based on tin dioxide Russ. Phys. J. 51 831–9
[17] Tian W-C, Ho Y-H, Chen C-H and Kuo C-Y 2013 Sensing
performance of precisely ordered TiO2 nanowire gas sensors
fabricated by electron-beam lithography Sensors 13 865–74
Data availability statement
[18] Giannakoudakis D A, Chatel G and Colmenares J C 2020
Mechanochemical forces as a synthetic tool for zero-and
All data that support the findings of this study are included one-dimensional titanium oxide-based nano-photocatalysts
within the article (and any supplementary files). Top. Curr. Chem. 378 2

12
Nanotechnology 32 (2021) 325501 M Shooshtari et al

[19] Lashkov A V et al 2020 The Ti wire functionalized with inherent [36] Bagheri S, Shameli K and Abd Hamid S B 2013 Synthesis and
TiO2 nanotubes by anodization as one-electrode gas sensor: a characterization of anatase titanium dioxide nanoparticles
proof-of-concept study Sensors Actuators B 306 127615 using egg white solution via Sol−Gel method Journal of
[20] Zhao G et al 2020 In situ growing double-layer TiO2 nanorod Chemistry 2013 848205
arrays on new-type FTO electrodes for low-concentration [37] León A et al 2017 FTIR and Raman characterization of TiO2
NH3 detection at room temperature ACS Appl. Mater. nanoparticles coated with polyethylene glycol as carrier for
Interfaces 12 8573–82 2-methoxyestradiol Appl. Sci. 7 49
[21] Hu P et al 2010 Enhancement of ethanol vapor sensing of TiO2 [38] Brousse T and Schleich D 1996 Sprayed and thermally
nanobelts by surface engineering ACS Appl. Mater. evaporated SnO2 thin films for ethanol sensors Sensors
Interfaces 2 3263–9 Actuators B 31 77–9
[22] Munasinghe Arachchige H M, Zappa D, Poli N, [39] Ponzoni A et al 2017 Metal oxide gas sensors, a survey of
Gunawardhana N, Attanayake N H and Comini E 2020 selectivity issues addressed at the SENSOR Lab, Brescia
Seed-assisted growth of TiO2 nanowires by thermal (Italy) Sensors 17 714
oxidation for chemical gas sensing Nanomaterials 10 935 [40] Sun Y-F et al 2012 Metal oxide nanostructures and their gas
[23] Ramgir N et al 2020 TiO2/ZnO heterostructure nanowire based sensing properties: a review Sensors 12 2610–31
NO2 sensor Mater. Sci. Semicond. Process. 106 104770 [41] Kirner U et al 1990 Low and high temperature TiO2 oxygen
[24] Yang X et al 2019 Enhanced gas sensing performance based sensors Sensors Actuators B 1 103–7
on the fabrication of polycrystalline Ag@ TiO2 core–shell [42] Lee J-S, Katoch A, Kim J-H and Kim S S 2016 Growth of
nanowires Sensors Actuators B 286 483–92 networked TiO2 nanowires for gas-sensing applications
[25] Zhou M, Liu Y, Wu B and Zhang X 2019 Different crystalline J. Nanosci. Nanotechnol. 16 11580–5
phases of aligned TiO2 nanowires and their ethanol gas [43] Ramanavicius S and Ramanavicius A 2020 Insights in the
sensing properties Physica E 114 113601 application of stoichiometric and non-stoichiometric
[26] Shi J and Wang X 2011 Growth of rutile titanium dioxide titanium oxides for the design of sensors for the
nanowires by pulsed chemical vapor deposition Cryst. determination of gases and VOCs (TiO2−x and TinO2n−1
Growth Des. 11 949–54 versus TiO2) Sensors 20 6833
[27] Li L, Qin X, Wang G, Qi L, Du G and Hu Z 2011 Synthesis of [44] Guo W, Feng Q, Tao Y, Zheng L, Han Z and Ma J 2016
anatase TiO2 nanowires by modifying TiO2 nanoparticles using Systematic investigation on the gas-sensing performance of
the microwave heating method Appl. Surf. Sci. 257 8006–12 TiO2 nanoplate sensors for enhanced detection on toxic
[28] Ashkarran A 2011 Metal and metal oxide nanostructures gases Mater. Res. Bull. 73 302–7
prepared by electrical arc discharge method in liquids [45] Tong X, Shen W, Zhang X, Corriou J-P and Xi H 2020
J. Cluster Sci. 22 233 Synthesis and density functional theory study of free-
[29] Nechache R, Nicklaus M, Diffalah N, Ruediger A and Rosei F standing Fe-doped TiO2 nanotube array film for H2S gas
2014 Pulsed laser deposition growth of rutile TiO2 sensing properties at low temperature J. Alloys Compd. 832
nanowires on Silicon substrates Appl. Surf. Sci. 313 48–52 155015
[30] Mohammad S N 2008 Analysis of the vapor–liquid–solid [46] Karunagaran B, Uthirakumar P, Chung S, Velumani S and
mechanism for nanowire growth and a model for this Suh E-K 2007 TiO2 thin film gas sensor for monitoring
mechanism Nano Lett. 8 1532–8 ammonia Mater. Charact. 58 680–4
[31] Al-Hajji L et al 2020 Impact of calcination of hydrothermally [47] Park S-H, Ryu J-Y, Choi H-H and Kwon T-H 1998 Zinc oxide
synthesized TiO2 nanowires on their photocatalytic thin film doped with Al2O3, TiO2 and V2O5 as sensitive
efficiency J. Mol. Struct. 1200 127153 sensor for trimethylamine gas Sensors Actuators B 46 75–9
[32] Schneider C, Liu N, Romeis S, Peukert W and Schmuki P 2019 [48] Chachuli S A M, Hamidon M N, Ertugrul M, Mamat M S,
Easy room temperature synthesis of high surface area Jaafar H and Shamsudin N 2020 TiO2/B2O3 thick film gas
anatase nanowires with different morphologies sensor for monitoring carbon monoxide at different
ChemistryOpen 8 817–21 operating temperatures Journal of Physics: Conf. Series
[33] Zhu S, Jiang J, Zhang X, Liang Y, Cui Z and Yang X 2017 p 012040
Novel nanosized anatase TiO2 hexagonal prism filled with [49] Heilig A, Barsan N, Weimar U, Schweizer-Berberich M,
nanoporous structure Mater. Des. 116 238–45 Gardner J and Göpel W 1997 Gas identification by
[34] Dai S, Wu Y, Sakai T, Du Z, Sakai H and Abe M 2010 modulating temperatures of SnO2-based thick film sensors
Preparation of highly crystalline TiO2 nanostructures by Sensors Actuators B 43 45–51
acid-assisted hydrothermal treatment of hexagonal- [50] Wang Y, Zhou Y and Wang Y 2020 Humidity activated ionic-
structured nanocrystalline titania/cetyltrimethyammonium conduction formaldehyde sensing of reduced graphene oxide
bromide nanoskeleton Nanoscale Res. Lett. 5 1829–35 decorated nitrogen-doped MXene/titanium dioxide
[35] Theivasanthi T and Alagar M 2013 Titaniumdioxide (TiO2) composite film Sensors Actuators B 323 128695
nanoparticles XRD analyses: an insight Cornel University [51] Henrich V E and Cox P A 1996 The Surface Science of Metal
Library arXiv:1307.1091 Oxides (Cambridge: Cambridge University Press)

13