Applied Surface Science 578 (2022) 151983

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Applied Surface Science

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Full Length Article

Optimal Pt mesoporous layer modified nanocomposite film with highly

sensitive detection of ethanol at low temperature
Xin Tian , Huitong Cao , Hairong Wang *, Jiuhong Wang , Xinyu Wu , Xueyong Wei
School of Mechanical Engineering, Xi’an Jiaotong University, Xi’an, Shaanxi 710049, PR China
State Key Laboratory for Manufacturing Systems Engineering, Xi’an Jiaotong University, Xi’an, Shaanxi 710049, PR China

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

Keywords: Developing highly sensitive and selective gas sensing MOS materials with low working temperature is urgent to
Pt mesoporous layer fabricate high-performance ethanol gas sensors. Herein, we report a Pt mesoporous layer modified multi-layer
TiO2/SnO2 nanocomposite film TiO2/SnO2 nanocomposite thin film for improving sensitivity and selectivity of detecting ethanol at a low
High sensitivity
temperature. The Pt mesoporous layer is prepared by simple sputtering techniques, which are completely
Low working temperature
compatible with the MEMS process. The characterization results show the Pt sputtering time of 30 s and the
Ethanol
MEMS annealing temperature of 500℃ are the opening condition and forming condition of Pt mesoporous layer,
respectively, which has the most mesoporous of 5–50 nm. Because the Pt mesoporous layer has copious meso­
porous and there is an abundant Schottky barrier between Pt and TiO2, the thin film (optimal parameters: 30 s,
500℃) based sensor has the highest sensitivity to ethanol at 130 ℃ and its response is as high as 3.32 to 0.1 ppm
of ethanol, so the thin film is regarded as the optimal Pt mesoporous layer. Thus, the Pt mesoporous layer on the
multi-layer TiO2/SnO2 nanocomposite thin film prepared by sputtering techniques is a simple but effective
method to largely improve the gas sensing properties of the nanocomposite film.

1. Introduction
Volatile organic compounds (VOCs), such as ethanol, acetone,
formaldehyde, and benzene, etc, are inimical to human health and the
environment due to their mutagenicity, teratogenicity, and poisonous­
ness [1]. Ethanol, as one kind of the common and extreme VOCs in life, is
widely used in manufacturing [2], biomedical [3], and food industries
[4]. However, some serious symptoms like narcosis and impaired
perception will happen while a person gets in amounts of ethanol [5].
Thus, the detection of ethanol is of great significance for protecting
human health. There was an abundant investigation about the ethanol
gas sensors based on the metal oxide semiconductors (MOS) which are
extensively used as the gas sensing materials for their stable, remark­
able, and reversible surface resistance changes in the gas ambiance
[6–8].
In recent three decades, research on gas sensing properties of various
MOS (i.e., SnO2[9–11], TiO2[12–14], ZnO [15], Fe2O3[16],
In2O3[17,18], WO3[19], Co3O4[20,21], V2O5[22] have been investi­
gated and widely used to detect ethanol. Among them, SnO2 as the n-
type MOS material with a wide bandgap of 3.6 eV, attracted much
attention for its excellent chemical and electrical properties [23–26]. To
date, many studies have demonstrated good properties of SnO2 with
various microstructures (i.e., flower-like, nanofibers, hollow nano­
particles) which can provide high surface areas. For example, Zeng et al.
prepared the flower-like SnO2 nanostructures showing the response of
about 17 to 400 ppm of ethanol at 350℃ [27]. Zhang et al. revealed that
SnO2 nanofibers had a response of about 19 to 200 ppm of ethanol at
330℃ [28]. Zito et al. found that the hollow SnO2 particles can detect
100 ppm of ethanol with the response of 63.4 at 300℃ [29]. Although
the response to ethanol can be improved by different microstructures of
SnO2, there were still some problems, such as relatively low sensitivity
and high working temperature.
Previous research has proven that some measures (i.e., using heter­
ojunctions [30], metal surface modification [31,32]) can effectively
enhance the MOS gas sensing sensitivity and decrease the working
temperature. The heterojunctions may improve gas sensing properties
due to their synergistic effects in the composites [33,34]. For example,
Su et al. found the response of TiO2@SnO2 nanosphere to 10 ppm of
formaldehyde reached 49.3, which is better than that of TiO2 nano­
sphere under the same testing condition [35]. Feng et al. revealed that

* Corresponding author.
E-mail address: whairong@mail.xjtu.edu.cn (H. Wang).

https://doi.org/10.1016/j.apsusc.2021.151983
Received 11 August 2021; Received in revised form 14 November 2021; Accepted 18 November 2021
Available online 22 November 2021
0169-4332/© 2021 Elsevier B.V. All rights reserved.
X. Tian et al. Applied Surface Science 578 (2022) 151983

the response of TiO2//SnO2 nanofibers to 10 ppm of ethanol exhibited Table 2

about 7.5 at 368℃ [36]. Wang et al. prepared the TiO2-SnO2-TiO2 15 samples various in sputtering time of Pt or annealing temperature.
composite nanofibers showing the response of 13.3 to 1 ppm of acetone Process parameters Sputtering time of Pt [s]
at 280℃ [37]. Therefore, the gas sensing properties of SnO2 can be
0 10 20 30 40
enhanced by heterojunctions formed with TiO2 and greatly improved by Annealingtemperature[℃] 400 S1 S2 S3 S4 S5
multilayer heterojunctions of multi-layer TiO2/SnO2. However, the high 500 S6 S7 S8 S9 S10
working temperature is still a problem on many occasions. As another 600 S11 S12 S13 S14 S15
effective method, the metal surface modification can enormously
enhance the sensing properties and decrease the working temperature
sputtering time of Pt and annealing temperature of all 15 samples.
because of their catalysis activity to gas and Schottky Barrier formed at
the interface between metal and MOS. Huang et al. revealed that the
optimal working temperature of the Pt modified SnO2 nanorod is lower 2.2. Fabrication of the MEMS gas sensor.
than the pure SnO2 nanorods [38]. Mohammad et al. confirmed that Ag
modified SnO2 based sensor attains the high response as well as the low Fig. 1 demonstrates a schematic diagram describing the fabricating
working temperature of 180℃ compared to the pure SnO2 based sensor process of the MEMS ethanol sensor. A four-inch silicon wafer was
[32]. Therefore, the metal-modified heterojunctions are possible to selected as the substrate to be thermally oxidized to form 500 nm SiO2,
enhance the gas sensing sensitivity at the low working temperature. and later 150 nm Si3N4 was deposited on both sides of the substrate by
In this paper, we proposed a method to fabricate the high- low-pressure chemical vapor deposition (LPCVD). To improve the sta­
performance MEMS gas sensor for detecting ethanol. To enhance the bility of the MEMS ethanol gas sensor, 500 nm SiO2 and 150 nm Si3N4
gas sensing sensitivity of MOS material and decreasing the working was deposited on the front side of the substrate (Fig. 1a) by plasma-
temperature by the above-mentioned measures (microstructures, het­ enhanced chemical vapor deposition (PECVD, America Trion Orion
erojunctions, and metal modification), a Pt mesoporous layer modified III). A positive-type photoresist (PR) was spin-coated on the front side
multi-layer TiO2/SnO2 (Pt/TiO2/SnO2) nanocomposite thin film was and photolithography was used to define the sensing area (100 μm ×
prepared by magnetron sputtering technique. This Pt mesoporous layer 100 μm) after drying. (Fig. 1b) shows the Pt/TiO2/SnO2 nanocomposite
activated multi-layer MOS materials are compatible with the MEMS thin film was deposited by sputtering and the other part was removed
process, and as far as this method has not been reported yet. The (Fig. 1c) by acetone. The interdigital electrodes (IDE) and microheater
contribution of different Pt sputtering time and annealing temperature were patterned by the photolithography process. 50 nm Cr and 250 nm
to the formation of Pt mesoporous layer was investigated, showing the Au were deposited on the front side of the substrate by electron beam
Pt sputtering time of 30 s and the annealing temperature of 500℃ are evaporation (HHY, TF500) successively (Fig. 1d). The front structure of
the opening condition and forming condition of Pt mesoporous layer, the sensor was finished after the PR was removed with the annealing of
respectively, which has the most mesoporous of 5–50 nm. The MEMS 300℃ for 10 min followed (Fig. 1e). (Fig. 1f) shows the cavity structure
ethanol gas sensors with the Pt/TiO2/SnO2 nanocomposite thin film has in the backside was finished by inductive coupled plasma (ICP, Oxford
the high sensitivity to ethanol at 130℃ and shows the response of 3.32 ICP-180) etching. (Fig. 1g) and (Fig. 1h) show the top and back view of
to 0.1 ppm of ethanol, which can be attributed to the plenty of Pt the sensor, respectively, indicating that the IDE is attached to the gas
mesoporous and Schottky Barrier formed at the interface between Pt and sensing material with the microheater around.
TiO2. The Pt mesoporous layer and multilayer heterojunctions created
entirely by sputtering techniques verify the effectiveness of this method
2.3. Characterization
for preparing enhanced MOS gas sensing materials for the gas sensors.

The morphology of the Pt/TiO2/SnO2 nanocomposite thin film was

2. Experimental section
characterized by field emission scanning electron microscope (FE-SEM,
Zeiss, Gemini SEM 500) and atomic force microscope (AFM, Bruker AXS
2.1. Preparation of Pt/TiO2/SnO2 nanocomposite thin film
Innova). The thermal image was measured using an infrared thermog­
raphy camera (Flir X6520sc). The XRD patterns of the Pt/TiO2/SnO2
Pt mesoporous layer modified TiO2/SnO2 nanocomposite thin film
nanocomposite thin film were determined by X-ray diffraction (XRD,
was completely prepared by a sputtering technique. The pure Pt (three-
Bruker D8 Advance A25) using Cu-Kα radiation (λ = 1.5418 Å) under the
inch, 99.99%, Zhongnuo New Material Technology Co., Ltd.), SnO2(­
Bragg angle (2θ) with a scanning range from 20◦ to 80◦ and a scanning
three-inch, 99.99%, Zhongnuo New Material Technology Co., Ltd.), and
step of 0.02◦ . The XPS spectra of the Pt/TiO2/SnO2 nanocomposite thin
TiO2(three-inch, 99.99%, Zhongnuo New Material Technology Co., Ltd.)
film were obtained by X-ray photoelectron spectroscopy (XPS, Thermo
target were used to deposit Pt/TiO2/SnO2 nanocomposite thin film by
Fisher ESCALAB Xi + ) using mono aluminum anode with a spot of mono
magnetron sputtering in the order from Table 1. Five sets of parameters
500 μm.
for the sputtering time of Pt to explore its contribution to the formation
of Pt mesoporous layer. Each sputtering time was arranged for three
samples that were annealed at different temperatures to study its effects 2.4. Gas sensing test
on the optimization of the Pt mesoporous layer. Table 2 shows the
The properties of the MEMS gas sensor were evaluated with a
computer-controlled gas-sensing analysis system made of a multi-
Table 1
Sputtering order of Pt, TiO2, and SnO2. channel gas flow controller, a DC power source, a sealed chamber,
and a digit multimeter, as shown in Fig. 2. The ethanol gas and inter­
Sputtering Material Sputtering power Sputtering time (s)
fering gas were prepared by dry target gas and dry equilibrium air. The
orders (W)
DC power source is connected to the microheater to provide different
1 SnO2 100 1500
working temperatures for the sensor. The multimeter is connected with
2 TiO2 150 900
3 SnO2 100 1500 the IDE to record the dynamic change of the resistance of sensitive
4 TiO2 150 900 materials and display it on the computer. The sensor response (S) was
5 SnO2 100 1500 defined as S = Ra/Rg for reducing gases or S = Rg/Ra for oxidizing
6 TiO2 150 900 gases, where the Ra was the baseline resistance in the air and the Rg was
7 Pt 130 0 s; 10 s; 20 s;30 s; 40 s
the equilibrium resistance in the tested gas.

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X. Tian et al. Applied Surface Science 578 (2022) 151983

Fig. 1. Schematic diagram of the fabrication process of gas sensor based on Pt/TiO2/SnO2 nanocomposite thin film. (a) Four-inch silicon wafer was thermally
oxidized to form 500 nm SiO2, and later 150 nm Si3N4 was deposited on both sides of the substrate by LPCVD 500 nm SiO2 and 150 nm Si3N4 were deposited on the
front side of the substrate by PECVD. (b) The sputtering of Pt/TiO2/SnO2 nanocomposite thin film. (c) The Pt/TiO2/SnO2 nanocomposite thin film attach on the front
side of substrate in defined area. (d) The deposition of 50 nm Cr and 250 nm Au. (e) IDE and microheater was deposited on the defined area. (f) The cavity structure
in the back side of the substrate was etched. (g) The top view of the sensor. (h) The back view of the sensor.

Fig. 2. The schematic diagram of dynamic gas testing system.

3. Result and discussion
3.1. Structural and morphological characteristics
The microstructure and morphologies of the as-prepared samples S1,
S2, S3, S4, S5 were investigated by FESEM observation. Fig. 3 shows the
Pt layer with the different sputtering times of Pt at the same annealed
temperature of 400℃ in N2. The FESEM images in (Fig. 3a-b) clearly
show the smooth plane of sample S1 completely prepared by sputtering.
The Pt particles turned into larger from sample S2 to sample S3. The Pt
mesoporous layer is formed at sample S4 and disappears in sample S5, as
shown in (Fig. 3c-j). It shows the strong correlation between the for­
mation of Pt mesoporous layer with the sputtering time of Pt and
confirms that the 30 s sputtering time of Pt is the key to the opening of
the Pt mesoporous layer.
Fig. 4 demonstrates the FESEM images of Pt mesoporous layer varied
in annealing temperature with the same Pt sputtering time of 30 s. The
Pt layer gradually agglomerated into small particles, and Pt mesoporous
(size from 8 − 25 nm) began to appear in sample S4 shown in (Fig. 4a-b).
It can be found that the Pt layer agglomerates into large particles and Pt
mesoporous (size from 5 − 50 nm) also appear in a large area shown in
sample S9, as shown in (Fig. 4c-d). But as the annealing temperature
increased to 600℃ in sample S14, the Pt mesoporous disappeared
completely and were replaced by Pt super-large particles shown in
(Fig. 4e-f). One sees that the annealing temperature of 500℃ can enlarge
the size and increase the numbers of Pt mesoporous while annealing

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X. Tian et al.
Fig. 3. SEM images of samples S1 (a, b), S2 (c, d), S3 (e, f), S4 (g, h) and S5 (i, j)
annealed at 400℃ in N2 for different sputtering time. The cross section.
temperature of 600℃ will make the Pt mesoporous replaced by super
big Pt particles. Therefore, the Pt sputtering time of 30 s and the
annealing temperature of 500℃ is the opening condition and forming
condition of Pt mesoporous layer, respectively, which can be regarded as
the optimal parameters to form the Pt mesoporous. Such Pt mesoporous
might have a large specific surface area, which is critical for forming
high-performance gas sensors.
The roughness and 3-D morphologies of as-prepared samples S1, S4,
S9, S14 were further investigated by AFM to study the effect of
annealing temperature on the Pt surface. (Fig. 5a-d) shows the surface of
samples S1 and S4 were composed of the dense and homogeneous par­
ticles, both having the similar average roughness of 1.47 nm and 1.46
nm respectively, and showing the little effect of annealing temperature
of 400℃ on the Pt surface. It can be seen that the Pt particles on the
surface of samples S9 and S14 are inhomogeneous and irregular (Fig. 5e-
h), showing the average roughness are 3.56 nm and 18.2 nm respec­
tively, which indicates the accelerating coagulation of Pt due to the
excess high annealing temperature.
The crystal structure of the as-prepared samples S1, S4, S9, S14 were
characterized by XRD. Fig. 6 depicts the four samples consist of brookite
TiO2 corresponding (1 2 0) planes at 25.341◦ , Anatase TiO2 corre­
sponding (2 0 0) planes at 48.049◦ , and SnO2 corresponding (1 1 0)
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Applied Surface Science 578 (2022) 151983
Fig. 4. SEM images of samples S9 (a, b) and S14 (c, d) with Pt sputtering time
of 30 s for different annealing temperature.
(1 0 1) (2 0 0) (2 1 1) planes at 26.663◦ , 34.027◦ , 37.949◦ , and 51.691◦ .
And Pt (JCPDS Card No. 04-0802) was observed at 39.869◦ , 46.309◦ ,
and 67.716◦ corresponding to (1 1 1), (2 0 0), and (2 2 0) planes of S4, S9,
S14. Among them, sample S14 has the strongest diffraction peak of
(1 1 1) and (2 2 0) crystal plane of Pt while sample S4 has the worst. It
means that the Pt crystallinity is stronger with the increase of annealing
temperature, indicating that the larger Pt particles tend to have stronger
peaks than Pt mesoporous.
The elemental compositions and chemical state of as-prepared
samples S1, S4, S9, and S14 were elaborated by XPS analysis. The XPS
survey spectrum shown in (Fig. 7a) prove the existence of Sn, Ti, and O
in the four samples and Pt in sample S4, S9, and S14. To study the effect
of annealed temperature and the Pt mesoporous layer modification on
TiO2/SnO2 nanocomposite thin film, Pt 4f, Ti 2p, Sn 3d, and O 1 s re­
gions of the XPS spectra were analyzed and shown in (Fig. 7b-d) and
Fig. 8 respectively. The spin–orbit component (Pt 4f7/2 and Pt 4f5/2)
peaks are 71.99 eV and 75.19 eV for sample S4, which shift a little (-
0.12 eV) and (- 0.82 eV) for sample S9 and S14, respectively. Hence, it
can be attributed to a mixed oxidation state of Pt and confirm that the Pt
has been attached successfully on the TiO2/SnO2 nanocomposite thin
film[39–41]. (Fig. 7c) shows the two strong peaks (Ti 2p3/2 and Ti 2p1/2)
at 459.24 eV and 465.24 eV of Ti element for sample S1. These Ti 2p BE
values shift a little (+0.72) and (+0.59) for S4 and S9 respectively. And
the sample S14 obtain the two peaks at 459.17 eV and 465.36 eV for Ti
2p3/2 and Ti 2p1/2. It can be attributed to electronic transference from
TiO2 to Pt and SnO2[42–44]. Meanwhile, due to the SnO2 got the elec­
trons from TiO2, an inverse shift of Sn 3d can be observed in (Fig. 7d),
where the BE values of Sn 3d5/2 and Sn 3d3/2 for S1 are 487.22 eV and
496.32 eV respectively, which is higher than S4, S9, and S14. Therefore,
the presence of Pt increased the number of electrons lost by TiO2, and
less electrons will be lost from TiO2 with the annealing temperatures
increasing. The XPS spectrums of O 1 s of the samples S1, S4, S9, and S14
are exhibited in (Fig. 8a-d), respectively. Generally, the O 1 s spectra
could be decomposed into two Gaussian function peaks corresponding to
lattice oxygen and adsorbed oxygen [45]. The adsorbed oxygen is usu­
ally the key role in promoting the gas sensing properties while the lattice
oxygen is very stable without any contribution to it [46,47]. However,
The O 1 s spectra of sample S1 can be fitted well with one Gaussian
X. Tian et al.
Fig. 5. AFM images various in process parameters showing the different surface morphologies of S1 (a, b), S4 (c, d), S9 (e, f) and S14 (g, h).
Fig. 6. XRD spectra for S1, S4, S9, S14.
function peak at 530.52 eV. This means sample S1 has almost only lat­
tice oxygen. It can be seen that the peak of lattice oxygen shifts from
530.52 eV to 531.07 eV with the appearance of the mesoporous layer of
Pt, and what matters is that the peak of adsorbed oxygen firstly appears
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Applied Surface Science 578 (2022) 151983
at 532.91 eV. In addition, it is obvious that the proportion of adsorbed
oxygen has increased a lot from sample S4 to sample S9, then decreased
a lot form sample S9 to sample S14.
The fitting results of O 1 s XPS spectra of the samples S1, S4, S9, and
S14 are shown in Table 3. The relative percentage of lattice oxygen in
sample S1 was 100%, which shows the annealing of 400℃ in N2 will
destroy the existence of the absorbed oxygen. The relative percentages
of lattice oxygen and absorbed oxygen in the samples S4, S9, and S14
were 54.05 % and 45.95 %, 31.51 % and 68.49 %, and 51.81 % and
48.19 % respectively. One sees that the introduction of Pt mesoporous
will dramatically increase the proportion of the absorbed oxygen. And
the more numbers of Pt mesoporous lead to a higher proportion of
absorbed oxygen from sample S4 to S9. The disappear of Pt mesoporous
also decrease the proportion of absorbed oxygen from sample S9 to S14.
3.2. Gas sensing properties
The relation between the working temperature with the power
consumption and voltage of the MEMS gas sensor was set up before gas
testing. (Fig. 9a) shows the microheater power consumption and voltage
as the function of the working temperature of the MEMS sensor. At
320℃, the microheater power consumption was only 39 mW which was
about 9-fold lower than that of the MEMS gas sensor [48]. Therefore, the
low power consumption of the MEMS sensor provides the possibility to
the utility of commercial. The different process parameters forming the
samples will result in discrepancies in the resistance in the air, as shown
X. Tian et al. Applied Surface Science 578 (2022) 151983

Fig. 7. (a) XPS survey spectra of S1, S4, S9, and S14. (b) The different annealing temperature result in the BE value of Pt 4f (Pt 4f7/2, Pt 4f5/2) showing (71.99 eV,
75.19 eV), (71.87 eV, 75.07 eV), and (71.17 eV, 74.37 eV) for sample S4, S9, and S14, respectively. (c) The Ti 2p (Ti 2p3/2, Ti 2p1/2) peaks are found at (459.24 eV,
465.24 eV), (459.96 eV, 465.96 eV), (459.83 eV, 465.83 eV), (459.17 eV, 465.376 eV) and for S1, S4, S9, and S14, respectively. (d)Sn 3d (Sn 3d5/2, Sn 3d3/2)spectra
of S1, S4, S9, and S14 is (487.24 eV, 496.32), (486.32 eV, 494.75 eV), (487.22 eV, 495.72 eV), and (487.07 eV, 495.67 eV), respectively, which can be attributed to
the electronic transference from TiO2 to Pt and SnO2.

in (Fig. 9b). At the working temperature of 70℃, the resistance of the
samples S2, S3, and S4 gradually increase (Fig. 9c), which can be
explained by the Schottky barrier. Especially, the ultra-low resistance of
sample S5 may be due to the connection of IDE and Pt, confirming that
the excess Pt sputtering time will havoc on the resistance. Obviously, the
resistance of sample S3 decreases faster than that of sample S2 while
sample S1 got the lowest, indicating that the working temperature has
great influences on the resistance of the samples with Pt modification.
(Fig. 9d) shows the resistance changes of samples S4, S9, and S14 with
different annealing temperatures. Sample S9 obtain the maximum
resistance due to its plenty of Pt mesoporous and numbers of oxygen
adsorptions. The change of the resistance can be commonly attributed to
the influences of temperature and oxygen adsorption on the MOS ma­
terials. High temperatures can actuate the electrons in the top of value
band of the MOS materials to jump into the conduction band, becoming
the freedom electrons and participating in the conduction process,
which can reduce the resistance of the MOS materials. However, the
oxygen adsorption on the surface of the MOS materials will take the
electrons from the conduction band, resulting in the increase of the MOS
materials. In addition, the effects of the abundant Schottky barrier be­
tween Pt with TiO2 on the resistance of the MOS materials also can’t be
neglected, which will improve the resistance of the MOS materials due
to the electrons transferring from TiO2 to Pt. Interestingly, the oxygen
adsorption and Schottky barrier can be influenced by the working
temperatures. Therefore, the changes in the resistance of the samples are
the results of the above three factors.
To investigate the cross effect of annealed temperature and sput­
tering time of Pt, the response of the as-prepared 15 samples to 25 ppm
ethanol at a series of working temperatures were obtained, as shown in
(Fig. 10a). From (Fig. 10b), the sensor based on S1, S2, S3, S4, S5
demonstrated the highest response of 1.03, 1.70, 1.02, 2.27, and 1.68 at
the optimal working temperature of 130, 170, 160, 150, and 160℃,
respectively. It can be clearly seen that the S4 with 30 s sputtering time
of Pt has the best response, which is approximately 2.2-fold higher than
that of S1 without Pt, showing the modification of Pt mesoporous layer
can effectively promoting the response of TiO2/SnO2 nanocomposite
thin film. However, the reason for the abnormal two peaks at such close
working temperature for gas detection is still unclear and leaves lots of
confusions for us and other researchers [6,49]. Here, the reason for the
obvious two peaks at 110℃ and 130℃ in while testing the gas response
to 25 ppm ethanol under different working temperature maybe the
unstable TiO2 showing the P-type properties. Thus, the effect of

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X. Tian et al. Applied Surface Science 578 (2022) 151983

Fig. 8. O1 s XPS spectra of S1 (a), S4 (b), S9 (c), and S14 (d) .

A fast response (20 s) was obtained at the working temperature of 130℃

Table 3
while a relatively slow recovery time (973 s) was also observed. After
Fitted results of O 1 s XPS spectra of S1, S4, S9, and S14.
the consideration of the response value in (Fig. 10c), the working tem­
Samples Oxygen species BE values (eV) Relative percentage (%) perature of 130℃ can be regarded as the optimum working temperature
S1 Lattice oxygen 530.52 100 of the MEMS ethanol gas sensor.
S4 Lattice oxygen 531.07 54.05 Fig. 11a shows the response of the sensor based on S1, S4, S9, S14 to
Adsorbed oxygen 532.91 45.95
various ethanol concentrations at 130℃, exhibiting the considerable
S9 Lattice oxygen 531.13 31.51
Adsorbed oxygen 532.62 68.49 effect of sputtering time of Pt and annealing temperature to multilayer
S14 Lattice oxygen 531.44 51.81 TiO2/SnO2 nanocomposite thin film. The dynamic response curve of the
Adsorbed oxygen 532.50 48.19 sensor based on S9 to various ethanol concentrations at 130℃ was
shown in Fig. 11b. The response to 0.1, 0.5, 1, 5, 25, 100, 300, 500, 700,
and1000 ppm of ethanol is approximately 3.32, 6.27, 7.59, 9.72, 14.58,
annealing temperature on the properties of TiO2 needs to be explored.
18.31, 33.68, 72.67, 119.02 and 167.45, respectively. It is extraordi­
Besides the sputtering time of Pt, the annealing temperature also have an
narily noteworthy that the sensor still shows a response of 3.32 even at
important effect on the formation of Pt mesoporous. Based on the 30 s
the ethanol concentration as low as 0.1 ppm, demonstrating that the
sputtering time of Pt, the influence of annealing temperature on the
sensor can be used to detect ethanol with ultra-low concentration, which
sensing response was investigated, as shown in (Fig. 10c). It can be seen
shows the high sensitivity to ethanol.
that the sensor based on S9 annealed at 500℃ shows the highest
The previous gas sensing materials based on the sputtering technique
response of 14.58 to 25 ppm of ethanol at the working temperature of
was also investigated, as shown in Table 4. Among them, Husam et al.
130℃, which is greatly larger than those of the sensor based on S4 and
prepared the ZnO nanostructures by RF-magnetron sputtering showing
S14 annealed at 400 and 600℃, respectively. Hence 30 s sputtering time
the relatively high sensitivity to ethanol but with the high working
of Pt and annealing temperature of 500℃ can be regarded as the opti­
temperature of 250℃ [50] while Supab et al. revealed that the ZnO
mum process parameters to the MEMS ethanol gas sensor based on
nanobelt exhibited a lower working temperature but with the low
multilayer TiO2/SnO2 nanocomposite thin film modified by Pt meso­
sensitivity to ethanol [51]. Obviously, the ethanol sensor based on S9
porous layer. In addition, Fig. 10d exhibits the response time and re­
demonstrates the high sensitivity to ethanol and the response of 7.59 to
covery time of the sensor based on S9 various in working temperatures.

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X. Tian et al. Applied Surface Science 578 (2022) 151983

Fig. 9. (a) The correlation between the applied voltage and power with the temperature of the sensing layer. (b) The resistance in the air of the sensors based on 15
samples as a function of working temperatures, which can be attributed to the common action of working temperature, oxygen adsorption, and the Schottky barrier.
(c) The resistance in the air of the sensors based on the samples with different Pt sputtering times (S1, 0 s; S2, 10 s; S3, 20 s; S4, 30 s; S5, 40 s) various in working
temperatures. (d) The resistance in the air of the sensors based on the samples with the different annealing temperatures (S4, 400℃; S9, 500℃; S14, 600℃) at the
different working temperatures.

1 ppm of ethanol at the low working temperature of 130℃, which is
better than the sensing materials mentioned in Table 4. Besides, the
sensor based on S9 fabricated by complete MEMS process even with low
power consumption, which is lower than most of the reported sensors.
Fig. 12a shows the dynamic response and recovery curves of the S9 to
25 ppm ethanol at 130℃. One sees that the resistance of S9 based sensor
decreased dramatically when ethanol gas was injected into the chamber,
demonstrating the S9 display as the typical n-type behavior as previ­
ously reported. The response/recovery time of the S9 is about 20/973 s.
(Fig. 12b) shows the response and recovery time of S9 to a series of
concentrations of ethanol at 130℃. It can be seen that as the concen­
tration of ethanol increases, the response and recovery time are basically
reduced and increased, respectively. The quick response and long-term
recovery can be attributed to the fast adsorption of Pt mesoporous
layer to ethanol and low working temperature, respectively.
The stable and repeatable dynamic curve of the sensor based on S9 to
25 ppm of ethanol at 130℃ exhibits no obvious floating of resistance, as
shown in (Fig. 13a), showing the excellent sensing repeatability of the
sensor. Since selectivity is a significant criterion of gas properties and
also the prerequisite for the practical application, the responses of sen­
sors based on S9 were investigated to 25 ppm of different and extremely
common toxic gases at 130℃, as shown in (Fig. 13b). The response to
ethanol, SO2, NH3, NO2, CO, H2 shows 14.58, 2.99, 2.56, 1.16, 1.88, and
2.57, respectively, demonstrating the excellent selectivity of the sensor
based on S9. The important effects of humidity on the gas sensor based
on MOS material must be considered, and high humidity will seriously
weaken the response. (Fig. 13c) shows the response and baseline resis­
tance of the sensor based on S9 to 25 ppm of ethanol at 130℃ with
relative humidity in the range of 0%-97% RH. It can be seen that the
response and the baseline resistance of the sensor gradually decrease as
the relative humidity increase. Especially when the humidity of 11% RH
is just introduced, the response and baseline of the sensor drop
dramatically from 14.58 and 42.75 MΩ to 5.86 and 8.62 MΩ, respec­
tively, which can be attributed to the replacement of oxygen species to
water molecules on the SnO2 surface. The introduction of water mole­
cules hinders the electrons transferring from TiO2 to oxygen in the air
and increases the electron concentrations in the surface of TiO2, which
causes the reduction of the baseline resistance and response of the
sensor. As the humidity continues to increase, the decrease of the
response and baseline resistance gradually slows down, especially from
56% RH to 97% RH, the response and baseline resistance almost have no
change, which indicates that the influence of humidity on the sensor has
a saturation value. Furthermore, the long-term stability of the gas sensor
is one of the most significant properties in a practical application. The
response of the sensor based on S9 to 25 ppm of ethanol at 130℃ was
tested, and the obtained results are shown in (Fig. 13d). One sees that
the response of the sensor based on S9 nearly kept at around 15 in the
three-week test, demonstrating the S9 based gas sensor has wonderful
long-term stability toward ethanol. Therefore, the MEMS ethanol gas
sensor based on S9 shows excellent repeatability, good selectivity, long-
term stability as well as high sensitivity at low working temperature,
which are adapted for its practical application.

8
X. Tian et al.
Fig. 10. (a) The response of sensors based on the 15 samples to 25 ppm of ethanol at different temperatures. (b) The response of sensors based on the samples S1, S2,
S3, S4, and S5 to 25 ppm of ethanol at different temperatures. (c) The response of sensors based on the S4, S9, and S14 to 25 ppm of ethanol at different temperatures.
(d) The response time and recovery time of the sensor based on S9 various in working temperatures. It can be concluded that 130℃ is the optimal working tem­
perature of the sensor based on S9 according to the analysis of Fig. 10c-d.
3.3. Gas sensing mechanism
It is widely discussed that the fundamental sensing mechanism of
MOS materials involves adsorption and desorption of target gas, which
results in the surface reaction with the absorbed oxygen finally leading
to the resistance change of the MOS materials [5,45,57,58]. For ethanol
sensor based on multilayer TiO2/SnO2 nanocomposite thin film, the
resistance can be guided by the concentration of free electrons in the
conduction band of the uppermost layer of TiO2 and the multilayer
heterojunction between TiO2 and SnO2. While for the gas sensor based
on the multilayer TiO2/SnO2 nanocomposite thin film modified by the Pt
mesoporous layer, the conduction of the electrons will be more
complicated. To be explained clearly, the detailed energy band diagram
[59,60] of the Pt/TiO2/SnO2 nanocomposite thin film was demonstrated
in (Fig. 14a). The multilayer TiO2/SnO2 nanocomposite thin film can be
regarded as an electronic system, which drives the electrons transferring
from TiO2 to SnO2 due to the work function of SnO2 is higher than TiO2,
resulting in the band bending and the forming of depletion layer and
accumulation layer, as shown in (Fig. 14b). While for the Pt layer
attaching on uppermost TiO2, Pt -TiO2 Schottky barrier was formed for
the electrons transferring from TiO2 to Pt, also leading to the band
bending (Fig. 14b) and resistance more increasing of the film [61–63].
When exposed to air, oxygen molecules will be adsorbed on the surface
9
Applied Surface Science 578 (2022) 151983
of TiO2 and capture electrons to generate the different chemisorbed
oxygen species (O2–, O-, O2–), which will broaden the depletion layer
[64,65]. However, chemisorption is an energy activated processes and
each oxygen species requires different temperature to take place on the
grains surface. And The O2− (ads) always exist in high temperatures duo
to its adsorption requiring high activation energy[66]. In particular, as
know, in the range 100 – 200 ◦ C the O− (ads) is the predominant species
[67]. In the lower working temperature range (T < 100 ◦ C), O2– is the
main oxygen species[68]. Thus, the state change of the oxygen species
on the surface of Pt/TiO2/SnO2 film can be described as the Eq. (1–3)
with the working temperature increasing from 70 ◦ C to 180 ◦ C.
O2 (gas)→O2 (ads) (1)
O2 (ads) + e− →O−2 (ads) (2)
O−2 (ads) + e− →2O− (ads) (3)
CH3 CH2 OH(ads) + 6O− (ads)→2CO2 (gas) + 3H2 O(gas) + 6e− (4)
Pt
O2 (ads) + 2e− ̅̅̅̅̅̅→ O− (5)
Once the reducing gas of ethanol is introduced to the Pt/TiO2/SnO2
film, the reaction between ethanol with O- will be happened forming
X. Tian et al. Applied Surface Science 578 (2022) 151983

Fig. 12. (a) The real-time resistance of the sensor based on the S9 to 25 ppm of
ethanol at 130℃. (b) The response and recovery time of the sensor based on the
Fig. 11. (a) The response of the sensor based on the S1, S4, S9 and S14 to S9 to different concentrations of ethanol at 130℃.
different concentrations of ethanol at 130℃. (b) The dynamic response curve of
the sensor based on the S9 to different concentrations of ethanol at 130℃.
layer shown in (Fig. 14c). Accordingly, the resistance of the Pt/TiO2/
SnO2 film dramatically decreases to a low resistance state while the Pt/
Table 4 TiO2/SnO2 film will get into the high resistance state again with the
Comparison of sensitivity and working temperature of sensing material of this sensor is out of ethanol.
work and those reported in the literatures[6,50–56]. The Pt mesoporous layer attached to the multi-layer TiO2/SnO2
Sensing element Preparing Ethanol Op. Response Ref nanocomposite thin film can be proved an effective way to fabricate the
method (ppm) tem. (Ra/Rg) MEMS sensor with highly sensitive detection of ethanol at the low
(℃) temperature. Firstly, there is almost no O- in sample S1 while samples S4
Ag implanted ZnO Sputtering 5 260 2.5 [52] and S9 have 45.95% and 68.49% (Table 3), respectively. It proves that
Nb-doped ZnO Sputtering 20 250 3.56 [53] the process of 30 s Pt sputtering can enormously enhance the proportion
ZnO nanobelts Sputtering 50 220 7.3 [51] of O- and the annealing temperature of 500℃ is better than that of 400℃
ZnO Sputtering 2 250 3.6 [50]
nanostructures
in facilitating the adsorption of oxygen. The numbers of O- will facilitate
NiO thin film Sputtering 5 250 7 [56] the reaction with ethanol (Eq. (4)) and increase the sensitivity to low
MgIn2O4 thin film Sputtering 100 300 3.5 [54] concentration of ethanol due to many electrons was released to the
SnO2 : NiO Sputtering 5 300 5 [55] surface of Pt/TiO2/SnO2 film. Secondly, a great number of Schottky
networks
barriers were formed at the interface between the Pt mesoporous layer
Pd-doped SnO2 : Sputtering 5 350 5.1 [6]
NiO with the uppermost TiO2, which results in the conducting electrons
Pt/TiO2/SnO2 Sputtering 1 130 7.59 This transferring from TiO2 to Pt. The substantial reduction of conducting
nano-composite work electrons in surface of TiO2 cause the difficulties of electrons trans­
thin film porting in multi-layer TiO2/SnO2 nanocomposite thin film, leading to
the increase of resistance of the sensor and resulting in a large response
CO2 and H2O according to Eq. (4). One notes that the sensors also have a value to ethanol. Thirdly, the Pt mesoporous layer can catalytically
response to ethanol at the low working temperature of 70 ◦ C and 90 ◦ C, dissociate the adsorbed oxygen into oxygen ions (O2– and O-) at a low
which can be attributed to the dissociation of O2 (ads) into oxygen ions working temperature which can’t automatically facilitate the O2 (ads)
(O2– and O-) by Pt mesoporous layer (Eq. (5)). The rapid release of the into the chemisorption O-. Therefore, lots of O- still spill over onto the
electrons from the O- to Pt/TiO2/SnO2 film leads to a shrinker depletion surface of TiO2 even at the low working temperature of 130 ◦ C, which

10
X. Tian et al. Applied Surface Science 578 (2022) 151983

Fig. 13. (a) The resistance repeatability curve of the sensor based on the S9 to 25 ppm ethanol at 130℃. (b) The response of the sensor based on the S9 to 25 ppm of
ethanol and other typical air pollutants (SO2, NH3, NO2, CO, H2). (c) The response and baseline resistance of the S9 based sensor to 25 ppm of ethanol under the
different relative humidity at 130℃. (d) The response stability curve of the S9 based sensor to 25 ppm ethanol at 130℃.

provide a possibility for the use of gas sensor at low working tempera­
ture. The gas testing data (Fig. 10d and Fig. 11a) of the sensor based on
S9 is better than that of the sensor based on S4 when S9 has more Pt
mesoporous than S4, confirming the great numbers of Pt mesoporous is
the most critical factor to enhancing the gas properties of the sensor to
ethanol.
4. Conclusion
In summary, a complete MEMS process was developed to prepare the
Pt mesoporous layer modified the multi-layer TiO2/SnO2 nano­
composite thin film as the gas sensing material for ethanol sensing,
which can be integrated with the microheater and IDE. The morphology
and microstructure of the Pt/TiO2/SnO2 nanocomposite thin film were
characterized by various instruments, which demonstrates that the
optimal preparing process of Pt mesoporous is 30 s sputtering time of Pt
and annealing temperature of 500℃. Gas sensing properties measure­
ment showed that Pt/TiO2/SnO2 nanocomposite thin film (the 30 s, the
500℃) based sensor had a high response of 14.58 to 25 ppm of ethanol,
which is about 13-fold more than that of the pure multi-layer TiO2/SnO2
nanocomposite thin film. Besides the ethanol gas sensor shows the ultra-
sensitivity to ethanol as low as 0.1 ppm with the response of 3.32 at the
low working temperature of 130℃. Furthermore, the ethanol gas sensor
fabricated by completely MEMS technology exhibits a low power con­
sumption (39 mW to 320℃), which provides a guarantee for the inte­
grated manufacturing of MEMS gas sensors. The enhanced sensing
properties of the Pt/TiO2/SnO2 nanocomposite thin film (the 30 s, the
500℃) can be explained by the Pt mesoporous layer with lots of mes­
oporous, catalytic action, more oxygen vacancies or absorbed oxygen as
well as the abundant Schottky barrier between Pt with TiO2. The method
of preparing Pt mesoporous introduced here can be extended to prepare
other similar noble metal mesoporous with excellent gas sensing
properties.
CRediT authorship contribution statement
Xin Tian: Conceptualization, Methodology, Formal analysis, Data
curation, Writing – original draft, Writing – review & editing. Huitong
Cao: Conceptualization, Data curation, Investigation, Formal analysis,
Writing – review & editing. Hairong Wang: Writing – review & editing,
Data curation, Conceptualization, Funding acquisition. Jiuhong Wang:
Conceptualization, Project administration. Xinyu Wu: Conceptualiza­
tion, Investigation. Xueyong Wei: Conceptualization.

11
X. Tian et al.
Fig. 14. The schematic diagram of the proposed sensing mechanism of sample S9.
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.
Acknowledgement
This work is supported by Science and Technology Planning Project
of Shenzhen (Grant No. JSGG20191129102808151), NSAF (Grant No.
U1930205), Key Research and Development Projects of Shaanxi Prov­
ince (Grant No. 2019GY-121, 2020GY-137), Fundamental Research
Funds for the Central Universities (Grant No. xzd012019020). We
appreciate the support from International Joint Laboratory for Micro/
Nano Manufacturing and Measurement Technologies
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