Pan et al.

Microsystems & Nanoengineering (2024)10:4

https://doi.org/10.1038/s41378-023-00627-8
Microsystems & Nanoengineering
www.nature.com/micronano

ARTICLE Open Access

A passive wireless surface acoustic wave (SAW)

sensor system for detecting warfare agents based
on fluoroalcohol polysiloxane film
Yong Pan1, Cancan Yan1, Xu Gao2,3, Junchao Yang1, Tengxiao Guo1, Lin Zhang1 ✉ and Wen Wang 2,3 ✉

Abstract
Long-term monitoring of environmental warfare agengts is a challenge for chemical gas sensors. To address this issue,
we developed a 433 MHz passive wireless surface acoustic wave (WSAW) gas sensor for dimethyl methylphosphonate
(DMMP) detection. This WSAW gas sensor includes a YZ lithium niobate (LiNbO3) substrate with metallic interdigital
transducers (IDTs) etched on it, and an antenna was placed near the IDT. A DMMP-sensitive viscoelastic polymer
fluoroalcoholpolysiloxane (SXFA) film was prepared on a LiNbO3 substrate, and mode modeling coupling was used to
optimize the design parameters. The sensor can function properly in an environments between −30 °C and 100 °C
with humidity less than 60% RH. When the wireless transmission distance was within the range of 0–90 cm, the sensor
noise increased with distance, and the stability was less than 32°/h. While optimizing the film thickness of SXFA, a
relationship was observed between sensor sensitivity and film thickness. When the film thickness of SXFA reached
450 nm, the optimal value was reached. At a distance of 20 cm between the transmitting and receiving antennas,
DMMP was detected at different concentrations with the developed WSAW gas sensor. The lower detection limit of
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DMMP was 0.48 mg/m3, the sensitivity of the sensor was 4.63°/(mg/m3), and repeatable performance of the sensor
was confirmed.

Introduction associated toxicological properties1–4, have often been

As chemical warfare agents (CWAs) threaten the studied in place of real CWAs.
security of the world, the development of a gas sensor Among the various types of CWAs, the nerve agent
with features such as fast response, high sensitivity, and sarin (O-isopropyl methylphosphonofluoridate, GB) is the
small size is imperative for use in early detection of most lethal because of its high toxicity and moderate
CWAs. Simultaneously, accurate detection, identification, volatility. It can cause death at a very low concentration.
and monitoring of CWAs is essential for effective military Thus, dimethyl methylphosphonate (DMMP) is often
and civilian defense operations. Because CWAs are highly used as a GB simulant, not only because its polar (P = O-,
toxic and deleterious, for security reasons, they are only P-O-) and nonpolar (-CH3) functional groups are the
studied in specific places, which are limited to authorized same as sarin but also because of its nontoxic physico-
laboratories. Therefore, their simulants, which can closely chemical property during testing experiments5–8.
mimic the chemical structures of real CWAs without Surface acoustic wave (SAW)-based sensors have
attracted substantial interest as sensing platforms to
detect physical, chemical, and biological substances9–11.
Because SAWs have exhibited many unique advantages,
Correspondence: Lin Zhang ([email protected]) or Wen Wang
([email protected]) such as fast response, ambient-temperature operation,
1
2
State Key Laboratory of NBC Protection for Civil, Beijing 102205, China high sensitivity, low cost, easy reproducibility, and favor-
Institute of Acoustics, Chinese Academy of Sciences, Beijing 100190, China
3 able stability12–16, it has been widely used in detecting
The School of Electronic, Electrical and Communication Engineering,
University of Chinese Academy of Sciences, Beijing 100049, China CWAs17–22 in recent years. However, for all CWA alarms
These authors contributed equally: Yong Pan, Xu Gao.

© The Author(s) 2024

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Pan et al. Microsystems & Nanoengineering (2024)10:4 Page 2 of 12

Antenna Exciting signals

Guiding layer

SPUDT R1 R2 R3

R1 R2 R3

Sensing signals
Transceiver unit Antenna 41qqYX-LiNbO3 Sensitive film

Fig. 1 Schematic and working principle of the proposed SAW chemical sensor

powered by batteries, problems such as short duration, By evaluating the phase shifts, we extractd the gas
large power consumption in a low-temperature environ- concentration.
ment, and the impact of battery replacement during Compared with the currently available gas sensors, the
detection have not been solved. To address this situation, developed passive WSAW sensor has many advantages.
we coupled passive wireless surface acoustic wave First, batteries or any power supply was not needed to
(WSAW) gas sensing; this technology ran on battery operate the sensor. Second, the sensor can be used in
power and could also perform CWA detection through hazardous areas that are not easily accessible to personnel,
radar transmission. The development of WSAW sensors and the sensor can be operated wirelessly. Third, it can be
has been reviewed in recent years23–27. An increasing operated without a complicated detection system. Finally,
number of passive wireless sensors have been used in the sensor was lightweight, small, and could withstand
physical parameter detection of temperature28–31, pres- extremely harsh environmental conditions.
sure32–34, and moisture35,36. Passive SAW-based sensors
for wirelessly sensing harmful gases, such as CO237–43, SAW device design and fabrication
NO244,45, NH346, O247,48, and other volatile organic Design considerations of reader unit
compounds, were proposed, where the phase signal from A hardware structure for the reader includes the main
the reflectors of the SAW reflective delay line configura- control unit (MCU), transmitting unit, and receiving unit,
tion induced by gas adsorption between the sensitive as shown in Fig. 2. A frequency-stepped continuous wave
interface and target gas was picked for gas sensing49. All radar technique, which can generate a continuously
these studies provide favorablesuitable references for variable frequency sine wave excitation signal, was used in
developing a real practical wireless and passive SAW our research50. The arrow direction in Fig. 2 indicates the
chemical sensor. propagation direction of the signal, transmitting unit, and
In this study, we developed a new passive WSAW receiving unit that share a transceiver antenna. The MCU
chemical sensor with a 433 MHz central frequency and an communicated with the PC through 3-wire UART, the
associated viscoelastic sensitive layer fluoroalcohol poly- antenna, and the SAW sensor exchange through EM
siloxane (SXFA) compatible with the transducer, which waves.
enabled detection of DMMP. The schematic and working The MCU comprised an STM32 single-chip micro-
principle of the sensor are illustrated in Fig. 1. The computer and its auxiliary circuit. STM32 is a powerful
developed platform consists of a SAW reflective delay embedded microprocessor chip that is powerful for
line, reader unit, and connected antennas. In the reflective computing and integrated many peripheral units. This
delay line, single-phase unidirectional transducers unit also included radar control, digital-to- analog con-
(SPUDTs) and reflectors were placed in a row along the version, display, and communication interface functions.
SAW propagation direction on a YZ LiNbO3 piezoelectric The transmitting unit comprised a frequency synthesi-
substrate39. When the SPUDTs received electromagnetic zer and a transceiver separating circuit. The frequency
(EM) energy from the reader unit through a connected synthesizer was responsible for providing signals for the
antenna, the SPUDTs generated a SAW on the surface local oscillator end of the transmission circuit and the
through the piezoelectric effect and propagated it toward mixing circuit. The main function of the frequency syn-
the reflectors. The propagating SAW was partially thesizer was to generate sine waves of different fre-
reflected from the reflectors, and the reflected SAW was quencies and simultaneously ensure that the power of the
reconverted into EM waves by the SPUDTs and trans- signal provided would meet the requirements of the
mitted to a reader unit. Then, the adsorption of DMMP subsequent parts. The transceiver separation circuit was
on the SXFA polymer film can induce a change in mass responsible for the separation of high-frequency trans-
loading and SAW velocity, which results in a phase shift. mitted signals and received signals so that they could
Pan et al. Microsystems & Nanoengineering (2024)10:4 Page 3 of 12

Transmission unit

Frequency Transceiver
synthesizer separating reader
excitation

SAW
response

resonant

Mixer
MCU Small-signal
amplifier

Signal conditioning

Reciver unit

Fig. 2 Structure of the FSCW reader unit used

move forward according to the predetermined signal Table 1 SAW sensor design parameters
transmission without mutual interference or conflict.
The receiving unit comprised a small signal amplifier, a Structure parameters Value
frequency mixer, and a signal conditioning component.
The small signal amplifier is responsible for preliminary Piezoelectric YZ-LiNbO3
amplification of the received reflected signal to prevent Acoustic wavelength 8 μm
excessive noise in the circuit from obfuscating the useful IDT pairs 25
received signal and to simultaneously prevent introducing
Electrode Al
excessive noise. The frequency mixer is responsible for
mixing the received signal with the local oscillator signal Reflector electrodes 10
to reduce the received signal to the low-frequency band Type of reflectors short-circuited gratings
that can be sampled. The signal conditioning part is Aperture 100λ
responsible for amplifying and shaping the low-frequency
signal after mixing to ensure that the signal meets the
requirements of the subsequent sampling circuit and does peak is consistent with that of the sensor design, and a
not affect the information carried in the signal. high S/N is obtained.

Design and fabrication of the SAW sensor Optimal selection of devices with different structures
A reflective delay line structure was used as a SAW The stability of sensor devices is crucial, as it directly
sensor. To obtain sensor devices with favorable perfor- affects the detection effect of the sensor on the target gas.
mance, we consider designs that improve the signal-to- To obtain SAW sensor devices with favorable perfor-
noise ratio (S/N) and reduce the insertion loss, as well as mance in simulation, six types of SAW devices with dif-
factors influencing sharp reflection peaks in the time ferent structures are designed and manufactured, as
domain and spurious noise51. Thus, the YZ LiNbO3 shown in Table 2.
piezoe-lectric crystal was selected as the sensor substrate For types 1 and 2 devices, the reflection peak S/N of the
due to its large electromechanical coupling Factor K2 bidirectional acoustic transmission IDT structure was
(4.5%). SPUDTs were used in the fabricated SAW sensor approximately 10 dB higher than that of the SPUDT
because they could direct most of the SAW energy to the structure device. More narrowly, the prepared SPUDT
reflectors, and thus, high S/N and lower insertion loss structure device had more line defects due to the limita-
were ensured52. The operation frequency of the SAW tion of the production process level, which results in poor
sensor was set to 433 MHz to meet the requirement of the device performance, such that it was not used. For types 3,
sweep frequency bandwidth of the reader unit. The SAW 4, and 5 devices, the difference between the devices with
sensor used for sensing gas was simulated to obtain S11 in and without aluminum film, that is, the second reflection
the time domain. Table 1 shows the design parameters, peak, was approximately 3–5 dB smaller than the first
and Fig. 3 shows that the relative position of the reflection because of the acoustic attenuation caused by the
Pan et al. Microsystems & Nanoengineering (2024)10:4 Page 4 of 12

a b
0 Experimemt result
Simulation result
–20
R1 R2
–40

S11 (dB)
–60

–80
SPUDT Reflector
–100

–120
0 1 2 3 4 5
Time (Ps)
Pm
8P

Fig. 3 a Prepared physical diagram of the delay line device. b Comparison between experimentally measured and simulated reflection peaks in the
time domain

Table 2 Structure and peaks (reflectors 1 and 2) of SAW devices

SAW device structure Peak value (dB)

Device type IDT structure Position of reflectors Metal thin film Reflector 1 Reflector 2 S/N

1 IDT Right side of IDT / −28.0 −29.7 52

2 SPUDT Right side of IDT / −45.9 −47.9 35
3 IDT Right side of IDT Al film −29.0 −32.3 48
4 SPUDT Right side of IDT Al film −40.1 −43.3 40
5 IDT Both sides of IDT Al film −28.4 −30.6 50
6 IDT Both sides of IDT / −27.7 −29.4 53

discontinuity of the aluminum film boundary. The sub- reader unit was connected to the PC with transmission
sequent coating of the sensitive film also led to acoustic lines. The working process of the entire system was as
attenuation. The greater the thickness is, the greater the follows: the EM wave signal emitted by the reader was
acoustic attenuation, and the lower the S/N, so a decrease transmitted to the sensor through the antenna and then
in the S/N ratio affects the performance of the sensor. For converted into a SAW signal by an interdigital transducer.
type 6 devices, the second reflection peak was approxi- This SAW signal propagated along the substrate to the
mately 0.5 dB because of the high utilization of acoustic reflector and was reflected back and then converted back
waves and high S/N of the two-sided reflector structure into an electrical signal through an interdigital transducer,
compared with the single-sided reflector structure. with the reader receiving the signal through the antenna.
According to the S/N, loss, and ability of the device to
withstand film thickness during the later coating process, Temperature and humidity experiments for the WSAW
type 6 (bidirectional acoustic propagation IDT + , bilat- sensor system
eral reflectors + aluminum film free structure) devices Temperature and humidity experiments were carried
have higher S/Ns and peak values, which make them more out to further verify the environmental adaptability of the
suitable as sensor structures for detecting gases, thereby test system. This temperature test setup is illustrated in
achieving the maximum sensitivity of the prepared sensor. Fig. 5.
Within the range of −30–100 °C, a temperature mea-
Measurement setup surement point was set at every 10 °C interval, and 150
Figure 4 shows the experimental setup used for sensing sets of tests were conducted at each temperature mea-
data collection. Two fabricated antennas were connected surement point. The test results are shown in Fig. 6. The
to the reader unit and fabricated microsensor, and the temperature measurement sensitivity was approximately
Pan et al. Microsystems & Nanoengineering (2024)10:4 Page 5 of 12

40

20

S11 (dB)
0

–20
PC
–40
0 1 2
Ps)
(P

Transmission line

SAW
sensor

Reader Unit

Antenna Antenna

Fig. 4 Wireless measurement setup of the SAW gas sensor system

when the ambient humidity is greater than 60% RH, the

stability of the sensor can be affected.

RF Results and discussion

SAW Sensor Transceiver Experimental section
To prepare the WSAW gas sensor, SXFA was prepared
according to ref. 8, and SXFA with a concentration of
9.5 mg/ml was prepared in benzene and spun onto a
Antenna
quartz wafer with delay line patterns. The spinning speed
Temperature
and duration were set at 1200 rpm and 10 s, respectively.
Chamber Then, the WSAW sensor could be obtained after stand-
ing, high-temperature aging, cutting, and packaging. To
obtain realistic data, a new gas generating system was
established by our laboratory, as shown in Fig. 8. In this
PC setup, ambient air was used as the dilution and recovery
gas, and DMMP was placed in a sample cell of the
Fig. 5 WSAW sensor detection system for the temperature test homemade gas generation system. When DMMP was
blown with N2 and diluted with ambient air, a given
concentration of DMMP was formed, the mixture gas
concentration was monitored in real time using a gas
36.2 °C, and the temperature measurement accuracy concentration monitor, which was developed by our
reached ±0.5 °C. The results showed that the test platform laboratory, and the prepared WSAW sensor was placed in
worked well within the temperature range of −30–100 °C. a response test chamber with a gas inlet and outlet. When
The humidity experiment was conducted with a dis- the generated gases with different concentrations have
tance of 15 cm between the transmitting and receiving directly entered the chamber, the response signals of the
antennas, and the tests were conducted on five humidity sensor toward DMMP were recorded and collected in real
points with relative humidities of 15%, 30%, 45%, 60%, and time by a PC. All testing was conducted at room
75% RH. The results are shown in Fig. 7a. When the temperature.
humidity was less than 60% RH, the phase change became
larger as the humidity increased, with a sensitivity of Relationship between the wireless transmission distance
approximately 1°/% RH. However, when the humidity and baseline noise
reached 60% RH and 75% RH, a large fluctuation occurred For WSAW gas sensors, during wireless signal trans-
in the sensor baseline. As shown in Fig. 7b, the error of mission, the S/N was not only affected by uncontrollable
the system is large, and the accuracy is low, indicating that environmental factors but also decreased exponentially as
Pan et al. Microsystems & Nanoengineering (2024)10:4 Page 6 of 12

a 5000
b 300
Phase
Linear fitted curve
4000 250

Number of samples
Phase (q) 200
3000
150
2000
100
1000 y = 36.2 x + 1084.6
R-Square: 0.99985 50

0 0
–30 0 30 60 90 –0.9 –0.6 –0.3 0.0 0.3 0.6 0.9
Temperature (qC) Difference in temperature (qqC))

Fig. 6 a System temperature test and (b) temperature test error diagram

phase shift Δ∅ between the two reflections because of gas

a 50 adsorption was obtained by the fractional change in the
propagation velocity in Eq. (2).
40 75%RH

30

Δv
Phase shift (qq)

Δ+ ¼ 2πf 0 Δτ ¼ 2πf 0 ´ 2l1 =v0 ´ ð2Þ

20 60%RH vo
10
45%RH where f0 is the central frequency, l1 is the distance
0 30%RH
15%RH between the first and second reflectors, Δτ is the time
–10
delay change, v0 is the acoustic velocity, and Δvov is the
–20 fractional change in propagation velocity.
0 20 40 60 80 100 120 140 160 180 200
Time (s)
b Simultaneously, the baseline noise of the WSAW
50 sensors is affected by environmental factors. The sta-
data
40 linear bility tests were conducted with distances between the
transmitting and receiving antennas of the WSAW
30
sensor within a range of 5, 10, 20, 30, 40, 50, 60, 70, 80,
Phase shift (q)

20 and 90 cm. Figure 9 and Table 3 show the changes in

10 baseline noise of the WSAW sensor at different
distances.
0
These results showed that the shorter the distance
–10 between the transmitting and receiving antennas, the
–20
more stable the baseline noise would be, and the higher
10 20 30 40 50 60 70 80 the S/N. The longer the distance is, the greater the
Humidity (%RH) baseline noise, and the lower the S/N, as shown in Fig. 10.
Fig. 7 a System humidity test and (b) humidity detection error Considering factors such as sensor noise, sensitivity, and
diagram (21 °C, 30% RH) environmental impact, we applied a wireless transmission
distance of 20 cm for additional testing.

the wireless distance increased, as shown by Eq. (1). Stability of the WSAW sensor
4πR As discussed above, when the distance between the
Loss ¼ 20ln ¼ 32:45 þ 20lnfðMHzÞ þ 20lnRðkmÞ transmitting and receiving antennas is less than 30 cm, the
λ
ð1Þ WASW might be stable. Three devices were selected to
confirm the stability of the prepared WSAW sensors, and
where Loss is the transmission loss (dB), R is the the distance was set to 20 cm. We found that the phase
transmission distance (km), and f is the frequency shift was approximately 25°/h, 32°/h, and 35°/h, which
(MHz). When the sensor was coated with a sensitive indicated that the sensor could achieve long-term stability
polymer film between the first and second reflectors, the at this distance, as shown in Fig. 11.
Pan et al. Microsystems & Nanoengineering (2024)10:4 Page 7 of 12

Blowing gas (N2) Blowing gas (N2)

Saturated gas

Inlet Mass flow controller-1 Gas Inlet

N2

Sample cell

Temperature controller
Dilution gas (room air)
Mixture

Inlet Outlet Response test chamber

Mass flow controller-2

Fig. 8 Schematic diagram of the instrument and setup used for data acquisition and management

Relationship between WSAW sensor response signal and

45
20
S/N

10 Fitted curve
Phase shift (qq)

5 cm 10 cm 20 cm 30 cm 40 cm 50 cm 60 cm 70 cm 80 cm 90 cm
40
0 Signal to noise ratio (dB)

–10
35
–20
0 100 200 300 400 500
Points

Fig. 9 Baseline noise value at different wireless distances (25 °C, 40% 30
RH)

Table 3 Changes in baseline noise over different wireless 25

0 10 20 30 40 50 60 70 80 90
distances Wireless transmission distance (cm)

Distance 5 10 20 30 40 50 60 70 80 90 Fig. 10 S/N under different wireless distances (21 °C, 40% RH)
(cm)
Phase shift 1.35 2.33 4.30 4.51 4.85 5.19 5.50 6.52 8.50 11.63
Relationship between the sensor response and SXFA film
(°)
thickness
As a type of glassy-rubbery polymer material, the
baseline noise characteristic functional group -CF3 in SXFA has hydro-
DMMP with a concentration of 3.8 mg/m3 was tested gen bond acidity and can selectively adsorb DMMP, an
using the prepared sensors at different wireless trans- organic phosphorus compound with hydrogen bond
mission distances, as shown in Fig. 12. The figure shows alkalinity at room temperature. This condition mainly
the baseline noise fluctuation value and response value to occurs due to the reversible hydrogen bonds that are
DMMP detection at various wireless distances. As the formed between weak acid and weak base functional
distance increased, the baseline noise fluctuation of the groups. The main effects of polymer films on the propa-
WSAW sensor gradually increased, but the response gation characteristics of SAW are viscoelastic effects and
values of the WSAW sensor to DMMP at different mass loading effects, as reported in Eq. (3).
wireless distances were basically consistent and did not
change. This result indicated that the response signal of ΔY Δα Δv X
i
ci β MðiÞ  
¼ j ¼ ¼1 i tanh jβi h ð3Þ
the WSAW sensor to a certain concentration of target gas Ko Ko vo 3
ω
was independent of the wireless distance, but as the
transmission distance increased, the baseline noise gra- In Equation (3), β2i ¼ ω2 ðρ  E i =ðV 20 ÞÞ=M ðiÞ , V0 is the
dually increased, ultimately resulting in an S/N that was SAW velocity after disturbance, and Ei is the deformation
too small to enable accurate detection. modulus, E1 = G, E2 = 0, E3 = 4 G(3 K + G)/(3 K + 4 G),
Pan et al. Microsystems & Nanoengineering (2024)10:4 Page 8 of 12

–30 60
0.7
1
–70 0.6
0 1000 2000 3000 4000

Response time (s)

–206
Phase (qq)

Phase shift (qq)

0.5 40
2 0.4
–246
0 1000 2000 3000 4000
–46 0.3
20
3 0.2
–86
0 1000 2000 3000 4000 0.1
Time (s)
0 0
Fig. 11 Stability of the WSAW sensor (23 °C, 38% RH) 0 200 400 600 800 1000 1200
Thickness of SXFA (s)

Fig. 13 Relationship between the sensor response and SXFA film

thickness (22 °C, 35% RH)

12
because of the viscoelastic effect of SXFA as a polymer-
10 sensitive material. As SXFA used in this manuscript is a
kind of multiple molecular layer, according to linear sol-
Phase shift (qq)

8 vation energy relations (LSERs) and gas‒liquid equili-

brium theory7,8,53, at a certain temperature, the ratio of
6 the concentration of molecules in the gas phase Cv to the
concentration on the membrane surface Cs is a constant
4
K. When the concentration of molecules in the gas phase
Baseline noise
Response to DMMP
is constant, under its pressure drive, if the membrane is
2
very thin, it will quickly reach equilibrium. If the mem-
brane is too thick, the permeation of gas molecules in it
0
–10 10 30 50 70 90 leads to a longer equilibrium time. Therefore, the film
Wireless transmission distance (cm) must be prepared based on an optimal thickness. In
addition, the response time of the sensor also increases
Fig. 12 Relationship between WSAW sensor baseline noise and
response to DMMP (21 °C, 35% RH)
with increasing membrane thickness, which is due to the
gas permeation effect between multilayer membrane
materials. The thicker the membrane is, the longer it takes
for the gas to resolve from the adsorption surface.
M1 = M3 = G, M2 = K, where G and K are the shear Therefore, the optimized SXFA film thickness of
modulus and bulk modulus of the polymer, respectively, approximately 450 nm is suitable.
and are usually complex quantities.
SXFA sensitive films with different thicknesses were Polarizing microscopy analysis of the SXFA Film
prepared by the spin method. The SXFA toluene solution The performance consistency of gas sensors has always
with a concentration of 10 mg/mL was prepared, and the been an important aspect of sensor research. Although
spinning speed and duration were set to 1500 rpm and the same preparation methods have been used in the
15 s, respectively. The SXFA toluene solution was spun preparation process of sensors, the surface morphology of
onto the Y-cut quartz wafer with delay-line patterns to the obtained sensor material and its response to the
form the gas sensor. Then, the SAW sensor was obtained measured gas are not completely consistent, and some-
using high-temperature aging, cutting, and packaging times significant differences occur. Using spin coating
after standing. When the concentration of the measured method, SXFA was applied over the SAW delay line. By
gas DMMP was 2 mg/m3, and the distance between the selecting two sensors, which are marked by device (a) and
transmitting and receiving antennas was 20 cm. The device (b), we found that the majority of the film area was
relationship between the response value of the SAW uniform under the polarizing microscope, which is shown
sensor and the film thickness is shown in Fig. 13. by the green transparent region of Fig. 14. However, as a
As shown in Fig. 13, no monotonically increasing kind of viscoelastic material, cluster particles will inevi-
change is observed between the sensor response signal tably form during high-temperature aging because of the
and the film thickness, but an optimal thickness is found evaporation of solvent. In the range of 200 μm × 200 μm,
Pan et al. Microsystems & Nanoengineering (2024)10:4 Page 9 of 12

a b
P2 = 12.29 Pm
P7 = 5.66 Pm
P3 = 12.25 Pm P1 = 13.64 Pm

P1 = 20.51 Pm P6 = 7.90 Pm
P5 = 4.24 Pm
P4 = 13.88 Pm P5 = 10.98 Pm
P4 = 5.50 Pm
P6 = 11.64 Pm
P2 = 7.39 Pm

P3 = 5.86 Pm P7 = 10.81 Pm

Fig. 14 Polarizing microscopy analysis of SXFA films. a and b represent device a and device b, respectively

Table 4 Particle sizes of different SAW-SXFA films obtained using polarizing microscopy

Device P1 (μm) P2 (μm) P3 (μm) P4 (μm) P5 (μm) P6 (μm) P7 (μm) Average (μm)

a 20.51 7.39 5.86 5.50 4.24 7.90 5.66 8.15

b 13.64 12.29 12.25 13.88 10.98 11.64 10.81 12.21

seven cluster particles in a region with more clusters were difference between the darkest and brightest parts of the
selected to analyze the surface uniformity separately, and uneven structure. As the dark part is clearly more uniform
the particle sizes of various clusters are shown in Table 4 and regular than the bright part, the surface of the surface
and Fig. 14. facial mask is considered uniform. This result is further
Table 4 shows that the selected cluster shapes are ran- confirmed by cluster particle state of the polarization
dom. The seven cluster diameters in (a) or (b) in Fig. 14 micrograph.
are basically similar: the average diameters of cluster Generally, when the surface roughness Sq of the film is
particles in device (a) and device (b) are 8.15 μm and less than 20 nm, the surface of the film is considered
12.21 μm, respectively, most clusters have diameters of uniform. Table 5 shows that the Sq value of the SXFA film
approximately 10 μm, and the particle diameters between is 10.786 nm, indicating that the prepared SXFA film is
devices (a) and (b) are also substantially the same. uniform, as shown in Table 5.
At the same time, the areas beyond the 14 clusters are
transparent, indicating the absence of clustering in these SEM interface analysis of the SXFA film
areas because SXFA is a transparent gel-like polymer. The To verify the morphology and surface coverage of SXFA
results show that a uniformly sensitive film with favorable thin films and confirm their surface morphology, we
performance can be obtained by controlling the spin performed SEM for surface analysis of the films coated on
coating conditions. the SAW delay line. Figure 16 shows an enlarged cross-
sectional view of the film. The image shows that the
Atomic Force Microscopy (AFM) interface analysis of the grown film is porous and contains particle morphology
SXFA Film throughout the substrate. After spin coating and solvent
For imaging of a 10 μm × 10 μm area, interface analysis volatilization, the specific surface area of the film increa-
of the surface of the SXFA film was performed using ses, indicating that the microstructure is conducive to 3D
atomic force microscopy (AFM) within the image range to adsorption of the measured gas. Figure 16 also shows that
further obtain more relevant surface information (Fig. 15 the polymer has an irregular geometric shape. Therefore,
and Table 5). In the 2D photograph in Fig. 15a, light the prepared SXFA film is an amorphous polymer.
colors correspond to upward bumps in the film, while
dark colors correspond to downward depressions. They WSAW gas sensor performance
are considered uniform because of their low color con- At room temperature, we set the distance between the
trast. The 3D photo shown in Fig. 15b shows the height transmitting antenna and receiving antenna to 20 cm and
Pan et al. Microsystems & Nanoengineering (2024)10:4 Page 10 of 12

a Amplitude-Scan forward Line fit b Z-Axis-Scan-forward Line fit

10 Pm

Line fit 68.7 mV

Line fit 43.5 nm

24.7 n
Y*

Amplitude range
–18.8 n

Y*10 Pm
X*10 Pm
0 Pm

0 Pm X* 10 Pm

Fig. 15 Analysis of the SXFA film by AFM. a 2D and (b) 3D spectra of SXFA

Table 5 Roughness analysis of the SXFA film surface by AFM

Area Sa Sq Sy Sp Sv Sm

100.8 pm^2 5.4797 nm 10.786 nm 155.44 nm 123.37 nm −32.079 nm −20.125 fm

10
Equation y = a + b*x
Adj. R-Squa 0.97558
Value Standard Err
8 B Intercept -0.9521 0.51439
B Slope 4.62729 0.3266
Phase shift (qq)

0
0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4
S4800 15.0 kV x100 k SE (U) 500 nm Concentration of DMMP (mg/m3)

Fig. 16 SEM image of the SXFA film on the SAW delay line Fig. 17 Relationship between the WSAW sensor response signal and
DMMP concentration (21 °C, 33% RH)

used the gas dynamic generation method to obtain var-

ious concentrations of DMMP gas53. Then, the DMMP concentration of 0.48 mg/m3. This curve indicates that a
was detected using the developed WSAW sensors. The specific and selective interaction relationship can be
linear relationship and repeatability are shown in Figs. 17 formed between the gas and polymer at low concentra-
and 18. tions. This interaction further confirms that the hydrogen
In Fig. 17, a favorable linear relationship is shown bond between the gas and the membrane surface is
between the detection concentration and response signal, formed between the hydroxyl hydrogen bond donor on
y = −0.95212 + 4.63x, R = 0.97558, and the sensitivity of the SXFA surface and the oxygen atom hydrogen bond
the sensor is 4.63°/(mg/m3). When the DMMP con- acceptor in the DMMP gas. The eight consecutive DMMP
centration increases, the response signal of the SXFA detections in Fig. 18 show favorable repeatability of the
sensor also increases, with a minimum detection sensor.
Pan et al. Microsystems & Nanoengineering (2024)10:4 Page 11 of 12

Received: 5 June 2023 Revised: 11 October 2023 Accepted: 26 October

3
2023
820 DMMP 1.9 mg/m

815
Phase shift (qq)

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