RESEARCH ARTICLE

www.aem-journal.com

Ultrareproducible Capacitive Soft Pressure Sensor Using a

Self-Integrated Fibrous Network of Urethane Equipped
with Diels–Alder Adducts
Yoo Bin Shin, Chul Jong Han, Youngmin Kim, and Jong-Woong Kim*

devices. For example, when a skin-like

A pressure sensor based on a composite structure comprising air and polymer stretchable device with a highly sensitive
fibers is suggested to develop a capacitive pressure sensor that is virtually pressure sensor is adhered to the human
unaffected by repeated pressurization. Reversibly cross-linkable urethane (RCU) body, it is possible to measure one’s blood
pressure and heart rate, as well as the pres-
derived from polybutadiene is newly synthesized for electrospinning, which
sure from the inside of the human body
exhibits the Diels–Alder (DA) reaction under mild conditions. RCU-based originated from the inflammatory reactions
microfibril film is fabricated and it succeeds in welding the intersections of the such as rheumatoid arthritis.[11] Due to the
fibers without a collapse of their shape at mild temperature. This is accomplished social distancing triggered by the coronavi-
via the DA reaction to prevent shearing between microfibrils when physical stress rus disease-19 (COVID-19), the importance
of non-face-to-face diagnosis-treatment has
is applied to the film. The porous film is mechanically robust and reacts stably
strongly increased, and thus the rapid
when the film is deformed or pressed. Electrodes are formed on both surfaces of development of such devices is vital.
the film using Ag nanowires (AgNWs). Vapor-assisted partial melting of retro-DA Because an external stress applied to the
adducts is used to promote fusion of the polymer through the surface of the human body or other types of physical con-
AgNWs and implement a robust stretchable electrode. The capacitance changes tacts can also be detected by such devices, it
exceptionally uniformly with the magnitude of the applied pressure and is possible to track the wearer’s body reac-
tion in response to the external environ-
deformation. Using this sensor, its functionality is successfully demonstrated by
ment in earnest. When this information
implementing a pressure sensor array composed of 9 px and measuring the is correlated with the pressure from the
external force applied to the balloon injected with air. inside of the human body, new insights
on the reactions of the human body to
the external environment can be provided.
To implement this technology, various
sensing mechanisms are being actively developed; for exam-
1. Introduction ple, piezoresistive,[12–14] piezocapacitive,[15–17] and thin-film
The ability to detect micropressures corresponding to a human’s transistor (TFT)-based sensors[18–20] are being studied most
tactile sense has recently attracted considerable attention, as it is actively. According to recent reports, TFT-based sensors
one of the essential functions required in various human-friendly appear to be the most advantageous in terms of sensitivity,
electronic devices; these devices include wearable devices, soft but they have a highly complicated structure and process com-
robotics, electronic skins (e-skins), prosthetics, and human– pared with other devices. Thus, the design to ensure the
machine interactive systems.[1–10] Specifically, because these mechanical elasticity of this sensor has an extremely high level
devices can be used to detect the wearer’s biosignals as well of difficulty. By comparison, the most common type of piezor-
as the interactions between the wearer and the surrounding envi- esistive sensor is to use a composite in which conductive fillers
are dispersed in a soft polymer, and the change in electrical
ronment, they are highly valuable as next-generation medical
resistance of the composite with respect to a pressure is used
as a sensory parameter.[12–14] These sensors have a simple
Y. Bin Shin, J.-W. Kim structure and an intuitive driving principle, and some high-
School of Advanced Materials Engineering
Jeonbuk National University sensitivity sensors have also been reported. However, because
567 Baekje-daero, Deokjin-gu, Jeonju 54896, Republic of Korea the interfacial state between the fillers and the matrix and the
E-mail: [email protected] mechanical properties of the matrix have a strong influence on
C. Jong Han, Y. Kim the characteristics of the device, considerable research must
Display Research Center be accumulated to determine the optimal combination.
Korea Electronics Technology Institute More importantly, because most of these devices are based
68 Yatap-dong, Bundang-gu, Seongnam 13509, Republic of Korea
on the change in resistance of the percolated filler networks,
The ORCID identification number(s) for the author(s) of this article in most cases, a continuously increasing electrical resistance
can be found under https://doi.org/10.1002/adem.202100903. during repeated stretching is indispensable, which is a fatal
DOI: 10.1002/adem.202100903 disadvantage.

Adv. Eng. Mater. 2021, 2100903 2100903 (1 of 9) © 2021 Wiley-VCH GmbH

www.advancedsciencenews.com www.aem-journal.com

Piezocapacitive sensors that transduce a physical touch with a 2. Results and Discussion
conductive medium into a change in capacitance are applicable to
most commercial touch panels, as the device structure is simple Unlike the capacitive touch sensor driven by charge transfer to
and the response time is short because of simple read-out mech- the conductive medium, the capacitive pressure sensor is based
anism of the sensors.[11,15–17] Furthermore, the sensitivity is high on the change in the structure of the sensor that forms the capac-
enough to detect even an exceedingly weak contact with a con- itance. Therefore, to implement a highly sensitive capacitive
ductive material; moreover, it is less affected by the increase pressure sensor, a capacitor structure, e.g., thickness of the sen-
in the resistance of the electrode because the capacitance is sor, that can change sensitively even with a small amount of pres-
varied mainly by the variation of the stored charges and the struc- sure, is needed. Because most of the capacitive sensors developed
tural shape change of the sensor rather than the resistance to date are implemented as a dielectric solid layer (or film)
change of the electrode. Therefore, unlike resistive sensors, a between two opposing electrodes or an electrode pattern formed
more consistent signal detection is possible during repeated on the solid-film surface, a relatively large pressure is required to
touching or even pressurization. The most common approach change the structure by pressing. To deform a film full of poly-
for implementing a piezocapacitive pressure sensor is to bond mers inside, the film should be sufficiently soft. In contrast, if it
two facing electrode films using a dielectric adhesive layer and is too soft, the possibility of tearing or damaging the film during
use the capacitance change as a sensory parameter resulting the sensor manufacturing or use increases, thus implying that
from the decrease in the thickness of the dielectric layer caused caution should be taken when using a polymer with low strength
by the pressure application. This is the most widely used struc- in the sensor fabrication. Therefore, it is common for the poly-
ture because of its simple process and structure; however, the mer used in the pressure sensor to be a material with a certain
thickness of the sensor is large, and the interface between the degree of strength. However, as shown in Figure 1a,b, it is diffi-
dielectric layer and the electrode can be unstable when repeatedly cult to substantially change the shape of the film with low pres-
pressurized, thereby hampering long-term reliability. Another sure. When this film is applied to a capacitive pressure sensor,
approach is to form a pattern for forming capacitance on the sur- the decrease in the thickness (deformation amount) of the film in
face of a single film and use the capacitance change in response response to pressure directly induces the capacitance change,
which is used as a sensory parameter. Eventually, there is a con-
to the shape change of the pattern when pressed.[21,22] This can
cern that a small amount of pressure may not be detected or a
reduce the thickness of the sensor, but a process for pattern for-
sensor with a low sensitivity may be implemented. To address
mation is essential and the sensitivity is reported to be somewhat
this issue, a material that is soft enough to be easily deformed
low. A method of inducing capacitance within a film by forming
even under a small pressure and has high mechanical strength
electrodes on both surfaces of the film is also used in the fabri-
against repeated deformation should be used. However, it is vir-
cation of commercial touch sensors.[23] This method can reduce
tually impossible to simultaneously satisfy these two opposite
the thickness of the sensor as well as simplify the fabrication pro-
factors with the existing solid film. In this study, we solve this
cess because it is not necessary to implement an electrode pat-
through a microfibril-based porous network film. As shown in
tern. However, as the capacitance change is induced by the
Figure 1c,d, the porous network film is a type of composite struc-
change in the thickness of the film, the pressure must be large
ture of polymer microfibril and air, so it is easily deformed by
enough to cause a decrease in the thickness of the film. This small pressure even when high strength polymer is used in
approach is not suitable for small pressure sensing, and the microfibril fabrication. This can be considered suitable for small
capacitance change to the applied pressure is not large. pressure sensing and high-sensitivity sensor implementation.
Furthermore, the film should also be soft enough to deform However, developing a pressure sensor through this approach
via light pressing. is premised on solving several issues.
Herein, a new concept of pressure sensor is proposed to solve To implement a pressure sensor using a microfibril-based
the aforementioned shortcomings of the existing piezocapacitive porous network, the following requirements must be satisfied:
sensors. The basic structure of this sensor is that electrodes are 1) mechanically stable contact between the microfibrils, 2) high
formed on both surfaces of a single film, and that the increase in elasticity of the microfibril polymer, and 3) compatibility with
capacitance with the thickness decrease in the film when the sur- electrodes for sensor fabrication. First, the most ideal approach
face is pressed is used as a sensory parameter. To improve the for stable contact between microfibrils is to induce chemical inte-
small pressure sensing ability and low sensitivity, which is rec- gration between them. The contact areas between the microfi-
ognized as a problem of this sensor, the film was implemented as brils that are not chemically integrated may be damaged by
a polymer microfibril-based porous network instead of a solid repeated sliding during pressing or stretching. Our strategy to
polymer. To form a porous film with excellent mechanical stabil- address this problem is to chemically tie them together; in that
ity, we newly synthesized a reversibly cross-linkable urethane case, the fabricated porous network behaves like a porous film
(RCU) polymer derived from polybutadiene capable of self- rather than a tangled structure, so excellent mechanical stability
integration at mild conditions, which enables a solid integration can be expected. Next, a high elasticity of the microfibril material
between each microfibrils, thus preventing separation is needed, which is one of the most basic requirements of a skin-
between them. The formed porous film was largely deformed like stretchable device. However, polycarbonate,[24] polybenzimi-
even under small surface pressure, and by forming a silver nano- dazole,[25] polyacrylonitrile,[26] or polylactic acid[27] generally used
wire (AgNW)-based stretchable electrode on its both surfaces, a as materials for the electrospinning for fabricating microfibrils
highly sensitive and stretchable pressure sensor could be have a high strength but low elasticity so that cannot satisfy
implemented. the condition. Therefore, it is necessary to develop an elastic

Adv. Eng. Mater. 2021, 2100903 2100903 (2 of 9) © 2021 Wiley-VCH GmbH

www.advancedsciencenews.com www.aem-journal.com

Figure 1. Schematic descriptions for deformation behavior of film when pressed by a finger. a) Unpressed solid film, b) pressed solid film, c) unpressed
microfibrils-based porous film, and d) pressed microfibrils-based porous film.

polymer applicable to the electrospinning. Finally, a stretchable network. If this was repeated, irreversible positional movement
electrode must be formed on the surface of the developed and damage to the fibers indispensably accumulated, which
microfibril-based porous network, as it is impossible to imple- resulted in a loss of initial physical characteristics. Therefore,
ment a pressure sensor unless process compatibility and integration or bonding between microfibrils was necessary,
interfacial stability with a stretchable electrode are secured. but at that time, the initial shape of fibrils or network structure
We used a polymer that satisfies these three basic require- should not be changed. Instead, we implemented crosslinking
ments and evaluated its properties. As this polymer forms between polymers of adjacent fibrils occurs at a moderate tem-
Diels–Alder (DA) adducts at low temperatures, integration of perature where polymer melting did not occur through the DA
the polymer is possible without significantly changing the shape reaction in this study. As shown in Figure 2b, the microfibrils
of the microfibrils. However, as the retro-DA reaction occurs at a that were heat treated at 40  C for 10 h were welded only in
higher temperature than the DA reaction, the collapse of the the area where they intersected without changing their overall
polymer fibrils at low temperatures is not an issue. In addition, shape. If the polymer had elasticity, elongation was possible with-
this polymer has high elasticity, so it is suitable for implementing out sliding at the interface when the fabricated network film was
a stretchable pressure sensor. This polymer (RCU) is crosslinked stretched. Figure 2c shows the contact surface of the film with the
through the reaction between furan ring and maleimide to form PDMS/glass surface thus produced, and Figure 2d shows the
DA adduct at low temperature.[28] As crosslinking of polymers at opposite surface. In both cases, the intersecting microfibrils were
low temperatures does not accompany excessive thermal expan- self-integrated with each other to exhibit a robust network struc-
sion or instantaneous increment in fluidity, excessive fusion ture. The difference in shape between the microfibrils in the two
between stacked microfibrils can be prevented. Instead, it ena- micrographs was caused by the presence or absence of contact
bles covalent bonding between intersecting electrospun microfib- with the PDMS. Because the examples in Figure 2c show the bot-
ers, resulting in a mechanically stable porous film structure.[29] tom surface of microfibrils ejected to the PDMS surface initially,
The porous film structure was implemented by electrospinning the diameter of the fibrils was somewhat larger than those in
the RCU 2 including the furan ring. The incorporation of the Figure 2d, which had not yet come into contact with any material.
furan ring into the polyurethane backbone was achieved using Even in the inset of Figure 2d (a micrograph showing an
diol 1 featuring furan ring.[30] enlarged area of the 3d), the intersection of the fibrils was thor-
First, to form a supporter for electrospinning of the polymer to oughly welded by the DA reaction (marked by the red dotted cir-
become synthesized, we formed a polydimethylsiloxane (PDMS) cle). Figure 2e shows the cross section of the film created and
layer on the glass. This was to prevent the electrospun fibers from formed using a cutter knife. As expected, no signs of severe
attaching to the supporter through the hydrophobicity of PDMS. agglomeration or melting of the electrospun fibrils were found,
A voltage of 10 kV was applied to the RCU 2 solution with and a composite structure in which fibril and air coexisted was
bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI) added successfully formed.
thereon, and microfibrils with a diameter of
30–40 μm were To utilize this composite as a pressure sensor, we formed
electrospun. In this case, microfibrils were prepared at a rate stretchable electrodes on both surfaces of the film using
of
3.34 μm min1, and porous films of various thicknesses AgNWs. AgNW-based electrodes have been reported to exhibit
were fabricated by controlling the electrospinning time. As excellent optoelectrical performance and mechanical stabil-
shown in Figure 2a, the microfibrils immediately after electro- ity,[31,32] but only when nanowires are solidly attached to the sub-
spinning were stacked without interaction with each other. If strate. In other words, to form an AgNW-based stretchable
the polymer was cured while maintaining this structure, sliding electrode on the surface of a microfibril-based porous film,
between microfibrils was caused when stress was applied to the the nanowires should be firmly attached to the RCU fibers

Adv. Eng. Mater. 2021, 2100903 2100903 (3 of 9) © 2021 Wiley-VCH GmbH

www.advancedsciencenews.com www.aem-journal.com

(a) (b)

100 µm 100 µm

(c) (d)

200 µm 200 µm

(e) (f)

AgNWs

100 µm 100 µm

Figure 2. Optical micrograph of a) as-electrospun microfibril network, and b) microfibril network after crosslinking by DA reaction at 40  C for 10 h.
FESEM micrograph of c) the contact surface of the microfibrils-based film with the PDMS/glass surface, d) opposite side of the film that had not experi-
enced contact with the PDMS/glass surface, e) cross section of the crosslinked microfibrils-based porous film, and f ) microfibrils-based film surface with
AgNWs formed.

exposed to the air, so that they are not separated from the fiber film, causing a short circuit between the two electrode surfaces.
surfaces even when repeatedly pressed or stretched. Due to the In this study, we solved this problem using the reversible cross-
structural characteristics of this film composed of a porous net- linking characteristic of the synthesized RCU. First, the fully
work, it was impossible to attach AgNWs to the film surface cured porous film was heat treated at 120  C for 1 min to induce
using an adhesive. This not only reduced the softness of the a partial retro-DA reaction. This process did not completely melt
porous network, but also it was not easy to implement an adhe- the fibers and destroyed the shape of the network, but it regen-
sive that concurrently exhibited high adhesion to the nanowire erates the furan ring and maleimide via the retro-DA reaction on
and polymer surface. A more intuitive method to firmly attach the surface of the fibers, which enabled chemical interaction with
nanowires to the film was to impregnate them under the surface the NWs. To further accelerate this phenomenon, the heat-
of the exposed fibers. This can be implemented simply by first treated film surface was exposed to vaporized methyl ethyl ketone
coating AgNWs on a temporary substrate and electrospinning (MEK) for 10 min, which melted the furan ring and maleimide so
RCU on it. However, the problem of determining how to impreg- that it became fused to the AgNWs to be subsequently trans-
nate NWs on the surface opposite to the surface impregnated ferred. AgNWs formed on the Kapton film were transferred to
with the nanowire remained. When AgNW dispersion was the treated film surface. Afterward, when the DA reaction was
coated on the surface of a fully cured RCU microfibril-based induced again through heat treatment at 40  C for 1 h, as a result,
porous film, NWs were formed on the polymer surface, but an electrode with nanowires attached firmly to the RCU fiber sur-
the adhesion between the two materials was exceedingly low, face was formed. We repeated this process twice to form the
and most were peeled off simply through rubbing with a finger- AgNW electrodes on both surfaces of the porous film. The sur-
tip. Furthermore, a significant amount of AgNWs penetrated the face of the microfibril-based porous film with AgNWs electrodes

Adv. Eng. Mater. 2021, 2100903 2100903 (4 of 9) © 2021 Wiley-VCH GmbH

www.advancedsciencenews.com www.aem-journal.com

is shown in Figure S1a,b, Supporting Information. The AgNWs the pressure sensor sensitivity enhanced, specifically
were formed on the surface of the exposed fiber as well as in the 0.024 kPa1 (up to 1 kPa) and 0.001 kPa1 (from 1 to 10 kPa)
empty spaces between fibers, which came from the Kapton when at 130 μm in film thickness, but with 0.174 kPa1 (up to
the porous film was peeled. Because these AgNWs can adversely 1 kPa) and 0.022 kPa1 (from 1 to 10 kPa) at 350 μm in thickness.
affect long-term reliability of the sensor, they were removed by As the sensor thickness increased from 130 to 350 μm, the sen-
applying ultrasonication for 10 min. Figure 2f, and S1c,d, sitivity of the sensor was improved by
7–22 times. Even when
Supporting Information, shows the sample surface after ultraso- electrospinning occurred for more than 60 min, it was impossi-
nication, where AgNWs are formed only on the exposed micro- ble to form a sensor thicker than 350 μm due to the electromag-
fibril surface. To evaluate the mechanical stability of the formed netic repulsive force, thus implying that the values obtained from
electrode, we carried out an adhesion test on the electrode sur- 350 μm thickness were the best results of this study. To compare
face using a commercial adhesive tape (Magic tape, 3M, USA). As this result with that of a pressure sensor based on a solid film
shown in Figure S2, Supporting Information, the resistance of made of the same material (RCU), we separately fabricated a
the AgNW electrode after exposure to vaporized MEK for pressure sensor of a AgNWs/RCU solid film (350 μm in thick-
10 min was almost unchanged even after ten tape tests, which ness)/AgNWs structure and conducted the same evaluation
proved that the AgNWs were firmly attached to the surface of (Figure S3, Supporting Information). The sensitivity of this
the RCU fibers. sensor was 0.016 kPa1 (up to 1 kPa), 0.0025 kPa1 (from 1 to
We evaluated the functionality of the fabricated AgNWs/RCU 10 kPa), and 0.00096 kPa1 (from 10 to 50 kPa). At pressures
microfibril-based film/AgNWs structure as a pressure sensor. up to 10 kPa, the sensitivity of the sensor developed in this study
Because the thickness of the pressure sensor affects the sensitiv- was at least ten times higher than that of the solid film-based
ity of the sensor, first, the thickness of the porous film was mea- sensor, which proved the initial hypothesis of this study. The sen-
sured according to the electrospinning time (Figure 3a). Through sitivity of the porous network-based pressure sensor imple-
this approach, films of various thicknesses ranging from
130 to mented was higher than those of most film-based capacitive
350 μm were fabricated. Next, as shown in Figure 3b, the capaci- and resistive pressure sensors reported so far,[33–35] and the for-
tance change according to the applied pressure was measured. At mer was comparable with those of pressure sensors using micro-
all thicknesses, the capacitance was increased with the applied pillars or spacers.[36–38] This resulted from the soft nature of the
pressure because the thickness of the porous film decreased porous network. When a pressure exceeding 10 kPa was applied,
by the pressure. Interestingly, as the film thickness increased, the capacitance change range was greatly reduced, which was

Figure 3. a) Thickness of the RCU-based porous film with increasing electrospinning time, b) changes in capacitance with the applied pressure onto
sensors implemented with films in various thicknesses, c) changes in resistance of sensor electrodes when applying various strains repeatedly, and
d) changes in capacitance of sensor (350 μm in thickness) when applying various strains repeatedly.

Adv. Eng. Mater. 2021, 2100903 2100903 (5 of 9) © 2021 Wiley-VCH GmbH

www.advancedsciencenews.com www.aem-journal.com

possibly due to the severe local deformation of the electrodes. Finally, we conducted various performance evaluations to
This meant that the applicable range of this sensor was from verify the practicality of the developed capacitive pressure sensor.
0.5 to 10 kPa. First, as shown in Figure 5a, real-time capacitance change
Regarding the stability of the transferred electrode against according to repeated pressurization was measured. The capaci-
repeated stretching Figure 3c shows the resistance change of tance increased very instantly and uniformly with the applied
the electrode by repeatedly applying strain from 10% to 50%. pressure and was quickly restored in the off state. This indicated
As the applied strain increased, the amplitude of resistance incre- that the developed sensor detected various dynamic motions
ment increased, and after a rapid increase in resistance up to based on repeated pressurization. Next, we manufactured a sen-

100 cycles at the beginning of the test, a stable amplitude sor array consisting of 9 px (pixel size: 10  10 mm2), placed rub-
was observed in all cases. This result indicated a high mechanical ber balls of various sizes on each pixel (Figure 4b), and measured
stability of the implemented electrode against the expansion and the change in capacitance of each pixel (Figure 4c). The change in
contraction of the sensor, which meant that it can also be used as capacitance of individual pixels changed extremely delicately
a resistive strain sensor. However, in that case, because there was according to the weight of the rubber ball. This proved that
a difference in resistance change depending on the time of the developed technology has excellent reproducibility and reli-
stretching, it was not suitable for precise sensor implementation. ability, especially considering that no treatment for electromag-
Interestingly, in the capacitance change in the sensor according netic wave shielding was carried out in this experiment. Finally,
to repeated stretching shown in Figure 3d, the hysteresis previ- after attaching this sensor to the surface of the balloon injected
ously shown in the resistance change was not observed at all. Up with air, we measured the capacitance while pressing the sensor
to the repeated stretching of
1000 cycles, the capacitance (Figure 4d). The red square marked on the inductance–
showed a highly uniform change regardless of the applied strain, capacitance–resistance (LCR) meter next to the balloon repre-
thus implying that the developed sensor can be used as a precise sents the measured capacitance value, indicating that the value
capacitive strain sensor. The initially formed capacitance increased as the force pressing the balloon increased. This result
increased proportional to the applied strain during the stretching provided two insights: the first was that the developed sensor had
and recovered during the release, which is considered as one of sufficient elasticity to withstand a large multiaxial strain applied
the most important features of a mechanical sensor. This stable to the balloon surface, and the other was that the developed
behavior likely resulted from the high elasticity of the synthe- sensor had sufficiently high sensitivity. Based on these results,
sized polymer, the high structural stability of the sensor, and we determined that this sensor could be used in various fields,
the robust bonding between the AgNWs and microfibrils. In such as measuring the degree of epidermal swelling caused by
addition to this, it is a result of reflecting the characteristics of inflammatory reactions inside the human body or measuring a
most capacitors, which are more greatly affected by the structural small external force applied to the human body. Considering that
shape change than the material characteristics caused by the it is necessary to develop a highly complicated process and struc-
mechanical deformation. ture to implement a high-sensitivity pressure sensor, the results

Figure 4. a) Capacitance change of the fabricated pressure sensor over repeated pressure cycles with various pressures. b) 3  3 sensor matrix with nine
different rubber balls placed on each pixel, and c) capacitance change as a function of the location of the rubber balls shown in (b). d) Measuring
capacitance while pressing a sensor attached to an air-infused balloon with a finger. The values marked with red squares on the LCR meter indicate
the capacitance values.

Adv. Eng. Mater. 2021, 2100903 2100903 (6 of 9) © 2021 Wiley-VCH GmbH

www.advancedsciencenews.com www.aem-journal.com

Table 1. Comparison with the recently reported capacitive pressure sensors.

Material Sensitivity and pressure range Minimum detection [Pa] Strain range References
1 1
Porous PDMS 0.046 kPa (0.01–0.05 kPa), 0.051 kPa (0.1–0.5 kPa) 10 – [39]
Bubble-trapped PDMS 0.0055 kPa1 (0–10 kPa) 1000 – [40]
PDMS 0.068 kPa1 (0.01–0.05 kPa), 0.095 kPa1 (0.1–0.5 kPa) 1 – [41]
1
Pyramidal PDMS 2.24 kPa (0–10 kPa) 2 – [42]
RCU fiber 0.174 kPa1 (0–1 kPa), 0.022 kPa1 (1–10 kPa) 500 50% This work

presented in this study provide a new breakthrough for imple- response to the pressing force than a solid film made of the same
menting a high-performance pressure sensor with only a simple material. We formed electrodes using AgNWs on both surfaces
process that is easy to implement. Finally, we compared the per- of the porous film. In this case, vaporized solvent-assisted partial
formance of the developed capacitive pressure sensor with those melting of the retro DA adducts (the furan ring and maleimide)
of recently reported sensors (Table 1).[39–42] As can be confirmed, was utilized to form high adhesion between the AgNWs and
the sensitivity and applicable strain range of our sensor had high RCU fibers. This promoted the fusion between the AgNWs
competitiveness. In addition, considering the reversible cross- and the polymer transferred after vapor treatment, which
linking characteristics of the RCU polymer, the potential appli- resulted in highly robust stretchable electrodes. The RCU
cation to future self-healable pressure sensor development is also fibril-based film with AgNWs electrodes formed on both surfaces
an advantage of this study. was operated as a stretchable capacitor, and the capacitance sen-
sitively varied with the magnitude of the applied pressure. In
addition, unlike many resistive sensors, the capacitance change
3. Conclusion
caused by repeated deformation and pressurization was uniform
In this study, we successfully developed a stretchable pressure regardless of the number and timing of the application.
sensor with an electrospun fibril-based porous network that Furthermore, the sensitivity was at least ten times higher than
exhibited a highly improved sensitivity compared with a solid that of a solid film-based capacitor made of the same material,
film-based pressure sensor. We synthesized the RCU polymer, which proved the initial hypothesis of this study. We succeeded
which not only enabled electrospinning but also underwent a in implementing a 9 px pressure sensor array using this
DA reaction in mild conditions to ensure that the electrospun sensor, and this array was used to accurately map the mass of
fibrils would be self-integrated without melting. Using this poly- objects placed on each pixel. A sensor attached to a balloon
mer, a film capable of stretching without shearing between indi- injected with air was also used to measure the pressure applied
vidual fibers was fabricated, and this film was mechanically to its surface. Considering the simplicity of the structure
robust and did not show any change in shape or physical char- and fabrication process, the results of this study may potentially
acteristics even after up to 1000 exposures of 50% strain. In addi- be used to implement various wearable devices or skin-
tion, as it originated from the unique composite structure of air implantable devices for detecting biosignals or external pressures
and microfibrils, this film showed a much greater physical in the near future.

Figure 5. Fabrication process of the microfibril-based soft pressure sensor.

Adv. Eng. Mater. 2021, 2100903 2100903 (7 of 9) © 2021 Wiley-VCH GmbH

www.advancedsciencenews.com www.aem-journal.com

4. Experimental Section Acknowledgements

Materials: HLBH-P 2000 (polyol) was purchased from Cray Valley. MEK, This work was supported by a National Research Foundation of Korea
isophorone diisocyanate (IPDI), furfurylamine, glycerol 1,2-carbonate, and (NRF) grant (Nos. 2020M3H4A3081895 and 2016M3A7B4910) funded
BMI were purchased from the Tokyo Chemical Industry. Dibutyltin dilau- by the Korean government (MSIP). Further support was provided by
rate was purchased from Sigma-Aldrich. A SYLGARD 184 elastomer kit the Industry Technology R&D program (20006467 and 20006511) funded
was purchased from Dow Corning, USA. All chemicals were used as- By the Ministry of Trade, Industry & Energy (MOTIE, Korea).
received without purification. AgNWs (average diameter ¼ 21 nm, average
length ¼ 22 μm) dispersed in isopropyl alcohol (IPA) were purchased from
Flexio, Korea.
Synthesis of the Polymers: Diol 1 was synthesized referring to the known Conflict of Interest
method.[30] The flask was charged with diol 1 (1.29 g, 6.0 mmol), MEK The authors declare no conflict of interest.
(15.0 g), HLBH-P 2000 (12.0 g, 6.0 mmol), and IPDI (2.67 g, 12.0 mmol)
and mixed. Once the mixture became homogeneous, a catalytic amount of
dibutyltin dilaurate was added to this solution. The mixture was stirred at
60  C for 2 h to create a viscous solution containing RCU 2. PDMS was Data Availability Statement
prepared by mixing the base and curing agent in the SYLGARD 184
elastomer kit at a weight ratio of 10:1. Research data are not shared.
Fabrication of the Pressure Sensor: The fabrication process of the
microfibril-based soft pressure sensor is schematically shown in
Figure 5. First, a supporter for electrospinning was prepared by spin coat-
ing of PDMS onto the glass (600 rpm for 30 s), degassed (30 min storage Keywords
in a vacuum desiccator), and thermally cured at 120  C for 1 h. For electro-
spinning, BMI (1.32 g, 3.0 mmol) and the as-prepared RCU 2 solution chemical syntheses, Diels–Alder, microstructures, polybutadiene,
(31 g) was mixed. One hour after stirring, the solution was used in the urethane
electrospinning without further purification. Electrospinning of the solu-
tion was carried out using a high-voltage electrospinning apparatus Received: July 18, 2021
(ESR200R2, NanoNC, Korea) on the PDMS/glass supporter at 10 kV. Revised: August 19, 2021
The fabricated microfibril-based network film was dried at room tempera- Published online:
ture for 10 min and further heat treated at 40  C for 8 h to induce a DA
reaction. To form a layer of AgNW electrode on a surface of the microfi-
bril-based film, AgNW dispersion of a 0.5 wt% was separately spin coated [1] M. Kaltenbrunner, T. Sekitani, J. Reeder, T. Yokota, K. Kuribara,
(500 rpm for 30 s) on a Kapton film (a temporary substrate). The microfi- T. Tokuhara, M. Drack, R. Schwödiauer, I. Graz, S. Bauer-
bril-based film was heat treated at 120  C for 1 min to induce a partial retro- Gogonea, S. Bauer, T. Someya, Nature 2018, 499, 458.
DA reaction. Then a surface of the film was treated with MEK vapor heated
[2] C. Larson, B. Peele, S. Li, S. Robinson, M. Totaro, L. Beccai,
at 70  C for 10 min (Figure S4, Supporting Information), and then the MEK
B. Mazzolai, R. Shepherd, Science 2016, 351, 1071.
condensed on the porous film surface was allowed to evaporate at room
temperature for 30 min. Immediately after the MEK was completely dried, [3] C. M. Boutry, Y. Kaizawa, B. C. Schroeder, A. Chortos, A. Legrand,
the vapor-treated surface of the film was laminated onto AgNWs/Kapton Z. Wang, J. Chang, P. Fox, Z. Bao, Nat. Electron. 2018, 1, 314.
that were separately prepared and heated at 40  C for 1 h to induce another [4] Q. Hua, J. Sun, H. Liu, R. Bao, R. Yu, J. Zhai, C. Pan, Z. L. Wang, Nat.
DA reaction. The Kapton was carefully peeled off from the microfibril- Commun. 2018, 9, 244.
based film, thus leaving AgNWs on the surface of the film. Then, the [5] C. Zhang, S. Liu, X. Huang, W. Guo, Y. Li, H. Wu, Nano Energy 2019,
AgNWs/microfibril-based film was peeled from the PDMS/glass 62, 164.
supporter, then turned over and laminated again on the PDMS/glass. [6] T. Bu, T. Xiao, Z. Yang, G. Liu, X. Fu, J. Nie, T. Guo, Y. Pang, J. Zhao,
To form a second layer of AgNW electrode on an opposite side of the F. Xi, C. Zhang, Z. L. Wang, Adv. Mater. 2018, 30, 1800066.
microfibril-based film, the same process as when forming the first elec- [7] G. Ge, Y. Zhang, J. Shao, W. Wang, W. Si, W. Huang, X. Dong, Adv.
trode was repeated. The two AgNW layers and microfibril-based film were Funct. Mater. 2018, 28, 1802576.
carefully peeled from the PDMS/glass. Finally, the fabricated structure was
[8] F. He, X. You, H. Gong, Y. Yang, T. Bai, W. Wang, W. Guo, X. Liu,
sonicated for 10 min, followed by drying at room temperature for 30 min.
M. Ye, ACS Appl. Mater. Interfaces 2020, 12, 6442.
Characterization: The glass transition temperature (Tg) and molecular
weights were measured using a DSC-4000 (Perkin Elmer) and Agilent [9] G. Zhao, Y. Zhang, N. Shi, Z. Liu, X. Zhang, M. Wu, C. Pan, H. Liu,
1100 (Agilent), respectively. The viscosity was measured on a digital viscom- L. Li, Z. L. Wang, Nano Energy 2019, 59, 302.
eter (DV1MLVTJ0, AMETEK Brookfield). A field-emission scanning electron [10] S. Cheng, S. Han, Z. Cao, C. Xu, X. Fang, X. Wang, Small 2020, 16,
microscope (FESEM; JSM6700F, JEOL Ltd., Japan) was used to investigate 1907461.
the microstructure of the sensor surfaces. An LCR meter (HP4284A, Agilent, [11] S. Jun, C. J. Han, Y. Kim, B.-K. Ju, J.-W. Kim, J. Mater. Chem. A 2017, 5,
USA) was used to measure the resistance and capacitance formed in the 3221.
samples. Mechanical stability when subject to repeated cycles of stretching [12] L. Gao, C. Zhu, L. Li, C. Zhang, J. Liu, H. D. Yu, W. Huang, ACS Appl.
was investigated using an automatic stretch-testing machine (Jaeil Optical Mater. Interfaces 2019, 11, 25034.
System, Korea). In the stretching test, tensile strains up to 50% were used, [13] H. Sun, N. Pan, X. Jin, K. Deng, Z. Liu, C. Te Lin, T. Pan, Y. Chang,
and the samples were stretched at a rate of 10 cycle min1. Pressure sensing J. Mater. Chem. A 2020, 8, 358.
tests were conducted using an in-house equipment. More than ten different
[14] W. Li, K. He, D. Zhang, N. Li, Y. Hou, G. Cheng, W. Li, F. Sui, Y. Dai,
samples were fabricated and evaluated for each parameter.
H. Luo, Y. Feng, L. Wei, W. Li, G. Zhong, M. Chen, C. Yang, ACS Appl.
Energy Mater. 2019, 2, 2803.
[15] S. Sharma, A. Chhetry, M. Sharifuzzaman, H. Yoon, J. Y. Park, ACS
Supporting Information Appl. Mater. Interfaces 2020, 12, 22212.
Supporting Information is available from the Wiley Online Library or from [16] S. Zhao, W. Ran, D. Wang, R. Yin, Y. Yan, K. Jiang, Z. Lou, G. Shen,
the author. ACS Appl. Mater. Interfaces 2020, 12, 32023.

Adv. Eng. Mater. 2021, 2100903 2100903 (8 of 9) © 2021 Wiley-VCH GmbH

www.advancedsciencenews.com www.aem-journal.com

[17] S. R. A. Ruth, L. Beker, H. Tran, V. R. Feig, N. Matsuhisa, Z. Bao, Adv. [30] K. H. Pyo, D. H. Lee, Y. Kim, J. W. Kim, J. Mater. Chem. C 2016, 4, 972.
Funct. Mater. 2020, 30, 1903100. [31] W. Yang, Y. Zhang, Y. Zhang, W. Deng, X. Fang, Adv. Funct. Mater.
[18] M. J. Yin, Z. Yin, Y. Zhang, Q. Zheng, A. P. Zhang, Nano Energy 2019, 2019, 29, 1905923.
58, 96. [32] J. Xu, W. Yang, H. Chen, L. Zheng, M. Hu, Y. Li, X. Fang, J. Mater.
[19] M. Amit, L. Chukoskie, A. J. Skalsky, H. Garudadri, T. N. Ng, Adv. Chem. C 2018, 6, 3334.
Funct. Mater. 2020, 30, 1905241. [33] B. You, C. J. Han, Y. Kim, B. K. Ju, J. W. Kim, J. Mater. Chem. A 2016, 4,
[20] M. Jung, E. Lee, D. Kim, K. Kim, C. Yun, H. Lee, H. Kim, K. Rhie, 10435.
S. Jeon, npj Flex. Electron. 2019, 3, 8. [34] H. Shi, M. Al-Rubaiai, C. M. Holbrook, J. Miao, T. Pinto, C. Wang,
[21] S. Jun, S. O. Kim, H. J. Lee, C. J. Han, C. J. Lee, Y. T. Yu, C. R. Lee, X. Tan, Adv. Funct. Mater. 2019, 29, 1809116.
B. K. Ju, Y. Kim, J. W. Kim, J. Mater. Chem. A 2019, 7, 3101. [35] J. Kim, E. F. Chou, J. Le, S. Wong, M. Chu, M. Khine, Adv. Healthc.
[22] L. W. T. Ng, X. Zhu, G. Hu, N. Macadam, D. Um, T. C. Wu, F. Le Mater. 2019, 8, 1900109.
Moal, C. Jones, T. Hasan, Adv. Funct. Mater. 2019, 29, 1807933. [36] Z. Wang, X. Guan, H. Huang, H. Wang, W. Lin, Z. Peng, Adv. Funct.
[23] X. Yang, Y. Wang, H. Sun, X. Qing, Sens. Actuators A. 2019, 285, 67. Mater. 2019, 29, 1807569.
[24] S. Megelski, J. S. Stephens, D. Bruce Chase, J. F. Rabolt, [37] Y. Luo, J. Shao, S. Chen, X. Chen, H. Tian, X. Li, L. Wang, D. Wang,
Macromolecules 2002, 35, 8456. B. Lu, ACS Appl. Mater. Interfaces 2019, 11, 17796.
[25] J. S. Kim, D. H. Reneker, Polym. Compos. 1999, 20, 124. [38] J. Yang, S. Luo, X. Zhou, J. Li, J. Fu, W. Yang, D. Wei, ACS Appl. Mater.
[26] Y. Wang, S. Serrano, J. J. Santiago-Aviles, J. Mater. Sci. Lett. 2002, 21, Interfaces 2019, 11, 14997.
1055. [39] Bijender, A. Kumar, ACS Omega 2020, 5, 16944.
[27] X. Zong, K. Kim, D. Fang, S. Ran, B. S. Hsiao, B. Chu, Polymer 2002, [40] Y. Jang, J. Jo, K. Woo, S.-H. Lee, S. Kwon, H. Kim, H. S. Lee, Phys. Rev.
43, 4403. Appl. 2019, 11, 014037.
[28] J. C. de Oliveira, M.-P. Laborie, V. Roucoules, Molecules 2020, 25, 243. [41] Bijender, A. Kumar, Sens. Biosens. Res. 2021, 33, 100434.
[29] G. A. Appuhamillage, J. C. Reagan, S. Khorsandi, J. R. Davidson, [42] Z. Zhang, X. Gui, Q. Hu, L. Yang, R. Yang, B. Huang, B. Yang, Z. Tang,
W. Voit, R. A. Smaldone, Polym. Chem. 2017, 8, 2087. Adv. Electron. Mater. 2021, 7, 2100174.

Adv. Eng. Mater. 2021, 2100903 2100903 (9 of 9) © 2021 Wiley-VCH GmbH