Carbon xxx (2016) 1e9

Contents lists available at ScienceDirect

Carbon
journal homepage: www.elsevier.com/locate/carbon

Flexible piezoresistive sensors based on “dynamic bridging effect” of

silver nanowires toward graphene
Yong Wei, Song Chen, Xuchu Dong, Yong Lin, Lan Liu*
College of Materials Science and Engineering, Key Lab of Guangdong Province for High Property and Functional Macromolecular Materials, South China
University of Technology, Guangzhou, 510641, PR China

a r t i c l e i n f o a b s t r a c t

Article history: The essence of piezoresistive sensors is the variation in charge transport property under external me-
Received 31 July 2016 chanical stresses (compression, bending, twisting, et al.), thus how to build such difference in charge
Received in revised form transport property before and after external loadings is crucial to design high performance piezoresistive
31 October 2016
sensors. In the current study, a bio-based flexible piezoresistive sensor based on the “dynamic bridging
Accepted 11 November 2016
Available online xxx
effect” of silver nanowires (AgNWs) toward reduced graphene oxide (rGO) is presented, in which the
highly conductive welded AgNWs networks cross and bridge the neighboring high-resistive grain
boundaries and rGO contacts when applied with mechanical stresses. The variation of the charge
transport behavior results in drastic decrease in resistance even under subtle loadings. The obtained
piezoresistive sensor shows high sensitivity (5.8 kPa
1), fast response and relaxation properties (29.5 ms
and 15.6 ms, respectively), ultralow detection limit (0.125 Pa) and excellent stability (>10000 loading/
unloading cycles). The high performance piezoresistive sensor demonstrates great potentials in detection
of wrist pulse waves, smart wearable electronics, monitoring or simulation of human body's motions and
movements.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction (sensitivity, response time and detection limit) of piezoresistive

Flexible force-sensitive materials exhibit great potentials in
various fields such as electronics skins (E-skins), wearable elec-
tronics and smart robotic systems because they can easily trans-
duce mechanical stresses (compression, bending, twisting, et al.)
into electrical signals [1,2]. To date, various categories of flexible
force-sensitive materials such as piezoresistive [3e13], capacitive
[14e16], piezoelectric [17e19] and organic field effect transistors
[20] have been introduced into the design strategies for realization
of the transduction. Particularly, flexile piezoresistive materials or
sensors have been extensively researched and aroused great con-
cerns owning to the facile fabrication process and effective re-
sponses to various mechanical stresses. It is proved that nano/
micro-geometrical structures such as reversible interlocked nano-
fibres, microdomes or microwrinkles [3e7], silk-molded micro-
structures [8], Gaussian random rough surfaces [9], mimosa leaves,
rose petals or gecko-inspired microstructures or architectures
[10e12] are favorable for improving the sensing performances
* Corresponding author.
E-mail address: psliulan@scut.edu.cn (L. Liu).
sensors. However, all these artificial or nature-inspired micro-
structures are based on the photolithography and etching tech-
niques or polymer replication processes that are complicated and
strongly rely on the costly equipments, making it difficult for large-
scale manufacturing. Moreover, almost all the progresses in such
piezoresistive sensors involve non-renewable and non-
biodegradable elastic substrates, such as polydimethylsiloxane
(PDMS) or polyurethane (PU), which are unsuitable for the current
frequent updating trend of consumer electronics and will signifi-
cantly restrict the promising applications of the piezoresistive
sensors.
It is generally known that piezoresistive sensors are working
through the change in resistance after loading with external me-
chanical stresses, but the essence of which is based on the variation
in charge transport property, so build such difference in charge
transport property (or current transmission pathways) is crucial to
design high performance piezoresistive sensors. However, most of
the previous reported piezoresistive sensors are only focus on the
variation of contact area (Ac) and contact resistance (Rc) of the two
adjacent contact microstructures (Ac increases and Rc decreases in
most cases) [3e13]. The decisive effect of the charge transport

http://dx.doi.org/10.1016/j.carbon.2016.11.027
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Please cite this article in press as: Y. Wei, et al., Flexible piezoresistive sensors based on “dynamic bridging effect” of silver nanowires toward
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2 Y. Wei et al. / Carbon xxx (2016) 1e9
property on the piezoresistive sensor is frequently neglected under
such circumstance. Actually, the selection of suitable conductive
materials including carbon nanotubes (CNTs) [5,6,21], graphene
[22e24], metal nanowires (NWs) [25,26], zinc oxide nanowires
(ZnO NWs) [4,27], carbon black (CB) [11,28,29], and conductive
polymers [30,31] show tremendous influences on the charge
transport inner piezoresistive sensors and the sensing perfor-
mances. Generally, it is easy for electrons to travel in highly
conductive materials (such as metals, ideal graphene or CNTs, et al.)
while it is relative difficult in conductive materials with intrinsic
defects such as reduced graphene oxide (rGO, in which defects and
residual oxygen containing functional groups always exist on the
surfaces and edges) due to the electrons need get over a stronger
potential barrier [32].
Herein, we report a new type of piezoresistive sensor in which
renewable and biodegradable cotton fiber films with inherent
rough surfaces serve as the skeleton materials and flexible sup-
porting substrates for silver nanowires (AgNWs) and rGO. The
sensing mechanism of is based on the “dynamic bridging effect” of
highly stable and conductive AgNWs networks toward defective
rGO, in which AgNWs cross and bridge the neighboring high-
resistive grain boundaries and rGO contacts when applied with
mechanical stresses. The piezoresistive sensor in this study shows
high sensitivity (5.8 kPa
1), fast response and relaxation properties
(29.5 ms and 15.6 ms, respectively), ultralow detection limit
(0.125 Pa) and excellent stability (>10000 loading/unloading cy-
cles). The high performance piezoresistive sensor may be a robust
candidate in physiological diagnosis, detection or simulation of
human body's movements, et al.
2. Results and discussion
Fig. 1 illustrates the overall design concept of this work. The GO
(2 mg mL
1) wrapped bio-based cotton fiber film is fabricated
through a simple, efficient dip-coating process, during which GO is
self-assembled onto the surface of cotton fibers and the color of the
film change from white to claybank and then into black after being
reduced under H2N2 vapor (100  C for 2 h), demonstrating rGO is
coated on cotton fibers and rGO based conductive cotton fiber films
are obtained (Fig. S1 and Fig. 1a). Similarly, AgNWs are coated on
cotton fiber according to our previous work (FESEM images of
AgNWs are shown in Fig. S2) [33]. Fig. S3 shows the mass of the rGO
and AgNWs based conductive cotton fiber films almost linearly
increase and the resistivity gradually decrease with dip-coating
cycles, revealing the amount of rGO and AgNWs and the conduc-
tivity of the films can be simply controlled by varying the dip-
coating cycles. The resistivity of rGO based cotton fiber film rea-
ches 5.1 U cm and 0.26 U cm after 1 and 8 dip-coating cycles,
respectively. Differently, much more conductive cotton fiber film
can be fabricated using AgNWs to construct conductive pathways
due to the high conductivity of AgNWs (resistivity of the bulk silver
is 1.62  10
6 U cm), the resistivity of obtained AgNWs based
cotton fiber films reach 3.2 U cm after only one dip-coating cycle
and 9.16  10
4 U cm after 8 dip-coating cycles (Fig. S3). The FESEM
images of the two kinds of conductive cotton fiber films show the
cotton fibers are gradually wrapped with dip-coating cycles and
conductive rGO and AgNWs networks are built on the surface of
cotton fibers (Figs. S4 and S5, FESEM image of the cotton fiber is
shown as Fig. 1c). It is should be noted that the durability of rGO or
AgNWs networks on the surface of cotton fiber is very important to
the practical applications of these materials. In this study, AgNWs
are consolidated through thermal treatment at 250  C for 10 min to
obtain a continuous and welded AgNWs network (the selection of
sintering temperature and FESEM images of the AgNWs networks
with different sintering time are shown as Figs. S6 and S7). As
Please cite this article in press as: Y. Wei, et al., Flexible piezoresistive sensors based on “dynamic bridging effect” of silver nanowires toward
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shown in Figs. S8 and S9, the conductivity and durability are
significantly improved after thermal treatment (the durability is
reflected by the resistance change against 280 W ultrasonic shaking
in water bath). Due to the inherent hydrophobicity (contact angle:
126 ) and laminated structure of rGO, the water molecules are
difficult to infiltrate the rGO networks, endowing the excellent
durability of rGO networks on the surface of cotton fibers (Fig. S9).
Moreover, the rGO and AgNWs based conductive cotton fiber films
demonstrate outstanding flexibility and can be easily tailored into
different shapes (Fig. S10), which are highly desirable for diversified
and multifunctional applications of piezoresistive sensors.
As depicted as Fig. 1e, the piezoresistive sensors are built by the
cotton fiber films decorated with rGO and welded AgNWs networks
and the two copper electrodes are mounted on the two terminals of
the rGO based cotton fiber film. Fig. 1f shows the simplified sensing
mechanism of the piezoresistive sensor, the key point of the design
relies on the inequality of the resistance of the bottom rGO based
cotton fiber film (Rbo) and the upper AgNWs based cotton fiber film
(Rup), in which Rbo should be far greater than Rup. When external
mechanical stresses loaded onto the piezoresistive sensor, the
bottom and up cotton fiber films contact each other more tightly
and the charge transport property is changed, resulting in variation
of the current transmission pathways, the current preferentially
flows through the AgNWs based cotton fiber films and the total
resistance of the piezoresistive sensor greatly decreases. The
sensing mechanism of the asymmetric piezoresistive sensor will be
discussed in details in the following text. Fig. 1gei demonstrate the
piezoresistive sensors are highly flexible and conform well to hu-
man fingers, wrists and necks, indicating their potential applica-
tions in wearable electronics. Fig. 1j represents the typical FESEM
image of the cross section of a piezoresistive sensor that is built by
rGO and AgNWs based cotton fiber films with rough surfaces
(Fig. 1k and l) and micro-sized gaps exist between bottom and up
cotton fiber films, which provides more electronic pathways under
external loadings.
In order to study the sensing performance, the piezoresistive
sensor is connected into a resistance analyzer (TEGAM 1740,
Fig. 2a), when an external mechanical force (0e2 N, the pressure
ranges from 0 kPa to 5 kPa, Fig. 2b) is applied onto the piezoresistive
sensor and the resistance signals are recorded. As shown in Fig. 2c,
the rGO and AgNWs based cotton fiber films respectively serve as
the bottom and upper sections of piezoresistive sensor, the resis-
tance of all types of piezoresistive sensors greatly decreases with
applied pressure owning to the elastic deformations of the
conductive cotton fiber films that leads to closer contact and more
contacting sites between bottom and upper conductive cotton fiber
films [34]. Noteworthy, we find that the sensitivity in the range of
0e0.1 kPa (S, defined as S ¼ DR/R0/DP, where DR is the initial
resistance (R0) minus the measured resistance (R) and DP is the
applied pressure) of the unsymmetrical piezoresistive sensors is
strongly dependent on resistance ratio of the bottom rGO and up-
per AgNWs based cotton fiber films (Rbo/Rup). As demonstrated in
Fig. 2e (Region I), the sensitivity is only 0.214 kPa
1 if the resistance
of bottom rGO based cotton fiber film is equal to the upper AgNWs
based cotton fiber film (Rbo/Rup ¼ 1) while it increases to 0.66 kPa
1
if Rbo/Rup ¼ 500, 3.08 times higher than the piezoresistive sensor
with Rbo/Rup ¼ 1. A sharply increase in sensitivity is observed if
sequentially increases the value of Rbo/Rup, the piezoresistive sensor
shows sensitivity as 3.72 kPa
1 and 5.8 kPa
1 when Rbo/Rup reach
7500/1 and 10000/1, respectively, illustrating the significantly ef-
fect of internal structure on the sensitivity of the unsymmetrical
piezoresistive sensors.
To clarify the sensing mechanism of this piezoresistive sensor,
XPS analysis is performed to study the structure of rGO (Fig. S11). It
is found that some levels of carbon-oxygen single (CeO) and double
 Y. Wei et al. / Carbon xxx (2016) 1e9 3

Fig. 1. (a) Schematic of fabrication of conductive cotton fiber decorated with rGO and AgNWs networks; FESEM image of the welded AgNWs networks on the surface of cotton fiber
(b), pristine cotton fiber (c) and conductive cotton fiber decorated with rGO; Schematic (e) and sensing mechanism of the piezoresistive sensor (f); (gei) the piezoresistive sensors
show outstanding flexibility and conform well to human fingers, necks and wrists; (j) cross sectional FESEM image of the piezoresistive sensor; (k, l) 3D surface morphologies of
AgNWs (Ra ¼ 39.4 mm) and rGO (Ra ¼ 36.8 mm) based conductive cotton fiber films. (A colour version of this figure can be viewed online.)

bonds (C]O) exist on the rGO surfaces, reflecting intrinsic bottle-
necks exist that divide rGO into several monocrystal domains
(MDs) and grains boundaries (GBs, interfaces between MDs), thus
electrons may be periodically trapped in the domains and the high-
resistive grain boundaries (see Fig. 2f) [32,35e38]. The intrinsic
topological defects of a rGO and the high contact potential barrier
adjacent two pieces of rGO are the most important sources of
scattering that significantly hinder the carrier transport and
mobility, simultaneously contributing to the high resistivity of rGO
based cotton fiber films [39]. In this study, the highly conductive
AgNWs based cotton fiber film serves as the upper section of the
piezoresistive sensor, in which the welded AgNWs networks well
cross and bridge the neighboring high-resistive grain boundaries
and rGO contacts when applied with a pressure., making the cur-
rent preferentially flows through the AgNWs based cotton fiber
film, thus the resistance of the piezoresistive sensor greatly de-
creases. For example, the resistance of a rGO based cotton fiber film
(2.0 cm  4.0 cm  100 mm, fabricated after only one dip-coating
cycle) is about 2400 U and a resistance of the AgNWs based cot-
ton fiber film is about 0.22 U (2.0 cm  3.5 cm  100 mm, fabricated
after 6 dip-coating cycles), the piezoresistive sensor constructed by
these two conductive films is about 1800 U (without any external
pressure at this time). The resistance of piezoresistive sensor de-
creases to around 1000 U when applied with 0.1 kPa pressure.
Meanwhile, the cross sectional SEM images of the piezoresistive
sensor before and after applying with an external pressure imply

Please cite this article in press as: Y. Wei, et al., Flexible piezoresistive sensors based on “dynamic bridging effect” of silver nanowires toward
graphene, Carbon (2016), http://dx.doi.org/10.1016/j.carbon.2016.11.027
4 Y. Wei et al. / Carbon xxx (2016) 1e9

Fig. 2. (a) Schematic of the resistance measurement; (b) applied force on the piezoresistive sensor during the measurement, insert is the digital photograph to show the mea-
surement; (c, d) resistance change of piezoresistive sensors with different types and Rbo/Rup; (e) sensitivity of the piezoresistive sensors with different types and Rbo/Rup; (f)
schematic to show the monocrystal domains (MDs) and grain boundaries (GBs) of rGO; (g, h) illustration of the current transmission pathways of piezoresistive sensor without
external loadings (g) and under external loadings (h), in which high-resistive grain boundaries and rGO-rGO contact are shown as solid red line and the AgNWs are shown as solid
blue line, current transmission pathways are indicated by solid arrows. (A colour version of this figure can be viewed online.)

that the contact sites of the bottom and up cotton fiber films
significantly increases after applying with a pressure (Fig. S12),
suggesting more electronic pathways under external loadings are
provided. Under such circumstance, the polycrystalline rGO is
bridged by highly conductive AgNWs. To distinguish this bridging
effect by metal NWs under mechanical stresses from those con-
ventional bridging with metal contact under static conditions
[35,36,40e43], we propose a novel concept “dynamic bridging”
toward graphene with metal NWs networks to ensure high sensi-
tivity of piezoresistive sensor. The dynamic bridging effect to
improve the sensitivity of piezoresistive sensors it not due to the
free electrons densities increase but rather the electronic pathways
effectively increase, in which AgNWs bridge neighboring high-
resistive grain boundaries and rGO contacts when loaded with

Please cite this article in press as: Y. Wei, et al., Flexible piezoresistive sensors based on “dynamic bridging effect” of silver nanowires toward
graphene, Carbon (2016), http://dx.doi.org/10.1016/j.carbon.2016.11.027
 Y. Wei et al. / Carbon xxx (2016) 1e9 5

external mechanical stresses (Fig. 2g and h). The metal NWs net-
works should be highly conductive and the “dynamic” means the
bridging mainly occurs after loading with external mechanical
stresses (compression, bending, twisting, et al.). To verify the
effectiveness of the dynamic bridging by AgNWs, the resistance
change of piezoresistive sensor with AgNWs and rGO based cotton
fiber films respectively serve as the bottom and upper sections is
investigated (the copper electrodes are connected to the AgNWs
based cotton fiber film in this case, Fig. 2d). However, the maximum
sensitivity of the piezoresistive sensor with Rbo/Rup ¼ 0.0001 is only
0.186 kPa
1 (Region II in Fig. 2e), much lower than the sensitivity of
the piezoresistive sensors shown in Fig. 2c. From the results of
Fig. 2d, we can also conclude that even if the surface roughness (Ra)
of rGO based cotton fiber films nearly linearly decreases with dip-
coating cycles (Fig. S13) and a positive correlativity of sensitivity
and Ra is observed (Fig. 2e, Region I), it shows limited impacts on
the sensitivity of piezoresistive sensors. Additionally, the sensitivity
of piezoresistive sensors built by single AgNWs and rGO based
cotton fiber film is also studied. Different from sensing mechanism
of the unsymmetrical piezoresistive sensors that based on the dy-
namic bridging effect, the sensing mechanism of piezoresistive
sensors built by single AgNWs and rGO based cotton fiber film
mainly influenced by the bulk resistance of the conductive cotton
fiber film, which show very low sensitivity as 0.03 kPa
1 and
0.056 kPa
1 (Fig. S14), respectively, indirectly reflecting the validity
of “dynamic bridging effect” and the superiority of the working
mechanism unsymmetrical piezoresistive sensors of this work.
Furthermore, the piezoresistive sensor shows rapid response
and relaxation properties to instantaneous pressure (100 Pa) with
good reproducibility due to the negligible viscoelastic delay of the
cotton fiber skeleton, the test is repeated for 3 times and the
average response and relaxation time are about 29.5 ms and
15.6 ms, respectively (Fig. 3a). To estimate the detection limit,
relative resistance change of the piezoresistive sensor is measured
with decreasing loadings. As Fig. 3b shows, the resistance drops
about 0.75% and 0.5% when loaded with 15 mg and 10 mg weight
on the piezoresistive sensor (the relevant pressure is about 0.375 Pa
and 0.25 Pa), respectively. Even loaded with 5 mg weight, the
resistance still drops about 0.25%, showing the ultralow detection
limit of the piezoresistive sensor (about 0.125 Pa). The compression
stability is investigated by real-time recording the resistance with
periodic loading/unloading cycles (the maximum applied pressure
is 100 Pa and the compression frequency is 1 Hz, Fig. 3c), the total
resistance and waveform almost keep unchanged even after 10000
loading/unloading cycles, indicating the excellent reliability,
reproducibility and stability of the piezoresistive sensor. Although
piezoresistive materials are widely researched in recently years, it
is still full of challenge to simultaneously obtain piezoresistive
sensor with high sensitivity, fast response and ultralow detection
limit. In the current study, the sensitivity and response property is
superior to majority of the typically reported piezoresistive sensors
and the detection limit is lower compared with them (Table S1).
More importantly, the skeleton material of the piezoresistive
sensor is renewable and biodegradable and the simple process
make the piezoresistive sensors can be easily scaled up fabricated.
The piezoresistive sensors also respond to various mechanical
forces such as compression, bending and twisting (Fig. 4aec) and
the corresponding resistance signals with good repeatability about

Fig. 3. (a) The piezoresistive sensor show rapid response and relaxation time; (b) resistance change after 5 mg, 10 mg and 15 mg weight on the piezoresistive sensor; (c) the total
resistance and waveforms of the piezoresistive sensor show excellent working stability even after 10000 loading/unloading cycles; (d) comparison of the sensing performance
(sensitivity, detection limit and response time) of the typical previous reported piezoresistive sensors up to now (the detailed information is listed as Table S1). In this Figure, the
Rbo/Rup ¼ 10000/1, the rGO based cotton fiber film serves as the bottom section and the AgNWs based cotton fiber film serves as the upper section, the copper electrodes are
connected on the two terminals of rGO based cotton fiber film. (A colour version of this figure can be viewed online.)

Please cite this article in press as: Y. Wei, et al., Flexible piezoresistive sensors based on “dynamic bridging effect” of silver nanowires toward
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6 Y. Wei et al. / Carbon xxx (2016) 1e9

Fig. 4. Digital photographs to show the detection of three typical mechanical stimulus and the corresponding resistance signals for several loading/unloading cycles: (a, d)
compression (pressure is about 50 Pa), (b, e) bending and (c, f) twisting (bending and twisting are about 120 and 180 , respectively); (gei) the piezoresistive sensor can be mounted
on wrist to detect the wrist pulse waves, Figure (i) is the enlarged view of the selected area of Figure (h). (A colour version of this figure can be viewed online.)

these three typical deformations can be well obtained (Fig. 4def),
demonstrating the multifunctionalities and versatilities of the
piezoresistive sensors. Therefore, a piezoresistive sensor with the
size of 2 cm  1 cm is fabricated and fixed on a woundplast (Fig. 4g),
which can be well mounted onto human wrist to detect wrist pulse
waves caused by blood pressure. Fig. 4h shows a real-time
recording of wrist pulse waves of a volunteer (male, 28 years
old); it is clearly observed that the pulse frequency of the volunteer
is 70 beats/min with repeatable and regular waveforms. From the
enlarged view of pulse wave (Fig. 4i), three typical peaks of the
wrist pulse: P1 (incident forward wave), P2 (late systolic peak
pressure) and P3 (diastolic pulse waveform) can be clearly distin-
guished [44], indicating the ultralow detection limit and piratical
potentials in physiological diagnosis.
Owning to the excellent flexibility, sensing capability and can be
easily tailored into various shapes, a smart wearable ring (width
and diameter are 0.8 cm and 2.0 cm, respectively) is fabricated
(Fig. 5a and b) to monitor or detect the finger motions and human
body postures, which is crucial for wearable electronics. As shown
in Fig. 5c and d, when a volunteer wears the smart ring and bends
the finger with a gradual increase in bending angle (0 e120 ), the
bending of finger joint drives the movements of muscle on the
finger, thus the smart wearable ring shows a gradual increase in
relative resistance and the resistance change almost linearly de-
creases with bending angle. Based on the measured resistance
signals, the finger motions can be well assessed. If the volunteer
makes scissor hand gestures (alternately opening and closing the
finger posture, insert in Fig. 5e and f), the finger postures can be
monitored due to a small compressional force is generated once the
middle and index finger contact each other that decreases the
resistance of the smart wearable ring. The collected resistance
signals may be employed as the parameters to control the finger
motions in computer virtual environment. Moreover, like other
commercial smart wearable devices (smart bands, smart textiles,
smart watches, et al.), the smart wearable ring with smaller in size
and lighter in weight can also detect the human body's movements.
As demonstrated as Fig. 5g, when the volunteer is swing the arm
when walking or running, a normal force will be generated and
applied onto the wearable ring to increase the contact sites, a
downward resistance peak is clearly observed for every step and
the working pace of the volunteer is about 90 steps/min and the
running pace is about 210 steps/min (Fig. 5h and i), making the
smart wearable ring a robust candidate for detection of the physical
exercise conditions.
3. Conclusions
In summary, a flexible piezoresistive sensor with high sensi-
tivity (5.8 kPa
1), fast response and relaxation properties (29.5 ms
and 15.6 ms, respectively), ultralow detection limit (0.125 Pa) and

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 Y. Wei et al. / Carbon xxx (2016) 1e9 7

Fig. 5. (a, b) Digital photograph and schematic illustration of the smart wearable ring; (c) digital photograph to show a volunteer wears the ring and the definition of the bending
angle; (d) real-time recording of the resistance when bending the finger with different angles,; (e) digital photograph to show the scissor gesture; (f) relative resistance change of
the wearable ring when the volunteer makes a scissor gesture; (gei) the smart wearable ring can well detect human body motions such as standing, walking and running. (A colour
version of this figure can be viewed online.)

excellent stability (>10000 loading/unloading cycles) is presented.
The novel concept “dynamic bridging effect” of AgNWs toward
graphene (mainly occurs under external loadings) is proposed to
clarify the sensing mechanism. The piezoresistive sensor can well
detect various mechanical forces (such as compression, bending
and twisting) and can be used to detect wrist hand pulses with
good distinguishability and repeatability. Finally, a smart wearable
ring is demonstrated to detect or monitor human body's motions
and movements.
4. Experimental
4.1. Fabrication of conductive cotton sheets fiber films decorated
with rGO and AgNWs
GO suspension (2 mg mL
1, the diameter of the GO is 1.5e2 mm,
see Fig. S1a) was prepared through a modified Hummer's method
[45]. To prepare conductive cotton fiber films coated with rGO, a
pristine cotton fiber film (5 cm  6 cm  100 mm) was dipped into a
GO suspension and dried in an oven at 80  C for 30 min (Fig. S1),
then cotton sheet decorated with GO was reduced under hydrazine
hydrate (H2N2) vapor in polytetrafluoroethylene (PTFE) tank
(100  C for 2.0 h). AgNWs suspension (2 mg mL
1, the length and
diameter of AgNWs are about 15 ±5 mm and 50 nm, respectively,
see Fig. S2) were synthesized through polyol process [46,47] and
the highly conductive cotton fiber films were fabricated according
to our previous published work [33].
4.2. Preparation of flexible piezoresistive sensors
As shown in Fig. 1a, the flexible piezoresistive sensors were
constructed by conductive rGO and AgNWs based cotton fiber films
with face-to-face orientation. Different form conventional flexible
piezoresistive sensors [3e13], the copper electrodes should be
mounted on the terminals of the bottom rGO based conductive
cotton fiber film by carbon conductive adhesive tapes. After that the
edges were encapsulated by 3 M Scotch tape to form flexible pie-
zoresistive sensors. To prepare the smart wearable ring, a
0.8 cm  7 cm 3 M Scotch tape was wrapped onto a cylinder (radius
of the cylinder is about 1.1 cm) with sticky side outward, then a
0.8 cm  6 cm  100 mm rGO based cotton fiber film was wrapped
and bonded onto the Scotch tape. After that, a
0.8 cm  5.5 cm  100 mm AgNWs based cotton fiber film was
attached onto the rGO based cotton fiber film and the edges were
encapsulated by 3 M Scotch tape. The two electrodes were con-
nected to the two terminals of the rGO based cotton fiber film; the
schematic illustration of the smart wearable ring is shown as
Fig. 5b.

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4.3. Characterization
The scanning electron microscope (SEM) and transmission
electron microscope (TEM) images were taken by Nano SEM 430
instrument and JEOL JEM-2100HR instrument, respectively. The 3D
surface morphologies of the conductive cotton fiber films were
studied through BMT Expert 3D instrument. X-ray photoelectron
spectroscopy (XPS) was analyzed by a Kratos Axis Ultra DLD elec-
tron spectrometer. The resistance (R, U) of the cotton fiber film was
measured using a TEGAM 1740 microhmmeter (applying current is
100 mA) and the resistivity (r, U$cm) was calculated by: r ¼ RS/L, in
which S and L are the cross sectional area length of the conductive
cotton fiber film, respectively. During the investigation of the
sensitivity of flexible piezoresistive sensors to pressure (S), a
computer controlled force gauge (CKe50HB, Fuzhou Aipu in-
struments Co., Ltd.) was performed to apply the external force (F,
N), the corresponding applied pressure (P) was calculated by P ¼ F/
Af, where Af was the forced area. Noteworthy, a thin glass slide
(2.0 cm  2.0 cm) was covered on the piezoresistive sensor during
the test to avoid the unstability of the resistance signals, thus Af was
the area of the glass slide [8]. The sensitivity was defined as: S ¼ DR/
R0/DP, where DR was the original resistance (R0) minus the
measured resistance (R) and the DP was the applied pressure.
Notes
The authors declare no competing financial interest.
Acknowledgments
This work was financially supported by the National Natural
Science Foundation of China (Grant No. 51573053), the Science and
Technology Planning Project of Guangdong Province (Grant No.
2014A010105022) and the Students Research Funding of Guang-
dong Province (Grant No. pdjh2016b0047).
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.carbon.2016.11.027.
References
[1] J. Park, Y. Lee, M. Ha, S. Cho, H. Ko, Micro/Nanostructured surfaces for self-
powered and multifunctional electronic skins, J. Mater. Chem. B 4 (2016)
2999e3018.
[2] Y. Zang, F. Zhang, C. Di, D. Zhu, Advances of flexible pressure sensors toward
artificial intelligence and health care applications, Mater. Horiz. 2 (2015)
140e156.
[3] C. Pang, G.Y. Lee, T. Kim, S.M. Kim, H.N. Kim, S.H. Ahn, et al., A flexible and
highly sensitive strain-gauge sensor using reversible interlocking of nano-
fibres, Nat. Mater. 11 (2012) 795e801.
[4] M. Ha, S. Lim, J. Park, D.S. Um, Y. Lee, H. Ko, Bioinspired interlocked and hi-
erarchical design of ZnO nanowire arrays for static and dynamic pressure-
sensitive electronic skins, Adv. Funct. Mater. 25 (2015) 2841e2849.
[5] J. Park, Y. Lee, J. Hong, Y. Lee, M. Ha, Y. Jung, et al., Tactile-direction-sensitive
and stretchable electronic skins based on human-skin-inspired interlocked
microstructures, ACS Nano 8 (2014) 12020e12029.
[6] J. Park, Y. Lee, J. Hong, M. Ha, Y.D. Jung, H. Lim, et al., Giant tunneling pie-
zoresistance of composite elastomers with interlocked microdome arrays for
ultrasensitive and multimodal electronic skins, ACS Nano 8 (2014)
4689e4697.
[7] Y. Wei, S. Chen, X. Yuan, P. Wang, L. Liu, Multiscale wrinkled microstructures
for piezoresistive fibers, Adv. Func. Mater. 26 (2016) 5078e5085.
[8] X. Wang, Y. Gu, Z. Xiong, Z. Cui, T. Zhang, Silk-molded flexible, ultrasensitive,
and highly stable electronic skin for monitoring human physiological signals,
Adv. Mater. 26 (2014) 1336e1342.
[9] Y. Shu, H. Tian, Y. Yang, C. Li, Y. Cui, W. Mi, et al., Surface-modified piezor-
esistive nanocomposite flexible pressure sensors with high sensitivity and
wide linearity, Nanoscale 7 (2015) 8636e8644.
[10] B. Su, S. Gong, Z. Ma, L.W. Yap, W. Cheng, Mimosa-inspired Design of A
Please cite this article in press as: Y. Wei, et al., Flexible piezoresistive sensors based on “dynamic bridging effect” of silver nanowires toward
graphene, Carbon (2016), http://dx.doi.org/10.1016/j.carbon.2016.11.027
Flexible pressure sensor with touch sensitivity, Small 11 (2015) 1886e1891.
[11] T. Kim, J. Park, J. Sohn, D. Cho, S. Jeon, Bioinspired highly stretchable, and
conductive dry adhesives based on 1D
2D hybrid carbon nanocomposites for
all-in-one ECG electrodes, ACS Nano 10 (2016) 4770e4778.
[12] Y. Wei, S. Chen, Y. Lin, Z. Yang, L. Liu, CueAg coreeshell nanowires for elec-
tronic Skin with A Petal molded microstructure, J. Mater. Chem. C 3 (2015)
9594e9602.
[13] B. Zhu, Z. Niu, H. Wang, W.R. Leow, H. Wang, Y. Li, et al., Microstructured
graphene arrays for highly sensitive flexible tactile sensors, Small 10 (2014)
3625e3631.
[14] D.J. Lipomi, M. Vosgueritchian, B.C.K. Tee, S.L. Hellstrom, J.A. Lee, C.H. Fox, et
al., Skin-like pressure and strain sensors based on transparent elastic films of
carbon nanotubes, Nat. Nanotechnol. 6 (2011) 788e792.
[15] S.Y. Kim, S. Park, H.W. Park, D.H. Park, Y. Jeong, D.H. Kim, Highly sensitive and
multimodal all-carbon skin sensors capable of simultaneously detecting
tactile and biological stimuli, Adv. Mater. 27 (2015) 4178e4185.
[16] J. Lee, H. Kwon, J. Seo, S. Shin, J.H. Koo, C. Pang, et al., Conductive fiber-based
ultrasensitive textile pressure sensor for wearable electronics, Adv. Mater. 27
(2015) 2433e2439.
[17] C. Wu, X. Wang, L. Lin, H. Guo, Z.L. Wang, Paper-based triboelectric nano-
generators made of stretchable interlocking kirigami patterns, ACS Nano 10
(2016) 4652e4659.
[18] K.Y. Lee, M.K. Gupta, S.W. Kim, Transparent flexible stretchable piezoelectric
and triboelectric nanogenerators for powering portable electronics, Nano
Energy 14 (2015) 139e160.
[19] J.W. Park, J. Jang, Fabrication of graphene/free-standing nanofibrillar PEDOT/
P(VDF-HFP) hybrid device for wearable and sensitive electronic skin appli-
cation, Carbon 87 (2015) 275e281.
[20] X. Wu, Y. Ma, G. Zhang, Y. Chu, J. Du, Y. Zhang, et al., Thermally stable,
biocompatible, and flexible organic field-effect transistors and their applica-
tion in temperature sensing arrays for artificial skin, Adv. Funct. Mater. 25
(2015) 2138e2146.
[21] S. Ryu, P. Lee, J.B. Chou, R. Xu, R. Zhao, A.J. Hart, et al., Extremely elastic
wearable carbon nanotube fiber strain sensor for monitoring of human mo-
tion, ACS Nano 9 (2015) 5929e5936.
[22] L. Qiu, M.B. Coskun, Y. Tang, J.Z. Liu, T. Alan, J. Ding, et al., Ultrafast dynamic
piezoresistive response of graphene-based cellular elastomers, Adv. Mater. 28
(2016) 194e200.
[23] D. Du, P. Li, J. Ouyang, Graphene coated nonwoven fabrics as wearable sen-
sors, J. Mater. Chem. C 4 (2016) 3224e3230.
[24] Y. Cheng, R. Wang, J. Sun, L.A. Gao, Stretchable and highly sensitive graphene-
based fiber for sensing tensile strain, bending, and torsion, Adv. Mater. 27
(2015) 7365e7371.
[25] K.K. Kim, S. Hong, H.M. Cho, J. Lee, Y.D. Suh, J. Ham, et al., Highly sensitive and
stretchable multidimensional strain sensor with prestrained anisotropic metal
nanowire percolation networks, Nano Lett. 15 (2015) 5240e5247.
[26] J. Ge, L. Sun, F.R. Zhang, Y. Zhang, L.A. Shi, H.Y. Zhao, H.W. Zhu, H.L. Jiang,
S.H. Yu, A stretchable electronic fabric artificial skin with pressure-, lateral
strain-, and flexion-sensitive properties, Adv. Mater. 28 (2016) 722e728.
[27] X. Liao, Q. Liao, Z. Zhang, X. Yan, Q. Liang, Q. Wang, et al., A highly stretchable
ZnO@Fiber-based multifunctional nanosensor for strain/temperature/UV
detection, Adv. Funct. Mater. 26 (2016) 3074e3081.
[28] K. Ke, P. Po€ tschke, N. Wiegand, B. Krause, B. Voit, Tuning the network struc-
ture in poly(vinylidene fluoride)/carbon nanotube nanocomposites using
carbon black: toward improvements of conductivity and piezoresistive
sensitivity, ACS Appl. Mater. Interfaces 8 (2016) 14190e14199.
[29] J.H. Kong, N.S. Jang, S.H. Kim, J.M. Kim, Simple and rapid micropatterning of
conductive carbon composites and its application to elastic strain sensors,
Carbon 77 (2014) 199e207.
[30] H. Park, Y.R. Jeong, J. Yun, S.Y. Hong, S. Jin, S.J. Lee, et al., Stretchable array of
highly sensitive pressure sensors consisting of polyaniline nanofibers and Au-
Coated polydimethylsiloxane micropillars, ACS Nano 9 (2015) 9974e9985.
[31] Q. Shao, Z. Niu, M. Hirtz, L. Jiang, Y. Liu, Z. Wang, et al., High-performance and
tailorable pressure sensor based on ultrathin conductive polymer film, Small
10 (2014) 1466e1472.
[32] K.W. Clark, X.G. Zhang, I.V. Vlassiouk, G. He, R.M. Feenstra, A.P. Li, Spatially
resolved mapping of electrical conductivity across individual domain (grain)
boundaries in graphene, ACS Nano 7 (2013) 7956e7966.
[33] Y. Wei, S. Chen, Y. Lin, X. Yuan, L. Liu, Silver nanowires coated on cotton for
flexible pressure sensors, J. Mater. Chem. C 4 (2016) 935e943.
[34] Z. Lou, S. Chen, L. Wang, K. Jiang, G. Shen, An ultra-sensitive and rapid
response speed graphene pressure sensors for electronic skin and health
monitoring, Nano Energy 23 (2016) 7e14.
[35] C. Jeong, P. Nair, M. Khan, M. Lundstrom, M.A. Alam, Prospects for nanowire-
doped polycrystalline graphene films for ultratransparent, highly conductive
electrodes, Nano Lett. 11 (2011) 5020e5025.
[36] R. Chen, S.R. Das, C. Jeong, M.R. Khan, D.B. Janes, M.A. Alam, Co-percolating
graphene-wrapped silver nanowire network for high performance, highly
stable, transparent conducting electrodes, Adv. Funct. Mater. 23 (2013)
5150e5158.
[37] H.W. Tien, S.T. Hsiao, W.H. Liao, Y.H. Yu, F.C. Lin, Y.S. Wang, et al., Using self-
assembly to prepare a graphene-silver nanowire hybrid film that is trans-
parent and electrically conductive, Carbon 58 (2013) 198e207.
[38] O.V. Yazyev, Y.P. Chen, Polycrystalline graphene and other two-dimensional
materials, Nat. Nanotechnol. 9 (2014) 755e767.
 Y. Wei et al. / Carbon xxx (2016) 1e9 9

[39] A. Venugopal, L. Colombo, E.M. Vogel, Contact resistance in few and multilayer
graphene devices, Appl. Phys. Lett. 96 (2010) 013512.
[40] G. Giovannetti, P.A. Khomyakov, G. Brocks, V.M. Karpan, J.V.D. Brink, P.J. Kelly,
Doping graphene with metal contacts, Phys. Rev. Lett. 101 (2008) 026803.
[41] S. Liu, B. Weng, Z.R. Tang, Y.J. Xu, Constructing one-dimensional silver
nanowire doped reduced graphene oxide integrated with CdS nanowire
network hybrid structures toward artificial photosynthesis, Nanoscale 7
(2015) 861e866.
[42] H.O. Choi, D.W. Kim, S.J. Kim, S.B. Yang, H.T. Jung, Role of 1D metallic nano-
wires in polydomain graphene for highly transparent conducting films, Adv.
Mater. 26 (2014) 4575e4581.
[43] B.T. Liu, H.L. Kuo, Graphene/Silver nanowire sandwich structures for trans-
parent conductive films, Carbon 63 (2013) 390e396.
[44] Y.R. Jeong, H. Park, S.W. Jin, S.Y. Hong, S.S. Lee, J.S. Ha, Highly stretchable and
sensitive strain sensors using fragmentized graphene foam, Adv. Funct. Mater.
25 (2015) 4228e4236.
[45] Y. Lin, S. Liu, L. Liu, A new approach to construct three dimensional segregated
graphene structures in rubber composites for enhanced conductive, me-
chanical and barrier properties, J. Mater. Chem. C 4 (2016) 2353e2358.
[46] Y. Wei, S. Chen, F. Li, Y. Lin, Y. Zhang, L. Liu, Highly stable and sensitive paper-
based bending sensor using silver nanowires/layered double hydroxides hy-
brids, ACS Appl. Mater. Interfaces 7 (2015) 14182e14191.
[47] C. Yang, H. Gu, W. Lin, M.M. Yuen, C.P. Wong, M. Xiong, et al., Silver nano-
wires: from scalable synthesis to recyclable foldable electronics, Adv. Mater.
23 (2011) 3052e3056.

Please cite this article in press as: Y. Wei, et al., Flexible piezoresistive sensors based on “dynamic bridging effect” of silver nanowires toward
graphene, Carbon (2016), http://dx.doi.org/10.1016/j.carbon.2016.11.027