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Highly Stretchable Strain Sensors Based on


Graphene/Silver Nanoparticles Synergic
Conductive Networks and...

Article in Journal of Materials Chemistry C April 2016


DOI: 10.1039/C6TC00300A

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A highly stretchable strain sensor based on a


graphene/silver nanoparticle synergic conductive
Cite this: J. Mater. Chem. C, 2016,
4, 4304 network and a sandwich structure
Song Chen, Yong Wei, Xue Yuan, Yong Lin and Lan Liu*

Strain sensors with superb stretchability are highly desirable for applications in wearable devices. Here
we report a simple method via immersion-swelling followed by in situ reduction to fabricate a highly
stretchable strain sensor with a graphene/AgNPs synergic conductive network and a sandwich structure
(i.e., one insulating layer sandwiched between two conductive layers). In the strain sensor, AgNPs were
in situ formed without adding any other organic stabilizer, and graphene nanosheets acted as a
conductive bridge between them, ensuring the wearable sensor excellent initial electrical conductivity
(s E 1.4  105 S m1). During stretching, the pure graphene/TPU insulating layer of the sandwich
Received 21st January 2016, structure maintained the high stretchability, and the graphene located between the cracks of AgNPs
Accepted 1st April 2016 resulted in the connection of conductivity networks under high strain (1000% maximum strain). What is
DOI: 10.1039/c6tc00300a more, the low detection limit (0.5%), high gauge factor (7 at 50% strain, 476 at 500% strain) and high
working stability (more than 1000 cycles at 50% strain) of the strain sensor enable it to meet the needs
www.rsc.org/MaterialsC for numerous applications in wearable devices.

1. Introduction conductive fillers gained wide attention because of their large


aspect ratios and conducting pathways that can bridge cracked
With the development of stretchable and flexible sensors, regions while being subjected to large strains.32,33 Carbon
conductors with eective response and conductivity under nanotubes or metal nanowires are often used by either embed-
large strains become quite critical for many new applications, ding directly in the elastomeric material or depositing on the
such as stretchable displays,1,2 wearable electronics,35 human- surface of stretchable substrates. There also exists a shortcoming
motion sensors610 and artificial muscles.11 Traditional piezo- to this strategy, where incorporation of high concentrations of
resistive sensors1214 are often used in wearable devices because conductive fillers such as CNTs into the polymer matrix increases
of their high sensitivity to external forces. However, the above- the stiffness and decreases the stretchability of the resultant
mentioned traditional strain sensors are not suitable for these composite.34 Therefore, it is very important to fabricate reason-
new applications because they can withstand only very limited able conductive networks in a facile and safe way with high
strain (o5%) before fracture. To overcome this hurdle, one sensitivity and high mechanical stretchability at the same time.
approach is to design wave-like or spring-shaped structures.1518 To obtain strain sensors with high sensitivity and stretch-
However, structuring metal strips with wavy or spring geometries ability used as wearable devices, hybrids of conductive silver
involve time-consuming, sequential lithography and etching nanoparticles (AgNPs) and 1D CNTs35 or silver nanowires
processes that are not easily scalable.1921 Additionally, very low (AgNWs)36 were adopted as conductive fillers. In the strain
sensitivities or gauge factors (GF r 1) limit their applications sensors 1D conductive fillers tend to bridge the disconnected
as wearable devices.22 Another route takes advantage of the networks of AgNPs under strain, maintaining the conductors
structure of multi-dimensional conductive fillers, such as metal with both high stretchability and sensitivity. To the best of our
nanoparticles,23,24 graphene,2528 carbon nanotubes (CNTs),9,22 knowledge, 2D nanosheets have more eective contact area
and silver nanowires.2931 In this route, one-dimensional (1D) with AgNPs in comparison with 1D nanofillers. Graphene (GE),
a two-dimensional (2D) hexagonally structured material, con-
sisting of sp2-bonded carbon atoms, is an ideal candidate for
College of Materials Science and Engineering, Key Lab of Guangdong Province for
strain sensors and has been used extensively because of its
High Property and Functional Polymer Materials, South China University of
Technology, Guangzhou 510641, P. R. China. E-mail: psliulan@scut.edu.cn
outstanding electrical and mechanical properties. Appropriate
Electronic supplementary information (ESI) available. See DOI: 10.1039/ strategies such as creating buckled or spring structures37,38 or
c6tc00300a developing three dimensional (3D) micro-wrinkled graphene39

4304 | J. Mater. Chem. C, 2016, 4, 4304--4311 This journal is The Royal Society of Chemistry 2016
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for originally rigid materials have been widely used for strain GE/TPU strip was removed from the Ag precursor solution and
sensors. These strategies can be employed to improve the dried at room temperature for 5 min. After that, the swollen
stretchability of graphene to 3050%, which unfortunately are GE/TPU strip was put on a steel wire gauze in a PTFE tank,
still unsatisfying for efficient human-motion detection where about 2 mL of N2H4H2O solution (50 wt%) was dropped into
the maximum strain exceeds 50%. the PTFE tank to reduce the swollen GE/TPU strip at 70 1C for
In this article, we describe a simple immersion-swelling 15 min. Finally, the residual reducing agent was rinsed out
followed by an in situ reduction method to develop a TPU strain several times using DI water and ethanol, and the strip was
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sensor composed of a GE/AgNP synergic conductive network dried on a hot plate for 15 min at 70 1C. Since hydrazine hydrate
and a sandwich structure. In the strain sensors since AgNPs is very dangerous, the material must be handled very carefully.
were formed in situ without adding other stabilizers they
showed high original conductivity (s E 1.4  105 S m1) and 2.4 Fabrication of the GE/AgNPs/TPU strain sensor
due to the pure graphene/TPU insulating layer of the sandwich The GE/AgNPs/TPU strain sensor was fabricated by simply mounting
structure and the graphene located between the cracks of two tinned electrodes on the two ends of the GE/AgNPs/TPU strip
AgNPs under strain, the strain sensors had a high stretchability using conductive silver paste.
of 1000%. Additionally, the strain sensors exhibited a low
detection limit (0.5%), high gauge factor (7 at 50% strain, 2.5 Integration of the GE/AgNPs/TPU strain sensor with the
476 at 500% strain) and high working stability (more than PDMS film
1000 cycles at 50% stretching). To demonstrate the capability of The GE/AgNPs/TPU strain sensor was integrated into a PDMS
the strain sensors, wearable applications were fabricated and film for sensing bending. The PDMS mixture (a 10 : 1 mixture of
their performances were characterized. the PDMS prepolymer and the curing agent, Sylgrad-184, Dow
Corning) was stirred for 2 min and dropped into a mould
(60 mm  10 mm  3 mm), the PDMS was cured at 90 1C for
2. Experimental 2 h and carefully peeled o to get a PDMS film (60 mm 
2.1 Materials 10 mm  3 mm). Tinned wires (2 mm in diameter) were
Thermoplastic polyurethane (TPU, polyester-based, E270) was connected to the two ends of the GE/AgNPs/TPU strip as
provided by Shandong Miracll Chemicals Co., Ltd. The TPU external electrodes with the help of conductive silver paste.
exhibited high elongation at break up to 1250%, and the stress Then the strip (40 mm in length) was put on to the PDMS film
strain curve of pure TPU is shown in Fig. S1 (ESI). Graphite and the two ends were fixed by adhesive tape.
powder was purchased from Shanghai Colloidal Co. Ltd. Silver
trifluoroacetate (AgCF3COO, 98%) was bought from J&K tech- 2.6 Characterization
nology Co., Ltd. (Beijing, China). N-Methylpyrrolidone (NMP), X-ray photoelectron spectroscopy (XPS) analysis was carried out
hydrazine hydrate (N2H4H2O), and anhydrous ethanol were using a Kratos Axis Ultra DLD electron spectrometer (Kratos Co.
obtained from Tianjin DaMao Chemical Reagents Factory. Ltd, Manchester, England). SEM and TEM images were taken
Toluene was bought from Guangzhou Chemical Reagents using a NanoSEM 430 instrument (FEI Co. Ltd, Hillsboro,
Factory. All the chemicals were commercially available analytical America) and a JEOL JEM-2100HR instrument (EDAX Inc.,
grade reagents and were used without further purification. Mahwah, America), respectively. The mechanical properties
were measured using a U-CAN UT-2060 instrument at room
2.2 Preparation of the composite GE/TPU strip temperature with a tensile rate of 30 cm min1. The stretching
Graphene/NMP suspension (0.2 mg mL1) was obtained from of the samples, progressive cycling experiments, recycle experi-
exfoliation of natural graphite powder based on Colemans ments and LED test were conducted at room temperature using
liquid exfoliation method.40,41 After that, dierent amounts of a digital force gauge (CK-50HB, Fuzhou Aipu Instruments Co.,
TPU were dissolved in graphene/NMP suspension at 50 1C Ltd, as shown in Fig. 4e and f) with a constant strain rate of
using a magnetic stirring mixer, the solution was then homo- 1 mm s1. Simultaneously, the resistance of the samples was
genized in an ultrasonic bath for 2 h. NMP was subsequently recorded using a TEGAM 1740 micro ohmmeter (data acquisition
removed by evaporation for 6 h at 120 1C. The resultant GE/TPU rate was 20 s1). Two copper sheets were attached tightly on the
film was peeled o from the hotplate after cooling down. The two ends of sample with clamps (as shown in Fig. 4e and f) for
GE/TPU strip was obtained by cutting the GE/TPU film into contacting the sample.
a long rectangle strip with the thickness, width, and length of
300 mm, 800 mm, and 5 cm, respectively.
3. Results and discussion
2.3 Fabrication of the GE/AgNPs/TPU strip with high 3.1 Fabrication of the GE/AgNPs/TPU strip with high
conductivity and stretchability conductivity and stretchability
The GE/TPU strip was immersed in 20 wt% AgCF3COO/toluene High quality graphene was prepared by a liquid exfoliation
solution (the solution was prepared by dissolving 400 mg of process in NMP. Fig. S2 (ESI) shows the TEM image of graphene,
AgCF3COO in 1.6 g of toluene) for 120 min. Next, the swollen and the nanosheets are approximately 400500 nm in size.

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By dissolving TPU in the graphene suspension and drying, the


GE/TPU strip is obtained. Intrinsically, the TPU molecular
chain shrinks and curls under natural conditions. When the
GE/TPU strip is immersed in toluene, the TPU swells and the
molecular chain extends greatly and becomes loose. Therefore,
Ag ions can be absorbed into the GE/TPU strip in a short time
and reduced into AgNPs in the hydrazine hydrate steam. Fig. S3a
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and b (ESI) present the typical change in GE/TPU strips before


and after swelling in toluene solution with a AgCF3COO mass
fraction of 20 wt%. It is clearly observed that the length of the
GE/TPU strip extends to 130% from 5 cm to 6.5 cm after swelling.
After AgCF3COO is reduced into AgNPs, the length of the strip
shortens from 6.5 cm to 5.3 cm and the color of the strip turns
from black to argent and to silver gray after removing AgNPs Fig. 2 Plot of the relative resistance change of strips fabricated with
variable amounts of graphene under increasing strain.
from the surface using 3 M tape (shown in Fig. S3c and d, ESI).
To explore the swelling process, the swelling ratio of the GE/TPU
strips was investigated by measuring the change in mass and lateral Fig. 2 shows the relative resistance change (R/R0, where R and
dimensions as a function of the swelling time and AgCF3COO R0 are the real-time and the original resistance, respectively) of
concentration. The swelling degree gradually approaches a the strips as a function of applied strain. As can be seen,
saturated value of 130133% in length when the swelling time the R/R0 of AgNPs-embedded TPU strips without graphene
is 60 minutes and the concentration of AgCF3COO is 13 wt% increases drastically to 1000 at 310% strain. In contrast, the
(Fig. 1a and b). However, the swelling ratio in mass reaches a GE/AgNPs/TPU strips do not lose their electrical conductivity
saturated value of 228% when swelling time is 90 minutes and significantly and their relative resistance increases to 1000 with
the AgCF3COO solution concentration is 19 wt%. Evidently, the strains at 410%, 470% and 365% corresponding to the gra-
swelling ratio in mass lags behind the swelling ratio in length, phene concentrations at 0.15, 0.5 and 1.0 wt%, respectively.
which is because Ag+ can interact with the secondary amino Moreover, the strips containing 0.25 wt% graphene show
group (NH) and the ester group (COO) on the TPU molecular the best performance in terms of resistance change under
chain, resulting in Ag+ absorbing into the strip after the swelling applied strain, the relative resistance is as low as 360 with
process was finished (Fig. 1c). The XPS spectra of AgCF3COO and 500% applied strain. This is attributed to the fact that excess
the swollen TPU strip reveal that the binding energies of Ag 3d5/2 graphene (40.25 wt%) tends to aggregate in highly viscous TPU
and 3d3/2 peaks shift from 367.8 eV and 373.7 eV to 363.8 eV and polymer solution due to the van der Waals interactions,42 the
374.2 eV (Fig. 1d) after swelling, demonstrating the interaction aggregated graphene would hinder the charge transfer between
between AgCF3COO and the TPU molecular chain (Fig. 1c). conductive fillers under strain, thereby increasing the R/R0
The GE/AgNPs/TPU strips with dierent amounts of gra- faster. The GE/AgNPs/TPU strip containing 0.25 wt% graphene
phene were characterized with regard to the applied strain. was chosen as the strain sensor and the bending sensor in the
later sections.
The good stretchability of the strips could be explained by
the structure of the GE/AgNPs/TPU strip. As shown in Fig. 3ac,
AgNPs are successfully synthesized inside and on the outside of
the GE/TPU strip, and most diameters of AgNPs are less than
100 nm (shown in Fig. 3c insert). The thickness of AgNPs in the
strips reaches 10 mm, which makes the GE/AgNPs/TPU strip to
obtain a sandwich structure (shown in Fig. 3a) containing two
conductive layers on the top and bottom and one insulating
layer in the middle. The two conductive layers containing
AgNPs and graphene ensure the GE/AgNPs/TPU strips high
initial conductivity (Fig. 3b insert, R = 2.490 O, s E 1.4 
105 S m1). In addition, it is well known that the addition of
rigid fillers (such as AgNPs and AgNWs) into the matrix could
lead to the increase in the stiffness of the composite,34 but in
Fig. 1 (a) Swelling ratio in length and mass of the GE/TPU strip with our work the insulating layer in the middle of the sandwich
dierent swelling times in AgCF3COO solution. (b) Swelling ratio in length structure precisely maintains the high flexibility and stretch-
and mass of the GE/TPU strip with dierent concentrations of AgCF3COO.
ability. Therefore, the sandwich structure of the GE/AgNPs/TPU
(c) Schematic illustration of the swelling process and the Ag+ absorption
process resulting from the interaction between Ag+ and the TPU mole-
strips ensures both initial conductivity and stretchability.
cular chain. (d) XPS spectra of Ag3d5/2 and 3d3/2 for AgCF3COO and the On the other hand, the graphene embedded GE/AgNPs/TPU
swollen TPU strip. strips present higher stretchability than the AgNPs/TPU strips

4306 | J. Mater. Chem. C, 2016, 4, 4304--4311 This journal is The Royal Society of Chemistry 2016
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graphene lose their conductivity. In contrast, the GE/AgNPs/TPU


strips can maintain high conductivity under high strain. This is
attributed to the reason that the addition of graphene can help
connect the networks between AgNPs to provide a synergic effect
in conductivity. Fig. 4d shows that graphene is located between
the cracks of AgNPs. Consequently, graphene and AgNPs can form
a synergic conductive network in the GE/AgNPs/TPU strips, when
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high strain is applied, the graphene and AgNP synergic conductive


network plays an important role inside the GE/AgNPs/TPU strips,
resulting in an enhancement of the electrical conductivities.
A series circuit was fabricated to test the enhancement of
conductivities under high stretchability by integrating a red
light emitting diode (LED) with the GE/AgNPs/TPU strip and
the operating voltage was 9 V. Fig. 4e and f show photographs
of the illuminated LED without strain and 1000% strain. As can
Fig. 3 (a and b) Cross-sectional SEM images of the GE/AgNPs/TPU strip be seen in the photographs, the LED can still work even under
with dierent magnifications, the insert in (b) shows the digital photograph 1000% strain, illustrating the high stretchability of the strip.
of the GE/AgNPs/TPU strip and resistance measurement. (c) Surface SEM
image of the GE/AgNPs/TPU strip, the insert shows the diameter distribu- 3.2 Performance of the GE/AgNPs/TPU strain sensor
tion of AgNPs.
The GE/AgNPs/TPU strip containing 0.25 wt% graphene was
chosen as the strain sensor in the later sections. Fig. 5a depicts
without graphene. This could be explained by that graphene the relative resistance variation of the strain sensor in a 50%
can act as a conductive bridge between the broken AgNP stretchingreleasing cycle, from the curve, it is obvious that the
networks under large stretchability. The comparison of the R/R0 of the strain sensor can return to 1.0 after a stretching
AgNPs/TPU strips (with and without graphene) is illustrated releasing cycle, so the strain sensor has superb elasticity and
in Fig. 4ad. The longitudinal regions inside the AgNPs/TPU resilience. To investigate the application of the strain sensors,
strips with and without graphene before (Fig. 4a and c) and the gauge factor (G = (R/R0)/(DL/L)) was adopted to measure the
after (Fig. 4b and d) stretching are investigated. Once the data for our strain sensor under variable strains. Fig. 5b
concentration of AgNPs is enough to meet the percolation illustrates the gauge factor (semilog plot) of the strain sensors
threshold, AgNPs in the strips can connect with each other, as a function of strain. The exponential change in the gauge
forming long-range connectivity thereby exhibiting electrical con- factor at higher strain levels is attributed to the change in
ductivity by the electron hopping36,43 (shown in Fig. 4a and c). GE/AgNPs synergetic networks at higher levels of elongation
After a higher strain is applied, the longitudinal distance between (gauge factor of 7 at 50% strain to a gauge factor of 476 at
AgNPs is too far and cracks form between the AgNP networks 500% strain). Compared with other reported stretchable strain
(shown in Fig. 4b and d). So the AgNPs/TPU strips without sensors, our strain sensor has both high stretchability and high

Fig. 4 (a and b) SEM and the corresponding schematic images of AgNPs inside the AgNPs/TPU strips without graphene before (a) and after (b) stretching
(100% strain). (c and d) SEM and the corresponding schematic images of AgNPs and graphene inside the GE/AgNPs/TPU strips with graphene before (c)
and after (d) stretching (100% strain). (e and f) Digital photographs showing that the 0.25 wt% graphene embedded GE/AgNPs/TPU strip is conductive
after applying 1000% strain.

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Fig. 5 (a) Changes in relative resistance under a 50% strain stretchingreleasing cycle. (b) Gauge factor of the 0.25 wt% graphene embedded GE/AgNPs/
TPU strain sensor under variable strain. (c) Relative resistance variation under gradually increasing step strain from 0.5% to 8% strain, the inset shows the
response signal input step strain of 0.5%. (d) Dynamic stretch-and-release cycle response of the sensor for various strains 25300%. Inset is the closeup
of the stretch-and-release cycles for 25%, 50%, 100% strains. (e) Change in the resistance of 0.25 wt% graphene embedded GE/AgNPs/TPU strip with no
strain and 50% applied strain during 1000 stretch and release cycles. Insets: Closeup of the selected areas.

gauge factor (see Table S1, ESI), which makes it an ideal the chord length (c) has a relationship with curvature radius (r)
candidate for wearable devices. as: c = 2r  sin(l/2r), where l is the arc length of the sensor in the
The detection limit of the strain sensor was determined by bending state. The relative resistance of the bending sensor was
applying strain in gradually increasing steps (Fig. 5c). Benefiting modulated by varying the chord length. Remarkably, the relative
from the high sensitivity in a small strain range, the detection resistance of the bending sensor depends on the dierent
limit can reach 0.5%, and the output signal is highly reprodu- bending directions (Fig. 6a and d). If the PDMS was bent upward
cible at 0.5% strain (inset in Fig. 5c). To study the dynamic as Fig. 6a shows, the relative resistance increased with the chord
performance of the device under larger strain, the strain sensors length. But if the PDMS was buckled downward as Fig. 5d shows,
were subjected to dierent levels of larger strain while their the relative resistance decreased with the chord length. The
resistance was continuously measured. Fig. 5d shows the results concrete change in resistance is illustrated in Fig. 6b and e and
of five stretchingreleasing cycles at 25%, 50%, 100%, 200% and their dierence is compared in Fig. 6g. What is more, in both
300% strain, respectively, showing the outstanding stability and bending directions the strips have good mechanical stability and
elasticity under different strains. reliability under bending or buckling after they were bent upward
In addition to high sensitivity and wide sensing range, the or buckled downward for eight cycles and the resistance change in
performance stability of the sensor was further evaluated by real time is recorded in Fig. 6c and f respectively.
periodic stretchingreleasing cycles (50% applied strain). After It is clearly seen that the resistance of the GE/AgNPs/TPU
1000 cycles, the normalized resistance increase is still less than sensor depends on the contact conditions of AgNPs and graphene
5% (at the lowest resistance) and demonstrates high repeat- networks in the GE/AgNPs/TPU strip. Due to the sandwich
ability, stability and durability. structure of the strip, the resistance of the bending sensor
under natural conditions can be illustrated as
3.3 Performance of the GE/AgNPs/TPU bending sensor
R0  R0
Because the GE/AgNPs/TPU strip has a sandwich structure R1 1=2R0
R0 R0
(graphene and AgNPs synergic conductive networks on the
upper and bottom conductive layers, and pure GE/TPU in the where R0 is the resistance of each graphene/AgNPs conductive
middle insulating layer), the networks of two conductive layers layer. When the PDMS is bent upward (Fig. 6a), the GE/AgNPs/
present dierent deformation under bending, so it can also be TPU strip has the same chord length (c) as PDMS, but their radii
used as a bending sensor. To detect the performance of bending, of curvature (r) are dierent. Using the relationship, c = 2r 
we fixed the GE/AgNPs/TPU strip on a PDMS film. The relative sin(l/2r), we obtain the arc length L = 2r  arc sin(c/2r), the
resistance values were measured as a function of chord length of length of the GE/AgNPs/TPU strip will also change during
the bending sensor (Fig. 6b and e). It is generally accepted that bending. The strain Dl of the strip outside the PDMS film can

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Fig. 6 (a) Photographs of the bending sensor. (b) Resistance variation of the bending sensor in bending upward directions. Inset: the definition of the
chord length in a schematic structure. (c) Resistance variation during eight cycles of bending (chord length from 40 mm to 25 mm). (d) Photographs of
the buckling downward of PDMS. (e) Resistance variation of the bending sensor in buckling downward directions. Inset: the definition of the chord length
in a schematic structure. (f) Resistance variation during eight cycles of buckling downward (chord length from 40 mm to 25 mm). (g) A comparison of
response of the sensor to applied bending and buckling. (h) Schematic illustration of the sensing mechanism and the accompanying circuit variations
under bending. (i) Schematic illustration of the sensing mechanism under buckling and accompanying circuit variations.

be expressed as: DL = h/2r,44 where h is the thickness (about sensor was attached to a latex glove to detect the joint bending
3.3 mm) of the bending sensor, since the strip is attached outside motion as shown in Fig. 7. The index finger under test was kept
the PDMS, DL 4 0 (presented in Fig. 6h). The GE/AgNPs/TPU strip straight naturally, then the index finger had a moderate curva-
is stretched in this condition, thus the relative resistance of the ture and the strain sensor had a strain as presented in Fig. 7a,
bending sensor increases. leading to a relative increase in resistance, the mechanism of
In contrast, when the PDMS film is buckled downward as this process is the same as the PDMS in the bending sensor
illustrated in Fig. 6d, the strip bends independent of PDMS. bending upward. Next, the sensor relaxed after the index finger
The thickness h = 300 mm, so the upper layer is tensed, and was straightened, and then the strain decreased, accompanied
the bottom layer is compressed as illustrated in Fig. 6i. The by a decrease in resistance to the original state (Fig. 7b). The
resistance of the bending sensor changes to tests were also adopted to detect the other four fingers as
R0 DR1  R0  DR2 shown in Fig. 7cf, every time the text is repeated four cycles.
R2 To demonstrate the sensing capability, the strain sensor was
R0 DR1 R0  DR2
also attached to a volunteers neck to monitor the voice vibra-
where DR1 and DR2 are the changes in the upper layer and the tions (Fig. 8a), and the relative resistance change is presented
bottom layer respectively. Since graphene is located between in Fig. 8b and c. It is clearly observed that there are two peaks in
the cracks of AgNPs, DR1 { DR2. Thus the relative resistance of Fig. 8b when the volunteer says a disyllabic Hello. After the
the bending sensor decreases. volunteer says a short sentence Hi, how are you, four peaks
are observed in Fig. 8c, it is because there are four main
3.4 Applications in wearable devices syllables in this sentence. The result shows that the strain
Owing to its high sensitivity and low detection limit, our strain sensor has superb distinguishing capability for voice vibra-
sensor can be used in wearable devices. At first, the strain tions. Every word and sentence were spoken and the resistance

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Fig. 7 (a) Photographs showing the strain sensor attached to a latex glove for recording the movements of the index finger. (bf) The results of motion
detection of the index finger (b) and the other four fingers (cf).

networks and a sandwich structure. When 0.25 wt% graphene and


AgNPs were embedded in the GE/AgNPs/TPU strip, the strip
exhibits superior initial conductivity of 1.4  105 S m1, high
stretchability (1000%), low detection limit (0.5%), high gauge
factor (7 at 50% strain, 476 at 500% strain) and high working
stability (more than 1000 cycles at 50% stretching). The high
stability and high stretchability are attributed to the fact that the
strip has a sandwich structure and graphene can act as a bridge
between the disconnected networks of AgNPs generated by
stretching. Critically, the resistance strongly depends on the
strain allowing the composite to function as a wearable device.
It is simple to operate and it has been developed to monitor the
human motions and shows good repeatability and stability.

Fig. 8 (a) Digital photograph of the strain sensor attached to the human
neck to monitor the muscle motion during speech; (b and c) the relative Acknowledgements
resistancetime curve for the strain sensor in response to different voices
saying Hello and Hi, how are you, respectively. This work was financially supported by the National Natural
Science Foundation of China (Grant No. 51573053) and the
Science and Technology Planning Project of Guangdong Province
changes were recorded three times to study the repeatability of (Grant No. 2014A010105022).
the strain sensor in monitoring voice, and it was observed that
similar peaks are obtained when the volunteer says the same
word or sentence. All the results reveal that the strain sensor in
this study exhibits good repeatability, stability, and responsive-
Notes and references
ness, and could meet the needs of innumerous applications in 1 T. Sekitani, H. Nakajima, H. Maeda, T. Fukushima, T. Aida,
wearable devices. K. Hata and T. Someya, Nat. Mater., 2009, 8, 494499.
2 Z. Yu, X. Niu, Z. Liu and Q. Pei, Adv. Mater., 2011, 23,
4. Conclusion 39893994.
3 S. Yao and Y. Zhu, Nanoscale, 2014, 6, 23452352.
In summary, this work presents a very simple immersionswelling 4 R. Matsuzaki and K. Tabayashi, Adv. Funct. Mater., 2015, 25,
followed by an in situ reduction method to fabricate a highly 38063813.
stretchable strain sensor with graphene/AgNPs synergic conductive 5 G. Huang, H. Xiao and S. Fu, Sci. Rep., 2015, 5, 1397113979.

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6 F. Yi, L. Lin, S. Niu, P. Yang, Z. Wang, J. Chen, Y. Zhou, Y. Zi, 24 M. Park, J. Im, M. Shin, Y. Min, J. Park, H. Cho, S. Park,
J. Wang, Q. Liao, Y. Zhang and Z. Wang, Adv. Funct. Mater., M. Shim, S. Jeon, D. Chung, J. Bae, J. Park, U. Jeong and
2015, 25, 36883696. K. Kim, Nat. Nanotechnol., 2012, 7, 803809.
7 Y. Wei, S. Chen, Y. Lin, X. Yuan and L. Liu, J. Mater. Chem. 25 C. Yan, J. Wang and P. Lee, ACS Nano, 2015, 9, 21302137.
C, 2016, 4, 935943. 26 C. Yan, J. Wang, W. Kang, M. Cui, X. Wang, C. Foo, K. Chee
8 P. Yang, L. Lin, F. Yi, X. Li, K. Pradel, Y. Zi, C. Wu, J. He, and P. Lee, Adv. Mater., 2014, 26, 20222027.
Y. Zhang and Z. Wang, Adv. Mater., 2015, 27, 38173824. 27 Y. Wang, L. Wang, T. Yang, X. Li, X. Zang, M. Zhu, K. Wang,
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9 S. Ryu, P. Lee, J. Chou, R. Xu, R. Zhao, A. Hart and S. Kim, D. Wu and H. Zhu, Adv. Funct. Mater., 2014, 24, 46664670.
ACS Nano, 2015, 9, 59295936. 28 H. Tian, Y. Shu, Y. Cui, W. Mi, Y. Yang, D. Xie and T. Ren,
10 C. Boland, U. Khan, C. Backes, A. ONeill, J. McCauley, Nanoscale, 2014, 6, 699705.
S. Duane, R. Shanker, Y. Liu, I. Jurewicz, A. Dalton and 29 M. Amjadi, A. Pichitpajongkit, S. Lee, S. Ryu and I. Park,
J. N. Coleman, ACS Nano, 2014, 8, 88198830. ACS Nano, 2014, 8, 51545163.
11 Z. F. Liu, S. Fang, F. A. Moura, J. N. Ding, N. Jiang, J. Di, 30 J. Pyo, B. Kim, H. Park, T. Kim, C. Koo, J. Lee, J. Son, S. Lee
M. Zhang, X. Lepro, D. S. Galvao, C. S. Haines, N. Y. Yuan, and J. Park, Nanoscale, 2015, 7, 1643416441.
S. G. Yin, D. W. Lee, R. Wang, H. Y. Wang, W. Lv, C. Dong, 31 Y. Wei, S. Chen, F. Li, Y. Lin, Y. Zhang and L. Liu, ACS Appl.
R. C. Zhang, M. J. Chen, Q. Yin, Y. T. Chong, R. Zhang, Mater. Interfaces, 2015, 7, 1418214191.
X. Wang, M. D. Lima, R. Robles, D. Qian, H. Lu and 32 T. Sekitani, Y. Noguchi, K. Hata, T. Fukushima, T. Aida and
R. H. Baughman, Science, 2015, 349, 400404. T. Somey, Science, 2008, 321, 14681472.
12 C. Pang, G. Lee, T. Kim, S. Kim, H. Kim, S. Ahn and K. Suh, 33 K. Chun, Y. Oh, J. Rho, J. Ahn, Y. Kim, H. Choi and S. Chun,
Nat. Mater., 2012, 11, 795801. Nat. Nanotechnol., 2010, 5, 853857.
13 Y. Wei, S. Chen, Y. Lin, Z. Yang and L. Liu, J. Mater. Chem. C, 34 H. Ki, J. Jang, Y. Jo, D. Kim, S. Chee, B. Oh, C. Song, S. Lee,
2015, 3, 95949602. S. Choi, Y. Choi, S. Jeong and M. Ham, ACS Macro Lett.,
14 S. Gong, W. Schwalb, Y. Wang, Y. Chen, Y. Tang, J. Si, 2015, 4, 769773.
B. Shirinzadeh and W. Cheng, Nat. Commun., 2014, 5, 3132. 35 R. Rahimi, M. Ochoa, W. Yu and B. Ziaie, ACS Appl. Mater.
15 Y. Yu, S. Luo, L. Sun, Y. Wu, K. Jiang, Q. Li, J. Wang and Interfaces, 2015, 7, 44634470.
S. Fan, Nanoscale, 2015, 7, 1017810185. 36 S. Lee, S. Shin, S. Lee, J. Seo, J. Lee, S. Son, H. Cho, H. Algadi,
16 D. Qi, Z. Liu, Y. Liu, W. Leow, B. Zhu, H. Yang, J. Yu, S. Al-Sayari, D. Kim and T. Lee, Adv. Funct. Mater., 2015, 25,
W. Wang, H. Wang, S. Yin and X. Chen, Adv. Mater., 2015, 31143121.
27, 55595566. 37 Y. Wang, R. Yang, Z. Shi, L. Zhang, D. Shi, E. Wang and
17 Y. Shang, X. He, Y. Li, L. Zhang, Z. Li, C. Ji, E. Shi, P. Li, G. Zhang, ACS Nano, 2011, 5, 36453650.
K. Zhu, Q. Peng, C. Wang, X. Zhang, R. Wang, J. Wei, 38 W. Yuan, Q. Zhou, Y. Li and G. Shi, Nanoscale, 2015, 7,
K. Wang, H. Zhu, D. Wu and A. Cao, Adv. Mater., 2012, 24, 1636116365.
28962900. 39 C. Feng, Z. Yi, L. Dumee, C. Garvey, F. She, B. Lin, S. Lucas,
18 Y. Cheng, R. Wang, J. Sun and L. Gao, ACS Nano, 2015, 9, J. Schutz, W. Gao, Z. Peng and L. Kong, Carbon, 2015, 93,
38873895. 878886.
19 X. Wang, H. Hu, Y. Shen, X. Zhou and Z. Zheng, Adv. Mater., 40 Y. Hernandez, V. Nicolosi, M. Lotya, F. M. Blighe, Z. Sun,
2011, 23, 30903094. S. De, I. T. McGovern, B. Holland, M. Byrne, Y. GunKo,
20 D. Kim, W. Choi, J. Ahn, H. Kim, J. Song, Y. Huang, Z. Liu, J. Boland, P. Niraj, G. Duesberg, S. Krishnamurthy,
C. Lu, C. Koh and J. Kim, Appl. Phys. Lett., 2008, 93, 044102. R. Goodhue, J. Hutchison, V. Scardaci, A. C. Ferrari and
21 D. S. Gray, J. Tien and C. S. Chen, Adv. Mater., 2004, 16, J. N. Coleman, Nat. Nanotechnol., 2008, 3, 563568.
393397. 41 J. N. Coleman, Acc. Chem. Res., 2013, 46, 1422.
22 M. Amjadi, Y. Yoon and I. Park, Nanotechnology, 2015, 42 H. Zhao and J. Bai, ACS Appl. Mater. Interfaces, 2015, 7, 96529659.
26, 375501. 43 Z. J. Han and B. K. Tay, J. Appl. Polym. Sci., 2008, 107, 33323336.
23 M. Hu, X. Cai, Q. Guo, B. Bian, T. Zhang and J. Yang, 44 X. Liao, Q. Liao, X. Yan, Q. Liang, H. Si, M. Li, H. Wu, S. Cao
ACS Nano, 2016, 10, 396404. and Y. Zhang, Adv. Funct. Mater., 2015, 25, 23952401.

This journal is The Royal Society of Chemistry 2016 J. Mater. Chem. C, 2016, 4, 4304--4311 | 4311

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