ARTICLE

Stretchable Graphene Thermistor

with Tunable Thermal Index
Chaoyi Yan, Jiangxin Wang, and Pooi See Lee*

School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798

ABSTRACT Stretchable graphene thermistors with intrinsic high stretchability

were fabricated through a lithographic filtration method. Three-dimensional
crumpled graphene was used as the thermal detection channels, and silver
nanowires were used as electrodes. Both the detection channel and electrodes were
fully embedded in an elastomer matrix to achieve excellent stretchability. Detailed
temperature sensing properties were characterized at different strains up to 50%. It
is evident that the devices can maintain their functionalities even at high stretched
states. The devices demonstrated strain-dependent thermal indices, and the
sensitivity of the thermistors can be effectively tuned using strain. The unique
tunable thermal index is advantageous over conventional rigid ceramic thermistors
for diverse and adaptive applications in wearable electronics.

KEYWORDS: stretchable electronics . wearable electronics . graphene . thermistor . temperature sensor .

embedded elastic conductor

S
tretchable electronics represent a type stretchable materials. Herein we demon-
of innovative electronic device which is strate the fabrication of stretchable graphene
mechanically soft and conformal and thermistors with high intrinsic stretchability
can comply to complex nonplanar surfaces arising from the fully embedded device
for emerging applications such as wearable structure.
electronics.1 Recent rapid developments of Among the several types of temperature
stretchable components and devices such sensors, the ceramic-based thermistor is
as elastic conductors,2
7 transistors,8
11 advantageous in terms of fabrication cost,
sensors,12
16 light-emitting devices,17
21 sensitivity, and response speed.31 Transition
and energy sources22
25 have greatly pro- metal oxides in bulk or thin film form are
pagated the fabrication of complex, inte- the most commonly used materials in
grated stretchable systems for practical thermistors;32
34 however, the lacking of
applications.26 Temperature sensing is one mechanical flexibility limits their applica-
of the key capabilities of integrated stretch- tions in emerging stretchable and wearable
able systems; however, very limited work devices. Graphene, a one-atom-thick car-
has been reported to date. Someya et al. bon mesh with extraordinary electrical,
used organic field-effect transistors mounted mechanical, and thermal (high thermal con-
on a stretchable mesh for temperature ductivity and strong sensitivity to sample
sensing.27 Buckled Si nanoribbons created size) properties,35
38 was recently used in
by the prestrain strategy28 were employed innovative temperature sensors39,40 as
as a temperature sensor.29 Rogers' group alternatives to conventional rigid ceramics.
demonstrated temperature sensing compo- For example, Kong et al. reported the inkjet-
nents in epidermal electronics using serpen- printed graphene thermistors on flexible * Address correspondence to
[email protected].
tine metal (such as platinum26 or gold30) or polyethylene terephthalate (PET) substrates
Si diodes.30 However, all those works are for efficient temperature sensing.40 Note Received for review December 29, 2014
based on a structural engineering method that the strain upon bending is very small and accepted February 6, 2015.
that limits the device stretchability to 25
(usually below 1%),41 and most conven-
Published online
30%.26,27,29,30 Advancements leap-frogging tional rigid device structures can be readily 10.1021/nn507441c
the stretching limit would require alter- adopted onto flexible substrates. It is much
native strategies such as using intrinsically more challenging to fabricate stretchable C XXXX American Chemical Society

YAN ET AL. VOL. XXX ’ NO. XX ’ 000–000 ’ XXXX A

www.acsnano.org
 ARTICLE
Figure 1. (a,b) Schematic diagram and (c,d) representative images of the stretchable graphene thermistors at relaxed
and twisted states. Highly conductive AgNWs were used as electrodes, and resistive graphene was used as tem-
perature sensing channels. The stretchable devices are mechanically robust and can be deformed into various shapes
without fracture.

devices where the strain is much higher (>30%); that is, electrodes and detection channels were fully em-
the electronic device has to maintain its functionality bedded inside a polydimethylsiloxane (PDMS) matrix
even when the device is severely mechanically de- (Figure 2d) vto achieve intrinsic high stretchability
formed. In this report, graphene thermistors were while maintaining thermal sensing properties (up to
stretched up to 50% and the corresponding tempera- 50% strain as demonstrated in this work). The highly
ture sensing performances were characterized. The conductive AgNWs were selected as stretchable elec-
devices possess high intrinsic stretchability with fully trodes for easy and consistent electrical measure-
embedded silver nanowire (AgNW) electrodes and ments. The graphene channel was designed into
graphene detection channels. Interestingly, we found serpentine shape to augment its resistance within
that the thermal index (an indicator of thermistor limited space and enhance its dominant role in the
sensitivity defined by B = Ea/2k, where B is thermal thermistor devices. For example, the resistances of
index, Ea is activation energy, and k is Boltzmann AgNW electrodes and the graphene detection channel
constant)42 of our graphene thermistors can be effec- are compared in Figure S1, Supporting Information.
tively tuned by mechanical strain. The observed unique The resistance of AgNWs is ∼6 orders of magnitude
property is intrinsic to soft electronics and is in sharp lower than that of graphene, thus its contribution to
contrast to conventional rigid thermal sensors where the overall device resistance is negligible.
the device characteristics cannot be tuned once the Microstructural characterizations of the graphene
device is made. The tunable thermal sensitivity to- thermistors are shown in Figure 2. Figure 2a is the scan-
gether with the soft nature of our graphene devices ning electron microscopy (SEM) image of the AgNW

paves the way for future diverse and adaptable appli- graphene junction after filtration but before being
cations such as temperature sensing, mapping, and embedded into the PDMS matrix (see also Figure S2,
compensation in stretchable and wearable electronics. Supporting Information). The AgNW film lies on the
bottom with graphene film covered on top. Enlarged
RESULTS AND DISCUSSION views of the AgNW electrodes and graphene channel
Figure 1 shows the schematic diagrams and corre- are shown in Figure 2b,c, respectively. The assembled
sponding images of the stretchable graphene thermis- AgNW and graphene films exhibited macroporous
tors at relaxed and mechanically deformed states. The structures, which are critical for their successful em-
devices were fabricated using a lithographic filtration bedding into the PDMS substrate to achieve excellent
method we developed earlier,13 which allows facile stretchability. In particular, unlike previous compact
nanomaterial assembly into desired patterns for differ- graphene paper based on planar graphene nano-
ent target applications. AgNWs were used as elec- sheets,43 the macroporous structure of our graphene
trodes, and graphene (with nanocellulose binder) detection channel originates from its unique crumpled
was used as the temperature sensing channel. All morphology.12 Figure 2d is the SEM image of the

YAN ET AL. VOL. XXX ’ NO. XX ’ 000–000 ’ XXXX B

www.acsnano.org
 ARTICLE
Figure 2. (a) SEM image of the AgNW
graphene junction before being embedded into PDMS. (b,c) Enlarged views of the
AgNW electrode and graphene detection channel. Nanocellulose was used as the binder to improve the processability of
crumpled graphene. (d) SEM image of the junction area after being embedded into the PDMS matrix.

junction area after being embedded into PDMS. Note k is the Boltzmann constant, and B is the thermal index.
that the AgNW film which was originally below the Equation 1 can be rewritten as
graphene channel (Figure 2a) is now exposed on top as
Ea B
the contacting electrodes (see schematic illustration in ln(R) ¼ ln(R0 ) þ ¼ ln(R0 ) þ (2)
2kT T
Figure S2, Supporting Information). It is evident that
both AgNW film and graphene channels are fully where a linear relationship between ln(R) and 1/T is
embedded inside the PDMS substrate, enabling out- expected. The dependence of ln(R) on 1/T for our
standing stretchability and mechanical robustness. graphene thermistor is shown in Figure 3d, where
Figure 3a shows the images of the stretchable the straight line is the linear fitting result for measured
graphene thermistor at relaxed (0% strain) and data (open circles). The linear relationship is of great
stretched (50% strain) states. We first measured the importance for practical applications as it simplifies the
thermistor performance at the relaxed state. Figure 3b post-measurement processing steps.
shows the I
V curves of the thermistor when tempera- The graphene thermistor performances at stretched
ture was increased from 30 to 100
C (plotting step is states were characterized in Figure 4. The device was
10
C for clarity, although the measurement step is placed on a glass slide substrate, stretched to desired
5
C). At a fixed voltage of 10 V, the current of the strains, and fixed using binder clips (Figure S4, Sup-
device increased from 0.79 μA at 30
C to 1.34 μA at porting Information). Good Ohmic conductions were
100
C, a clear indicator of negative temperature observed at all strains within 0
50% (Figure S5, Sup-
coefficient (NTC) behavior.31 Figure 3c shows the resis- porting Information). The dependence of thermistor
tance variation with temperature, which provides a resistance on temperature at different strains is shown
direct view of the decreasing device resistance upon in Figure 4a (strain step 10%). It is evident that the
heating. The resistance decreased from 12.63 MΩ at graphene thermistor can maintain its functionality
30
C to 7.45 MΩ at 100
C. A closer examination of even when being stretched up to 50%. The decreasing
Figure 3c suggests that the resistance did not vary trends of resistance with temperature indicate consis-
linearly with temperature (see fitting curves in Figure tent NTC behaviors. Fitting curves for ln(R) versus 1/T at
S3, Supporting Information) but can be described with different strains are shown in Figure 4b, and excellent
the following expression:37 linear relationships were observed for all strains,


 although the fitted slopes (corresponding to thermal
Ea B
R ¼ R0 exp ¼ R0 exp (1) index B, based on eq 2) changed with strains. While a
2kT T
low index of 847 K was obtained at 0% strain, the index
where R is the resistance at temperature T, R0 is the increased to 1203 K at 10% strain. Relatively stable
resistance at T = ¥, Ea is the thermal activation energy, thermal indexes within 1200
1400 K were maintained

YAN ET AL. VOL. XXX ’ NO. XX ’ 000–000 ’ XXXX C

www.acsnano.org
 ARTICLE
Figure 3. (a) Images of the stretchable graphene thermistor at 0 and 50% strains. (b) I
V curves of the thermistor at 0% strain
in the temperature range of 30
100
C (temperature step set as 10
C for clarity). (c) Resistance variation with temperature
showing a nonlinear relationship. (d) Dependence of ln(R) on 1000/T showing a linear relationship.

Figure 4. Graphene thermistor performance variation upon stretching. (a) Resistance variation with temperature (30
100
C)
within 0
50% strains (step 10%). (b) Fitting curves showing the linear dependence of ln(R) on 1/T at all strains. (c) Thermal
index B variation with strains (0
50%).

within 10
40% strains but increased to 1712 K upon thermistors are stable. The thermal index can return
further stretching to 50%. Figure 4c shows the ther- to initial values after repeated mechanical stretch-
mal index variation upon stretching based on mea- ing to 50% for 100 cycles (Figure S6, Supporting
surements of three devices. An increasing trend of Information).
thermal index was observed upon stretching. Note Other important characteristics of thermistors such
that the thermal sensing properties of graphene as Ea and temperature coefficient of resistance (TCR)

YAN ET AL. VOL. XXX ’ NO. XX ’ 000–000 ’ XXXX D

www.acsnano.org
 ARTICLE
semiconductor or even insulator at high oxygen
TABLE 1. Device Performance Variation with Strains
coverage.48,49 This is consistent with our observations,
within 0
50%
where the measured NTC characteristics of our stretch-
strain (%) thermal index, B (K) activation energy, Ea (eV) TCR at 300 K (% K
1) able graphene thermistors are clear indicators of intrin-
0 945 ( 252 0.16 ( 0.04
1.05 ( 0.28 sic semiconducting behaviors. Meanwhile, we suggest
10 1411 ( 181 0.24 ( 0.03
1.57 ( 0.20 that the chemically derived, more defective graphene is
20 1463 ( 76 0.25 ( 0.01
1.63 ( 0.08 beneficial to the thermistor sensitivity. Structural defects
30 1432 ( 294 0.25 ( 0.05
1.59 ( 0.33 such as those derived from chemical processing steps
40 1530 ( 211 0.26 ( 0.04
1.70 ( 0.23 can reduce carrier densities as well as thermal conduc-
50 1895 ( 204 0.33 ( 0.04
2.11 ( 0.23 tivity. A lower carrier density is preferred to achieve
higher sensitivity of NTC thermistors. For example, Wang
et al.50 reported that the temperature coefficient of
within 0
50% strains are also calculated, as shown in
resistance of Si nanowire temperature sensors increased
Table 1. From eq 2, Ea can be obtained using
from
0.15 to
0.37% K
1 when the doping concentra-
Ea ¼ 2kB (3) tion was reduced from 3  1016 to 4  1015/cm3. The
thermally activated carriers can induce larger resistance
TCR is defined by the following expression:40
variations when the carrier density is low.
dR 1 Thermal index B is an indicator of thermistor sensi-
TCR ¼ (4)
dT 3 R tivity. Devices with low B values are useful in circuit
Combining eqs 2 and 4, we can correlate TCR to temperature compensation and cryogenic measure-
thermal index as follows: ments, and high B value devices are desired for high-
temperature sensing.31 Most ceramic materials (typically
B
TCR ¼
2 (5) transition metal oxides) exhibit thermal indexes within
T 2000
5000 K.31 The thermal indexes of our graphene
thermistor are lower than those for conventional
The TCR values for graphene thermistors in Table 1 ceramic devices but are comparable with previous
are calculated at room temperature (300 K) as univer- graphene-based devices. For example, graphene on
sally adopted for conventional ceramic devices.31 The flexible PET substrates showed a thermal index of 1860 K
negative signs indicate the NTC behaviors of graphene within the temperature range of 298
358 K.37 Interest-
thermistors. ingly, this is the first demonstration of thermistors with
The temperature-dependent electrical properties of tunable thermal index. Conventional rigid thermistors
graphene have received significant attention. Due to have fixed device structure and hence performance
its unique electrical properties (semi-metal with zero characteristics which cannot be tuned for diverse appli-
band gap), studies on pristine graphene (mainly fabri- cations. However, our stretchable graphene thermistors
cated by mechanical exfoliation) have led to quite with robust mechanical properties allow facile tuning of
diverse results, where both increasing44,45 and de- electrical resistances and thermal sensitivity, which may
creasing46 trends of device resistivity at increasing open up innovative practical applications. Although the
temperature were reported. The resistivity dependence thermistors in this work are yet capable of sensing tem-
on temperature is a combined effect of semiconducting perature where the strain also changes (since stretching
behavior (dominated by thermally activated charge also induces resistance change), they can find applica-
carriers; resistance decreases at higher temperature) tions like temperature mapping of nonplanar curvilinear
and metallic behavior (dominated by charge carrier surfaces where there is no variations of strains; more-
scattering; resistance increases at higher temperature). over, the thermal indexes can be effectively tuned for
The diverse results originate from the distinct device applications at different occasions.
and measurement conditions, such as graphene crystal- The strain-dependent thermal sensitivity can be un-
linity, layer number, carrier density, scatter wave inter- derstood based on the contact-resistance-dominated
ference, etc.47 For example, metallic behaviors are electrical conduction, although detailed mechanisms
usually observed for graphene with high carrier density, will require further studies. The device resistances are
which might be induced by gate bias, but semiconduct- dominated by contact resistances. For example, the
ing behavior is usually observed for samples with a resistance (at 30
C) changed from 12 MΩ at 0% strain
Fermi level near the Dirac (charge neutrality) point. to 147 MΩ at 50% strain (Figure 4a). The resistance
However, studies on chemically derived graphene variation mainly comes from the contact resistance
(reduced graphene oxide) suggested quite consistent since the crumpled graphene balls are analogous to
semiconductor-like behaviors.39,40 This is because it is crumpled conducting paper balls with structures simi-
very difficult to completely reduce graphene oxide; lar to those of buckled structures/surfaces that showed
the remnant oxygen and hydroxyl groups on the no resistance change with strains.1,25 Upon stretching,
surface convert zero-gap graphene into a finite-gap the interconnected crumpled graphene “balls” were

YAN ET AL. VOL. XXX ’ NO. XX ’ 000–000 ’ XXXX E

www.acsnano.org
 ARTICLE
which the device was allowed to recover to its back-
ground temperature (50
C) naturally. Response behav-
iors at 0 and 50% strains are shown in Figure 5a.
Detailed views of a single response cycle from 0 and
50% strains are compared in Figure 5b. The resistance
increased rapidly upon cooling and then gradually re-
covered when the cooling perturbation was stopped.
Similar response and recovery behaviors were ob-
served at 0 and 50% strains (Figure 5b). The thermal
responses of graphene thermistors were dominated by
the heat transfer processes. Since the graphene detec-
tion channel was exposed on top of the PDMS matrix
(Figure S7, Supporting Information), cool air was in
direct contact with the graphene channel and a fast
response process was observed. The recovery process
(∼20 s, Figure 5b) was slower than the response pro-
cess because the recovery was determined by the rate
of heat transfer from the underlying heating stage,
through the glass slide and PDMS substrates to the
graphene detection channel. PDMS has a low thermal
conductivity of 0.15 W 3 m
1 3 K
1 (at 25
C),53 and for
comparison, glass substrates (soda lime microscope
Figure 5. (a) Response behaviors of the graphene thermis-
glass) typically exhibit thermal conductivity of 0.9

tor at 0 and 50% strains. (b) Detailed view and comparison 1.3 W 3 m
1 3 K
1 (at 25
C),54 which is at least 6 times as
of a single response at 0 and 50% strains, showing the high as that for PDMS. Thus, the thermal conduction
similar response behaviors at different strains.
through the PDMS substrate is the rate-limiting step for
the recovery process. Note that the PDMS substrate
stretched, resulting in decreased contact areas and and hence embedded graphene layer may undergo
hence increased contact resistances, which is equiva- slight relaxation during the response measurements at
lent to the increase of conduction barrier height. 50% strain. The relaxation may induce contact instabil-
That is, charge carriers have to overcome higher ity between the crumpled graphene balls and lead to
conduction barriers at stretched states. Analogous larger noise on the measurements, as observed in
conduction-barrier-dominated resistance was also Figure 5. It is evident that our graphene thermistors
observed in previous percolating semiconductor nano- can respond and recover very fast within tens of
wire films.51 The conduction barrier at the semiconductor
seconds, which is beneficial for their practical applica-
semiconductor interface is composed of two back-to- tions such as wearable temperature sensing. The re-
back surface depletion layers, and the width of the sponse speed can be further optimized. For example,
depletion layer W can be described using52 the substrate thickness can be reduced to expedite the
rffiffiffiffi heat transfer process; a thinner substrate with lower
V
W (6) thermal capacity will lead to faster heating or cooling
N rates. Alternative stretchable substrates with higher
where V is the barrier height and N is the carrier density. thermal conductivity are also desired to improve the
Thus, for a certain increase of charge carrier density response speeds.
(thermally activated), a larger decrease of depletion
layer width is expected for higher barriers based CONCLUSIONS
on eq 6. This may help to explain the fact that our In conclusion, we demonstrate the fabrication and
graphene thermistors exhibited a trend of higher characterizations of highly stretchable graphene thermis-
sensitivity at stretched states due to the more signifi- tors based on conductive AgNW electrodes and a resis-
cant conduction barrier modulations at higher strain. tive graphene detection channel. Typical semiconductor-
Response behaviors of the graphene thermistors are like NCT behaviors were observed. The devices were
shown in Figure 5. The device was held at 50
C with stretched up to 50% and could maintain their func-
intentionally introduced temperature perturbations tionality even at highly stretched states. Linear rela-
for response measurements. To prevent the effect of tionships between ln(R) and 1/T were observed at all
strain-induced resistance change, a touchless tem- strains within 0
50%, indicating consistent device
perature perturbation was employed by blowing cool characteristics. An increasing trend of thermal index
air (room temperature, 25
C) to the hot device surface. B upon stretching was observed, which was attributed
A typical cooling perturbation period was 3 s, after to the strain-induced electrical connection change

YAN ET AL. VOL. XXX ’ NO. XX ’ 000–000 ’ XXXX F

www.acsnano.org
 ARTICLE
between adjacent crumpled graphene. The tunable revealed fast response speeds of the stretchable therm-
thermal index is a unique feature of soft electronics as istors at both relaxed and stretched states. Fast response
compared with conventional ceramic thermal sensors and recovery within tens of seconds were achieved.
with unchangeable device characteristics and is ex- The innovative stretchable graphene thermistor holds
pected to enable diverse applications for the same great promise for future wearable temperature sensing
graphene thermistor. Response behavior measurements applications.

METHODS 3. Yun, S.; Niu, X. F.; Yu, Z. B.; Hu, W. L.; Brochu, P.; Pei, Q. B.
Compliant Silver Nanowire
Polymer Composite Electro-
Device Fabrication. The stretchable graphene thermistors
des for Bistable Large Strain Actuation. Adv. Mater. 2012,
were fabricated using our innovative lithographic filtration
24, 1321.
methods as described earlier.12 Briefly, crumpled graphene
4. Lee, P.; Lee, J.; Lee, H.; Yeo, J.; Hong, S.; Nam, K. H.; Lee, D.;
(Time Nano, China) was fabricated by thermal reduction at
Lee, S. S.; Ko, S. H. Highly Stretchable and Highly Con-
1200
C with inert N2 atmosphere. The unique crumpled
ductive Metal Electrode by Very Long Metal Nanowire
morphology was attributed to the capillary force as has also
Percolation Network. Adv. Mater. 2012, 24, 3326.
been observed during graphene ball formation.55 Nanocellu-
5. Moon, G. D.; Lim, G.-H.; Song, J. H.; Shin, M.; Yu, T.; Lim, B.;
lose fibril (University of Maine, USA) was used as the binder to
Jeong, U. Highly Stretchable Patterned Gold Electrodes
improve the processability of crumpled graphene. For device
Made of Au Nanosheets. Adv. Mater. 2013, 25, 2707.
fabrication, AgNWs (diameter 40
100 nm, length 20
100 μm,
6. Zhu, Y.; Xu, F. Buckling of Aligned Carbon Nanotubes as
Seashell Technology LLC, USA) dispersed in ethanol (1 mg mL
1)
Stretchable Conductors: A New Manufacturing Strategy.
were first filtered as electrodes using polycarbonate (PC) filter
Adv. Mater. 2012, 24, 1073.
membranes (Millipore GTTP, pore size 220 nm). Graphene and
nanocellulose dispersed in deionized water (1 mg mL
1, weight 7. Lacour, S. P.; Wagner, S.; Huang, Z.; Suo, Z. Stretchable Gold
ratio 1:1) were then filtered as the detection channel to connect Conductors on Elastomeric Substrates. Appl. Phys. Lett.
the AgNW electrodes. Filtration masks with straight (for AgNW 2003, 82, 2404.
filtration) and serpentine (for graphene/nanocellulose filtration) 8. Xu, F.; Wu, M.-Y.; Safron, N. S.; Roy, S. S.; Jacobberger, R. M.;
patterns were used to obtain nanomaterial films with desired Bindl, D. J.; Seo, J.-H.; Chang, T.-H.; Ma, Z.; Arnold, M. S.
patterns. The PDMS base and curer (Sylgard 184, Dow Corning, Highly Stretchable Carbon Nanotube Transistors with Ion
USA) in liquid form was thoroughly mixed, poured on top of the Gel Gate Dielectrics. Nano Lett. 2014, 14, 682.
filtered AgNW and graphene films, degassed in a vacuum 9. Chae, S. H.; Yu, W. J.; Bae, J. J.; Duong, D. L.; Perello, D.;
desiccator for 30 min, and then cured at 60
C for 2 h. The Jeong, H. Y.; Ta, Q. H.; Ly, T. H.; Vu, Q. A.; Yun, M.; et al.
functional AgNW electrodes and graphene detection channels Transferred Wrinkled Al2O3 for Highly Stretchable and
were fully embedded inside the PDMS matrix, and highly Transparent Graphene
Carbon Nanotube Transistors.
stretchable devices were obtained after peeling off the solidi- Nat. Mater. 2013, 12, 403.
fied PDMS from the PC filter membrane. 10. Chortos, A.; Lim, J.; To, J. W. F.; Vosgueritchian, M.;
Device Characterization and Testing. The devices were character- Dusseault, T. J.; Kim, T.-H.; Hwang, S.; Bao, Z. Highly
ized using field-emission SEM (JSM 7600F, Japan). Electrical Stretchable Transistors Using a Microcracked Organic
properties of the thermistors were measured using a Keithley Semiconductor. Adv. Mater. 2014, 26, 4253.
analyzer (model 4200) equipped with a heating stage. For mea- 11. Lee, S.-K.; Kim, B. J.; Jang, H.; Yoon, S. C.; Lee, C.; Hong, B. H.;
surements at stretched states, the device was placed on a glass Rogers, J. A.; Cho, J. H.; Ahn, J.-H. Stretchable Graphene
slide substrate, stretched to desired strains, and then fixed at Transistors with Printed Dielectrics and Gate Electrodes.
the two ends using binder clips. The temperature was increased Nano Lett. 2011, 11, 4642.
from 30 to 100
C with a step of 5
C. The device was stabilized 12. Yan, C.; Wang, J.; Kang, W.; Cui, M.; Wang, X.; Foo, C. Y.;
for 5 min to achieve thermal equilibrium at each temperature Chee, K. J.; Lee, P. S. Highly Stretchable Piezoresistive
point before electrical measurements. A stainless steel block Graphene
Nanocellulose Nanopaper for Strain Sensors.
was placed under the glass slide substrate for heat transfer Adv. Mater. 2014, 26, 2022.
between the heating stage and thermistor device. Home-built 13. Yan, C.; Wang, J.; Wang, X.; Kang, W.; Cui, M.; Foo, C. Y.; Lee,
stretching stages were also used to show the excellent stretch- P. S. An Intrinsically Stretchable Nanowire Photodetector
ability of the graphene thermistors. with a Fully Embedded Structure. Adv. Mater. 2014, 26,
943.
Conflict of Interest: The authors declare no competing 14. Ko, H. C.; Stoykovich, M. P.; Song, J. Z.; Malyarchuk, V.; Choi,
financial interest. W. M.; Yu, C. J.; Geddes, J. B.; Xiao, J. L.; Wang, S. D.; Huang,
Y. G.; et al. A Hemispherical Electronic Eye Camera Based
Supporting Information Available: AgNW and graphene
on Compressible Silicon Optoelectronics. Nature 2008,
resistance comparison, schematics of device structure, and
454, 748.
I
V curves at different strains. This material is available free of
charge via the Internet at http://pubs.acs.org. 15. Song, Y. M.; Xie, Y.; Malyarchuk, V.; Xiao, J.; Jung, I.; Choi, K.-
J.; Liu, Z.; Park, H.; Lu, C.; Kim, R.-H.; et al. Digital Cameras
with Designs Inspired by the Arthropod Eye. Nature 2013,
Acknowledgment. This work was supported in part by the 497, 95.
Singapore National Research Foundation (CREATE Programme 16. Lipomi, D. J.; Vosgueritchian, M.; Tee, B. C. K.; Hellstrom,
of Nanomaterials for Energy and Water Management). The S. L.; Lee, J. A.; Fox, C. H.; Bao, Z. N. Skin-like Pressure and
authors thank X.W. Lu and X.W. Yan for their technical support Strain Sensors Based on Transparent Elastic Films of
and insightful discussions. Carbon Nanotubes. Nat. Nanotechnol. 2011, 6, 788.
17. Filiatrault, H. L.; Porteous, G. C.; Carmichael, R. S.; Davidson,
G. J. E.; Carmichael, T. B. Stretchable Light-Emitting Elec-
REFERENCES AND NOTES trochemical Cells Using an Elastomeric Emissive Material.
1. Rogers, J. A.; Someya, T.; Huang, Y. G. Materials and Adv. Mater. 2012, 24, 2673.
Mechanics for Stretchable Electronics. Science 2010, 327, 18. Yu, Z. B.; Niu, X. F.; Liu, Z. T.; Pei, Q. B. Intrinsically
1603. Stretchable Polymer Light-Emitting Devices Using Carbon
2. Xu, F.; Zhu, Y. Highly Conductive and Stretchable Silver Nanotube
Polymer Composite Electrodes. Adv. Mater.
Nanowire Conductors. Adv. Mater. 2012, 24, 5117. 2011, 23, 3989.

YAN ET AL. VOL. XXX ’ NO. XX ’ 000–000 ’ XXXX G

www.acsnano.org
 ARTICLE
19. Sekitani, T.; Nakajima, H.; Maeda, H.; Fukushima, T.; Aida, T.; 41. Yu, T.; Ni, Z.; Du, C.; You, Y.; Wang, Y.; Shen, Z. Raman
Hata, K.; Someya, T. Stretchable Active-Matrix Organic Mapping Investigation of Graphene on Transparent Flex-
Light-Emitting Diode Display Using Printable Elastic Con- ible Substrate: The Strain Effect. J. Phys. Chem. C 2008, 112,
ductors. Nat. Mater. 2009, 8, 494. 12602.
20. Liang, J.; Li, L.; Niu, X.; Yu, Z.; Pei, Q. Elastomeric Polymer 42. Cao, J. L.; Wang, Z. X.; Zhan, X. Y.; Wang, Q. S.; Safdar, M.;
Light-Emitting Devices and Displays. Nat. Photonics 2013, Wang, Y. J.; He, J. Vertical SnSe Nanorod Arrays: from
7, 817. Controlled Synthesis and Growth Mechanism to Thermis-
21. White, M. S.; Kaltenbrunner, M.; Glowacki, E. D.; tor and Photoresistor. Nanotechnology 2014, 25, 105705.
Gutnichenko, K.; Kettlgruber, G.; Graz, I.; Aazou, S.; Ulbricht, 43. Sumboja, A.; Foo, C. Y.; Wang, X.; Lee, P. S. Large Areal Mass,
C.; Egbe, D. A. M.; Miron, M. C.; et al. Ultrathin, Highly Flexible and Free-Standing Reduced Graphene Oxide/
Flexible and Stretchable PLEDs. Nat. Photonics 2013, 7, Manganese Dioxide Paper for Asymmetric Supercapacitor
811. Device. Adv. Mater. 2013, 25, 2809.
22. An, K. H.; Kim, W. S.; Park, Y. S.; Choi, Y. C.; Lee, S. M.; Chung, 44. Morozov, S. V.; Novoselov, K. S.; Katsnelson, M. I.; Schedin,
D. C.; Bae, D. J.; Lim, S. C.; Lee, Y. H. Supercapacitors Using F.; Elias, D. C.; Jaszczak, J. A.; Geim, A. K. Giant Intrinsic
Single-Walled Carbon Nanotube Electrodes. Adv. Mater. Carrier Mobilities in Graphene and Its Bilayer. Phys. Rev.
2001, 13, 497. Lett. 2008, 100, 016602.
23. Gaikwad, A. M.; Zamarayeva, A. M.; Rousseau, J.; Chu, H. W.; 45. Bolotin, K. I.; Sikes, K. J.; Hone, J.; Stormer, H. L.; Kim, P.
Derin, I.; Steingart, D. A. Highly Stretchable Alkaline Temperature-Dependent Transport in Suspended Graph-
Batteries Based on an Embedded Conductive Fabric. ene. Phys. Rev. Lett. 2008, 101, 096802.
Adv. Mater. 2012, 24, 5071. 46. Shao, Q.; Liu, G.; Teweldebrhan, D.; Balandin, A. A. High-
24. Lee, J.; Wu, J. A.; Shi, M. X.; Yoon, J.; Park, S. I.; Li, M.; Liu, Z. J.; Temperature Quenching of Electrical Resistance in
Huang, Y. G.; Rogers, J. A. Stretchable GaAs Photovoltaics Graphene Interconnects. Appl. Phys. Lett. 2008, 92,
with Designs That Enable High Areal Coverage. Adv. Mater. 202108.
2011, 23, 986. 47. Skákalová, V.; Kaiser, A. B.; Yoo, J. S.; Obergfell, D.; Roth, S.
25. Lipomi, D. J.; Tee, B. C. K.; Vosgueritchian, M.; Bao, Z. N. Correlation between Resistance Fluctuations and Tem-
Stretchable Organic Solar Cells. Adv. Mater. 2011, 23, 1771. perature Dependence of Conductivity in Graphene. Phys.
26. Kim, D. H.; Lu, N. S.; Ma, R.; Kim, Y. S.; Kim, R. H.; Wang, S. D.; Rev. B 2009, 80, 153404.
Wu, J.; Won, S. M.; Tao, H.; Islam, A.; et al. Epidermal 48. Ito, J.; Nakamura, J.; Natori, A. Semiconducting Nature of
Electronics. Science 2011, 333, 838. the Oxygen-Adsorbed Graphene Sheet. J. Appl. Phys.
27. Someya, T.; Kato, Y.; Sekitani, T.; Iba, S.; Noguchi, Y.; Murase, 2008, 103, 113712.
Y.; Kawaguchi, H.; Sakurai, T. Conformable, Flexible, Large- 49. Boukhvalov, D. W.; Katsnelson, M. I. Modeling of Graphite
Area Networks of Pressure and Thermal Sensors with Oxide. J. Am. Chem. Soc. 2008, 130, 10697.
Organic Transistor Active Matrixes. Proc. Natl. Acad. Sci. 50. Wang, C.-P.; Liu, C.-W.; Gau, C. Silicon Nanowire Tempera-
U.S.A. 2005, 102, 12321. ture Sensor and Its Characteristic. IEEE International Con-
28. Khang, D. Y.; Jiang, H. Q.; Huang, Y.; Rogers, J. A. A ference on Nano/Micro Engineered and Molecular Systems
Stretchable Form of Single-Crystal Silicon for High- (NEMS), February 20
23, 2011; p 630.
Performance Electronics on Rubber Substrates. Science 51. Yan, C.; Singh, N.; Lee, P. S. Wide-Bandgap Zn2GeO4
2006, 311, 208. Nanowire Networks as Efficient Ultraviolet Photodetectors
29. Yu, C.; Wang, Z.; Yu, H.; Jiang, H. A Stretchable Temperature with Fast Response and Recovery Time. Appl. Phys. Lett.
Sensor Based on Elastically Buckled Thin Film Devices on 2010, 96, 053108.
Elastomeric Substrates. Appl. Phys. Lett. 2009, 95, 141912. 52. Vanheusden, K.; Seager, C. H.; Warren, W. L.; Tallant, D. R.;
30. Webb, R. C.; Bonifas, A. P.; Behnaz, A.; Zhang, Y.; Yu, K. J.; Voigt, J. A. Correlation between Photoluminescence and
Cheng, H.; Shi, M.; Bian, Z.; Liu, Z.; Kim, Y.-S.; et al. Ultrathin Oxygen Vacancies in ZnO Phosphors. Appl. Phys. Lett.
Conformal Devices for Precise and Continuous Thermal 1996, 68, 403.
Characterization of Human Skin. Nat. Mater. 2013, 12, 938. 53. Mark, J. E. Polymer Data Handbook; Oxford University
31. Feteira, A. Negative Temperature Coefficient Resistance Press: New York, 1999.
(NTCR) Ceramic Thermistors: An Industrial Perspective. 54. Janssen, L. P. B. M.; Warmoeskerken, M. M. C. G. Transport
J. Am. Ceram. Soc. 2009, 92, 967. Phenomena Data Companion; VSSD: Delft, The Nether-
32. Feltz, A.; Polzl, W. Spinel Forming Ceramics of the System lands, 2006.
FexNiyMn3‑x‑yO4 for High Temperature NTC Thermistor 55. Luo, J.; Jang, H. D.; Sun, T.; Xiao, L.; He, Z.; Katsoulidis, A. P.;
Applications. J. Eur. Ceram. Soc. 2000, 20, 2353. Kanatzidis, M. G.; Gibson, J. M.; Huang, J. Compression and
33. Nobre, M. A. L.; Lanfredi, S. Grain Boundary Electric Aggregation-Resistant Particles of Crumpled Soft Sheets.
Characterization of Zn7Sb2O12 Semiconducting Ceramic: ACS Nano 2011, 5, 8943.
A Negative Temperature Coefficient Thermistor. J. Appl.
Phys. 2003, 93, 5576.
34. Park, K.; Bang, D. Y. Electrical Properties of Ni-Mn-Co-(Fe)
Oxide Thick-Film NTC Thermistors Prepared by Screen
Printing. J. Mater. Sci. 2003, 14, 81.
35. Geim, A. K.; Novoselov, K. S. The Rise of Graphene. Nat.
Mater. 2007, 6, 183.
36. Balandin, A. A. Thermal Properties of Graphene and Nano-
structured Carbon Materials. Nat. Mater. 2011, 10, 569.
37. Shahil, K. M. F.; Balandin, A. A. Thermal Properties of
Graphene and Multilayer Graphene: Applications in Thermal
Interface Materials. Solid State Commun. 2012, 152, 1331.
38. Renteria, J.; Nika, D.; Balandin, A. Graphene Thermal
Properties: Applications in Thermal Management and
Energy Storage. Appl. Sci. 2014, 4, 525.
39. Al-Mumen, H.; Fubo, R.; Lixin, D.; Wen, L. Design, Fabrica-
tion, and Characterization of Graphene Thermistor. 8th
IEEE International Conference on Nano/Micro Engineered
and Molecular Systems (NEMS), April 7
10, 2013; p 1135.
40. Kong, D.; Le, L. T.; Li, Y.; Zunino, J. L.; Lee, W. Temperature-
Dependent Electrical Properties of Graphene Inkjet-
Printed on Flexible Materials. Langmuir 2012, 28, 13467.

YAN ET AL. VOL. XXX ’ NO. XX ’ 000–000 ’ XXXX H

www.acsnano.org