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Highly Stretchable Piezoelectric-Pyroelectric Hybrid
Nanogenerator
Ju-Hyuck Lee, Keun Young Lee, Manoj Kumar Gupta, Tae Yun Kim,
Dae-Yeong Lee, Junho Oh, Changkook Ryu, Won Jong Yoo, Chong-Yun Kang,
Seok-Jin Yoon, Ji-Beom Yoo, and Sang-Woo Kim*
Energy harvesting systems which are highly flexible, stretch-
able, transformable to any surface topology, and mechanically
durable may be used in a wide range of applications such as
robotic sensory skins, wearable communication devices, elec-
tronic textile, and especially biomedical devices due to their
high sustainability of all movements and body deformations.[1–5]
Human body has promising harvesting energy sources like
thermal energy (i.e., body device interfacing thermal differen-
tial) and mechanical energy (such as flow of body fluid, blood
flow, heartbeat, contraction of blood vessels, muscle stretching
or eye blinking).[6–13]
Some piezoelectric materials show pyroelectric behavior,
in which an electric signal is generated upon application of a
thermal gradient. Among the many piezoelectric materials,
the poly(vinylidenefluoride-co-trifluoroethylene) [P(VDF-TrFE)]
polymer has excellent pyroelectric properties with pyroelectric
coefficient up to ≈200 μC m−2K−1.[14] Recently, zinc oxide,[15]
potassium niobate,[16] lead zirconate titanate,[17] polyvinylidene
fluoride[18] based piezoelectric and pyroelectric nanogenerators
J.-H. Lee, T. Y. Kim, D.-Y. Lee, Prof. W. J. Yoo,
Prof. J.-B. Yoo, Prof. S.-W. Kim
SKKU Advanced Institute of Nanotechnology (SAINT)
Center for Human Interface Nanotechnology (HINT)
SKKU-Samsung Graphene Center
Sungkyunkwan University (SKKU)
Suwon, 440–746, Republic of Korea
E-mail: kimsw1@skku.edu
K. Y. Lee, Dr. M. K. Gupta, Prof. S.-W. Kim
School of Advanced Materials Science and Engineering
Sungkyunkwan University (SKKU)
Suwon, 440–746, Republic of Korea
J. Oh, Prof. C. Ryu
School of Mechanical Engineering
Sungkyunkwan University (SKKU)
Suwon, 440–746, Republic of Korea
Dr. C.-Y. Kang
Electronic Materials Research Center
Korea Institute of Science and Technology (KIST)
Seoul 136–791 (Republic of Korea)
KU-KIST Graduate School of Converging Science and Technology
Korea University
Seoul, 136–701, Republic of Korea
Dr. S.-J. Yoon
Research Planning & Coordination Division
Korea Institute of Science and Technology (KIST)
Seoul, 136–791, Republic of Korea
DOI: 10.1002/adma.201303570
Adv. Mater. 2014, 26, 765–769 © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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(NGs) have been reported and used to harvest either mechan-
ical energy or thermal energy. Therefore, it would be highly
desirable to harvest both types of energy from a single cell of
NG at the same time not only to miniaturize an NG device
but also to obtain high output performance from the device.[18]
Until now, there has been no report on stretchable pyroelectric
NGs; hence, the realization of highly stretchable NGs, although
still a challenge, would support their sustained power output
performance and their commercialization.
In this work, we fabricated a highly stretchable, hybrid
energy-scavenging NG based on the micro-patterned piezo-
electric P(VDF-TrFE) polymer, micro-patterned polydimethyl-
siloxane (PDMS)-carbon nanotubes (CNTs) composite and
graphene nanosheets. The PDMS-CNT made the NG device
fully stretchable and flexible, and also served as a robust elec-
trode on the bottom side of the device.[19–21] Graphene was
used as a top flexible electrode for fast temperature gradient
on the device due to its high thermal conductivity.[22,23] Usu-
ally metal electrodes have very low stretchability/flexibility as
compared to graphene and PDMS/CNT composite. Further-
more three-dimensional microstructure patterning of metals
usually involves complicate experimental procedures.[24–26]
With this micro-line pattern structure, the piezoelectric and
pyroelectric hybrid stretchable NG (HSNG) provided highly
robust and stable performance even after a number of stretch-
and-release cycles. The piezoelectric and pyroelectric output
electric signals of the fabricated HSNG were measured under
various mechanical strains and temperature gradient, respec-
tively, and output electric signals were successfully integrated
together under application of mechanical and thermal energy
at the same time. The working mechanism of the hybrid NG is
discussed in the context of piezoelectric and pyroelectric prop-
erties in detail.
Figure 1a shows a schematic illustration of the HSNG. The
device is mainly composed of three layers; PDMS-CNT, which
acts as the bottom electrode, P(VDF-TrFE) as the piezoelectric
and pyroelectric material and graphene as the top electrode. To
begin with, the PDMS-CNT composite was prepared: the liquid
PDMS elastomer, cross-linker, and multi walled CNT were
mixed homogeneously, degassed, and uniformly spin-coated on
the surface of the Si master. Then, the micro-patterned PDMS-
CNT composite was obtained using a Si wafer master mold
fabricated by photolithography and etching process (Figure S1,
Supporting Information, shows all fabrication processes in
detail). The high crystalline P(VDF-TrFE) thin film (thickness
≈7 μm) was synthesized by spin coating directly on the top layer
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Figure 1. (a) Schematic illustration of the device, (b) photo image of the HSNG, (c) photo images of the HSNG at various locations on human body,
showing good compatibility of the device with various parts of body, and (d) piezoelectric output voltage from the HSNG under stretch-release condi-
tion, and pyroelectric output voltage under a thermal gradient (heat and cool).

of the micro-patterned PDMS-CNT composite and annealed at We demonstrate that the output voltage and current of
140 °C for 2 hours. The formation of β-phase in the P(VDF- HSNG can be enhanced by the coupling of the piezoelectric
TrFE) thin film was confirmed by X-ray diffraction (XRD) and effect and the pyroelectric effect via controlled applications of
Fourier transform infrared (FT-IR) spectroscopy measurements stretching-releasing/compressing-releasing and heating-cooling
(Figure S2).[27,28] Lastly, multilayer graphene, grown by thermal
chemical vapor deposition (CVD), was transferred on the top
surface of the P(VDF-TrFE) film (the CVD growth procedure of
graphene is given in Supporting Information). In order for the
pyroelectric NG to produce a high electric output, a fast thermal
gradient is desired; therefore, graphene was used as the top
electrode to take advantage of its high flexibility, super high
thermal conductivity and ultra-low thickness.
Figure 1b presents a photo image of the fabricated highly
stretchable HSNG. Figure 1c shows its high compatibility with
different parts of the human body, which depicts the device’s
suitability to wearable devices, robotics and biomedical appli-
cations. The piezoelectric output voltage from HSNG under
stretching and releasing conditions and the pyroelectric output
voltage under thermal gradients i.e., heating and cooling near
the device are shown in Figure 1d. Initially, we measured the
piezoelectric and pyroelectric electric outputs from the fabricated
HSNG device separately at different strains and thermal gradi-
ents. A high pyroelectric electric output was obtained when a heat Figure 2. (a) Piezoelectric output voltage of the HSNG under stretch-
gradient was applied on the graphene side of HSNG, but a tiny release condition, pyroelectric output voltage of the device under heat-
output voltage was observed when the same thermal gradient cool condition, and the total output voltage by the coupling between
the piezoelectric and pyroelectric effects, and (b) piezoelectric output
was applied on the PDMS-CNT side of the device; this result is
voltage of the device under compress-release condition, pyroelectric
attributed to the superior thermal conductivity of graphene over output voltage of the device under heat-cool condition, and the total
PDMS-CNT. This structure is a unique innovation in the fabrica- output voltage of the HSNG by the coupling between the piezoelectric
tion of high performance pyroelectric NGs (Figure S4 and S5). and pyroelectric effects.

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on HSNG at the same time. Figure 2 shows
the enhancement of output voltage from
HSNG by the coupling of the piezoelectric
effect and the pyroelectric effect of the HSNG
device. Piezoelectric output voltage of up to
0.7 V was observed under the stretching and
releasing condition, while pyroelectric output
voltage up to 0.4 V was observed under the
thermal heating and cooling condition. Sub-
sequently, the piezoelectric and pyroelectric
output voltages from a single cell of HSNG
were successfully integrated to produce a
total output voltage of up to 1.1 V under the
simultaneous application of applied strain
(stretch-release mode) and thermal gradient
(heat and cool mode) (Figure 2a). Further-
more, the output voltages from the HSNG
were also measured separately and success-
fully integrated; the total output voltage
reached up to 1.4 V upon simultaneous
application of a different mode of strain i.e.,
compress-release (output voltage ≈1.0 V) and
applied thermal gradient i.e., heat and cool
(output voltage ≈0.4 V) (Figure 2b). There-
fore, using this unique design and taking
advantage of the piezoelectric and pyroelec-
tric properties of P(VDF-TrFE), we could har-
vest mechanical and thermal energies from
the HSNG. This is the first demonstration of
simultaneous harvesting of mechanical and
thermal energies from a single cell of highly
stretchable NG.
According to piezoelectric and pyroelectric
theories, the change of polarization ΔP can
be expressed as[29,30]

P = d · X + p · T (1)
where d is the piezoelectric coefficient, X is
the applied stress, p is the pyroelectric coef- Figure 3. Schematic illustration of the power output, and piezoelectric and pyroelectric cou-
ficient, and ΔT is the change in temperature. pling mechanism: (a) no signal is observed when no strain and temperature fluctuation is
Therefore, the output potential of a hybrid applied; (b) electric signal due to piezoelectric effect from device when stretch and release
NG (i.e., piezoelectric and pyroelectric) strain is applied (c) electric signal under application of release and heating gradient due to
strongly depends on the thermal gradient dipole movement from equilibrium position (d) electric charge generation under application
of compressive and release strain and (e) with application of heating along with compressive
and applied stress, and the total electric strain due to dipole fluctuation from equilibrium position.
output depends on the small changes in tem-
perature (detailed explanation of the equation
is given in Supporting Information). in the dipole moment via the piezoelectric effect (sponta-
Figure 3 presents the power generation mechanism of the neous polarization is proportional to the dipole moment per
HSNG based on the coupling effect between the piezoelec- unit volume), and a positive piezoelectric signal is observed
tric and pyroelectric effects. In the absence of any strain and across the electrodes. On the other hand, a negative piezo-
thermal fluctuation, the output voltage and current from the electric potential is generated across the electrodes when it is
HSNG is zero. Due to the randomly oscillating electric dipoles released (Figure 3b).[27,31] Furthermore, if the heating process
within a degree from their respective aligning axes (shown is applied along with releasing at same time on the HSNG
as by black arrows in Figure 3a), the electric dipoles remain cell, a high negative output voltage would be observed. At high
in equilibrium state because the spontaneous polarization of temperature, aligned electric dipoles oscillate within a larger
P(VDF-TrFE) is constant at room temperature (Figure 3a). degree of their respective aligning axes range (θ1 to θ2; θ2 >
When mechanical stretching is applied into the HSNG, the θ1) which significantly decreases the strength of spontaneous
P(VDF-TrFE) film is stretched and the total spontaneous polar- polarization, resulting in high potential generation at the same
ization of the film is increased significantly due to the increase polarity.[18,32] Therefore, due to same signal polarity generated

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in the releasing and heating condition, both
piezoelectric and pyroelectric potentials can
be easily integrated (Figure 3c).
On the other hand, when a compressive
strain is applied along the lateral direction
of the HSNG, negative piezoelectric poten-
tial is created at the compressive side of the
HSNG due to the piezoelectric P(VDF-TrFE)
film and a negative pulse is observed, and a
positive piezoelectric potential is generated
when it is released as shown in Figure 3d.
Furthermore, when heat is applied onto
the HSNG, aligned electric dipoles oscil- Figure 4. (a) Pyroelectric output voltage with lateral strain from 0% to 30%, and (b) simulation
late within a larger degree of their respec- results of temperature fluctuation for original-state device and 30%-strained device.
tive aligning axes range (θ3 to θ4; θ4 > θ3)
which significantly decreases the strength of spontaneous
polarization, resulting in a negative electric signal. Again,
due to the generation of a same polarity electric signal, the
piezoelectric and pyroelectric potentials were integrated
(Figure 3e). Such a unique, combined application of applied
strain and thermal gradient in the HSNG device is a key
factor in improving the performance of any piezoelectric-
pyroelectric HSNG. Furthermore, we also demonstrated that
the total output potential generated from the HSNG was
reduced when we measured the output performance under
simultaneous application of stretching and heating gradient
(Figure S6).
In the present study, to enhance stretchability, stability,
durability, and robustness of the HSNG, we specially designed
our hybrid device with micro-line patterning architecture. The
line-type micro-patterned PDMS-CNT composite was selected
to synthesize the wavy micro-patterned P(VDF-TrFE) film,
which greatly enhanced the stretchability of the piezoelectric
film. In addition, to investigate the excellent stretchability
and stable pyroelectric output performance of the HSNG, we
stretched our device by 0, 5, 10, 15, 20, 25, and 30%, respec-
tively, and maintained it at the corresponding stretched posi-
tions. Thereafter we applied a thermal gradient (heat) at each
case of applied strain and the corresponding pyroelectric
output voltage was measured (Figure 4a). There was no varia-
tion in the output voltage up to 30% applied strain, and nearly
a stable output potential (≈0.4 V) was observed from HSNG.
To understand this behavior, a numerical simulation of each
condition was performed using a commercial computational
fluid dynamic (CFD) code (FLUENT 6.3). Figure 4b presents
the simulation results of the case of P(VDF-TrFE) film applied
with a thermal gradient along with 0% strain, i.e., the orig-
inal state of P(VDF-TrFE), and the case of P(VDF-TrFE) film
applied with a thermal gradient and 30% strain. The simula-
tion results show similar behaviors of device in both cases,
which shows good agreement with the experimental results. In
the simulation, the original P(VDF-TrFE) film was heated up
to 325.28 K and its cooling time up to 308.15 K was 6.72 sec;
the stretched P(VDF-TrFE) film was heated up to 327.57 K
and its cooling time was 8.47 sec. These results provide good
evidence that pyroelectric performance of the HSNG is not
changed by applied strain, possibly due to the same orientation
of the electric dipoles from their equilibrium positions under
heat fluctuation and under the original or stretching condition
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of the HSNG device. These results confirm that the device is
able to provide thermal energy under any stretchable condition
because of its pyroelectric behavior and that it can produce
a stable and significant electric output. Figure S7 shows the
image of the heat gradient distributions of the original and
stretched HSNG devices in detail.
Furthermore, in order to confirm the stretchability and
robustness of the HSNG at every stage of applied strain,
we obtained the optical microscope images of the device, as
shown in Figure 5. The surface morphology of the non-pattern
hybrid device exhibits many cracks and wrinkles, for 0 to 30%
applied strain. On the other hand, the surface morphology
of the micro-line patterned HSNG device shows only a small
amount of wrinkles and no cracks under the same strain condi-
tion. Therefore, the above results prove the high stretchability,
mechanical durability, and robustness of the micro-line pattern-
based HSNG. Furthermore, it was found that graphene and
CNT/PDMS composite electrodes have a very stable electrical
property even at stretched conditions as shown in Figure S8. A
durability test was also conducted to confirm the mechanical
durability of the HSNG (Figure S9).
In summary, we developed the first fully stretchable
and flexible hybrid energy harvesting NG device based on a
micro-patterned piezoelectric polymer P(VDF-TrFE) thin film,
PDMS-CNT composite, and graphene. We successfully har-
vested mechanical and thermal energies from a single cell of
the HSNG device under various modes of applied strain and
thermal gradient as piezoelectric and pyroelectric power out-
puts, respectively. The total output voltage generated from the
HSNG due to the coupling of the piezoelectric and pyroelec-
tric effects was obtained under controlled experiments. The
working mechanism of the HSNG was discussed in detail in
term of the polarization and oscillation of the electric dipoles
of P(VDF-TrFE). We also demonstrated the stable pyroelectric
output voltage of the HSNG device for various stretchable
modes. The thermal gradient in the case of stretching and
non-stretching conditions of device was further simulated in
order to confirm stability of pyroelectric power output and
found to be in good agreement with the experimental results.
Finally, we successfully showed the stretchability, mechanical
durability and robustness of the device due to the line based
micro-pattern design of the HSNG, compared to the flat
(non-pattern) based hybrid NG. The present results suggest
that such a stretchable and flexible hybrid energy harvester
Adv. Mater. 2014, 26, 765–769

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Figure 5. Optical microscope images of surface morphology of flat and
line type micro patterned devices (a) before stretching, (b-d) after 10,
20%, and 30% stretching of device, respectively. The flat based (non-
pattern) hybrid NG shows various cracks and wrinkles, while the micro-
pattern device shows high uniformity, robustness and fewer wrinkles.
would have high applicability in many fields where stretch-
able electronics are needed. The results of this study can also
contribute to advancements in wireless sensors, temperature
imaging, and medical diagnostics and self-powered biomedical
applications.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This work was supported by the Base Convergent Research Program
(2010–0019086), Global Frontier Research Center for Advanced Soft
Electronics (2011–0031635) and the Basic Research Program (2009–
Adv. Mater. 2014, 26, 765–769 © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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0083540) of the National Research Foundation of Korea (NRF) grant
funded by the Ministry of Science, ICT & Future Planning (MSIP).
Received: July 31, 2013
Revised: September 18, 2013
Published online: October 25, 2013
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