Article

Cite This: ACS Appl. Nano Mater. 2019, 2, 2013−2025 www.acsanm.org

A Self-Powered Wearable Pressure Sensor and Pyroelectric

Breathing Sensor Based on GO Interfaced PVDF Nanofibers
Krittish Roy,† Sujoy Kumar Ghosh,† Ayesha Sultana,† Samiran Garain,†,∥ Mengying Xie,§
Christopher Rhys Bowen,§ Karsten Henkel,∥,⊥ Dieter Schmeiβer,∥ and Dipankar Mandal*,†,‡
†
Organic Nano-Piezoelectric Device Laboratory (ONPDL), Department of Physics, Jadavpur University, Kolkata 700032, India
‡
Institute of Nano Science and Technology, Phase-10, Sector-64, Mohali 160062, India
§
Department of Mechanical Engineering, University of Bath, Bath BA27AY, U.K.
∥
Brandenburg University of Technology Cottbus-Senftenberg, Applied Physics and Sensor Technology, K.-Wachsmann-Allee 17,
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03046 Cottbus, Germany

⊥
Brandenburg University of Technology Cottbus-Senftenberg, Applied Physics and Semiconductor Spectroscopy, K.-Zuse-Str. 1,
03046 Cottbus, Germany
*
S Supporting Information

ABSTRACT: This paper reports a self-powered, flexible, piezo- and pyro-electric hybrid
from https://pubs.acs.org/doi/10.1021/acsanm.9b00033.

nanogenerator (NG) device that can be fixed on different locations of human skin for
detecting static and dynamic pressure variations and can also monitor temperature
fluctuations during the respiration process. An efficient and cost-effective fabrication
strategy has been developed to create electrospun poly(vinylidene fluoride) (PVDF)/
graphene oxide (GO) nanofibers, which are used to create a highly sensitive wearable
pressure sensor and pyroelectric breathing sensor. The sensor can accurately and rapidly
detect pressures as low as 10 Pa with a high sensitivity (4.3 V/kPa), a key performance
indicator for wearable sensors. Importantly, the sensor exhibits a high sensitivity to
bending and stretching by finger, wrist, and elbow. The pressure sensor is also highly
sensitive to vocal vibrations when attached to the human throat. The device can generate
a maximum output power density of ∼6.2 mW/m2 when subjected to a compressive
stress, which enhances its range of applications. Moreover, it is demonstrated that doping
with GO improves the pyroelectric energy harvesting and sensing performance of the device under repeated temperature
fluctuations. The PVDF/GO-based nanogenerator has a maximum pyroelectric output power density of ∼1.2 nW/m2 and can
sense temperature changes during respiration, which makes it promising as a pyroelectric breathing sensor. It is demonstrated
that processing of the PVDF-GO self-powered multifunctional pressure and pyroelectric breathing sensor can be up-scaled for
fabricating compact and high-performance electronic skins for application in health monitoring, motion detection, and portable
electronics.
KEYWORDS: piezo- and pyro-electric hybrid nanogenerator, poly(vinylidene fluoride) (PVDF)/graphene oxide (GO) nanofibers,
wearable pressure sensor, breathing sensor

■ INTRODUCTION
Recent progress in wearable pressure sensors and electronic
for self-powered sensing applications.17 However, triboelectric
sensors are based on capacitors with an air-gap which may be
skins (E-skins) that are able to mimic human skin and organs sensitive to undesired side-effects such as static electricity, stray
by transducing external stimuli such as strain, pressure, capacitances, and temperature variations. In contrast, piezo-
temperature, and humidity have led to research interest1−4 in electricity is driven by the material polarization because of the
new materials for sensing during physiological activities, health separation of electrical charges where the resulting polarization
care monitoring, and medical diagnosis.5−10 A number of is changed as a result of an external mechanical stimulus. To
research groups have demonstrated flexible and sensitive date, several NGs have been developed using a range of
pressure sensors based on gold nanowires,11 metal nano- inorganic piezoelectric materials such as lead zirconate titanate
particles,12,13 carbon-based materials such as carbon nano- (PZT), BaTiO3, ZnSnO3, CdS, ZnO, and GaN which have
tubes,14,15 graphene,16 and polymers incorporated with a range exhibited promising vibrational energy-harvesting perform-
of sensing materials that exploit a variety of sensing ance.18−22 However, the high cost, high stiffness, high density,
mechanisms which include piezoresistive, piezoelectric,
piezocapacitive, and triboelectric effects. Among these Received: January 7, 2019
mechanisms, sensors based on piezoelectric and triboelectric Accepted: March 7, 2019
materials, often termed nanogenerators (NGs), are promising Published: March 7, 2019

© 2019 American Chemical Society 2013 DOI: 10.1021/acsanm.9b00033

ACS Appl. Nano Mater. 2019, 2, 2013−2025
ACS Applied Nano Materials Article

Figure 1. Schematic route for the fabrication of GPPNG. (a) Preparation and molecular structure of graphene oxide using the modified Hummer’s
method. (b) Preparation of spinning solution. (c) Experimental setup for preparation of pure PVDF and PVDF/GO nanofibers. (d) Image of large
piece PVDF/1 wt % GO fiber prepared via electrospinning (7 × 18 cm2). (e) A sketch of the nanogenerator stack. (f) Images of the fabricated
flexible GPPNG sensor and its bending and twisting ability, respectively.

complex processing route, brittleness, and toxic components ing because of its biocompatibility and excellent energy storage
during processing restrain their utilization in wearable potential.31,32 The incorporation of nanofillers, which include
electronics and health-care monitoring. However, organic 2D- materials such as transition metal dichalcogenides
ferroelectric polymers such as poly(vinylidene fluoride) (TMDCs), graphene, and graphene nanocomposites, for
(PVDF) (chemical formula: −(CH2−CF2)−n) and its example, Ce3+/graphene and CdS/rGO nanocomposites, can
copolymers are advantageous in terms of flexibility, low increase the polar content of the PVDF nanofibers and have
density, large-area, and low cost processing and environ- been employed for energy-harvesting applications.26,29,30
mental-friendly (lead-free) fabrication which has led to interest Despite their noticeable energy-harvesting performance,
in these materials toward NG engineering and sensor Ce3+/graphene and CdS/rGO nanocomposites doped PVDF
implementation. The piezoelectric and ferroelectric behavior nanofibers have yet to be used as a wearable pressure sensor
of semicrystalline PVDF is attributed to the polar phases such and pyroelectric breathing sensor. For example, a Ce3+/
as β- (TTTT conformation) and γ-phase (T 3 GT 3 G′ graphene-based device was used as an acoustic sensor and
conformation), whereas the α-phase (TGTG′ conformation) wind energy harvester.26 In other work, a CdS/rGO-based
is nonpolar.23−28 device was demonstrated as a mechanical energy harvester with
Therefore, efforts have been made to achieve effective β- a relatively low output voltage.30 A current challenge in the use
phase nucleation in a PVDF matrix; this includes the use of of graphene in biomedical applications stems from its costly
uniaxial or biaxial mechanical stretching at elevated temper- manufacturing process and lack of batch production efficiency.
ature, electrical poling, and spin coating. In this regard, the To overcome these disadvantages, graphene oxide (GO), a
electrospinning process is a relatively simple technique for β- graphene derivative, can be used with a similar functionality
phase transformation, whereby large stretching forces are and is capable of being used in mass production.
applied on electrified solution jets for producing in situ poled In this work, a facile and low-cost approach to fabricate a
nanofibers that can be several centimeters in length and have a highly flexible, sensitive, and self-powered wearable pressure
micro/nanosize diameter.26,29,30 More recently, graphene as a and temperature sensor is presented for the creation of
highly conductive, rigid, and thin 2D- material, has gathered epidermal devices based on GO encapsulated PVDF nano-
significant attention as a promising material in the field of fibers. The graphene oxide was synthesized using a solution-
multifunctional wearable electronics and biomedical engineer- based chemical treatment approach. The graphene-based
2014 DOI: 10.1021/acsanm.9b00033
ACS Appl. Nano Mater. 2019, 2, 2013−2025
ACS Applied Nano Materials Article

Figure 2. FE-SEM micrographs of (a) PVDF/1 wt % GO fibers and corresponding fiber diameter distribution are shown in the inset. (b) TEM
image of PVDF/1 wt % GO including the SAED pattern in the inset. (c) FE-SEM image of as-synthesized few layered GO with HR-TEM image in
inset. (d) High-resolution deconvoluted C1s XPS spectra of GO. (e) FT-IR spectra of pure PVDF and PVDF/1 wt % GO fibers in the wavenumber
range of 1600−600 cm−1. (f) Curve deconvolution of the XRD pattern in the 2θ range of 15−25° for pure PVDF and PVDF/1 wt % GO. The
degree of crystallinity of β, γ, and α-phases is also provided.

piezo- and pyro-electric nanogenerator (GPPNG) is shown to 6 g of graphite powder was thoroughly mixed with 3 g of NaNO3 in
exhibit a high sensitivity to both static and dynamic tactile the 100 mL of cold concentrated sulfuric acid. The solution was then
stimuli with a high pressure sensitivity of up to 4.3 V/kPa and stirred well in an ice bath that was maintained below 5 °C. A mass of
can also detect a pressure as low as 10 Pa. The low-range 15 g of KMnO4 was then gradually added to the resulting solution
while being continuously stirred. After removal from the cooling bath,
detection limit makes it favorable as a wearable pressure stirring of the mixture was continued at room temperature. Afterward,
sensor. In addition, it is demonstrated that there is potential to 200 mL of water was added to the solution and the temperature was
generate an output power density up to ∼6.2 mW/m2 and increased to 98 °C while being continuously stirred. Then, 500 mL of
∼1.2 nW/m2 under mechanical and thermal fluctuations, deionized water and 30 mL of 30% H2O2 were added until
respectively. We further demonstrate that the GPPNG sensor effervescence has ceased and the color of the solution changed to
can accurately detect and discriminate different skin related light brown and was left overnight. The brown precipitate was then
stresses induced by finger bending and stretching, wrist separated from the supernatant and then washed repeatedly with 5%
bending, vocal vibrations (speech signals), and other human (v/v) HCl. Finally the material was centrifuged with deionized (DI)
body motions. Finally, the PVDF/GO-based device can be water followed by drying in a vacuum oven. Then, 100 mg of the as-
prepared GO was collected and dissolved in EG for further synthesis
utilized as a pyroelectric breathing sensor. These wide ranging and analysis.
properties extend the potential application of GPPNG toward Preparation of PVDF/GO Nanofibers. To prepare the spinning
energy harvesting, low power electronics, and biomedical solutions, first, 12 wt % PVDF was dissolved in a mixed solvent of
fields, which include personal health monitoring, acute heart DMF and acetone (6:4) and it was stirred for 3 h at 60 °C.
and respiratory disorder diagnosis, human-computer inter- Successively, GO powder with different weight ratios (0.25, 0.5, and 1
action as well as portable electronic devices. (w/v)%) was immersed into the PVDF solution while being

■
vigorously stirred for 8 h at 60 °C. In order to achieve a homogeneous
dispersion of GO, the resulting solution was sonicated in an ultrasonic
EXPERIMENTAL SECTION bath for half an hour. A reference PVDF solution without GO was
Materials. Graphite powder, sulfuric acid (H2SO4), hydrochloric also prepared and electrospun under the same condition to execute
acid (HCl), potassium permanganate (KMnO4), hydrogen peroxide control experiments.
(H2O2), ethylene glycol (EG), N,N-dimethylformamide (DMF), The electrospinning solution was filled into a 10 mL hypertonic
acetone, and ethanol were obtained from Merck India Ltd. PVDF syringe with a diameter of 0.8 mm to initiate the eletrospinning
pellets (Mw ≈ 275 000) were received from Sigma-Aldrich, U.S.A. process. All nanofibers were prepared under a high bias voltage of 12.5
Graphene Oxide synthesis. Graphene oxide was produced by kV using a commercial electrospinning instrument. A schematic in
oxidizing graphite powder using the modified Hummers’ method.33 Figure 1c demonstrates the typical electrospinning setup. The
Figure 1a shows the synthesis and molecular structure of GO. In brief, solution was forced by a syringe pump and injected into the needle

2015 DOI: 10.1021/acsanm.9b00033

ACS Appl. Nano Mater. 2019, 2, 2013−2025
ACS Applied Nano Materials Article

at a flow rate of 1.2 mL/hour. The nanofibers were deposited on a Al- transparent, and wrinkled structure of GO due to sheet folding;
foil wrapped collector plate, as shown in Figure 1c, where the this is also confirmed by the FE-SEM images.34,35 GO was
collector was positioned at a 12 cm distance to the needle tip. Finally homogeneously dispersed in the PVDF matrix because of its
the four sets of nanofibers were dried at 60 °C for 8 h to ensure that carbon-based structure and presence of oxygen linked
all of the solvents are released and to obtain stable nanofibers for
further characterization and nanogenerator device fabrication. Nano- functional groups and no agglomeration was observed on the
fibers, with and without GO are indexed as PVDF/1 wt % GO, surface of the PVDF/GO fibers. The XPS (C1s) spectra
PVDF/0.5 wt % GO, PVDF/0.25 wt % GO, and pure PVDF for (Figure 2d) of GO confirms the presence of oxygen functional
decreasing wt % content of GO (1, 0.5, 0.25, and 0 wt %) in PVDF, groups (−CO and −COO−), which will be described in
respectively. more detail below. In addition, no agglomerates are observed
Fabrication of Nanogenerators (NGs). A schematic describing on as-prepared nanofibers. Furthermore, the prepared fibers
the complete fabrication procedure of the NG is shown in Figure 1a− are formed with a stable morphology, and no cracks were
f. The flexible, low-cost, lightweight hybrid nanogenerators were detected so that the fibers did not become brittle. The PVDF/
fabricated using a copper (Cu)−nickel (Ni) plated fine knit polyester
fabric (Coatex Industries, India) as the electrode material. First, a
1 wt % GO nanofibers have a relatively smaller diameter (∼125
(∼25 mm × 50 mm) area of nanofiber was cut from the electrospun nm) compared with the pure PVDF fiber (∼270 nm) prepared
fiber. Then, the top and bottom electrodes were prepared using a under the same conditions as presented in the inset of Figure
polyester fabric with an active contact area of ∼18 mm × 44 mm. 2a and Supporting Information, Figure S1a. The incorporation
Finally, the electrode/nanofiber/electrode configuration was enclosed of GO considerably reduces the average fiber diameter, and
between two layers of PDMS (thickness ∼0.8 mm, prepared in a this is a result of the cumulative charge density of the dispersed
mixture with a curing agent (ratio 10:1) which was cured in an oven GO sheets due to the application of a high voltage to the
at 60 °C for 1 h) to form the desired NG, as shown in Figure 1d. solution and the fiber jet during electro-spinning. This also
Nanogenerators comprising PVDF/1 wt % GO (1 wt % GO) and facilitates the electrostatic repulsion and Coulombic force on
pure PVDF (0 wt % GO) are termed GPPNG and NPPNG
respectively.
the Taylor cone which leads to a relatively reduced fiber
Characterization Methods. The X-ray diffraction patterns and diameter of the PVDF/GO nanocomposites.29,37 The crystal-
crystalline phases of the as-prepared GO and composite nanofibers linity, mechanical properties, and overall energy-harvesting
were recorded by X-ray diffractometer (Bruker, D8 Advance) with a performance are also improved due to a decrease in fiber
Cu Kα (λ = 0.154 nm) with an X-ray source at an operating voltage diameter for the PVDF/1 wt % GO composites.26,38 It is also
and current of 40 kV and 40 mA, respectively. The characteristic evident from the TEM image in Figure 2b that the GO is well
vibrational bands and crystalline phases of the nanofibers were further dispersed in the fiber matrix since GO contains several
characterized by Fourier Transform Infrared Spectroscopy (FT-IR, functional groups. Thus, it is expected that the embedded GO
TENSOR II, Bruker). Morphological analysis of GO and nanofibers
in the fiber matrix can influence the electrical conductivity,
were carried out by FE-SEM (INSPECT F50) operating at an
acceleration voltage of 20 kV and high-resolution transmission piezoelectric properties, and pressure−temperature sensitivity.
electron microscope HRTEM (JEOL-JEM 2100) operating at 200 The selected area electron diffraction (SAED) pattern of the
kV. The Raman spectra of the exfoliated GO were measured using a doped fiber, as shown in the inset of Figure 2b, revealed the
Micro-Raman spectrometer (Lab RAM HR, Jobin Yvon). The presence of electroactive β- and γ-phases. From electron
piezoelectric open circuit voltage was recorded using a National dispersive X-ray spectroscopy (EDX) (Supporing Information,
Instrument (NI) Data acquisition (DAQ) device (NI, USB 6000) Figure S1b), the presence of carbon, fluorine, and oxygen in
using a sampling rate of 1000 samples per second, interfaced with a PVDF/1 wt % GO can be observed, which indicates the
computer with a standalone program created using LabVIEW presence of oxygen functional groups in the fiber matrix.
software. X-ray photoelectron spectroscopy (XPS) was performed
by a thermo-electron system equipped with a Al Kα excitation source
The FT-IR spectra of electrospun pure PVDF nanofibers
and a hemispherical electron analyzer made by Leybold-Heraeus. The and PVDF/1 wt % GO composite fibers are shown in Figure
d33 values of the samples were measured by d33-meter (Piezoest, 2e. For the pure PVDF nanofibers, the characteristic
PM300) in HI/d33 mode (capacitance, C measurement of the vibrational peaks are observed at υ = 613, 764, 796, and 975
material is inactive) under an applied force of 0.4 N and a frequency cm−1, which correspond to the nonpolar α-phase. The
of 110 Hz. The instrument was calibrated with a piezometer reference appearance of two additional intense peaks at 1275 and 1233
sample with a d33 value of 349 pC/N. cm−1 confirm the nucleation of the polar β-phase (TTTT) and

■ RESULTS AND DISCUSSION

Materials Characterization. The surface morphology of
the semipolar γ-phase (TTTG), respectively.23−26
For the PVDF/GO nanofiber based on PVDF/1 wt % GO,
all α- peaks are diminished, and signals corresponding to the
the PVDF/1 wt % GO nanofibers is presented in Figure 2a. electroactive β- and γ-phases have appeared. A systematic
The surface of the as-prepared composite nanofiber is rougher study of other fibers with other GO contents (PVDF/0.25 wt
than that of the PVDF electrospun fibers (refer to Supporting % GO, PVDF/0.5 wt % GO) revealed that the intensity of
Information, Figure S1a) because of the incorporation of the electro-active β- and γ-phases gradually increases with an
GO nanofiller. The TEM image, shown in Figure 2b, indicates increasing GO concentration (Supporting Information, Figure
that the PVDF/1 wt % GO nanofibers consist of randomly S1c,e). In order to undertake a qualitative analysis of the α-, β-,
oriented fibers without any agglomeration, which is in and γ-phases, the absorbance intensities are normalized to the
accordance with the FE-SEM image in Figure 2a. From the 1072 cm−1 peak as it is linearly dependent on fiber thickness,
FE-SEM micrographs, shown in Figure 2c, it can be seen that regardless of crystalline modification.28 Generally, the vibra-
the prepared GO consists of randomly aggregated, crumpled, tional bands of the β- and γ-phases of the PVDF coincide since
thin, and wrinkled sheet-like structures. These closely both contain the same TTT in the chain conformation and
associated layered sheets form a disordered solid, which is give rise to common vibrational peaks, such as at 841
due to the formation of sp3 carbon from the planar sp2 carbon cm−1.26,28,39,40 The peak at 841 cm−1 for the PVDF/1 wt %
during the oxidation and heating process.36 In addition, the GO nanofibers is more intense than pure PVDF, which
HR-TEM image in the inset of Figure 2c reveals the thin, indicates the specific electrostatic interaction between the π-
2016 DOI: 10.1021/acsanm.9b00033
ACS Appl. Nano Mater. 2019, 2, 2013−2025
ACS Applied Nano Materials Article

electron cloud and the oxygen containing functional groups γ- (Dγ) phases are calculated using the Debye−Scherrer
(carbonyl and carboxylic groups) in GO and the −CH2/−CF2 equation, as shown below, and these values are tabulated in
dipoles of PVDF.41,42 It can be clearly observed from the Supporting Information, Table S1:
absorption band intensity ratio I1276/I1233 (Supporting Kλ
Information, Figure S1d) that the γ-crystalline growth is D=
almost negligible with respect to the β-phase when the GO β cosθ
concentration is increased gradually (Supporting Information, where, K is a constant (0.89), λ is the wavelength (0.1541 nm)
Figure S1f). Thus, it can be concluded that the PVDF/1 wt % of the Cu Kα X-ray radiation, β is the full-width (in radian) at
GO nanofibers consist of the largest proportion of ferroelectric half maxima (fwhm) of the intense diffraction peak and θ is the
β-phase. diffraction angle.
In addition, it is worth noting that a strong absorption band To understand the compositional changes related to
appears at 841 cm−1, which is a common characteristic of both conformational ordering of the PVDF chain due to the
β- and γ-phases. Thus, the absorption intensity of 841 cm−1 incorporation of GO in the PVDF nanofiber, XPS was
band is used to quantify the relative proportion of the performed over GO, pure PVDF, and the PVDF/1 wt % GO
electroactive phase (FEA), as a result of both β- and γ- nanofibers. In the high-resolution C1s core level spectrum of
phases43,44 (Supporting Information, Note S1). pure PVDF, which is shown in Figure 3a, two main peaks are
A FEA of 96% is achieved for the PVDF/1 wt % GO fiber as
shown in Supporting Information, Figure S1e. Furthermore,
the absorbance peak at 764 cm−1 (nonpolar α-phase) which
appears as a result of CF2 bending and the skeletal bending
vibrational mode, is completely diminished in the FT-IR
spectra of the PVDF/1 wt % GO fiber (Figure 2e). The 841
cm−1 has been deconvoluted to calculate the relative fraction of
electroactive β- and γ-phases and is shown in the Supporting
Information, Figure S2 and Note S1.
To evaluate the crystallinity of the nanofibers from the XRD
pattern of the related polarized phases, a curve deconvolution
technique was performed.26,29,44 From the curve deconvoluted
XRD pattern, as shown in Figure 2f, the data of pure PVDF
nanofibers show a diffraction peak at 18.2° (202), which is
characteristic of α- crystalline phase, and this is in accordance
with the FT-IR spectra presented in Figure 2e. Furthermore,
two additional crystalline phases can be observed at 20.3°
(110) and 20.8° (110/200),23,26 which are attributed to
electroactive γ- and β-phases, respectively. The reason behind
the electroactive phase formation in the pure PVDF nanofibers
is that the molecular chains of PVDF are uniaxially stretched
by the high electrical forces during the electrospinning process,
which forces the −CH 2 / −CF 2 dipoles for in situ
orientation.37,45 Furthermore, characteristic nonpolar α-phase
peaks at 17.6° (100), 18.2° (202), and 19.9° (110) are
diminished in the PVDF/1 wt % GO nanofibers. The presence Figure 3. High-resolution XPS spectra of pure PVDF and PVDF/1 wt
of intense diffraction peaks at 20.5° emphasizes the dual % GO in the (a) C1s and (b) F1s core level regions. (c) Schematic of
signature of both the β- and γ-phases.23,39 Curve deconvolu- a hypothetical model for electroactive phase nucleation and
tion assigns the sharp peak at 20.5° as the predominant β- interactions present in PVDF/1 wt % GO nanofibers.
phase with the coexistence of lower content of γ-phase at 20.3°
and at 18.5°. The total degree of crystallinity (χC) and the present with binding energies of 287.1 and 291.7 eV, which
crystallinity of the individual phases are calculated using curve indicate two main carbon species, CH2 and CF2, respectively.
deconvolution methodology as detailed in Supporting A chemical shift toward lower binding energies can be detected
Information, Note S2. The deconvoluted XRD patterns of for the CH2 and CF2 peaks in PVDF/1 wt % GO, with binding
PVDF/0.5 wt % GO and PVDF/0.25 wt % GO are also shown energies of 286.3 and 290.7 eV. Furthermore, a substantial
in Supporting Information, Figure S3a. The highest degree of decrease in intensity of the CF2 peak and an increase of the
crystallinity was obtained for the PVDF/1 wt % GO fiber, peak area of the CH2 species for the PVDF/1 wt % GO
which is almost 68% whereas the pure PVDF is 53% and the nanofibers are also observed in comparison to the pure PVDF.
degree of crystallinity gradually increases with the incorpo- These two observations suggest that there is significant
ration of GO. In particular, the incorporation of GO improves distinction in the electronic environment of the −CH2 and
β-phase crystallinity significantly.41,46 This is due to complete −CF2 dipoles in the PVDF chain of the PVDF/1 wt % GO
adsorption of the PVDF chain on the large surface provided by nanofibers. To investigate the formation of GO and to confirm
GO and this adsorption leads to the complete conversion of the presence of oxygen functionalities, XPS was carried out on
TGTG′ chains into TTTT chains. The heterogeneous the as-synthesized GO. The XPS survey spectra of GO
nucleation of β- and γ-phase of the PVDF chain on the GO (Supporting Information, Figure S4d) shows peaks associated
surface increases the crystallinity and the crystallization with C1s and O1s, which appeared at 285 and 533 eV,
temperature. The average crystallite size of the β- (Dβ) and respectively. The high-resolution spectral analysis of the C1s
2017 DOI: 10.1021/acsanm.9b00033
ACS Appl. Nano Mater. 2019, 2, 2013−2025
ACS Applied Nano Materials Article

Figure 4. (a) Open-circuit output voltages from pure PVDF (NPPNG) and PVDF/1 wt % GO (GPPNG) nanogenerator devices in forward
connection during repetitive impact by a human finger at ∼4 Hz. (b) Output voltage (circuit diagram shown as inset) and output power density of
the GPPNG as a function of different load resistances. (c) Capacitor charging performance of different capacitors (1, 2.2, 4.7 μF) as a function of
time during repeated finger impact on the GPPNG (10 illuminating blue LEDs as shown in the inset). (d) Open-circuit output voltage of the
GPPNG under different applied pressure.

characteristic peak, shown in Figure 2d, indicates the presence was recorded using a repetitive motion applied by a finger on
of five different peaks at 283.7, 285, 286.2, 287.7, 288 eV, the surface of the NGs at a frequency of ∼4 Hz. The process
which correspond to the sp2C, sp3C, −C−O, −CO, and was performed using a bare finger covered by a polyethylene
−COO− groups, respectively.47 Other characterization glove under the repeating compressive force of 7 N and
techniques on GO are detailed in Supporting Information, associated applied stress amplitude of 8.8 kPa, respectively. An
Note S3. open circuit voltage of ∼7 V was measured for the PVDF/1 wt
In addition, the high-resolution F1s core level spectrum, % GO-based device (GPPNG), whereas ∼1 V was generated
which is positioned at 688.1 eV, as shown in Figure 3b, reveal for the pure PVDF-based device (NPPNG), which is shown in
that PVDF/1 wt % GO exhibits a minor asymmetry at the Figure 4a. The recorded output voltages from other NGs are
higher binding energy level compared to pure PVDF. These shown in Supporting Information, Figure S5a. The output
results indicate an interaction between the −CH2/−CF2 voltage with a reverse electrode connection was also measured
dipoles of PVDF and oxygen functional groups present in (Supporting Information, Figure S5b), which clearly indicated
GO. Frequency shifts of the CH2 symmetric and CH2 that an output of similar amplitude, but with reversed polarity,
asymmetric vibrational FT-IR modes in the frequency region was observed. This indicates that the potential difference is a
of 3060−2940 cm−1 for PVDF/1 wt % GO compared to pure result of the change in dipole moment of the system under
PVDF (Supporting Information, Figure S3b) support this fact. stress; that is, it is a stress-induced polarization change due to
A noticeable shift of these bands toward a lower frequency can the piezoelectric effect.52 As a control, we have tested a
be observed, which points toward the presence of an interfacial nanogenerator in the same configuration but with only
interaction between the superficial charge existing on the GO poly(methyl methacrylate) (PMMA) nanofibers and did not
sheet and −CH2/−CF2 dipoles of PVDF in the nanocomposite observe any output voltage response (Supporting Information,
system.24,44 Figure S5c). Therefore, it can be concluded that the response
Therefore, it is evident from the above-mentioned data that is piezoelectric. When the GPPNG is subjected to a vertical
β- and γ-phase nucleation has occurred in the PVDF/GO mechanical stress, the piezoelectric β-crystal structures of the
composite nanofibers because of an interaction between the nanofibers are deformed, and thus, a potential difference is
negatively charged GO nanosheet and the dipoles of the PVDF developed between the two electrodes. As an outcome, the
fiber.41 The conversion of the nonpolar α-phase to the external free electrons are forced to the GPPNG, leading to a
electroactive β- and γ-phase is a result of the electrostatic strong enhancement in piezoelectric response by converting
interaction and/or the intermolecular hydrogen bonding the distorted structure into its stable form. When the external
between the oxygen containing functional groups and strain is released from the GPPNG surface, the potential
−CH2/−CF2 dipoles of the PVDF,41,48,49 which leads to difference between the two electrodes diminishes and the
improved ferroelectric performance for piezoelectric-based accumulated free electrons gradually move back through the
sensing and energy-harvesting applications.50,51 To understand external circuit, generating an electric current in the reverse
the interaction present between the PVDF chain and GO direction.53 As shown in Figures 4a and Supporting
sheet, a hypothetical model is constructed on the basis of the Information, S5a, the open circuit voltage gradually increased
results, as described in the schematic in Figure 3c. with an increase of the GO content in the PVDF mat. The
Piezoelectric Energy Harvesting. The piezoelectric maximum recorded output voltage is 7 V at a 1 wt % filler
performance with respect to the open circuit output voltage loading, which is approximately 7 times higher than that
2018 DOI: 10.1021/acsanm.9b00033
ACS Appl. Nano Mater. 2019, 2, 2013−2025
ACS Applied Nano Materials Article

Figure 5. Time dependent cyclic temperature change (upper panels) and rate of change of temperature (dT/dt, lower panels) in the switching
frequency of (a) 0.01 Hz and (b) 0.1 Hz. (c and d) Pyroelectric short circuit current (upper panels) and open circuit voltage (lower panels)
measurement of the GPPNG under same switching frequency. (e) Output voltage and (f) power density as a function of external resistance varying
from 250 MΩ to 1 TΩ when the GPPNG was driven by periodic thermal cycling (at 0.1 Hz).

exhibited by the NG containing pure PVDF nanofibers. This with respect to RL in Figure 4b was quantified using the
enhancement is associated with the increased longitudinal 1 V2
following equation, P = , where V is the voltage drop
piezoelectric charge coefficient, d33 ∼ −30 pC/N (Supporting A RL
Information, Figure S5e) in comparison with the pure PVDF across RL and A is effective electrode area. The maximum
nanofiber (∼ −22 pC/N) (Supporting Information, Figure instantaneous output power density of ∼6.2 mW/m2 was
S5d; details given in Supporting Information Table S2). The achieved at a RL of 1 MΩ. It has been observed that the output
reason behind the increased output performance is due to the power density of our GPPNG is found to be superior with
electrostatic interaction between the negatively charged GO respect to current state of the art nanogenerators (Supporting
nanosheet embedded in PVDF nanofibers with the −CH2/− Information, Table S3). The power is also sufficient to
CF2 dipoles present in PVDF. This interaction not only illuminate more than 10 blue LEDs in series by repeated
incorporates the nucleation but also stabilizes the electroactive human finger impact of similar load, as shown in the inset of
β-phase (surface charge induced polarization) in the PVDF Figure 4c. Thus, the GPPNG can be used as a power generator
nanofiber mat.54 Therefore, the high quality crystal structure or small-scale energy scavenger to drive self-powered electronic
and the existence of delocalized π- electrons and oxygen devices.
functional groups present in the layered structure of the GO In addition to output voltage performance, to demonstrate
improve the piezoelectric performance of the hybrid system. the energy storage ability and the application of piezoelectric
Thus, the PVDF/GO system (GPPNG) can be used as a real energy conversion performance, three capacitors (i.e., 1, 2.2,
time power source in various self-powered portable electronic 4.7 μF) were individually connected to the GPPNG through a
devices. Further experiments and applications are now carried full wave bridge rectifying circuit and charged by repeated
out and discussed using the GPPNG due to its better human finger taping (Figure 4c). It was observed that the
piezoelectric performance. PVDF/GO-based device (GPPNG) efficiently charged up the
To evaluate the instantaneous electrical power output capacitors when subjected to a periodic pressure of 8.8 kPa.
performance, the GPPNG was directly connected to electrical The charging voltage across the capacitors reached a steady
loads at different resistances (RL) ranging from 100 kΩ to 60 state (4.9, 3.6, and 2.3 V) following an exponential path within
MΩ (while applying force of 7 N at a frequency of ∼4 Hz). a short time scale of 54, 80, and 80 s for the 1, 2.2, and 4.7 μF
The measured output voltage as a function of external load capacitors, respectively. The energy stored (Estored) within the
resistances is shown in Figure 4b. The output voltage gradually capacitors reached a maximum in the case of 2.2 μF and
increases with increasing load resistance, since the discharge of reached up to 14.25 μJ. Here, Estored can be calculated as
the devices is reduced and approaches the open circuit voltage CV 2
of 7 V at a high load resistance; i.e. on approaching an Estored = 2 , where C is the capacitance of the capacitor and V
infinitely high resistance. The variation of power density (P) is the voltage across the capacitor.
2019 DOI: 10.1021/acsanm.9b00033
ACS Appl. Nano Mater. 2019, 2, 2013−2025
ACS Applied Nano Materials Article

Figure 6. (a) Photograph of wrist joint bending, stretching when GPPNG sensor is attached on the top surface of the wrist and corresponding
piezo-response with respect to output voltage signal is illustrated. Monitoring the (b) elbow joint and (c) finger bending and stretching motion by
detecting relative changes in output voltage signal as a function of time.

Furthermore, to investigate the low-range-pressure (σa) When exposed to temperature changes, it can be observed that
sensing performance of the GPPNG composed of PVDF/1 wt the short circuit current (Isc) shows a positive peak if the
% GO nanofibers, lightweight substances of different masses material is heated (dT/dt > 0) and a negative peak during the
were dropped on the upper surface of the GPPNG from a convective cooling process (dT/dt < 0). This is due to the
height of 3 cm. The GPPNG could detect an external pressure decrease in the level of spontaneous polarization during
as low as ∼10 Pa and generated an output response of 0.06 V. heating process, forcing the surface charges to flow between
The generated output voltage changes almost linearly with the two polar surfaces. When the device is subsequently
respect to the increased implied pressure in the low-pressure cooled, current flows in the reverse direction due to the
regime as seen in Figure 4d. The calculated mechanical impact attractive force of the free charges to the polar surfaces.56−58 In
ΔV
sensitivity (S) can be expressed as S = Δσ , where ΔV and Δσa Figure 5 (c, d), the GPPNG generates approximately 60 mV
a and 100 mV at a switching frequency of 0.01 and 0.1 Hz,
are termed as differences of V and σa, respectively, and the respectively. Thus, it can be concluded that incorporation of
sensitivity of the GPPNG in the low-pressure region (S = 4.3 the GO sufficiently increased the pyroelectric performance of
V/kPa) is higher than several previously reported piezoelectric the GPPNG. This improved performance can be described in
pressure sensors. A detailed comparison table of piezoelectric terms of the following two factors:
pressure sensitivity is provided in Supporting Information,
Table S4. In the large-pressure range, the sensitivity of the (1) The existence of a variety of oxygen-oriented functional
GPPNG gradually decreases. The output voltage of 7 V is groups within GO enhances the absorption in the mid-
obtained at a pressure of 8.8 kPa, which is the maximum IR region. The absorbed IR is converted into heat, which
output performance during periodic impact by a human finger. increases the temperature of GO by exciting the C−C
The output performance was also measured at 10 kPa and the bond, yielding phonons. Due to this effect, a decrease in
recorded output voltage is almost 7 V (Supporting resistance is caused by the incident IR, which triggers a
Information, Figure S5f). Therefore, the output signal becomes temperature-sensitive conductance change.59
saturated in a higher pressure range. This is possibly due to the (2) The thermal conductivity of GO can be ascribed by the
theoretical limits of effective strain in piezoelectric materials in increase in the interlayer coupling, which is provided by
the high-pressure region.55 Hence, the GPPNG has the the covalent interactions of the oxygen atoms.
capability to be used as a self-powered E-skin for biomedical The pyroelectric coefficient of the GPPNG is described in
applications such as sensing static tactile stimuli, vocal cord terms of the following equations. Under short circuit
vibrations during coughing, swallowing movements of human
conditions, Isc = P*A dT /dt and in open circuit condition,
throat and speech signal recognition due to its sensitive
P*
pressure-sensing capability. Voc = ε t ΔT ,56,60 where Isc is the short circuit pyroelectric
Pyroelectric Energy Harvesting. To evaluate the pyro- current, Voc is the open circuit pyroelectric voltage, A is the
electric short circuit peak current and open circuit peak electrode area, dT/dt is the rate of change in temperature, ΔT
voltage, the GPPNG was placed under an IR radiation test is the change of temperature, ε is the relative permittivity of
setup and a controlled temperature oscillation was applied to the material, t is the thickness across the polarization direction,
the device under periodic illumination of IR light and and P* is the pyroelectric coefficient, respectively. Appling our
convective cooling. The GPPNG can readily harvest thermal experimental data, the projected pyroelectric coefficient of the
energy due to the pyroelectric properties of the PVDF/1 wt % PVDF/1 wt % GO is 27 nCm−2 K−1, which is almost 6 times
GO nanofibers.52 When a periodic thermal fluctuation is higher than the pure PVDF fiber (4 nCm−2 K−1). The
applied to the PVDF/GO-based device (GPPNG), there is a maximum generated output power density (Figures 5e,f) was
clear enhancement of output performance with respect to the found to be ∼1.2 nW/m2, which is assessed using the relation
device made from pure PVDF nanofibers (NPPNG). When 1 Voc
2

the temperature increases from room temperature to 318 K P= A RL

, when periodic thermal energy was applied to the
(ΔT = 22K and dT/dt = 2.12 K s−1) (Figure 5a), the GPPNG GPPNG at a switching frequency of 0.1 Hz. Thus, our device
shows an output peak current of 45 pA at a lamp switching can be used as a promising waste heat energy harvester in
frequency of 0.01 Hz, which is nearly 7 times higher than that addition to its piezoelectric energy harvesting and biomedical
of NPPNG, as shown in Figure 5c. When the switching implementation.
frequency changes from 0.01 to 0.1 Hz, (ΔT = 6K and dT/dt = Physiological Signal Monitoring. Piezoelectric Pressure
1.3 K s−1) (Figure 5b), the increase in peak output current is Sensing. In order to demonstrate the GPPNG as a self-
around 10 times higher than that of NPPNG (Figure 5d). powered wearable pressure sensor, it was attached to various
2020 DOI: 10.1021/acsanm.9b00033
ACS Appl. Nano Mater. 2019, 2, 2013−2025
ACS Applied Nano Materials Article

Figure 7. (a) Photograph of the GPPNG attached to the throat of a male participant during speaking of “A”, “B”, “C”, “D”, “E”. Recorded output
voltage response curves during pronunciation of these letters with FFT signal in the upper part are also shown. (b) Relative changes in the output
voltage signal as a function of time when monitoring a coughing action (enlarged view is depicted in the inset). (c) Responsive curves of a
swallowing exercise. (d) Magnified view of one swallowing signal marked in part (c). Inset shows the application of GPPNG on the human throat.
(e) The temperature fluctuation and (f) recorded open circuit voltage of the GPPNG (photo of the GPPNG attached to a N95 breathing mask is
shown in the inset) driven by human respiratory at room temperature.

human body parts for monitoring physiological signals. The the cell phone of a doctor.61 Such a data glove may be useful in
GPPNG was employed on the wrist to evaluate the sensing the field of fine motion control in robotics such as drones and
features of the wearable nanogenerator for mechanical stimuli radio controlled cars as well as to examine human body
such as stretching and bending, and the sensing performance configuration.61−63 More importantly, this wearable skin
and generated voltage was measured, as depicted in Figure 6a. interactive strain sensor does not limit any human motion
During a quick downward wrist-bending motion, a sudden due to its high flexibility and lightweight nature.
static tensile strain was exerted on the sensor, resulting in an Moreover, to allow the graphene-based sensors to be worn
overall increase of the voltage, and it was retrieved by near the skin for a real-world application, the whole system was
straightening the wrist to its original configuration. The sandwiched using two layers of PDMS (Figure 1e). However,
response of the bending/relaxation motion of the wrist is a it should be emphasized that graphene oxide exhibits itself no
combined result of the stretching/bending effect of the skin cytotoxic reactions on human skin64,65, and graphene-based
(skin deformation), and the pressure is imparted by joint materials are also appropriate for neural prosthetic devices,
motion during repeated wrist bending. Additionally, flexion which are based on carbon,66 which indicate the potential
and extension of the elbow can be clearly distinguished by biocompatibility of our GPPNG.
fixing the strain sensor on the joint area of the elbow using The GPPNG sensor can also be utilized to detect and
adhesive tape, as shown in Figure 6b. Therefore, it can be monitor phonation (speech). When the sensor was fixed to the
concluded that the GPPNG strain sensor exhibits distinct subject’s throat, it was able to precisely monitor the pressure
output signals of different patterns related to numerous stimuli difference created by the muscle movement during speaking.
of synovial joints such as the wrist and elbow. Our device As shown in Figure 7a, it shows sensitivity toward specific
comprising electrospun PVDF/1 wt % GO nanofibers may be phonation recognition. During the pronunciation of different
valuable in epidermal electronic systems fabrication and in alphabetic characters such as “A”, “B”, “C”, “D” and “E”, the
medical applications such as monitoring patient and athlete stress that originated from vocal vibrations due to the complex
motion. muscle movement all over the throat was transferred to the
Furthermore, to demonstrate the potential of the GPPNG as sensor. Thus, the sensor exhibits distinguishable output signal
a human motion detector, the GPPNG sensor was mounted on waveforms for each alphabetic character. It can be concluded
the top surface of individual fingers of a right-hand and the from the short time Fourier transform (STFT) processed
corresponding sensing performance was monitored. As shown spectrograms for all five characters that maximum amplitude of
in Figure 6c, the sensor can readily detect and discriminate all characters is approximately inside the frequency range of
between bending and stretching motion of each finger such as 250−300 Hz and in the higher frequency range of ∼450 Hz
the thumb, index, middle, ring, and little finger. The sensor and is in accordance with the fast Fourier transform (FFT)
exhibits different patterns of output signals by measuring profile of each alphabetic character (Supporting Information,
voltage changes associated with variations in the bending. In Figure S6). These results show that the self-powered wearable
addition, these five independent strain sensors can be pressure sensor has potential application as a sound detecting
assembled into a wearable glove (data glove) to utilize it in skin and in speech rehabilitation training.67−69 In addition, our
remote patient monitoring system using wireless communica- device shows a reproducible sensing property and repeatability
tion module to transmit the information on a sick patient to toward thoracic pressure developed due to vibration of the
2021 DOI: 10.1021/acsanm.9b00033
ACS Appl. Nano Mater. 2019, 2, 2013−2025
ACS Applied Nano Materials Article

tissue around vocal cord during repeated coughing action. The

GPPNG sensor can successfully detect the two or three
■ CONCLUSIONS
In conclusion, we have presented a novel wearable pressure
distinct phases of cough (Figure 7b), consisting of the initial sensor based on biocompatible graphene oxide doped PVDF
opening burst, the blaring airflow (second phase), and possibly nanofibers, which exhibited superior piezoelectric and pyro-
a final glottal closure,70,71 as shown in the inset of Figure 7b. electric sensing performance compared with pure PVDF
The STFT processed signal of one single cough waveform nanofibers. The preparation of the PVDF/GO nanofibers via
(Supporting Information, Figure S7) validates its generation electrospinning and the complete fabrication strategy of the
due to vibration of the vocal cord (200−450 Hz). Therefore, pressure and temperature sensor device are relatively simple
the GPPNG can be used to monitor the airway flow mechanics with the combined advantages of a cost-effective fabrication
during coughing and for successive analysis and diagnosis of process and potential for large-scale production and flexibility.
coughing related to asthma and other bronchopulmonary We have demonstrated that the PVDF/GO nanofiber-based
respiratory diseases.70,72,73 Furthermore, the complex gulping sensor exhibits a high pressure sensitivity of 4.3 V/kPa, with a
(swallowing) behavior was also recorded reliably and low detection limit up to 10 Pa. The sensor exhibits
repeatedly via the pressure sensor when attached to a human outstanding response for detecting a variety of human
throat (Figure 7c,d). The relative change in voltage indicates physiological signals such as joint movements, coughing
the opening and closing event of the glottis associated with the signals, swallowing and monitoring throat muscle movement
muscle movement of the throat during agglutination behavior. in real-time during repeated speaking of different alphabetic
Such devices can be useful in a sensor-operated rehabilitation characters, confirming its potential for voice recognition.
game for patients undergoing dysphagia and odynophagia Moreover, the PVDF/GO nanofiber-based device exhibits
(painful swallowing).74 All results indicate that the as-prepared superior pyroelectric performance compared to pure PVDF
GPPNG sensor showed high sensitivity, repeatability, and with a maximum output power density of ∼1.2 nW/m2.
stability toward subtle pressure changes near human skin, Furthermore, it can sense periodic temperature fluctuation
stretching, bending, and other physiological signals, indicating during continuous breathing process and the potential
its wide futuristic application in personal health assessment and temperature sensing ability makes it promising as a breathing
clinical diagnosis. sensor. The fabricated system has promising applications in
Pyroelectric Breathing Sensor. In addition to the piezo- wearable smart skin for medical diagnostics, human health
electric sensing applications reported above, the GPPNG can monitoring, and power sources for wearable electronics and E-
be used as a self-powered breathing sensor as well as skin applications.

■
temperature sensor for human health monitoring and
diagnosis. To demonstrate its use, the GPPNG was mounted ASSOCIATED CONTENT
on a N95 mask at the location where most of the airflow
during respiration process is condensed (inset of Figure 7f). *
S Supporting Information

The whole system was worn on the human face and a The Supporting Information is available free of charge on the
temperature sensor was attached to the GPPNG during the ACS Publications website at DOI: 10.1021/acsanm.9b00033.
experiment to record the real-time temperature fluctuations Calculation of the FEA and crystallinity of the different
during breathing. The continuous breathing process led to composite fibers (PVDF/GO), table of degree of
periodic temperature differences around the mouth and the crystallinity and β-, γ- crystallite size, FE-SEM micro-
recorded temperature fluctuation during this respiratory graph of pure PVDF, EDX spectra of PVDF/1 wt % GO,
process is almost 5K, as shown in Figure 7e. Figure 7f clearly FT-IR spectra of PVDF/0.25 wt % GO and PVDF/0.5
indicates the open circuit voltage of the GPPNG, which is wt % GO fibers in the wavenumber range of 1600−600
generated due to pyroelectric effect under the given cm−1, variation of the FT-IR absorption intensity ratio of
experimental condition. The temperature of the airflow during β and γ phases (I1276/I1233) of pure PVDF and PVDF/
respiration is similar to body temperature. Therefore, it is GO fibers with respect to the concentration of GO,
possible to harvest waste heat energy from respiration75 by relative percentage of FEA as a function of the GO
wearing the above-mentioned system on the face in low- concentration, the bar diagram of the relative percentage
temperature regions and in the winter season. Moreover, the of F(β) and F(γ) for PVDF/GO fibers, the deconvolu-
breathing rate and breathing pattern are the vital signs of tion of the FT-IR spectra (920−780 cm−1) for different
human health in detecting medical problems as they provide GO doped PVDF fibers (1, 0.5, 0.25 wt %), the curve
the information about how the cardiorespiratory system is deconvolution of the XRD pattern in the 2θ range of
working. The normal respiration rate for an adult at rest is 14 15−25° for PVDF/0.5 wt % GO and PVDF/0.25 wt %
to 18 breaths per minute. Unusual respiration rates such as GO, FT-IR spectra of pure PVDF and PVDF/1 wt %
bradypnea (abnormally slow rate) and tachypnea (abnormally GO fibers in the wavenumber range of 3060−2940
rapid rate) are the alarming signs of various hidden diseases cm−1, Raman spectra of graphite powder and GO, XRD
and psychological stress. In addition, unusual breathing pattern and XPS survey spectra of GO, open-circuit
patterns are also associated with different health conditions. output voltages of the NGs made of PVDF/0.25 wt %
For an example, Cheyne−Stokes breathing is an accurate sign GO and PVDF/0.5 wt % GO, PMMA nanofibers, open-
of left ventricular dysfunction, especially for older patients circuit output voltages of NPPNG and GPPNG in
(∼80 years). From the featured results, it is clear that the reverse connection, open-circuit output voltage of
GPPNG is able to provide the information (rate and pattern) GPPNG at 10 kPa, FFT processed frequency spectrum
regarding human respiration. Moreover, its lightweight and profile during pronunciation of the letters “A”, “B”, “C”,
high-sensitivity characteristics make it a high-potential “D” and “E” and the STFT processed spectrogram for
candidate for breathing sensor for real-time health monitoring one single cough signal, comparison tables of piezo-
of aged persons and patients. electric charge coefficient (d33), output power density
2022 DOI: 10.1021/acsanm.9b00033
ACS Appl. Nano Mater. 2019, 2, 2013−2025
ACS Applied Nano Materials Article

and sensitivity of GPPNG with respect to the nano- Sensor with Ultrathin Gold Nanowires. Nat. Commun. 2014, 5,
generators reported in the literatures (PDF) 3132−3139.
(12) Segev-Bar, M.; Landman, A.; Nir-Shapira, M.; Shuster, G.;

■ AUTHOR INFORMATION
Corresponding Author
Haick, H. Tunable Touch Sensor and Combined Sensing Platform:
Toward Nanoparticle-Based Electronic Skin. ACS Appl. Mater.
Interfaces 2013, 5, 5531−5541.
(13) Maheshwari, V.; Saraf, R. F. High-Resolution Thin-Film Device
*E-mails for D.M.: [email protected]; dmandal@inst. to Sense Texture by Touch. Science 2006, 312, 1501−1504.
ac.in. (14) Jiang, M. J.; Dang, Z. M.; Xu, H. P. Giant Dielectric Constant
ORCID and Resistance-Pressure Sensitivity in Carbon Nanotubes/Rubber
Dipankar Mandal: 0000-0003-2167-2706 Nanocomposites with Low Percolation Threshold. Appl. Phys. Lett.
2007, 90, 042914−042916.
Notes (15) Dang, Z.-M.; Jiang, M.-J.; Xie, D.; Yao, S.-H.; Zhang, L.-Q.; Bai,
The authors declare no competing financial interest. J. Supersensitive Linear Piezoresistive Property in Carbon Nano-

■ ACKNOWLEDGMENTS
Authors acknowledge DST, Govt. of India for awarding
tubes/Silicone Rubber Nanocomposites. J. Appl. Phys. 2008, 104,
024114−024119.
(16) Chen, L.; Chen, G. H.; Lu, L. Piezoresistive Behavior Study on
Finger Sensing Silicone Rubber/Graphite Nanosheet Nanocompo-
INSPIRE fellowship to Mr. Krittish Roy (IF160559), Mr. sites. Adv. Funct. Mater. 2007, 17, 898−904.
Sujoy Kumar Ghosh (IF130865) and for the development of (17) Fan, F. R.; Tang, W.; Wang, Z. L. Flexible Nanogenerators for
instrumental facilities under FIST-II programme. Ayesha Energy Harvesting and Self-Powered Electronics. Adv. Mater. 2016,
Sultana is supported by Maulana Azad National Fellowship 28, 4283−4305.
(F1-17.1/2015-16/MANF-2015-17-WES-53885/(SA-III/ (18) Lang, S. B.; Das-Gupta, D. K. Pyroelectricity: Fundamentals
Website)) from UGC. Samiran Garain was partially supported and Applications. Handbook of Advanced Electronic and Photonic
by German Federal Ministry for Economic Affairs and Energy Materials and Devices 2001, 4, 22−50.
(BMWi, ZIM, 16KN033522). Authors are also grateful to the (19) Lin, Y.-F.; Song, J.; Ding, Y.; Lu, S.-Y.; Wang, Z. L. Piezoelectric
Science and Engineering Research Board (EEQ/2018/ Nanogenerator Using CdS Nanowires. Appl. Phys. Lett. 2008, 92,
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to complete the work. (20) Kang, H. B.; Chang, J.; Koh, K.; Lin, L.; Cho, Y. S. High

■
Quality Mn-Doped (Na,K)NbO3 Nanofibers for Flexible Piezoelectric
Nanogenerators. ACS Appl. Mater. Interfaces 2014, 6, 10576−10582.
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