Article

Cite This: ACS Nano 2018, 12, 5637−5645 www.acsnano.org

Protein-Based Electronic Skin Akin to

Biological Tissues
Minsik Jo,†,∥ Kyungtaek Min,†,‡,∥ Biswajit Roy,† Sookyoung Kim,† Sangmin Lee,§ Ji-Yong Park,†,§
and Sunghwan Kim*,†,§
†
Department of Energy Systems Research and §Department of Physics, Ajou University, Suwon 16499, Republic of Korea
‡
Department of Nano-Optical Engineering, Korea Polytechnic University, Siheung 15073, Republic of Korea
*
S Supporting Information
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ABSTRACT: Human skin provides an interface that transduces external stimuli into
Downloaded via UNIV OF EDINBURGH on January 29, 2019 at 01:11:53 (UTC).

electrical signals for communication with the brain. There has been considerable
effort to produce soft, flexible, and stretchable electronic skin (E-skin) devices.
However, common polymers cannot imitate human skin perfectly due to their poor
biocompatibility, biofunctionality, and permeability to many chemicals and
biomolecules. Herein, we report on highly flexible, stretchable, conformal,
molecule-permeable, and skin-adhering E-skins that combine a metallic nanowire
(NW) network and silk protein hydrogel. The silk protein hydrogels offer high
stretchability and stability under hydration through the addition of Ca2+ ions and
glycerol. The NW electrodes exhibit stable operation when subjected to large
deformations and hydration. Meanwhile, the hydrogel window provides water and
biomolecules to the electrodes (communication between the environment and the
electrode). These favorable characteristics allow the E-skin to be capable of sensing
strain, electrochemical, and electrophysiological signals.
KEYWORDS: electronic skin, silk protein, hydrogel electronic device, stretchable, water permeability

E lectronic skin (E-skin), an artificial mimic of human skin

and capable of transducing external stimuli such as
pressure, heat, and humidity to electrical signals, has
been the subject of intense study for decades with the ultimate
goal of enabling applications such as human/computer
interfaces, continuous health monitoring, and sensory skin for
robotics.1−5 To obtain reliable signals from the skin or other
biological tissues subjected to large deformation under
mechanical loading, E-skin devices should ideally be capable
of being conformally attached to three-dimensionally curved
tissue surfaces.6,7 The most common approach to realizing E-
skin devices involves the embedding of conductive fillers or
rigid electrical devices into an elastomeric matrix formed from
the likes of polydimethylsiloxane (PDMS) and Ecoflex
elastomer. Through the integration of micro- or nanostructures
into the elastomeric matrix by means of lithographic, molding,
and/or printing methods, various revolutionary multifunctional
and high-sensitivity E-skin devices have been realized.3−5,7,8
Further, the engineered synthetic elastomeric matrices, for
better permeability and skin adhesion, have been adapted to
epidermal electronics on human skin.9−11 Nevertheless, it is still
challenging to develop materials that are biocompatible, adhere
well to biological tissues, and have high permeability to water,
which has many essential functions in the human body,
including the transport of nutrients and enabling chemical and
metabolic reactions. Hence, the fabrication of stretchable and
conformal E-skins by using protein hydrogels, which are
biocompatible polymer networks filled with water or an
aqueous solution, can provide a seamless interface between
the human and E-skins.12−15
In the food and medical industries, protein-based biopol-
ymers are attracting interest as a green alternative to petroleum-
based polymers due to their biocompatibility, processing
versatility, and low cost.16,17 Among proteins, silk fibroin
protein has been identified as being particularly suitable for
biopolymer applications due to its mechanical durability,
tunable secondary structure, all-aqueous processing, and in
vivo biocompatibility.18 The excellent oxygen permeability of
silk films in the wet state, which is of a level similar to that of
human skin, also points to their potential for application in
artificial skin systems.19 Additionally, over the past decade, silk
has been the subject of high-technology reinvention in the
fields of optics and electronics. Electronic and optical micro/
nanodevices such as transistors, electrodes, and photonic
crystals have been successfully integrated onto silk films to
realize the functions of the devices (controlling the behaviors of
two quanta: photons and electrons) in a biological context.20−26
However, pure silk films tend to be stiff and brittle in the dry
Received: February 23, 2018
Accepted: May 24, 2018
Published: May 24, 2018

© 2018 American Chemical Society 5637 DOI: 10.1021/acsnano.8b01435

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Figure 1. Skin-adhering, stretchable, conforming silk protein-based hydrogel electronic skin (E-skin). (a) Fabrication process and working
principle of the skin-like hydrogel E-skin. To make the silk film stretchable and stable under hydration, Ca2+ ions and glycerol are added to the
silk aqueous solution. The solidified silk film with the silver nanowire (AgNW) electrode can act as an E-skin device under mechanical strain
and hydration. (b) Silk E-skin adhered to a wrist. No detachment is observed under bending/unbending of the wrist. (c) Polydimethylsiloxane
(PDMS) and silk membranes. A drop of water is trapped between the PDMS membrane and the substrate due to the low water permeability,
whereas the water is absorbed by the silk membrane and subsequently evaporates. (d,e) Light-emitting diode chips integrated into the AgNW
electrode are turned on when the silk E-skin is attached to biological tissue, even when the E-skin is stretched.

state. Although the blending of suitable plasticizers like glycerol
is one means of making silk films flexible and water-insoluble,
their lack of stretchability still hinders their E-skin applica-
tions.27,28 Recently, Ling et al. reported on silk films that had
been made stretchable through the addition of Ca2+ ions, but
these films proved unstable in humid environments and lost
their optical transparency, both when immersed in water and
when subjected to stretching.29
In the present study, we successfully fabricated skin-
compatible E-skin that is a stretchable, conforming, molecule-
permeable, and skin-adhering electronic device fabricated using
silk fibroin protein and a conductive silver nanowire filler
(AgNW). The incorporation of glycerol (inducer of the β-
sheets of silk molecules) and Ca2+ ions (bonder of silk
molecules via chelation and charge interaction) into the silk
matrix simultaneously offers a useful route to generate
polymorphically regenerated protein membranes with desirable
physical properties for E-skin application, and this enables the
silk E-skin to offer high stretchability (up to 400%) and on-skin
adhesion in a living environment. A nanowire (NW) network of
an arbitrary pattern was buried in the stretchable silk
membrane, allowing it to be applied as an electrode for
electrochemical sensing, electrocardiograms (ECGs), radio
frequency (RF) antennas, and the integration of optoelectronic
devices. Even when subjected to mechanical strain and
hydration, the electrodes were able to operate stably. Sensing
electrodes fabricated in this way proved capable of being
activated by analytes/water that permeated through the protein
membrane, indicating that the silk E-skin devices communicate
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with their environments through the silk skin in the same way
as real human skin. Our protein-based E-skin devices can be
used for the continuous monitoring of vital signals under
normal everyday living conditions.
RESULTS AND DISCUSSION
The preparation of stretchable silk E-skin is illustrated in Figure
1a. Briefly, an adhesive tape layer with patterns was attached to
a silicone-coated polyethylene terephthalate (PET) film to
allow the better release of the silk E-skin. An aqueous NW
solution was poured into the patterns, and then the adhesive
tape layer was peeled off, leaving the NW network. The device
was completed by releasing the silk film with the patterned NW
network after the assembly of the silk fibroin, Ca2+ ions, and
glycerol. The resulting silk film was optically transparent and
highly stretchable when subjected to mechanical strain.
To mimic human skin, high conformability, on-skin
adhesion, and permeability are highly desirable features. Figure
1b shows the silk E-skin attached to a human wrist before and
after wrist bending to demonstrate the high conformability and
on-skin adhesion of the device. In addition, when the human
skin was wrinkled, the silk membrane accurately followed the
irregular surface of the skin, whereas the PDMS membrane
became detached from the skin (Figure S1). The skin adhesion
of our silk membrane could be estimated quantitatively by
measuring peel forces for detachment of the silk film from pig
skin, the mimic of human skin (Figure S2).30 The obtained peel
forces (∼10 N/m) were comparable to those of commercial
medical-grade adhesives31 and were enhanced with increasing
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Figure 2. Structural and mechanical characterizations of stretchable silk hydrogel membranes. (a) Silk membranes before/after application of
mechanical tension. (b,c) Stress−strain plots of silk membranes at various silk/Ca2+ and silk/glycerol weight ratios at a constant humidity
(50%). (d) Fourier transform infrared spectra of silk membranes from 1750 to 1450 cm−1. This region includes two bands, corresponding to
β-sheet (1630 cm−1) and random coil (1655 cm−1). (e) Optical transmission spectra of the stretched silk membrane. Elongation induces
contraction in the vertical direction (inset), thereby making the membrane more transparent.

humidity. Moisture on an arbitrary surface could sustainably
hydrate the silk membrane and infiltrate through the network
of silk molecules (which is not possible with PDMS), such that
the buried or attached electronic devices would be able to
communicate with the analytes in the body fluid (Figure 1c).
Figure 1d,e shows light-emitting diodes (LEDs) that are
integrated into the AgNW network in the silk. All the blue,
green, and red LEDs, which were connected in series, were
successfully turned on by an electric current flowing through
the AgNW network even when attached to moist tissue subject
to stretching.
The mechanical properties of the stretchable silk membrane
can be tuned by adjusting the Ca2+ ion and glycerol contents.
We measured the stress−strain relationship of the silk
membrane to find the optimum combination of silk protein,
Ca2+ ions, and glycerol (Figure 2a). Figure 2b shows the typical
stress−strain curves for the silk membranes with different silk/
Ca2+ weight ratios when the silk solution was mixed with
glycerol at a fixed weight ratio of 10:6 (silk/glycerol). The Ca2+
ions in the silk membrane bonded to the silk molecules via
chelation and charge interaction and captured water molecules
from the air. Therefore, as the number of Ca2+ ions in the silk
membrane increased, more water molecules could be
captured.29 This resulted in a much softer and stretchable
membrane. The addition of Ca2+ ions reduces the Young’s
modulus from 69.5 to 10.5 kPa when the silk/CaCl2 weight
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ratio was changed from 83:17 to 75:25, as shown in Figure 2b.
At a weight ratio of 67:33, the resulting silk membrane was
mechanically too weak and soft (like a soft gel cream) to be
used in an E-skin application. Interestingly, the obtained
Young’s moduli are much lower than those of both PDMS and
the human epidermis (140−600 kPa),32,33 indicating that our
silk E-skin devices would have less of a feeling of “tightness” as
the wearer’s skin naturally deformed. The glycerol content also
influences the mechanical properties of the silk membrane
because glycerol can be hydrogen-bonded to the peptide matrix
and then induce β-sheet formation.27 As the glycerol content
increased, the Young’s modulus decreased (Figure 2c). Note
that the stretchability could be tuned by the humidity
condition, as shown in Figure S3. Additionally, we could
observe a hysteresis behavior in the stress−strain curve that
indicated the viscoelasticity of the silk membrane (Figure S4).
This provides useful information to estimate the fatigue lifetime
of the silk E-skin device as the absorbed energy for a cycle is
obtained.34 In the present study, those silk membranes with a
silk/CaCl2 weight ratio of 75:25 and silk/glycerol weight ratio
of 10:6 were used for E-skin applications.
Unlike the as-cast silk membrane prepared from a pure silk
solution, the redesigned stretchable silk membranes were highly
stable and robust even after soaking in water. Fourier transform
infrared (FTIR) spectroscopy was performed to investigate
their molecular structures. Figure 2d shows that our silk
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Figure 3. Electronic characterization of permeable silk E-skin. (a) Resistance of rectangular AgNW electrodes of various widths buried in a silk
film under tensile strain. Tensile strain induces an increase in the length of the electrode and therefore increases the resistance. (b)
Measurements of water vapor transmission rates (WVTRs) for PDMS membranes (black), silk membranes (red), and silk membranes
incorporating AgNW (blue). WVTRs were measured at 23 °C/40% RH. (c) Short-circuit current of a rectangular electrode as a function of
time. No change in the current is observed when a drop of water (at 50 s) and saline (at 1600 s) infiltrated to the AgNW/silk layer. (d)
Schematic of permeable silk E-skin device. (e) Short-circuit resistance between the two buried electrodes as a function of time. The permeated
water bridges the gap between the electrodes and reduces the resistance. After racking the electrode by electrolysis reaction, the resistance is
recovered. (f) Schematic of dopamine (DA) sensor using two disconnected electrodes. DA molecules combined with permeated water induce
current flow. (g) Electrical current responses upon addition of DA solutions with increasing concentrations as a function of time.

membranes contained extensive β-sheets, a secondary protein- and stable in solvents.35 The β-sheet formation in the
based structure, indicating that silk molecules were cross-linked stretchable silk was induced by the addition of glycerol,27,28
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whereas the random coil was the dominant protein structure in
the self-assembled silk. In addition, there was no significant
difference between the spectra before and after stretching. This
proved that the unstretched silk membrane already had the
maximum β-sheet content, and therefore, the high stretchability
originated from the interplay between the highly cross-linked
silk molecules and the captured water molecules.29 As shown in
Figure 2e, the silk films exhibited good optical transparency
(75% at 550 nm for the unstretched film and 90% for the
stretched film) over a broad spectral range. The transmission
increases as the thickness of the silk film decreases as a result of
the elongation of the film (thus obeying the Beer−Lambert law
T = exp(−αt), where α is the absorption coefficient and t is the
thickness of the silk film). In addition, we could obtain a
Poisson ratio (ν) = 0.33, which is comparable to those of
rubbery materials, using the equation εz = −νεx, where εz (εx) is
the strain along the direction normal to the film surface
(elongation).
The percolated network of metal NWs provides a continuous
electron transport pathway with high conductivity and good
mechanical flexibility.36−40 In particular, the infiltrated silk
protein can strongly anchor the NWs and bury the NW
network, thus forming mechanically robust and flexible
electrodes in the silk protein (Figure S5). To understand the
electrical properties of the NW electrodes in the stretchable silk
membranes, we generated rectangular electrodes of different
widths (3, 5, and 7 mm) but a fixed length (10 mm) using
AgNWs, which had an average diameter of 40 nm and an
average length of 20 μm. Figure 3a shows the measured
resistances as a function of the strain. At zero strain, as shown
in Figure S6, the AgNW/silk electrodes, regardless of their
width, all exhibited a similar electrical resistivity ρ of around 3 ×
10−6 Ω·m (200 times greater than that of bulk Ag but
comparable to that of AgNW/elastomer electrodes),41 as
L
obtained from Pouillet’s law R = ρ A , where R is the resistance,
L is the length, and A is the cross-sectional area of the
electrode. This indicates that the topology of the percolating
AgNW network is homogeneous. Under strain, the number of
junctions maintaining contact in the stretched AgNW network
decreased, and the distance between the NWs increased,
thereby increasing the value of ρ.36 Hence, the value of R for all
the electrodes increased significantly as a result of the strain
caused by the increased ρ and L, as well as the decreased A.
Additionally, we obtained the tunable gauge factors, defined as
ΔR / R 0
, where ΔR/R0 is the fraction change in the resistance
ε
and ε is the strain, over a range of 1−15, which were larger than
those of conventional strain sensors. As such, we can
confidently state that the membrane could be used for strain
sensor applications.33,42,43 The mechanical robustness of the
AgNW networks buried in the silk film can also expand the
applicability of our approach. Our previous study showed that
the AgNW/silk electrodes was very stable under cyclic bending
tests.40 As shown in Figure S7, cyclic loading and unloading
tests exhibited that resistances of the AgNW/silk electrodes
were increased as increasing the number of cycles. Never-
theless, high electrical conductivity was maintained during
cycles of strains up to 20%.
To induce communication at the biological−electrical
interface and prevent tissue damage, the on-skin (or implanted)
devices must permit the transmission of water vapor, oxygen,
and other chemical compounds. These properties are often
overlooked for bioelectronic devices. Accordingly, as shown in
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Figure 3b, we investigated the water vapor transmission rate
(WVTR) of three types of membranes: silk (660 μm
thickness), silk incorporating AgNW (700 μm thickness), and
PDMS (630 μm thickness). All the WVTRs were measured at
23 °C/40% RH. The water was heated on a hot plate at 50 °C.
The bulk silk and AgNW-buried silk membranes were found to
have WVTRs ranging from a high of 4046 g·m−2·day−1 to a low
of 1720 g·m−2·day−1. These values are comparable to those of
common bandages and wound dressings.44 On the other hand,
the WVTR of a PDMS membrane was negligible, which would
be detrimental to epidermal and biological tissues over
prolonged usage. The electrode also exhibited a stable
resistance when smeared with water and saline, indicating
that it would operate reliably on wet skin and tissue, even in
humid environments (Figure 3c). Even if the wettability of the
electrode surface worsened due to the presence of the buried
AgNWs (Figure S8), the droplets of water and saline could fully
infiltrate the membrane in a few minutes. Additionally, we
examined the diffusion properties of the silk hydrogel by using
rhodamine B dye solution (Figure S9). Based on a
simplification of Fick’s law, diffusion coefficients of 9.7 ×
10−3 mm2·s−1 for the silk membrane and 7.1 × 10−3 mm2·s−1
for the silk membrane incorporating AgNW, both of which are
comparable to those of porous silica gel,45 were obtained.
These results indicate that the silk hydrogel membrane provides
a reliable and speedy hydrogel window between the E-skin
device and the environment.
Using the skin-like traits of the silk protein membrane, the
buried electrode and device can communicate with the
environment via the transportation of molecules through the
silk hydrogel window (Figure 3d). As a proof-of-concept
experiment (Figure 3e), we investigated the resistance between
two separated line electrodes when a small amount of water was
dropped onto the opposite surface of the hydrogel
window.12,46,47 Upon reaching the electrodes, the infiltrated
water induces a decrease in the resistance, such that water
electrolysis can start. Due to the high surface-area-to-volume
ratio of the AgNW network, the bubbling of the electrolysis
rapidly damages the AgNW electrode such that the resistance
level is restored. Meanwhile, the bulk electrodes exhibited only
a low level of electrolysis (Figure S10), and the same
electrolysis reaction occurred when a small amount of saline
was dropped instead of water (Figure S11). It should be noted
that the small amount of ions in the permeated liquid (water or
saline) had an even weak influence on the electrical
conductivity of the AgNW electrode, as already shown in
Figure 3c. This concept could be applied to the electrochemical
recording of dopamine (DA) levels, which is an electroactive
and critical neurotransmitter enabling neuronal communica-
tion.48−50 We generated a silk insulating gap (around 500 μm
in width) between the electrodes such that the electrical current
could not flow in the dry state. As shown in Figure 3f,g, a
droplet of DA aqueous solution infiltrated the silk insulating
gap, making it conductive. The current flow increased with the
DA concentration, indicating that this configuration could be
used as an electrochemical sensor. It should be noted, however,
that even pure water in the silk gap would induce a current due
to the presence of ions. In this case, however, the current
continuously decayed, while there was no current flow once the
device had stabilized. A stable current flowed when the gap was
bridged by the infiltrated DA.
Our electrode is capable of conformal and intimate contact
with human skin, making it a viable alternative to conventional
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Figure 4. Wearable AgNW/silk electrodes for electrocardiograms (ECGs). (a) Schematic diagram of fabrication of AgNW/silk electrode. (b)
ECG recording with commercial Ag/AgCl and AgNW/silk electrodes. In the case of the AgNW/silk electrode, ECGs were captured before
and after the subject exercised. The records show that the heart rate increased after exercising. (c) Enlarged ECG signal traces, comparing P,
Q, R, S, and T waves obtained by commercial Ag/AgCl and AgNW/silk electrodes. (d) Schematics and photos of conformal attachment of
AgNW/silk electrode. (e) ECG signals captured by electrodes attached to bump of the wrist. The nonconforming nature of the commercial
electrode induces a large amount of noise in the signal.

Ag/AgCl wet electrodes for the recording of electrophysio-
logical signals. Although Ag/AgCl wet electrodes are of high
quality and suitable for short-term clinical use, they cannot be
used for long-term wearable applications due to need for an
electrolytic gel layer, which irritates the skin and causes signal
degradation.51 By adding a metal cap to the patterned AgNW
network and performing silk curing, a wearable silk protein
electrode for measuring ECG signals was produced (Figure 4a).
Figure 4b shows the ECG signals captured with a commercial
Ag/AgCl electrode and the silk/AgNW electrode, both being
applied to a forearm. Although the ECG signal from the silk/
AgNW electrode is slightly noisier and weaker, each wave (P,
QRS complex, and T) is clearly defined, and the absence of a
wandering baseline shows that our electrode is well-attached to
the skin, as shown in Figure 4c. The noise can be reduced by
adding a postprocess filter to the Arduino-based signal
processing circuit used here. For long-term and daily use, the
capture of ECG signals must be possible despite increasing
degrees of movement. The conformally attached silk/AgNW
electrode could record ECG signals even when attached to the
sweaty skin of a subject who had been running, producing
clearly visible P, QRS complex, and T signals (Figure 4b). The
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silk hydrogel film could be better adhered to the hydrated or
moistened skin (Figure S2), which led to reduction of the
skin−silk interface impedance. Therefore, the noise of the ECG
signal from the sweaty skin after exercise was reduced.
Meanwhile, the commercial electrode lost its adhesion (Figure
S12).
A device that is incapable of conformal contact cannot
acquire a clear ECG signal on highly curvilinear skin surfaces
(e.g., the skin covering protruding bones). Figure 4d shows
electrodes attached to the bump of the wrist. We attempted to
apply a commercial electrode to the skin, but it was inevitable
that some part of the electrode was released from the skin. This
led to there being a higher signal-to-noise ratio and a weaker
voltage of the ECG signal (Figure 4e). The silk/AgNW
electrode perfectly conformed to the protrusion and therefore
was able to capture a relatively clear ECG signal. These results
show the remarkable potential of the silk/AgNW electrode as a
skin-compatible, skin-conforming, and skin-adhering electrode
for long-term daily health monitoring.
A useful component that could be incorporated into a
functional E-skin device is an RF antenna for wireless
communications. For telemedicine applications, mechanically
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deformable RF antennas are incorporated into wearable
systems.52 Using our method, a stretchable loop RF antenna
was successfully fabricated (Figure 5a). At zero strain, the
fabricated RF antenna exhibited resonance at the frequency of
3.6 GHz (corresponding to a half-wavelength) with a return
loss (S11) of −16.1 dB, indicating that more than 97.3% power
could be transmitted at the resonant frequency, as shown in
Figure 5b. As the applied strain increased, S11 increased due to
the deterioration in the electrical conductivity of the AgNW
Figure 5. Stretchable radio frequency (RF) antenna. (a) Loop RF
antenna before (top) and after (bottom) stretching. (b,c) Return
loss (S11) of antenna for different strains. For (b) small and (c)
large strains, the resonant frequency increases with the strain.
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network, which was accompanied by a shift in the resonant
frequency. Additionally, at large strains of over 100%, resonant
behavior was successfully obtained from the stretched RF
antenna (Figure 5c).
CONCLUSION
In summary, we have successfully fabricated stretchable,
conformal, and water-permeable E-skins by using silk protein
and a conductive nanomesh. The NW electrodes buried in the
protein membranes exhibited high and stable conductivity
despite the application of mechanical forces and the infiltration
of water/saline in the environments in which E-skin devices are
applied and could be designed to sense strain, electrochemical,
and electrophysiological signals by recording the changes in the
electrical conductivity. Like real skin, the stretchable silk
hydrogel membranes provided a communicating channel to
interface with vital biological signals from the soft tissues, while
also having other biofriendly traits. Our approach has opened
up the possibility of implementing skin-like E-skin devices in
important applications such as the monitoring of human health
and environmental conditions, and the treatment and
prevention of diseases.
METHODS
Silk Fibroin Solution Preparation. The Bombyx mori cocoon
fibers were boiled in 0.02 M Na2CO3 solution for 30 min to remove all
sericin protein. The remaining fibroin fibers were rinsed with distilled
water more than three times and then dried in air for 24 h. To prepare
silk solutions with the required silk/Ca2+/glycerol ratios for fabricating
the stretchable silk films, the degummed silk fibers were dissolved in
CaCl2/glycerol/formic acid solution. In a typical experiment, 1 g of
CaCl2 (Sigma-Aldrich, C1016-100G) was first dissolved into 20 g of
formic acid (Sigma-Aldrich, F0507-1L), and then 3 g of fibroin fibers
was also dissolved into the solution. After these processes, glycerol
(Sigma-Aldrich, A16205) was added at a ratio of 60% by weight to
make the silk films highly stable in water.
Fabrication Process. To generate a patterned AgNW electrode in
a silk film, a stencil mask of an arbitrary pattern was prepared using
commercial adhesive tape and then attached to a silicone-coated PET
substrate (silicone release film, i-ONE FILM). The patterns in the tape
mask were generated using a medical scalpel and razor blade. Next, a
AgNW aqueous solution (Nanopyxis Co., Ltd., 0.3 wt %, I27D-
KNS6KL) was poured onto the PET film with the patterned mask and
then dried at 50 °C on a hot plate. After the adhesive tape mask was
released to yield the patterned AgNW on the PET substrate, the
prepared silk solution was poured onto the PET substrate with the
AgNW pattern and then dried under ambient conditions for >24 h. To
connect the silk E-skin to other electronics, fine copper wires (Nilaco,
CU-111267) were attached to the buried AgNWs using Ag paste. Red
LEDs (WELED, 1000001407), green LEDs (WELED, 1000001408),
and blue LEDs (WELED, 1000001410) were applied to the silk E-
skin, again using Ag paste.
Tensile Strain Measurement. Stretchable silk films measuring 20
mm (W) × 30 mm (L) × 0.5 mm (H) were prepared. The films were
suspended vertically relative to the ground. Then, force was applied by
hanging weights from the films, and the stretched length was
measured.
Optical Characterization of Silk Films. Fourier transform
infrared spectroscopy (Thermo Scientific, Nicolet iS50) was used to
analyze the molecular structure of the chemically cross-linked silk. To
measure the transmission, white light from a halogen lamp was used to
illuminate the silk films. The transmitted light was captured by the tip
of a multimode fiber with a 200 μm core diameter placed on the
opposite side of the film and sent to a spectrometer (Ocean Optics,
USB-2000). A reference signal was collected using an aluminum
mirror. The silk film was mounted in a holder and stretched while the
transmission was being measured.
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Electrocardiography. A AgNW circular pattern with a 2 cm
diameter was generated on the PET substrate, and then a metal cap,
taken from a commercial ECG electrode (3M, Monitoring Electrode),
was superposed on the AgNW pattern using Ag paste. ECG signals
were obtained from the electrodes that were connected to the ECG
amplifier of an Arduino Uno system and an ECG sensor (Single Lead
Heart Rate Monitor - AD8232, SparkFun). Three prepared electrodes
were attached to the skin: the negative electrode to the right wrist, the
positive electrode to the left wrist, and the ground electrode to the
right thigh.
Radio Frequency Antenna. A loop antenna was designed with a
resonant frequency of 3.5 GHz, corresponding to a half-wavelength.
To connect the RF antenna to the measurement setup, a copper wire
was indium-soldered to the AgNW pattern in the silk film, and then
the other end of the copper wire was connected to the SMA
connector. Using a network analyzer (Anritsu, 37247D), the
electromagnetic reflection of the AgNW/silk RF antenna was analyzed
by observing the impedance matching. Prior to the measurements, the
analyzer was calibrated to minimize errors in the reflection
measurements, including the directivity, source matching, and
frequency tracking, while ensuring a better frequency response from
the RF antenna.
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsnano.8b01435.
Adhesion to skin performance (S1); adhesion properties
of a silk hydrogel on skin (S2); mechanical properties of
a silk hydrogel film at different humidity conditions (S3);
viscoelasticity of a silk hydrogel membrane (S4);
morphology of silk film incorporating a AgNW (S5);
electromechanical response of AgNW/silk nanocompo-
site (S6); mechanical durability of AgNW/silk electrodes
under cyclic strains (S7); wettability of a stretchable silk
hydrogel membrane (S8); diffusion characteristics of
permeable silk hydrogel membranes (S9); water-
permeable silk hydrogel membrane (S10); electrolysis
reaction by the permeated saline (S11); peel-off adhesion
of a commercial ECG electrode (S12) (PDF)
AUTHOR INFORMATION
Corresponding Author
*E-mail: sunghwankim@ajou.ac.kr.
ORCID
Kyungtaek Min: 0000-0001-7626-043X
Ji-Yong Park: 0000-0001-5117-3532
Sunghwan Kim: 0000-0002-6097-5630
Author Contributions
∥
M.J. and K.M. contributed equally to this work.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
The authors acknowledge support from the National Research
Foundation (NRF) of Korea (No. 2017R1A2B4010807), the
GRRC program of Gyeonggi province (GRRC-AJOU-2016-
B01, Photonics-Medical Convergence Technology Research
Center), and the Korea Institute of Energy Technology
Evaluation and Planning (No. 20164030201380, Human
Resources Program in Energy Technology).
5644
Article
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5645 DOI: 10.1021/acsnano.8b01435

ACS Nano 2018, 12, 5637−5645