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org Research Article

Bioinspired, High-Sensitivity Mechanical Sensors Realized with

Hexagonal Microcolumnar Arrays Coated with Ultrasonic-Sprayed
Single-Walled Carbon Nanotubes
Changyoon Jeong, Hangil Ko, Hyun-Tak Kim, Kahyun Sun, Tae-Hyuk Kwon,* Hoon Eui Jeong,*
and Young-Bin Park*
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sı Supporting Information

ABSTRACT: The development of a flexible electronic skin (e-skin) highly

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sensitive to multimodal vibrations and a specialized sensing ability is of great

interest for a plethora of applications, such as tactile sensors for robots,
seismology, healthcare, and wearable electronics. Here, we present an e-skin
design characterized by a bioinspired, microhexagonal structure coated with
single-walled carbon nanotubes (SWCNTs) using an ultrasonic spray
method. We have demonstrated the outstanding performances of the device
in terms of the capability to detect both static and dynamic mechanical
stimuli including pressure, shear displacement, and bending using the
principles of piezoresistivity. Because of the hexagonal microcolumnar array,
whose contact area changes according to the mechanical stimuli applied, the
interlock-optimized geometry shows an enhanced sensitivity. This produces
an improved ability to discriminate the different mechanical stimuli that
might be applied. Moreover, we show that our e-skins can detect,
discriminate, and monitor various intensities of different external and internal vibrations, which is a useful asset for various
applications, such as seismology, smart phones, wearable human skins (voice monitoring), etc.
KEYWORDS: electronic skin, interlock-optimized geometry, hexagonal microcolumnar structure, ultrasonic spray method,
mechanical sensing

1. INTRODUCTION discriminate a vast number of mechanical stimuli including

Electronic skins have been developed to mimic the sensing
capabilities of human skin and have numerous applications
including robotics, healing process monitoring, wearable
electronics, and medical diagnosis.1−12 A number of ongoing
studies aimed at developing electronic skins and other similar
sensors exploit different physical properties of the materials,
namely, resistivity,13,14 capacitive effect,3,15−17 optical ef-
fect,18−22 piezoelectricity,23−25 and triboelectricity.1,5,26−28
Resistive devices, transducing applied mechanical stimuli into
electrical signals, are particularly noteworthy for their simple
structure. Moreover, these devices tend to simplify the
postacquisition signal processing. A plethora of materials can
be used to realize different kinds of sensors, from carbon
nanofiber 29 to graphene, 30−33 from carbon nanotubes
(CNTs)8,34,35 to metals (Cu,Au and Ag),2,12 as well as
conductive polymers36 and semiconducting nanomaterials.7,11
Each of these materials leads to different device designs and
sensing capabilities. Many sensors with unique designs using
piezoresistive sensing materials have been reported.3,9,11,12,37
Among these sensors, the devices with interlocked geometrical
features show high sensitivity and the capability to detect and
pressure, shear, bending, and torsion.38,39 However, most of
these devices employ a structure in which two sets of
interlocking geometries are simply put together against each
other, which leads to difficulties in reliably sensing various
directional forces such as shear, bending, and vibration. For
instance, sensors with multiscale patterned structures have been
proposed for improved stability and sensitivity.3,11,12 In the
previous work on patterned nanocomposites, a general approach
of dispersing the CNTs in the polydimethylsiloxane (PDMS)
matrix has been employed.6,8,25,33,37−39 This results in the
CNTs, which essentially serve as nanoscale sensing elements,
embedded in the matrix, thus preventing uniform coverage of
CNTs on the sensor surface. To overcome this limitation, a
number of wet techniques to coat substrates with CNTs have
Received: January 2, 2020
Accepted: April 1, 2020
Published: April 1, 2020

© 2020 American Chemical Society https://dx.doi.org/10.1021/acsami.9b23370

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Figure 1. Bioinspired, SWCNT-coated hexagonal microcolumnar arrays. (a) Various coating methods (drop casting, air spray, and ultrasonic spray)
for coating in micropatterned structure. (b) Coating method comparisons by SEM and real images. (c) Tilted SEM image of the SWCNTs sprayed
hexagonal microcolumnar structures. (d) Photograph showing the flexibility and partial transparency of the SWCNT-coated microcolumnar arrays.

been employed, including dip coating,40 spin coating,41 spray
coating,42 printing,9,43 and electrophoretic deposition,44 espe-
cially for single-walled carbon nanotubes (SWCNTs). Although
these techniques are easy to implement and can be scaled up to a
commercial level, drawbacks lie in their multistep nature and the
necessity to employ harsh chemicals. The SWCNTs have to be
pretreated, dispersed, deposited, and finally dried. Moreover,
such a process degrades the intrinsic electrical properties, as
grafting of functional groups onto the sp2 framework often
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damages the individual SWCNTs, which increases the number
of junctions. Here, we demonstrate a multifaceted approach to
enhance the sensing performance of a patterned polymeric
sensor. First, inspired by the compound eye, hexagonal basalt
columns, and honeycombs, whose tightly fit hexagonal
structures show stability in buckling and compact geometry in
biological systems, we have developed a sensor based on
interlocked hexagonal microcolumnar arrays for enhanced
sensing stability.45−47 Second, we employed the ultrasonic
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spray method to evenly coat the arrays with SWCNTs for
maximized sensing performance. The formation of nano-
structured SWCNT layer using ultrasonic spray coating was
studied and compared with conventional air-spraying and dip-
coating methods. In ultrasonic spray coating, an aqueous
SWCNT solution is ultrasonically atomized, and fine droplets
are sprayed on micropatterned PDMS by compressed nitrogen
carrier gas, resulting in highly uniform SWCNT coatings. The
pressure wave generated by ultrasound (180 kHz) in solution
generates small vacuum bubbles that violently collapse.48 This
cavitation produces strong hydrodynamic shear forces, high-
speed impinging liquid jets, and thereby de-agglomeration of the
solutes. Using the ultrasonic spray coating method, which
provides a route to cost-effective production of extremely
uniform coatings, we have developed a highly sensitive, rapidly
responding, and versatile (capable of sensing both static and
dynamic mechanical stimuli) sensor based on tightly interlocked
hexagonal microcolumnar polymeric arrays coated with
SWCNT. In particular, we demonstrate that our e-skins exhibit
reliable sensing capabilities with an operating voltage of only 1 V.
This is achieved for both static and multiple dynamic mechanical
stimuli. We also demonstrate that our design, which relies on
direct contact within SWCNT under external stimuli, can be
exploited to perceive high-frequency dynamic stimuli associated
as well as different intensities of external and internal vibration.
Moreover, our e-skins can also detect very small physical weights
(10 mg) and even tiny amounts of sprinkled water (10 μL).
2. EXPERIMENTAL SECTION
2.1. Fabrication of Interlocked SWCNT-Coated Microhex-
agonal Structured Columnar Arrays. For the fabrication of the
PDMS microhexagonal structured columnar arrays, a mixture of PDMS
base (Sylgard 184, Dow Corning) and a curing agent (Sylgard 184,
Dow Corning) in a 10:1 ratio was poured into a microhexagonal
patterned Si mold. Microhexagonal structured columnar arrays of
different heights were fabricated by conventional photolithographic
technique with a dry etching process and using permanent epoxy
negative photoresist (Su-8 2025, 2050, 2075, and 2100). The patterned
Si mold was coated with a self-assembled monolayer (SAM, FOTS
(1H,1H,2H,2H-Perfluorooctyltrichlorosilane)) (Sigma-Aldrich) to
help the demolding of the PDMS microcolumnar arrays with high
aspect ratio (25, 50,75, and 100 μm). After the PDMS was cured at 70
°C in the dry oven for 2 h, the patterned PDMS arrays were coated with
SWCNT (KH Chemicals Co., Ltd.) using a high-precision ultrasonic
spray-coating machine (Sonotek Inc.). The ultrasonic spray coating was
performed with an ExactaCoat system fixed with 180 kHz impact
ultrasonic nozzles (Sono-Tek Corp.). The prepared SWCNT solution
(0.1 wt % in H2O) was fed into the ultrasonic nozzle system at the spray
rate of 0.3 mL min−1. The nozzle-to-substrate distance (10 cm) and the
compressed N2 gas pressure (3.0 psi) were used to the PDMS patterned
array at a spray rate of 20 mm s−1 on a temperature-controlled (100 °C)
stage.
To compare with the ultrasonic spray coating, air spray coating was
performed with a conventional air spray gun (IWATE Corp. Japan, 0.5
mm of nozzle diameter). The SWCNT solutions was fed into the air
spray nozzle at the fixed spray rate of 1 mL min−1, and sprayed to the
PDMS patterned array on a heating plate (100 °C). In the drop casting
method, 2 mL of SWCNT solution was dropped on the surface of
PDMS patterned array by micro pipet (EPPENDORF Corp. Germany)
and annealed at 100 °C for 1 h.
2.2. Characterization. The morphologies of the microhexagonal
columnar array coated with SWCNT were characterized using a field-
emission scanning electron microscopy (FE-SEM; S-4800, Hitachi).
The sheet resistances of the samples with different heights were
measured using a four-point probe measurement system (CMT-
SR1000N, Advanced Instrument Technology, Korea). The piezor-
esistive properties of the electronic skins were measured using a two-
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probe method at 1 V (6430-SMU, Keithley, US) with a Cu wire
electrode and silver paste to reduce the contact resistance. To evaluate
and apply mechanical forces on the electronic skins, we used a high-
precision universal material testing system (Instron 5982) (pressure
and bending) and bonded an acrylic plate to a compression and
bending jig in order to prevent any disturbance of the electrical signal.
For the shear-displacement measurement, Kapton tape was attached on
the stand of the experimental equipment to tightly fix together sample
and equipment; shear displacement was then applied on the e-skins
using a reciprocating friction wear test system (NEO-TRIBO RFW 16).
To investigate the different levels of external vibration and control the
intensity of vibration, a vibration motor used for smartphones was
connected to a regulated DC power supply (DAUNANOTEK Co.,
Ltd., Korea) capable of generating different intensities of vibration, and
a digital vibration meter (1332B, Showa Sokki Co., Japan) was used to
measure the applied vibration.
3. RESULTS AND DISCUSSION
The outstanding feature of our device is the interlocked
hexagonal micrcolumnar arrays uniformly coated with
SWCNTs. They were easily fabricated by micromolding, i.e.,
pouring the mixture of polydimethylsiloxane (PDMS) prepol-
ymer and curing agent into a microhexagonal-patterned silicon
mold. The micromolding process produces a flexible film with
hexagonal shaped micro arrays, characterized by a lateral
dimension of ∼100 μm, a pitch of 100 μm, and heights of 25,
50, 75, and 100 μm. The resulting structures were optimized for
interlocking. To fabricate the electronic skins in an easy way, two
flexible PDMS films with arrays of microhexagonal pillars were
ultrasonic sprayed with SWCNTs and combined with patterned
sides perfectly interlocking each other. The thickness and
density of SWCNT coating are controlled by the number of
spray-coating cycles and the speed of the spray head. The head
moves in a rectangular pattern over an area wider than the
sample size and side wall is uniformly coated with SWCNTs
(Figure S1). Compared to conventional process, the results
obtained from ultrasonic spray coating showed rapid drying, less
material usage, reduced roughness, and better filling of the pores,
resulting in optimized adhesion. On the other hand, conven-
tional air spray and dip coating processes show high roughness
and significant aggregation of SWCNTs because of hydrophobic
interactions in a slow-dry process (Figure 1a). The magnified
SEM images of ultrasonic and air sprayed samples show clear
differences in surface roughness and coating uniformity of
hexagonal structure (Figure S2a, b). It is clearly shown in both
the scanning electron microscopy and real images that because
of the nature of ultrasonically atomized droplets (13 μm
diameter), the micropatterned surface of PDMS (for all column
sizes of 25, 50, 75, and 100 μm) is filled with the SWCNT
(Figure 1b). We also measured the sheet resistance of samples
with various heights using a four-point probe method. As shown
in Figure S3, there are no significant variations in sheet
resistance, evidencing uniform SWCNT coating.
Our electronic skin exhibits a microhexagonal pillar-patterned
conductive film with configurations for optimized mechanical
interlocking due to their structures coated with SWCNTs
(Figure 1c). Figure 1d shows that our structure is flexible and
partially transparent. The taller the hexagonal structures sprayed
with SWCNTs, the lower the transparency, as shown in Figure
S4. In this study, we systematically varied the aspect ratio of the
microhexagonal, uncoated and SWCNT-coated pillars (Figure
S5a−c) and investigate the effect of their shape on the sensing
performance of our e-skin as well as the strain-induced change in
the contact area between the interlocked columnar structures.
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Figure 2. Pressure and shear sensing capability of the electronic skins. (a) Schematic of the comparison of the pressure and shear sensing mechanism of
the circular and hexagonal micro columnar arrays (height 25 μm). (b) Comparison of the pressure-sensing capabilities and (c) shear-sensing
capabilities of the circular and hexagonal microcolumns. Change in the relative resistance as a function of(d) pressure and (e) shear displacement for
different heights of the e-skins. (f) Compressive strain and (g) shear displacement cyclic test (100 cycles in 1 Hz) under 5% strain and 1 mm shear
displacement variations.

The basic working principles of piezoresistive hexagonal and pressure and shear force induce either direct contact or
circular columnar structures are illustrated in Figure 2a. External separation between the interlocked microcolumnar arrays
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Figure 3. Change in relative electrical resistance of an electronic skin under three-point bending. (a) Static and (b) cyclic bending sensing capability of
the e-skin.
coated with SWCNTs. When pressure or shear force is applied
to the samples, the circular pillars show only line contact (i.e.,
the two pillars touch only along a line), whereas full surface
contact occurs between interlocked hexagonal pillars in the same
conditions. A simple circuit model can be developed to
understand the sensitivity differences between circular and
hexagonal pillars subject to pressure and/or shear forces. The
resultant resistance (R) of a hexagonal pillar under external
forces is the sum of two components: the two resistances of the
hexagonal pillars coated with SWCNT (RH) and the contact
resistance at the interface (Rc). This is summarized in eq 1:
R = 2RH + R c (1)
The contact resistance as a function of the physical and
geometrical parameters of the hexagonal structures is given in eq
2, whereas eq 3 gives the expression for RH.
ρ2 3
Rc =
d (2)
where ρ is the specific resistivity and d is the contact length.
ρ (l − d )
RH =
3 3 a2
2 (3)
where l is the height of the pillar and a is the length of one side of
the hexagonal structure. To demonstrate the impact of the
geometrical parameters (height and length of the contact surface
in particular) and the shape on the resistance of our SWCNT
sprayed e-skins, we have done a comparison among the
hexagonal arrays, the circular arrays, and a planar structure
and Their SEM images are shown in Figure S6a−d. We also
tested microhexagonal pillar arrays with different heights. All
samples showed a decrease in electrical resistance when the
pressure was increased, whereas the resistance increased when
the shear displacement was reduced. However, sensitivity and
sensing range were modulated by configurations and heights.
Figure 2b shows the relative electrical resistances (ΔR/R0) of
the SWCNT-coated samples for different configurations. It is
evident that the structure with microhexagonal pillars with
tightly interlocked geometrical arrays exhibits higher sensitivity
than the structure with microcircular pillars with interlocked
geometrical arrays when the applied compressive strain is
increased from 0 to ∼1%. We attribute the sensitivity difference
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between these two structures primarily to the extent of the
contact area (we have a line contact for the second and a surface
contact for the first): the resulting contact resistance (Rc)
changes as a result of the change of direct SWCNT contact area
between two interlocked arrays. Theoretical calculations of
stress distribution and contact area variation verify that, under
normal and shear forces, larger contact area changes occur in the
structure with the interlocked hexagons than in the one with
circular shapes (Figure S7a−c). Compared to previously
interlocked sensors,3,11,12,49 there is a relative resistance increase
when shear displacement is increased, as shown in Figure 2c.
Before applying shear displacement, the SWCNT-sprayed
samples were preloaded with a 1 N normal force to engage
the upper and lower arrays of microcolumns and form a
conductive electrical network via direct contact of the SWCNTs
between the upper and the lower microcolumns. The
subsequent variation of the shear displacement resulted in
multiple separations of the SWCNT sprayed microcolumnar
structures, which led to a decrease in contact area in the opposite
direction of the applied shear displacement. To study the impact
of the microstructures on the capabilities of the sensor, the
relationship between different heights of the microcolumns, and
the response to mechanical stimuli (pressure and shear), we
compared the piezoresistive effect of the SWCNTs on the
microcolumnar arrays with varying heights and that of SWCNTs
on a planar sample. Figure 2d shows that the relative resistance
of e-skins decreases rapidly with increasing normal pressure and
that the rate of decrease is then reduced when high-pressure
regimes are reached. The largest decrease in relative resistance is
observed in the sensor with the shortest pillars (25 μm); on the
other hand, the planar sample shows no response. The amount
of variation in the relative resistance with the height of the
microcolumnar arrays can be attributed to the contact area
before pressure is applied. Because the contact area affects the
sensitivity, the interlocked microhexagonal surface with the
shortest microcolumns rapidly maximizes the contact area,
causing an abrupt variation of the relative resistance but also
reducing the sensing range as predicted by eqs 2 and 3. Figure 2e
shows that the relative resistance increases as larger shear
displacements are applied. Both initial resistance and adhesion
between interlocked microcolumnar arrays vary with pillar
height and this affects the response to variations to shear
displacement; the shortest structures (25 μm) show outstanding
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Figure 4. Electrical response of the e-skin operating with a small applied weight (10 mg). (a) Fall time and (b) rise time.
Figure 5. Compressive strain-resolved measurements of the output signal as a function of the applied ∼5% compressive strain at different frequencies:
(a) 1, (b) 2, and (c) 3.6 Hz.
sensitivity compared to the other sensors with higher pillars. For
a quantitative analysis of the shear sensitivity of the sensors, we
define the shear-displacement sensitivity (S) in the linear range
for the same normal pressure loadings as S = (R/R0)/(s), where
R and s are the resistance and shear displacement, respectively.
The interlocked hexagonal arrays exhibited a shear-displace-
ment sensitivity of 1.39 mm−1 with a 25 μm pillar height.
Relatively short interlocked microcolumnar arrays are easily
separated by shear displacement, resulting in a large variation of
relative resistance. Other samples with larger characteristic
heights (≥50 μm) and preloaded with 1 N normal force are
strongly interlocked by each other, and this leads to smaller
changes of relative resistance under shear displacement in
comparison to samples with short microcolumns. Multiple
mechanical cyclic tests of compression (Figure 2f) and shear
displacement (Figure 2g) were performed. The relative
resistance changes are well matched with compressive strain
and shear displacement changes. The hysteresis stress−strain
curves under compression are shown in Figure S8. In addition to
mechanical stimuli, such as pressure and shear displacement, we
were also able to detect and discriminate bending, because the
tightly interlocked geometry of the microhexagonal arrays
provided different deformation patterns. Figure 3 shows the
sensing behavior when subjected to three-point bending, in
which the sensor is transversely loaded at the midspan (with a
concentrated load) while being supported at both ends. When
the load carrier locally presses down on the sensor, contacts are
created in the central zone, whereas separations occur at the
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edges, resulting in relative resistance changes. Figure 3a shows
the change in the relative electrical resistance under static
curvature (i.e., static bending). As the bending is increased,
direct SWCNT contacts are formed in the middle region of the
interlocked structures causing a proportional decrease of the
relative resistance. For quantitative analysis, we define the
bending curvature sensitivity (B) in the linear range as B = (ΔR/
R0)/(C), where R and C are the resistance and applied bending
curvature, respectively. Our sensor exhibited a bending-
curvature sensitivity of 705.14 mm. Figure 3b shows the change
in the relative electrical resistance with multiple-cyclic bending
test. Signal patterns under pressure were compared to those
under bending. Response to bending is much smoother than
that to compression because while contacts are created in the
central zone of the sample, separations appear at the same time
at its edges. In addition, the responses to compressive and tensile
bending were also measured, as shown in Figure S9a, b. Because
the hexagonal interlocking sensor is a completely symmetric
structure, there were no significant differences between
compressive and tensile bending. In such a fashion, we have
demonstrated that different mechanical stimuli (pressure, shear,
and bending) produce electrical signals with characteristic shape
and amplitude and can thus be discriminated. We also tested
durability under compression, shear, and bending during 1000
cycles (Figure S10a−c).
Our piezoresistive sensor using tightly interlocked geometry
shows very fast response times, with the fall time being 28 ms
(Figure 4a), whereas the rise is 14 ms (Figure 4b) when the mass
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Figure 6. External vibration detection systems for earthquake-monitoring. (a) Schematic of the external vibration measurement. A smart phone
vibration motor is used to generate vibrations, and a vibrometer is used to measure the vibration intensity near the motor. (b) Relative variations of
resistance as a function of the vibration intensity. (c) Real-time monitoring of external vibrations as the intensity of the vibrations increases.

Figure 7. Real-time tests of the human voice and smart phone app sound sensing capabilities of the sensors. (a) Schematic of the human voice
measurement. (b) Relative changes in resistance in response to different intensities of voice and (c) prolongated sound. (d) Change in relative
electrical resistance of an electronic skin in response to various sound vibration intensities (20, 50, and 100 Hz) in sound generator software.

is 10 mg. This is due to immediate direct SWCNT contact in the
interlocked geometry system. To further examine response
times to external pressure of our sensors, we compared the
relative resistance with the dynamic pressure at a frequency of
1−3.6 Hz (Figure 5). Note that the signals of the electrical
resistance variations followed exactly the input signal of the
pressure under a 5% compressive strain at low (Figure 5a),
middle (Figure 5b), and high frequencies (Figure 5c). The signal
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of the electrical resistance remained very stable without any
evident amplitude variation up to 3.6 Hz. The responses under
bending (Figure S11a−c) and shear (Figure S11d−f) as well as
compression show stable signals at various frequencies.
Detecting vibrations, such as earthquakes, is very important
for people living in the circum-pacific seismic zones. High
sensitivity to external vibrations makes our sensors particularly
well suited for seismographic tasks. Figure 6a shows the
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Figure 8. Vibration detection for wearable voice-monitoring systems. (a) Photograph of electronic skin attached to a human neck for voice monitoring.
(b) Relative change in resistance in response to different vocal organs and (c) syllables.
schematic of the vibration measurement systems. When a sound
and voice wave are applied to a sample, they flow to the sides of
the sample due to breath screen. When sound or voice waves are
applied to a sample, they flow to the sides of the sample due to
breath screen. The sound waves applied along the sides of the
sample create a scattering effect between the top and bottom of
sample due to vibrations, thereby increasing the resistance.50−52
A vibration motor was placed 150 mm away from our sensor,
and a vibrometer was used to measure the vibrations generated
by the motor. The relative resistance of our sensor showed an
increase with vibration intensity (2−21.6 mm/s2). The
detection was very stable and reliable throughout the time of
the vibration as shown in Figure 6b. Figure 6c shows the real-
time monitoring of external vibrations and the significant
variation in relative resistance as the intensity of the vibrations
increased from 2 to 21.6 mm/s2. During the vibrations, our
tightly interlocked microhexagonal geometry was capable of
delivering a stable signal that promptly returned to the original
value (R/R0 = 1) when the vibrations disappeared.
Our sensor can also detect sound waves, such as acoustic
vibrations, which are commonly encountered in everyday life.
The capability to detect sound waves is useful for a number of
applications, including the detection of noise between floors,
hearing aids for hearing impaired people and the tuning of
musical instruments. Figure 7a shows the schematic of the
human voice detection system. The apparatus conceived also
prevents the breathing noise from passing into the sensor. The
sensor detects the magnitude of the human voice when the word
“Ah” is spoken (Figure 7b), and it can also sense the state in
which the sound is maintained, as shown in Figure 7c. Minute
vibrational forces from repeated sounds at various frequencies
could be detected. The relative resistance signals in response to
the frequency of acoustic vibration could be detected when the
sensor was 30 mm away from the sound source, as shown in
Figure 7d.
When worn as voice vibration monitoring systems, the e-skins
are attached to the skin of the neck to capture the vocal tremor as
shown in Figure 8a. There are five vocal organ movements
involved in the pronunciation of a word. Our e-skins distinctly
discriminate the different voice vibration patterns when we
pronounce 5 letters, which involve different pronunciation
movements of the vocal organ, such as “ga,” “na,” “ma,” “ah,” and
“ha,” as shown in Figure 8b. The sensor can also detect and
discriminate syllables, which is particularly important for singers
during the process of checking the state of their voice, and for
tuning musical instruments as shown in Figure 8c. Under the
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action of an external force our e-skins with direct SWCNT
contact between interlocked geometries are capable of detecting
not only a small water droplet but also the process of sprinkling
small amounts of water (40, 30, 20, and even 10 μL; Figure
S12a−d and Movie S1). Gentle water sprinkling is detectable
because of the resistance decreasing mechanism of e-skins.
4. CONCLUSIONS
We developed highly sensitive e-skins with a simple fabrication
process exploiting the ultrasonic spray method. The e-skins are
characterized by bioinspired structures consisting of tightly
interlocked microhexagonal columnar arrays. We demonstrated
that our SWCNT-sprayed microhexagonal columnar structured
e-skins show reliable detection of both static and cyclic
mechanical stimuli (pressure, shear, and bending). The working
principle of our devices relies on piezoresistivity due to a
contact-separation mechanism between the surfaces of the
hexagonal structures. We showed that the tightly interlocked
hexagonal structures allow direct SWCNT contact under
external stimuli, and this bestows them the capability to detect
extremely very small stimuli (e.g., internal and external minute
vibrations, and even water droplets sprinkled in tiny quantities
(10 μL)). The hexagonal microcolumnar structure presented in
this study lays the groundwork for maximizing the piezoresistive
effect. We believe that in the future we will be able to enhance
the performances of our flexible e-skins in terms of sensitivity,
stability, mechanical properties, and other important elements of
the sensor. Finally, we expect that our e-skin, thanks to its
sensitivity to multimechanical stimuli, will be able to find
applications in fields where static and dynamic detections are
highly required, such as seismography, robot skins (tactile
sensors), and music tuning and localized vibrations.
■
ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsami.9b23370.
Micro droplet size of ultrasonic spray calculation;
schematic illustration of the ultrasonic spray method for
coating in overall patterned shapes and uniformly coated
with sidewall of hexagonal structure in SEM image; SEM
images of different height size of hexagonal structured
PDMS micro pillar arrays, of circular-shaped PDMS
micropillar arrayys, and of SWCNT-sprayed circular
micropillar arrays; theoretical and numerical analysis of
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ACS Appl. Mater. Interfaces 2020, 12, 18813−18822
ACS Applied Materials & Interfaces
the stress distribution and contact area between the
interlocked circle and hexagonal structures under normal
and shear forces; hysteresis stress−strain curves in
compression; sheet resistance of films SWCNT-sprayed
hexagonal micropillar arrys with vairous heights; resist-
ance change in the interlocked sensor with hexagonal
structure under progressively increasing strain from 0 to
5% (low strain) in tensile and compressive bending mode;
cyclic stability test of our sensor under repetitive (1000
cycles) compressive strain, shear displacement, and
curvature at a frequency of 1 Hz; bending curvature and
shear displacement-resolved measurements of the output
signal as a function of the applied ∼0.1752 mm−1 bending
curvature and ∼0.1 mm shear displacement at different
frequencies (1, 2, and 3.6 Hz); water droplet detection
capability of e-skins showing the different weight of small
sprinkle water on the e-skin (PDF)
Movie S1 showing that e-skins with direct SWCNT
contact between interlocked geometries are capable of
detecting not only a small water droplet but also the
process of sprinkling small amounts of water (AVI)
■
AUTHOR INFORMATION
Corresponding Authors
Tae-Hyuk Kwon − Department of Chemistry, Ulsan National
Institute of Science and Technology, Ulsan 44919, Republic of
Korea; orcid.org/0000-0002-1633-6065; Email: kwon90@
unist.ac.kr
Hoon Eui Jeong − Department of Mechanical Engineering, Ulsan
National Institute of Science and Technology, Ulsan 44919,
Republic of Korea; orcid.org/0000-0002-1413-3774;
Email: hoonejeong@unist.ac.kr
Young-Bin Park − Department of Mechanical Engineering, Ulsan
National Institute of Science and Technology, Ulsan 44919,
Republic of Korea; orcid.org/0000-0001-5936-7155;
Email: ypark@unist.ac.kr
Authors
Changyoon Jeong − Department of Mechanical Engineering,
Ulsan National Institute of Science and Technology, Ulsan
44919, Republic of Korea
Hangil Ko − Department of Mechanical Engineering, Ulsan
National Institute of Science and Technology, Ulsan 44919,
Republic of Korea
Hyun-Tak Kim − Department of Chemistry, Ulsan National
Institute of Science and Technology, Ulsan 44919, Republic of
Korea
Kahyun Sun − Department of Mechanical Engineering, Ulsan
National Institute of Science and Technology, Ulsan 44919,
Republic of Korea
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsami.9b23370
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the National Research Foundation
of Korea (NRF) grant funded by the Ministry of Science and
ICT, Korea (NRF-2017R1A5A1015311).
18821
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www.acsami.org Research Article
REFERENCES
(1) Chen, S. W.; Cao, X.; Wang, N.; Ma, L.; Zhu, H. R.; Willander, M.;
Jie, Y.; Wang, Z. L. An Ultrathin Flexible Single-Electrode Tribo-
electric-Nanogenerator for Mechanical Energy Harvesting and
Instantaneous Force Sensing. Adv. Energy Mater. 2017, 7 (1), 1601255.
(2) Gong, S.; Schwalb, W.; Wang, Y.; Chen, Y.; Tang, Y.; Si, J.;
Shirinzadeh, B.; Cheng, W. A Wearable and Highly Sensitive Pressure
Sensor with Ultrathin Gold Nanowires. Nat. Commun. 2014, 5, 3132.
(3) Cho, S. H.; Lee, S. W.; Yu, S.; Kim, H.; Chang, S.; Kang, D.;
Hwang, I.; Kang, H. S.; Jeong, B.; Kim, E. H.; Cho, S. M.; Kim, K. L.;
Lee, H.; Shim, W.; Park, C. Micropatterned Pyramidal Ionic Gels for
Sensing Broad-Range Pressures with High Sensitivity. ACS Appl. Mater.
Interfaces 2017, 9 (11), 10128−10135.
(4) Jiang, X. Z.; Sun, Y. J.; Fan, Z.; Zhang, T. Y. Integrated Flexible,
Waterproof, Transparent, and Self-Powered Tactile Sensing Panel. ACS
Nano 2016, 10 (8), 7696−7704.
(5) Li, T.; Zou, J.; Xing, F.; Zhang, M.; Cao, X.; Wang, N.; Wang, Z. L.
From Dual-Mode Triboelectric Nanogenerator to Smart Tactile
Sensor: A Multiplexing Design. ACS Nano 2017, 11 (4), 3950−3956.
(6) Pang, Y.; Tian, H.; Tao, L.; Li, Y.; Wang, X.; Deng, N.; Yang, Y.;
Ren, T.-L. Flexible, Highly Sensitive, and Wearable Pressure and Strain
Sensors with Graphene Porous Network Structure. ACS Appl. Mater.
Interfaces 2016, 8 (40), 26458−26462.
(7) Schwartz, G.; Tee, B. C.; Mei, J.; Appleton, A. L.; Kim, D. H.;
Wang, H.; Bao, Z. Flexible Polymer Transistors with High Pressure
Sensitivity for Application in Electronic Skin and Health Monitoring.
Nat. Commun. 2013, 4, 1859.
(8) Amjadi, M.; Yoon, Y. J.; Park, I. Ultra-Stretchable and Skin-
Mountable Strain Sensors Using Carbon Nanotubes-Ecoflex Nano-
composites. Nanotechnology 2015, 26 (37), 375501.
(9) Harada, S.; Honda, W.; Arie, T.; Akita, S.; Takei, K. Fully Printed,
Highly Sensitive Multifunctional Artificial Electronic Whisker Arrays
Integrated with Strain and Temperature Sensors. ACS Nano 2014, 8
(4), 3921−3927.
(10) Trung, T. Q.; Lee, N. E. Flexible and Stretchable Physical Sensor
Integrated Platforms for Wearable Human-Activity Monitoringand
Personal Healthcare. Adv. Mater. 2016, 28 (22), 4338−4372.
(11) Ha, M.; Lim, S.; Park, J.; Um, D.-S.; Lee, Y.; Ko, H. Bioinspired
Interlocked and Hierarchical Design of ZnO Nanowire Arrays for Static
and Dynamic Pressure-Sensitive Electronic Skins. Adv. Funct. Mater.
2015, 25 (19), 2841−2849.
(12) Bae, G. Y.; Pak, S. W.; Kim, D.; Lee, G.; Kim, D. H.; Chung, Y.;
Cho, K. Linearly and Highly Pressure-Sensitive Electronic Skin Based
on a Bioinspired Hierarchical Structural Array. Adv. Mater. 2016, 28
(26), 5300−5306.
(13) Aguilar-Bolados, H.; Yazdani-Pedram, M.; Contreras-Cid, A.;
López-Manchado, M. A.; May-Pat, A.; Avilés, F. Influence of The
Morphology of Carbon Nanostructures on The Piezoresistivity of
Hybrid Natural Rubber Nanocomposites. Composites, Part B 2017, 109,
147−154.
(14) Zheng, Y.; Li, Y.; Dai, K.; Liu, M.; Zhou, K.; Zheng, G.; Liu, C.;
Shen, C. Conductive Thermoplastic Polyurethane Composites with
Tunable Piezoresistivity by Modulating The Filler Dimensionality for
Flexible Strain Sensors. Composites, Part A 2017, 101, 41−49.
(15) An, B. W.; Heo, S.; Ji, S.; Bien, F.; Park, J. U. Transparent and
Flexible Fingerprint Sensor Array with Multiplexed Detection of Tactile
Pressure and Skin Temperature. Nat. Commun. 2018, 9 (1), 2458.
(16) Lee, K.; Lee, J.; Kim, G.; Kim, Y.; Kang, S.; Cho, S.; Kim, S.; Kim,
J. K.; Lee, W.; Kim, D. E.; Kang, S.; Kim, D.; Lee, T.; Shim, W. Rough-
Surface-Enabled Capacitive Pressure Sensors with 3D Touch
Capability. Small 2017, 13 (43), 1700368.
(17) Kwon, D.; Lee, T.-I.; Shim, J.; Ryu, S.; Kim, M. S.; Kim, S.; Kim,
T.-S.; Park, I. Highly Sensitive, Flexible, and Wearable Pressure Sensor
Based on a Giant Piezocapacitive Effect of Three-Dimensional
Microporous Elastomeric Dielectric Layer. ACS Appl. Mater. Interfaces
2016, 8 (26), 16922−16931.
(18) Wang, X.; Que, M.; Chen, M.; Han, X.; Li, X.; Pan, C.; Wang, Z.
L. Full Dynamic-Range Pressure Sensor Matrix Based on Optical and
Electrical Dual-Mode Sensing. Adv. Mater. 2017, 29 (15), 1605817.
https://dx.doi.org/10.1021/acsami.9b23370
ACS Appl. Mater. Interfaces 2020, 12, 18813−18822
ACS Applied Materials & Interfaces
(19) Cho, H.; Lee, H.; Kim, Y.; Kim, J. Design of an Optical Soft
Sensor for Measuring Fingertip Force and Contact Recognition.
International Journal of Control, Automation and Systems 2017, 15 (1),
16−24.
(20) Sulejmani, S.; Sonnenfeld, C.; Geernaert, T.; Luyckx, G.; Van
Hemelrijck, D.; Mergo, P.; Urbanczyk, W.; Chah, K.; Caucheteur, C.;
Mégret, P.; et al. Shear Stress Sensing with Bragg grating-based Sensors
in Microstructured Optical Fibers. Opt. Express 2013, 21 (17), 20404−
20416.
(21) Ito, Y.; Minakuchi, S.; Mizutani, T.; Takeda, N. Cure Monitoring
of Carbon−Epoxy Composites by Optical Fiber-Based Distributed
Strain−Temperature Sensing System. Adv. Compos. Mater. 2012, 21
(3), 259−271.
(22) Bosman, E.; Van Steenberge, G.; Van Hoe, B.; Missinne, J.;
Vanfleteren, J.; Van Daele, P. Highly Reliable Flexible Active Optical
Links. IEEE Photonics Technol. Lett. 2010, 22 (5), 287−289.
(23) Bhavanasi, V.; Kumar, V.; Parida, K.; Wang, J.; Lee, P. S.
Enhanced Piezoelectric Energy Harvesting Performance of Flexible
PVDF-TrFE Bilayer Films with Graphene Oxide. ACS Appl. Mater.
Interfaces 2016, 8 (1), 521−529.
(24) Sirohi, J.; Chopra, I. Fundamental Understanding of Piezo-
electric Strain Sensors. J. Intell. Mater. Syst. Struct. 2000, 11 (4), 246−
257.
(25) Gullapalli, H.; Vemuru, V. S.; Kumar, A.; Botello-Mendez, A.;
Vajtai, R.; Terrones, M.; Nagarajaiah, S.; Ajayan, P. M. Flexible
Piezoelectric ZnO−Paper Nanocomposite Strain Sensor. Small 2010, 6
(15), 1641−1646.
(26) Wang, X.; Zhang, Y.; Zhang, X.; Huo, Z.; Li, X.; Que, M.; Peng,
Z.; Wang, H.; Pan, C. A Highly Stretchable Transparent Self-Powered
Triboelectric Tactile Sensor with Metallized Nanofibers for Wearable
Electronics. Adv. Mater. 2018, 30 (12), 1706738.
(27) Ha, M.; Lim, S.; Cho, S.; Lee, Y.; Na, S.; Baig, C.; Ko, H. Skin-
Inspired Hierarchical Polymer Architectures with Gradient Stiffness for
Spacer-Free, Ultrathin, and Highly Sensitive Triboelectric Sensors. ACS
Nano 2018, 12 (4), 3964−3974.
(28) Guo, H.; Li, T.; Cao, X.; Xiong, J.; Jie, Y.; Willander, M.; Cao, X.;
Wang, N.; Wang, Z. L. Self-Sterilized Flexible Single-Electrode
Triboelectric Nanogenerator for Energy Harvesting and Dynamic
Force Sensing. ACS Nano 2017, 11 (1), 856−864.
(29) Tallman, T. N.; Gungor, S.; Wang, K. W.; Bakis, C. E. Tactile
Imaging and Distributed Strain Sensing in Highly Flexible Carbon
Nanofiber/Polyurethane Nanocomposites. Carbon 2015, 95, 485−493.
(30) Wang, X.; Meng, S.; Tebyetekerwa, M.; Li, Y.; Pionteck, J.; Sun,
B.; Qin, Z.; Zhu, M. Highly Sensitive and Stretchable Piezoresistive
Strain Sensor based on Conductive Poly(styrene-butadiene-styrene)/
Few Layer Graphene Composite Fiber. Composites, Part A 2018, 105,
291−299.
(31) Xia, X.; Chen, J.; Liu, G.; Javed, M. S.; Wang, X.; Hu, C. Aligning
Graphene Sheets in PDMS for Improving Output Performance of
Triboelectric Nanogenerator. Carbon 2017, 111, 569−576.
(32) Chen, H.; Xu, Y.; Bai, L.; Jiang, Y.; Zhang, J.; Zhao, C.; Li, T.; Yu,
H.; Song, G.; Zhang, N.; Gan, Q. Crumpled Graphene Triboelectric
Nanogenerators: Smaller Devices with Higher Output Performance.
Advanced Materials Technologies 2017, 2 (6), 1700044.
(33) Yang, J.; Liu, P.; Wei, X.; Luo, W.; Yang, J.; Jiang, H.; Wei, D.; Shi,
R.; Shi, H. Surface Engineering of Graphene Composite Transparent
Electrodes for High-Performance Flexible Triboelectric Nanogener-
ators and Self-Powered Sensors. ACS Appl. Mater. Interfaces 2017, 9
(41), 36017−36025.
(34) Kim, M.-K.; Kim, M.-S.; Kwon, H.-B.; Jo, S.-E.; Kim, Y.-J.
Wearable Triboelectric Nanogenerator Using a Plasma-Etched
PDMS−CNT Composite for a Physical Activity Sensor. RSC Adv.
2017, 7 (76), 48368−48373.
(35) Luo, S.; Liu, T. SWCNT/Graphite Nanoplatelet Hybrid Thin
Films for Self-Temperature-Compensated, Highly Sensitive, and
Extensible Piezoresistive Sensors. Adv. Mater. 2013, 25 (39), 5650−
5657.
(36) Zhai, W.; Zhao, S.; Wang, Y.; Zheng, G.; Dai, K.; Liu, C.; Shen, C.
Segregated Conductive Polymer Composite with Synergistically
18822
www.acsami.org Research Article
Electrical and Mechanical Properties. Composites, Part A 2018, 105,
68−77.
(37) Lee, Y.; Park, J.; Cho, S.; Shin, Y. E.; Lee, H.; Kim, J.; Myoung, J.;
Cho, S.; Kang, S.; Baig, C.; Ko, H. Flexible Ferroelectric Sensors with
Ultrahigh Pressure Sensitivity and Linear Response over Exceptionally
Broad Pressure Range. ACS Nano 2018, 12 (4), 4045−4054.
(38) Park, J.; Lee, Y.; Hong, J.; Lee, Y.; Ha, M.; Jung, Y.; Lim, H.; Kim,
S. Y.; Ko, H. Tactile-Direction-Sensitive and Stretchable Electronic
Skins Based on Human-Skin-Inspired Interlocked Microstructures.
ACS Nano 2014, 8 (12), 12020−12029.
(39) Park, J.; Kim, J.; Hong, J.; Lee, H.; Lee, Y.; Cho, S.; Kim, S.-W.;
Kim, J. J.; Kim, S. Y.; Ko, H. Tailoring Force Sensitivity and Selectivity
by Microstructure Engineering of Multidirectional Electronic Skins.
NPG Asia Mater. 2018, 10 (4), 163−176.
(40) Song, Y. I.; Kim, G. Y.; Choi, H. K.; Jeong, H. J.; Kim, K. K.; Yang,
C. M.; Lim, S. C.; An, K. H.; Jung, K. T.; Lee, Y. H. Fabrication of
Carbon Nanotube Field Emitters Using a Dip-Coating Method. Chem.
Vap. Deposition 2006, 12 (6), 375−379.
(41) Kymakis, E.; Stylianakis, M. M.; Spyropoulos, G. D.; Stratakis, E.;
Koudoumas, E.; Fotakis, C. Spin Coated Carbon Nanotubes as The
Hole Transport Layer in Organic Photovoltaics. Sol. Energy Mater. Sol.
Cells 2012, 96, 298−301.
(42) Holubowitch, N. E.; Landon, J.; Lippert, C. A.; Craddock, J. D.;
Weisenberger, M. C.; Liu, K. Spray-Coated Multiwalled Carbon
Nanotube Composite Electrodes for Thermal Energy Scavenging
Electrochemical Cells. ACS Appl. Mater. Interfaces 2016, 8 (34),
22159−22167.
(43) Honda, W.; Harada, S.; Arie, T.; Akita, S.; Takei, K. Wearable,
Human-Interactive, Health-Monitoring, Wireless Devices Fabricated
by Macroscale Printing Techniques. Adv. Funct. Mater. 2014, 24 (22),
3299−3304.
(44) Lee, Y. D.; Cho, W.-S.; Kim, Y. C.; Ju, B.-K. Field Emission of
Ribonucleic Acid−Carbon Nanotube Films Prepared by Electro-
phoretic Deposition. Carbon 2012, 50 (3), 845−850.
(45) Alkbir, M. F. M.; Sapuan, S. M.; Nuraini, A. A.; Ishak, M. R. Effect
of Geometry on Crashworthiness Parameters of Natural Kenaf Fibre
Reinforced Composite Hexagonal Tubes. Mater. Eng. 2014, 60, 85−93.
(46) Cekan, P.; Balog, K.; Kuracina, R.; Szabova, Z.; Harangozó, J.
Development of The Hexagonal Structure in the Processes of
Improving Vibration Insulating Properties of Products. Appl. Mech.
Mater. 2014, 525, 536−540.
(47) Ding, F.-x.; Li, Z.; Cheng, S.; Yu, Z.-w. Composite Action of
Hexagonal Concrete-Filled Steel Tubular Stub Columns under Axial
Loading. Thin-Walled Structures 2016, 107, 502−513.
(48) Kim, H. T.; Shin, H.; Jeon, I. Y.; Yousaf, M.; Baik, J.; Cheong, H.
W.; Park, N.; Baek, J. B.; Kwon, T. H. Carbon-Heteroatom Bond
Formation by an Ultrasonic Chemical Reaction for Energy Storage
Systems. Adv. Mater. 2017, 29 (47), 1702747.
(49) Choong, C. L.; Shim, M. B.; Lee, B. S.; Jeon, S.; Ko, D. S.; Kang,
T. H.; Bae, J.; Lee, S. H.; Byun, K. E.; Im, J.; Jeong, Y. J.; Park, C. E.;
Park, J. J.; Chung, U. I. Highly Stretchable Resistive Pressure Sensors
Using a Conductive Elastomeric Composite on a Micropyramid Array.
Adv. Mater. 2014, 26 (21), 3451−3458.
(50) Tao, L. Q.; Tian, H.; Liu, Y.; Ju, Z. Y.; Pang, Y.; Chen, Y. Q.;
Wang, D. Y.; Tian, X. G.; Yan, J. C.; Deng, N. Q.; Yang, Y.; Ren, T. L. An
intelligent artificial throat with sound-sensing ability based on laser
induced graphene. Nat. Commun. 2017, 8, 14579.
(51) Gao, Y.; Yan, C.; Huang, H.; Yang, T.; Tian, G.; Xiong, D.; Chen,
N.; Chu, X.; Zhong, S.; Deng, W.; Fang, Y.; Yang, W. Microchannel-
Confined MXene Based Flexible Piezoresistive Multifunctional Micro-
Force Sensor. Adv. Funct. Mater. 2020, 30 (11), 1909603.
(52) Li, H.; Wu, K.; Xu, Z.; Wang, Z.; Meng, Y.; Li, L. Ultrahigh-
Sensitivity Piezoresistive Pressure Sensors for Detection of Tiny
Pressure. ACS Appl. Mater. Interfaces 2018, 10 (24), 20826−20834.
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