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Honeycomb-like MoS2 Nanotube Array-Based Wearable Sensors for

Noninvasive Detection of Human Skin Moisture
Shuvra Mondal, Seong Jun Kim, and Choon-Gi Choi*
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ABSTRACT: Technological advances in wearable electronics have driven the necessity

of a highly sensitive humidity sensor that can precisely detect physiological signals from
the human body in real time. Herein, we introduce the anodic aluminum oxide (AAO)-
assisted MoS2 honeycomb structure as a resistive humidity sensor with superior sensing
Downloaded via JADAVPUR UNIV on October 11, 2023 at 11:15:54 (UTC).

performance. The unique honeycomb-like structure consists of MoS2 nanotubes, which

can amplify the sensing performance because of their open pores and wider surface
absorption sites. The formation of uniform MoS2 nanotubes inside the AAO membrane
was manipulated by the number of vacuum filtration cycles of the (NH4)2MoS4 solution.
The proposed humidity sensor exhibits an elevated sensitivity that is 2 orders of
magnitudes higher than the MoS2 film-based humidity sensor at the relative humidity
range of 20−85%. Moreover, the sensor showed significantly faster response and recovery
times of 0.47 and 0.81 s. In addition, we demonstrate the multifunctional applications
such as noncontact sensation of human fingertips, human breath, speech recognition, and
regional sweat rate, which show its promising potential for the next-generation wearable
sensors.
KEYWORDS: molybdenum disulfide (MoS2), sweat rate sensor moisture, human breath, wearable humidity sensor, skin patch

■ INTRODUCTION
The progress of noninvasive sensing technology for the real-
(dehydration) or hyperhydration, respectively. This causes
physical and mental degradation and also increases the risk of
time monitoring of human physiological biomarkers has heatstroke or illness.8 Moreover, the regional sweat rate could
attracted considerable interest in recent years because of its be used to diagnose autonomic nervous system dysfunctions
multifunctional applications such as e-skin, noncontact caused by diseases like diabetes.9 Analyzing the human skin
sensation, and skin patch for healthcare.1 In particular, the humidity level by a skin patch can be an intriguing
efficient and real-time monitoring of humidity levels from development in the real-time monitoring and prevention of
human skin can yield crucial information about the metabolic fatal illnesses caused by dehydration in infants, elderly, and
and physiological states, growth and aging statuses, and healing professional athletes.
Two-dimensional (2D) materials such as graphene,
progression of wounds in the human body.2,3 The noncontact
graphene oxide (GO), and reduced GO (rGO) have been
sensing of human skin humidity can also open up a new era of
widely studied as humidity-sensing materials because of their
the touchless interface in public places or hospitals to prevent
outstanding properties with high surface-to-volume ratios to
bacterial infections from conventional touch screens.4 When
achieve higher responses to humidity. Nevertheless, these
breathing, the humidity in exhaled air is different from the
sensors suffer from a low sensitivity and longer response time
inhaled (ambient) air because of the presence of water vapor in
because of the doping effect or structural deformation from
the exhaled air. Monitoring human breathing patterns from
chemical bonding during H2O molecule absorption.10,11
humidity in exhaled air can provide essential information on
Molybdenum disulfide (MoS2), a 2D-layered transition-metal
health issues associated with the initial stage of heart attacks,
dichalcogenide, is considered an excellent candidate for
asphyxia, anxiety, and epilepsy.5−7 In addition, the human
humidity sensing because of the presence of inherent
voice or speech recognition using humidity in exhaled air can
be helpful to overcome intrusions such as using recorded voice.
Furthermore, skin attachable sensors can detect human skin Received: December 19, 2019
humidity at different physical conditions, including skin Accepted: March 16, 2020
humidity levels based on the regional sweat rate, which Published: March 16, 2020
could enable real-time monitoring of vital biological
information on health conditions. For example, the fluid
intake of less or more than required can lead to hypohydration

© 2020 American Chemical Society https://dx.doi.org/10.1021/acsami.9b22915

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Scheme 1. Schematic Representation of the Fabrication Procedure for the AMHS-Based Humidity Sensor
defects.12,13 However, there has not been any significant
improvement in humidity sensing based on pure MoS2. Zao et
al. showed a MoS2 humidity sensor with good potential but
only within a narrow relative humidity (RH 0−35%) range,
and it required a high gate voltage.14 Park et al. showed a
higher response with their rGO/MoS2 humidity sensor, but the
sensor was not practical because of its long recovery time of
30.8 s.15 To the best of our knowledge, the previously reported
humidity sensors based on pure or film MoS2 are limited to
low sensitivity, narrow RH range, and slower response time
because of their atomically thin layers and relatively low
concentration of absorption sites for water molecules. Thus,
challenges such as a narrow sensing range, a tradeoff between
sensitivity and response time, and a top-bottom gated complex
design have limited the promising noninvasive monitoring of
human skin humidity with traditional humidity sensors. In
recent years, the humidity effects on the electrical character-
istics of 3D nanostructures, nanoparticles, nanotubes, and
nanowires have been intensively studied with the aim to
increase the moisture absorption sites and sensing perform-
ance.16,17
In this study, we introduce a unique resistive-type humidity
sensor based on an anodic aluminum oxide (AAO)-assisted
MoS2 honeycomb structure (AMHS) with an outstanding
sensing performance. The 3D honeycomb structure based on
MoS2 nanotubes can respond very quickly to humidity from
the atmosphere, human skin, and human breath in a range of
RH from 20 to 85%. At the measured RH range, our AMHS-
based humidity sensor showed a high sensitivity of 668, which
is over 26 times higher than the previously reported MoS2 film-
based humidity sensors (Table S1). The sensitivity and
response speeds were strongly influenced by the honeycomb
structure with a wider surface area and open pores for higher
moisture absorption, which will be carefully discussed later in
the sensing mechanism section. Based on the as-fabricated
sensor, we show the multifunctional sensing applications such
as noncontact sensation using skin humidity, human
respiration pattern, and speech recognition using humidity in
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exhaled air. Lastly, we reveal a wearable skin humidity patch
with an AMHS-based sensor to explore the regional human
skin humidity and regional sweat rates under different physical
conditions. Our experimental results show the potential to
enable the noncontact monitoring of human skin humidity for
the future generation of wearable devices.
■ RESULTS AND DISCUSSION
Scheme 1 shows the overall fabrication process of the AMHS-
based humidity sensor. In order to form MoS2 nanotubes, the
vacuum filtration (VF) method was employed.18 The 1.25 wt
% (NH4)2MoS4 solution was infiltrated inside a pristine AAO
membrane of 0.2 μm pore diameter nanotubes by the vacuum
setup, as illustrated in Scheme 1. During the VF process, large
particles (>0.2 μm) from the (NH4)2MoS4 solution were
aggregated on the AAO surface. This filtration process allowed
the (NH4)2MoS4 solution to accumulate on the walls of
nanotubes in the AAO membrane as the solution penetrated
through them. Next, the vacuum-filtered (NH4)2MoS4 solution
was collected and again vacuum-filtered with pristine AAO
membranes in repeated cycles. A uniform solution coating
inside the AAO membrane without surface aggregation was
achieved after third repeated cycles of VF. The final vacuum-
filtrated sample (4 cycles) yielded a homogenous accumulation
of (NH4)2MoS4 solution on the wall and surface of the AAO
membrane nanotubes. Then, the (NH4)2MoS4 solution coated
inside the AAO membrane was annealed in a vacuum furnace
for MoS2 synthesis. Subsequently, poly(methyl methacrylate)
was coated on the AMHS, and selective etching of alumina
from the AMHS was carried out in 3 M NaOH solution for 15
min until the rigid AMHS was flexible enough to transfer on a
target substrate. Finally, the AMHS-based humidity sensor was
created after the deposition of the metal electrodes.
Field-emission scanning electron microscopy (FESEM) was
employed to observe the morphology of pristine AAO and the
AMHS. Figure 1a,b shows the top-view FESEM images of
AMHS prepared with the (NH4)2MoS4 solutions by VF for 1
and 4 cycles through pristine AAO membranes. The
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Figure 1. Top-view FESEM images of the MoS2 nanotubes inside the AAO membrane created by the (NH4)2MoS4 solution with VF for (a) one
cycle and (b) four cycles through pristine AAO membranes, respectively. (c) Low-magnification cross-sectional FESEM image of the AMHS. (d)
Cross-sectional FESEM images of (d) pristine AAO and (e) AMHS. Cross-sectional FESEM images of AMHS (f) before and (g) after selective
etching in NaOH solution. FESEM−EDS elemental mapping of the AMHS with (h) secondary electron image and corresponding elemental
mapping images of (i) Mo, (j) S, and (k) Si elements. (l) Raman spectra of a pristine MoS2 film and AMHS with different VF conditions. Mo 3d
core-level XPS spectra of (m) the MoS2 film and (n) AMHS created with four cycle VF of the (NH4)2MoS4 solution.

aggregation of nanosized MoS2 particles was observed on the
surface of AMHS with one cycle of the VF condition (Figure
1a). In contrast, no MoS2 particles were observed on the
surface after the solution was vacuum-filtered for two or more
cycles, as shown in Figure 1b and Figure S1. The 1.25 wt %
(NH4)2MoS4 solution contained some large particles (>0.2
μm) of (NH4)2MoS4 powder, which was filtered by the AAO
membrane because of the 0.2 μm pore size. During the first VF
process, these large particles of (NH4)2MoS4 powder were
aggregated on the surface of AAO membrane that formed into
MoS2 flakes after the thermolysis as shown in Figure S1a. By
repeating the VF (2−4 cycles) of the (NH4)2MoS4 solution
using a pristine AAO membrane each time, all the remaining
large MoS2 particles were eliminated gradually as shown in
Figure S1b−d. Additionally, the repeated VF yielded a
homogenous (NH4)2MoS4 solution by filtering or reducing
undissolved (NH4)2MoS4 powders, thus, after thermolysis or
annealing ensured a clean and uniform coating of the MoS2
nanotubes inside the AAO membrane. The repetition of VF
cycles (1−4 cycles) ensured a connected network of uniform
MoS2 nanotubes of microscale height, forming a honeycomb-
like structure, as shown in Figure 1c, and detailed top-view
FESEM images are shown in Figure S4. These honeycomb-like
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MoS2 nanotubes with nanosized open pores provide a large
number of absorption sites for H2O molecules that can
influence the humidity-sensing performance significantly. To
confirm the uniform coating of MoS2 inside the AAO
nanotubes, the cross-section of pristine AAO membrane and
MoS2 nanotubes in the AMHS was compared by FESEM
analysis (Figure 1d,e). As shown in Figure 1e, the MoS2 coated
on the walls inside of nanotubes was observed. Figure 1f,g
shows the cross-sectional view of the AMHS before and after
selective etching of alumina with 3 M NaOH solution for 15
min. After the selective etching, the weak bottom of the MoS2
nanotubes, laid on the transferred substrate, is because of
reduced alumina density, as depicted in Figure 1g. As a result,
the height of the transferred AMHS on the SiO2/Si substrate
decreased from 56.3 μm to about 23.2 μm after etching. This
reduced length of the nanotubes did not affect the upper
structure or surface of the AMHS. However, at some critical
height of the nanotubes, the overall structure becomes
unstable, resulting in emergence of cracks and inconsistences
at the surface of the honeycombs. As shown in Figure S6, this
critical length is defined to be less than 15 μm. Figure 1h−k
shows the FESEM−energy-dispersive X-ray spectrometry
(FESEM−EDS, Bruker) mapping images of the transferred
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Figure 2. I−V curves of (a) the MoS2 film- and (b) the AMHS (4 cycles VF)-based humidity sensors with the variation of RH. (c) Sensitivity as a
function of RH of the MoS2 film and AMHS (1−4 cycles VF) sensors. A bar chart in inset illustrating sensitivity dependence on the RH. (d) Time-
dependent current response of the AMHS (4 cycles VF) sensor under repeated RH between 30 and 70%. (e) Response and (f) decay time of the
AMHS (4 cycles VF) sensor for RH variation from 45 to 85%. (g) Dependence relation between the temperature and resistance in the AMHS (4
cycles VF) sensor under RH 55% condition.
AMHS on a SiO2/Si substrate. The FESEM−EDS analysis
confirmed that Mo and S elements were uniformly distributed
throughout the AMHS.
Raman spectroscopy is a powerful and effective tool to
confirm the quality of 2D materials such as graphene or MoS2
through the vibrational signals. As shown in Figure 1l, two
prominent peaks observed at ∼388 and ∼411 cm−1 correspond
to the E12g (in-plane vibration) and A1g (out of plane vibration)
modes of MoS2, respectively. According to previous studies,
the presence of defects can be indicated by broadening the E1g
peak.19 Moreover, the S-vacancy in the basal plane of MoS2
affects the in-plane vibration that results in the red-shift
behavior of the E1g peak (Figure 1l).20 The E1g peak width of
the AMHS appeared to be wider than that of the MoS2 film, as
shown in Figure 1l. This broadening and red-shift behavior of
the E12g peak indicates induced S-vacancies in the AMHS
compared to the MoS2 film. Vacancy defects on the surface
and edge sites of the AMHS nanotubes are a feasible key factor
for enhanced humidity-sensing performance.
Furthermore, X-ray photoelectron spectroscopy (XPS) was
conducted to identify the surface element composition and
chemical states of the MoS2 film and the AMHS. Figures 1m,n
and S2 show the high-resolution XPS spectra of Mo 3d and S
2p core level for the MoS2 film and AMHS (4 cycles VF). All
samples were calibrated by the C 1s peak at 284.6 eV as a
reference. Two predominant peaks related to the Mo4+ 3d5/2
and Mo4+ 3d3/2 of MoS2 were observed at binding energies of
229.7 and 232.8 eV, respectively, as shown in Figure 1m,n.21
The other peak located at the binding energy of 226.8 eV
corresponds to the S 2s of MoS2. The Mo4+ 3d5/2 and Mo4+
3d3/2 doublet peaks of the MoS2 film and AMHS (4 cycles VF)
were deconvoluted into two components by XPS curve-fitting,
respectively. The first component peaks at the binding energies
of 232.9 and 229.8 eV were associated with the stoichiometric
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intrinsic MoS2 (i-MoS2), whereas the other component peaks
at slightly lower binding energies of 232.2 and 229.1 eV were
related to defective MoS2 with sulfur vacancies (d-MoS2).22
The peak intensity associated with the d-MoS2 of the AMHS
was higher than that of the MoS2 film (Figure 1m,n). The
reason is that a connected network of MoS2 nanotubes with
open nanopores on the surface has more defects at the edges
and boundaries of the AMHS compared to the MoS2 film.
In addition, it was confirmed that the peak intensity related
to the d-MoS2 of the AMHS gradually increased with an
increase in the VF cycles of (NH4)2MoS4 solutions (Figure
S2a). This is because of the reduction in the flake size of the
(NH4)2MoS4 solution by repeated VF that significantly
increased S-vacancies at the edge sites of the AMHS.23−26
The XPS S 2p core level spectra of the MoS2 film and the
AMHS with different VF cycles are shown in Figure S2b. The
two main peaks observed at binding energies of 163.7 and
162.5 eV correspond to S 2p1/2 and S 2p3/2 of MoS2,
respectively.27 The peak intensity of S 2p1/2 in the AMHS
was smaller compared to the MoS2 film. Furthermore, in the
case of the AMHS, the peak intensities of S 2p1/2 were
gradually reduced with an increase in the VF cycles (1−4
cycles) of the (NH4)2MoS4 solution (Figure S2b). The
variation in S 2p1/2 peak intensity also supported the expansion
of S-vacancy sites in the AMHS with increasing VF cycles of
(NH4)2MoS4 solution.22,26
The sensing performance of the AMHS was evaluated at
different RH conditions, as shown in Figure 2. Figure 2a,b
shows the current−voltage (I−V) characteristics of the MoS2
film and the AMHS-based humidity sensors for different RH
levels at 23.5 °C. The I−V curves exhibited an approximately
linear relationship, regardless of RH exposure, indicating an
ohmic contact. The electrical conductivity of all sensors
gradually increased as the RH increased from 20 to 80%, as
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Figure 3. Schematic diagram of the humidity sensing mechanism of the AMHS-based humidity sensor at (a) low humidity and (b) high humidity
conditions.
shown in Figure S5. This result implies that the adsorbed water
molecules on MoS2 act as electron donors. When the RH
changed from 20 to 80%, the current in the AMHS-based
humidity sensors significantly increased because of the unique
honeycomb structure with open pores on the surface compared
to the MoS2 film-based humidity sensors.23 The sensitivities as
a function of RH of the MoS2 film and AMHS (1−4 cycles
VF)-based sensors are presented in Figure 2c. The sensitivity
(S) that depends on the number of absorbed H2O molecules
can be defined as
IH
S= −1
I0 (1)
where IH is the measured current of the device in the presence
of humidity, and I0 is the measured current in dry air (N2) in
the chamber.28,29
The AMHS sensor showed a significantly high sensitivity of
668 at RH 83%, whereas the MoS2 film sensor only showed a
sensitivity of 80.23 at the same RH condition, as depicted in
Figure 2c. This is because of the unique AMHS structure that
contains more defect sites for H2O molecules, compared to the
MoS2 film-based sensor. Furthermore, the sensitivity of the
AMHS sensors gradually increased with the repeated number
of VF cycles (1−4) of the (NH4)2MoS4 solution. This is
because of the gradual elimination of large MoS2 particles from
the surface of AMHS with repeated filtration cycles, which
revealed more absorption sites for water molecules (Figure 2c).
This elevated sensing behavior is discussed in detail in the
sensing mechanism section.
In addition, the proposed AMHS sensor exhibited excellent
repeatability and nondegradation, even after 1.5 h of repeated
humidity exposure, as shown in Figure 2d. Additionally, the
sensor was exposed to three steps of RH level (40, 65, and
80%), and the response was monitored for six continuous
cycles. The AMHS sensor showed very stable response
amplitude for different RH conditions during each cycle,
suggesting good repeatability property of the sensor as
depicted in Figure S8. The sensing speed of AMHS (4 cycles
VF)-based sensor was investigated by measuring the response
and recovery times (Figure 2e,f). When the sensor was exposed
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to high humidity (RH 85%) from an ambient humidity
condition (RH 45%) and then restored, the response and
recovery times were measured as 0.47 and 0.81 s, respectively.
This result implies that the AMHS humidity sensor can
respond with an ultrafast speed compared to the previously
reported humidity sensors.15,24 Furthermore, the stability of
the AMHS-based humidity sensor in relation to temperature
(T) was explored under RH 55% condition, as shown in Figure
2g. At a constant mid-level humidity of 55%, the sensor was
exposed to temperatures ranging from 22.5 to 50 °C, and the
I−V response was measured at every 5 °C intervals. The
temperature-dependent resistance (log R) curve showed a
linear response from the AMHS-based humidity sensor for the
measured range of 22.5−45 °C. In contrast, according to our
experimental data the human skin temperature can vary from
32.6 to 36.1 °C at different physical conditions. Therefore, we
have carried out a test over human body temperature range
(31−38 °C) of the AMHS sensor at room RH condition.
When the MoS2 nanotube-based sensor was placed on a heater
(SiO2−substrate side), a slight change in resistance was
observed as the temperature increased from 31 to 38 °C. On
the other hand, according to our concept of noncontact
moisture detection from human skin, when the sensor was
placed above the heater at about 3.8 mm distance (the Ecoflex
skin patch’s thickness), the resistance change was almost
negligible in the temperature range from 31 to 38 °C as shown
in Figure S7a. This behavior shows that, at 3.8 mm distance or
above, the AMHS sensor is not affected by the human body
temperature (31−38 °C). Thus, the proposed humidity sensor
can be applied within the human body temperature range
without degrading the humidity-sensing performance.
The unique honeycomb structure plays a dominant role in
promoting the humidity sensing performance in the AMHS-
based sensor. Previous studies have shown that reducing the
MoS2 flake size leads to the formation of S-vacancies as active
sites for water molecule absorption.30 As described in Figures 1
and S2, the repeated VF (1−4 cycles) reduces the aggegation
of MoS2 particles that generate a large number of S-vacancies
in AMHS. The AMHS honeycomb structure with MoS2
nanotubes contains a large surface with defect sites for
absorbing H2O molecules (Figure 3). Subsequently, some of
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Figure 4. (a) Current response of the AMHS-based humidity sensor as a function of the finger distance. (b) Reversibility test of AMHS sensor in
response to the human fingertip at 3 and 5 mm distance from the sensor. (c) Relative current variation of AMHS-based humidity sensor before and
after applying moisturizer on a fingertip from the same distance. (d) Photograph of the experimental setup to measure breathing patterns based on
humidity variation in exhaled air. (e) Relative current variation of the AMHS sensor according to normal, fast, and rapid rate of breathing. (f)
Detection of human voiceprints from variation in humidity during speaking.

these absorbed molecules can easily diffuse into the MoS2
nanotubes through the open pores of the honeycomb
structure.31 The defect-rich surface of AMHS with large
quantities of S-vacancies on the open nanotube edges along
with the convex shape aids water molecules to absorb and
assemble easily.32−34 This phenomenon can accelerate the
absorption and desorption speeds of water molecules, which
contribute to the ultrafast response time of the AMHS
sensor.35 The increase in the current and high sensitivity of the
sensor can be explained by two conduction methods, which are
known as the Grotthuss mechanism that takes place
simultaneously in the AMHS-based humidity sensor.36
i. Chemisorption of hydroxyl ions at lower RH and
ii. Proton hopping through continuous water layers formed
by physisorption37
It has been reported that the superoxides (O2−) play a
dominant role at room temperature in the dissociation of water
molecules through the following reaction37
At a low RH condition, these released protons (H+) cannot
hop freely on the discontinued first physisorbed water layer.
Thus, the response is low.36 At this stage, the dominant factor
for increasing conductivity is the charge transfer from water to
the sensing layer.40 At higher humidity levels, a larger amount
of dissociated H2O molecules can continue to be absorbed in
the defect sites of the MoS2 honeycomb structure, as shown in
Figure 3b. The availability of vast absorption sites in the
AMHS allows more H2O molecules to condensate on top of
the “first physisorbed water layer”. This leads to the formation
of another aquatic layer called the “second physisorbed layer”,
which is less ordered than the first physisorbed layer.
Consequently, the free proton hopping can take place on the
second physisorbed layer, resulting in increased conductivity at
a high humidity level.36 Moreover, at a high humidity level, the
water molecules can dissociate into hydronium ions as the
following reaction
H 2O + H 2O → H3O+ + OH− (4)
The dissociated hydronium (H3O ) ions, along with (H+)
+

1 − 3 ions, can also contribute to channel conductance. This

H 2O + O2 + e− ↔ 2OH−(absorbed)
2 2
At a low humidity, these OH− from the dissociated water get
chemisorbed on the defect sites of MoS2 and act as an electron
donor (Figure 3a). This increases the conductivity of
inherently n-type semiconducting MoS2.38,39 Additional water
molecules can form a thin aquatic layer, which is known as the
first physisorption of water on this chemisorbed OH− ions at
the defect sites of the AMHS sensors.37 According to the
Grotthuss mechanism, proton hopping could occur on this
thin aquatic layer, as shown in the following formula36
H + + H 2O → H 2O + H +
(2) mechanism significantly increases the sensing performance of
the AMHS-based humidity sensor. Lastly, the intrinsic
hydrophobic nature of MoS2 and the convex nanotube
structure of the AMHS-based humidity sensor accelerate the
desorption of H2O molecules that can be attributed to their
fast recovery.28
Being inspired by the high sensing performance of the
AMHS humidity sensor, a variety of studies for multifunctional
applications were carried out. First, the proposed sensor was
used to detect humidity from human skin at an ambient air
condition for noncontact switching applications, as mentioned
in previous reports.41 To demonstrate its excellent sensitivity
(3) to human skin humidity, a commercial humidity meter was
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Figure 5. (a) Photograph of the AMHS skin humidity patch. (b) Schematic diagram of the AMHS skin humidity patch attached on a hand. (c)
Photograph of the attached skin humidity patch on the neck before and after sweating from exercise (top), and the variation in body temperature
measured by the IR image camera (bottom). (d) Comparison of the relative current variation in volunteers measured by the skin humidity patch
from the neck at different physical conditions. (e) IR images for the regional temperature variation (e.g., wrist, neck, and forehead) before and after
exercise. (f) Comparison of the regional relative current variation (e.g., wrist, neck, and forehead) based on the regional sweat rate.

used to calibrate the RH values of a human fingertip at the
range of 312 mm distance in the ambient air condition.
Figure 4a shows a rapid real-time variation in the current
responding to finger skin humidity when a fingertip was placed
at approximately 3−12 mm above the AMHS sensor. The
highest current variation (ΔI) was detected at the closest finger
distance of 3 mm (without touching the sensor) and the lowest
current variation at a distance of 10 mm. The AMHS sensor
showed a linear response to finger skin humidity from 3 to 10
mm distances, as illustrated in the inset of Figure 4a. To
evaluate the continuous noncontact switching behavior, a
finger repeatedly approached the AMHS sensor at distances of
3 and 5 mm. The sensor showed excellent response to finger
skin humidity with an almost identical current variation
(Figure 4b). For practicality, we also considered the difference
in human skin type (e.g., dry, oily). The humidity of a dry
fingertip and same fingertip after lotion (moisturizer) applied
from the same distance was monitored with the AMHS sensor.
As shown in Figure 4c, a higher current response was observed
for the moisturized fingertip compared to the dry fingertip.
Therefore, the AMHS sensor successfully demonstrated
noncontact switching behavior using human skin humidity,
which open-up the possibilities of touchless interfaces or
screens.42
Analyzing human breath to monitor breath rate, breath
depth, and exhaled air components has been an important
index to monitor human health. Figure 4d shows the
measurement setup for analyzing human breathing patterns
from humidity in exhaled air. The tube end of a general oxygen
supply mask was placed on the AMHS sensor. A commercial
RH meter was attached next to the AMHS sensor to monitor
the RH variation in real-time during a healthy male inhalation
and exhalation. The test was carried out in ambient air
condition for practicality, and only nasal breathing was
monitored to avoid interference from mouth saliva. The
variation of RH during exhales showed a sharp rise in the
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current value of the device and dropped to an ambient value
during inhales, as shown in Figure 4e. Furthermore, the AMHS
sensor could efficiently follow normal, fast, and rapid rates of
breathing variations from 0.8 to 4.1 s per cycle. The
experimental results exhibit promising potential as a portable
or wearable human respiratory monitoring system for athletic
training and healthcare. In addition, the detection of human
voiceprints from the variation in RH during speaking was
conducted with the AMHS-based humidity sensor. As shown
in Figure 4f, the sensor was able to detect features of voice
tones though variation of humidity in exhaled air from a 15 cm
distance. The AMHS sensor could identify fine fluctuation
from humidity in exhaled air when speaking words such as
“mango”, “banana”, and “pineapple” in real-time. The unique-
ness of individual voices starts down in the lungs where the air
is exhaled to create an airstream. Thus, using this core
ingredient (exhaled air) along with conventional speech
recognition systems, voice recognition for personal identi-
fication can be much safer in the next-generation devices.
Skin humidity or the water content of human skin is a crucial
parameter for noninvasive health monitoring and skincare.
Analysis of the skin humidity level or sweat could enable
noninvasive healthcare, as it contains diverse biomolecules
ranging from metabolites, electrolytes, and hormones.
Although analysis of sweat (which is mostly water)
composition is important, it is just as crucial to examine
sweating patterns, such as the sweat rates at different regions of
the body, which contain vital information about hydration and
health condition of athletes, elderlies, and infants. We
demonstrate a wearable skin humidity patch fabricated with
the AMHS humidity sensor to detect human skin humidity
levels at different physical conditions. First, the AMHS-based
humidity sensor of 5 × 5 mm2 size was transferred on a PET
substrate and attached on a round Ecoflex mold of 3.8 mm
thickness, as shown in Figure 5a. Normalized electrical
resistance (R/R0) of AMHS sensor as a function of bending
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ACS Applied Materials & Interfaces
radius during mechanical bending test is shown in Figure S9,
which indicates the strength of the device. The Ecoflex mold
with an open hole at the center was carefully designed with
appropriate thickness to avoid physical contact between the
sensor and human skin. The Ecoflex, a certified skin safe
material, served as the skin patch. Sweat caused by temperature
or activity changes the skin humidity level that can be detected
by the skin humidity patch when placed at a distance of 3 mm
from the skin in the noncontact method, as shown in Figure
5b. The predesigned mini holes in the PET were used for
ventilation.
To validate the skin humidity patch, trials were carried out
with three male volunteers. The participants completed an
exercise protocol (Table 1) for 20 min, including 10 min
Table 1. Parameters for Calculating the Sweat Rate from
Each Volunteer
pretest weight weight loss duration sweat rate
gender [kg] [L] [min] [L/h]
Male 70.5 >0.3 20 0.9
Male 75.6 >0.2 20 0.6
Male 65.3 >0.1 20 0.3
walking and 10 min running in the same weather condition
that generated sweat. The sweat rates for the three volunteers
were measured as 0.9, 0.6, and 0.3 L/h, respectively, using the
equation below.
Sweat rate (SR) = W [L]/T [h]
where W is the weight (kg) loss converted to fluid (liter) loss
after exercise, and T is the time in hour, and no liquid was
(5)
taken during the trial.43 The skin humidity patches were worn
on the same position for all three participants to explore their
change in skin humidity in a steady state, walking for 10 min,
and running for 10 min (Figure 5c,d). The IR images shown in
Figure 5c are the differences in the volunteer neck skin surface
temperature after exercise, which correspond to the sweat rate.
During any physical activity, the human core body temperature
increases from its ideal state. The process of sweating is a
crucial part of thermoregulation, which allows the body to
maintain its core temperature.44 The natural cooling method of
the human body through evaporation reduces the skin
temperature after sweating, which can vary in different regions
of the body because of different sweat rates. The AMHS-based
skin humidity patch showed excellent response, according to
the calculated sweat rate for each volunteer (Table 1). When
the patch was attached to the neck of the volunteers, the
relative variation in the current ((I − I0)/I0) for volunteer 1
was the highest after exercise, which was consistent with the
calculated sweat rate in Table 1 (Figure 5d). Furthermore,
according to the sweat zone body map, the sweating pattern in
the different regions of a male body (e.g., wrist, neck, forehead)
suggests that the human forehead has the highest sweat rate,
followed by the neck and then the wrist.45
In Figure 5e, the temperature difference (ΔT) in body
regions such as wrist, neck, and forehead was recorded by the
IR thermal imaging camera after exercise. The IR images
showed the highest drop in body temperature at the forehead,
which indicates the maximum sweating zone. For further
experiment, the skin humidity patch was attached at the wrist,
neck, and forehead to measure sweating patterns after exercise.
As shown in Figure 5f, the highest current variation was
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observed at the volunteer forehead, followed by the neck and
wrist with the AMHS-based skin humidity patch, which is also
consistent with the previously reported sweat zone body
map.45 The AMHS-based wearable skin humidity patch
showed notable potential in real-time monitoring of the skin
humidity level and regional sweat rate [Movies S1 and S2],
which paves the way to overcome limitations of the traditional
method of off-body sweat rate measurements.
■ CONCLUSIONS
In summary, we present a facile methodology to fabricate the
AMHS using the VF process. From the structural analysis by
FESEM and FESEM−EDS, we confirmed that the uniform
MoS2 tubes inside the AAO membrane and formation of the
honeycomb structure were achieved by VF of two or more
cycles. The as-fabricated AMHS-based humidity sensor
showed an elevated sensing performance with a high sensitivity
of 668 and a rapid response speed compared to the MoS2 film-
based humidity sensors. Furthermore, sophisticated sensing
applications such as human respiration and noncontact
epidermal sensing for continuous health monitoring were
demonstrated using the AMHS-based humidity sensor. In
addition, a smart wearable patch was shown with the proposed
sensor to detect human skin humidity under different physical
conditions and regional sweat rates. We thoroughly believe
that this work may open up the way to implement 2D material-
based humidity sensing technology of fast response and high
sensitivity in the next generation of skin sensors.
■ EXPERIMENTAL SECTION
Synthesis of the MoS2 Honeycomb Structure. A VF process
and the annealing method was followed to achieve the honeycomb-
like structure with MoS2 nanotubes. The (NH4)2MoS4 powder
(99.95%, Acros Organics) was mixed with ethylene glycol (anhydrous,
99.8%, Sigma-Aldrich) to produce an (NH4)2MoS4 solution with a
concentration of 1.25 wt %. Thereafter, the (NH4)2MoS4 solution was
stirred at room temperature for 40 min using a magnetic bar. A
modified VF setup was used for 1.25 wt % (NH4)2MoS4 solution
coating on a pristine AAO membrane with 0.2 μm pore diameter. The
setup consists of a Buchner funnel, a porous plate, and a Buchner flask
connected to a pump, as shown in Scheme 1. The AAO membrane
was placed in between the porous plate and Buchner funnel. Then, 40
mL solution of 1.25 wt % (NH4)2MoS4 was slowly added to the
Buchner funnel. The filtration gravity generated inside the flask by the
vacuum pump provided the force to draw the liquid through the AAO
membrane. Subsequently, the 1.25 wt % (NH4)2MoS4 solution-coated
AAO membrane was dried on a hotplate at 90 °C for 20 min. Next, a
two-step thermal decomposition process was followed to synthesize
MoS2. The (NH4)2MoS4 solution-coated AAO membrane was
annealed at 280 °C for 30 min and subsequently annealed at 600
°C for 30 min under a Ar (150 sccm) flow to form MoS2 nanotubes
inside the AAO membrane.
Fabrication of the AMHS-Based Humidity Sensor. The sensor
was prepared with physical vapor deposition by a thermal evaporation
method. Ti and Au (ratio 1:10) interdigitated electrodes were
deposited on AMHS. The sensing device contained 3 × 3 sensor
arrays with each cell size of 5 × 5 mm2. Each sensor had two pairs of
Ti/Au finger electrodes with a distance of 0.7 mm between the
adjacent fingers. In addition, the width of each finger was 0.5 mm. An
image of the sensor is provided in Figure S3. The AMHS-based
humidity sensors were dried overnight before exposing to humidity.
Humidity Measurement Setup. A custom-made humidity
sensing setup was used to investigate the AMHS sensing performance
(Figure S3). The setup contains a water bubbler, compressed air
supply, a micro vacuum probe station (NEXTRON Co.) humidity
chamber, Keithley 2636B system, and a computer. The sensor was
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ACS Appl. Mater. Interfaces 2020, 12, 17029−17038
ACS Applied Materials & Interfaces
probed inside a chamber that has two separate inlet lines for dry air
and humid air. The RH was controlled by a molecular flow controller
with a range of 100−500 sccm. Reference humidity and temperature
sensors were connected to the chamber. The data were collected in a
GUI-based characterization software from the computer. The
humidity sensing setup is similar to what has been reported
elsewhere.46 The current (I) value of the samples was measured in
response to the RH (%) variation at 1 V.
■
ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsami.9b22915.
SEM images of MoS2-coated (1.25 wt % (NH4)2MoS4
VF 1,2,3, and 4 cycles) on AAO top and cross-sectional
view; XPS core level spectra for Mo 3d and S 2p of
MoS2 film and MoS2 (1.25 wt % (NH4)2MoS4) VF (1, 2,
3, and 4) cycle honeycomb structures; schematic
representation of the humidity measurement system;
detailed SEM top view and slightly tilted view of pristine
AAO membranes and AMHS; the I-RH curves of MoS2
film and AMHS (4 cycles V.F.)-based sensors; additional
SEM cross-sectional view of the critical height of
AMHS; the resistance variation of AMHS in the
human body temperature range; repeatability perform-
ance of AMHS sensor when exposed to RH (a) 40, (b)
65, and (c) 80%; normalized electrical resistance (R/R0)
of the AMHS sensor as a function of bending radius
during the mechanical bending test; and comparison of
sensing performance between AMHS humidity sensors
and other conventional humidity sensors (PDF)
Noncontact moisture sensing performance of AMHS-
based skin humidity patch from human finger (AVI)
Detection of dry and wet (sweat) human skin (AVI)
■ AUTHOR INFORMATION
Corresponding Author
Choon-Gi Choi − Graphene Research Team, ICT Creative
Research Laboratory, Electronics and Telecommunications
Research Institute (ETRI), Daejeon 34129, Republic of Korea;
School of ETRI (ICT-Advanced Device Technology), University
of Science and Technology (UST), Daejeon 34113, Republic of
Korea; orcid.org/0000-0002-4023-1749; Phone: +82-42-
860-6834; Email: cgchoi@etri.re.kr; Fax: +82-42-860-5211
Authors
Shuvra Mondal − Graphene Research Team, ICT Creative
Research Laboratory, Electronics and Telecommunications
Research Institute (ETRI), Daejeon 34129, Republic of Korea;
School of ETRI (ICT-Advanced Device Technology), University
of Science and Technology (UST), Daejeon 34113, Republic of
Korea
Seong Jun Kim − Graphene Research Team, ICT Creative
Research Laboratory, Electronics and Telecommunications
Research Institute (ETRI), Daejeon 34129, Republic of Korea
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsami.9b22915
Author Contributions
S.M. and S.J.K. contributed equally. The manuscript was
written through contributions of all the authors. All the authors
have given approval to the final version of the manuscript.
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Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the Korea Institute of Energy
Technology Evaluation and Planning (KETEP) grant funded
by the Korea government (MOTIE) (20181510102340,
Development of a real-time detection system for unidentified
RCS leakage less than 0.5 gpm) and the Institute of Civil
Military Technology Cooperation funded by the Defense
Acquisition Program Administration and Ministry of Trade,
Industry, and Energy of Korean government under grant (19-
CM-MU-13).
■
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