nanomaterials
Article
A Graphene-Based Polymer-Dispersed Liquid Crystal Device
Enabled through a Water-Induced Interface Cleaning Process
Eun Mi Kim 1,2,† , Su Jin Kim 1,2,† , Go Bong Choi 3 , Jaegeun Lee 4 , Min Mo Koo 5 , Jaewoong Kim 5 ,
Young Won Kim 1 , Jongho Lee 1 , Jin Hyeok Kim 2,6, * and Tae Hoon Seo 1, *
Citation: Kim, E.M.; Kim, S.J.; Choi,
G.B.; Lee, J.; Koo, M.M.; Kim, J.; Kim,
Y.W.; Lee, J.; Kim, J.H.; Seo, T.H. A
Graphene-Based Polymer-Dispersed
Liquid Crystal Device Enabled
through a Water-Induced Interface
Cleaning Process. Nanomaterials 2023,
13, 2309. https://doi.org/10.3390/
nano13162309
Received: 20 July 2023
Revised: 4 August 2023
Accepted: 9 August 2023
Published: 11 August 2023
Copyright: © 2023 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Nanomaterials 2023, 13, 2309. https://doi.org/10.3390/nano13162309
1 Green Energy and Nano Technology & R&D Group, Korea Institute of Industrial Technology (KITECH),
Gwangju 61012, Republic of Korea; kimeunmi@kitech.re.kr (E.M.K.); ksjhy4@kitech.re.kr (S.J.K.);
ywkim@kitech.re.kr (Y.W.K.); jholee@kitech.re.kr (J.L.)
2 School of Materials Science & Engineering, Chonnam National University, Gwangju 61186, Republic of Korea
3 Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Republic of Korea;
gbchoi@kaist.ac.kr
4 School of Chemical Engineering, Pusan National University, Busan 46261, Republic of Korea;
jglee@pusan.ac.kr
5 Automotive Materials & Components R&D Group, Korea Institute of Industrial Technology (KITECH),
Gwangju 61012, Republic of Korea; mmkoo@kitech.re.kr (M.M.K.); kjw0607@kitech.re.kr (J.K.)
6 Optoelectronic Convergence Research Center, Department of Materials Science and Engineering,
Chonnam National University, Gwangju 61186, Republic of Korea
* Correspondence: jinhyeok@jnu.ac.kr (J.H.K.); thseo@kitech.re.kr (T.H.S.)
† These authors contributed equally to this work.
Abstract: We report the use of four-layer graphene (4LG) as a highly reliable transparent conduc-
tive electrode (TCE) for polymer-dispersed liquid crystal (PDLC)-based smart window devices.
The adhesion between 4LG and the substrate was successfully improved through a water-induced
interface-cleaning (WIIC) process. We compared the performance of a device with a WIIC-processed
4LG electrode with that of devices with a conventional indium tin oxide (ITO) electrode and a 4LG
electrode without a WIIC. With the application of the WIIC process, the PDLC smart window with a
4LG electrode exhibited reduced turn-on voltage and haze compared to 4LG without the WIIC pro-
cess and characteristics comparable to those of the ITO electrode. The WIIC-processed 4LG electrode
demonstrated enhanced electrical properties and better optical performance, leading to improved
device efficiency and reliability. Furthermore, our study revealed that the WIIC process not only
improved the adhesion between 4LG and the substrate but also enhanced the compatibility and inter-
facial interactions, resulting in the superior performance of the smart window device. These findings
suggest that 4LG with WIIC holds great promise as a transparent conductive electrode for flexible
smart windows, offering a cost-effective and efficient alternative to conventional ITO electrodes.
Keywords: adhesion; four-layer graphene; polymer-dispersed liquid crystal; smart window; water-
induced interface cleaning
1. Introduction
The concept of a “net-zero-energy building”, which refers to the balance of emissions
and energy in a building, attracts considerable attention and is considered a feasible solution
instead of a distant future objective [1]. Several efforts have been made to reduce the en-
ergy consumed by building services such as ventilation, heating, and air conditioning [2,3].
Smart window technology is expected to play a crucial role in achieving eco-friendly energy
savings in buildings because windows are among the most energy-efficient components. In
particular, smart window devices based on PDLC offer various advantages, including a
simple electrode-sandwiched design, straightforward fabrication process, quick response
time, and durability [4–6]. Despite decades of steady and intensive research on liquid
crystal (LC) coatings, polymer matrices, and ultraviolet aging, TCEs continue to pose
https://www.mdpi.com/journal/nanomaterials
Nanomaterials 2023, 13, 2309 2 of 10

major challenges. TCEs require low sheet resistance, high transparency, flexibility, and low
cost. ITO has been commercially utilized as a TCE in PDLC-based smart windows, owing
to its high optical transmittance and low sheet resistance. However, the ITO layer has
several drawbacks such as rising prices due to the scarcity of indium, chemical instability
towards acidic and basic sources, and high processing temperatures [7,8]. Furthermore,
its application in flexible smart windows is severely hampered by its fragility when the
substrate is bent or stretched by external force [9,10]. Therefore, alternative electrodes that
can match or surpass ITO’s optical and electrical properties, without any disadvantages, are
required. Numerous alternative materials such as carbon nanotubes [11], graphene [12–15],
conductive polymers [16,17], and metal nanowires [18,19] have been explored and devel-
oped to replace ITO layers. Graphene has recently emerged as a promising alternative
owing to its outstanding optical and electrical properties and thermal and chemical sta-
bilities. Furthermore, graphene exhibits the flexibility required for use in smart windows.
Pioneering studies have demonstrated PDLC-based smart window devices that employ
graphene layers as TCEs on glass and other flexible plastic substrates. However, the lack
of adhesion between graphene and its substrate can lead to local delamination, folding,
and bending when exposed to a weak external force, resulting in the mechanical failure
of graphene-based devices at their interface [20–22]. Despite the successful enhancement
of adhesion to the substrate, graphene’s application as a TCE in smart windows has not
yet surpassed the performance of conventional ITO-based smart windows. This is due
to the fact that single-layer graphene (1LG) has a high sheet resistance of approximately
1.0 KΩ/sq [12–14]. Consequently, in order to commercialize a PDLC-based smart window
with graphene, it is necessary not only to achieve strong adhesion properties between the
substrate and the graphene interface, but also to apply an electrode, such as 4LG, with
sheet resistance comparable to that of ITO. In this study, we report a graphene-based PDLC
device using a 4LG TCE with a WIIC process. 4LG is the optimal layer for balancing the
trade-offs between sheet resistance and transmittance, showing electrical characteristics
comparable to ITO in contrast to 1LG. The WIIC process is simple and highly effective for
eliminating impurities and improving the adhesion between graphene and the substrate.
We demonstrated that the performance and stability of our graphene-based PDLC device
are not only enhanced through the WIIC process but also comparable to those achieved
using conventional ITO electrodes as conducting layers.

2. Materials and Methods

2.1. Synthesis of Graphene and Transfer to Glass Substrate
Low-pressure chemical vapor deposition (LPCVD) was utilized to grow a graphene
layer on Cu foils (Nippon Mining, Tokyo, Japan) that were 35 µm thick. In order to
reduce the surface roughness of the Cu foils and remove the impurity particles, for the
first time, electro-chemical polishing (ECP) was conducted in a diluted 3H3 PO4 :H2 O acid
solution for 12 min at a constant voltage of 3.0 V using a Cu plate as the cathode and a
Cu foil (200 mm × 200 mm) as the working electrode. Cu foils were then placed inside an
8-inch quartz tube and heated using a split-tube furnace. Meanwhile, the quartz tube was
pumped down to 0.068 Torr, and 100 standard cubic centimeters per minute (sccm) of H2
gas permeated the reactor during the temperature increase to 1020 ◦ C. Subsequently, the
Cu foils were annealed for 60 min. CH4 of 10 sccm and H2 of 100 sccm were provided
at 1020 ◦ C for 18 min under a growth pressure of 0.13 Torr. Finally, the samples were
swiftly cooled to room temperature with a cooling rate of 40 ◦ C min−1 at an H2 flow rate
of 100 sccm through removing the furnace from the substrate region. This is the optimal
condition to achieve large and uniform graphene domains. Figure 1a shows the SEM image
of the graphene layer synthesized on Cu foils. One can notice that the graphene layer is
continuous, uniform, and clean without noticeable particles, whereas Cu surface steps,
grain boundaries, and wrinkles are formed. Wrinkles associated with thermal coefficient
difference between the Cu substrate and graphene formed during the cooling process across
the Cu grain boundaries indicate that the graphene is continuous [23]. In addition, Figure 1b
 achieve large and uniform graphene domains. Figure 1a shows the SEM image of the gra-
phene layer synthesized on Cu foils. One can notice that the graphene layer is continuous,
uniform, and clean without noticeable particles, whereas Cu surface steps, grain bounda-
Nanomaterials 2023, 13, 2309 ries, and wrinkles are formed. Wrinkles associated with thermal coefficient difference 3 ofbe-
10
tween the Cu substrate and graphene formed during the cooling process across the Cu
grain boundaries indicate that the graphene is continuous [23]. In addition, Figure 1b is a
isselected area
a selected electron
area diffraction
electron diffraction(SAED)
(SAED)pattern
patterndisplaying
displaying aa typical hexagonal pattern
typical hexagonal pattern
for graphene. In Figure 1c, we also confirm that the graphene synthesized in this work isis
for graphene. In Figure 1c, we also confirm that the graphene synthesized in this work
mostly composed
mostly composed of ofaasingle
singlelayer.
layer. Further
Further details
details can
canbe
befound
foundininRef.
Ref.[24].
[24].Following
Following
growth,the
growth, thegraphene
graphenewaswastransferred
transferredtotoaaglass
glasssubstrate 110◦°C
substrateatat110 usingaathermal
C using thermalrelease
release
tape.We
tape. Weobtained
obtained4LG4LGusing
usingaafour-step
four-steptransfer
transferprocedure.
procedure.

Figure1.1.(a)
Figure (a)SEM
SEMimage,
image,(b)
(b)selected
selected area
area electron
electron diffraction
diffraction (SAED)
(SAED) pattern,
pattern, andand (c) high-resolu-
(c) high-resolution
tion transmission
transmission electron
electron microscopy
microscopy (HRTEM)
(HRTEM) of graphene
of graphene layer
layer grown
grown onon
Cu Cufoils
foils(White
(Whitearrows
arrows
indicating 1LG).
indicating 1LG).

2.2.
2.2.Water-Induced
Water-Induced Interface
Interface Cleaning
Cleaning(WIIC)
(WIIC)Process
Process
Figure 2a presents a schematic representation
Figure 2a presents a schematic representation of of
thethe
experimental
experimental design employed
design employed in
this study.
in this To enhance
study. To enhance the the
adhesion between
adhesion graphene
between graphene andand
the the
glass substrate,
glass we we
substrate, imple-
im-
mented
plemented the water-induced
the water-induced interface-cleaning (WIIC)
interface-cleaning process.
(WIIC) The 4LG/glass
process. configuration
The 4LG/glass configu-
was immersed
ration in deionized
was immersed water forwater
in deionized a duration
for a of 1 min. Subsequently,
duration the 4LG/glass
of 1 min. Subsequently, the
sample underwent heat treatment in a chamber at 200 ◦ C under vacuum conditions for
4LG/glass sample underwent heat treatment in a chamber at 200 °C under vacuum condi-
10 min,for
tions utilizing
10 min,fast thermalfast
utilizing processing
thermal equipment. The unique characteristics
processing equipment. of graphene,
The unique characteristics
specifically its smallest kinetic diameter [25–28], make it impermeable
of graphene, specifically its smallest kinetic diameter [25–28], make it impermeable to gas molecules,
to gas
preventing
molecules, preventing their passage through it. Consequently, water molecules between
their passage through it. Consequently, water molecules confined confined
graphene and the substrate
between graphene can only move
and the substrate laterally
can only move rather than
laterally vertically,
rather allowingallow-
than vertically, them
to efficiently sweep away impurities. This leads to a remarkable
ing them to efficiently sweep away impurities. This leads to a remarkable improvement improvement in the
adhesion force, as the removal of impurities significantly enhances the
in the adhesion force, as the removal of impurities significantly enhances the bonding bonding strength.
Finally, in the last stage of the process, the sample was cooled to room temperature while
strength. Finally, in the last stage of the process, the sample was cooled to room tempera-
maintaining an argon flow of 500 standard cubic centimeters per minute (sccm). Through
ture while maintaining an argon flow of 500 standard cubic centimeters per minute4(sccm).
Nanomaterials 2023, 13, x FOR PEER REVIEW of 11
these carefully orchestrated steps, the WIIC process was effectively applied, resulting in
Through these carefully orchestrated steps, the WIIC process was effectively applied, re-
optimized adhesion properties between graphene and the glass substrate.
sulting in optimized adhesion properties between graphene and the glass substrate.

Schematicdiagram
Figure2.2.Schematic
Figure diagramofof(a)
(a)WIIC
WIICprocess
processand
and(b)
(b)fabrication
fabricationprocess
processofofgraphene-based
graphene-based
PDLCdevice.
PDLC device.

2.3. Fabrication of PDLC Device

2.3. Fabrication of PDLC Device
To fabricate the PDLC devices, we prepared three different transparent conductive
To fabricate the PDLC devices, we prepared three different transparent conductive
electrodes (TCEs): (1) conventional ITO, (2) four-layer graphene without the WIIC process
electrodes (TCEs): (1) conventional ITO, (2) four-layer graphene without the WIIC process
(4LG w/o WIIC), and (3) four-layer graphene with the WIIC process (4LG w/WIIC). The
PDLC material, consisting of a liquid crystal, pre-polymer, and photo-initiator, was ob-
tained from Qingdao QY Liquid Crystal Co., Ltd., Qingdao, China (QYPDLC-100). To
achieve a uniform PDLC device thickness, we incorporated 20 µm silica microspheres as
Nanomaterials 2023, 13, 2309 4 of 10

(4LG w/o WIIC), and (3) four-layer graphene with the WIIC process (4LG w/WIIC). The
PDLC material, consisting of a liquid crystal, pre-polymer, and photo-initiator, was obtained
from Qingdao QY Liquid Crystal Co., Ltd., Qingdao, China (QYPDLC-100). To achieve a
uniform PDLC device thickness, we incorporated 20 µm silica microspheres as spacers. The
PDLC and microsphere spacer solution were carefully deposited onto the bottom electrode
of the glass substrate. Next, another sample with the same electrode was placed on top to
form a sandwich configuration with a defined gap. Finally, the PDLC mixture was cured
through exposing the device to a UV lamp with an intensity of 1 mW/cm2 at 365 nm for a
duration of 60 s. Figure 2b shows a schematic of the fabricated PDLC device with 4LG as
the TCE.

2.4. Characterization
Raman spectroscopy (Renishaw, Hongkong, China) was used to determine the number
of layers and evaluate the quality of the graphene. The 514 nm line of an Ar-ion laser
served as the excitation source for the Raman measurements. Additionally, we utilized
field-emission scanning electron microscopy (FESEM, Thermo Fisher Scientific, Waltham,
MA, USA) to investigate the surface morphology of graphene transferred to a SiO2 /Si sub-
strate. To validate the uniformity and electrical properties, we conducted sheet resistance
mapping measurements using a non-contact sheet resistance meter and a Hall measure-
ment system. For optical characterization, we measured the transmittance and haze as
functions of various driving voltages using a UV-Vis-NIR spectrophotometer (Lambda750,
Perkin Elmer, Hongkong, China) and a haze meter (Nippon Denshoku, NDH5000, Tokyo,
Japan), respectively. These comprehensive analyses allowed us to thoroughly examine the
characteristics and performance of graphene in our smart window devices. High-resolution
transmission electron microscopy (HRTEM, Thermo Fisher Scientific, Waltham, MA, USA)
investigations were performed utilizing a FEI TITAN G2, equipped with an image Cs
corrector and a monochromator. The instrument was operated at an optimized acceleration
voltage of 60 kV to prevent knock-on damage to the graphene.

3. Results
3.1. Number of Graphene Layer
The two crucial considerations for the use of TCEs in PDLC devices are optical transmit-
tance and sheet resistance, because these two parameters significantly impact the device’s
performance. Achieving a balance between these parameters is of utmost importance when
selecting transparent conductive electrodes (TCEs). While the use of 1LG is desirable due
to its high optical transmittance, it comes with the drawback of high sheet resistance. As a
potential solution, we sought to strike a balance between sheet resistance and transmittance
through increasing the number of graphene layers. Drawing from our expertise, we hypoth-
esized that four-layer graphene (4LG) could serve as an ideal TCE in PDLC devices, offering
both high transmittance and low sheet resistance. To verify this hypothesis, our first step
involved ensuring the successful transfer of high-quality 1LG and 4LG onto substrates.
We meticulously transferred 1LG and 4LG onto SiO2 /Si substrates and performed Raman
spectroscopy to thoroughly investigate their quality and quantity, shedding light on their
suitability as TCE candidates for PDLC devices. In Figure 3a, we present the Raman spectra
obtained using the 514 nm line of an Ar-ion laser. The Raman spectrum of 1LG reveals two
prominent peaks: the G band located at 1594 cm−1 and the 2D band at 2703 cm−1 . These
peaks demonstrate typical characteristics of monolayer graphene, including a remarkably
sharp Lorentzian peak with a narrow full width at half maximum (FWHM) of 30 cm−1 ,
a symmetrical shape, and a 2D-to-G intensity ratio exceeding two. Interestingly, as the
number of graphene layers increases, the 2D peak broadens and diminishes in intensity,
whereas the G peak becomes more pronounced [29,30]. The spectra of 4LG had a lower
2D-to-G intensity ratio (0.79) and a larger FWHM (38 cm−1 ) than those of 1LG. Moreover,
the so-called defects-induced or disorder-induced D-band peak at 1350 cm−1 is minuscule,
indicating that 4LG is high quality with few defects. The transmittances and sheet resis-
 Nanomaterials 2023, 13, 2309 5 of 10

tances of the four TCEs are shown in Figure 3b. The transmittances of the conventional
ITO, 1LG, and 4LG without the WIIC process and 4LG with the WIIC process at 550 nm
were 90.0%, 97.5%, 89.6%, and 89.8%, respectively. As expected, the 1LG TCE exhibits the
highest transmittance. Nevertheless, the transmittance of the 4LG TCE is comparable to
that of the ITO TCE. The sheet resistance was also determined. Sheet resistance measure-
ments were performed using a Hall measurement system. The obtained sheet resistance
values of conventional ITO, 1LG, 4LG without WIIC, and 4LG with WIIC are 30 ± 2 Ω/sq,
202 ± 10 Ω/sq, 49 ± 4 Ω/sq, and 57 ± 2 Ω/sq, respectively. The sheet resistance of 4LG
with the WIIC process was slightly higher than that of 4LG without the WIIC process. This
can be attributed to the fact that some defects in 4LG are linked to oxygen groups during
the WIIC process. Overall, the 4LG TCEs simultaneously exhibited high transmittance
and low sheet resistance, which is consistent with our hypothesis. Due to the fact that
monolayer graphene has an opacity of 2.3% at the wavelength of 550 nm, the transmittance
of 4LG without the WIIC process is about 89.6%, which deviates slightly from the predicted
value of 90.6%. However, this is a typical trend since CVD-grown graphene contains a
small amount of bilayer or trilayer, depending on growth conditions. When the WIIC
process is used to apply 4LG on glass substrate, transmittance increase by approximately
0.2% compared with that of 4LG without WIIC process. This might be because impurities
in the interface of the artificially constructed weak van der Waals stacked layers have
Nanomaterials 2023, 13, x FOR PEER REVIEW 6 ofbeen
11
removed. Consequently, the transmittance of 4LG with the WIIC process is comparable to
that of ITO.

(a)Raman
Figure3.3.(a)
Figure Ramanspectra
spectraofof1LG
1LGand
and4LG
4LGtransferred
transferredto
to aa SiO
SiO22/Si
/Sisubstrate.
substrate.(b)
(b)Transmittance
Transmittance
and
andsheet
sheetresistance
resistanceofofITO,
ITO,1LG,
1LG,4LG
4LGwith
withWIIC,
WIIC,and
and4LG
4LGwithout
withoutWIIC,
WIIC,respectively.
respectively.

3.2. Effect of WIIC

3.2. Effect of WIIC
Our second strategy to improve the performance of graphene-based PDLC devices
Our second strategy to improve the performance of graphene-based PDLC devices
was to employ the WIIC process to remove impurities at the interface between the TCE
was to employ the WIIC process to remove impurities at the interface between the TCE
and substrate. We firmly believe that the WIIC process offers two key advantages that
and substrate. We firmly believe that the WIIC process offers two key advantages that
greatly contribute to device improvement. Firstly, it ensures the remarkable uniformity
greatly contribute to device improvement. Firstly, it ensures the remarkable uniformity of
of the TCE across the entire study area. Secondly, it significantly enhances the adhesion
the TCE across the entire study area. Secondly, it significantly enhances the adhesion be-
between the TCE and the substrate, promoting overall device performance. The uniformity
tween the TCE and the substrate, promoting overall device performance. The uniformity
of the TCE was already evident during the sheet resistance measurements, where the sheet
ofresistance
the TCE was already
of 4LG evident
without during
the WIIC the sheet
process andresistance
4LG withmeasurements,
the WIIC process where
werethe sheet
recorded
resistance of 4LG without the WIIC process and 4LG with the WIIC process
as 49 ± 4 Ω/sq and 57 ± 2 Ω/sq, respectively. Remarkably, the standard deviation of were recorded
asthe
49sheet
± 4 Ω/sq and 57of±4LG
resistance 2 Ω/sq,
withrespectively. Remarkably,
the WIIC process was only the standard
half deviation for
of that observed of the
4LG
sheet resistance of 4LG with the WIIC process was only half of that observed
without the WIIC process. To further corroborate the uniformity of 4LG on a larger scale, for 4LG
without the WIIC performed
we meticulously process. Tofour-point
further corroborate the uniformity
mapping over a substantial of200
4LGmmon ×a larger
200 mm scale,
area
we meticulously performed four-point mapping over a substantial 200 mm
for both 4LG with and without the WIIC process, as depicted in Figure 4a,b. The resulting× 200 mm area
for bothresistance
sheet 4LG with value
and without
for 4LG thewith
WIIC process,
the WIIC as depicted
process wasinmeasured
Figure 4a,b.
as The
58 ± resulting
2 Ω/sq,
sheet
slightly higher than the value of 51 ± 5 Ω/sq obtained for 4LG without the WIICslightly
resistance value for 4LG with the WIIC process was measured as 58 ± 2 Ω/sq, process.
higher than the
This result valueseamlessly
aligned of 51 ± 5 Ω/sq obtained
with the Hallformeasurements,
4LG without the WIIC process.
providing furtherThis result
evidence
aligned seamlesslyachieved
of the uniformity with the through
Hall measurements, providing
the WIIC process. Despitefurther evidence
the slight of the
increase in uni-
sheet
formity achieved through the WIIC process. Despite the slight increase in sheet
resistance brought about by the WIIC procedure, it is important to emphasize that the entire resistance
brought about by
area exhibited the WIICand
a consistent procedure,
uniform itsheet
is important
resistanceto emphasize
value. This canthat
be the entire to
attributed area
the
exhibited a consistent and uniform sheet resistance value. This can be attributed to the
effective elimination of impurities, as indicated by the white circle in Figure 4a, and is
likely a significant factor responsible for the observed improvements in the device perfor-
mance. The effect of the WIIC process is further supported by the on/off optical images
Nanomaterials 2023, 13, 2309 6 of 10

effective elimination of impurities, as indicated by the white circle in Figure 4a, and is likely
a significant factor responsible for the observed improvements in the device performance.
The effect of the WIIC process is further supported by the on/off optical images shown in
Figure 5a,b. The optical image of the PLDC device with a 4LG electrode without the WIIC
process at an applied voltage is unclear and shows the graphene-burning phenomenon
resulting from the high-power consumption of graphene [31,32], as marked by the blue
circle in Figure 5a. Because of the current crowding induced by impurities and adhesion
between the graphene and the substrate at 60 V injection, an excessive quantity of power
builds up under the graphene electrode in the device, destroying the graphene with Joule
heat. As illustrated in Figure 5b, in the case of the 4LG electrode following the application
of the WIIC process, the device in the ON state was nearly transparent and uniform across
the entire operation region. This clearly indicates that the 4LG electrode with the WIIC
process as a transparent conductive layer can act as an efficient lateral current diffusion
channel. The WIIC process effect can be evaluated using the above results obtained from
the PDLC device, but the adhesion between the 4LG electrode and the substrate could not
be verified. In order to ascertain the effectiveness of the WIIC process in enhancing
Nanomaterials 2023, 13, x FOR PEER REVIEW
the
7 of 11
adherence of the 4LG electrode to the substrate, we undertook the fabrication of patterned
graphene using photolithography and etching, spanning a considerable area of 200 mm
× 200 mm, as depicted in Figure 6a. The process involved transferring the chemical
to form
vapor the patterned
deposition graphene.graphene
(CVD)-grown Subsequently, the times
films four patterned
onto region
a glass was safeguarded
substrate to form
through applying
the patterned a protective
graphene. photoresistthe
Subsequently, (PR) as an etchant
patterned regionmask,
was and the graphene
safeguarded was
through
selectively patterned using an inductively coupled plasma reactive-ion
applying a protective photoresist (PR) as an etchant mask, and the graphene was selectively etcher with O2
plasma. Lastly, the PR was meticulously removed using acetone. Optical
patterned using an inductively coupled plasma reactive-ion etcher with O2 plasma. Lastly, images of the
resulting
the PR was patterned
meticulouslygraphene without
removed and
using with the
acetone. WIIC process
Optical images ofarethe
shown in Figure
resulting 6b,c,
patterned
respectively.
graphene withoutThe surface
and with of the
patterned graphene
WIIC process are without
shown ina Figure
WIIC process is readily and
6b,c, respectively. The
partially
surface ofpeeled-off
patterned during
graphene fabrication
without aowing
WIIC to the lack
process of chemical
is readily reactivity
and partially of gra-
peeled-off
phene,
during which consists
fabrication of the
owing C-Clack
to the bondof of sp2 hexagonally
chemical reactivityarranged carbon
of graphene, atoms
which with no
consists of
dangling bonds
the C-C bond of sp 2 hexagonally
[20–22,33]. When the WIIC
arranged process
carbon atoms was applied,
with we observed
no dangling a cleanly
bonds [20–22,33].
patterned
When the graphene
WIIC process surface
waswithout
applied, peeling. This is as
we observed a resultpatterned
a cleanly of the fact graphene
that the adhesion
surface
of graphene
without to the
peeling. substrate
This is as a was
resultstronger than
of the fact its the
that attachment
adhesiontoofthe PR, which
graphene is indicative
to the substrate
of enhanced
was strongeradhesion. We believe that
than its attachment thisPR,
to the observed
which effect can be ascribed
is indicative of enhancednot only to the
adhesion.
We believeremoval
successful that thisofobserved
impurities,effect
butcan
alsobe to ascribed not only
the interaction to the
of an successful
oxygen group withremoval
the
of impurities,
graphene butresulting
defect, also to the
in ainteraction
transformationof anofoxygen grouphydrophobicity
its inherent with the graphene defect,
into hydro-
resulting[34].
philicity in a transformation of its inherent hydrophobicity into hydrophilicity [34].

Figure 4.
Figure Four-pointmapping
4. Four-point mappingimages
images
ofof
(a)(a)
4LG4LG without
without WIIC
WIIC process
process andand (b) 4LG
(b) 4LG withwith
WIICWIIC
pro-
process at a 200 mm × 200 mm
cess at a 200 mm × 200 mm area.area.

Figure 5. Optical images for PDLC devices of (a) 4LG without WIIC process and (b) 4LG with WIIC
Nanomaterials 2023, 13, 2309 7 of 10
Figure 4. Four-point mapping images of (a) 4LG without WIIC process and (b) 4LG with WIIC pro-
cess at a 200 mm × 200 mm area.

Nanomaterials 2023, 13, x FOR PEERFigure

REVIEW5. 5.
Figure Optical images
Optical forfor
images PDLC devices
PDLC ofof
devices (a)(a)
4LG without
4LG WIIC
without process
WIIC and
process (b)(b)
and 4LG with
4LG 8 WIIC
of 11
WIIC
with
process
processininon/off state.
on/off state.

Figure
Figure 6.
6. (a)
(a)Schematic
Schematicdiagram
diagramofoffabrication
fabrication process
process for
forthe
thepatterned
patterned4LG
4LGusing
usingphotolithography
photolithography
and etching. Optical images of the patterned 4LG (b) without WIIC process
and etching. Optical images of the patterned 4LG (b) without WIIC process and and
(c) (c)
withwith
WIICWIIC pro-
process.
cess.
3.3. Performance of PDLC Device
3.3. Performance
The propertiesof PDLC Device
of the PDLC device were examined to understand the potential of
the WIIC process. Figure
The properties 6a,b show
of the PDLC device thewere
transmittance
examined to at understand
550 nm andthe haze of the PDLC
potential of the
devices
WIIC with conventional
process. Figure 6a,b show ITO,the4LG without theat
transmittance WIIC
550 nm process,
and hazeandof4LGthewith
PDLC the WIIC
devices
process, respectively, as a function of the applied voltage. All devices
with conventional ITO, 4LG without the WIIC process, and 4LG with the WIIC process, scattered or reflected
almost all theasincident
respectively, a function light when
of the turned
applied off. As
voltage. Allthe applied
devices voltage
scattered or increased, more
reflected almost
incident
all light was
the incident transmitted
light when turned through
off. Asthe the
device, reaching
applied voltagea saturation
increased,statemoreat aincident
critical
voltage.
light wasAs shown in Figure
transmitted through 7a,the
thedevice,
transmittance
reachingofathe device with
saturation statethe
at conventional ITO
a critical voltage.
electrode
As shownrapidly
in Figure increased at injection voltages
7a, the transmittance exceeding
of the device with the15 V and reachedITO
conventional a maximum
electrode
transmittance
rapidly increasedof 68% at 60 V.voltages
at injection For the bare 4LG electrode,
exceeding 15 V and the transmittance
reached a maximum increased
transmit- at
driving voltages above 35 V and reached a maximum transmittance
tance of 68% at 60 V. For the bare 4LG electrode, the transmittance increased at driving of 48% at 60 V. The
relativelyabove
voltages high turn-on
35 V andvoltage
reachedand low transmittance
a maximum associated
transmittance of 48%with
at 60theV.bare graphene
The relatively
electrode were due to insufficient current spreading due to poor contact
high turn-on voltage and low transmittance associated with the bare graphene electrode between graphene
and the
were duesubstrate.
to insufficient When the WIIC
current process
spreading duewas applied
to poor to the
contact bare 4LG
between electrode,
graphene the
and the
transmittance-voltage curves revealed a considerable reduction
substrate. When the WIIC process was applied to the bare 4LG electrode, the transmit- in the turn-on voltage of
17 V and an increase in the maximum transmittance of 20% compared
tance-voltage curves revealed a considerable reduction in the turn-on voltage of 17 V and to those of the 4LG
electrode-based
an increase in thedevice
maximum without the WIIC process.
transmittance This is attributed
of 20% compared to those oftothe
the4LG
improvement
electrode-
based device without the WIIC process. This is attributed to the improvement in that
in the adhesion level between the graphene layer and substrate, which indicates the
the ad-
4LG electrode with the WIIC process serves as the current-spreading
hesion level between the graphene layer and substrate, which indicates that the 4LG elec- electrode of the PDLC
device.
trode The
with thehaze
WIICasprocess
a function
serves ofasthe
theinjection voltage forelectrode
current-spreading the PDLC devices
of the PDLCwith the
device.
The haze as a function of the injection voltage for the PDLC devices with the three differ-
ent TCEs, as shown in Figure 7a, is illustrated in Figure 7b. The haze values of ITO, 4LG
without WIIC, and 4LG with WIIC at 60 V were measured to be 5, 22, and 10%, respec-
tively. Through applying the WIIC process, the haze was significantly reduced by approx-
 Nanomaterials 2023, 13, 2309 8 of 10

three different TCEs, as shown in Figure 7a, is illustrated in Figure 7b. The haze values of
ITO, 4LG without WIIC, and 4LG with WIIC at 60 V were measured to be 5, 22, and 10%,
respectively. Through applying the WIIC process, the haze was significantly reduced by
approximately 12% compared with that of the 4LG electrode without the WIIC process. As
shown in Figure 7a,b, even if the sheet resistance increased after utilizing the WIIC process,
this was due to the improved interfacial adhesion. However, the haze and turn-on voltages
for the PDLC device with the 4LG electrode and the WIIC process were still slightly higher
than those of the PDLC device with the conventional ITO electrode owing to the relatively
high sheet resistance. If the opto-electrical performance of graphene is further improved
Nanomaterials 2023, 13, x FOR PEER REVIEW 9 of 11
through optimizing the graphene transfer and improving the electrical properties of the
graphene layer in the CVD synthesis, it will be suitable for use as a TCE in flexible devices
owing to the lack of flexibility in ITO. Figure 7c illustrates the temporal characteristics of
all the PDLC devices. During the off-to-on and on-to-off voltage transitions, the rise and
all the PDLC devices. During the off-to-on and on-to-off voltage transitions, the rise and
decay times were defined as the times required for the transmittance to increase from 10%
decay times were defined as the times required for the transmittance to increase from 10%
toto90%,
90%,respectively.
respectively.RiseRisetimes
timesofofITO,
ITO,4LG
4LGwithout
withoutWIIC,
WIIC,andand4LG4LGwith
withWIIC
WIICwere
were1.1,1.1,
1.4,
1.4,and
and1.6
1.6ms,
ms,respectively,
respectively,and
andtheir
theirdecay
decaytimes
times41,41,27,
27,and
and29 29ms,
ms,respectively.
respectively.The
Therise
rise
time
timeofof4LG
4LGwith
withWIIC
WIICwas
wasshorter
shorterthan
thanthat
thatofof4LG
4LGwithout
withoutWIICWIICowing
owingtotothe
thereduced
reduced
sheet
sheet resistance. While all other material properties are constant, it is widely knownthat
resistance. While all other material properties are constant, it is widely known that
the
thedecay
decaytime
timeincreases
increaseswith
withthe
thedroplet
dropletsize.
size.WeWebelieve
believethat
thatthe
thedecrease
decreaseininthe
thedecay
decay
time
timeofofPDLC
PDLCdevices
deviceswith
withgraphene
grapheneelectrodes
electrodesisisaaresult
resultofofsmaller
smallerLCLCdroplets
dropletsininthe
the
polymer
polymermatrix
matrix[14].
[14].Details
Detailsofofthe
thedecay
decaytime
timeresults
resultswill
willbe
bediscussed
discussedin infuture
futurestudies.
studies.

Figure
Figure7.7.(a)
(a)Transmittance
Transmittance (at
(at 550
550 nm)
nm) and (b) haze
and (b) haze according
accordingto toapplied
appliedvoltage
voltageininPDLC
PDLCdevices
devicesof
ofITO,
ITO, 4LG with WIIC process, and 4LG without WIIC process, respectively. (c) Rise
4LG with WIIC process, and 4LG without WIIC process, respectively. (c) Rise and decay and decay
time
time for PDLC devices of three different TCEs investigated in this
for PDLC devices of three different TCEs investigated in this work. work.

4.4.Conclusions
Conclusions
We
Weinvestigated
investigatedthetheeffect
effectofofadhesion
adhesionon onthe
theperformance
performanceofof4LG 4LGas asaaTCE
TCEininPDLC
PDLC
devices.The
devices. The successful
successful implementation
implementation of the
of the WIIC WIIC process
process effectively
effectively increased
increased the
the ad-
adhesion
hesion between
between 4LG 4LG andsubstrate.
and the the substrate. Theresistance
The sheet sheet resistance of 4LG
of 4LG with thewith
WIICthe WIIC
process
process
used used
in this in this
work was work
measuredwas tomeasured
be 58 ± 2 to be 58
Ω/sq, ± 2 Ω/sq,
exhibiting exhibitinguniform
a remarkably a remarkably
sheet
uniform sheet
resistance resistance
across across
the entire area.theToentire
furtherarea. To further
confirm confirmimpact
the positive the positive
of theimpact
WIIC of the
pro-
WIICwe
cess, process, we fabricated
fabricated a PDLC
a PDLC device device
with the with
4LG the 4LG electrode
electrode incorporating
incorporating the WIIC thetreat-
WIIC
treatment.
ment. The device
The device created
created with with the WIIC
the WIIC process
process exhibited
exhibited significant
significant improvements
improvements in
in various performance metrics. Notably, it demonstrated a considerable
various performance metrics. Notably, it demonstrated a considerable 17 V reduction 17 V reduction
in
in turn-on
turn-on voltage,
voltage, a remarkable
a remarkable 20%20% enhancement
enhancement in maximum
in maximum transmittance,
transmittance, andap-
and an an
appreciable
preciable 12%12% reduction
reduction in hazein compared
haze compared to the created
to the device device without
created without
the WIICthe WIIC
process.
process.
Our Ourunderscore
findings findings underscore
the potentialtheof potential
graphene of with
graphene with adhesion
increased increasedand adhesion and
ultra-low
ultra-low resistance as a TCE in flexible devices, owing to its enhanced
resistance as a TCE in flexible devices, owing to its enhanced stability and superior per- stability and
superior performance
formance characteristics.
characteristics. The successful The successfulofintegration
integration of the WIIC
the WIIC process opens process opens
up exciting
opportunities for leveraging 4LG as a highly reliable and efficient TCE in a wide rangeinofa
up exciting opportunities for leveraging 4LG as a highly reliable and efficient TCE
wide range
flexible of flexible
electronic electronic and applications.
and optoelectronic optoelectronic applications.

Author Contributions: Conceptualization, E.M.K. and T.H.S.; investigation, E.M.K., S.J.K. and
M.M.K.; data curation, E.M.K., G.B.C., J.K., Y.W.K. and T.H.S.; experiments, E.M.K. and S.J.K.; for-
mal analysis, E.M.K. and S.J.K.; writing—original draft, E.M.K.; visualization, G.B.C., validation, J.L.
(Jongho Lee) and J.H.K.; writing, J.L. (Jaegeun Lee) and T.H.S.; review, J.L. (Jaegeun Lee) and T.H.S.;
editing, J.L. (Jaegeun Lee) and T.H.S.; methodology, J.L. (Jongho Lee) and J.H.K.; supervision, J.H.K.
and T.H.S. All authors have read and agreed to the published version of the manuscript.
Nanomaterials 2023, 13, 2309 9 of 10

Author Contributions: Conceptualization, E.M.K. and T.H.S.; investigation, E.M.K., S.J.K. and
M.M.K.; data curation, E.M.K., G.B.C., J.K., Y.W.K. and T.H.S.; experiments, E.M.K. and S.J.K.; formal
analysis, E.M.K. and S.J.K.; writing—original draft, E.M.K.; visualization, G.B.C., validation, J.L.
(Jongho Lee) and J.H.K.; writing, J.L. (Jaegeun Lee) and T.H.S.; review, J.L. (Jaegeun Lee) and T.H.S.;
editing, J.L. (Jaegeun Lee) and T.H.S.; methodology, J.L. (Jongho Lee) and J.H.K.; supervision, J.H.K.
and T.H.S. All authors have read and agreed to the published version of the manuscript.
Funding: This study was conducted with the support of the Korea Institute of Industrial Technology
under the Development of Core Technologies for Smart Mobility (KITECH JA-23-0011) project.
This work was supported by the Basic Science Research Program through the National Research
Foundation of Korea (NRF), funded by the Ministry of Education, Science, and Technology (NRF-
2022R1F1A1074422), and by the Korea Institute of Marine Science and Technology Promotion (KIMST),
funded by the Ministry of Oceans and Fisheries, Korea (20200599).
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Conflicts of Interest: The authors declare no conflict of interest.

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