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In situ planar photoalignment of liquid crystals:

two-step interfacial modifications through
Cite this: J. Mater. Chem. C, 2020,
8, 1722 light–matter interactions actuated by linearly
polarized UV-light†
Aboozar Nasrollahi,a Vineet Kumar,a Myong-Hoon Lee b
and Shin-Woong Kang *a

Photopolymerizable, photoisomerizable, photodimerizable and photoluminescent dichroic chromophores

Received 13th October 2019,
Accepted 11th December 2019
DOI: 10.1039/c9tc05607f
rsc.li/materials-c
are deliberately designed and used for comprehending the sequential realization of the polyimide-free
in situ photoalignment of liquid crystals (LCs). Upon a linearly polarized UV-light (LPUV) treatment, the
multifunctional photoaligning additive, homogeneously dissolved in a LC mixture, is interfacially
polymerized at the inner surfaces as a thin photo-responsive polymer layer. Subsequently, the molecular
orientational anisotropy is induced by the dichroic photochromic responses, resulting in a uniaxial planar
LC alignment. The reversible trans/cis-isomerization plays a crucial role for the LC alignment, rather than
irreversible [2+2] dimerization. Therefore, the LC aligning effect is strongly influenced by the wavelengths
of LPUV. Under the longer wavelength UV-irradiation (l 4 350 nm), the reversible isomerization is more
preferable to the irreversible dimerization, resulting in a rewritable LC alignment with much better
alignment quality. Such sequential processes are evidenced by monitoring spatial and orientational
distributions of the self-labeled dichroic fluorescent monomers during the process. The conclusions are
further corroborated by the wavelength dependencies of the photochromic responses, LC aligning effect,
and rewritable LC alignment.

1. Introduction improvements in its high-energy process, additional cleaning,

A liquid crystal (LC) is a fascinating phase of matter, adopted
for various biological and optoelectronic device applications.1,2
It exhibits unique and distinct phase behaviors from the
conventional phases of matter. However, the first step for
utilizing such beneficial materials for relevant applications is
to control a molecular orientational order.3,4 Conventionally, a
thin polymer coating, combined with mechanical rubbing, was
used for a uniaxial LC alignment.5 Although it was predominantly
employed for laboratory and industrial applications, the various
alignment techniques have been developed because of their
intrinsic drawbacks.5
The most recent success, which reached mass production,
was a selective photo-degradation of polymeric materials. Thin
polymer films were pretreated by high-energy linearly polarized
ultraviolet light (LPUV) prior to a cell assembly. Although it is
employed for commercial production, the process requires
a
Department of BIN Convergence Technology, Jeonbuk National University,
Jeonju 54896, Korea. E-mail: swkang@jbnu.ac.kr
b
The Graduate School of Flexible and Printable Electronics,
Jeonbuk National University, Jeonju 54896, Korea
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c9tc05607f
and long term reliability attributable to the dissolution of
photodegraded segments.6,7 Other representative photoalignment
techniques, extensively studied, utilized photoresponsive chromo-
phores to remotely induce a surface anisotropy.8–13 The azo-
benzene and cinnamoyl chromophores, covalently introduced
to a polymer backbone, were exposed to linearly polarized light
and resulted in a molecular orientational anisotropy in the
alignment layer. Such anisotropy can be induced by either
photochromic isomerization and consequent reorientations of
the dichroic chromophores or a dichroic photochemical reaction
and subsequent segmental reorientation.14–17 Both mechanisms
are generally accepted depending on the material properties. In
the same way, polymer-based coumarin and chalcone chromo-
phores were also used for the pretreated photoalignments.18,19 As a
result of molecular orientational anisotropy, a LC director aligned
uniaxially along a specific direction at surfaces.
Concerning the fabrication process, the aforementioned
approaches require pretreatments of alignment layers, such as
coating, soft and hard baking, and rubbing or LPUV exposure,
followed by an additional cleaning and drying step. Recently,
however, in situ photoalignment, without using pretreated alignment
layers, has been reported (so called PI-less in situ photoalignment).
In this case, photoresponsive additives were doped into LCs and the

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one-bottled mixture was loaded into an electrooptical cell with no
pretreated alignment layer. The remotely controlled in situ photo-
alignment was performed by irradiating light.20–22 This can reduce
the many fabrication steps required for a conventional LC align-
ment, and therefore it is very beneficial for mass production. This
approach is not only cost-effective but it also complies well with a
current trend in display markets, demanding large-sized and
ultra-high resolution displays. In addition to uniformity in a
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large area, the small-sized pixels cause uneven inner surfaces of
a LC cell. In particular, such uneven surfaces make the rubbing
method unsuitable for mass production.
The PI-less in situ photoalignment is not an optional
approach anymore. It became a crucial required process to comply
with a current trend in the display industry. In particular, the
cinnamoyl acrylate-based chromophores showed great potential
and were, therefore, extensively investigated for industrial
applications.23–25 However, the research studies were mainly
focused on developing effective materials. The photoaligning
process was understood on the analogy of previous photo-
alignments, based on the pretreated cinnamate polymers.26–28
Although it is a very promising approach, the precise stepwise
mechanisms are not clearly comprehended yet.
In this report, we investigated the effect of multifunctional
acrylic cinnamate monomers for the PI-less in situ planar
photoalignment of liquid crystals. Using a purposely designed
model compound, the sequential processes of the PI-less in situ
photoalignment were comprehended by monitoring the spatial
and orientational distributions of the self-labeled fluorescent
cinnamic acrylate. The primary role of each functionality was
systematically examined by employing UV-vis spectrophotometry,
polarized optical microscopy (POM), confocal fluorescence micro-
scopy (CFM), polarized fluorescence microscopy (PFM), polarized
fluorescence spectroscopy (PFS), and scanning electron micro-
scopy (SEM). On the basis of the experimental results, we con-
cluded that the photopolymerization of acrylic groups produced
interfacial polymer layers first and consecutively the surface
anisotropy was induced by the dichroic cinnamoyl chromophore
during a LPUV irradiation. The wavelength dependence of UV-vis
absorption and the corresponding photoaligning effects evidenced
that the molecular reorientation via trans/cis-isomerization played a
crucial role in LC alignment, rather than [2+2] photodimerization.
Our conclusions can provide useful information on designing
efficient chromophores and appropriate processing conditions
for the PI-less in situ photoalignment.
2. Experimental section
2.1 Materials
The cinnamate-based acrylic monomers C1, C2, and C3 were
used for the PI-less in situ planar alignment. 1H NMR spectra
can be found in the ESI† (Fig. S1). The photo-responsive acrylic
monomer was homogeneously dissolved in the host nematic
MLC 6686 system (Merck Performance Materials, Korea) by
gentle heating. The concentration was varied in a range of
0.2–1.0 wt%. The nematic to isotropic transition temperature
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(TNI) was 80 1C. The host LC showed a positive dielectric
anisotropy (De = 10) and optical birefringence (Dn = 0.095). No
photoinitiator was used for polymerization.
2.2 UV-vis spectroscopy
Photochemical responses were examined by UV-vis spectroscopy
in a dilute toluene solution (B10 5 M). The UV-vis absorption
spectra of the solutions, contained in a quartz cuvette, were
recorded by a UV-vis spectrophotometer (JASCO, ARSN-733). By
employing various filters, proper wavelengths of UV-light were
selected to investigate trans/cis-isomerization and [2+2] cyclo-
addition reaction of the cinnamoyl chromophore.
2.3 Cell fabrication
Electro-optical cells were fabricated by using either unpatterned
indium-tin-oxide coated glass (ITO glass), or patterned ITO glass
with in-plane-switching (IPS) electrodes. The UV-polarizer
was aligned 151 off from the stripe-patterned electrode. The
dimensions of the IPS electrode pattern were 4 mm  6 mm. For a
deep UV-irradiation, flat quartz plates were used as substrates.
The bare substrates with no pretreated alignment layer were
assembled into an opposing sandwiched cell. The gaps were
maintained by ball spacers (B6.4 mm) or tape spacers (B10.0 mm).
For the CFM study, a 100 mm thick glass coverslip was used as a top
substrate and the cell gap was B60 mm. The LC mixture was loaded
at isotropic temperature by a capillary action.
2.4 In situ photoalignment
The mixture loaded LC cells were treated by LPUV with various
wavelengths. Metal halide (UVSMT, UCH 1000) and Mercury-
Xenon (Ushio SP-9) lamps were employed as light sources. The
measured intensity varied in the range of 1.8–10.0 mW cm 2.
The treatments were completed at isotropic temperature of the
LC mixture (85 1C). The quality of LC alignment was examined
via POM (Nikon Eclipse LV 100 POL), equipped with a Nikon
DS-Ri1 CCD camera.
2.5 Electro-optical characterization
Electro-optical switching characteristics were examined using
the IPS cells. The switching textures were observed by employing
POM. The voltage vs. transmittance (V–T) curve and gray-level
switching times were measured by using an LCMS-200 (Sesim
Photonics Technology, Korea).
2.6 Fluorescence microscopy and spectroscopy
Spectroscopic photoluminescence of the C3 compound was
measured by a spectrofluorophotometer (JASCO FP-6500, Japan)
in 0.01 mM toluene solution. Confocal fluorescence microscopy
(CFM) was performed by employing a confocal laser scanning
microscope (LSM 510 Meta, Carl Zeiss, Inc., Germany),
equipped with a VIS laser module. The z-scan resolution was
0.98 mm. No additional filter was used during the LPUV treat-
ment. Polarized fluorescence properties of the cell after the
LPUV treatment were characterized by employing polarized
fluorescence microscopy (PFM) and polarized fluorescence
spectroscopy (PFS). A Nikon Eclipse TE2000-U, equipped with
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a Nikon LWD 0.52 CCD camera, and a photoluminescence
spectrometer (RMS-1000, Olis, Inc.) were used for PFM and PFS,
respectively. For both PFM and PFS, a single polarizer was placed
for either excitation or emission light. For all fluorescence studies,
no additional fluorescent marker was used in the mixture. Instead,
the methoxy biphenyl group of the C3 compound was used to
detect the spatial distribution and molecular orientational
anisotropy of the photoresponsive additive molecules. Various
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3. Results and discussion
3.1 Material design for a sequential mechanism study
Three cinnamoyl compounds, shown in Fig. 1a, were used for
the in situ planar photoalignment of nematic LCs. The compounds
consist of three different functional groups: a photopolymerizable
acryl group (marked by red), a photoresponsive cinnamoyl group
with different substituents (marked by blue), and a hexyleneoxy

filters were placed during LPUV treatments.
2.7 Morphology and thickness measurements
The in situ created alignment layers were examined by a field
emission scanning electron microscope (Hitachi S-4800, Japan).
A bare alignment layer was obtained by dipping the dismantled
substrates in hexane and subsequent drying. Because the linear
polymer chain, formed from the C3 compound, dissolved in
common organic solvents, it was difficult to prepare a bare
polymer surface. To selectively dissolve out LC components,
therefore, we added a small amount of cross-linking agent
(TMPTA, trimethylolpropane triacrylate) to the LC mixture
(B1.0 wt% to the C3 monomer). A bare polymer surface of
the cross-linked polymer, formed by [2+2] photodimerization,
was obtained without using the TMPTA. The thickness of thin
polymer layers, acting as alignment layers, was measured by
using a high accuracy noncontact surface profiler, NanoView-
E1000 (NanoSystem, Korea).
cyclohexyl group (black). In general, a cinnamate group with a
phenyl ester substituent undergoes three different photochemical
reactions under UV light irradiation: A reversible trans/cis-
isomerization, irreversible [2+2] cycloaddition and photo-Fries
rearrangement.29–35 For our chromophore design, the cyclohexyl
group was added not only for extending a rigid-core but also for
excluding the photo-Fries rearrangement, requiring an aromatic
ester group. The flexible hexylene group was adopted to decouple
photoresponsiveness of the cinnamoyl chromophore from the
polymer backbone. The sidechain chromophores with a hexylene
spacer group are supposed to be much decoupled from the linear
polymer backbone, compared to the cross-linked polymers with no
spacer group. Therefore, it is beneficial for the current study on the
effect of different photo-chemical responses to LC alignment.
As reported earlier,26–28,36,37 the photopolymerizable cinnamate
monomers induced a uniform planar alignment by an in situ
irradiation of LPUV. All three compounds exhibited essentially
the same photoaligning behaviour, revealing photopolymeriza-
tion, trans/cis-isomerization, and [2+2] cycloaddition reactions,

Fig. 1 Chemical structures, absorptions, and photoluminescence properties of the cinnamoyl chromophores used for the study. (a) Chemical structures
of the C1, C2, and C3 compounds and a 3D space filling model of C3, (b) UV-vis absorption spectra of the C3 solution in toluene, depending on the UV
irradiation energy; 0 (black), 0.6 (red), 3.0 (blue), and 6.0 J cm 2 (pink). The inset magnifies a wavelength region above the isosbestic point (marked by
blue arrows), (c)/(d) photoluminescence of the C3 compound dissolved in a host LC and toluene, respectively. The line colors match the excitation
wavelengths to the corresponding emission spectra.

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as schematically shown in Fig. S2 (ESI†). No Photo-Fries
rearrangement was expected for the C1, C2, and C3 compounds.
As shown in Fig. 1b and Fig. S3 (ESI†), the major difference was
the peak position of UV-vis absorption, originating from their
molecular electronic structures. In addition to the red-shift in
absorptions, the C3 compound with an extended p-electron
conjugation exhibited photoluminescence at the visible wave-
lengths. It was very useful to investigate the spatial distribution
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and molecular orientational anisotropy of the chromophore.
Therefore, we mainly focused on the C3 compound to elucidate
the underlying mechanisms in the in situ photoaligning effect of
cinnamoyl acrylate chromophores.
Fig. 1b shows the photochromic absorbance of the C3
compound. The UV-vis spectra, measured in toluene solution
(0.01 mM) with a quartz window, exhibited sensitive responses
to the radiation from a Hg–Xe lamp with no filter. Upon
unfiltered UV irradiation, the absorption peak at 325 nm for
a fresh solution (black curve) decreased and a new absorption,
peaked at 290 nm, rapidly increased. In addition, a weak broad
peak appeared near B390 nm. This absorption was increased
with an irradiation dose and saturated at B6.0 J cm 2, indicated
by the arrow in the inset. Such spectral changes were interpreted in
the literature by using the reversible trans/cis-isomerization and
irreversible [2+2] cycloaddition (i.e., photodimerization).35,38–40
Fig. 2 Polarized optical images and electro-optical characteristics of the IPS cell, fabricated using the C3 additive dissolved in a LC host.
(a-i) Macroscopic and (a-ii) microscopic cell images before LPUV treatment; uniform (b-i)/(b-ii) light and (c-i)/(c-ii) dark states at 0 V after LPUV
treatment; (d-i)/(d-ii) turn-on state at 6.0 Vpp; (e) the V–T curve; (f) the gray-level rise (black) and decay (blue) times. The single arrow denotes a
polarization direction of the LPUV. The ellipses represent LC orientation.
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The isosbestic point at B368 nm confirms a photostationary
state of the trans- and cis-isomers.41 Because of the extended
p-conjugation, C3 exhibited photoluminescence in the visible
range.42 Such a self-labeled fluorescent monomer was designed
deliberately to monitor the sequential processes of LC alignment.
Fig. 1c and d display emission spectra of the C3 compound as a
function of excitation wavelength, either in the LC host or
toluene, showing intense emission peaks at 400 and 396 nm,
respectively. The emission maxima were observed at 340 and
327 nm excitation, respectively.
3.2 PI-less in situ photoalignment
The in-plane-switching (IPS) cell was fabricated using glass
substrates with no pretreated alignment layer. The LC mixture,
doped by 0.5 wt% C1, C2, or C3 monomer, was loaded into the
sandwiched cell with an B6.4 mm gap. Fig. 2 represents the
polarized optical and electro-optical properties of the IPS cell,
obtained using the C3 monomer. After LC loading, the cell
showed no uniform LC alignment. As shown in Fig. 2(a-i) and
2(a-ii), a completely random planar state was observed through-
out the cell. A uniformly aligned planar state was achieved by
the in situ LPUV treatment (1.2 J cm 2) at the isotropic
temperature (85 1C). Fig. 2(b-i) and (c-i) correspond to the
macroscopic cell images: (b-i)/(c-i) with no applied electric field
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and with different orientations to the crossed polarizers. The
corresponding POM images (b-ii/c-ii) confirm a high-quality LC
alignment at a microscopic level. The LC director was aligned
perpendicular to the polarization direction of LPUV and 151 off
from the striped electrodes. The polarization direction and
director orientation are denoted by the double-ended arrow and
ellipse, respectively, in the figures. As shown in Fig. 2c and d, the
dark extinction state was switched to the bright state by applying
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UV light illumination, each process may not be equally susceptible
to different wavelengths. Indeed, the UV-vis absorption spectra
indicated such wavelength dependent selectivity of the processes.
It seemed that a reversible trans/cis-isomerization was more
preferable to the irreversible reactions under long wave-
length UV-illumination. In contrast, the [2+2] cycloaddition
reaction occurred favorably under short wavelength ultraviolet
irradiation.39–41,43 Besides, the cis- to trans-isomerization was

6.0 Vpp ac-field at 1 kHz. The measured transmittance vs. voltage
(V–T) curve is presented in Fig. 2e. It represents the typical V–T
characteristics of an IPS LC cell. The on- and off-switching times
were 34.2 ms and 38.1 ms, respectively. The gray-level response
times are also shown in Fig. 2(f). It shows comparable electro-
optical responses to a conventional IPS cell. A similar level of
in situ photoalignment was achieved by doping either the C1
or C2 monomer into the same LC host. The corresponding
polarized optical images, at both macroscopic and microscopic
levels, can be found in the ESI† (Fig. S4 and S5).
3.3 Photochemical responses of the cinnamate-based acrylic
monomer
Although trans/cis-isomerization, [2+2] cycloaddition, and photo-
polymerization reactions simultaneously occur under unfiltered
encouraged by long wavelength UV irradiation (l 4 B370 nm),
whereas the trans- to cis-isomerization was preferred under a
short wavelength UV-illumination (l o B370 nm). It was
confirmed that no relaxation from the cis- to trans-isomer
occurred through a thermal process.
Fig. 3a presents the spectral changes after a thermal treat-
ment and a long wavelength UV-irradiation (l 4 350 nm). The
absorption curve (dotted blue), measured after 1 h of heating at
90 1C, almost completely overlapped the red curve, obtained by
10 min UV irradiation from the pristine black curve. No thermal
relaxation to the trans-form was observed, which is crucially
different from the azobenzene chromophores.44,45 However, a
long wavelength UV irradiation significantly repressed the
absorption near B390 nm, as shown in Fig. 3a (indicated by the
blue arrow in the inset). The green and pink curves correspond to

Fig. 3 UV-vis absorption properties of the C3 solution in toluene after UV exposure with different wavelengths. (a) Black (fresh solution), red (6.0 J cm 2 with no
filter), blue dashed (1 h heating at 90 1C), and green/pink curves (3.0/6.0 J cm 2 with the 350 nm long-pass filter). (b) With the 308 nm bandpass filter; black (fresh
solution), red (3.0 J cm 2), blue (6.0 J cm 2), and green/pink (3.0/6.0 J cm 2) with the 375–425 nm filter. (c) With the ITO-glass filter; black (fresh solution), red
(0.1 J cm 2), blue (1.0 J cm 2), and green (3.0 J cm 2) and pink (6.0 J cm 2). (d) With the 350 nm long-pass filter; black (fresh solution), red (0.5 J cm 2), blue
(1.5 J cm 2), green (3.0 J cm 2) and pink (6.0 J cm 2). The transmittance of the adopted filters is shown in yellow. The insets magnify the absorptions of longer
wavelengths above the isosbestic point. The increase and decrease in absorption were designated by the black and blue arrows, respectively, in the insets.

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the absorption after 3.0 J cm 2 UV-vis (l = 350–700 nm) and
additional 6.0 J cm 2 UV (l = 375–425 nm) irradiation, respectively.
The cis-form population was decreased by irradiating with long
wavelength light (l 4 350 nm). In all cases, however, the
suppression of a strong peak at 290 nm was insignificant.
These observations may indicate that both the irreversible
[2+2] cycloaddition and reversible isomerization reactions
occur simultaneously under unfiltered UV light illumination
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with a quartz window. It seems that some portions are in a
photostationary state of trans/cis-isomers and some portions
contain irreversible cyclobutane adducts. The blue shifted
intense peak at 290 nm may also be attributed to the aggregate
formations of the cis-form isomer, as frequently observed in
azobenzene compounds, and/or photopolymerized acrylate
chromophores.20,46–48 Because both processes are irreversible,
the corresponding absorption change also may not be reversible,
as observed.
Fig. 3b shows absorption spectra with the 308 nm filter
(FWHM = B25 nm). The orange curve represents the transmittance
of the 308 nm filter. With the increased irradiation energy from
0 (black) to 3.0 J cm 2 (red) and 6.0 J cm 2 (blue), both the
absorptions at B290 nm and B390 nm were enhanced, whereas
the 325 nm peak was decreased (denoted by the arrows). In
these cases, the increase in B390 nm absorption was much
more prominent, compared to Fig. 3a, c, and d. The peak at
290 nm was relatively weaker than that in Fig. 1b and 3a. The
relatively much enhanced absorption at B390 nm was attributed to
the absence of a long wavelength UV light illumination (l 4
B370 nm), inducing cis- to trans-isomerization. It was further
confirmed that cis- to trans-relaxation was promoted by irradiating
long wavelength UV light (l = 375–425 nm). As shown in the inset of
Fig. 3b, the absorption near 390 nm was significantly repressed by
illuminating 375–425 nm radiation (indicated by the blue arrows).
The green and pink curves correspond to 3.0 and 6.0 J cm 2
illumination energy. It was clear that the trans- to cis- and cis- to
trans-isomerization required different wavelengths, falling in each
absorption range. Therefore, both ranges of UV-wavelengths are
necessary for repeated cycles of reversible isomerization, which
could be crucial for the LPUV-induced LC alignment.
Fig. 3c presents the UV-vis absorption characteristics of the
0.01 mM C3 solution in toluene using the indium-tin-oxide
coated glass (ITO glass) filter. The transmittance of the filter is
shown in Fig. 3c (orange curve). The transmittance rapidly
drops near 350 nm and completely cuts off the wavelengths
below B300 nm. As observed in Fig. 3c, the absorption properties
of the C3 solution were changed in a similar manner to the
previous illuminations. In these cases, however, the absorption
near B390 nm was much weaker, compared to Fig. 3b. This is
probably ascribed to the existence of a long wavelength UV,
promoting a cis- to trans-relaxation of the cinnamic vinyl group.
With the isosbestic point at B368 nm (the inset in Fig. 3c),
it was obvious that trans/cis-isomers were in an equilibrium
state through repeated cycles of isomerization. Under LPUV
illumination, this can play an important role in the reorientation
of cinnamoyl chromophores, which can induce LC alignment at
surfaces.
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Fig. 3d corresponds to the absorption spectra for the C3
solution (0.01 mM) with a 350 nm long-pass filter. The trans-
mittance of the filter is shown in Fig. 3d (orange line). In these
cases also, the spectra exhibited weak absorption near B390 nm,
as shown in Fig. 3c. However, it was evident that trans/cis-isomers
were in a photostationary state upon repeating the photo-
chemical isomerization. This could be attributed to the irradiated
UV wavelengths. The shorter wavelengths were further cut off,
compared to the ITO glass filter, whereas the full range of long
wavelengths, promoting cis- to trans-relaxation, was largely included
in the photo-irradiation. In addition, although the general spectral
characteristics were more or less the same as those in Fig. 3c, the
absorption near B290 nm was significantly decreased, as shown
in Fig. 3d. This could also be understood by the irradiated
UV-wavelengths. It seemed that the formation of [2+2] cyclo-
adducts and photopolymerized aggregates was significantly
suppressed by irradiation with the long-pass filter (l 4 350 nm).
As noticed in Fig. 3a–d, the peak intensity near 290 nm is
proportional to the amount of short wavelength radiation,
controlled by the filters. It seemed clear that, under a short-
wavelength UV irradiation, the irreversible [2+2] photodimerization
was favored over the reversible isomerization. Therefore, it was
concluded that the reversible trans/cis-isomerization reaction was
preferable to the irreversible [2+2] photodimerization reaction under
the long wavelength UV-irradiation. In contrast, the [2+2] cyclo-
addition reaction could be more effectively induced by relatively
shorter wavelength UV-light.43
3.4 Wavelength dependence of the in situ photoalignment
On the basis of the wavelength dependent photochemical
responses, the PI-less in situ photoalignment of a nematic LC
was performed by using properly selected wavelengths of LPUV
light. The LC cells were fabricated by employing quartz plates
as a substrate. The LPUV treatment (3.6 J cm 2) was completed
by independently applying no filter, a 308 nm bandpass filter,
an ITO-glass filter, and a 350 nm long-pass filter. As shown in
Fig. 4a, the quartz cell, treated without using a filter, resulted in
no uniform LC alignment. Before and after LPUV treatment, the
cell exhibited a completely random planar alignment although
the surfaces were modified, as evidenced in Fig. 4(a-i) and (a-ii).
The random planar texture shown in Fig. 4(a-iii) was observed
after an additional LPUV treatment (3.6 J cm 2) with the ITO-
glass filter to the same quartz cell, corresponding to Fig. 4(a-ii).
The corresponding polarized optical images of the entire cell
can be found in Fig. S6 (ESI†). It was evident that a uniform
alignment was not obtained if the LC cell was treated by full
range UV light with a quartz window. The change was irreversible.
This indicated that an irreversible reaction was dominant in the
full UV range and resulted in a random planar alignment.
If the 308 nm bandpass filter was employed, the LPUV
treatment (3.6 J cm 2) resulted in a distinct LC alignment from
the bare quartz cell, as shown in Fig. 4b. Fig. 4(b-i), (b-ii) and (b-iii)
correspond to the POM textures before and after the LPUV
treatment with different orientations. Even though it exhibited
numerous line defects, it was obvious that the filtered UV light
induced a planar LC alignment. The LC alignment was more
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Fig. 4 POM images representing LC alignment, achieved by employing the quartz LC cells and the LPUV treatments with different wavelengths. (a) With
no use of a filter; (a-i) before treatment, (a-ii) after 3.6 J cm 2 LPUV, and (a-iii) additional 3.6 J cm 2 LPUV with the ITO-glass filter. (b) With the 308 nm
bandpass filter; (b-i) before and (b-ii)/(b-iii) after 3.6 J cm 2 LPUV. (c) With the ITO-glass filter; (c-i) before and (c-ii)/(c-iii) after 3.6 J cm 2 LPUV. (d) With
the 350 nm long-pass filter; (d-i) before and (d-ii)/(d-iii) after 3.6 J cm 2 LPUV with different orientations of crossed polarizers. The single and crossed
arrows denote the polarization direction of the LPUV, and polarizers used for inspection, respectively. The scale bars correspond to 200 mm.

dramatic when the ITO-glass filter was placed in front of the LC
cell with quartz substrates. As presented in Fig. 4c, a uniform LC
alignment was accomplished upon filtered LPUV irradiation.
The random planar state shown in Fig. 4(c-i) was converted to
the uniaxially aligned planar state shown in Fig. 4(c-ii) and
(c-iii). The macroscopic cell images are presented in Fig. S7
(ESI†) (308 nm filter) and S8 (ITO-glass filter) in the ESI.† It was
confirmed that the LC director was aligned perpendicular to the
transmission axis of a linear polarizer. The LC alignment,
presented in Fig. 2, was achieved by using essentially the same
wavelength range of UV-light (i.e., glass filter as a substrate). The
LC alignment was further improved by employing the 350 nm
long-pass filter. Fig. 4d shows the POM images, observed before
and after the LPUV treatment with the wavelengths longer than
350 nm (l 4 350 nm). Although both Fig. 4c and d represent a
high-quality LC alignment, the alignment quality was even
better for the irradiation with the long-pass filter. The entire
cell images are shown in Fig. S9 (ESI†).
The improvement of LC alignment can be understood by the
effect of UV wavelength, and the associated photochromic
responses of the C3 chromophore. By cutting-off short wave-
lengths of UV, especially below B300 nm, the LC alignment was
considerably improved, as evidenced in Fig. 4a–c. In addition,
the presence of long wavelength UV light, including wavelengths
B390 nm for the cis- to trans-isomerization, turned out to be
crucial for an efficient LC alignment. As observed in Fig. 4b, the
quality of alignment was poor with numerous defects if the cell
was LPUV-treated in the absence of B390 nm UV light. This can
be explained by the photochromic response, requiring B390 nm
wavelengths. For the C3 compound, this process was the cis- to
trans-isomerization. This was discussed above, in terms of UV-vis
absorption spectra, as shown in Fig. 3.
The best result was obtained by further cutting-off short
wavelengths (l o B350 nm) and including long wavelengths
(B390 nm) of UV-light. In this case, the isomerization in a
photostationary state seemed to be a major photochromic
process, whereas the [2+2] photodimerization could be minimized.
It seemed obvious that the irreversible dimerization process
resulted in a negative influence and trans/cis-isomerization had
a positive effect on the uniform photoalignment. Therefore, we
conclude that the reversible isomerization and thus the related
long wavelengths of UV light play a crucial role in the LC
alignment. On the other hand, short wavelength light (especially,
l o B300 nm) and associated irreversible [2+2] cyclodimerization
arouse a negative influence. This conclusion was further corro-
borated by the reversibility of LC alignment, demonstrated by

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Paper Journal of Materials Chemistry C

the rewritable in situ photoalignment. This will be discussed in
the later sections, together with a wavelength effect on the
rewritable LC alignment.
3.5 Polymerization and molecular reorientation actuated by
LPUV
In the earlier sections, we investigated the wavelength dependent
photochromic reactions and their effect on the in situ photo-
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mixture and uniformly distributed throughout the LC cell. Upon
LPUV treatment (3.6 J cm 2), however, the fluorophore distribution
was dramatically changed. As observed in Fig. 5(b-i) and (b-ii), the
fluorophores were completely localized at the inner surfaces of the
cell although they revealed a uniform blue color on the substrate
plane, similarly to Fig. 5(a-i). The polymer aggregates, formed by the
photopolymerized C3 monomer, moved and adsorbed equally at
both surfaces. It was conclusive that homogeneously dissolved

alignment. However, it is uncertain when the photochromic
additives move to the surface and how they induce LC alignment
at surfaces. To understand such processes, we performed CFM,
PFM, and PFS. No additional fluorescence marker was used
because the C3 chromophore exhibited photoluminescence in
the visible range. The CFM, PFM, and PFS results provided
important information on the spatial distribution and molecular
orientational anisotropy of the chromophore.
Fig. 5 presents the CFM, PFM, and PFS results, obtained
before and after a LPUV-treatment. Fig. 5(a-i) and (a-ii) represent
a spatial distribution of the C3 monomer prior to the LPUV
irradiation. Both top and side views clearly demonstrate a
uniform distribution of the fluorophores. It was obvious that
the aligning agent C3 was homogeneously dissolved in the LC
monomers moved to the surfaces during polymerization, rather
than prior to polymerization.49 As a result, the inner surfaces were
modified by the interfacial polymerization and thus the polymeric
alignment layers were formed at both surfaces.
We supposed that the molecular orientational anisotropy of
the modified surface, induced by LPUV, could be responsible
for surface-mediated LC alignment. The orientational order of
chromophores was inspected by using PFM, as shown in Fig. 5c
and d. Before the UV light irradiation, the fluorescence image
shows a featureless blue emission excited at 340 nm (Fig. 5(c-i)),
observed with no polarizer. By placing a single polarizer, the
PFM images disclosed randomly textured fluorescence, as shown
in Fig. 5(c-ii) and (c-iii), indicating random orientations of the
chromophore both at surfaces and in the LC host. However, the

Fig. 5 Spatial distributions and polarized photoluminescence of the uniaxially aligned C3 chromophore. (a)/(b) CFM images of the C3 LC cell; (a-i)/(b-i)
top views and (a-ii)/(b-ii) cross-sectional views of the cell, observed before and after LPUV treatment, respectively. (c)/(d) FM images of the C3 LC cell;
(c-i)/(d-i) with no polarizer before and after LPUV treatment, the photoluminescence recorded with a single polarizer (c-ii)/(c-iii) before LPUV irradiation,
and the polarized photoluminescence, measured after the treatment, (d-ii) parallel and (d-iii) perpendicular to the polarization direction of the LPUV
(marked by the orange arrow). The direction of a polarizer, used for inspection, was specified by the white arrow. (e) The photoluminescence spectra
measured by PFS; (black) no polarizer, the analyzer perpendicular (blue), and parallel (red) to the LPUV direction.

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uniaxial orientation of fluorophores was evident after the LPUV
treatment (3.6 J cm 2). Although the unpolarized fluorescence
image (Fig. 5(d-i)) showed a similar featureless emission, as
shown in Fig. 5(c-i), the PFM images exhibited obvious orientational
anisotropy. Fig. 5(d-ii) and (d-iii) show that the fluorescent C3
molecules were aligned perpendicular to the polarization direction
of the LPUV (specified by the orange arrow). A minimum and
maximum fluorescence was observed when the inspecting polarizer
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cycles of E/Z-isomerization of the dichroic chromophore, in a
photostationary state, actuate a uniaxial molecular reorientation
perpendicular to the LPUV. Consequently, the uniform LC
alignment was mediated by the polymer surfaces with a uniaxial
molecular orientational anisotropy. This conclusion is also
supported by the rewritable LC alignment, discussed later.
3.6 Reversibility of the in situ photoalignment

(denoted by the white arrow) was placed parallel and perpendicular
to the LPUV, respectively. The PFS also verified the conclusion, as
presented in Fig. 5e. Depending on the polarizer direction, the cell
showed a sinusoidal variation of the emission intensity. When
the polarizer was perpendicular to the LPUV, the emission was
maximum (the blue curve in Fig. 5e). This also verified the
uniaxial orientation of the rigid-rod fluorophores.
From the CFM study, we demonstrated that the LC aligning
agent moved to the surfaces. The PFM and PFS investigations
elucidated the orientational anisotropy of the C3 chromophore.
Such a molecular orientational anisotropy was induced by the
interaction between the surface localized polymer and the
LPUV radiation. It was proposed that both the [2+2] dimerization
and E/Z-isomerization may induce such surface anisotropy, both
perpendicular to the LPUV.40,41,50,51 On the basis of our previous
discussion, as shown in Fig. 3 and 4, however, we conclude that
the reversible photochromic isomerization, preferable to the
irreversible photodimerization, is much more influential in a
uniform LC alignment. With the LPUV irradiation, the repeated
It was clarified via CFM that the interfacial polymer layer was
formed during photo-polymerization. However, it is still uncertain
when its orientational anisotropy accrued. The anisotropy could be
induced either while the polymer aggregates were assembling into
the interfacial polymer layer or after the layer was formed. When
and how was the molecular orientational anisotropy induced? To
answer this question, we carried out the in situ photoalignment
with the stepwise UV treatments. In addition, we investigated the
reversibility of the photoaligning process and its UV-wavelength
dependence.
Fig. 6 presents POM images of the LC cell, fabricated with
glass substrates and employed for multistep UV treatments.
Fig. 6a corresponds to the POM texture of the LC cell before a
UV irradiation. It shows a random planar state. The cell was
treated by the unpolarized UV (UPUV) radiation with no additional
filter (3.6 J cm 2). Although the surface modification was evident,
no uniform alignment was achieved, as shown in Fig. 6(b-i) and
(b-ii). It seemed that the interfacial polymer layers, formed
by polymerization, modified the surfaces and resulted in the

Fig. 6 The in situ creation of an interfacial alignment layer, a rewritable LC alignment, and defect formation, investigated using a glass LC cell. (a) The
random planar state observed before UV irradiation, (b-i)/(b-ii) the altered random planar state after unpolarized UV exposure (3.6 J cm 2), (c-i)/(c-ii)/
(c-iii) uniform uniaxial LC alignment accomplished by the LPUV treatment (3.6 J cm 2), the dark and light states observed after (d-i)/(d-ii) the second,
(e-i)/(e-ii) the third, and (f-i)/(f-ii) the fourth writings with the 251, 451, and 701 rotated polarizer (denoted by the arrow) from the first direction. The scale
bars correspond to 200 mm.

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altered random planar texture. Both images show no complete
extinction state. Like the second step, the cell was exposed to
LPUV (3.6 J cm 2) and the observed LC alignment is shown
in Fig. 6c. The macroscopic cell image shown in Fig. 6(c-i)
discloses a complete extinction in an active area. The micro-
scopic images in Fig. 6(c-ii) and (c-iii) represent a high-quality
LC alignment. These two-step UPUV and LPUV treatments pro-
vide very useful information about the question raised above. The
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results suggest that the molecular orientational anisotropy of
the C3 chromophore was produced after the formation of
interfacial layers. The interfacial polymer layer was formed first
by the photopolymerization of the C3 acrylate monomer and
subsequently its surface anisotropy was induced by a prolonged
LPUV irradiation. In this case, the situation is similar to the
conventional photoalignment, where the preformed photo-
sensitive polymer layer was treated by LPUV.
Fig. 6d–f display the POM images for dark and light states,
obtained after additional LPUV treatments in different polari-
zation directions. The polarization direction of LPUV was
rotated by 251, 451, and 701 from the first LPUV (denoted by
the arrow). The corresponding entire cell images can be found
in Fig. S10 and S11 (ESI†). The achieved LC alignment was
rewritable multiple times to the different director orientations.
It was also reversible multiple times between two different
director orientations. Such a rewritable LC alignment provides
a crucial insight into the origin of the LC aligning capability
of the C3 monomer. As discussed above, it seemed that the
LC alignment was influenced primarily by the reversible
E/Z-photoisomerization, rather than the [2+2] dimerization. If the
irreversible dimerization was the main cause of LC alignment, the
process should not be reproducible multiple times with different
director orientations.
This became certain by performing the rewriting process
with different wavelengths of UV light. As mentioned in Fig. 4(a-ii)
and (a-iii), the LC cell with quartz substrates, obtained without
applying a filter, showed no LC alignment. If it was polymerized
the first time, no rewritable LC alignment could be achieved even
with the proper cut-off filters. In addition, for the glass LC cell, the
continued LPUV treatments increased the defect density, as
observed in Fig. 6d–f. This may be attributed to the [2+2]
cycloaddition reaction, promoted by shorter wavelength UV
light. It is interesting that the thin loop defects initially formed
evolved to become thick line defects. Although the [2+2] cyclo-
addition produces the dimer in which the fluorescent group
aligned perpendicular to the LPUV, the substituents in the
cyclobutane may not be in the same plane because of the
sp3-hybridized carbons. Presumably, the fluorescent biphenyl
group was largely tilted from the surface, as shown in the
molecular model (Fig. S12, ESI†). In this case, the LC may form
reverse tilt domains whose appearance is similar to the loops
shown in Fig. 6(d-ii) and (e-ii).52,53 The shift in interference colors
(magenta to yellow) may also be attributed to the director tilt
from the substrate plane, assuming that the cell gap is constant.
As presented in Fig. S13 (ESI†), the ITO-glass cell showed the
formation of an interfacial polymer layer upon UPUV treatment
and the subsequent in situ photoalignment with LPUV irradiation.
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The ITO-glass cell revealed similar changes for the rewritable
process. It was rewritable at least eight times (accumulated
irradiation energy B28.8 J cm 2), as shown in Fig. S14 (ESI†).
However, the quartz cell with the 308 nm filter revealed much
worse defect formation and the alignment was completely
lost at the fourth treatment (total B14.4 J cm 2), as shown in
Fig. S15 (ESI†). In contrast, the glass cell treated together with
the long-pass filter (l 4 350 nm) exhibited excellent quality of
LC alignment. It maintained remarkably good characteristics with
no defects, even after 5 cycles of rewriting (total B18.0 J cm 2), as
shown in Fig. S16 and S17 (ESI†). For the quartz LC cell, however,
the LC alignment was rapidly exacerbated if the well aligned cell
was exposed to additional LPUV light without using the filter. After
the unfiltered UV treatment (B3.6 J cm 2), the LC alignment
disclosed a defected texture and was no longer reversible. Even-
tually, the LC cell lost alignment after additional irradiation with
no filter (B3.6 J cm 2). Its behaviors were similar to the cell
shown in Fig. 4(a-iii). It seemed that the unfiltered UV light
promoted the [2+2] cycloaddition reaction and thus the polymer
chains were cross-linked. The aligned chromophores could be
more vulnerable to the photodimerization. Consequently, not
enough chromophores were available for the reversible photo-
chromic isomerization, crucial for the LC alignment.
The molecular orientational anisotropy was also reproducible
during the rewriting of LC alignment. The orientational anisotropy
was probed by monitoring the polarized photoluminescence of the
C3 chromophore. The quartz LC cell, treated by LPUV light with a
350 nm long-pass filter, exhibited a polarized photoluminescence,
as shown in Fig. 5e. The same cell was treated with additional
LPUV (l 4 350 nm) multiple times in different polarization
directions. Fig. 7 presents the results obtained from the multistep
PFS investigations. Fig. 7a depicts the experimental conditions.
The colored arrows and circled numbers denote the polarization
directions and the order of the LPUV treatments. The polarizer
direction, used for inspections, was designated by degrees outside
the circle. After the 2nd LPUV8B (451), the measured emissions
corresponded to the blue (P1351) and red (P451) curves shown in
Fig. 7b, where the intensity at 400 nm was maximum and
minimum, respectively. The results indicate that the dichroic
chromophores are aligned perpendicular to the 2nd LPUV.
However, the pink and green dotted lines, measured at P01
and P901 (the same conditions as in Fig. 5e), are precisely
overlapped, indicating no anisotropy in photoluminescence in
these directions. The uniaxial orientation, induced by the 1st LPUV,
completely lost its anisotropic nature. After the 3rd treatment
(LPUV8C, 901), the maximum and minimum intensities were
observed at P01 and P901, as shown in Fig. S18 (ESI†). By rotating
the LPUV direction by 901, the chromophore orientation was
also rotated 901, as compared to the 1st LPUV treatment.
After the 4th treatment (LPUV8D, 1351) with the ITO-glass
filter, a new peak appeared at B378 nm and both peaks exhibited
maximum and minimum at P451 (blue) and P1351 (red), respectively
(Fig. 7c). Overall, the fluorophores were aligned again perpendicular
to the 4th LPUV. The polarized photoluminescence at P01
and P901, as shown in Fig. 7c (the pink and green dotted
curves), was almost overlapped except for the new peak region
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Fig. 7 Polarized fluorescence spectra, measured after a consecutive rewriting process, and the morphologies of interfacial polymer layers. (a) The
scheme for consecutive measurements. The colored numbers and arrows designate the order and the polarization direction of LPUV, respectively.
(b) The PFS data measured after the 2nd writing (the LPUV along the green arrow in (a)). The red and blue spectra correspond to the polarizer direction for
an inspection at 451 and 1351 in (a). The dotted pink and green curves represent the polarized photoluminescence with the polarization direction at 01
and 901, respectively. The polarized fluorescence after (c) the 4th and (d) the 7th writings (the LPUV along the pink and red arrows in (a), respectively). The
analyzer directions are indicated in parentheses. The FE-SEM images of a bare alignment layer, formed by the in situ LPUV (e) with the added cross-linker
and (f) cross-linked by photodimerization without using an external cross-linking agent. (e-i)/(f-i) The layer thicknesses measured by white light
interferometry.

(B378 nm, marked by the arrow). The appearance of a new
blue-shifted peak seems to be ascribed to the irreversible [2+2]
photodimerization. Upon the 5th LPUV8E (1801), no change in
the LC alignment was observed. The LC alignment was not
rewritable any more. The anisotropy in orientational order
became smaller, as shown in Fig. S18c (ESI†). In this step,
the chromophore reorientation did not occur, and thus the
maximum and minimum fluorescence was observed at P451 and
P901, the same as that obtained upon the 4th LPUV treatment.
No meaningful anisotropy was induced by the new irradiation
(P901 and P1801 in Fig. S18c, ESI†). This result corroborates the
LC alignment, which was not realigned by the 5th LPUV, as
shown in Fig. S19 (ESI†). After the 6th LPUV treatment with the
ITO-glass filter, the orientational anisotropy was further
decreased, as shown in Fig. S18d (ESI†). After the 7th LPUV
with no filter, the polarized photoluminescence at P01/P901 and
P451/P1351 was almost the same and showed a weak anisotropy
near the new peak, as observed in Fig. 7d. The PFS results
strongly indicate that the linear polymer chains are cross-
linked by the [2+2] photodimerization. As a result, the LC
aligning process becomes irreversible and the LC alignment
is exacerbated, as observed in Fig. S19c (ESI†), as also con-
firmed by the decrease in fluorescence anisotropy.
The POM and PFS results on the rewritable LC alignment
substantiate our previous postulate that the reversible E/Z-
isomerization is the primary driving force for the in situ photo-
alignment of the C3 compound. This was confirmed by the
reversible LC alignment with the long-pass filter and subsequent
worsening with the short wavelength radiation. It was obvious
that the wavelengths of UV had a significant influence on the
photochemical responses and thus crucially affected the quality
of LC alignment. The long wavelength UV light, necessary for
reversible E/Z-isomerization, is essential for the in situ photo-
alignment, whereas the short wavelengths have a negative
influence on the LC alignment by creating defects.
3.7 Interfacial alignment layer formed by in situ
photoalignment
The PI-less in situ photoalignment was accomplished by remotely
controlled interfacial modifications. The first modification was
carried out by photopolymerizing acrylate monomers, forming
a thin interfacial polymer layer. The second modification was

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actuated by dichroic cinnamate chromophores under LPUV
irradiation. The molecular orientational anisotropy was induced
through reversible trans/cis-isomerization, resulting in a uniaxial
LC alignment. The in situ created interfacial layer functioned as a
new alignment layer.
The interfacial polymer layer was inspected by employing
FE-SEM and white light interferometry. The bare polymer layer,
exhibiting a good LC alignment, could not be obtained by
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without using a cross-linker. The layer thickness was B20 nm, as
shown in Fig. 7(f-i). The normal and highly-tilted FE-SEM views,
shown in Fig. 7(f-ii) and (f-iii), represent a much smoother surface
than the previous one. Essentially the same results were found
on both the inner surfaces. It was obvious that the photo-
polymerization of acrylate monomers formed interfacial polymer
layers, acting as an alignment layer. Furthermore, the different
sampling processes substantiate our conclusions on the role of

dipping in organic solvents. Because the polymer was a linear
chain with no high-density cross-linking, the polymer layer was
completely washed out when it was dipped in a solvent. There-
fore, the robust polymer layer was prepared by adding a small
amount of a cross-linker. Fig. 7e presents the layer thickness
(B23 nm) and FE-SEM images for an inner surface of the LC
cell, prepared by adding a cross-linker. Fig. 7(e-ii) and (e-iii)
correspond to the top and tilted views of a bare polymer surface
with different magnifications. The ITO-grain boundaries are barely
visible with a thin polymer overlay on the ITO-surface. The polymer
layer consists of small polymer aggregates of several nanometer size.
Cracks, presumably formed by a volume shrinkage, are also visible.
The existence of a thin polymer layer was manifested by Fig. 7(e-i)
and Fig. 7(e-iii). It was confirmed that the photopolymerized acrylate
monomers formed the interfacial polymer layer. This in situ created
polymer layer acts as a photoalignment layer.
On the other hand, the bare polymer layer, highly cross-linked
by [2+2] photodimerization, was obtained from the quartz cell after
the short-wavelength UV irradiation (the cell used for Fig. 7d)
each functionality of the multifunctional C3 monomer.
3.8 Stepwise understanding of the PI-less in situ photoalignment
On the basis of the results discussed above, we summarize the
sequential process of the PI-less in situ photoalignment. Fig. 8
schematically illustrates the sequential occurrences that the
system undergoes during LPUV irradiation. Initially, the photo-
aligning additives are homogeneously dissolved in a random
planar LC host with no pretreated alignment layer (Fig. 8a). The
first important step, occurring upon the in situ LPUV treatment,
is photo-induced polymerization of acrylic monomers. As a
result, the thin photo-responsive polymer layers are formed at
an inner surface (the yellow color in Fig. 8b).
Intrinsically, the LC alignment is mediated by this polymer
surface. In this step, however, the surface has no anisotropy, as
depicted in Fig. 8b. Under a continued LPUV irradiation, the
molecular orientational anisotropy is induced by the dichroic
photochromic responses (the green color in Fig. 8c). Although
both trans/cis-isomerization and [2+2] dimerization may induce

Fig. 8 Schematic illustrations of the sequential process of the in situ photoalignment, adopting the multifunctional C3 chromophore. (a) The C3-doped
LC mixture sandwiched by untreated surfaces, (b) the in situ creation of an interfacial polymer layer (designated by yellow) by photopolymerizing acrylic
monomers, (c) the remotely induced surface orientational anisotropy (the green layer), actuated by trans/cis-isomerization and the consequent
molecular reorientations, (d) the disordered alignment layer (specified by red), caused by the irreversible [2+2] photodimerization. The simplified
molecular order at a surface was depicted for each step and highlighted with different colors. The ellipses in (c) represent aligned LC molecules after the
treatment.

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the molecular orientation perpendicular to the electric vector of
the LPUV,54–56 the reversible trans/cis-isomerization plays a crucial
role in the LC alignment. The [2+2] cycloaddition reaction turned
out to be a negative influence. These results were confirmed by the
rewritable reversibility of LC alignment in the previous section.
Fig. 8c represents the uniaxially reoriented side-chain chromo-
phores at a polymer surface, actuated by the LPUV and the
subsequent dichroic isomerization. As a result of the induced
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molecular anisotropy, the LCs are aligned perpendicular to the
LPUV, verified by PFM and PFS. Surprisingly, it seems that the
photo-dimerization exacerbates a surface molecular order, rather
than enhancing a LC alignment. As illustrated in Fig. 8d, the
prolonged UV irradiation, especially short wavelengths, produces
the [2+2] cycloadducts and thus deteriorates the LC alignment.
This conclusion is corroborative to the previous report that an
excessive irradiation energy worsens the LC alignment for a
cinnamate-based in situ photoalignment.25
4. Conclusions
The PI-less in situ photoalignment has been successfully
demonstrated by employing the cinnamoyl-based acrylic mono-
mers. The multifunctional C3 model compound was beneficially
adopted for a comprehensive understanding of the in situ-photo-
aligning process. In addition to the functionalities for photo-
polymerization, photodimerization, and trans/cis-isomerization,
its dichroic photoluminescence was very useful to comprehend
the sequential occurrences in the in situ photoaligning process of
LCs. In the first step, the acrylic monomers were photopolymerized
and formed a thin interfacial polymer layer. The surface anisotropy
was induced by the interaction between remotely controlled
LPUV and dichroic photochromic responses of the cinnamoyl
chromophores.
The conclusions on a key process were drawn on the basis
of the wavelength dependent photochemical processes and
the associated LC alignment effect. The reversible trans/cis-
isomerization and subsequent reorientation were the most
crucial processes, whereas the irreversible photodimerization
showed a negative influence on the LC alignment. Therefore,
the photoalignment was more effective with the longer wave-
lengths of UV light (l 4 350 nm), including both ranges of
wavelengths near the isosbestic point for trans- to cis- and cis- to
trans-isomerization. By cutting-off the short wavelengths of UV
light, the photodimerization process was suppressed and thus
the defect formation was significantly diminished under a
high-dose UV irradiation.
The conclusion was further corroborated by the rewritable
LC alignment and its wavelength dependency. It was evident
that the reversible isomerization was preferable to the photo-
dimerization under the relatively longer wavelength UV light
and played a crucial role in the LC alignment. The spatial
distribution and molecular orientational order of the chromophore
were monitored during the processes. It was confirmed that
the photopolymerization occurred first for forming interfacial
alignment layers, followed by the second process inducing a
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molecular orientational anisotropy in the polymer alignment
layer. We used the model compound with an effective responsive-
ness in the polymerized state, on purpose, for the mechanism study.
As a result, the LC alignment was rewritable, indicating an
instability of the alignment. For practical applications, however,
the photoaligning additives need to be designed for securing a
permanent stability of the LC alignment.
The cinnamate-based PI-less in situ planar alignment has
been attracting great attention for industrial applications since
the pioneering work reported in 2017.23 It has great potential,
meeting various device parameter requirements, and rigorous
optimization is currently being undertaken. In this respect, our
comprehensive understanding of the process can provide very
beneficial information for realizing industrial applications. For
instance, a proper design of chromophores, by considering
their absorption spectra, and a selection of UV-wavelength are
of great importance for enhancing the efficiency of the process.
The molecular designs, securing an alignment stability, are also
crucial in the same context.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This research was supported by the ‘‘BK21 Plus Project’’ through
the National Research Foundation of Korea funded by the Korea
Government (MSIT). The authors appreciate Merck Performance
Materials and Samsung Display for providing the LC materials
and IPS-cells, respectively.
Notes and references
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4 C. Xue, J. Xiang, H. Nemati, H. K. Bisoyi, K. Gutierrez-Cuevas,
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