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Japanese Journal of Applied Physics 56, 071701 (2017) REGULAR PAPER
https://doi.org/10.7567/JJAP.56.071701

Homogenous photoalignment of nematic liquid crystals

doped with photoalignable materials
Yuki Hashimoto1, Mizuho Kondo1, Tomoyuki Sasaki2, Hiroshi Ono2, and Nobuhiro Kawatsuki1*
1
Department of Applied Chemistry, Graduate School of Engineering, University of Hyogo, Himeji, Hyogo 671-2280, Japan
2
Department of Electrical Engineering, Nagaoka University of Technology, Nagaoka, Niigata 940-2188, Japan
*E-mail: kawatuki@eng.u-hyogo.ac.jp
Received February 15, 2017; accepted April 11, 2017; published online June 9, 2017

We demonstrate the homogeneous photoalignment of low-molecular-weight liquid crystals (LC) using nematic LCs (NLCs) doped with photo-
alignable low-molecular-weight LC materials, achieved in the absence of substrate surface treatment; in-plane switching (IPS) is also shown using
an IPS-mode LC cell. The exposure of the LC cells to linearly polarized (LP) light in the isotropic temperature range of the NLC composites
generates homogenous NLC orientation, but exposure at room temperature results in the random orientation of the NLCs. Small amounts of
photoalignable LC materials on the substrates, which have undergone axis-selective photoreaction, are found to control the NLC alignment.
© 2017 The Japan Society of Applied Physics

of these cases, a thin NLC alignment layer forms on the

1. Introduction
The photoalignment of liquid crystals (LCs) has become an
emergent technology for clean and precise device fabrication,
offering various advantages over the conventional rubbing
method such as minimized mechanical damage, no electric
charge, and patterning ability.1–3) Several types of photo-
alignments have recently been explored for uniaxial LC
orientation in practical LC display (LCD) fabrication proc-
esses.1–5) Moreover, photoalignment has great potential for
the fabrication of polarization-selective patterned diffrac-
tion devices owing to its facile control of the molecular
orientation in bulk.6,7)
In general, by using a linearly polarized (LP) light source
for the photoexposure of a photoalignment layer on a
substrate, optical and physical anisotropies can be generated
from the axis-selective photoreaction.1,8) LC molecules on
such photoexposed photoalignment layers tend to uniaxially
self-organize owing to anisotropic chemical and physical
interactions between the two materials. We previously con-
ducted a systematic study on photoalignment materials.9) An
axis-selective photoreaction of the photoreactive liquid
crystalline polymeric material (PLCP) reveals photoinduced
molecular reorientation when the thermally stimulated self-
organization of thin films is generated.9) The resultant
oriented PLCP films are applicable as the homogeneous
photoalignment layer of LCs.10,11) To further develop the
photoalignment technique, the elimination of the photoalign-
ment layer is strongly desired, as the LC alignment induced
by the direct exposure of the LC cell would reduce
processing complexity and costs for the fabrication of LCDs
and polarization diffraction devices.
Several studies have reported that LC alignment can be
achieved without using precoated alignment layers.12–16) Kim
et al. demonstrated out-of-plane (VA) orientation in nematic
LCs (NLCs) by doping with silsesquioxane (POSS) deriva-
tives, where the introduction of mesogenic side groups to the
POSS derivatives improves their compatibility with NLCs.12)
Haba et al. found that a blend of NLC and a small amount of
a LC dendrimer exhibited spontaneous, homeotropic align-
ment.15) In another study, photoswitching between VA and
homogenous NLC alignments was demonstrated by adding a
surfactant with azobenzene-side groups to the NLCs.16) In all
071701-1
substrate after LC cell fabrication, which controls the VA-LC
alignment. However, few studies have explored in-plane
NLC alignment without the use of a precoated alignment
layer.
Recently, we have reported that hybrid in-plane photo-
alignment could be achieved by using rubbed, polyimide-
coated substrates injected with a NLC doped with a small
amount of PLCP.17,18) We found that exposure to LPUV light
can alter the NLC homogeneous alignment direction, which
is initially determined by the rubbed polyimide layer, and
that the rubbing strength affects the photoalignment control.
However, this route is limited by the low compatibility of
PLCP with NLCs, which restricts the degree of doping in
this system. Therefore, new photoalignable materials for
homogeneous NLC alignment, which not only improve the
alignability of NLCs but are also strongly compatible with
NLCs, are much desired.
In this study, we demonstrate uniaxial homogeneous NLC
photoalignment without the use of a photoalignment thin
film by doping the NLC with photosensitive low-molecular-
weight LC materials containing cinnamate mesogenic groups
[PM; PM1–PM3, as shown in Fig. 1(a)]; such LC materials
exhibit improved compatibility with the NLC compared with
PLCP, as well as improved photoalignablity. Homogeneous
NLC alignment is generated by the exposure of the NLC=PM
cell to LPUV light within an isotropic temperature range.
Additionally, NLC alignment is retained after exposure to
elevated temperatures, and even after rinsing out and refilling
the cell with the NLC when using PMs containing siloxane
end groups. Finally, we demonstrate the in-plane switching
of an IPS-mode LC cell. The axis-selective photoreaction
of the photosensitive materials and their presence on the
substrate play an important role in the formation of a stable
NLC alignment.
2. Experimental methods
2.1 Materials
The NLC (Merck ZLI-4792) was used as received, and
the synthetic procedure for PMs will be described elsewhere.
All PMs exhibited a nematic LC phase and were found to be
miscible with the NLC (Table I).
© 2017 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 56, 071701 (2017) Y. Hashimoto et al.

(a) (a)
1.5

Absorbance (arb. unit)

1
Exposure energy (J/cm2)

Initial
0.5 J
0.5
1J

0
250 300 350 400 450 500
Wavelength (nm)

(b)
1.5
(b)

Absorbance (arb. unit)

Exposure energy (J/cm2)
1 Initial (||)
3 J (||)
3 J (⊥)
18 J (||)
0.5
18 J (⊥)

0
250 300 350 400 450 500
Wavelength (nm)

Fig. 1. (a) Chemical structures of PMs used in this study. (b) Schematic Fig. 2. (Color online) Changes in the UV–vis absorption spectra of
illustration of a patterned electrode for IPS LC cell fabrication. (a) PM1 in NLC (5 wt %) cell and (b) PM1 in PMMA (5 wt %) film on
exposure to LPUV light.

Table I. Thermal properties of PMs and NLC=PM mixtures.

Thermal propertyb) absorption spectra of PM1 in a NLC (5 wt %) cell (6 µm
Material
(°C)
thick) and the polarized UV–vis absorption spectra of PM1
PM1 K 111 N 180 I doped in a poly(methyl methacrylate) (PMMA) (5 wt %) film
PM2 K 119 N 199 I on exposure to LPUV light at room temperature, respectively.
PM3 K 151 N 267 I The absorption band at 315 nm decreased in intensity for both
NLC=PM1a) N 99 I specimens and a negative optical anisotropy (A∥ < A⊥) at
NLC=PM2a) N 102 I 315 nm appears in the PM1=PMMA film owing to an axis-
NLC=PM3a) N 100 I selective photodimerization reaction of cinnamate mesogens
a) 5 wt % PM in NLC. in PM1. Because the photoreaction of the PM1 in the
b) Determined by differential scanning calorimetry. NLC (5 wt %) cell was carried out in the LC state, optical
anisotropy was not clearly detected. Additionally, a new
absorption band appeared at 370 nm, indicating that photo-
2.2 Cell fabrication Fries rearrangement occurs. PM2 and PM3 in the film
A LC cell was fabricated from a mixture of NLC and showed similar spectral changes to PM1. The photo-Fries
PM (5 wt %) at room temperature using glass substrates rearrangement of cinnamate mesogens occurs owing to the
(Matsunami slide glass S1126), and those with a patterned low concentration of PMs in the matrix, which is similar to
electrode for IPS LC cell fabrication [Fig. 1(b)]. A cell the photoreaction of polymethacrylate derivatives with the
thickness of 6 µm was attained using bead spacers. After same mesogenic side groups, which occurs in solution.19)
filling an empty cell with the NLC=PM mixture, the cell was 3.2 Homogeneous LC cell using NLC/PM mixture
exposed to LPUV light using a high-pressure Hg lamp When a LC cell filled with a PM1-doped NLC (5 wt %) was
equipped with Gran–Taylor prisms and a cut-filter below exposed for 1.0 J=cm2 at 110 °C (isotropic temperature of
300 nm wavelength (intensity: 50 mW=cm2 at 365 nm) at the mixture), homogeneous LC alignment was uniaxially
various temperatures, followed by cooling to room temper- observed after cooling the cell to room temperature in the
ature. LC alignment performance and its direction were direction perpendicular to the polarization of LPUV light
evaluated by doping with dichroic dye (DB14) with polarized [Fig. 3(a)]. The LC alignment direction was confirmed by
optical microscopy (POM). DB14 in the NLC, where the dichroic ratio (DR) of DB14 at
650 nm was 0.48, which was similar to that using rubbed
3. Results and discussion polyimide substrates (DR = 0.49). Doping PM2 and PM3
3.1 Photoreaction of NLC/PM mixture into the NLC also achieved a similar uniaxial LC alignment
Figures 2(a) and 2(b) show the changes in the UV–vis as shown in Figs. 3(b) and 3(c). Homogeneous LC alignment
071701-2 © 2017 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 56, 071701 (2017)
(a) (b) (c)
(d) (e)
Fig. 3. (Color online) Photographs of LC cells containing different PM
dopants between crossed polarizers. The cells were exposed to LPUV light
for 1.0 J=cm2 at (a–d) 110 °C, and (e) 45 °C. (a) NLC=PM1 (5 wt %),
(b) NLC=PM2 (5 wt %), (c) NLC=PM3 (5 wt %), (d) NLC without PM, and
(e) NLC=PM1 (5 wt %). Insets show POM photos. White arrows indicate
polarizer and analyzer directions.
was observed when the exposure energy fell between 0.05
and 2.0 J=cm2, but the NLCs aligned in a random-planar
fashion when the exposure energy exceeded 3 J=cm2. The
degree of photoreaction of cinnamate moieties in the NLC
alignment energy range (0.05–2.0 J=cm2) was measured to be
approximately 7–25%. In the control experiment, we found
that NLCs could not align after the LPUV irradiation when
the LC cell does not contain PMs [Fig. 3(d)]. These results
indicate that suitable axis-selective photoreacted products
of PMs generate NLC alignment, even in the fluid state.
In contrast, uniaxial LC alignment was hardly observed
when the NLC=PM1 (5 wt %) cell was exposed to LPUV
light at 45 °C (LC temperature of NLC) [Fig. 3(e)]; this is
attributed to a distortion in the polarization characteristics of
incident LPUV light traveling to the opposite side of the cell
by randomly oriented NLC molecules in the initial LC state.
As a result, the PM molecules could not photoreact in an
axis-selective fashion. Additionally, uniform NLC alignment
was recovered when the uniaxially oriented LC cell was
reannealed at its isotropic temperature (120 °C) and sub-
sequently cooled at room temperature. As such, it may be
concluded that the photoexposed PM is structurally stable,
allowing for the photoalignment of the NLC in the LC cell at
elevated temperatures. Namely, a certain amount of photo-
exposed PM existed on the substrate as the photoalignment
layer.
Figure 4 shows the absorption spectra of the homoge-
neously aligned NLC=PM1 (5 wt %) cell. It shows that PM1
molecules align parallel to the alignment direction of the
NLC, suggesting the cooperative orientation of PM mole-
cules dissolved in the NLC. Additionally, azimuthal anchor-
071701-3
Y. Hashimoto et al.
1.5
Absorbance
1 A||
Absorption band of PM1
0.5 A⊥
0
250 300 350 400 450 500
Wavelength (nm)
Fig. 4. (Color online) Polarized UV–vis absorption spectra of the
homogeneously aligned LC cell fabricated from NLC=PM1 (5 wt %), and
inset shows the observed Neel wall in it.
0.5
0.4
Absorbance
0.3
0.2 PM1
PM3
0.1 Glass only
0
250 300 350 400 450 500
Wavelength (nm)
Fig. 5. UV–vis absorption spectra of rinsed substrates from LC cells of
NLC=PM1 (5 wt %) and NLC=PM3 (5 wt %).
ing energy was measured to be approximately (1–4) × 10−6
J=m2 by the Neel-wall method (inset of Fig. 4).20) This value
is comparable to that of the poly(vinyl cinnamate) photo-
alignment layer for the NLC20) and smaller than that of the
photoalignment layer with similar photoreactive mesogenic
side groups, where the anchoring energy of the molecularly
oriented photoalignment layer was 1 × 10−4 J=m2.11) This is
due to the fact that the amounts of anisotropically photo-
reacted PMs on the substrate are insufficient to achieve
the strong anchoring of NLC alignment attributed to the
molecular reorientation. Namely, most of the PMs that
dissolved in the NLC may not be attributed to the LC orien-
tation, while a small amount of PM anisotropically placed
on the substrate without the molecular reorientation regulates
the NLC alignment.
To confirm the existence of a photoalignment layer on the
substrate, a homogeneous LC cell was rinsed with diethyl
ether to remove the NLC. If all PM molecules are present on
the substrate, the PM thickness should be 150 nm (5 wt %
in the PM=NLC mixture of 6-µm-thick LC cell), which is
measurable using the absorption spectrum. However, as
shown in Fig. 5, a small absorption band of PM was detected
for the rinsed substrates when using PM1 and PM2, where
the remaining PM thickness was estimated to be less than
25 nm, while the absorption was negligible for PM3. These
results suggest that thin photoalignment layers (PM1 and
PM2) remain intact after substrate rinsing, although most of
the PMs dissolved in the NLC. Therefore, after refabricating
© 2017 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 56, 071701 (2017)
(a) (b) (c)
Fig. 6. (Color online) Photographs of refabricated LC cells using the
rinsed substrates. (a) PM1, (b) PM2, and (c) PM3 cells. Insets show POM
photos. Arrows indicate polarizer and analyzer directions.
(a)
(b)
Fig. 7. (Color online) (a) In-plane switching of a LC cell. The cell was
fabricated using NLC=PM1 (5 wt %). The switching voltage was 8.0 V at
1.0 kHz. (b) Change in transmittance of the IPS-LC cell between crossed
polarizers when applied voltage is turned on and off. The inset photograph
shows POM after repeating on–off 100 times.
the LC cell by refilling with the NLC, homogeneous NLC
alignment was achieved, along with several defects, for cells
using rinsed PM1 and PM2, but not for the PM3 substrate
[Figs. 6(a)–6(c)]. The thin photoalignment layers (PM1 and
PM2) could remain after substrate rinsing when they contain
siloxane groups owing to the interaction between the glass
substrates and the Si–O moieties of the photoalignment
materials. In a previous study on VA-NLC alignment using
POSS derivatives, it was also suggested that alignment mole-
cules are present on the substrates owing to the interaction
between the substrate and Si–O in POSS.12,13) However,
we could not determine which material remained on the
substrate, photoreacted or un-photoreacted PMs.
3.3 IPS-LC cell
An in-plane switching-mode (IPS) LC cell was fabricated
using NLC=PM1 (5 wt %) as shown in Figs. 7(a) and 7(b).
In-plane switching was achieved and the NLC molecules
adopted their initial alignment state when the applied voltage
was turned on and off over 100 times. From these results,
it may be concluded that the formation of a stable PM
photoalignment layer in the LC cell controls the NLC
071701-4
Y. Hashimoto et al.
orientation. However, toff was longer than 100 ms owing to its
weak azimuthal anchoring and several defects appeared at
the electrode area after repeated switching 100 times [insets
of Fig. 7(b)]. This indicates the lower interaction between
the PM photoalignment layer and the electrode. Upon
switching, some photoalignment molecules change their
direction owing to their monomeric structure and the absence
of chemical bonds with the electrode. The anchoring energy
and stability of the PM photoalignment layer should therefore
be improved.
4. Conclusions
The homogeneous photoalignment of NLCs was attained
without cell surface treatment. Doping a small amount of PM
into the NLCs and subsequent exposure to LPUV light at the
isotropic temperature of the mixture led to the uniaxial orien-
tation of NLC molecules. The axis-selective photoreaction
of PM controls the NLC orientation, and the orientation is
stable even after reannealing the LC cell at the isotropic
temperature, suggesting that the increased interaction be-
tween the photoreacted PM and the substrate substantially
contributes to the stability of the NLC alignment. However,
the azimuthal anchoring is not sufficient for the display
quality of the IPS-LC cell. The synthesis of new PMs to
improve the anchoring energy is in progress.
Acknowledgment
This work was partially supported by Nissan Chemical Co.,
Ltd.
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© 2017 The Japan Society of Applied Physics