CH3 Photo-Stimulated Phase Transformations of LCs Photocontrollable LC Actuators I 102 上課版

3 Photo-Stimulated Phase
Transformations of LCs &

Photocontrollable LC Actuators I
1. Introduction
2. Photomodulation of LCs
3. LMWLC Actuators
4. LCP Actuators
5. LCE Actuators
References
6. LCBC Actuators
* Photocontrollable Liquid-Crystalline Actuators,
Adv. Mater. 2011, 23, 21492180
7. Outlook
Haifeng Yu and Tomiki Ikeda
* Q. Li, Liquid Crystal Beyond Display
By Prof. Chia-Rong Lee
Liquid crystal Photonics lab.
1. Introduction
The history of human civilization is accompanied by
the development of novel materials, from the period of
natural stone, the bronze and iron age, to the modern
times of synthetic materials and promising advanced
materials.
Liquid crystals (LCs) are one of such kind of materials
that greatly influence our daily life, and which are not
limited to displays, including cell phones, TVs and
personal computers, and various photonic applications,
including optical storage, optical switching, optical
computers and integrated optical devices for
communication.
Combined with LCs photoresponsive properties,

photocontrollable LC actuators () have
enabled a variety of applications in various fields
including FPD, photonics, photo-driven devices, and more
recently nanotechnology.
The LCs unique features provide soft materials in a LC
state with interesting properties such as
X self-assembly
Y fluidity with long-range order
Z molecular & supramolecular cooperative motion (MCM

& SMCM)
[ large birefringence & anisotropy in various physical
properties (optical, mechanical, electrical, & magnetic)
\ alignment change induced by external fields at surfaces
& bulk
] deformation of LC elastomers in response to stimuli
Based on the alignment of rod-like molecules, LCs can

change their characteristics of dielectric constant,
magnetic constant, viscosity, elasticity, and so on.
Due to their optical properties, LC materials can be used
as actuators for light, which lays the foundation for the
modern industry of LC displays (LCDs).
When low-molecular-weight LC (LMWLC) materials are
placed in a cell and sandwiched between two transparent
electrodes (ITO) coated with alignment layers, an LC cell
is obtained.
Upon application of an electric field with a driving voltage
between the two electrodes, LMWLCs in the cell change
their alignment directions from parallel (homogeneous) to
perpendicular (homeotropic) with respect to the
conductive substrates (via electrical Freedericksz
transition).
Since LC molecules can change the polarization

direction of light when linearly polarized light (LPL)
passes them, the transmittance through a pair of
crossed polarizers, with the LC cell placed between
them, decreases due to the loss of birefringence. As a
result, a bright/dark contrast is produced at each pixel,
and 2D images can be displayed in the flat panel of
LCDs.
Modulation of LC alignment not only induces an
extreme change in refractive index (which is very
difficult to achieve with amorphous materials), but also
gives rise to some engrossing phenomena, e.g.,
photomechanical and photomobile effects in LCEs, MCM
in LMWLCs and LC polymers (LCPs), and SMCM in LC
block copolymers (LCBCs).
2. Photomodulation of LCs
On one hand, LCs have been widely utilized as good
light actuators for beam steering, phase retardation,
wavefront modulation, and polarization switching and
control. On the other hand, the change in LC alignment
can also be reflected by its optical properties. Both of
them are the bases of LC actuators for photonic
applications.
As one of green and neat energies, light is particularly
fascinating since it supplies precise and reversible controls
with a noncontact way. LC materials with photo-active
functions can be easily photo-modulated into
hierarchical patterns by adjusting the actinic light with
wavelength, intensity, polarization, phase retardation,
interference, and so on.

Fig. 1 Different ways of photocontrollable LC actuators in various LCassociated materials LMWLCs, LCPs, LCEs and LCBCs

2.1. Photomodulation of LMWLCs and LCPs

In LMWLCs and LCPs, the photomodulation among three
states of LC alignment can be easily obtained by choosing
suitable input actinic light. Detecting with LPL, LC
materials show different refractive indices of ne and no,
and ni (isotropic), respectively, when they are in parallel
and perpendicular alignment (ordered states) and in a
random isotropic phase (disordered state).
Fig. 1A
ni
LPL with E-vector oscillating in the vertical direction

detects ne, when LC molecules are in vertical alignment.
Whereas no can be measured by LPL if the LC molecules
change their alignment from perpendicular to parallel
orientated state. The photoinduced change in LC
alignment usually brings about a large change in
refractive index.
ni
Fig. 1A
Different from the order-order change in Fig. 1A(1), Figs.

1A(2) & 1A(3) are order-disorder changes, which are
correlated with neni and nino, respectively. The order
of the refractive index is usually ne >ni >no, thereby the
change in the LC directors (order-order change) gives
rise to a larger change in refractive index than the
order-disorder changes, although the order-disorder
changes still give a large alteration of refractive index
comparing with amorphous materials.
ni
Fig. 1A

2.2. Photomodulation of LCEs

In LCEs, LC molecules cannot be singly photo-modulated
because they are three-dimensionally (3D) crosslinked to form
freestanding films, enabling them to be macroscopically
induced change in shape by stimuli.
De Gennes first theoretically proposed thermally-induced
uniaxial contraction of LCEs in the direction of the optic
axis or director axis by combination the anisotropic
aspects of LC phases and the rubber elasticity of polymer
networks, which was then developed and experimentally
obtained by Finkelmann et al.
A large change in volume of LCEs enables them to be
explored as novel materials for artificial muscles and soft
actuators.
The deformation of LCEs can be induced by actinic light,

bringing about photomechanical and photo-mobile properties
of LCEs.
Upon irradiation, photomodulation of LCs occurs only in
the surface region of LCE films because of the large molar
extinction coefficient of photochromic LCs and light cannot
penetrate through a thick film (thickness >10 m), which
induces the volume change only in film surface and generates
photomechanical effect.
Fig. 1B

When the alignment of LC molecules is parallel to the

surface of substrates, volume contraction is produced just
along this pre-aligned direction, contributing to the
anisotropic bending behavior towards a light source.
On the contrary, volume expansion is brought about when
the LC molecules are aligned perpendicularly to the
substrates, resulted in different bending behavior, away
from the light source.
Fig. 1B

Furthermore, the photomechanical behavior is reversible if

azobenzene (AZ) molecules are used as photoresponsive
mesogens. By this way, light energy can be directly
transferred into mechanical energy, which attracts much
attention of scientists in the present LC research.
Fig. 1B
2.3. Photomodulation of LCBCs

In LCBCs with at least one LCP chain as one constituent
block, LC molecules in the continuous substrates of bulk
films can be used as ordering actuators to control the
alignment of microphase-separated nanostructures by SMCM.
Fig. 1C
By the interplay processes between regular periodicity of LC

ordering and thermally controlled microphase separation, the
ordering of mesogens can be transferred to the
nanostructures inside them, leading to periodically ordered
nanostructures.
The orientation of the hierarchically assembled
nanomaterials strongly correlated with the LC alignment,
which makes the microphase-separated nanostructures in
LCBCs superior to
those in amorphous
ones since the LC
alignment can be
easily achieved in
an arbitrary scale
with well developed
techniques.
Fig. 1C

The supramolecularly assembled nanostructures in LCBC films

show excellent reproducibility and mass production, which
provides reliable templates for nanofabrication processes and
leads to widely applications in macromolecular
engineering.
Fig. 1C
The engrossing LC materials for photocontrollable

actuators offer an effective and convenient chance to
adjust properties of advanced materials by integrating
photoresponsive molecules with LC properties, which has
become one of the emerging topics in the present and
future LC research.
It is timely to compile a comprehensive review on the
nature of this type of materials and the ongoing progress
in this research area, which will be useful to professional
working in this field.
The goals of this chapter are to summarize previous work,
provide new insights into this class of LC actuators, and
add to the understanding of the potential applications in
flat panel display, photonics, photomobile devices and
nanotechnology.
3. LMWLC Actuators
3.1. Photoinduced Phase Transition
A photochromic molecule shows reversible photochemical
reactions, such as
X photoisomerization () and Y photo-dimerization
(), which is often accompanied by a change in
its molecular configuration.
Azobenzenes (AZs) are one of the typical chromophores
(), famous for their photoisomerization with a
large change in molecular structures, which have been
widely used as ultra-small phototriggers () for
LC actuators in gust/host mixtures.
Fig. 2A Two isomerization states are a thermally stable

trans isomer (E state) and a meta-stable cis isomer (Z state).
The longer the excitation wavelength of the actinic light, the
greater the proportion of the trans configuration in the photo
stationary (dynamically) state. The cis-AZ isomer can
thermally relax back to the trans-AZ isomer with a
lifetime that strongly correlated with the particular AZs
substitution.
Fig. 2A Photoinduced phase transition and its mechanism in AZ and

AZ/photoinert LC mixture. A) Photoisomerization of an AZ molecule.
Fig. 2B Photoinduced NLC-isotropic (N-I) phase transition

occurs upon photoisomerization from trans-AZ to cis-AZ.
Observed with a polarizing optical microscope (POM)
with crossed polarizers, a dark image is obtained in the
UV-irradiated area due to the lost of birefringence in an
isotropic phase.
Fig. 2B Photoinduced phase transition of AZ LCs, in which

an AZ acts as both a mesogen and a photosensitive moiety.

Fig. 2C Even though the AZ molecules show no LC

phase, they can be used to photo-modulate photoinert
mesogens via the LC inherent property of MCM (molecular
cooperative motion), triggered by actinic light.
If a small mole proportion of LC molecules changes
their alignment in response to an external stimulus, the
other LC molecules nearby also change their alignment,
coinciding with the pre-aligned LCs called MCM.
In fact, only a small amount of energy as to induce an
alignment change of about 1 mol% of LC molecules is
enough to bring about the alignment change of the
whole LC mixtures. That is to say, a huge amplification is
possible in LC photonic systems owing to the
phototriggered MCM.

When a small amount of photochromic molecules is

incorporated into LC molecules and the resulting
host/guest mixtures are irradiated, an N-I phase transition
can be isothermally photoinduced.
<ex> Isothermally Photoinduced
transition in AZ/NLC mixtures
NLC-isotropic
phase
Since the trans-AZ is in a rodlike shape, which

stabilizes the phase structure of an LC phase, while its
cis-isomer is bent and tends to destabilize the phase
structure of the LC mixture.
Fig.
2C
Phase
diagram of photo
chemical
phase
transition
of
AZ/photoinert
LC
mixture systems.
The LC-isotropic phase transition temperature (Tc) of

the mixture with the cis-form (Tcc) is much lower than
that with the trans-isomer (Tct).
If the temperature (T) of the mixture is set between
Tct and Tcc (Tcc < T < Tct ), and the sample is irradiated
to cause transcis photoisomerization of AZ guest
molecules, then Tc decreases with an accumulation of
the number of cis-isomer. When Tc becomes lower than
the irradiation temperature (T), the LC-isotropic phase
transition is induced.
Fig. 2C Phase diagram
of photo chemical
phase transition of
AZ/photoinert
LC
mixture systems.

The photoinduced phase transitions are interpreted in

terms of a change in the phase transition temperature of LC
host/guest systems on accumulation of one isomer of
the photo chromic guest molecule.
T=TctTcc is one of the most important parameters
in the phase transition. When the temperature of LC
mixtures is set below Tcc, no phase transition is induced.
When the temperature is set close to Tct, the amount of
cis-AZ needed to lower Tc below the irradiation
temperature is small, enabling one to effectively
photoinduce phase transition.
Fig. 2C Phase diagram
of
photo
chemical
phase transition of
AZ/photoinert
LC
mixture systems.

Photoisomerization is usually reversible, and with

cistrans back-isomerization the sample can revert to the
initial LC phase by photo or thermal treatment. This
means that phase transitions of LC systems can be
reversibly induced by photochemical reactions of
photoresponsive guest molecules.
Moreover, the molecular structures of chromophores
greatly influence the photoinduced phase transition of
host/guest LC mixtures.

Fig. 2 D Upon photoirradiation of 5CB/trans-AZ, dark

spots in the samples are observed with POM, due to the
formation of isotropic domains at the irradiated areas
where a NLC-isotropic phase transition takes place in the
local phase-segregated domains. Increasing the irradiated
dose, the isotropic domains grow and the dark areas
increase and finally the whole vision area becomes dark
and isotropic due to the occurrence of photoinduced
phase transition.
Fig. 2D Mechanism of
photochemical phase
transition
in
AZ/photoinert
LC
systems.
The photochemical phase transition in the AZ/photoinert

LC mixture has been systematically studied on a series of
LC molecules.
When the photochromic molecules alter their
molecular shapes upon photoirradiation, changes in other
properties such as polarity are usually generated. Such
photochromic reactions are reversible and two isomers
can be effectively interchanged by light with different
wavelengths.
Furthermore, most of photochromic reactions are very
fast and occur in a time region of pico-seconds (ps). In
addition to AZs, various photochromic molecules such as
stilbenes, spiropyrans, diarylethenes and fulgides, have
been adopted to study the photoinduced phase transition.

3.2. Photoalignment Layers

LMWLCs change their pre-alignment directors under an
electric field, in which one of the most successful applications
is LCD.
In fabrication of commercialized LCDs, both of
transparent electrodes should be precoated with
alignment layers to produce pre-tilt angle for preventing
the creation of reverse tilt disclinations in displays.
The uniform alignment of LC molecules on pre-treated
substrate surfaces is greatly related with interfacial
properties between LC molecules and the surface
morphologies of alignment layers.

LCs can be aligned along the rubbing direction on

polyimide (PI) films because of the lower energy level along
the unidirectional rubbing-induced grooves, which has
been widely used in the present LCD industry.
But the rubbing method has some obvious demerits
such as the contaminated dust and static charge
produced during the rubbing process, which may cause
serious problems such as the speckles () and reduced
display contrast of LCDs.

Moreover, the rubbing method can only be applied on flat

surfaces, which shows no function on curves. Therefore,
the noncontact method of photo-alignment is considered to be
one of the promising ways to solve the above-mentioned
problems and can be easily used to assemble LCDs with
high quality, wide viewing angles and large-area screen.
According to reaction mechanism, the photoalignment
of LMWLCs on surfaces of alignment layers can be divided
into:
photoisomerization,
degradation.
photocrosslinking
and
photo-

Command Surface
Linearly photodimerized (LPD)

Method
Photoactive PI

3.2.1. Command Surface

(1) Ichimura et al. first reported possibility of photoalignment
of LCs with self-assembled monolayers of AZ dyes formed on
glass substrates.
In LC cells made from the surface-treated substrates,
NLCs show a homeotropic alignment when AZs
immobilized on the substrates are in the trans form. Light
irradiation to cause trans-cis isomerization of AZs enables LC
alignment to repeatedly change from homeotropic to
planar states. Similarly, photoinduced alignment change in
plane can be acquired by the command surfaces via
photoalignment of AZs in plane.
Fig. 3A Photoalignment
methods
of
LMWLC
molecules. A) Command
surface.
(2) The photoalignment effect of AZ dyes does not limited

on the surface, and a similar effect was found in volume of
polymer films doped with AZ molecules.
Gibbons et al. employed an AZ-doped PI film to control
LMWLC alignment by LPL. They demonstrated that the
direction of the homogeneous alignment of LC molecules
can be altered by changing the polarization direction of
LPL.
A NLC cell fabricated from one substrate coated with an
AZ/PI mixture and the other substrate coated only with PI,
with the rubbing directions of both substrates mutually
parallel, was exposed to LPL with polarization parallel to the
rubbing direction. It was revealed that the alignment of LC
molecules at the irradiated area of dye-doped surface
changed from rubbing direction to perpendicular to the
polarization of LPL, whereas those at the un-doped PI
surface remained unchangeable, resulting in a TN structure
within the irradiated region.
The photoalignment can be subsequently erased or

rewritten by altering the polarization of LPL to induce a
change in AZ alignment. Furthermore, unidirectional
alignment of LCs has been also achieved by PVA thin
films containing AZ dyes.
3.2.2. Linearly photo-dimerized (LPD) Method

Different from photoisomerization of AZ dyes, Schadt et al.
developed a novel photoalignment method based on
anisotropic photocrosslinking of optically active molecules.
One linearly photo-dimerized (LPD) method is
illustrated for alignment layers using poly(vinyl
cinnamate)(), in which photo-dimerization
of cinnamates ( ) in the side chain occurs
anisotropically, leading to optical dichroism in films.
<Def> Photo-dimerization ()
A bimolecular photochemical process involving an
electronically
excited unsaturated molecule that
undergoes addition with an unexcited molecule of the
same species.
The formed cyclobutane ( ) derivatives and

hydrocarbon chains result in anisotropically dispersive
surface interactions with LC molecules, which is
responsible for the homogeneous alignment of LCs,
perpendicular to the polarization direction of the
irradiated LPL.
Other photosensitive polymers like epoxy, PI and
polyurethane with cinnamates in side chain also showed a
similar photoalignment behavior.
Fig. 3B
Photoalignment
methods of
LMWLC molecules.
B) Linearly photodimerized (LPD)
method.
3.2.3. Photoactive PI
The main problem hindering commercial exploitation of
photoalignment layers is their poor thermal stability.
Therefore, much attention was back paid to PIs due to
the high thermal stability of LC alignment.
A unique LC alignment technique based on a novel
principle has been proposed: a dynamic and static control
of LCs by means of photoactive PIs as alignment layers.
The most significant feature of this system is to control
LC alignment without photochemical reactions.

Aromatic ( ) PIs exposed to LPL with a longer

wavelength were reported to show a high efficiency of
photoalignment without any significant change in
chemical structures of PIs.
To evaluate the alignment, a PI film formed on a glass
substrate was irradiated with LPL at 366 nm, and then an
LC cell was fabricated with two pieces of these exposed
PI-coated substrates, sandwiching with 5CB between
them. It has been demonstrated that unidirectionally
homogeneous alignment of 5CB is successfully induced
with the photo active PI film.

Fig. 3C The alignment layer prepared by exposure to LPL

after completing imidization () of PAA (
) films enables LC alignment perpendicular to
the polarization of LPL. However, if LPL exposure is carried
out during thermal imidization of PAA, alignment of LC
molecules was induced parallel to the polarization of LPL.
This approach is referred to as the in-situ method,
which might restrain the degradation process since the
photoirradiation and thermally-induced imide cyclization
were performed simultaneously.
With the same structure of a
photo active PI, two different LC
alignment directions can be
conveniently achieved upon
exposure to LPL merely by
changing the thermal-treatment
process.
Fig. 3C
<ex> (polyimidePI)1
(polyamic acidPAA)
(thermal imidization)
IC
IC (Passivation
coating)LCD

3.3. Phototuning of Cholesteric LCs (CLCs)

Fig. 4A Cholesteric LCs (CLCs) can self-assemble into a
helically ordered structure with a helical pitch (p) in an
order of wavelength of visible light. One of their unique
optical properties is selective reflection of light when their
helix axes are perpendicular to the LC cell surface. The
wavelength () of the reflective light is determined by p
and the angle of incidence from the cell normal which
can be calculated by
= navpcos.
Fig. 4A
Selective reflection of CLC
If the helical pitch of the CLCs can be tuned by light,

photocontrol of selective reflection could be achieved.
Furthermore, as the helical pitch is very sensitive to
temperature, pressure and impurity, the wavelength of
the selective reflection is also strongly dependent on
these factors.
Fig. 4A Phototuning of CLCs.

A) Scheme of photocontrol of helical structures.
CLCs are expected as active media for reflection-type

displays, particularly if the wavelength of the reflective
light is in the visible region, these CLC materials are
highly potential for full-color LCDs with high quality and
extremely low energy consumption.
It has been demonstrated that CLCs can be induced in a
NLC system by doping chiral compounds, which provides
a good chance for phototuning of helical structures via
introducing photochromic molecules.
Helical twisting power (HTP), defined as the ability of a
chiral group to induce a CLC phase in a NLC host, can be
used to describe the photocontrol of CLCs.
HTP = 1/pc,
where c is the dopant concentration. Thus, a higher HTP
value requires less chiral dopant to yield the same value
of wavelength.
HTP depends on the dipole-quadruple interactions of

the chiral molecules with its nematic neighbors, the
optical anisotropy (n) of the nematic host phase, and
the order parameter (S).
Sackman first reported the photochemical change in
alignment of CLCs by irradiating a mixture of AZ
dispersed CLCs. It was found that the CLC pitch could be
altered by this photochemical process, which was
confirmed by the change in the wavelength of reflection
light.

Fig. 4B In addition to AZ chromophores, many studies

have been carried out on phototuning of helical structures
of CLCs through photoisomerization of various types of
photochromic compounds, with/without chiral groups in
molecules, such as stilbenes, diarylethenes, overcrowded
alkenes, menthones, flugides, spiropyran and so on.
In these CLC systems, the photochromic compounds
with chiral groups are dissolved in NLCs, and the induced
helical structures are photocontrollable, leading to a
difference
in
HTP
among
isomers
through
photochemically-induced
change
in
molecular
configurations.

Fig. 4A Phototuning of CLCs. B) Various photochromic molecules

used in the photochemical induced change
(1) AZ; (2) diarylethene; (3) overcrowded alkene; (4) fulgide; (5)
spiropyran; (6) menthane. UV: ultraviolet light

Optical switching of selectively reflective colors was

investigated based on photoinduced change in the helical
pitch of CLCs doped with a chiral AZ. Photoirradiation of
CLCs containing chiral AZ resulted in a change in the
helical pitch due to trans-cis isomerization of the chiral AZ,
followed by the change in reflective band. Such a change
in p can be interpreted in terms of change in phase
transition temperature caused by changing the molecular
shape of the guest AZs.

Figure 8. Change in transmittance of CNLC cell at 633 nm

under various handedness induced by alternate irradiation at
366 nm (B, 15 mW cm-2) and >420 nm (G). Transmittance was
followed with a left-handed circularly polarized wavw.

3.6. Photoinduced Phase Transition in

LMWLC/Polymer Composites
Microphase separation occurring in LMWLC/polymer
composites scatters the visible light because of the
formed large domain size (on the order of m), resulting
in poor optical transparence (an opaque state). Exerted
with an external E-field, a highly transparent sate can be
obtained by eliminating the scattering from the
micrometer-sized domains.
Different from LC film in LCD, the composite film does not
need any polarizers to show the scattering/transparent
contrast and exhibit high processability and flexibility
because of no need of alignment layers, so that they have
been extensively explored in recent year for practical
applications.
Several kinds of LMWLC/polymer composites have been

explored, including nematic curvilinear aligned phase
materials with an encapsulated LC structure, polymerdispersed LCs (PDLCs) with LC droplets dispersed in a
polymer matrix by means of polymerization-induced or
solvent-induced phase separation, polymer network LCs
(PNLC) with micrometer-scaled LC domains, and
polymer-stabilized LCs (PSLC) with a small amount of
polymer network.

Photoinduced phase transition in the microphaseseparated domains of LMWLC/polymer composites may

give rise to novel optical effects.
<ex> Takizawa et al. reported a photonic application of
the LMWLC/polymer composite films: a spatial light
modulator (SLM) that displays large images on a screen
by projecting an image created on a small valve.
<ex> Kajiyama et al. showed light addressing and optical
image recording by means of LMWLC/polymer
composite films showing electric field frequencydependent optical properties.

In confined polymer matrices by microphase separation,

the photocontrollable LMWLC/polymer composite films
driven by photon-mode process without electric fields
have been achieved via photochemical phase transitions.
<ex> Kawanishi et al. prepared polymer/LMWLC
composite films with a thickness of 23m using a
mixture of a NLC and an AZ derivative dispersed in an
aqueous solution of PVA by solvent-induced phase
separation. Although the composite films showed very
low transmittance because of opacity, they became
transparent upon irradiation at 366 nm, resulting from
nematic LC-isotropic phase transitions of LC droplets
within the polymer matrix due to trans-cis isomerization
of AZs. The recovery of the initial opaque state could be
achieved by irradiation of visible light to cause cis-trans
back-isomerization of the AZs.

Examples of LMWLC/Polymer Composites
Selective color filter

Smart window
Flexible display
E-paper
3.7. Photocontrolled Orientation of LMWLCs by

Photophysical Processes
Upon LPL irradiation, photoactive LMWLCs can be
photomanipulated into ordered states by photochemical
processes. According to the Weigert effect, the
transition moments of LMWLC molecules can be
photocontrolled perpendicularly to the polarization
direction of the actinic light. AZ-containing LCs and
AZ/LMWLC gust-host systems are typical for such kind of
photoalignment.
Fig.
8A
Photocontrolled
orientation of LMWLCs with
photochemical
and
photophysical processes A)
The Weigert, Jnossy and
photothermal effects induce
the
alignment
of
LCs
perpendicular, parallel and
random to the polarization
direction of the actinic light.
Different from the photochemical

processes, Jnossy et al. found that a
small amount of certain anthraquinone
dye (AQ dye) dissolved in a NLC, which
makes the system absorb light and
undergoes only photophysical process
upon excitation. Jnossy effect
induces an LC alignment parallel to the
direction of LPL, which has attracted
considerable attention since such
highly light-sensitive dyes are of great
interest for optical applications.
Fig.
8A
Photocontrolled
orientation of LMWLCs with
photochemical
and
photophysical processes A)
The Weigert, Jnossy and
photothermal effects induce
the
alignment
of
LCs
perpendicular, parallel and
random to the polarization
direction of the actinic light.
Unlike photochemical and photophysical effects for orderorder transition processes, photothermal effect
induces an orderdisorder transition, which brings about
random arrangement of LMWLCs (Fig. 8A). Such an
effect is the simplest effect connected with light
absorption.
* In general, LMWLCs show large temperature gradients of
refractive indices, dne/dt and dno/dt. The changes in LC
alignment are observed due to light absorption and
heating of the LCs. For instance, ne of 5CB decreases
from 1.682 to 1.635, and no of 5CB increases from 1.517
to 1.532 with an increase in temperature from 23 to 35oC,
respectively. This temperature dependence of ne(T) and
no(T) may be interpreted in terms of the change in an
order parameter of the LC and the change in density.
Photoinduced director reorientation of LMWLCs by

photophysical processes gives rise to a large change in
refractive index measured by incident beams. The
reorientated LCs can in turn affect the optical properties of
the incident beams.
<ex> When a laser beam with a Gaussian traversing intensity
distribution is used as an excitation source, non-uniform
director reorientation corresponding to the traversing
intensity profile leads to a spatial self-phase modulation,
resulting in a self-socusing. Once the phase difference of the
light between the beam center and edge is larger than 2,
self-diffraction of the incident light can be observed, leading
to the formation of typical diffraction rings on the screen.
Fig.
8B
Schematic
illustration
of
selfphase
modulation
effect and self-focusing
effect,
leading
to
typical diffraction
rings formed on the
screen.
As one of the applications of the Jnossy effect of

LMWLCs, planar microlenses and microlens arrays were
fabricated by combination of photophysically-induced
reorientation of dye-doped LC/monomer mixtures with
their simultaneous photopolymerization.
Fig. 8D Microlens array

fabricated by combination
of
photoinduced
reorientation
of
dyedoped
LC/monomer
mixtures & simultaneous
photopolymerization.
Photoisomerization
Azobenzene may exist as two geometric isomers, the
trans & cis form (E & Z forms). These two configurations
differ in the direction of the central bonds.
In the energetically stable trans state the two bonds
linking the azobenzene group to the aromatic rings are
parallel, resulting in an elongated shape of the molecule.
In the metastable cis state the molecules adopt a bent
conformation.
The two isomers also differ in their

absorption spectra. The absorption
spectrum of trans-azobenzene exhibits a
maximum at around 350nm due to the * electronic transition and another at
around 440nm due to the n-* transition.
350360nm
440450nm

Attractive feature is that the two forms are interconvertible by the use of actinic light.
The absorption of one light quantum of radiation in the
UV region (~350 nm) results in the EZ transformation
accompanied by changes in electronic spectra of the
material, the phenomenon being called photochromism.
On the other hand, the Z isomer can be converted back
to the E isomer by shining visible light (~440nm).
Since the E isomer is energetically more

stable than the Z isomer, the back
conversion also occurs spontaneously,
through a process known as thermal
back relaxation (TBR).
Temperature, host environment, type
of dye, and excitation wavelength are
among the parameters, which play a
decisive role in the character of
photoisomerization. p.11
Visible, UV
Weigert Effect
Trans-AZ exhibit -* transition moments approximately
parallel to the molecular long axis, thereby the trans-AZ
show angular-dependent absorption of LPL: trans-AZ
molecules with their transition moments parallel to the
polarization direction of LPL are activated very effectively to
their excited states, followed by trans-cis isomerization,
while molecules with their transition moments perpendicular
to the polarization direction of actinic light are inactive
towards isomerization.
After repetition of trans-cis-trans isomerization cycles, once
trans-AZ molecules have fallen perpendicular to the
polarization direction of the actinic light, they become
inactive towards the incident radiation. This means that at
the end of the multicycles, there will be a net population of
AZ molecules aligned perpendicular to the light polarization.
This is well known as the Weigert effect.
Transition
moment
E
inactivated
E
Transition
moment
// E
activated
Jnossy Effect
The accepted mechanism attributes the dye-induced
reorientation to selective excitation of dye molecules and a
consequent large change in guest-host interaction when dye
molecules are photoexcited.
1) Excitation of dye molecules with linearly polarized light
generates an anisotropic population of excited dye
molecules.
2) Relaxation to an equilibrium distribution of the dye molecule
in LC hosts produces a torque on the LC director. The
torque from excited dye molecules tends to reorient LC
hosts parallel to the excited dye molecules, e.g., parallel to
the polarization direction of the incident light. The torque
from ground dye molecules tends to reorient LC hosts
perpendicular to the light polarization.
If these two torques can not compensate each other, light

will generate an anisotropic molecular mean-field acting on
LC hosts and induce director reorientation.
The overall torque (d) on LC molecules exerted by guest
dye molecules is written in the form
where 0 is the optical electric field-induced reorientation

torque and is an enhancement factor of a dye in certain
guest-host LC systems.
If the intermolecular interaction between excited dye
molecules and host LC molecules is larger than that
between ground-state dye molecules and host molecules,
LC hosts tend to become aligned parallel to the light
polarization. experimental results showed.
Molecular cooperative motion

As mentioned above, LC molecules exhibit good cooperative
motion; thus, if a small portion of the LC molecules change
their alignment in response to an external stimulus, the
alignment of other LC molecules also changes (domino
effect()).
It has been proposed that an amount of energy so small as
to induce an alignment change of only 1 mol% of the LC
molecules is enough to bring about an alignment change of
the whole system.

CH3 Photo-Stimulated Phase Transformations of LCs Photocontrollable LC Actuators I 102 上課版

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CH3 Photo-Stimulated Phase Transformations of LCs Photocontrollable LC Actuators I 102 上課版

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3 Photo-Stimulated Phase

Transformations of LCs &

Combined with LCs photoresponsive properties,

Y fluidity with long-range order

Z molecular & supramolecular cooperative motion (MCM

Based on the alignment of rod-like molecules, LCs can

Since LC molecules can change the polarization

By Prof. Chia-Rong Lee

By Prof. Chia-Rong Lee

2.1. Photomodulation of LMWLCs and LCPs

LPL with E-vector oscillating in the vertical direction

Different from the order-order change in Fig. 1A(1), Figs.

By Prof. Chia-Rong Lee

2.2. Photomodulation of LCEs

The deformation of LCEs can be induced by actinic light,

By Prof. Chia-Rong Lee

When the alignment of LC molecules is parallel to the

By Prof. Chia-Rong Lee

Furthermore, the photomechanical behavior is reversible if

2.3. Photomodulation of LCBCs

By the interplay processes between regular periodicity of LC

By Prof. Chia-Rong Lee

The supramolecularly assembled nanostructures in LCBC films

The engrossing LC materials for photocontrollable

Fig. 2A Two isomerization states are a thermally stable

Fig. 2A Photoinduced phase transition and its mechanism in AZ and

Fig. 2B Photoinduced NLC-isotropic (N-I) phase transition

Fig. 2B Photoinduced phase transition of AZ LCs, in which

By Prof. Chia-Rong Lee

Fig. 2C Even though the AZ molecules show no LC

By Prof. Chia-Rong Lee

When a small amount of photochromic molecules is

Since the trans-AZ is in a rodlike shape, which

The LC-isotropic phase transition temperature (Tc) of

By Prof. Chia-Rong Lee

The photoinduced phase transitions are interpreted in

By Prof. Chia-Rong Lee

Photoisomerization is usually reversible, and with

By Prof. Chia-Rong Lee

Fig. 2 D Upon photoirradiation of 5CB/trans-AZ, dark

The photochemical phase transition in the AZ/photoinert

By Prof. Chia-Rong Lee

3.2. Photoalignment Layers

By Prof. Chia-Rong Lee

LCs can be aligned along the rubbing direction on

By Prof. Chia-Rong Lee

Moreover, the rubbing method can only be applied on flat

By Prof. Chia-Rong Lee

Linearly photodimerized (LPD)

By Prof. Chia-Rong Lee

3.2.1. Command Surface

(2) The photoalignment effect of AZ dyes does not limited

The photoalignment can be subsequently erased or

3.2.2. Linearly photo-dimerized (LPD) Method

The formed cyclobutane ( ) derivatives and

By Prof. Chia-Rong Lee

Aromatic ( ) PIs exposed to LPL with a longer

By Prof. Chia-Rong Lee

Fig. 3C The alignment layer prepared by exposure to LPL

By Prof. Chia-Rong Lee

3.3. Phototuning of Cholesteric LCs (CLCs)

If the helical pitch of the CLCs can be tuned by light,

Fig. 4A Phototuning of CLCs.

CLCs are expected as active media for reflection-type