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, 2149–2180
7. Outlook
Haifeng Yu and Tomiki Ikeda
* Q. Li, Liquid Crystal Beyond Display
By Prof. Chia-Rong Lee
Liquid crystal Photonics lab.

1. Introduction
ƒ 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.
ƒ 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.
By Prof. Chia-Rong Lee
Liquid crystal Photonics lab.

ƒ Combined with LC’s photoresponsive properties,
photocontrollable LC actuators (光控致動器) have
enabled a variety of applications in various fields
including FPD, photonics, photo-driven devices, and more
recently nanotechnology.
ƒ The LC’s 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

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

. photomechanical and photomobile effects in LCEs. the transmittance through a pair of crossed polarizers. As a result. but also gives rise to some engrossing phenomena. decreases due to the loss of birefringence. e. ƒ Modulation of LC alignment not only induces an extreme change in refractive index (which is very difficult to achieve with amorphous materials). and SMCM in LC block copolymers (LCBCs). with the LC cell placed between them. .g. Chia-Rong Lee Liquid crystal Photonics lab. By Prof.→ Since LC molecules can change the polarization direction of light when linearly polarized light (LPL) passes them. MCM in LMWLCs and LC polymers (LCPs). a bright/dark contrast is produced at each pixel. and 2D images can be displayed in the flat panel of LCDs.

polarization. Photomodulation of LCs ƒ On one hand. Both of them are the bases of LC actuators for photonic applications.2. Chia-Rong Lee Liquid crystal Photonics lab. ƒ As one of green and neat energies. By Prof. LC materials with photo-active functions can be easily photo-modulated into hierarchical patterns by adjusting the actinic light with wavelength. light is particularly fascinating since it supplies precise and reversible controls with a noncontact way. wavefront modulation. intensity. LCs have been widely utilized as good light actuators for beam steering. the change in LC alignment can also be reflected by its optical properties. phase retardation. . interference. and so on. phase retardation. and polarization switching and control. On the other hand.

.Fig. LCPs. 1 Different ways of photocontrollable LC actuators in various LCassociated materials — LMWLCs. LCEs and LCBCs By Prof. Chia-Rong Lee Liquid crystal Photonics lab.

.1. respectively. LC materials show different refractive indices of ne and no. Fig. the photomodulation among three states of LC alignment can be easily obtained by choosing suitable input actinic light. when they are in parallel and perpendicular alignment (ordered states) and in a random isotropic phase (disordered state). Chia-Rong Lee Liquid crystal Photonics lab. and ni (isotropic).2. Detecting with LPL. 1A ni By Prof. Photomodulation of LMWLCs and LCPs ƒ In LMWLCs and LCPs.

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. . when LC molecules are in vertical alignment. Chia-Rong Lee Liquid crystal Photonics lab. 1A By Prof.ƒ LPL with E-vector oscillating in the vertical direction detects ne. ni Fig.

. although the order-disorder changes still give a large alteration of refractive index comparing with amorphous materials.ƒ Different from the order-order change in Fig. thereby the change in the LC directors (order-order change) gives rise to a larger change in refractive index than the order-disorder changes. 1A By Prof. 1A(2) & 1A(3) are order-disorder changes. ni Fig. The order of the refractive index is usually ne >ni >no. which are correlated with ne–ni and ni–no. respectively. Chia-Rong Lee Liquid crystal Photonics lab. Figs. 1A(1).

Photomodulation of LCEs ƒ In LCEs. ƒ A large change in volume of LCEs enables them to be explored as novel materials for artificial muscles and soft actuators. Chia-Rong Lee Liquid crystal Photonics lab. .2. By Prof. 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. ƒ 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.2. which was then developed and experimentally obtained by Finkelmann et al.

ƒ The deformation of LCEs can be induced by actinic light. bringing about photomechanical and photo-mobile properties of LCEs. 1B By Prof. ƒ Upon irradiation. . Chia-Rong Lee Liquid crystal Photonics lab. Fig. 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 μm). which induces the volume change only in film surface and generates photomechanical effect.

contributing to the anisotropic bending behavior towards a light source. Chia-Rong Lee Liquid crystal Photonics lab.ƒ When the alignment of LC molecules is parallel to the surface of substrates. ƒ On the contrary. resulted in different bending behavior. Fig. volume expansion is brought about when the LC molecules are aligned perpendicularly to the substrates. away from the light source. volume contraction is produced just along this pre-aligned direction. 1B By Prof. .

By this way. 1B By Prof.ƒ Furthermore. the photomechanical behavior is reversible if azobenzene (AZ) molecules are used as photoresponsive mesogens. Fig. Chia-Rong Lee Liquid crystal Photonics lab. which attracts much attention of scientists in the present LC research. . light energy can be directly transferred into mechanical energy.

3.2. 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. . Chia-Rong Lee Liquid crystal Photonics lab. 1C By Prof. Fig. Photomodulation of LCBCs ƒ In LCBCs with at least one LCP chain as one constituent block.

ƒ By the interplay processes between regular periodicity of LC ordering and thermally controlled microphase separation. . Fig. 1C By Prof. leading to periodically ordered nanostructures. 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. Chia-Rong Lee Liquid crystal Photonics lab. ƒ The orientation of the hierarchically assembled nanomaterials strongly correlated with the LC alignment. the ordering of mesogens can be transferred to the nanostructures inside them.

. which provides reliable templates for nanofabrication processes and leads to widely applications in macromolecular engineering.ƒ The supramolecularly assembled nanostructures in LCBC films show excellent reproducibility and mass production. Chia-Rong Lee Liquid crystal Photonics lab. Fig. 1C By Prof.

ƒ 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.
ƒ 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.
ƒ 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.
By Prof. Chia-Rong Lee
Liquid crystal Photonics lab.

3. LMWLC Actuators
3.1. Photoinduced Phase Transition
ƒ A photochromic molecule shows reversible photochemical
reactions, such as
X photoisomerization (光致異構) and Y photo-dimerization
(光致二聚), which is often accompanied by a change in
its molecular configuration.
ƒ Azobenzenes (AZs) are one of the typical chromophores
(發色團), famous for their photoisomerization with a
large change in molecular structures, which have been
widely used as ultra-small phototriggers (光觸發器) for
LC actuators in gust/host mixtures.
By Prof. Chia-Rong Lee
Liquid crystal Photonics lab.

ƒ 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 AZ’s
substitution.

Fig. 2A Photoinduced phase transition and its mechanism in AZ and
AZ/photoinert LC mixture. A) Photoisomerization of an AZ molecule.
By Prof. Chia-Rong Lee
Liquid crystal Photonics lab.

ƒ Fig. . a dark image is obtained in the UV-irradiated area due to the lost of birefringence in an isotropic phase. in which an AZ acts as both a mesogen and a photosensitive moiety. Fig. Chia-Rong Lee Liquid crystal Photonics lab. 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. 2B Photoinduced phase transition of AZ LCs. By Prof.

. → In fact. triggered by actinic light. 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. they can be used to photo-modulate photoinert mesogens via the LC inherent property of MCM (molecular cooperative motion). 2C Even though the AZ molecules show no LC phase. By Prof. a huge amplification is possible in LC photonic systems owing to the phototriggered MCM. Chia-Rong Lee Liquid crystal Photonics lab.ƒ Fig. That is to say. the other LC molecules nearby also change their alignment. → If a small mole proportion of LC molecules changes their alignment in response to an external stimulus. coinciding with the pre-aligned LCs — called MCM.

. Chia-Rong Lee Liquid crystal Photonics lab. 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.When a small amount of photochromic molecules is incorporated into LC molecules and the resulting host/guest mixtures are irradiated. By Prof. an N-I phase transition can be isothermally photoinduced. which stabilizes the phase structure of an LC phase. <ex> Isothermally Photoinduced transition in AZ/NLC mixtures NLC-isotropic phase Since the trans-AZ is in a rodlike shape.

and the sample is irradiated to cause trans→cis photoisomerization of AZ guest molecules. then Tc decreases with an accumulation of the number of cis-isomer. Chia-Rong Lee Liquid crystal Photonics lab. Fig. the LC-isotropic phase transition is induced. When Tc becomes lower than the irradiation temperature (T). 2C Phase diagram of photo chemical phase transition of AZ/photoinert LC mixture systems. . If the temperature (T) of the mixture is set between Tct and Tcc (Tcc < T < Tct ). By Prof.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).

the amount of cis-AZ needed to lower Tc below the irradiation temperature is small. no phase transition is induced. ΔT=Tct–Tcc is one of the most important parameters in the phase transition. enabling one to effectively photoinduce phase transition. Chia-Rong Lee Liquid crystal Photonics lab. . 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. When the temperature is set close to Tct. By Prof. Fig. When the temperature of LC mixtures is set below Tcc.

This means that phase transitions of LC systems can be reversibly induced by photochemical reactions of photoresponsive guest molecules. Moreover. . and with cis→trans back-isomerization the sample can revert to the initial LC phase by photo or thermal treatment. the molecular structures of chromophores greatly influence the photoinduced phase transition of host/guest LC mixtures. By Prof. Chia-Rong Lee Liquid crystal Photonics lab.ƒ Photoisomerization is usually reversible.

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. 2D Mechanism of photochemical phase transition in AZ/photoinert LC systems. Fig. Increasing the irradiated dose. .ƒ Fig. 2 D Upon photoirradiation of 5CB/trans-AZ. 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.

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

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. In fabrication of commercialized LCDs.2. Photoalignment Layers ƒ LMWLCs change their pre-alignment directors under an electric field.3. Chia-Rong Lee Liquid crystal Photonics lab. in which one of the most successful applications is LCD. 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. By Prof. .

By Prof. which may cause serious problems such as the speckles (污跡) and reduced display contrast of LCDs. . which has been widely used in the present LCD industry. Chia-Rong Lee Liquid crystal Photonics lab.ƒ LCs can be aligned along the rubbing direction on polyimide (PI) films because of the lower energy level along the unidirectional rubbing-induced grooves. But the rubbing method has some obvious demerits such as the contaminated dust and static charge produced during the rubbing process.

which shows no function on curves. Therefore. the rubbing method can only be applied on flat surfaces. degradation. 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. . Chia-Rong Lee Liquid crystal Photonics lab. According to reaction mechanism. photocrosslinking and photo- By Prof. the photoalignment of LMWLCs on surfaces of alignment layers can be divided into: photoisomerization.ƒ Moreover.

Command Surface Linearly photodimerized (LPD) Method Photoactive PI By Prof. Chia-Rong Lee Liquid crystal Photonics lab. .

3A Photoalignment methods of LMWLC molecules. Light irradiation to cause trans-cis isomerization of AZs enables LC alignment to repeatedly change from homeotropic to planar states. Command Surface (1) Ichimura et al. By Prof.1. Fig. Chia-Rong Lee Liquid crystal Photonics lab. first reported possibility of photoalignment of LCs with self-assembled monolayers of AZ dyes formed on glass substrates. . NLCs show a homeotropic alignment when AZs immobilized on the substrates are in the trans form. In LC cells made from the surface-treated substrates. Similarly. A) Command surface.2.3. photoinduced alignment change in plane can be acquired by the “command surfaces” via photoalignment of AZs in plane.

By Prof.(2) The photoalignment effect of AZ dyes does not limited on the surface. with the rubbing directions of both substrates mutually parallel. and a similar effect was found in volume of polymer films doped with AZ molecules. Chia-Rong Lee Liquid crystal Photonics lab. employed an AZ-doped PI film to control LMWLC alignment by LPL. . Gibbons et al. whereas those at the un-doped PI surface remained unchangeable. They demonstrated that the direction of the homogeneous alignment of LC molecules can be altered by changing the polarization direction of LPL. 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. was exposed to LPL with polarization parallel to the rubbing direction. Â A NLC cell fabricated from one substrate coated with an AZ/PI mixture and the other substrate coated only with PI. resulting in a TN structure within the irradiated region.

.ƒ 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. By Prof. Chia-Rong Lee Liquid crystal Photonics lab.

Schadt et al. developed a novel photoalignment method based on anisotropic photocrosslinking of optically active molecules.3. Chia-Rong Lee Liquid crystal Photonics lab. Linearly photo-dimerized (LPD) Method ƒ Different from photoisomerization of AZ dyes. .2. <Def> Photo-dimerization (光致二聚反應) A bimolecular photochemical process involving an electronically excited unsaturated molecule that undergoes addition with an unexcited molecule of the same species. One linearly photo-dimerized (LPD) method is illustrated for alignment layers using poly(vinyl cinnamate)(聚肉桂酸乙烯酯). leading to optical dichroism in films. in which photo-dimerization of cinnamates ( 桂 皮 酸 鹽 ) in the side chain occurs anisotropically. By Prof.2.

Other photosensitive polymers like epoxy. By Prof.The formed cyclobutane ( 環 丁 烷 ) derivatives and hydrocarbon chains result in anisotropically dispersive surface interactions with LC molecules. PI and polyurethane with cinnamates in side chain also showed a similar photoalignment behavior. Chia-Rong Lee Liquid crystal Photonics lab. B) Linearly photodimerized (LPD) method. which is responsible for the homogeneous alignment of LCs. 3B Photoalignment methods of LMWLC molecules. perpendicular to the polarization direction of the irradiated LPL. . Fig.

 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. much attention was back paid to PIs due to the high thermal stability of LC alignment. Photoactive PI ƒ The main problem hindering commercial exploitation of photoalignment layers is their poor thermal stability.3. . The most significant feature of this system is to control LC alignment without photochemical reactions.2. Therefore.3. By Prof. Chia-Rong Lee Liquid crystal Photonics lab.

It has been demonstrated that unidirectionally homogeneous alignment of 5CB is successfully induced with the photo active PI film. . Chia-Rong Lee Liquid crystal Photonics lab. and then an LC cell was fabricated with two pieces of these exposed PI-coated substrates. By Prof.ƒ Aromatic ( 芳 香 族 ) 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. sandwiching with 5CB between them. a PI film formed on a glass substrate was irradiated with LPL at 366 nm.

3C By Prof. Chia-Rong Lee Liquid crystal Photonics lab. However. 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. This approach is referred to as the in-situ method. 3C The alignment layer prepared by exposure to LPL after completing imidization (高溫熟化脫水) of PAA (聚醯 胺酸高分子) films enables LC alignment perpendicular to the polarization of LPL. which might restrain the degradation process since the photoirradiation and thermally-induced imide cyclization were performed simultaneously. . if LPL exposure is carried out during thermal imidization of PAA.ƒ Fig. alignment of LC molecules was induced parallel to the polarization of LPL.

.<ex> 聚醯亞胺(polyimide;PI)薄膜是1種含有醯亞胺基的有機 高分子材料,其製備方式主要是由雙胺類及雙酣類反應聚 合成聚醯胺酸高分子(polyamic acid;PAA),之後經過高溫 熟化脫水(thermal imidization)形成聚醯亞胺高分子。 由於聚醯亞胺薄膜具有優異的熱安定性及良好的機械、 電氣及化學性質,一直是高性能高分子材料的首選,尤其 在對材料要求嚴格的電子IC工業上,一直處於關鍵性材料 的 地 位 , 如 高 溫 膠 帶 、 軟 板 、 IC 的 鈍 化 膜 (Passivation coating)、LCD的配向膜、漆包線等絕緣材等,產值也不斷 地增加中。聚醯亞胺薄膜除應用在電子材料上,如航太、 重機設備及油井等絕緣產業也需要用到。 By Prof. Chia-Rong Lee Liquid crystal Photonics lab.

The wavelength (λ) of the reflective light is determined by p and the angle of incidence θfrom the cell normal which can be calculated by λ = navpcosθ. Chia-Rong Lee Liquid crystal Photonics lab.3. Phototuning of Cholesteric LCs (CLCs) ƒ 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.3. Fig. . One of their unique optical properties is selective reflection of light when their helix axes are perpendicular to the LC cell surface. 4A Selective reflection of CLC By Prof.

pressure and impurity. .ƒ If the helical pitch of the CLCs can be tuned by light. photocontrol of selective reflection could be achieved. Furthermore. the wavelength of the selective reflection is also strongly dependent on these factors. By Prof. 4A Phototuning of CLCs. Chia-Rong Lee Liquid crystal Photonics lab. as the helical pitch is very sensitive to temperature. A) Scheme of photocontrol of helical structures. Fig.

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

which was confirmed by the change in the wavelength of reflection light. and the order parameter (S). It was found that the CLC pitch could be altered by this photochemical process. By Prof. . ƒ Sackman first reported the photochemical change in alignment of CLCs by irradiating a mixture of AZ dispersed CLCs.ƒ HTP depends on the dipole-quadruple interactions of the chiral molecules with its nematic neighbors. the optical anisotropy (Δn) of the nematic host phase. Chia-Rong Lee Liquid crystal Photonics lab.

many studies have been carried out on phototuning of helical structures of CLCs through photoisomerization of various types of photochromic compounds. such as stilbenes. Chia-Rong Lee Liquid crystal Photonics lab. the photochromic compounds with chiral groups are dissolved in NLCs. diarylethenes.ƒ Fig. spiropyran and so on. 4B In addition to AZ chromophores. In these CLC systems. with/without chiral groups in molecules. By Prof. flugides. overcrowded alkenes. and the induced helical structures are photocontrollable. . menthones. leading to a difference in HTP among isomers through photochemically-induced change in molecular configurations.

(4) fulgide. B) Various photochromic molecules used in the photochemical induced change (1) AZ. (6) menthane. (2) diarylethene. (3) overcrowded alkene.Fig. . 4A Phototuning of CLCs. UV: ultraviolet light By Prof. (5) spiropyran. Chia-Rong Lee Liquid crystal Photonics lab.

followed by the change in reflective band. Chia-Rong Lee Liquid crystal Photonics lab. Photoirradiation of CLCs containing chiral AZ resulted in a change in the helical pitch due to trans-cis isomerization of the chiral AZ. . By Prof.ƒ Optical switching of selectively reflective colors was investigated based on photoinduced change in the helical pitch of CLCs doped with a chiral AZ. 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.

By Prof. Chia-Rong Lee Liquid crystal Photonics lab. Transmittance was followed with a left-handed circularly polarized wavw.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).

6. Photoinduced Phase Transition in LMWLC/Polymer Composites ƒ Microphase separation occurring in LMWLC/polymer composites scatters the visible light because of the formed large domain size (on the order of μm). Exerted with an external E-field. so that they have been extensively explored in recent year for practical applications. 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. a highly transparent sate can be obtained by eliminating the scattering from the micrometer-sized domains. Chia-Rong Lee Liquid crystal Photonics lab.3. By Prof. resulting in poor optical transparence (an opaque state). . ƒ Different from LC film in LCD.

including nematic curvilinear aligned phase materials with an encapsulated LC structure. polymer network LCs (PNLC) with micrometer-scaled LC domains. and polymer-stabilized LCs (PSLC) with a small amount of polymer network. polymerdispersed LCs (PDLCs) with LC droplets dispersed in a polymer matrix by means of polymerization-induced or solvent-induced phase separation. Chia-Rong Lee Liquid crystal Photonics lab. . By Prof.ƒ Several kinds of LMWLC/polymer composites have been explored.

Chia-Rong Lee Liquid crystal Photonics lab.ƒ Photoinduced phase transition in the microphaseseparated domains of LMWLC/polymer composites may give rise to novel optical effects. showed light addressing and optical image recording by means of LMWLC/polymer composite films showing electric field frequencydependent optical properties. <ex> Kajiyama 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> Takizawa et al. . By Prof.

prepared polymer/LMWLC composite films with a thickness of 2–3μm using a mixture of a NLC and an AZ derivative dispersed in an aqueous solution of PVA by solvent-induced phase separation. resulting from nematic LC-isotropic phase transitions of LC droplets within the polymer matrix due to trans-cis isomerization of AZs.ƒ 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. By Prof. Chia-Rong Lee Liquid crystal Photonics lab. they became transparent upon irradiation at 366 nm. . Although the composite films showed very low transmittance because of opacity. <ex> Kawanishi et al. The recovery of the initial opaque state could be achieved by irradiation of visible light to cause cis-trans back-isomerization of the AZs.

Chia-Rong Lee Liquid crystal Photonics lab. .By Prof.

. Chia-Rong Lee Liquid crystal Photonics lab.Examples of LMWLC/Polymer Composites Selective color filter Smart window Flexible display E-paper By Prof.

Jánossy and photothermal effects induce the alignment of LCs perpendicular. 8A Photocontrolled orientation of LMWLCs with photochemical and photophysical processes A) The Weigert. photoactive LMWLCs can be photomanipulated into ordered states by photochemical processes. AZ-containing LCs and AZ/LMWLC gust-host systems are typical for such kind of photoalignment.7. parallel and random to the polarization direction of the actinic light. According to the Weigert effect. Photocontrolled Orientation of LMWLCs by Photophysical Processes ƒ Upon LPL irradiation. the transition moments of LMWLC molecules can be photocontrolled perpendicularly to the polarization direction of the actinic light. . Fig.3.

parallel and random to the polarization direction of the actinic light. . found that a small amount of certain anthraquinone dye (AQ dye) dissolved in a NLC. which has attracted considerable attention since such highly light-sensitive dyes are of great interest for optical applications. 8A Photocontrolled orientation of LMWLCs with photochemical and photophysical processes A) The Weigert. Jánossy and photothermal effects induce the alignment of LCs perpendicular. Jánossy et al. Jánossy effect induces an LC alignment parallel to the direction of LPL.ƒ Different from the photochemical processes. which makes the system absorb light and undergoes only photophysical process upon excitation. Fig.

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. * In general. Such an effect is the simplest effect connected with light absorption.635.682 to 1. ne of 5CB decreases from 1. 8A).517 to 1. dne/dt and dno/dt. which brings about random arrangement of LMWLCs (Fig. and no of 5CB increases from 1. LMWLCs show large temperature gradients of refractive indices. . For instance. photothermal effect induces an order–disorder transition.ƒ Unlike photochemical and photophysical effects for orderorder transition processes.532 with an increase in temperature from 23 to 35oC. respectively. The changes in LC alignment are observed due to light absorption and heating of the LCs.

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

Fig. 8D Microlens array fabricated by combination of photoinduced reorientation of dyedoped LC/monomer mixtures & simultaneous photopolymerization.ƒ As one of the applications of the Jánossy 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.

the trans & cis form (E & Z forms).Photoisomerization ƒ Azobenzene may exist as two geometric isomers. In the metastable cis state the molecules adopt a bent conformation. resulting in an elongated shape of the molecule. These two configurations differ in the direction of the central bonds. ƒ In the energetically stable trans state the two bonds linking the azobenzene group to the aromatic rings are parallel. .

The absorption spectrum of trans-azobenzene exhibits a maximum at around 350nm due to the ππ* electronic transition and another at around 440nm due to the n-π* transition. ↑↓ 350‐360 nm 440‐450 nm By Prof. Chia-Rong Lee Liquid crystal Photonics lab. .ƒ The two isomers also differ in their absorption spectra.

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

ƒ Since the E isomer is energetically more stable than the Z isomer. type of dye.11 Visible.  Temperature. the back conversion also occurs spontaneously. host environment. Δ ↑↓ UV . through a process known as thermal back relaxation (TBR). and excitation wavelength are among the parameters. which play a decisive role in the character of photoisomerization.  p.

This is well known as the ‘‘Weigert effect’’. while molecules with their transition moments perpendicular to the polarization direction of actinic light are inactive towards isomerization. ƒ After repetition of trans-cis-trans isomerization cycles. This means that at the end of the multicycles. followed by trans-cis isomerization. they become inactive towards the incident radiation. there will be a net population of AZ molecules aligned perpendicular to the light polarization. . once trans-AZ molecules have fallen perpendicular to the polarization direction of the actinic light. 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.Weigert Effect ƒ Trans-AZ exhibit π-π* transition moments approximately parallel to the molecular long axis.

Transition moment ⊥E ¨ inactivated E Transition moment // E ¨ activated .

The torque from ground dye molecules tends to reorient LC hosts perpendicular to the light polarization.. 2) Relaxation to an equilibrium distribution of the dye molecule in LC hosts produces a torque on the LC director. parallel to the polarization direction of the incident light.Jánossy Effect ƒ 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. The torque from excited dye molecules tends to reorient LC hosts parallel to the excited dye molecules. 1) Excitation of dye molecules with linearly polarized light generates an anisotropic population of excited dye molecules. .g. e.

.

light will generate an anisotropic molecular mean-field acting on LC hosts and induce director reorientation. LC hosts tend to become aligned parallel to the light polarization. If the intermolecular interaction between excited dye molecules and host LC molecules is larger than that between ground-state dye molecules and host molecules. . ¨ experimental results showed. The overall torque (τd) on LC molecules exerted by guest dye molecules is written in the form where τ0 is the optical electric field-induced reorientation torque and η is an enhancement factor of a dye in certain guest-host LC systems.If these two torques can not compensate each other.

. if a small portion of the LC molecules change their alignment in response to an external stimulus. ƒ 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. LC molecules exhibit good cooperative motion.Molecular cooperative motion ƒ As mentioned above. the alignment of other LC molecules also changes (domino effect,骨牌效應(指一事件連鎖性地引起一系列類似事件)). thus.