Photoalignment and Photoinduced Molecular Reorientation of Photosensitive Materials

Abstract

Photosensitive materials for photoalignment of liquid crystals (LCs) and photoinduced molecular reorientation are described, especially focusing on azobenzene-containing materials and photocrosslinkable polymers. All the materials generate photoinduced optical anisotropy by means of linearly polarized (LP) light exposure. The large optical anisotropy is induced when the axis-selective photoreaction is accompanied by molecular reorientation. Ç IntroductionDue to practical applications of the alignment layer of functional materials such as low-molecular-weight liquid crystals (LCs), photoalignment and photoinduced molecular reorientation of photosensitive films have received much attention. 13 Additionally, these films have been investigated for molecularly oriented birefringent devices due to the absence of mechanical damage, absence of electric charge, and patterning ability.13 Photoinduced optical and physical anisotropies can be generated in a photoreactive polymeric film by light exposure because the photoreaction changes the inherent refractive index of the molecules. Irradiating with linearly polarized (LP) light causes the photosensitive molecules parallel to the polarization (E) of LP light (y axis) to preferentially photoreact (Figure 1). This axis-selective photoreaction leads to optical anisotropy (birefringence) between the y axis and xz plane if the photoreaction changes the inherent refractive indices of the molecules.To obtain uniaxial alignment of LCs on thin polymeric films, the LC photoalignment layer should exhibit optical or physical anisotropy. Under this circumstance, a large molecular orientation of the film is unnecessary. The anisotropic interaction between the photoalignment layer and LC molecules induces uniaxially oriented LC molecules.1 Because the axis-selective photoreaction induces a small change in the refractive index of the photoalignment layer, 4 a thick film is necessary for optically anisotropic devices such as a birefringent film. Consequently, a large optical anisotropy in the photoreacted film is generated when molecular reorientation occurs during an anisotropic photoreaction. 3Various types of materials that undergo an axis-selective photoreaction to generate photoinduced optical anisotropy have been investigated, including azobenzene-containing polymers 2,57 and photocrosslinkable polymers. 1,3,4 For the azobenzene molecules, axis-selective photoisomerization is generated when the film is irradiated with linearly polarized (LP) light (Figure 2a). Similarly, irradiating with LP ultraviolet (LPUV) light induces both axis-selective [2 + 2] photo/cycloaddition (photocrosslinking) reaction and photoisomerization for cinnamic ester derivatives (Figure 2b). Low-molecular LC molecules easily align on these anisotropically photoreacted films. When an axis-selective photoreaction occurs without generating molecular reorientation, the photoinduced birefringence (¦n) is less than 0.01. 4 An anisotropic photoreaction combined with molecular motion may generate a large optica...

Designs of Plasmonic Metamasks for Photopatterning Molecular Orientations in Liquid Crystals

“…Photoalignment originates from the anisotropic molecular orientations in photoactive materials such as azo-dyes induced by linearly polarized light [28][29][30][31]. In particular, molecules with an azobenzene group tend to orient perpendicularly to the incident polarization to minimize optical absorption.…”

Comparison Study on Thermally Stimulated Photoinduced Orientation of Liquid Crystalline Polymer with Cinnamate Side Groups using 313 nm and 365 nm Light

“…When the photoreacted film exhibits LC characteristics, the photoinduced small anisotropy is occasionally amplified by annealing; the photoinduced reorientation with self-organization of LC moieties in the polymeric films has been investigated in the axis-selectively photoisomerizable and photo-cross-linkable groups of LC polymer (LCP) systems [11][12][13][14]. In these cases, a small amount of photoproducts, which is axis-selectively formed, plays an important role in the thermally stimulated molecular reorientation of the LCP films.…”

New strategies and implications for the photoalignment of liquid crystalline polymers

“…Photochromic reactions have frequently been incorporated in LC media because of their repeatability for controlling material properties. This approach has provided various types of smart, light-responsive materials 1 exhibiting surface-mediated photoalignment of LC materials, [2][3][4][5][6] photoinduced phase transitions, [7][8][9][10][11][12] photoorientation/addressing of polymer thin films, [13][14][15][16][17][18] photoinduced mass migrations, [19][20][21][22][23][24][25][26][27][28] phototactic sliding motions, [29][30][31] photo-driven motions and morphology of monolayers, [32][33][34][35] and macroscopic photomechanical deformations. [36][37][38][39][40][41][42][43][44][45][46] Photoalignment research and technology started in 1988 with the discovery of the reversible alignment control of nematic LCs by the photoisomerization of azobenzene on a substra...…”