Photoalignment of liquid crystals and development of novel glassy liquid crystals.

摘要

This thesis consists of two parts: (i) photoalignment of liquid crystals, including a nematic fluid, a glassy-namtic pentafluorene, and a cholesteric glassy liquid crystal; and (ii) development of cholesteric glassy liquid crystals comprising a hybrid chiral-nematic mesogen and of photochromic glassy liquid crystals with dithienylethene cores. Photoalignment behaviors were interpreted in terms of the kinetics of axis-selective photodimerization, the rotational mobility of pendant coumarin monomers, and the coumarin monomer's and dimer's absorption dipoles located by computational chemistry. Coumarin-containing polymethacrylate films were employed to elucidate the roles played by coumarin monomer's and dimer's orientational order, their relative abundance, and the energetics of their interactions with overlying liquid crystals. Under favorable conditions, photoalignment was shown to be comparable to rubbing polymimide film in the ability to orient liquid crystals. A hole-conducting copolymer film comprising triphenylamine and coumarin was used to unravel how the dilution of coumarin monomers, polarization ratio of UV-irradiation to induce dimerization of coumarin, and triplet energy transfer from triphenylamine to coumarin moieties affect the quality of photoalignment and its cross-over behavior.;Cholesteric glassy liquid crystals are comprised of a helical stack of quasi-nematic layers frozen in the solid state capable of selective wavelength reflection with simultaneous circular polarization. Potentially applications of this material class include robust non-absorbing circular polarizers, optical notch filters and reflectors, and polarized light-emitters and lasers. To facilitate material synthesis over prior arts, hybrid chiral-nematic mesogens were chemically bonded to benzene via enantiomeric 2-methylpropylene spacers, exhibiting a broad cholesteric fluid temperature range. Phase transition temperatures, glass-forming ability, morphological stability against crystallization, and selective reflection wavelength all depend on the number and the positions of substitution on the benzene core. The difference in helical twisting power was explained by computational chemistry, and the amenability to photoalignment was demonstrated to be equivalent to mechanical alignment. Furthermore, photochromism was incorporated in nematic, smectic, and cholesteric glassy liquid crystals using dithienylethene cores to which liquid crystal mesogens are chemically attached. A photochromic cholesteric glassy liquid crystalline film was characterized by ellipsometry for its orientational order parameter governing quasi-nematic layers, and by UV-Vis spectrophotometry for reflective coloration with photoswitchable absorptive coloration.