Masahiro Hosoda

SYNTHESIS OF AZO CHROMOPHORES CONTAINING A PERFLUOROCYCLO-ALKENYL MOIETY AND THEIR SECOND-ORDER OPTICAL NONLINEARITY

Abstract 1,2-Bis[4-[4-[ N -ethyl- N -(2-hydroxyethyl)amino]phenylazo]phenylthio]perfluorocyclopentene, having two independent intramolecular push-pull chromophores in a molecule, showed the highest second-order nonlinear coefficient ( d 33 ) among the cyclobutenyl, -pentenyl, -hexenyl, and cyclopentenyl nitro derivatives in both doped poly(methyl methacrylate) (PMMA) and polycarbonate (PC).

Enhancement of Third Order Nonlinearity on Phthalocyanine Compounds

Abstract : The third order optical susceptibilities X(3) (-3w ; w, w, w) for soluble metallophthalocyanine derivatives were determined by optical third harmonic generation measurements of molecularly doped polymer films at a wavelength of 1907nm. The X(3) value of tetra-tert-butylvanadylphthalocyanine is larger than that of metal-free derivative. We demonstrate experiment on modes of propagating light wave in molecularly doped films which exhibit excellent optical quality. The enhancement of third order optical nonlinear susceptibilities in phthalocyanine compounds are discussed in terms of molecular structure and molecular packing.

Second-order optical nonlinearity of 6-(perfluoroalkyl)benzothiazolylazo dyes

Abstract The perfluorobutyl derivative showed a large second-order nonlinear optical coefficient ( d 33 ) and improved relaxation behavior in a series of 6-substituted benzothiazolylazo nonlinear optical chromophores (NLOphores).

Molecular Design of Conjugated Systems for Nonlinear Optics

Abstract Three types of π-conjugated systems have been developed for the third order optical nonlinearity: polythiophene and its derivatives, alkane bridged- and/or phenyl bridged-polydiynes and thermally crosslinked ones, and tetra-tert-butylphthalocyanines dispersed in polymethylmethacrylate. The macroscopic third order nonlinear optical susceptibility χ(3) 1111(-3ω;ω,ω,ω) of the film was determined from the Maker fringes, and their application to the optical waveguide was discussed from the mode-line measurement.

Second-order optical nonlinearity of thiazolylazo chromophores containing hydroxyl groups

Bathochromic thiazolylazo second-order nonlinear optical chromophores (NLOphores) having 2-hydroxyethyl group(s) in a molecule have been prepared. The tris(2-hydroxyethyl) derivatives showed the best relaxation behaviour among the non-, mono-, bis- and tris(2-hydroxyethyl) ones doped in poly(methyl methacrylate-co-methacrylic acid).

Third-order optical nonlinearities and femtosecond responses in metallophthalocyanine thin films made by vacuum deposition, molecular beam epitaxy, and spin coating

The molecular design and assembly of metallophthalocyanine systems that have the enhanced macroscopic third-order nonlinear susceptibility (chi) (3)ijkl(-(omega) 4; (omega) 1, (omega) 2, (omega) 3) and show ultrafast responses are described. Enhancement of the third harmonic susceptibility (chi) (3)1111(-3(omega) ; (omega) , (omega) , (omega) ) was observed in vanadyl phthalocyanine vacuum-deposited film with the staggered stacking arrangement induced by thermal treatment. Processable polymeric system based on tert-butyl mono-substituted rich vanadyl phthalocyanine was developed and the favorable staggered stacking arrangement was induced in a polymer matrix to enhance (chi) (3)1111(- 3(omega) ;(omega) ,(omega) ,(omega) ). Femtosecond-time-resolved spectroscopy was performed on vanadyl phthalocyanine thin films with different morphological forms in order to elucidate the exciton dynamics. The exciton decay kinetics consists of three processes: exciton-exciton annihilation, exciton-phonon coupling, and much slower triplet state formation. The decay rate of the exciton population via exciton-exciton annihilation was found to have a time dependence of t-1/2. The vacuum-deposited film and spin-coated film of vanadyl phthalocyanine derivatives showed similar decay behavior, whereas molecular beam epitaxy film showed a faster decay with a time constant of several hundreds of femtoseconds.

Second-Order Optical Nonlinearities in Perfluoroalkylsulfonyl Substituted Azo Dyes

Abstract The second-order nonlinear optical coefficients d33 (-2ω:ω, ω) of polymer films doped with novel azo dyes, which have a perfluoroalkylsulfonyl group as an electron acceptor and an extended π-electron conjugated system, are determined by second-harmonic generation (SHG) measurements. Thin polycarbonate (PC) film doped with 4-(4-(4-perfluorobutylsulfonylphenylazo) naphthylazo)-N-ethyl-N-hydroxyethylaniline showed a large d33 value, 67 pm/V, at a wavelength of 1064 nm. The decay of the d33 values was slow due to the stability of the molecular arrangement in a polymer matrix at high temperature. In addition, a side-chain nonlinear optical polymer with this novel disazo dye is synthesized and the decay of d33 values is estimated.

Second-order optical nonlinearities of novel disazo dyes having a perfluoroalkylsulfonyl group

The second-order nonlinear optical coefficients d33 (-2(omega) :(omega) ,(omega) ) of polymer films doped with novel disazo dyes, that have a perfluoroalkylsulfonyl group as an electron acceptor and an extended (pi) - electron system, are determined by second-harmonic generation (SHG) measurements at wavelengths of 900 - 1550 nm. Thin polycarbonate (PC) film doped with 4-(4-(4- perfluorobutylsulfonylphenylazo) naphthylazo)-N-ethyl-N-hydroxyethylaniline showed a large d33 value, 67 pm/V, at a wavelength of 1064 nm. The decay of the d33 value was slow due to the stability of the molecular arrangement in a polymer matrix at high temperature. The large d33 values and the stability of polymer films doped with novel disazo dyes in this study are discussed in terms of electron acceptor substitution and an extended (pi) -electron system.