Development of Photorefractive Polymers: Synthesis and Characterization of Polymers with Donor-Pi-Acceptor Groups

Department of Polymer Science and Rubber Technology, Cochin University of Science and Technology

Local gratings due to angular hole burning in a photorefractive polymer

We investigate the processes involved in writing real-time holographic gratings in a photorefractive polymer (PRP) that incorporates an azo-dye. In such systems there may be gratings due to mechanisms associated with trans–cis isomerization (angular hole burning (AHB) and/or angular redistribution), which appear in addition to those arising from the photorefractive (PR) effect. The work presented here helps to understand the interactions which may occur between these different gratings. The formation of local gratings due to mechanisms associated with photoisomerization is studied, in a new PRP based on the photoconductor poly(N-vinylcarbazole):2, 4, 7-trinitro-9-fluorenone, plasticized with N-ethylcarbazole. The polymer includes the azo-dye 4-nitro-4'-pentyloxy-azobenzene and we observe both PR and photoisomerization gratings. The gratings are shown to be both polarization-sensitive and reversible. The presence of the photoisomerization gratings (which diffract almost as strongly as the PR gratings) significantly affects the field-dependent diffractive behaviour of the composite. A measurement of the lifetime of the cis state is made (τcis = 38 s) using photoinduced dichroism. This is close to the decay time constant of the local gratings (τdecay = 42 s), and it is suggested that the local grating mechanism is AHB of the azo-dye. This is the first time (to the knowledge of the authors) that a local grating due to AHB has been demonstrated in a PRP.

Light-induced lens analysis in photorefractive crystals employing phase-shifting real-time holographic interferometry

The purpose of this work is to study the potentialities of phase-shifting real-time holographic interferometry for the analysis of light-induced lens in photoreffactive and nonlinear optical materials. We show that this technique can be used for quantitative evaluation of the phase distribution of a wavefront changed by a light-induced lens and, consequently, the refractive index changes in these materials. The basic principle of this technique combines real-time holographic interferometry with phase-shifting technique for interferogram analysis. This method is demonstrated with in situ visualization, monitoring and analysis in real-time and uses a Bi(12)SiO(20) crystal as the holographic medium and a Bi(12)TiO(20) as the test sample. (C) 2008 Elsevier B.V. All rights reserved.

Strong and fast phase modulation for quantitative analysis of photorefractive gratings

A new approach for studying photorefractive gratings in two-wave mixing experiments by a phase modulation technique is presented. The introduction of a large-amplitude, high-frequency sinusoidal phase modulation in one of the input beams blurs the interference pattern and provides powerful harmonic signals for accurate measurements of the grating diffraction efficiency eta and the output phase shift rho between the transmitted and diffracted waves. The blurring of the light fringes can be used to suppress the higher spatial harmonics of the grating, allowing a space-charge field with sinusoidal profile to be recorded. Although the presence of such a strong phase modulation affects the beam coupling in a rather complicated way, it is shown that for the special case of equal intensity input beams, the effect of the phase modulation on eta and rho is reduced to a weakening of the coupling strength. The potentialities of the technique are illustrated in a study of refractive-index waves excited by running interference patterns in a Bi12TiO20 crystal. Expressions for the diffraction efficiency and the output phase shift are derived and used to match numerically calculated curves to the experimental data. The theoretical model is supported by the very good data fitting and allows the computation of important material parameters.

Light-induced lens analysis in photorefractive crystals employing phase-shifting real-time holographic interferometry

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Feedback-controlled running holograms in strongly absorbing photorefractive materials

We propose a mathematical model for the movement in absorbing materials of photorefractive holograms under feedback constraints. We use this model to analyze the speed of a fringe-locked running hologram in photorefractive sillenite crystals that usually exhibit a strong absorption effect. Fringe-locked experiments permit us to compute the quantum efficiency for the photogeneration of charge carriers in photorefractive crystals if the effect of bulk absorption and the effective value of the externally applied field are adequately taken into consideration. A Bi12TiO20 sample was measured with the 532-nm laser wavelength, and a quantum efficiency of φ = 0.37 was obtained. Disregarding absorption leads to large errors in φ. © 2000 Optical Society of America.

Atom transfer radical polymerisation - towards the synthesis of a fully-functional photorefractive polymer

Atom transfer radical polymerisation (ATRP) of styrene in xylene solution initiated with 1-phenylethyl bromide and mediated by CuBr/N-propyl-2- pyridinemethanimine catalyst complex was studied. The polymerisation was ill-controlled, yielding polymers with broad molecular weight distributions and values of number average molecular weight considerably higher than the theoretical values calculated from 100% initiator efficiency. The degree of control afforded over the polymerisation was enhanced by use of a more soluble catalyst complex, CuBr/N-octyl-2-pyridinemethanimine. Furthermore, the use of a more polar solvent, diglyme, generated a homogeneous catalyst complex that facilitated the production of polymers having narrow molecular weight distributions (1.10 < PDi < 1.20). The kinetics of the atom transfer radical polymerisation of methyl methacrylate at 90°C in diglyme solution initiated with ethyl-2-bromoisobutyrate and mediated by CuBr/N-octyl-2-pyridinemethanimine was studied and the orders of the reaction were established. The effect on the rate of polymerisation of the ratio of CuBr:N-octyl-2-pyridinemethanimine was also determined. The temperature dependencies of the rate of polymerisation of methyl methacrylate in diglyme solution and xylene solution were studied, and were found to be non-linear and dependent upon the polarity of the solvent. The use of highly polar aprotic solvents, such as N,N-dimethylformamide and dimethylsulphoxide, was found to be detrimental to the degree of control afforded over the polymerisation of methyl methacrylate. This was circumvented by use of a 5-fold excess, over that conventionally used, of catalyst complex. The atom transfer radical polymerisation of (4-nitrophenyl)-[3-[N-[2- (methacryloyloxy)ethyl]carbazolyl]]diazene in dimethyl sulphoxide solution was studied. Although homopolymerisation yielded only oligomers, copolymerisation of this monomer with methyl methacrylate was found to be readily achievable. Keywords: ATRP, Styrene; Methyl methacrylate; Polar solvents; Fully-functional photorefractive polymer. 2

Resonant two-wave mixing in photorefractive materials with the aid of dc and ac fields

A recently predicted resonant effect for the enhancement of two-wave mixing in photorefractive materials is investigated. The resonance occurs when the frequency of the applied ac field agrees with the eigenfrequency of the excited space-charge wave. Experimentally a clear resonance is found, as predicted by the theory, for high dc electric fields, but the resonance is smeared out for lower fields. A modified theory, taking into account the second temporal harmonic of the space-charge wave, shows good agreement with the experimental results.

Resonant two-wave mixing in photorefractive materials with the aid of dc and ac fields

A recently predicted resonant effect for the enhancement of two-wave mixing in photorefractive materials is investigated. The resonance occurs when the frequency of the applied ac field agrees with the eigenfrequency of the excited space-charge wave. Experimentally a clear resonance is found, as predicted by the theory, for high dc electric fields, but the resonance is smeared out for lower fields. A modified theory, taking into account the second temporal harmonic of the space-charge wave, shows good agreement with the experimental results.