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

Photorefractive subharmonics - a beam-coupling effect?

Using the so-called ac field technique, we investigate experimentally the influence of optical beam coupling on the generation of subharmonic gratings in a photorefractive sillenite crystal. By the use of two different recording configurations, we are able to distinguish between effects caused by material nonlinearities and effects caused by optical beam coupling.

Longitudinal parametric oscillation in photorefractive sillenites: comparison between theory and experiment

By using an alternative setup for photorefractive parametric oscillation in which wave mixing between the recording beams is avoided it has become possible to make more detailed comparisons with the space-charge wave theory. In the present paper we compare the experimental features of longitudinal parametric oscillation observed in a crystal of Bi12SiO20 with the theoretical predictions.

Optical activity in photorefractive Bi12TiO20

The influence of optical activity on two-wave mixing (TWM) in photorefractive BTO and BSO crystals in the absence of an applied field is studied both theoretically and experimentally. For the conventinal orientations of the grating vector, K [001] and K[001], the piezoelectric and photoelastic effects are either zero or negligible. This makes an analytical treatment of the TWM problem possible. We obtain an analytical solution for the coupled wave equations of TWM valid for arbitrary optical activity. This result is of special importance for BTO crystals. In these crystals under the condition of maximum energy transfer (|K|rD=1, where rD is the Debye radius) neither the approximation of small optical activity nor the one of dominating optical activity is applicable and our analytical solution becomes essential. Our experimental setup uses beams with a trapezoidal overlap that allows us to study the thickness-dependence of the gain in a single measurement. Experimental and theoretical results for a BTO crystal are compared with those for a BSO crystal and are explained in the framework of the model used.

Influence of beam-coupling on photorefractive parametric oscillation in a dc-field-biased Bi12SiO20 crystal

The influence of beam coupling on photorefractive parametric oscillation generated in a Bi12SiO20 crystal is investigated experimentally by comparing two configurations with and without the presence of beam coupling. It is shown that beam coupling has a great influence; for example, the transversal split of the K/2 subharmonic grating is seen only in the beam-coupling geometry. A case that resembles K/4 subharmonic generation can, however, still be found in the absence of beam coupling.

Fundamental characteristics of space-charge waves in photorefractive sillenite crystals

We investigate experimentally the fundamental characteristics of space-charge waves excited in a photorefractive crystal of Bi12SiO20. Features such as their transient rise and decay as well as their steady-state frequency response are investigated. Based on this, we find the dependence of the space-charge waves' quality factor on spatial frequency and electric-field biasing. The experimental findings are compared with the linear space-charge wave theory developed previously by Sturman et al. [J. Opt. Sec. Am. B 10, 1919 (1993)].

Photorefractive subharmonics - a beam-coupling effect?

Using the so-called ac field technique, we investigate experimentally the influence of optical beam coupling on the generation of subharmonic gratings in a photorefractive sillenite crystal. By the use of two different recording configurations, we are able to distinguish between effects caused by material nonlinearities and effects caused by optical beam coupling.

Excitation of higher harmonic gratings in AC-field biased photorefractive crystals

We analyze the nonlinear excitation of holographic gratings in a photorefractive crystal being subject to an alternating electric field and a stationary light interference pattern. The influence of the higher harmonics on the fundamental grating is illustrated for the case where a crystal of Bi12SiO20 is the recording medium. We analyze both the steady state and the transient consequences of the higher harmonic excitation.

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.

Investigation of photorefractive subharmonics in the absence of wavemixing

Using a new optical configuration free from the influence of photorefractive optical nonlinearity, we investigate the main characteristics of the spatial subharmonic K/2 excited in a Bi12SiO20 crystal by a light-intensity pattern with wave vector K and frequency O. It is shown that in a large region of intensity and applied electric field the optimum value O of the frequency corresponds to the conditions of parametric excitation of the weakly damped eigenmodes of the medium: the space-charge waves. The threshold and above-threshold characteristics of the subharmonic regime are in good agreement with the theory.

Low frequency peculiarities of the photorefractive response in sillenites

We investigate experimentally and theoretically the dependence of the amplitude of the spatial fundamental grating, created by a pair of coherent light beams while using the running grating technique [M.P. Petrov, S.I. Stepanov and A.V. Khomenko, Photorefractive Crystals in Coherent Optical Systems, Springer Series in Optical Sciences (Springer, 1991); P. Refregier, L. Solymar, H. Rajbenbach and J.P. Huignard, J. Appl. Phys. 58 (1985) 45], as a function of detuning frequency and beam ratio ß in photorefractive Bi12SiO20. It is shown that for ß > 0.05, in addition to the main peak in the frequency dependence of the amplitude, there is an additional peak of lower frequency which, as a rule, dominates the main peak. The position of the main peak depends on ß. The experimental results are in good agreement with the theoretical analysis and the general ideas about excitation and nonlinear interaction of weakly damped space-charge waves.

Verification of the standard model of the photorefractive nonlinearity in BSO crystals

On the basis of the standard model for the photorefractive nonlinearity we investigate whether a systematic description of the dependence of two-beam energy exchange on beam polarization and grating vector K is possible. Our result is that there is good agreement between theory and experiment with respect to the polarization properties and semi-quantitative agreement with respect to the K-dependence of the energy exchange.

Generation of spatial subharmonic gratings in the absence of photorefractive beam coupling

Using a new experimental geometry, we have proved for the first time that the generation of spatial subharmonic gratings in photorefractive crystals is not dependent on optical nonlinearity. We present results which confirm that the subharmonic gratings result from a parametric excitation of ultra low-frequency eigenmodes of a crystal by a time modulated fundamental grating.

Phase dependent forward three wave amplification in photorefractive BSO

The results of three wave mixing experiments in photorefractive Bi12SiO20 are presented. The results confirm theoretical predictions that amplification by three wave mixing is strongly dependent on the phase relationship between the three beams at the input to the medium.