The photorefractivity of an indole derivative and of its polymer blends has been studied at room temperature. The indole derivative 3-[2-(4-nitrophenyl)ethenyl]-1-(2-ethylhexyl)-2-methylindole (NPEMI-E) is a typical low-molecular-weight glass-forming molecule having peculiar nonlinear optics characteristics. It is unconditionally soluble in the photoconductive poly-(N-vinyl-2,3-dimethylindole) so that all the possible blends can be studied for a weight percent (wt. %) content of NPEMI-E ranging from zero to 100. A very high and sharp maximum of the photorefractive optical gain Gamma(2) approximately 2000 cm(-1) was obtained for a NPEMI-E wt. % content of about 90. On the basis of recently published theoretical calculations, we have made the hypothesis that the rapid change of Gamma(2) can also be ascribed to a correspondingly quick variation of the molecular electro-optic parameters of the dissolved chromophore for some well distinguished values of its concentration in the polymer matrix. Differential scanning calorimetry measurements were made and the results carefully analyzed with the aim of obtaining information on the intermolecular interactions. These last measurements also allowed rationalizing the unconditionally stable glass appearance of the obtained blends. Measurements of spectroscopic ellipsometry were also made on blends with different NPEMI-E content.
A derivative of 2-methylindole, 3-[2-(4-nitrophenyl)ethenyl]-1-allyl-2-methylindole, NPEMI-A, is studied for its photoconductivity and photorefractivity behaviour. Its blends with the organic polymer poly-(2,3-dimethyl-N-vinylindole), PVDMI, are also investigated. Due to the expected and devised mutual solubility of the two components of the blends, it is possible to carry out measurements with the weight percent of the chromophore NPEMI-A changing from zero to 100. Films were produced by a squeezing process between two ITO-covered glass sheets. No opacity phenomena, that are so common for many other organic blends due to the segregation of the dissolved chromophore, are observed. The photorefractive optical gain Gamma(2) is obtained as a function of the chromophore content. Differential scanning calorimetry measurements (DSC) are also carried out to obtain the whole change of the glass transition temperature T(g) as a function of the amount of chromophore contained in the blends. From the experimental trend of T(g) a meaningful quantitative estimate of the value of the electrostatic interactions acting in the studied blends, is obtained. The importance of the value of T(g), and of the electrostatic interactions, in determining the extent of the photorefractivity is clearly evident. The results are compared for NPEMI-A (Gamma(2) = 210 cm(-1)) and for NPEMI-E (Gamma(2) approximately = 2000 cm(-1)) that has a N-2-ethylhexyl group instead of a N-allyl group. The Pockels and Kerr contributions and--for the first time--a "collaborative effect" of the photorefractivity of NPEMI-A are distinguished and quantitatively evaluated.
Synthesis and electrooptical analysis of polysiloxane and poly-N-vinyl derivatives containing indolyl groups are reported. The indole group and some of its methyl derivatives have been taken into account in order to evaluate their behaviour, with respect to that of the widely employed carbazole group, when used as photoconductive centres attached to a polymer chain. The obtained data show that photoconductivity and traps formation mechanism can be inferred as functions of the physico-chemical parameters (electric dipole moment and ionization potential) of the different groups and polymers involved. To this end such parameters have been carefully computed for a series of pyrrole, indole and carbazole derivatives. The 2,3-dimethylindole derivative appears to be particularly promising due to its electrooptical behaviour in the red absorption region where measurements have been accomplished and are shown to be consistent with the theoretical predictions.
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