Journal of Polymer Science, Part B: Polymer Physics

Influence of the polymer structure on the achievement of polar orientation in high glass transition temperature nonlinear optical polyimides by photo-assisted poling

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We have used combinations of light, heat, and electrostatic fields to investigate the orientation of nonlinear azo-chromophores chemically incorporated into high glass transition temperature (Tg) polyimides. A number of nonlinear optical polyimides have been synthesized in which the interaction between the nonlinear optical chromophore and the polymer main chain was systematically altered to determine to what extent this steric interaction influences the orientation of the nonlinear chromophore. Chromophores in polymers may be oriented by a number of methods: (a) polarized light at room temperature (i.e., photo-induced orientation or PIO), (b) polarized light and electric fields (i.e., photo-assisted poling or PAP) at temperatures ranging from room temperature to the polymer Tg, and (c) electric fields at Tg (thermal poling). While thermal poling and PIO are usually possible, PAP depends strongly on the molecular structure of the polymer. Previously we have shown that PIO can be accomplished at room temperature in a system where the nonlinear chromophore is embedded into the polyimide main chain via the donor substituent, and this orientation can only be thermally erased at temperatures approaching Tg. In this article we show that, whereas photoisomerization can efficiently depole donor-embedded polyimides in a matter of few minutes at room temperature, PAP does not induce any polar order. This behavior is in marked contrast to a structurally related, side-chain, nonlinear polyimide, in which the azo chromophore is tethered via a flexible linkage to the polymer backbone. In this case some PAP occurs even at room temperature, while no PAP is observed for a donor-embedded system with a similar Tg. We suggest that the orientation during PAP below Tg in the side-chain polyimide is primarily due to the movement of the azo side chains, and there is a very little coupling of this motion to the main chain. © 1998 John Wiley & Sons, Inc.