Mechanism of Optically Inscribed High-Efficiency Diffraction Gratings in Azo Polymer Films

Abstract

A series of amorphous azobenzene-containing polymers were cast as thin films and shown to produce both reversible volume diffraction gratings and high-efficiency surface gratings by laser irradiation at an absorbing wavelength. The latter process involves localized mass transport of the polymer chains to a high degree, as atomic force microscopy reveals surface profile depths near that of the original film thickness. A mechanism for this phenomenon is proposed which involves pressure gradients as a driving force, present due to different photochemical behaviors of the azo chromophores at different regions of the interference pattern. The phase addition of the two beams in the interference pattern leads to regions of high trans-cis-trans isomerization by the absorbing azo groups, bordered by regions of low isomerization. As the geometrical isomerization requires free volume in excess of that available in the cast films, the photochemical reaction in these areas produces a laser-induced internal pressure ab...