Mechanism of optically inscribed high-efficiency diffraction gratings in azo polymer films

A series of amorphous azobenzene-containing polymers were cast as thin films and shown to produce both reversible volume diffraction gratings and high-efficiency sur-face 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 ar 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 above the yield point of the material. It is proposed that the resulting viscoelastic now from these high-pressure areas to lower-pressure areas leads to the formation of the regularly spaced sinusoidal surface relief gratings observed by a number of research groups, research groups, but previously unexplained. This mechanism of photoinduced viscoelastic flow agrees well with the results of experiments investigating the effect of the polarization state of the interfering writing beams and the photochemical behavior of the chromophore, the free volume requirements of the induced geometric changes, and the viscoelastic flow of the material.