Complex Dynamics of Photoinduced Mass Transport and Surface Relief Gratings Formation

The microscopic and semi-macroscopic mechanisms responsible for photoinduced mass transport in functionalized azo-polymers are far from deeply understood. To get some insight into those mechanisms on “microscopic” scale, we studied the directed photoinduced motion of single functionalized polymer chains under various types of polarized light illumination using Monte Carlo bond fluctuation model and our kinetic Monte Carlo model for photoinduced mass transport. We found sub-diffusive, diffusive and super-diffusive regimes of the dynamics of single chains at constant illumination and mostly super-diffusive regime for directed motion in the presence of the gradient of light intensity. This regime is more enhanced for long than for short chains and it approaches the ballistic limit for very long chains. We propose a physical picture of light-driven inscription of Surface Relief Gratings (SRG) as corresponding to a dynamical coexistence of normal and anomalous diffusion in various parts of the system. A simple continuous time random walk model of SRG inscription based on this physical picture reproduced the light-driven mass transport found in experiments as well as the fine structure of SRG.