Using computer simulations, we establish an approach for creating defect-free, periodically ordered polymeric materials. The system involves $ABC$ ternary mixtures where the $A$ and $B$ components undergo a reversible photochemical reaction. In addition, all three components are mutually immiscible and undergo phase separation. Through the simulations, we model the effects of illuminating a three-dimensional (3D) sample with spatially and temporally dependent light irradiation. Experimentally, this situation can be achieved by utilizing both a uniform background light and a spatially localized, higher intensity light, and then rastering a higher-intensity light over the 3D sample. We first focus on the case where the higher-intensity light is held stationary and focused in a distinct region within the system. The $C$ component is seen to displace the $A$ and $B$ within this region and replicate the pattern formed by the higher-intensity light. In effect, one can write a pattern of $C$ onto the $AB$ binary system by focusing the higher-intensity light in the desired arrangement. We isolate the conditions that are necessary for producing clearly written patterns of $C$ (i.e., for obtaining sharp interfaces between the $C$ and $A∕B$ domains). We next consider the effect of rastering a higher-intensity light over this sample and find that this light “combs out” defects in the $AB$ blend as it moves through the system. The resulting material displays a defect-free structure that encompasses both a periodic ordering of the $A$ and $B$ domains and a well-defined motif of $C$. In this manner, one can create hierarchically patterned materials that exhibit periodicity over two distinct length scales. The approach is fully reversible, noninvasive, and points to a novel means of patterning with homopolymers, which normally do not self-assemble into periodic structures.

• Received 31 January 2006

DOI:https://doi.org/10.1103/PhysRevE.74.011502