Pathway-Dependent Grain Coarsening of Block Copolymer Patterns under Controlled Solvent Evaporation.

Solvent evaporation annealing (SEA) is a straightforward, single-step casting and annealing method of block copolymers (BCP) processing yielding large-grained morphologies in a very short time. Here, we present a quantitative analysis of BCP grain-coarsening in thin films under controlled evaporation of the solvent. Our study is aimed at understanding time and BCP concentration influence on the rate of the lateral growth of BCP grains. By systematically investigating the coarsening kinetics at various BCP concentrations, we observed a steeply decreasing exponential dependence of the kinetics power-law time exponent on polymer concentration. We used this dependence to formulate a mathematical model of BCP ordering under nonstationary conditions and a 2D, time- and concentration-dependent coarsening rate diagram, which can be used as an aid in engineering the BCP processing pathway in SEA and also in other directed self-assembly methods that utilize BCP-solvent interactions such as solvent vapor annealing.