Microdomain homogeneity evaluation of perpendicular lamellar structures in block copolymer films: X-ray scattering and IR nanospectroscopy analyses

Self-assembled block copolymer (BCP) thin films necessarily require a distinct chemical contrast between the blocks (or microdomain homogeneity) for the purpose of high-resolution pattern transfer applications. Despite its importance, however, there has been difficulty in measuring the chemical distribution associated with the self-assembling processes, i.e. solvent vapor annealing (SVA) or thermal annealing (TA). Herein, we present a simple yet effective method to probe the chemical distribution over polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA) films that underwent the SVA or SVA + TA processes. An IR nanospectroscopy using scattering-type scanning near-field optical microscopy (s-SNOM), in concert with X-ray scattering analyses, provides the relative chemical concentration of the perpendicular lamellar patterns. The chemical mapping for the components based on the s-SNOM reveals that the SVA process leaves a considerable portion of the intermixed zones of PS and PMMA blocks, whereas the subsequent TA process facilitates the chain segregation towards high-contrast chemical distribution. Interestingly, such a microdomain homogeneity critically affects the quality of the unidirectional Al₂O₃ lines that were substituted from topographically guided lamellae. Our results substantiate an important insight into understanding the chain redistribution behavior in the self-assembled BCP films using non-destructive s-SNOM technique.