Time-resolved atomic force microscopy imaging studies of asymmetric PS-b-PMMA ultrathin films: Dislocation and disclination transformations, defect mobility, and evolution of nanoscale morphology

Time-sequenced atomic force microscopy (AFM) studies of ultrathin films of cylinder-forming polystyrene-block-polymethylmethacrylate (PS-b-PMMA) copolymer are presented which delineate thin film mobility kinetics and the morphological changes which occur in microphase-separated films as a function of annealing temperature. Of particular interest are defect mobilities in the single layer (L thick) region, as well as the interfacial morphological changes which occur between L thick and adjacent $\text{3L/2}$ thick layers, i.e., structural changes which occur during multilayer evolution. These measurements have revealed the dominant pathways by which disclinations and dislocations transform, annihilate, and topologically evolve during thermal annealing of such films. Mathematical combining equations are given to better explain such defect transformations and show the topological outcomes which result from defect–defect encounters. We also report a collective, Arrhenius-type flow of defects in localized L thick regions of the film; these are characterized by an activation energy of 377 kJ/mol. These measurements represent the first direct investigation of time-lapse interfacial morphological changes including associated defect evolution pathways for polymeric ultrathin films. Such observations will facilitate a more thorough and predictive understanding of diblock copolymer thin film dynamics, which in turn will further enable the utilization of these nanoscale phase-separated materials in a range of physical and chemical applications.