Nanoscale Block Copolymer Self‐Assembly and Microscale Polymer Film Dewetting: Progress in Understanding the Role of Interfacial Energies in the Formation of Hierarchical Nanostructures

Block copolymer (BCP) self‐assembly (SA) can be exploited for next‐generation lithography for the advanced nanopatterning of surfaces with versatile nanoscale features. To render BCP‐SA suitable for the creation of tailored surface patterns, a fundamental understanding of interfacial interactions is crucial. This progress report gives an overview on the interplay of BCP microscale film thickness modulation and nanoscale microphase separation during BCP‐SA. Light is shed on the role of interfacial energies in both events. Microscale processes determining the topography of BCP films, i.e., hole/island formation and dewetting into droplets, are presented. Nanoscale microphase separation into energetically favorable pattern orientations in dependency on the polymer film thickness and influenced by surface polarities are discussed critically. Finally, examples are shown in which the combination of microscale dewetting and nanoscale microphase separation are exploited to create hierarchical nanostructures from BCPs. An outlook is given presenting successful applications of both mechanisms on prepatterned surfaces in order to control position and morphology of the hierarchical nanostructures. This approach is particularly promising for the creation of advanced surface architectures. Block copolymer (BCP) self‐assembly allows for surface nanopatterning with advanced architectures. This progress report gives an overview on the interplay of BCP microscale film redistribution/dewetting and nanoscale phase separation and sheds light on the role of interfacial energies in both events. Examples of the combined microscale dewetting and nanoscale phase separation to create hierarchical nanostructures are shown.