Abstract
Self-assembly is a powerful paradigm, wherein molecules spontaneously form ordered phases exhibiting well-defined nanoscale periodicity and shapes. However, the inherent energy-minimization aspect of self-assembly yields a very limited set of morphologies, such as lamellae or hexagonally packed cylinders. Here, we show how soft self-assembling materials—block copolymer thin films—can be manipulated to form a diverse library of previously unreported morphologies. In this iterative assembly process, each polymer layer acts as both a structural component of the final morphology and a template for directing the order of subsequent layers. Specifically, block copolymer films are immobilized on surfaces, and template successive layers through subtle surface topography. This strategy generates an enormous variety of three-dimensional morphologies that are absent in the native block copolymer phase diagram.
Highlights
Self-assembly is a powerful paradigm, wherein molecules spontaneously form ordered phases exhibiting well-defined nanoscale periodicity and shapes
Our paradigm uses iterative assembly of Block copolymer (BCP) films, where each layer acts as both a structural component in the final morphology and a template that guides subsequent self-assembling layers
This is different from other layered-assembly approaches: one extreme is the simple stacking of independently ordered layers[8,9,10,11,12,13,14], which squanders the adaptive nature of self-assembly; on the other extreme is the direct replication of the first-layer pattern by subsequent layers[15,16,17], which cannot access non-native morphologies
Summary
Self-assembly is a powerful paradigm, wherein molecules spontaneously form ordered phases exhibiting well-defined nanoscale periodicity and shapes. We show how soft self-assembling materials—block copolymer thin films—can be manipulated to form a diverse library of previously unreported morphologies In this iterative assembly process, each polymer layer acts as both a structural component of the final morphology and a template for directing the order of subsequent layers. Self-assembly yields a very limited set of morphologies, such as lamellae or hexagonally packed cylinders[6,7] We overcome this challenge, and demonstrate how soft self-assembling materials can be manipulated to form a diverse library of previously unreported morphologies. We present an intermediate ‘responsive layering’ approach that leverages the adaptive nature of soft materials, with each layer responding in a controlled fashion to those underneath This strategy generates an enormous variety of three-dimensional (3D)morphologies that are not native to the bulk equilibrium BCP phase diagram
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