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Spontaneous phase separation of materials is a powerful strategy to generate highly defined 2D nanomorphologies with novel properties and functions. Exemplary are such morphologies in block copolymers or amphiphilic systems, whose formation can be well predicted based on parameters such as volume fraction and shape factor. In contrast, the formation of 2D nanomorphologies is currently unpredictable in materials perfectly defined at the molecular level, in which crystallinity plays a significant role. Here, we introduce a crystal lattice analysis to predict a priori the formation of 2D nanomorphologies from the crystalline units in phase-separated soft materials. We show that the formation of lamellar morphologies, their domain spacings, and thermal transition temperatures of such materials can be predicted using a straightforward crystal lattice analysis workflow. We envision this approach to facilitate the design and discovery of new materials with 2D nanomorphologies that are essential for next-generation electronic applications.

Crystallinity is seldomly utilized as part of the microphase segregation process in ultralow-molecular-weight block copolymers. Here, we show the preparation of two types of discrete, semicrystalline block co-oligomers, comprising an amorphous oligodimethylsiloxane block and a crystalline oligo-l-lactic acid or oligomethylene block. The self-assembly of these discrete materials results in lamellar structures with unforeseen uniformity in the domain spacing. A systematic introduction of dispersity reveals the extreme sensitivity of the microphase segregation process toward chain length dispersity in the crystalline block.