The Control of Colloidal Grain Boundaries through Evaporative Vertical Self‐Assembly

: Self-assembly continuously gains attention as an excellent method to create novel nanoscale structures with a wide range of applications in photonics, optoelectronics, biomedical engineering, and heat transfer applications. However, self-assembly is governed by a diversity of complex interparticle forces that cause fabricating defectless large scale (>1 cm) colloidal crystals, or opals, to be a daunting challenge. Despite numerous efforts to find an optimal method that offers the perfect colloidal crystal by minimizing defects, it has been difficult to provide physical interpretations that govern the development of defects such as grain boundaries. This study reports the control over grain domains and intentional defect characteristics that develop during evaporative vertical deposition. The degree of particle crystallinity and evaporation conditions is shown to govern the grain domain characteristics, such as shapes and sizes. In particular, the grains fabricated with 300 and 600 nm sphere diameters can be tuned into single-column structures exceeding ≈1 mm by elevating heating temperature up to 93 °C. The understanding of self-assembly physics presented in this work will enable the fabrication of novel self-assembled structures with high periodicity and offer fundamental groundworks for developing large-scale crack-free structures.