Nearest-neighbour nanocrystal bonding dictates framework stability or collapse in colloidal nanocrystal frameworks.

Block copolymers serve as architecture-directing agents for the assembly of colloidal nanocrystals into a variety of mesoporous solids. Here we report the fundamental order-disorder transition in such assemblies, which yield, on one hand, ordered colloidal nanocrystals frameworks or, alternatively, disordered mesoporous nanocrystal films. Our determination of the order-disorder transition is based on extensive image analysis of films after thermal processing. The number of nearest-nanocrystal neighbours emerges as a critical parameter dictating assembly outcomes, which is in turn determined by the nanocrystal volume fraction (fNC). We also identify the minimum fNC needed to support the structure against collapse.