Pressure-controlled formation of crystalline, Janus, and core-shell supraparticles.

Binary mixtures of nanoparticles self-assemble in the confinement of evaporating oil droplets and form regular supraparticles. We demonstrate that moderate pressure differences on the order of 100 kPa change the particles' self-assembly behavior. Crystalline superlattices, Janus particles, and core-shell particle arrangements form in the same dispersions when changing the working pressure or the surfactant that sets the Laplace pressure inside the droplets. Molecular dynamics simulations confirm that pressure-dependent interparticle potentials affect the self-assembly route of the confined particles. Optical spectrometry, small-angle X-ray scattering and electron microscopy are used to compare experiments and simulations and confirm that the onset of self-assembly depends on particle size and pressure. The overall formation mechanism reminds of the demixing of binary alloys with different phase diagrams.