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.