Controlling colloidal phase transitions with critical Casimir forces

The critical Casimir force provides a thermodynamic analogue of the quantum mechanical Casimir force that arises from the confinement of electromagnetic field fluctuations. In its thermodynamic analogue, two surfaces immersed in a critical solvent mixture attract each other due to confinement of solvent concentration fluctuations. Here, we demonstrate the active assembly control of colloidal equilibrium phases using critical Casimir forces. We guide colloidal particles into analogues of molecular liquid and solid phases via exquisite control over their interactions. By measuring the critical Casimir pair potential directly from density fluctuations in the colloidal gas, we obtain insight into liquefaction at small scales. We apply the van der Waals model of molecular liquefaction and show that the colloidal gas–liquid condensation is accurately described by the van der Waals theory, even on the scale of a few particles. These results open up new possibilities in the active assembly control of micro and nanostructures.