Confined Assembly of Colloidal Nanorod Superstructures by Locally Controlling Free‐Volume Entropy in Nonequilibrium Fluids

Long-range-ordered structures of nanoparticles with controllable orientation have advantages in applications toward sensors, photoelectric conversion, and field-effect transistors. The assembly process of nanorods in colloidal systems undergoes a nonequilibrium process from dispersion to aggregation. A variety of assembly methods such as solvent volatilization, electromagnetic field induction, and photoinduction are restricted to suppress local perturbations during the nonequilibrium concentration of nanoparticles, which are adverse to controlling the orientation and order of assembled structures. Here, a confined assembly method is reported by locally controlling free-volume entropy in nonequilibrium fluids to fabricate microstructure arrays based on colloidal nanorods with controllable orientation and long-range order. The unique fluid dynamics of the liquid bridge is utilized to form a local region, where the free volume entropy reduction triggers assembly near the three-phase contact line (TPCL), allowing nanorods to assemble in 2D closest packing parallel to the TPCL for the maximum Gibbs free energy reduction. By manipulating the orientation of liquid flow, microstructures are assembled with programmable geometry, which sustains polarized photoluminescence and polarization-dependent photodetection. This confined assembly method opens up perspectives on assemblies of nanomaterials with controllable orientation and long-range order as a platform for multifunctional integrated devices.