Evaporative self-assembly of noble metal nanoparticles into ordered structures holds great promise for fabricating optical and plasmonic devices by virtue of its low cost, high efficiency, and ease of operation. However, poor control of Marangoni flows is one of the challenges accounting for realizing a well-defined assembly. Herein, based on the theoretical analysis of the influence of evaporative intensity on the assembly, two simple but reliable flow-field-confinement platforms are designed to control the evaporative microflows and to work concurrently with depletion forces to enable the regulated self-assembly of gold nanorods. Orientationally ordered assemblies are realized by the designed strong unidirectional microflow in a capillary, and a device-scale assembly of monolayer membrane is obtained by the created weak convection in homemade glass cells. Morphologically diversified superstructure assemblies, such as spherulite-like, boundary-twisted, chiral spiral assemblies, and merging membranes with a π-twisted domain wall, are obtained due to the spontaneous symmetry breaking or in the presence of defects, such as surface steps and screw dislocations. Optical anisotropy and polarization-dependent behaviors of these assemblies are further revealed, implying the potential applications in plasmonic coupling devices and optoelectronic components. An understanding of the entropy-driven assembly behaviors and control of evaporative microflows to guide the self-assembly of gold nanorods provides insights into the general bottom-up approach that is helpful for constructing complex yet robust nanosuperstructures.
Keywords: evaporative microflows; large area; orientationally ordering; self-assemblies; structure regulating.