In Situ Self‐Assembly of Nanoscale Particles into Macroscale Ordered Monolayers with Enhanced Memory Performance

Abstract In situ fabrication of macroscale ordered monolayers of nanoparticles (NPs) on targeted substrates is highly desirable for precision electronic and optical devices, while it remains a great challenge. In this study, a solution is provided to address this challenge by developing a colloidal ink formulation and employing the direct‐ink‐writing (DIW) technique, where on‐demand delivery of ink at a targeted location and directional evaporation with controllable rate are leveraged to precisely guide the deposition of polystyrene‐grafted gold NPs (Au@PS NPs) into a macroscale monolayer with an ordered Au NP array embedded in a PS thin film. A 2D steady‐state diffusion‐controlled evaporation model, which explains the parameter dependence of the experimental results and gives semiquantitative agreement with the experimental evaporation kinetics is proposed. The ordered monolayer is used as both nanocrystal floating gates and the tunneling layer for nonvolatile memory devices. It shows significantly enhanced performance compared with a disordered NP film prepared by spin coating. This approach allows for fine control of NP self‐assembly to print macroscaleordered monolayers directly onto substrates, which has great promise for application in broad fields, including microelectronic and photoelectronic devices, sensors, and functional coatings.