Large-Area Uniaxial-Oriented Growth of Free-Standing Thin Films at the Liquid–Air Interface with Millimeter-Sized Grains

Manipulating materials at the atomic scale and assembling them into macroscopic structures with controlled dimensionalities and single-crystal quality are grand scientific challenges. Here, we report a general solvent evaporation method to synthesize large-area uniaxial-oriented growth of free-standing thin films at the liquid–air interface. Crystals nucleate at the solution surface and rotate into the same orientation under electrostatic interaction and then merge as large crystals and grow laterally into a large-area uniform thin film with millimeter-sized grains. The lateral dimension is confined only by the size of containers. The film thickness can be tuned by adjusting solvent evaporation rate (R) and solute diffusivity (D), and a characteristic length, L*∼DR, was derived to estimate the film thickness. Molecular dynamic (MD) simulations reveal a concentration spike at the liquid–air interface during fast solvent evaporation, leading to the lateral growth of thin films. The large-area uniaxial oriented films are demonstrated on both inorganic metal halides and hybrid metal halide perovskites. The solvent evaporation approach and the determination of key parameters enabling film thickness prediction are beneficial to the high throughput and scalable production of single crystal-quality thin film materials under controlled evaporation conditions.