Two-dimensional (2D) metal iodides have attracted significant attention in recent years due to their superior optoelectronic properties. However, the current synthesis methods for 2D metal iodides are either time-consuming or not able to synthesize large size crystal. Here we develop an undercooling control strategy based on hot plate assisted vertical vapor deposition for the synthesis of submillimeter-size 2D bismuth iodide (BiI3) single crystal. The whole synthesis process is efficient and only takes one minute in atmosphere. The problem of high nucleation density can be addressed by undercooling control, avoiding the collide of crystals before they grow into large size. This general approach is versatility and can be expanding to synthesize other 2D metal iodides. In addition, nonlinear optical property investigation of BiI3 crystal reveals a thickness-dependent and power-dependent second harmonic response. Our strategy presents a new solution for facile preparation of large-size 2D metal iodides, facilitating their fundamental physics studies and next-generation optoelectronics development.
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