Mechanism of Anisotropic Crystallization and Phase Transitions under Van der Waals Squeezing

Abstract

Mechanical confinement strategies, such as van der Waals (vdW) squeezing, have emerged as promising routes for synthesizing non-vdW two-dimensional (2D) layers, surprisingly yielding high-quality single crystals with lateral sizes approaching 100 micrometer. However, the underlying mechanisms by which such a straightforward approach overcomes the long-standing synthesis challenges of non-vdW 2D materials remains a puzzle. Here, we investigate the crystallization dynamics and phase evolution of Bi under vdW confinement through molecular dynamics (MD) simulations powered by a machine-learning force filed fine-tuned and distilled from a pre-trained model with DFT-level accuracy. We reveal that pressure-dependent layer modulation arises from a quantum confinement-driven anisotropic crystallization mechanism, in which out-of-plane layering occurs nearly two orders of magnitude faster than in-plane ordering. Two critical transitions are identified: an alpha-to-beta phase transformation at 1.64 GPa, and a subsequent collapse into a single-atomic layer at 2.19 GPa. The formation of large-area single crystals is enabled by substrate-induced orientational selection and accelerated grain boundary migration, driven by atomic diffusion at elevated temperatures. These findings resolve the mechanistic origin of high-quality 2D crystal growth under confinement and establish guiding principles for the controlled synthesis of metastable 2D single crystals, with implications for next-generation quantum and nanoelectronic devices.