Structural transitions in dense disordered silicon from quantum-accurate ultra-large-scale simulations

Abstract: Structurally disordered materials continue to pose fundamental questions, including that of how different disordered phases ("polyamorphs") can coexist and transform from one to another. As a widely studied case, amorphous silicon (a-Si) forms a fourfold-coordinated, covalent random network at ambient conditions, but much higher-coordinated, metallic-like phases under pressure. However, a detailed mechanistic understanding of the liquid-amorphous and amorphous-amorphous transitions in silicon has been lacking, due to intrinsic limitations of even the most advanced experimental and computational techniques. Here, we show how machine-learning (ML)-driven simulations can break through this long-standing barrier, affording a comprehensive, quantum-accurate, and fully atomistic description of all relevant liquid and amorphous phases of silicon. Combining a model system size of 100,000 atoms (ten-nanometre length scale) with a prediction accuracy of a few meV per atom, our simulations reveal a remarkable, three-step transformation sequence for a-Si under increasing external pressure. First, up to 10-11 GPa, polyamorphic low- and high-density amorphous (LDA and HDA) regions are found to coexist, rather than appearing sequentially. Then, we observe a structural collapse into a distinct, very-high-density amorphous (VHDA) phase at 12-13 GPa, reminiscent of the dense liquid but being formed at a much lower temperature. Finally, our simulations indicate the transient nature of this VHDA phase: it rapidly nucleates crystallites at 13-16 GPa, ultimately leading to the formation of a poly-crystalline, simple-hexagonal structure, consistent with experiments but not seen in earlier simulations.