Diverse polymorphs and phase transitions in van der Waals In$_2$Se$_3$

Abstract

Van der Waals In$_2$Se$_3$ has garnered significant attention due to its unique properties and wide applications associated with its rich polymorphs and polymorphic phase transitions. Despite extensive studies, the vast complex polymorphic phase space remains largely unexplored, and the underlying microscopic mechanism for their phase transformations remains elusive. Here, we develop a highly accurate, efficient, and reliable machine-learning potential (MLP), which not only facilitates accurate exploration of the intricate potential energy surface (PES), but also enables us to conduct large-scale molecular dynamics (MD) simulations with first-principles accuracy. We identify the accurate structure of the $β''$ polymorph and uncover several previously unreported $β'$ polymorph variants exhibiting dynamic stability and competing energies, which are elucidated by characteristic flat imaginary phonon bands and the distinctive Mexican-hat-like PES in the $β$ polymorph. Through the MLP-accelerated MD simulations, we directly observe the polymorphic phase transformations among the $α$, $β$, $β'$, and $β''$ polymorphs under varying temperature and pressure conditions, and build for the first time an ab initio temperature-pressure phase diagram, showing good agreement with experiments. Furthermore, our MD simulations reveal a novel strain-induced reversible phase transition between the $β'$ and $β''$ polymorphs. This work not only unveils diverse polymorphs in van der Waals In$_2$Se$_3$, but also provides crucial atomic insights into their phase transitions, opening new avenues for the design of novel functional electronic devices.