Single and bilayer bismuthene: stability at high temperature and mechanical and electronic properties

Based on first-principles phonon and finite temperature molecular dynamics calculations including spin-orbit coupling, we showed that free-standing single-layer phases of bismuth, namely buckled honeycomb and asymmetric washboard structures named as bismuthene, are stable at high temperature. We studied the atomic structure, mechanical, and electronic properties of these single-layer bismuthene phases and their bilayers. The spin-orbit coupling is found to be crucial in determining lattice constants, phonon frequencies, band gaps, and cohesion. In particular, phonons of 3D hexagonal crystal, as well as those of single-layer bismuthene phases, are softened with spin orbit coupling. By going from 3D hexagonal crystal to free-standing single-layer structures, 2D hexagonal lattice is compressed and semimetal is transformed to semiconductor as a result of confinement effect. On the contrary, by going from single-layer to bilayer bismuthenes, the lattice is slightly expanded and fundamental band gaps are narrowed. Our results reveals that interlayer coupling in multilayer and 3D Bi crystal is crucial for topologically trivial to nontrivial and semimetal to semiconductor transitions.