Soft-phonon dynamics of the thermoelectric β -SnSe at high temperatures

Results of inelastic neutron scattering experiments on SnSe single crystals at high temperatures along with theoretical studies based on the density functional theory are reported. Our experiments reveal significant softening of the transverse acoustic branch along the [ 0 , ξ , 0 ] direction in the low-temperature α-SnSe of P b n m symmetry as temperature approaches T c = 807 K from below. This process is followed by a condensation of the zone-boundary Y-phonon of the high-temperature β-SnSe with C m c m symmetry at the onset of phase transition. The employed theoretical approach supports experimental observations and demonstrates that the phase change in SnSe is mediated by an unstable zone-boundary phonon with the Y 2 + irreducible representation within the C m c m symmetry space group of the high-temperature β-SnSe. The present work provides a detailed understanding of the soft-mode dynamics in SnSe and conclusively shows that the α ⇌ β structural transformation in this currently topical thermoelectric material is of displacive type.