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The local atomic structure of SnSe was characterized across itsorthorhmbic-to-orthorhombic structural phase transition using x-ray pairdistribution function analysis. Substantial Sn off-centering distortionspersist in the high symmetry high temperature phase, with symmetry differentfrom that of ordered distortions below the transition. The analysis impliesthat the transition is neither order-disorder nor displacive, but rather acomplex crossover where the character of coupling changes from 3D-like at lowtemperature to 2D-like at high temperature. Robust ferro-coupled SnSeintra-layer distortions suggest a ferroelectric-like instability as the drivingforce. Complex local Sn off-centering is integral to the ultra-low latticethermal conductivity mechanism in SnSe.

Nanoscale Sn off-centering behind low thermal conductivity in SnSe thermoelectric