Structurally and electronically driven uniaxial negative thermal expansion in BaIrO3

Abstract

Negative thermal expansion is known to exist in a range of structure types but is extremely rare in hexagonal perovskites. Here we demonstrate that BaIrO₃ displays negative linear thermal expansion in the direction of its face-shared IrO₆ trimers, and apparent zero volume thermal expansion below 100 K. We present evidence that this anomalous thermal expansion is driven by an unusual form of rigid body phonon behaviour governed by the effective trimer valence state and therefore has structural and electronic components to the underlying mechanism.