Role of Anion Site Disorder in the Near Zero Thermal Expansion of Tantalum Oxyfluoride

Materials with the cubic ReO3-type structure are, in principle, excellent candidates for negative thermal expansion (NTE). However, many such materials, including TaO2F, do not display NTE. It is proposed that local distortions away from the ideal structure, associated with the need to accommodate the different bonding requirements of the disordered O/F, contribute to the occurrence of near zero thermal expansion rather than NTE. The local structure of TaO2F is poorly described by an ideal cubic ReO3-type model with O and F randomly distributed over the available anion sites. A supercell model featuring −Ta–O–Ta–O–Ta–F– chains along ⟨1 0 0⟩, with different Ta–O and Ta–F distances and O/F off-axis displacements, gives much better agreement with pair distribution functions (PDFs) derived from total X-ray scattering data for small separations (