Role of
Anion Site Disorder in the Near Zero Thermal
Expansion of Tantalum Oxyfluoride
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Abstract
Materials with the cubic ReO<sub>3</sub>-type structure are, in
principle, excellent candidates for negative thermal expansion (NTE).
However, many such materials, including TaO<sub>2</sub>F, 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 TaO<sub>2</sub>F
is poorly described by an ideal cubic ReO<sub>3</sub>-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 (<8 Å). Analyses
of PDFs derived from variable temperature measurements (80 to 487
K), over different length scales, indicate an average linear expansion
coefficient of close to zero with similar contributions from the geometrically
distinct Ta–OTa and Ta–FTa links in
TaO<sub>2</sub>F