Oxygen vacancies and pseudo Jahn‐Teller destabilization in cesium‐doped hexagonal tungsten bronzes

Abstract

Abstract Structural and compositional changes of Cs‐doped hexagonal tungsten bronzes ( HTB ) with respect to variations in oxygen deficiency and alkali content have been investigated in detail through x‐ray diffraction Rietveld analysis, x‐ray photoelectron spectroscopy, and Raman spectroscopy. Cs‐ HTB crystallized in a reductive atmosphere is evidenced to generally contain plenty of oxygen defects, and a general formula, Cs x WO 3− y (0.20 ≤ x ≤ 0.32, 0 < y ≤ 0.46), is proposed. Lattice parameters of Cs‐ HTB are observed to vary according to the relation, c (Å) = −3.436 a (Å) + 33.062. The coordinated modification of W–O octahedral dimensions suggests the origin of the structural change with increasing x and y to be a destabilization of the pseudo Jahn‐Teller distortion due to donated electrons. The dimensional change of lattice due to electrons emitted from oxygen defects is appraised only 1/18 as that due to electrons from doped alkali ions, suggesting that most electrons from oxygen defects should be localized in Cs‐ HTB .