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

02 engineering and technology 0210 nano-technology 01 natural sciences 0104 chemical sciences
DOI: 10.1111/jace.16414 Publication Date: 2019-03-05T06:01:38Z
ABSTRACT
AbstractStructural 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, CsxWO3−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) = −3.436a (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.
SUPPLEMENTAL MATERIAL
Coming soon ....
REFERENCES (52)
CITATIONS (46)
EXTERNAL LINKS
PlumX Metrics
RECOMMENDATIONS
FAIR ASSESSMENT
Coming soon ....
JUPYTER LAB
Coming soon ....