Developing new persistent luminescent phosphors, a unique class of inorganic materials that can produce a visible light emission lasting minutes to hours requires improving our understanding of their fundamental structure–property relationships. Research has shown that one of the most critical components governing persistent luminescence is the existence of lattice defects in a material. Specifically, vacancies and anti-site defects that coincide with substitution of the luminescent center, e.g. , Eu 2+ or Cr 3+ , are generally considered essential to generate the ultra-long luminescent lifetimes. This research solidifies the connection between defects and the remarkable optical properties. The persistent luminescent compound Zn(Ga 1−x Al x ) 2 O 4 ( x = 0–1), which adopts a spinel-type structure, is investigated by examining the X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine-structure (EXAFS) at the Cr K and Zn K edges. This investigation reveals a structural distortion of the octahedrally coordinated main group metal site concurrent with increasing Al 3+ content. Moreover, these results suggest there is a dependence between the local crystallographic distortions, the presence of defects, and a material's persistent luminescence. In combination, this work provides an avenue to understand the connection between the structure–defect–property relationships that govern the properties of many functional inorganic materials.
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Comparative analysis of XANES and EXAFS for local structural characterization of disordered metal oxides
In functional materials, the local environment around active species that may contain just a few nearest-neighboring atomic shells often changes in response to external conditions. Strong disorder in the local environment poses a challenge to commonly used extended X-ray absorption fine structure (EXAFS) analysis. Furthermore, the dilute concentrations of absorbing atoms, small sample size and the constraints of the experimental setup often limit the utility of EXAFS for structural analysis. X-ray absorption near-edge structure (XANES) has been established as a good alternative method to provide local electronic and geometric information of materials. The pre-edge region in the XANES spectra of metal compounds is a useful but relatively under-utilized resource of information of the chemical composition and structural disorder in nano-materials. This study explores two examples of materials in which the transition metal environment is either relatively symmetric or strongly asymmetric. In the former case, EXAFS results agree with those obtained from the pre-edge XANES analysis, whereas in the latter case they are in a seeming contradiction. The two observations are reconciled by revisiting the limitations of EXAFS in the case of a strong, asymmetric bond length disorder, expected for mixed-valence oxides, and emphasize the utility of the pre-edge XANES analysis for detecting local heterogeneities in structural and compositional motifs.
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- Award ID(s):
- 1911592
- NSF-PAR ID:
- 10319085
- Date Published:
- Journal Name:
- Journal of Synchrotron Radiation
- Volume:
- 28
- Issue:
- 5
- ISSN:
- 1600-5775
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1107/S1600577521007025
