Effects of rare-earth co-doping on the local structure of rare-earth phosphate glasses using high and low energy X-ray diffraction

Cramer, A.J., Cole, J.M., FitzGerald, V., Honkimaki, V., Roberts, M.A., Brennan, T., Martin, R.A., Saunders, G.A., Newport, Robert J. (2013) Effects of rare-earth co-doping on the local structure of rare-earth phosphate glasses using high and low energy X-ray diffraction. Physical Chemistry Chemical Physics, 15 (22). pp. 8529-8543. ISSN 1463-9076. (doi:10.1039/c3cp44298e)

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Abstract

Rare-earth co-doping in inorganic materials has a long-held tradition of facilitating highly desirable optoelectronic properties for their application to the laser industry. This study concentrates specifically on rare-earth phosphate glasses, (R2O3)x(R′2O3)y(P2O5)1−(x+y), where (R, R′) denotes (Ce, Er) or (La, Nd) co-doping and the total rare-earth composition corresponds to a range between metaphosphate, RP3O9, and ultraphosphate, RP5O14. Thereupon, the effects of rare-earth co-doping on the local structure are assessed at the atomic level. Pair-distribution function analysis of high-energy X-ray diffraction data (Qmax = 28 Å−1) is employed to make this assessment. Results reveal a stark structural invariance to rare-earth co-doping which bears testament to the open-framework and rigid nature of these glasses. A range of desirable attributes of these glasses unfold from this finding; in particular, a structural simplicity that will enable facile molecular engineering of rare-earth phosphate glasses with ‘dial-up’ lasing properties. When considered together with other factors, this finding also demonstrates additional prospects for these co-doped rare-earth phosphate glasses in nuclear waste storage applications. This study also reveals, for the first time, the ability to distinguish between P–O and P[double bond, length as m-dash]O bonding in these rare-earth phosphate glasses from X-ray diffraction data in a fully quantitative manner. Complementary analysis of high-energy X-ray diffraction data on single rare-earth phosphate glasses of similar rare-earth composition to the co-doped materials is also presented in this context. In a technical sense, all high-energy X-ray diffraction data on these glasses are compared with analogous low-energy diffraction data; their salient differences reveal distinct advantages of high-energy X-ray diffraction data for the study of amorphous materials.

Item Type: Article
DOI/Identification number: 10.1039/c3cp44298e
Additional information: Unmapped bibliographic data: LA - English [Field not mapped to EPrints] J2 - Phys. Chem. Chem. Phys. [Field not mapped to EPrints] AD - Cavendish Laboratory, University of Cambridge, J.J. Thomson Avenue, Cambridge CB3 0HE, United Kingdom [Field not mapped to EPrints] AD - Department of Physics, University of New Brunswick, P.O. Box 4400, Fredericton E3B 5A3, Canada [Field not mapped to EPrints] AD - Department of Chemistry, University of New Brunswick, P.O. Box 4400, Fredericton E3B 5A3, Canada [Field not mapped to EPrints] AD - School of Physical Sciences, University of Kent, Canterbury Kent CT2 7NR, United Kingdom [Field not mapped to EPrints] AD - European Synchrotron Radiation Facility, B. P. 220, Grenoble Cedex 9, France [Field not mapped to EPrints] AD - Synchrotron Radiation Source, Daresbury Laboratory, Warrington, Cheshire WA4 4AD, United Kingdom [Field not mapped to EPrints] AD - Department of Physics, University of Bath, Claverton Down, Bath BA2 7AY, United Kingdom [Field not mapped to EPrints] DB - Scopus [Field not mapped to EPrints]
Subjects: Q Science > QC Physics > QC173.45 Condensed Matter
Q Science > QD Chemistry > QD478 Solid State Chemistry
Divisions: Faculties > Sciences > School of Physical Sciences
Faculties > Sciences > School of Physical Sciences > Functional Materials Group
Depositing User: Giles Tarver
Date Deposited: 12 Feb 2015 15:05 UTC
Last Modified: 29 May 2019 14:09 UTC
Resource URI: https://kar.kent.ac.uk/id/eprint/46950 (The current URI for this page, for reference purposes)
Newport, Robert J.: https://orcid.org/0000-0002-2365-992X
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