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

A.J. Cramer, J.M. Cole, V. Fitzgerald, V. Honkimaki, M.A. Roberts, T. Brennan, R.A. Martin, G.A. Saunders, R.J. Newport

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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, (RO) (R′O)(PO ), where (R, R′) denotes (Ce, Er) or (La, Nd) co-doping and the total rare-earth composition corresponds to a range between metaphosphate, RPO, and ultraphosphate, RP O. 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 (Q = 28 Å) 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 PO 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.
Original languageEnglish
Pages (from-to)8529-8543
Number of pages15
JournalPhysical Chemistry Chemical Physics
Volume15
Issue number22
Early online date6 Mar 2013
DOIs
Publication statusPublished - 14 Jun 2013

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    Cramer, A. J., Cole, J. M., Fitzgerald, V., Honkimaki, V., Roberts, M. A., Brennan, T., Martin, R. A., Saunders, G. A., & Newport, R. 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), 8529-8543. https://doi.org/10.1039/c3cp44298e