Structural models for yttrium aluminium borate laser glasses: NMR and EPR studies of the system (Y2O3)0.2–(Al2O3)x–(B2O3)0.8−x
- 1 January 2011
- journal article
- Published by Royal Society of Chemistry (RSC) in Physical Chemistry Chemical Physics
- Vol. 13 (35), 16071-16083
- https://doi.org/10.1039/c1cp21404g
Abstract
The structure of laser glasses in the system (Y2O3)0.2{(Al2O3)x)(B2O3)0.8−x} (0.15 ≤ x ≤ 0.40) has been investigated by means of 11B, 27Al, and 89Y solid state NMR as well as electron spin echo envelope modulation (ESEEM) of Yb-doped samples. The latter technique has been applied for the first time to an aluminoborate glass system. 11B magic-angle spinning (MAS)-NMR spectra reveal that, while the majority of the boron atoms are three-coordinated over the entire composition region, the fraction of three-coordinated boron atoms increases significantly with increasing x. Charge balance considerations as well as 11B NMR lineshape analyses suggest that the dominant borate species are predominantly singly charged metaborate (BO2 /2O−), doubly charged pyroborate (BO1 / 2(O−)2), and (at x = 0.40) triply charged orthoborate groups. As x increases along this series, the average anionic charge per trigonal borate group increases from 1.38 to 2.91. 27Al MAS-NMR spectra show that the alumina species are present in the coordination states four, five and six, and the fraction of four-coordinated Al increases markedly with increasing x. All of the Al coordination states are in intimate contact with both the three- and the four-coordinate boron species and vice versa, as indicated by 11B/27Al rotational echo double resonance (REDOR) data. These results are consistent with the formation of a homogeneous, non-segregated glass structure. 89Y solid state NMR spectra show a significant chemical shift trend, reflecting that the second coordination sphere becomes increasingly “aluminate-like” with increasing x. This conclusion is supported by electron spin echo envelope modulation (ESEEM) data of Yb-doped glasses, which indicate that both borate and aluminate species participate in the medium range structure of the rare-earth ions, consistent with a random spatial distribution of the glass components.Keywords
This publication has 43 references indexed in Scilit:
- Luminescence characteristics of YAP:Ce scintillator powders and compositesOptical Materials, 2010
- Glass-to-Vitroceramic Transition in the Yttrium Aluminoborate System: Structural Studies by Solid-State NMRThe Journal of Physical Chemistry C, 2010
- Bi-functional laser and non-linear optical crystalsOptical Materials, 2006
- Flux growth and spectral properties of Yb:YAB single crystal with high Yb3+ concentrationJournal of Crystal Growth, 2004
- Modelling one‐ and two‐dimensional solid‐state NMR spectraMagnetic Resonance in Chemistry, 2001
- Field-swept pulsed electron paramagnetic resonance of Cr3+-doped ZBLAN fluoride glassJournal of Physics D: Applied Physics, 2001
- Structural and scintillation properties of new Ce3+-doped alumino-borateOptical Materials, 2001
- Self-frequency-summing NYAB laser for tunable blue generationOptical Materials, 1999
- Electron spin echo envelope modulation spectroscopy in mixed alkali silicate glassesThe Journal of Chemical Physics, 1999
- Properties of Yttria‐Aluminoborate GlassesJournal of the American Ceramic Society, 1990