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arXiv · 0708.1798

Theory of oxidation/reduction-induced chromium ion valence transformations in Cr,Ca:YAG crystals

Abstract

In their paper [Opt. Mater. 24, 333, 2003], Feldman et al conducted an experimental study of the dynamics of chromium ion valence transformations in Cr,Ca:YAG crystals among the trivalent Cr3+ state, and two tetravalent Cr4+ ones, of octahedral and tetrahedral coordination. The temperatures used ranged between ~800 and 1,000 C. The basic effects are the transition of Cr3+ into Cr4+ under high-temperature annealing in an oxidizing atmosphere, and the reverse transition under a reducing atmosphere, or in vacuum. In the present theory, we interpret the processes by oxygen-vacancy diffusion in the bulk of the YAG. The quasi-chemical reaction VO2- + Cr4+ = Cr3+/VO- between the chromium ions and the vacancies VO2- is responsible for the valence transformations. Dynamical analysis provides profiles of the Cr3+ and Cr4+ concentrations in the crystal during oxidation and during reduction. Reaction rate profiles are also calculated, establishing the reaction front position and width. A comparison with existing experimental results on the integrated Cr4+ concentration as a function of time during oxidation [Opt. Mater. 24, 333, 2003] shows reasonable agreement.

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Misha Sinder, Zeev Burshtein, Joshua Pelleg. 2007-08-16. Theory of oxidation/reduction-induced chromium ion valence transformations in Cr,Ca:YAG crystals. https://arxiv.org/abs/0708.1798

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