Study of divalent and trivalent chromium in forsterite by high-frequency EPR spectroscopy

Abstract

Divalent and trivalent chromium ions Cr2+ and Cr3+ replacing magnesium ions at octahedral positions in Mg2SiO4: Cr and Mg2SiO4: Cr: Li crystals are investigated by submillimeter EPR spectroscopy in the frequency range 65–230 GHz. The crystals are grown from the melt by the Czochralski method. The content of mixed-valence chromium species in forsterite is analyzed. It is demonstrated that, in crystals grown in argon (the oxygen partial pressure is \( P_{O_2 } \) = 0.01 kPa), approximately half of the chromium ions are in the divalent form. The Cr2+ ions are distributed over the M1 and M2 positions in a ratio of approximately 2: 1. A change in the oxygen partial pressure \( P_{O_2 } \) and the chromium concentration, as well as an additional doping with lithium, does not lead to substantial changes in the distribution of divalent chromium ions over the positions. It is shown that an increase in the oxygen partial pressure \( P_{O_2 } \) from 0.01 to 2.00 kPa results in a decrease in the coefficient of divalent chromium distribution between the crystal and the melt. Doping with lithium also decreases the concentration of Cr2+ centers. In crystals grown without lithium, approximately half of the trivalent chromium ions are associated with magnesium vacancies. The addition of lithium leads to the destruction of these associates, an increase in the concentration of individual Cr3+ centers, and the formation of lithium associates with trivalent chromium ions. The conditions for the formation of associates of trivalent chromium ions with lithium ions are optimum when the crystal contains approximately identical amounts of Cr3+ and Li+ ions. Doping with lithium increases the concentration of Cr3+ ions and, thus, decreases the fraction of Cr2+ and Cr4+ ions in the total content of chromium centers.