Influence of inversion level on the optical absorption spectra of Ti-doped transparent MgGa₂O₄ ceramics

Ti-doped (0.08, 0.30, and 1.00 atomic% [at.%]) transparent MgGa₂O₄ ceramics (possessing a high inversion level; i up to 0.8) were fabricated by pulsed electric current sintering, at 950°C, under vacuum for 30–90 min. Optical transmission, emission, and electron paramagnetic resonance spectra were recorded. The maximal transmission level was ∼70% (820 nm), for a thickness of ∼1 mm, which, while not very high, permitted the observation of the optical absorption bands location and profile. Interpretation of the fluorescence spectra suggests that some Ti⁴⁺ cations (mostly hexacoordinated) were accommodated by the host despite the scarcity of oxygen in the atmosphere during the sintering process. The Ti³⁺ cations substitute native ions located in tetrahedral sites, distorting the original T_d symmetry toward a D_2d symmetry. Comparing the Ti-doped MgGa₂O₄ (high inversion) and MgAl₂O₄ (low inversion) spinels, spectral characteristics revealed that a significant increase in the inversion level drives Ti³⁺ cations from octahedral toward tetrahedral sites. This is reflected in the optical absorption spectra by the disappearance of the band at ∼20 000 cm⁻¹ (detectable in MgAl₂O₄) in MgGa₂O₄; the two d–d bands, of MgA₂O₄, in MgGa₂O₄ are reduced to a single one, located at 11 800 cm⁻¹. These results, for MgGa₂O₄, strongly support a similar assignment—of the strong band at 12 800 cm⁻¹, in Ti-doped MgAl₂O₄—to a tetracoordinated Ti³⁺. Thus, while in MgAl₂O₄, Ti³⁺ appears in both octahedral and tetrahedral coordination and in MgGa₂O₄ only the latter state is stable. In both spinels, Ti dopant speciates into Ti³⁺ and Ti⁴⁺ cations.