Synthesis, spectroscopic and luminescence properties of Ga–doped γ–Al2O3

• Published in: Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy Vol. 227; p. 117658
• Main Authors: Baklanova, I.V., Krasil'nikov, V.N., Tyutyunnik, A.P., Enyashin, A.N., Baklanova, Ya.V., Gyrdasova, O.I., Samigullina, R.F., Vovkotrub, E.G.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 15.02.2020
• Subjects: Aluminum oxide; DFT calculations; Gallium; Infrared; Luminescence; Precursor method; Raman and NMR spectroscopy; Gallium; Precursor method; Infrared; Luminescence; Raman and NMR spectroscopy; DFT calculations; Aluminum oxide
• ISSN: 1386-1425
• DOI: 10.1016/j.saa.2019.117658

Gallium-doped aluminum oxide (Al1–xGax)2O3 with γ-Al2O3 (spinel) structure has been synthesized by the precursor method using the formate Al1-xGax(OH)(HCOO)2 as a precursor. The examination of Al1-xGax(OH)(HCOO)2 (x = 0.0, 0.1, 0.2, 0.3, 0.4) was carried out by X-ray powder diffraction, Infrared, Raman spectroscopy and differential-thermal methods. The solid solutions γ-(Al1-xGax)2O3 with х≤0.2 have been synthesized by thermolysis of precursors in helium atmosphere at 700 °C; they exhibit white-blue emission under UV excitation, whose intensity lowers with increasing dopant concentration. As an independent method, the DFT calculations confirmed thermodynamically the stability field of γ-(Al1-xGax)2O3 solid solutions and the NMR data on relative abundance of Al and Ga within the tetrahedral and octahedral sites in the metal sublattice. Furthermore, the structural and thermodynamic properties of carbon-containing impurities within these compounds were suggested theoretically as possible models of luminescence emission centers. The experimentally observed Ga-dependent quenching of luminescence was explained using the competition between C2p and Ga4p states within the band gap of γ-Al2O3. [Display omitted] •According to XRPD, Infrared and Raman data, Al1-xGax(OH)(HCOO)2 are isostructural.•Thermolysis of Al1-xGax(OH)(HCOO)2 with х ≥ 0.3 results in non-single-phase products.•The luminescence intensity is found to decrease with growing gallium concentration.