Luminescence of Mn4+ ions in CaTiO3 and MgTiO3 perovskites: Relationship of experimental spectroscopic data and crystal field calculations

• Published in: Optical materials Vol. 74; pp. 46 - 51
• Main Authors: Đorđević, Vesna, Brik, Mikhail G., Srivastava, Alok M., Medić, Mina, Vulić, Predrag, Glais, Estelle, Viana, Bruno, Dramićanin, Miroslav D.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.12.2017
• Subjects: Crystal field; LED; Mn4; Perovskite; Red luminescence; Perovskite; Mn4; LED; Crystal field; Red luminescence
• ISSN: 0925-3467; 1873-1252
• DOI: 10.1016/j.optmat.2017.03.021

Herein, the synthesis, structural and crystal field analysis and optical spectroscopy of Mn4+ doped metal titanates ATiO3 (A = Ca, Mg) are presented. Materials of desired phase were prepared by molten salt assisted sol-gel method in the powder form. Crystallographic data of samples were obtained by refinement of X-ray diffraction measurements. From experimental excitation and emission spectra and structural data, crystal field parameters and energy levels of Mn4+ in CaTiO3 and MgTiO3 were calculated by the exchange charge model of crystal-field theory. It is found that crystalline field strength is lower (Dq = 1831 cm−1) in the rhombohedral Ilmenite MgTiO3 structure due to the relatively longer average Mn4+O2− bond distance (2.059 Å), and higher (Dq = 2017 cm−1) in orthorhombic CaTiO3 which possess shorter average Mn4+O2− bond distance (1.956 Å). Spectral positions of the Mn4+2Eg → 4A2g transition maxima is 709 nm in MgTiO3 and 717 nm in CaTiO3 respectively in good agreement with calculated values. •Mn4+ doped titanates CaTiO3 and MgTiO3 via Molten salt assisted sol-gel method.•Calculated crystal field parameters and energy levels of Mn4+ in the hosts.•Smallest fraction of covalence in the Mn4+-O2− bonding in MgTiO3 among ATiO3.•The Mn4+2Eg → 4A2g emission transition in MgTiO3 is at the highest energy among ATiO3