Annealing-Induced Structural Behavior of Mn Dopant Ions in Calcium Orthovanadate Ca3(VO4)2Single Crystals

The crystal and local structures of Czochralski-grown calcium orthovanadate (Ca3(VO4)2) single crystals doped with over-stoichiometric 0.05 wt % Mn2O3 (CVO:0.05Mn) and annealed under different conditions are studied by single-crystal conventional and synchrotron X-ray diffraction, X-ray absorption spectroscopy, and electron paramagnetic resonance for the first time. Bottom (annealing in air) and top (annealing in air and in vacuum) parts of the CVO:0.05Mn crystal differ in the manganese content (higher in the bottom part), formal charge (Mn4+ and Mn(3+)+, respectively), and color (orange bottom part; light orange and yellow top parts annealed in air and vacuum, respectively). Manganese ions are located in one (Ca3, distorted two-capped trigonal prism) of five crystallographic Ca sites and have octahedral coordination, which is consistent with crystal-chemical properties of transition-metal ions. The presence of vacancies in one of three V sites is revealed. Formal charge 5+ for vanadium ions is confirmed by X-ray photoelectron spectroscopy. Different colors of CVO:Mn crystals and different formal charges of manganese are explained depending on the growth and post-growth treatment conditions. © 2022 American Chemical Society.

Kuz'micheva G.M. 1 , Ivleva L.I.2 , Kaurova I.A.1 , Khramov E.V. 3 , Lazarenko V.A. 3 , Rybakov V.B. 4 , Fionov Y.A. 5 , Fionov A.V.4
  • 1 Mirea - Russian Technological University, 78 Vernadskogo pr., Moscow, 119454, Russian Federation
  • 2 Prokhorov General Physics Institute, Russian Academy of Sciences, 38 Vavilova str., Moscow, 119991, Russian Federation
  • 3 National Research Center, Kurchatov Institute, 1 Akademika Kurchatova pl., Moscow, 123182, Russian Federation
  • 4 Chemistry Department, Lomonosov Moscow State University, Leninskie Gory 1/3, Moscow, 119991, Russian Federation
  • 5 Peoples' Friendship University of Russia, 6 Mikluho-Maklaya str., Moscow, 117198, Russian Federation
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