4.5 Article

Effect of chromium substitution on structural and optical properties of Ca3(VO4)2 for laser and SRS applications

Journal

SOLID STATE SCIENCES
Volume 146, Issue -, Pages -

Publisher

ELSEVIER
DOI: 10.1016/j.solidstatesciences.2023.107365

Keywords

Crystal growth; EPR; X-ray methods; Defects; Optical materials/properties

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The crystal structures of CVO:Cr single crystals doped with over-stoichiometric 0.01, 0.05, and 0.1 wt% Cr2O3 grown by the Czochralski method were determined. The presence of chromium in multiple calcium sites and its coordination as octahedral Cr3+ and tetrahedral Cr4+ were revealed. The green or yellow color of CVO:Cr was found to be attributed to the valence state of chromium, Cr3+ or Cr4+. The structural behavior of transition metal ions with variable formal charge in CVO structure was summarized and analyzed.
Crystal structures of Czochralski-grown Ca-3(VO4)(2) single crystals doped with over-stoichiometric 0.01, 0.05, and 0.1 wt% Cr2O3 (CVO:Cr) are solved and refined. A whitlockite-like structure with five Ca sites, two-capped (Ca1 and Ca3) and mono-capped (Ca2) trigonal prisms, distorted octahedron (Ca4) and tetrahedron (Ca5), is deter-mined for CVO:Cr. Single-crystal synchrotron X-ray diffraction analysis revealed the presence of chromium in Ca2, Ca3, Ca4 sites. In CVO:Cr, chromium has octahedral (Cr3+) and tetrahedral (Cr4+) coordination, which suggests structural superpositions of CaO8, CaO7, CaO6 and Cr3+O6 or Cr4+O4 polyhedra. X-ray diffraction, EPR and spectroscopic studies showed that green or yellow color of CVO:Cr is related to chromium valence state, Cr3+ or Cr4+, respectively. An increase in the Cr4+ concentration is accompanied by increased vacancy content in two of three vanadium sites. Structural behavior of transition metal ions with a variable formal charge (Co, Mn, Cr) in CVO structure is summarized, analyzed and discussed. Three absorption bands around 23900, 16300 and 14000 cm(-1), typical for Cr3+ ions, are revealed in the UV-VIS spectra of green samples. An additional broad band with a maximum at 21254 cm(-1) refers to Cr4+ ions, the appearance of which after annealing in air was established by X-ray diffraction analysis.

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