先端化学工学ジャーナル

概要

Structural Phase Transitions in FeVO4 – CrVO4 Solid Solutions and effect on Multiferroicity in FeVO4

Goverdhan Reddy Turpu

Thorough structural studies using XRD, Raman, Mossbauer and FT-IR Spectroscopic methods were performed to establish the structural phase diagram of FeVO4-CrVO4 solid solutions. Solid solutions Fe1–xCrxVO4 (0≤ x ≤1.0) were synthesized through the standard solid state route. FeVO4 and CrVO4 were found to be in triclinic (P-1 space group) and orthorhombic structures (Cmcm space group), respectively. Cr incorporation into the FeVO4 lattice leads to the emergence of a new monoclinic phase dissimilar to the both end members of the solid solutions. In Fe1–xCrxVO4 up to x = 0.10, no discernible changes in the triclinic structure were found. A new structural monoclinic phase (C2/m space group) emerges within the triclinic phase at x = 0.125, and with the increase in Cr content, it gets stabilized with clear single phase signatures in the range of x = 0.175–0.25 as evidenced by the Rietveld analysis of the structures. Beyond x = 0.33, orthorhombic phase similar to CrVO4 (Cmcm space group) emerges and coexists with a monoclinic structure up to x = 0.85, which finally tends to stabilize in the range of x¼ 0.90–1.00. The Raman spectroscopic studies also confirm the structural transition. FeVO4 Raman spectra show the modes related to three nonequivalent V ions in the triclinic structure, where up to 42 Raman modes are observed in the present study. With the stabilization of structures having higher symmetry, the number of Raman modes decreases and the modes related to symmetry inequivalent sites collate into singular modes from the doublet structure. 57Fe Mossbauer spectroscopic studies show a finger print evidence for disappearance of non-equivalent sites of Fe as the structure changes from Triclinic–Monoclinic–Orthorhombic phases with the increasing Cr content in Fe1–xCrxVO4. FT – IR studies also corroborate the results with similar band formations