Structural insight into $Co_{3-x}Mn_xTeO_6$; ($0 \lt x \le 2$) solid solutions using Synchrotron X-ray diffraction and XANES

Structural investigation on $Co_{3-x}Mn_xTeO_6$; ($0 \lt x \le 2$) solid solutions as a function of Mn concentration using Synchrotron X-ray diffraction (SXRD) and XANES measurements are presented. Phase diagram obtained from Rietveld Refinement on SXRD data as a function of Mn concentration indicates doping disproportionate mixing of both monoclinic (C2/c) and rhombohedral (R-3) structure (for $x \lt 0.5$) while only R-3 symmetry for $x \ge 0.5$. Furthermore, Rietveld analysis on SXRD data shows increase in lattice parameters and average transition metal oxygen (Co/Mn-O) bond lengths for $x \ge 0.5$. Co and Mn K-edge XANES spectra reveal that both Co and Mn are in mixed oxidation state of $Co^{2+}/Mn^{2+}$ and $Co^{3+}/Mn^{3+}$. Relative ratio of $Co^{3+}/Co^{2+}$ and $Mn^{3+}/Mn^{2+}$ using Linear combination fit (LCF) decrease with increasing $x$ for $x \ge 0.5$. These structural and spectroscopic evidences are used to provide possible interpretation of the reported observations of maximum Neel Temperature (TN) at $x ~\sim 0.5$ and enhancements of antiferro/ferro-magnetic interactions in $Co_{3-x}Mn_xTeO_6$ solid solutions.

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