Harishchandra Singh

Observation of high-spin mixed oxidation state of cobalt in ceramic Co3TeO6

We report coexistence of high spin Co3+ and Co2+ in ceramic Co3TeO6 using X-ray Absorption Near Edge Structure (XANES), DC magnetization, and first principles ab-initio calculations. The main absorption line of cobalt Co K-edge XANES spectra, along with a linear combination fit, led us to estimate relative concentration of Co2+ and Co3+as 60:40. The pre edge feature of XANES spectrum shows crystal field splitting of ∼1.26 eV between eg and t2g states, suggesting a mixture of high spin states of both Co2+ and Co3+. Temperature dependent high field DC magnetization measurements reveal dominant antiferromagnetic order with two Neel temperatures (TN1 ∼ 29 K and TN2 ∼ 18 K), consistent with single crystal study. A larger effective magnetic moment is observed in comparison to that reported for single crystal (which contains only Co2+), supports our inference that Co3+ exists in high spin state. Furthermore, we show that both Co2+ and Co3+ being in high spin states constitute a favorable ground state through fir...

Air annealing effects on lattice structure, charge state distribution of cations, and room temperature ferrimagnetism in the ferrite composition Co2.25Fe0.75O4

The ferrite composition Co2.25Fe0.75O4 has been prepared by chemical coprecipitation route. The as-prepared material has been annealed at different temperatures to investigate thermal activated changes in structural phase, charge states of cations, and room temperature magnetic properties. Synchrotron x-ray diffraction (SXRD) patterns have shown splitting of cubic spinel structure into Fe-rich and Co-rich phases for annealing temperature up to 800 ?C. Single phase cubic spinel structure has been stabilized at annealing temperature 900 ?C. The existence of Fe4+ ions, as confirmed from x-ray absorption near edge structure spectroscopy (XANES), is the new information for spinel ferrite. Raman spectra indicated normal spinel structure. The results of SXRD, XANES and Raman spectra have been used to estimate distribution of Co and Fe ions in spinel structure. The variation in population of Co and Fe ions and phase instability has affected the magnetic properties. The sample annealed at 800 ?C shows maximum coercivity (?567 Oe) and squareness (?0.38), whereas the single-phased sample showed lowest values of ferrimagnetic parameters. The tuning of magnetic parameters by thermal activated structural phase variation of a hetero-structured magnetic system appears to be a new technique for the development of magnetic materials.

Structural investigations on Co3-xMnxTeO6; (0 < x ≤ 2); High temperature ferromagnetism and enhanced low temperature anti-ferromagnetism

In the quest of materials with high temperature ferromagnetism and low temperature anti-ferromagnetism, we prepare Co3-xMnxTeO6; (0 < x ≤ 2) solid solutions. Room temperature structural investigations on these solid solutions as a function of Mn concentration using Synchrotron X-ray diffraction (SXRD) and X-ray absorption near edge structure measurements in corroboration with magnetism 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 < 0.5, while only R 3¯ structure for x ≥ 0.5. Further, it shows increase in both lattice parameters as well as average transition metal-oxygen (Co/Mn-O) bond lengths for x ≥ 0.5. Co and Mn K-edge XANES spectra reveal that both Co and Mn are in mixed oxidation state, Co2+/Mn2+ and Co3+/Mn3+. Relative ratios of Co3+/Co2+ and Mn3+/Mn2+ obtained using Linear combination fit decrease with increasing x (for x ≥ 0.5)....

Short range ferromagnetic, magneto-electric, and magneto-dielectric effect in ceramic Co3TeO6

We report observation of magneto-electric and magneto-dielectric couplings along with short range ferromagnetic order in ceramic Cobalt Tellurate (Co3TeO6, CTO) using magnetic, structural, dielectric, pyroelectric, and polarization studies. DC magnetization along with dielectric constant measurements indicate a coupling between magnetic order and electrical polarization. A strong anomaly in the dielectric constant at ∼17.4 K in zero magnetic field indicates spontaneous electric polarization, consistent with a recent neutron diffraction study. Observation of weak short range ferromagnetic order at lower temperatures is attributed to the Griffiths-like ferromagnetism. Furthermore, magnetic field dependence of the ferroelectric transition follows earlier theoretical predictions, applicable to single crystal CTO. Finally, combined dielectric, pyroelectric, and polarization measurements suggest that the ground state of CTO may possess spontaneous symmetry breaking in the absence of magnetic field.

Structural study in ceramic multiferroic Co3TeO6 and analysis of possible Co-Co networks

We show that there exist four networks (Co1-Co4, Co2-Co3-Co5, Co1-Co5 and Co2-Co3-Co4) in contrast to earlier observations of two networks (Co1-Co4 and Co2-Co3-Co5) in Co3TeO6 (CTO) multiferroic [Phys. Rev. B 88, 184427 (2013)]. Due to five crystallographically different sites of Co ions coordinated by [IV], [V] and [VI] oxygen atoms, the coordination polyhedra exhibit strong distortions from their respective ideal polyhedra, and thus potentially allow to resolve low-symmetry crystal field splittings of d-d electronic transitions. Our structural analysis using Rietveld refinements on the room temperature Synchrotron X-ray Diffraction data indicates possible magnetic order, and may provide a basis for the complex and multiple magnetic transitions of CTO at low temperature.

Effect of Zn doping on the magneto-caloric effect and critical constants of Mott insulator MnV2O4

X-ray absorption near edge spectra (XANES) and magnetization of Zn doped MnV2O4 have been measured and from the magnetic measurement the critical exponents and magnetocaloric effect have been estimated. The XANES study indicates that Zn doping does not change the valence states in Mn and V. It has been shown that the obtained values of critical exponents β, γ and δ do not belong to universal class and the values are in between the 3D Heisenberg model and the mean field interaction model. The magnetization data follow the scaling equation and collapse into two branches indicating that the calculated critical exponents and critical temperature are unambiguous and intrinsic to the system. All the samples show large magneto-caloric effect. The second peak in magneto-caloric curve of Mn0.95Zn0.05V2O4 is due to the strong coupling between orbital and spin degrees of freedom. But 10% Zn doping reduces the residual spins on the V-V pairs resulting the decrease of coupling between orbital and spin degrees of freedom.