Structural, spectroscopic, magnetic, and magneto-transport behavior of Ruddlesden-Popper Ca4Mn3-xWxO10 (x = 0, 0.05, 0.1) compounds

Abstract

This report comprehensively investigates the crystal structure, magnetism, and transport properties of tungsten (W6+) substituted polycrystalline Ca4Mn3-xWxO10 (x = 0, 0.05, 0.1) compounds. The compounds were synthesized using the solid-state method and found to exhibit a single-phase orthorhombic structure confirmed by the Rietveld refinement. The substitution of (W6+) induces a change in the Mn octahedron and enhances the unit cell volume. The morphology indicates the crystalline nature of all the samples. The FTIR spectroscopic study revealed the position of the IR bands, which is highly sensitive to the oxidation state of Mn-ions. The shift to higher wavenumbers indicates reduced oxidation from Mn4+ to Mn3+ species. The appearance of the Mn4+ oxidation state in (x = 0) and the emergence of Mn3+ on W6+ substitution for (x = 0.05, 0.1) compounds are explored. The electrical resistivity plots revealed that compounds are semiconducting. The magnitude of resistivity decreases with W6+ substitution. The reported compounds exhibit a significant negative magneto-resistance towards lower temperatures. The compounds also demonstrate short-range ferromagnetic (FM) behavior attributed to the charge compensation effect's double exchange interaction (DE) connecting Mn4+ and Mn3+. The negative value of thermoelectric power (S) suggests the presence of charge carriers such as electrons, and the value ofSfirst increased and then decreased in doped samples. The conduction in the studied compound is attributed to small polaron hopping.