MoO3/MeMoO4 (Me = Cu, Ni, Co, Fe, Mn, and Cr) composites as materials for prospective optical and electrical applications

Abstract

The composite MoO3/MeMoO4 (Me = Cu, Ni, Co, Fe, and Mn) ceramics were obtained by standard high-temperature sintering. Their structure was tested using XRD, SEM, EDS, and XPS. The occurrence of two phases was determined. The main MoO3 phase exhibited an orthorhombic Pnma space group related to the ceramic grain of micrometre size. The second phase was induced by doping with the Me atom. It showed various monoclinic structures and a smaller grain size. The XPS test confirmed the coexistence of the phases, which was reflected in several lines in the patterns. The valence band of the undoped MoO3 was located ∼3.3 eV below the Fermi level. An additional subband attributed to the Me 3d state was detected within the energy gap. The MoO3/MeMoO4 composites showed a valence band shifted toward the Fermi level and overlapped with the subband, originating from hybridized Mo 4d – Me 3d states. Magnetic susceptibility showed an antiferromagnetic state below ∼20 K for the Ni- and Fe-doped composites. The estimated magnetic moment magnitudes indicated the contribution from Me2+ and Me3+ ions that marked the occurrence of oxygen vacancies. Diffuse reflectance spectra exhibited anomalies in the Vis (∼500–650 nm) and the NIR (∼700–850 nm) ranges and tails in the ∼900–1000 nm range. The estimated magnitudes of energy gaps were attributed to defect-induced states. They corresponded to deduced oxygen vacancies (2.05–2.38 eV) and states or subbands induced by the introduced Me atoms (1.34–1.89 eV). Electric dc resistivity temperature dependence showed thermally activated dependence. The estimated activation energy varied from 0.27 eV to 0.58 eV, depending on the doping of the Me atom. The electric features were consistent with the electronic structure determined using XRD and XPS tests.