Polaronic Correlations in Magnetic Behavior of Oxygen Deficient V2O5

The undoped V2O5 sample is synthesized by thermal decomposition resulting in oxygen deficient polycrystalline nature. It has a crystallite size of about 80 nm and a chemical stoichiometry of V2O4.65 with a significant V4+ states in addition to V5+ as seen from X-ray diffraction and X-ray photoelectron spectroscopy respectively. The optical studies reveal a bandgap of 2.2 eV and a significant emission due to defects (1.8 eV) as well as Moss-Burstein effect(3.1 eV) which arises due to gap states and split in conduction band respectively. The temperature dependant electrical conductivity and thermopower measurements clearly demonstrate a polaronic conduction mechanism of small polaron hopping with hopping energy of 0.112 eV. The V2O5 sample is found to show a strong field as well as temperature dependent magnetic behaviour when measured using sensitive SQUID magnetometer. It shows a positive magnetic susceptibility at all temperatures (5-300 K) at low field (0.1 T). The observed behavior is found to be a mix of ferromagnetism (FM) and antiferromagnetism (AFM, {\theta}=-2.1 K in CW fit). On the other hand, for high field (1 T), it showed FM only at low temperatures and abruptly becomes diamagnetic at 31.2 K. This varied magnetic behavior has been attributed to small polaron hopping which arises because of oxygen vacancy defects compensated by charge defects of V4+ and transition from bound to free polarons seen from transport. This is further revealed as strong hybridization of V bonded to oxygen vacancy VO and neighboring V5+ ions, resulting in net magnetic moment per vacancy (3.959 {\mu}_B) as predicted from first principle calculations. The insignificantly low energy difference between FM and AFM interactions observed from calculations and their critical dependence on oxygen vacancy concentrations justify the varied magnetic behaviour of V2O5 reported in the literature