Influence of defect structure on colour tunability and magneto optical behaviour of WO₃ nanoforms

The present study reports the impact of thermal annealing on the structural, optical and magnetic properties of WO₃ nanostructures, synthesized using an acid precipitation method by, employing various spectroscopic and magnetic measurements. The X-ray diffraction and Raman measurements confirmed the orthorhombic structure of as dried WO₃·H₂O and monoclinic structure of WO₃ nanopowders annealed at or above 500 °C. The morphological characterization shows the formation of different microstructures like nanosheets, nanoplatelets and nanocuboids in the micro-scale with the variation of annealing temperatures. The optical band gap has been calculated using the Kubelka-Munk function. The room temperature photoluminescence (PL) spectra recorded at different excitation wavelengths show intense near ultraviolet (NUV) emission which might be due to the presence of localized states associated with oxygen vacancies, and the surface states in the conduction band. The emissions in visible region correspond to the structural defects such as oxygen vacancies present within the band gap and band to band transitions. The spectral chromaticity colour coordinates indicate that the light emitted from the prepared samples shows shift from violet to red region with the change of excitation wavelength. Magnetic measurements show decrease in room temperature ferromagnetism (FM) with annealing temperature. The X-ray absorption spectroscopy (XAS) measurements at O K-edge show the significant change in the W-O hybridizations. The decrease in PL intensity and ferromagnetic ordering with increase in annealing temperatures are directly correlated with the filling up of oxygen vacancies in the samples. The oxygen vacancies based F-Center exchange model is discussed to understand the origin of FM in WO₃ nanostructures.