Structural Refinement and Photoluminescence Properties of MnWO4 Nanorods Obtained by Microwave-Hydrothermal Synthesis
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Manganese tungstate (MnWO4) nanorods were prepared at room temperature by the co-precipitation method and synthesized after processing in a microwave-hydrothermal (MH) system at 140 °C for 6–96 min. These nanorods were structurally characterized by X-ray diffraction (XRD), Rietveld refinements and Fourier transform (FT)-Raman spectroscopy. The growth direction, shape and average size distribution of nanorods were observed by means of transmission electron microscopy (TEM) and high resolution TEM (HR-TEM). The optical properties of the nanorods were investigated by ultraviolet visible (UV-vis) absorption and photoluminescence (PL) measurements. XRD patterns, Rietveld refinement data and FT-Raman spectroscopy indicate that the MnWO4 precipitate is not a single phase structure while the nanorods synthesized by MH processing have a wolframite-type monoclinic structure without deleterious phases. FT-Raman spectra exhibited the presence of 17 Raman-active modes from 50 to 1,000 cm−1. TEM and HR-TEM micrographs indicated that the nanorods are aggregated due to surface energy by Van der Waals forces and grow along the  direction. UV–vis absorption measurements confirmed non-linear values for the optical band gap (from 3.2 to 2.72 eV), which increased as the MH processing time increased. The structural characterizations indicated that the presence of defects in the MnWO4 precipitate promotes a significant contribution to maximum PL emission, while MnWO4 nanorods obtained by MH processing decrease the PL emission due to the reduction of defects in the lattice.
KeywordsMnWO4 Microwave-hydrothermal Rietveld refinement Photoluminescence
The authors acknowledge the financial support of the Brazilian research financing institutions: FAPESP (No. 2009/53189-8/50303-4), CNPq and CAPES. Special thanks are extended to Prof. Dr. D. Keyson and Dr. D.P. Volanti for the development of microwave-hydrothermal system.