Titanium dioxide (TiO2) nanoparticles were prepared by the sol–gel method and the structural, morphological, and optical properties were investigated at different sintering temperatures of 500, 600, 700, 800, and 900°C. A tetragonal structure of anatase, mixed (anatase–rutile), and rutile phases are observed in the X-ray diffraction (XRD) analysis. Pure anatase phase formation occurred at 500°C, whereas anatase-to-rutile phase transformation began at 600°C, and reaching complete conversion to rutile at 800°C. The average crystallite size increased from 23 to 34 nm for anatase and 38 to 62 nm for the rutile when sintering temperature increased from 500 to 900°C. The scanning electron microscope (SEM) result presented the increase of grain size (25–100 nm) with increasing the sintering temperature. The Fourier transform infrared (FTIR) spectra demonstrated the presence of TiO2 vibrational bonds in all samples. The optical bandgaps of the sintered TiO2 nanoparticles decreased with rising sintering temperature. Photoluminescence spectra exhibited three characteristic peaks centered at 380, 450, and 550 nm. The emission intensity increased with increasing the sintering temperature. The Mie analysis was also studied to calculate scattering cross-section, forward scattering, and asymmetry for different grain sizes. The results showed that by increasing the nanoparticle diameters, the peaks of all spectra are redshifted for larger grain sizes and cross-section peaks shift to high values. In this study, the sintering temperature is observed to have a strong influence on crystalline phase transformation, microstructure, and optical properties of TiO2 nanoparticles. The TiO2 sample sintered at 900°C shows the best result to be used as luminescent material due to the low optical bandgap energy.

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