BaMoO4 was obtained via facile mechanochemical synthesis at room temperature and a solid-state reaction. An evaluation of the phase composition and structural and optical properties of BaMoO4 was conducted. The influence of different milling speeds on the preparation of BaMoO4 was explored. A shorter reaction time for the phase formation of BaMoO4 was achieved using a milling speed of 850 rpm. A milling speed of 500 rpm led to partial amorphization of the initial reagents and to prolongation of the synthesis time of up to 3 h of milling time. Solid-state synthesis was performed via heat treatment at 900 °C for 15 h. X-ray diffraction analysis (XRD), infrared (IR) and UV diffuse reflectance (UV-Vis) and photoluminescence (PL) spectroscopy were carried out to characterize the samples. Independently of the method of preparation, the obtained samples had tetragonal symmetry. The average crystallite sizes of all samples, calculated using Scherrer’s formula, were in the range of 240 to 1540 Å. IR spectroscopy showed that more distorted structural MoO4 units were formed when the compound was synthesized via a solid-state reaction. The optical band gap energy of the obtained materials was found to decrease from 4.50 to 4.30 eV with increasing crystallite sizes. Green- and blue-light emissions were observed for BaMoO4 phases under excitation wavelengths of 330 and 488 nm. It was established that the intensity of the PL peaks depends on two factors: the symmetry of MoO4 units and the crystallite sizes.
Nanocrystalline CoWO4 sampled were synthesized using a simple mechanochemical approach and a solid-state reaction, respectively. The formation of nanocrystalline CoWO4 was characterized by X-ray diffraction (XRD) and infrared spectroscopy (IR). The optical properties of the obtained samples were explored by diffuse reflectance UV–visible (DRS) and photoluminescence (PL) techniques. A milling speed of 850 rpm led to the direct synthesis of monoclinic CoWO4 with a short reaction time (1 h). The complete reaction did not occur in the solid-state synthesis. The obtained samples had monoclinic crystal systems with different lattice parameters. The average crystallite sizes of CoWO4 were in the range of 20 to 180 nm. The TEM investigation showed that the morphology of the CoWO4 particles differed depending on the preparation conditions. The values of the determined optical bandgap of CoWO4 were the range of 1.89 to 2.18 eV, according to diffusion reflectance spectroscopy in the ultraviolet-to-visible range. Broader blue–green emission spectra with peaks at 430 nm were observed for samples prepared via both routes. The CIE color coordinates of the CoWO4 samples lay in the blue and purple regions. The quantum yields of the CoWO4 samples synthesized after 1 h and 5 h milling times at 850 rom were 0.34 and 0.67%, respectively. This study proposes an affordable mechanochemical approach for blue–green phosphors that could possibly be used in various light-emitting diodes (LEDs).
This work investigated the optical characteristics of BaWO4 nanoparticles that were produced through direct mechanochemical synthesis at varying speeds and times. This research expands upon our previous study. We demonstrated that the mechanochemical activation of the precursor of BaCO3 and WO3, at elevated milling speeds (850 rpm), facilitates the formation of tetragonal BaWO4 in a reduced reaction time. The final products were characterized by scanning electron microscopy (SEM), as well as Raman, infrared (IR), UV-Vis diffuse reflectance, and photoluminescence spectroscopies. The crystallite sizes and particles shapes were determined by X-ray diffraction and SEM analysis. Round particles with a size below 50 nm formed under different milling conditions. The Raman spectra of the synthesized samples confirmed the presence of a scheelite-type structure with the typical six distinct vibrational peaks. The symmetry of the structural WO4 groups was determined by IR spectroscopy. The absorption spectra of both samples exhibited intensive peaks at 210 nm, and the calculated optical band gaps of BaWO4 were 5.10 eV (3 h/500 rpm) and 5.24 eV (1 h/850 rpm). A strong (400 nm) and weak (465 nm) emission were observed for the BaWO4 that was obtained at a higher milling speed, while wider emission at 410 nm was visible for the BaWO4 that was prepared at a lower milling speed. The CIE coordinates of the mechanochemically synthesized BaWO4 were located within the blue area, exhibiting various positions.