In this study, we conducted an extensive investigation into broadband near-infrared luminescence of Cr3+-doped Ca3Y2Ge3O12 garnet, employing first-principles calculations within the density functional theory framework. Our initial focus involved determining the site occupancy of Cr3+ activator ions, which revealed a pronounced preference for the Y3+ sites over the Ca2+ and Ge4+ sites, as evidenced by the formation energy calculations. Subsequently, the geometric structures of the excited states 2E and 4T2, along with their optical transition energies relative to the ground state 4A2 in Ca3Y2Ge3O12:Cr3+, were successfully modeled using the ΔSCF method. Calculation convergence challenges were effectively addressed through the proposed fractional particle occupancy schemes. The constructed host-referred binding energy diagram provided a clear description of the luminescence kinetics process in the garnet, which explained the high quantum efficiency of emission. Furthermore, the accurate prediction of thermal excitation energy yielded insights into the thermal stability of the compound, as illustrated in the calculated configuration coordinate diagram. More importantly, all calculated data were consistently aligned with the experimental results. This research not only advances our understanding of the intricate interplay between geometric and electronic structures, optical properties, and thermal behavior in Cr3+-doped garnets but also lays the groundwork for future breakthroughs in the high-throughput design and optimization of luminescent performance and thermal stability in Cr3+-doped phosphors.

• Klíčová slova
• Cr3+ ions, first-principles calculations, garnets, near-infrared emission, thermal stability,
• Publikační typ
• časopisecké články MeSH

The influence of Mo on the electronic states and crystalline structure, as well as morphology, phase composition, luminescence, and defects in ZnO rods grown as free-standing nanoparticles, was studied using a variety of experimental techniques. Mo has almost no influence on the luminescence of the grown ZnO particles, whereas shallow donors are strongly affected in ZnO rods. Annealing in air causes exciton and defect-related bands to drop upon Mo doping level. The increase of the Mo doping level from 20 to 30% leads to the creation of dominating molybdates. This leads to a concomitant drop in the number of formed ZnO nanorods.

• Klíčová slova
• ZnO nanorods, electron paramagnetic resonance, luminescence, molybdenum doping, morphology,
• Publikační typ
• časopisecké články MeSH

Cationic doping of ZnO nanorods has gained increased interest as it can lead to the production of materials with improved luminescent properties, electrical conductivity and stability. We report on various Mo-doped ZnO powders of nanorods synthesized by the hydrothermal growth method. Further annealing or/and cold hydrogen or oxygen plasma modification was applied. The atomic structure of the as-grown and plasma-modified rods was characterized by X-ray diffraction. To identify any possible changes in morphology, scanning electron microscopy was used. Paramagnetic point defects were investigated by electron paramagnetic resonance. In particular, two new types of defects were initiated by the plasma treatment. Their appearance was explained, and corresponding mechanisms were proposed. The changes in the luminescence and scintillation properties were characterized by photo- and radioluminescence, respectively. Charge trapping phenomena were studied by thermally stimulated luminescence. Cold plasma treatment influenced the luminescence properties of ZnO:Mo structures. The contact with hydrogen lead to an approximately threefold increase in intensity of the ultraviolet exciton-related band peaking at ~3.24 eV, whereas the red band attributed to zinc vacancies (~1.97 eV) was suppressed compared to the as-grown samples. The exciton- and defect-related emission subsided after the treatment in oxygen plasma.

• Klíčová slova
• EPR, Mo5+, photo-, radio- and cathodoluminescence, plasma treatment, shallow donors, zinc oxide nanorods,
• Publikační typ
• časopisecké články MeSH

Heat treatment is needed to increase the luminescence intensity of ZnO:Ga particles, but it comes at the cost of higher particle agglomeration. Higher agglomeration results in low transparency of scintillating powder when embedded in a matrix and constitutes one of the biggest disadvantages, besides low light yield and low stopping power, of ZnO:Ga powder. Limiting ZnO:Ga particle size is therefore a key step in order to prepare highly luminescent and transparent composites with prospects for optical applications. In this work, SiO2 coating was successfully used to improve luminescence intensity or limitation of crystallite size growth during further annealing. Furthermore, ZnO:Ga and ZnO:Ga-SiO2 core-shells were embedded in a polystyrene matrix.

• Publikační typ
• časopisecké články MeSH

Eu-doped ternary sulfides of general formula ALnS₂ (A = Na, K, Rb; Ln = La, Gd, Lu, Y) are presented as a novel interesting material family which may find usage as X-ray phosphors or solid state white light emitting diode (LED) lighting. Samples were synthesized in the form of transparent crystalline hexagonal platelets by chemical reaction under the flow of hydrogen sulfide. Their physical properties were investigated by means of X-ray diffraction, time-resolved photoluminescence spectroscopy, electron paramagnetic resonance, and X-ray excited fluorescence. Corresponding characteristics, including absorption, radioluminescence, photoluminescence excitation and emission spectra, and decay kinetics curves, were measured and evaluated in a broad temperature range (8-800 K). Calculations including quantum local crystal field potential and spin-Hamiltonian for a paramagnetic particle in D3d local symmetry and phenomenological model dealing with excited state dynamics were performed to explain the experimentally observed features. Based on the results, an energy diagram of lanthanide energy levels in KLuS₂ is proposed. Color model xy-coordinates are used to compare effects of dopants on the resulting spectrum. The application potential of the mentioned compounds in the field of white LED solid state lighting or X-ray phosphors is thoroughly discussed.

• Klíčová slova
• EPR, Eu2+, luminescence, ternary sulfide, white light emitting diode,
• Publikační typ
• časopisecké články MeSH