K. Smits

The role of Nb in intensity increase of Er ion upconversion luminescence in zirconia

It is found that Nb co-doping increases the luminescence and upconversion luminescence intensity in rare earth doped zirconia. Er and Yb-doped nanocrystalline samples with or without Nb co-doping were prepared by sol-gel method and thermally annealed to check for the impact of phase transition on luminescence properties. Phase composition and grain sizes were examined by X-ray diffraction; the morphology was checked by scanning- and high-resolution transmission electron microscopes. Both steady-state and time-resolved luminescence were studied. Comparison of samples with different oxygen vacancy concentrations and different Nb concentrations confirmed the known assumption that oxygen vacancies are the main agents for tetragonal or cubic phase stabilization. The oxygen vacancies quench the upconversion luminescence; however, they also prevent agglomeration of rare-earth ions and/or displacement of rare-earth ions to grain surfaces. It is found that co-doping with Nb ions significantly (>20 times) increases upconversion luminescence intensity. Hence, ZrO2:Er:Yb:Nb nanocrystals may show promise for upconversion applications.

Comparison of ZrO2:Y nanocrystals and macroscopic single crystal luminescence

The luminescence spectra of a tetragonally structured ZrO2:Y single crystal and nanocrystals were compared. It was found that the number of luminescence centers contributed to the spectra. The excitation of luminescence within the band gap region led to different luminescence spectra for the single crystal and nanocrystal samples, whereas recombinative luminescence spectra were the same for both samples. The origin of this difference is that in the nanocrystals, even under excitation within the band gap, charge carriers were created. Zirconium- oxygen complexes distorted by intrinsic defects were proposed to be the luminescence centres responsible for the wide luminescence band observed.

Luminescence of Er/Yb and Tm/Yb Doped FAp Nanoparticles and Ceramics

The nanoparticles of hydroxiapatite and fluorapatite doped with Er/Yb and Tm/Yb were synthesized and characterized by FTIR, XRD, SEM and TEM methods. The results of up-conversion luminescence studies were presented for the samples as prepared, annealed at 500°C and at 900-1000 °C. At annealing above 800°C the ceramic state was formed. It is shown that fluorapatite host is more appropriate than hydroxiapatite host for rare ions luminescence and up-conversion processes. The post preparing annealing of nanarticles significantly enhanced the luminescence intensity. The Tm/Yb doped fluorapatite shows intense up-conversion luminescence in 790-800 nm spectral region and is potentially useful for biomedical applications.

Luminescence of coesite

Coesite is a polymorph modification of crystalline silicon dioxide with a tetrahedral structure. The luminescence of a single crystal of synthetic coesite was studied under excitation using x-rays, an electron beam, and excimer lasers KrF (248 nm), ArF (193 nm) and F2 (157 nm). Luminescence bands in the regions of 2.5 eV and 4.4 eV appear. The blue band is dependent on temperature and is composed of decay kinetics. Three main decay times are revealed, exhibiting luminescence of a different nature in the same range of the spectrum. One is in the ns range of time with a time constant of about 2 ns. The two other decay times are in the regions of 5 μs and 700 μs. The 5 μs component is also seen under KrF excitation, whereas both the 5 μs and 700 μs components are seen under ArF excitation. The time resolved spectra are mutually similar and they correspond to those under x-ray and e-beam excitation. The UV band is fast with a time constant of less than 1 ns, independent of temperature. Only the 2 ns and 5 μs components are revealed for the blue band under the KrF laser excitation. Blue luminescence thermal quenching takes place for temperatures above 50 K, with good correspondence between the intensities of the thermal dependences under different excitation and that of the decay time constant. The quenching parameters used are 0.05 eV of energy and a frequency factor of 6 105 s−1. The UV band is practically independent of temperature in the range 10–290 K. The nature of luminescence is ascribed to the coexistence of a host defect and a self-trapped exciton. The defect is similar to the known oxygen-deficient luminescence center in pure silica glass. The blue luminescence at 700 μs is ascribed to the self-trapped exciton being characteristic of silicon dioxide with a tetrahedral structure.