Radioluminescence Sensitization in Scintillators and Phosphors: Trap Engineering and Modeling

The role of charge carrier trapping in determining radioluminescence (RL) efficiency increase during prolonged irradiation of scintillators has been studied by using YPO₄:Ce,Nd as a model material. The Nd³⁺ ions act as efficient electron traps minimizing the role of intrinsic defects. Different Nd contents were considered in order to point out the correlation between the trap concentration and the detected RL efficiency dose dependence. RL measurements as a function of temperature clarified the role of the trap thermal stability in determining the shape and the magnitude of such effect. We propose also a model based on trap filling which is able to describe accurately the complex processes which are involved

Eu Incorporation into Sol–Gel Silica for Photonic Applications: Spectroscopic and TEM Evidences of α‑Quartz and Eu Pyrosilicate Nanocrystal Growth

The problem of Eu incorporation into silica as dispersed dopants, clusters, separate-phase nanoparticles, or nanocrystals, which is of key importance for applications in the fields of lasers and scintillators, is faced by applying to sol–gel silica doped with nine different Eu³⁺ concentrations (0.001–10 mol % range) various spectroscopic techniques, including crystal field and vibrational mode analysis by means of Fourier transform absorption and microreflectivity (in the 200–6000 cm^–1 and 9–300 K ranges), radioluminescence, and Raman scattering studies at 300 K. The variety of methods revealed the following concordant results: (1) amorphous Eu clusters grow when the Eu concentration is increased up to 3 mol % and (2) Si–OH groups are completely removed and ordered phase separation occurs at 10 mol % doping, as suggested by the remarkable narrowing of the spectral lines. Comparison with polycrystalline Eu oxide, Eu silicates, and α-quartz spectra allowed the unequivocal identification of Eu₂Si₂O₇ pyrosilicate and α-quartz as the main components of nanocrystals in 10 mol % Eu-doped silica. Such conclusions were brilliantly confirmed by transmission electron microscopy and electron diffraction analysis. Phonon coupling and anharmonicity were analyzed and are discussed for a few vibrational modes of nanocrystals

Size-Dependent Luminescence in HfO₂ Nanocrystals: Toward White Emission from Intrinsic Surface Defects

Defect engineering operated on metal oxides by chemical and structural modifications may strongly affect properties suitable for various applications such as photoelectrochemical behavior, charge transport, and luminescence. In this work, we report the tunable optical features observed in undoped monoclinic HfO₂ nanocrystals and their dependence on the structural properties of the material at the nanoscale. Transmission electron microscopy together with X-ray diffraction and surface area measurements were used to determine the fine structural modifications, in terms of crystal growth and coalescence of crystalline domains, occurring during a calcination process in the temperature range from 400 to 1000 °C. The fit of the broad optical emission into spectral components, together with time-resolved photoluminescence, allowed us to identify the dual nature of the emission at 2.5 eV, where an ultrafast defect-related intrinsic luminescence (with a decay time of a few nanoseconds) overlaps with a slower emission (decay of several microseconds) due to extrinsic Ti-impurity centers. Moreover, the evolution of intrinsic visible bands during the material transformation was monitored. The relationship between structural parameters uniquely occurring in nanosized materials and the optical properties was investigated and tentatively modeled. The blue emissions at 2.5 and 2.9 eV are clearly related to defects lying at crystal boundaries, while an unprecedented emission at 2.1 eV enables, at relatively low calcination temperatures, the white luminescence of HfO₂ under near-UV excitation