On the Origin of the Light Yield Enhancement in Polymeric Composite Scintillators Loaded with Dense Nanoparticles.

Fast emitting polymeric scintillators are requested in advanced applications where high speed detectors with a large signal-to-noise ratio are needed. However, their low density implies a weak stopping power of high energy radiation and thus a limited light output and sensitivity. To enhance their performance, polymeric scintillators can be loaded with dense nanoparticles (NPs). We investigate the properties of a series of polymeric scintillators by means of photoluminescence and scintillation spectroscopy, comparing standard scintillators with a composite system loaded with dense hafnium dioxide (HfO2) NPs. The nanocomposite shows a scintillation yield enhancement of +100% with an unchanged time response. We provide for the first time an interpretation of this effect, pointing out the local effect of NPs in the generation of emissive states upon interaction with ionizing radiation. The obtained results indicate that coupling fast conjugated emitters with optically inert dense NPs could lead to surpassing the actual limits of pure polymeric scintillators.

Spectroscopic and laser characterization of Yb0.15:(LuxY1-x)3Al5O12 ceramics with different Lu/Y balance.

We report a broad comparative analysis of the spectroscopic and laser properties of solid solution Lutetium-Yttrium Aluminum Garnet (LuYAG, (LuxY1-x)3Al5O12) ceramics doped with Yb. The investigation was mainly aimed to assess the impact of the Lu/Y ratio on the Yb optical and laser properties. Therefore we analyzed a set of samples with different Y/Lu balance, namely 25/75, 50/50 and 75/25, with 15% Yb doping. We found that the Yb absorption and emission spectra changed from YAG to LuAG when gradually increasing in Lu content. Regarding the laser emission, remarkable results were achieved with all samples. Maximum output power was 8.2 W, 7.3 W and 8.7 W for Y/Lu balance 25/75, 50/50 and 75/25 respectively, at 1030 nm; the slope efficiency and the optical-to-optical efficiencies approached or exceeded 60% and 50% respectively. The tuning range was investigated using an intracavity ZnSe prism. The broadest tuning range (998 nm to 1063 nm) was obtained with Y/Lu balance 75/25, whereas the emission of the other two samples extended from 1000 nm to 1058 nm. To the best of our knowledge, this is the first comparative analysis of Yb:LuYAG ceramics or crystals as laser host across such a broad range of Y/Lu ratios.

First laser emission of Yb0.15:(Lu0.5Y0.5)3Al5O12 ceramics.

We report the first laser oscillation on Yb0.15:(Lu0.5Y0.5)3Al12 ceramics at room temperature. At 1030 nm we measured a maximum output power of 7.3 W with a corresponding slope efficiency of 55.4% by using an output coupler with a transmission of T = 39.2%. The spectroscopic properties are compared with those of the two parent garnets Yb:YAG and Yb:LuAG. To the best of our knowledge these are the first measurements reported in literature achieved with this new host.

Experimental evidence of a nonlinear loss mechanism in highly doped Yb:LuAG crystal.

We report a rigorous study of the spectroscopic, laser and thermal properties of a 10at.% and a 15at.% Yb:LuAG crystals. A loss mechanism is observed in the medium with the highest doping, pumped at 936 nm and 968 nm, as a sharp and dramatic decrease of the laser output power is measured at higher excitation densities. The nonlinearity of the loss mechanism is confirmed by the fluorescence data and by the thermal lens. In particular, the dioptric power of the thermal lens acquired at different pumping levels shows a strong deviation of the expected linear trend. Here we report the influence of both the concentration and the ion excitation density of Yb3+ on the output powers, the slope efficiencies and the thresholds. Conversely excellent results are achieved with the 10at.%, which does not show any loss mechanism as at 1046 nm it delivers 11.8 W with a slope efficiency of η(s) = 82%, which is, to the best of our knowledge, the highest value reported in literature for this material.

Charge Transfer and Charge Trapping Processes in Ca- or Al-Co-doped Lu2SiO5 and Lu2Si2O7 Scintillators Activated by Pr3+ or Ce3+ Ions.

Lutetium oxyorthosilicate Lu2SiO5 (LSO) and pyrosilicate Lu2Si2O7 (LPS) activated by Ce3+ or Pr3+ are known to be effective and fast scintillation materials for the detection of X-rays and γ-rays. Their performances can be further improved by co-doping with aliovalent ions. Herein, we investigate the Ce3+(Pr3+) → Ce4+(Pr4+) conversion and the formation of lattice defects stimulated by co-doping with Ca2+ and Al3+ in LSO and LPS powders prepared by the solid-state reaction process. The materials were studied by electron paramagnetic resonance (EPR), radioluminescence spectroscopy, and thermally stimulated luminescence (TSL), and scintillation decays were measured. EPR measurements of both LSO:Ce and LPS:Ce showed effective Ce3+ → Ce4+ conversions stimulated by Ca2+ co-doping, while the effect of Al3+ co-doping was less effective. In Pr-doped LSO and LPS, a similar Pr3+ → Pr4+ conversion was not detected by EPR, suggesting that the charge compensation of Al3+ and Ca2+ ions is realized via other impurities and/or lattice defects. X-ray irradiation of LPS creates hole centers attributed to a hole trapped in an oxygen ion in the neighborhood of Al3+ and Ca2+. These hole centers contribute to an intense TSL glow peak at 450-470 K. In contrast to LPS, only weak TSL peaks are detected in LSO and no hole centers are visible via EPR. The scintillation decay curves of both LSO and LPS show a bi-exponential decay with fast and slow component decay times of 10-13 ns and 30-36 ns, respectively. The decay time of the fast component shows a small (6-8%) decrease due to co-doping.

Energy Partitioning in Multicomponent Nanoscintillators for Enhanced Localized Radiotherapy.

Multicomponent nanomaterials consisting of dense scintillating particles functionalized by or embedding optically active conjugated photosensitizers (PSs) for cytotoxic reactive oxygen species (ROS) have been proposed in the last decade as coadjuvant agents for radiotherapy of cancer. They have been designed to make scintillation-activated sensitizers for ROS production in an aqueous environment under exposure to ionizing radiations. However, a detailed understanding of the global energy partitioning process occurring during the scintillation is still missing, in particular regarding the role of the non-radiative energy transfer between the nanoscintillator and the conjugated moieties which is usually considered crucial for the activation of PSs and therefore pivotal to enhance the therapeutic effect. We investigate this mechanism in a series of PS-functionalized scintillating nanotubes where the non-radiative energy transfer yield has been tuned by control of the intermolecular distance between the nanotube and the conjugated system. The obtained results indicate that non-radiative energy transfer has a negligible effect on the ROS sensitization efficiency, thus opening the way to the development of different architectures for breakthrough radiotherapy coadjutants to be tested in clinics.

Changes to Material Phase and Morphology Due to High-Level Molybdenum Doping of ZnO Nanorods: Influence on Luminescence and Defects.

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.

Free-Standing ZnO:Mo Nanorods Exposed to Hydrogen or Oxygen Plasma: Influence on the Intrinsic and Extrinsic Defect States.

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.

Localization of aluminium in tea (Camellia sinensis) leaves using low energy X-ray fluorescence spectro-microscopy.

Information on localization of Al in tea leaf tissues is required in order to better understand Al tolerance mechanism in this Al-accumulating plant species. Here, we have used low-energy X-ray fluorescence spectro-microscopy (LEXRF) to study localization of Al and other low Z-elements, namely C, O, Mg, Si and P, in fully developed leaves of the tea plant [Camellia sinensis (L.) O. Kuntze]. Plants were grown from seeds for 3 months in a hydroponic solution, and then exposed to 200 microM AlCl(3) for 2 weeks. Epidermal-mesophyll and xylem phloem regions of 20 microm thick cryo-fixed freeze-dried tea-leaf cross-sections were raster scanned with 1.7 and 2.2 keV excitation energies to reach the Al-K and P-K absorption edges. Al was mainly localized in the cell walls of the leaf epidermal cells, while almost no Al signal was obtained from the leaf symplast. The results suggest that the retention of Al in epidermal leaf apoplast represent the main tolerance mechanism to Al in tea plants. In addition LEXRF proved to be a powerful tool for localization of Al in plant tissues, which can help in our understanding of the processes of Al uptake, transport and tolerance in plants.

Scintillation Response Enhancement in Nanocrystalline Lead Halide Perovskite Thin Films on Scintillating Wafers.

Lead halide perovskite nanocrystals of the formula CsPbBr3 have recently been identified as potential time taggers in scintillating heterostructures for time-of-flight positron emission tomography (TOF-PET) imaging thanks to their ultrafast decay kinetics. This study investigates the potential of this material experimentally. We fabricated CsPbBr3 thin films on scintillating GGAG:Ce (Gd2.985Ce0.015Ga2.7Al2.3O12) wafer as a model structure for the future sampling detector geometry. We focused this study on the radioluminescence (RL) response of this composite material. We compare the results of two spin-coating methods, namely the static and the dynamic process, for the thin film preparation. We demonstrated enhanced RL intensity of both CsPbBr3 and GGAG:Ce scintillating constituents of a composite material. This synergic effect arises in both the RL spectra and decays, including decays in the short time window (50 ns). Consequently, this study confirms the applicability of CsPbBr3 nanocrystals as efficient time taggers for ultrafast timing applications, such as TOF-PET.

On the Role of Cs4PbBr6 Phase in the Luminescence Performance of Bright CsPbBr3 Nanocrystals.

CsPbBr3 nanocrystals have been identified as a highly promising material for various optoelectronic applications. However, they tend to coexist with Cs4PbBr6 phase when the reaction conditions are not controlled carefully. It is therefore imperative to understand how the presence of this phase affects the luminescence performance of CsPbBr3 nanocrystals. We synthesized a mixed CsPbBr3-Cs4PbBr6 sample, and compared its photo- and radioluminescence properties, including timing characteristics, to the performance of pure CsPbBr3 nanocrystals. The possibility of energy transfer between the two phases was also explored. We demonstrated that the presence of Cs4PbBr6 causes significant drop in radioluminescence intensity of CsPbBr3 nanocrystals, which can limit possible future applications of Cs4PbBr6-CsPbBr3 mixtures or composites as scintillation detectors.

The Sensitization of Scintillation in Polymeric Composites Based on Fluorescent Nanocomplexes.

The sensitization of scintillation was investigated in crosslinked polymeric composite materials loaded with luminescent gold clusters aggregates acting as sensitizers, and with organic dye rhodamine 6G as the emitting species. The evolution in time of the excited states population in the systems is described by a set of coupled rate equations, in which steady state solution allowed obtainment of an expression of the sensitization efficacy as a function of the characteristic parameters of the employed luminescent systems. The results obtained indicate that the realization of sensitizer/emitter scintillating complexes is the strategy that must be pursued to maximize the sensitization effect in composite materials.

Demonstration of cellular imaging by using luminescent and anti-cytotoxic europium-doped hafnia nanocrystals.

Luminescent nanoparticles are researched for their potential impact in medical science, but no materials approved for parenteral use have been available so far. To overcome this issue, we demonstrate that Eu3+-doped hafnium dioxide nanocrystals can be used as non-toxic, highly stable probes for cellular optical imaging and as radiosensitive materials for clinical treatment. Furthermore, viability and biocompatibility tests on artificially stressed cell cultures reveal their ability to buffer reactive oxygen species, proposing an anti-cytotoxic feature interesting for biomedical applications.

Synchrotron excitation, emission and theoretical simulation of lanthanide ions in hexachloroelpasolite crystals.

Emission and excitation spectra of Cs(2)NaLnCl(6) (Ln = Y, Eu, Gd, Er, Yb), Cs(2)NaYCl(6):Ce and Cs(2)NaYCl(6):Tm have been recorded using synchrotron radiation. With the possible exception of the case for Ce(3+), no [Formula: see text] transitions are observed and the emission spectra are entirely assigned to [Formula: see text] intraconfigurational transitions of Ln(3+) in LnCl(6)(3-) and impurity species. The excitation spectra comprise intraconfigurational, charge transfer and band-to-band transitions. Trace impurities of oxy-species or of other lanthanide ions have a profound effect upon the spectra. The 4f-5d absorption spectra have been simulated by employing the suite of programs of Professor M F Reid and the results have been included together with the experimental spectra.