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.

Ultrafast Zn(Cd,Mg)O:Ga nanoscintillators with luminescence tunable by band gap modulation.

Photo-induced synthesis was used for preparation of powder Zn(Cd,Mg)O:Ga scintillating nanocrystals featuring properties of solid solutions. Only ZnO phase was identified without any phase separation up to 10% of Cd after optimization of the preparation. Radioluminescence spectra show the exciton-related emission in UV spectral range with significant blue (ZnMgO:Ga) or red (ZnCdO:Ga) shifts. The emission wavelength is tunable by the Cd/Mg content. Defect-related emission is completely suppressed after treatment in reducing atmosphere. Photoluminescence and cathodoluminescence decays show extremely fast component. Subnanosecond decay together with band gap modulation make Zn(Cd,Mg)O:Ga good candidate for practical applications like X-ray induced photodynamic therapy (PDTX) or those requiring superfast timing.

Line-tunable Er:GGAG laser.

In this Letter, for the first time, to the best of our knowledge, a pulse and CW laser based on an Er-doped Gd3Ga2.7Al2.3O12 (Er:GGAG) active medium emitting laser radiation at 2.8 µm are presented. With the longitudinal diode pumping, the maximal output energy of 4.9 mJ and slope efficiency of 13.5% in the pulse regime were reached. Using the birefringent MgF2 plate, the line tunability of Er:GGAG at several spectral bands of 2800-2822 nm, 2829-2891 nm, and 2917-2942 nm were obtained.

Tetranuclear Copper(I) Iodide Complexes: A New Class of X-ray Phosphors.

We report intensive visible light radioluminescence upon X-ray irradiation of archetypal tetranuclear copper(I) iodide complexes containing triphenylphosphine or pyridine ligands in the solid state. These properties, attractive for the design of X-ray responsive materials, can be attributed to the heavy {Cu4I4} cubane-like core, the absence of oxygen quenching of the emissive triplet states, and the high photoluminescence quantum yields. Radioluminescence originates from the same emissive triplet states as those produced by ultraviolet excitation as confirmed by the observed radioluminescence thermochromism. The radioluminescence properties are also preserved after incorporation of these complexes into polystyrene films, making them appealing for the development of plastic scintillators.

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.

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.

Preparation and luminescence properties of ZnO:Ga - polystyrene composite scintillator.

Highly luminescent ZnO:Ga-polystyrene composite (ZnO:Ga-PS) with ultrafast subnanosecond decay was prepared by homogeneous embedding the ZnO:Ga scintillating powder into the scintillating organic matrix. The powder was prepared by photo-induced precipitation with subsequent calcination in air and Ar/H2 atmospheres. The composite was subsequently prepared by mixing the ZnO:Ga powder into the polystyrene (10 wt% fraction of ZnO:Ga) and press compacted to the 1 mm thick pellet. Luminescent spectral and kinetic characteristics of ZnO:Ga were preserved. Radioluminescence spectra corresponded purely to the ZnO:Ga scintillating phase and emission of polystyrene at 300-350 nm was absent. These features suggest the presence of non-radiative energy transfer from polystyrene host towards the ZnO:Ga scintillating phase which is confirmed by the measurement of X-ray excited scintillation decay with picosecond time resolution. It shows an ultrafast rise time below the time resolution of the experiment (18 ps) and a single-exponential decay with the decay time around 500 ps.

X-ray Inducible Luminescence and Singlet Oxygen Sensitization by an Octahedral Molybdenum Cluster Compound: A New Class of Nanoscintillators.

Newly synthesized octahedral molybdenum cluster compound (n-Bu4N)2[Mo6I8(OOC-1-adamantane)6] revealed uncharted features applicable for the development of X-ray inducible luminescent materials and sensitizers of singlet oxygen, O2((1)Δg). The compound exhibits a red-NIR luminescence in the solid state and in solution (e.g., quantum yield of 0.76 in tetrahydrofuran) upon excitation by UV-vis light. The luminescence originating from the excited triplet states is quenched by molecular oxygen to produce O2((1)Δg) with a high quantum yield. Irradiation of the compound by X-rays generated a radioluminescence with the same emission spectrum as that obtained by UV-vis excitation. It proves the formation of the same excited triplet states regardless of the excitation source. By virtue of the described behavior, the compound is suggested as an efficient sensitizer of O2((1)Δg) upon X-ray excitation. The luminescence and radioluminescence properties were maintained upon embedding the compound in polystyrene films. In addition, polystyrene induced an enhancement of the radioluminescence intensity via energy transfer from the scintillating polymeric matrix. Sulfonated polystyrene nanofibers were used for the preparation of nanoparticles which form stable dispersions in water, while keeping intact the luminescence properties of the embedded compound over a long time period. Due to their small size and high oxygen diffusivity, these nanoparticles are suitable carriers of sensitizers of O2((1)Δg). The presented results define a new class of nanoscintillators with promising properties for X-ray inducible photodynamic therapy.

Characterization of the lasing properties of a 5%Yb doped Lu2SiO5 crystal along its three principal dielectric axes.

The laser performance of a 5% Yb doped Lu2SiO5 (Yb:LSO) has been investigated in quasi continuous-wave pumping regime along the three principal dielectric axes of the crystal, to obtain a complete characterization of its laser properties. The comparison among the obtained results for differently polarized lasers, in term of relative slope efficiency and absolute efficiency, allows the exploitability of different orientations of the material in order to be determined to obtain efficient laser sources. The laser slope efficiency and the energy conversion efficiency were similar for emission polarized along the three indicatrix axes, with noticeable maximum values of slope efficiency around 90% for polarization along the Y and Z axes. Tunable laser action has been obtained in the range 990 nm - 1084 nm, with sizeable differences in the shape of the tuning curve for polarization along the X, Y and Z axes. In particular, the tuning for polarization along the Z axis is relatively flat and uniform in the range 1023 nm - 1083 nm.

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.

InGaN/GaN multiple quantum well for fast scintillation application: radioluminescence and photoluminescence study.

We prepare InGaN/GaN multiple quantum well (MQW) structure by metal-organic vapour phase epitaxy and characterize it by fine XRD measurements. We demonstrate its suitability for scintillator application including a unique measurement of wavelength-resolved scintillation response under nanosecond pulse soft x-ray source in extended dynamical and time scales. The photoluminescence and radioluminescence were measured: we have shown that the ratio of the intensity of quantum well (QW) exciton luminescence to the intensity of the yellow luminescence (YL) band IQW/IYL depends strongly on the type and intensity of excitation. Slower scintillation decay measured at YL band maximum confirmed the presence of several radiative recombination centres responsible for wide YL band, which also partially overlap with the QW peak. Further improvements of the structure are suggested, but even the presently reported decay characteristics of the excitonic emission in MQW are better compared to the currently widely used single crystal YAP:Ce or YAG:Ce scintillators. Thus, such a type of a semiconductor scintillator is highly promising for fast detection of soft x-ray and related beam diagnostics.

Ho3+ codoping of GGAG:Ce: a detailed analysis of acceleration of scintillation response and scintillation efficiency loss.

In this study, we investigate the effects of Ho3+ codoping on the luminescence and scintillation properties of GGAG:Ce, with a particular focus on timing properties and scintillator efficiency. The research reveals that Ho3+ codoping and subsequent resonant energy transfer from Ce3+ to Ho3+ can significantly reduce the 5d1 excited state decay time of Ce3+ and shorten scintillation pulses of GGAG:Ce registered by using photomultipliers, although this reduces scintillator efficiency as well. The study presents a detailed analysis of the loss of scintillator efficiency due to Ho3+ codoping, identifying the most significant loss pathways and estimating their impact. The findings suggest that Ho3+ codoping is an effective method for accelerating the scintillation response of GGAG:Ce. Furthermore, the study presents a high level of consistency of the Ce3+ kinetics with the Inokuti-Hirayama model and with results obtained in the previous studies on similar systems, demonstrating the predictability of the effect of RE3+ codoping on scintillator properties.

Exciton-harvesting enabled efficient charged particle detection in zero-dimensional halides.

Materials for radiation detection are critically important and urgently demanded in diverse fields, starting from fundamental scientific research to medical diagnostics, homeland security, and environmental monitoring. Low-dimensional halides (LDHs) exhibiting efficient self-trapped exciton (STE) emission with high photoluminescence quantum yield (PLQY) have recently shown a great potential as scintillators. However, an overlooked issue of exciton-exciton interaction in LDHs under ionizing radiation hinders the broadening of its radiation detection applications. Here, we demonstrate an exceptional enhancement of exciton-harvesting efficiency in zero-dimensional (0D) Cs3Cu2I5:Tl halide single crystals by forming strongly localized Tl-bound excitons. Because of the suppression of non-radiative exciton-exciton interaction, an excellent α/ß pulse-shape-discrimination (PSD) figure-of-merit (FoM) factor of 2.64, a superior rejection ratio of 10-9, and a high scintillation yield of 26 000 photons MeV-1 under 5.49 MeV α-ray are achieved in Cs3Cu2I5:Tl single crystals, outperforming the commercial ZnS:Ag/PVT composites for charged particle detection applications. Furthermore, a radiation detector prototype based on Cs3Cu2I5:Tl single crystal demonstrates the capability of identifying radioactive 220Rn gas for environmental radiation monitoring applications. We believe that the exciton-harvesting strategy proposed here can greatly boost the applications of LDHs materials.

Three-Layered Composite Scintillator Based on the Epitaxial Structures of YAG and LuAG Garnets Doped with Ce3+ and Sc3+ Impurities.

In this study, we propose novel three-layer composite scintillators designed for the simultaneous detection of different ionizing radiation components. These scintillators are based on epitaxial structures of LuAG and YAG garnets, doped with Ce3+ and Sc3+ ions. Samples of these composite scintillators, containing YAG:Ce and LuAG:Ce single crystalline films with different thicknesses and LuAG:Sc single crystal substrates, were grown using the liquid phase epitaxy method from melt solutions based on PbO-B2O3 fluxes. The scintillation properties of the proposed composites, YAG:Ce film/LuAG:Sc film/LuAG:Ce crystal and YAG:Ce film/LuAG:Ce film/LuAG:Sc crystal, were investigated under excitation by radiation with α-particles from a 239Pu source, ß-particles from 90Sr sources and γ-rays from a 137Cs source. Considering the properties of the mentioned composite scintillators, special attention was paid to the ability of simultaneous separation of the different components of mixed ionizing radiation containing the mentioned particles and quanta using scintillation decay kinetics. The differences in scintillation decay curves under α- and ß-particle and γ-ray excitations were characterized using figure of merit (FOM) values at various scintillation decay intensity levels (1/e, 0.1, 0.05, 0.01).

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.

Nd:YAG Single Crystals Grown by the Floating Zone Method in a Laser Furnace.

We report on single crystal growth of laser material Nd:YAG widely used in the applications by the innovative crucible-free floating zone method implemented in an advanced laser optical furnace. We have optimized the parameters for the production of high-quality single crystals of the size typical for laser rods. To reduce the strain and improve machinability, we have developed an afterheater to thermalize the grown part of a single crystal below the hot zone, which is a technique unavailable in common mirror furnaces. The high quality of the single crystals was verified by Laue diffraction, and the internal strain was documented by neutron diffraction. The absorption spectrum corresponds with the parameters of the commercially used material produced by the Czochralski method. The presented methodology for the single crystal growth by the floating zone method with laser heating is applicable for the preparation of other high-quality single crystals of oxide-based materials, particularly in an oxidizing environment unattainable in commonly used crucible methods.

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.

One-dimensional scintillator film with benign grain boundaries for high-resolution and fast x-ray imaging.

Fast and high-resolution x-ray imaging demands scintillator films with negligible afterglow, high scintillation yield, and minimized cross-talk. However, grain boundaries (GBs) are abundant in polycrystalline scintillator film, and, for current inorganic scintillators, detrimental dangling bonds at GBs inevitably extend radioluminescence lifetime and increase nonradiative recombination loss, deteriorating afterglow and scintillation yield. Here, we demonstrate that scintillators with one-dimensional (1D) crystal structure, Cs5Cu3Cl6I2 explored here, possess benign GBs without dangling bonds, yielding nearly identical afterglow and scintillation yield for single crystals and polycrystalline films. Because of its 1D crystal structure, Cs5Cu3Cl6I2 films with desired columnar morphology are easily obtained via close space sublimation, exhibit negligible afterglow (0.1% at 10 ms) and high scintillation yield (1.2 times of CsI:Tl). We have also demonstrated fast x-ray imaging with 27 line pairs mm-1 resolution and frame rate up to 33 fps, surpassing most existing scintillators. We believe that the 1D scintillators can greatly boost x-ray imaging performance.

High efficiency laser action of 1% at. Yb3+:2O3 ceramic.

We report the spectroscopic characteristics and the laser performances of a low-doped 1% at. Yb:Sc(2)O(3) ceramic sample. Under end- pumping at 933 nm and 968 nm in quasi-CW mode, at 1040.5 nm the laser delivers a maximum output power of 4.3 W and 1.77 W, respectively with a corresponding slope efficiency of 74% and 80%, which are, to the best of our knowledge, the highest value reported in literature for ceramics. We explored the tuning range of the sample, which spans from 1005 nm to 1050.5 nm, and finally we characterized the low losses tunable cavity at 1032 nm.

Achieving Efficient Neutron and Gamma Discrimination in a Highly Stable 6Li-Loaded Cs3Cu2I5 Perovskite Scintillator.

Low-dimensional Cu(I) perovskite halides with efficient exciton emissions have recently emerged as promising scintillation materials for X-ray and gamma-ray detection applications. Here, we demonstrate the possibility of using zero-dimensional Cs3Cu2I5 for the sensitive detection of thermal neutrons and neutron-gamma discrimination enabled by Li doping. Single crystals of Cs3Cu2I5 doped with 95% enriched 6Li were grown by the Bridgman method. Cs3Cu2I5:6Li offers a compelling combination of high stability against moisture and oxygen, a decent energy resolution of 4.8% for 662 keV 137Cs gamma-rays, a high light yield of 30 000 photons/MeV for gamma-rays, and 96 000 photons/neutron for thermal neutron, and a good neutron-gamma pulse shape discrimination figure of merit of 2.27. Our discovery of 6Li-doped low-dimensional perovskite halides opens up a new horizon for stable and high-performance neutron-gamma scintillator design.