Lead halide perovskites are reportedly a very promising group of materials for scintillation due to their fast sub-nanosecond exciton luminescence, small band-gaps, and high theoretical light yield. Unfortunately, they only show emission at cryogenic temperatures. In this work single crystals of CsPbBr₃ and CsPbCl₃ are studied at cryogenic temperatures. Upon comparing the 10 K emission spectra measured under X-ray and UV–vis excitation, a new near-infrared emission was found for both CsPbBr₃ and CsPbCl₃ only present under X-ray excitation. The integral light yields of CsPbBr₃ and CsPbCl₃ at 10 K are estimated to be 34,000 and 2,200 photons/MeV under 40 keV X-ray excitation, respectively. The main components of the light yield of CsPbBr₃ at 10 K are the near band-gap free exciton emission that suffers from self-absorption and the broad near-infrared emission that falls outside the typical detection range of a photo-multiplier tube. Due to the combination of the two aforementioned effects it was not possible to measure a γ-ray pulse height spectrum for CsPbBr₃ at 10 K. Despite all the suitable properties, like the fast decay, a small band-gap, and the positive prospects of 3D perovskite based scintillators, we conclude that these materials perform poorly as scintillation crystals.

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Small bandgap scintillators have gained significant attention in recent years. Especially Cs4PbBr6 is an interesting material, mitigating the small Stokes shift-related problem of perovskites like CsPbBr3. In this work, optical and scintillation properties of Cs4PbBr6 single crystals are investigated as a function of temperature, with a detailed focus at 10 K. The Cs4PbBr6 single crystals were grown using the vertical Bridgman method. Due to incongruent melting, CsPbBr3 inclusions are formed, generating a 540 nm emission band. Prepairing Cs4PbBr6 via solid-state synthesis yields CsPbBr3-inclusion-free material, showing no green 540 nm emission band. In Cs4PbBr6 samples with and without CsPbBr3 inclusions, a new emission band at 610 nm ascribed to an unknown defect was found. Based on the presented experiments, an emission mechanism is proposed for Cs4PbBr6. This shows that both defects and CsPbBr3 inclusions play a role in the emission behavior of Cs4PbBr6 but only the CsPbBr3 inclusions are responsible for the 540 nm emission.@en

Ytterbium-doped LiYF ₄ (Yb:YLF) is a commonly used material for laser applications, as a photon upconversion medium, and for optical refrigeration. As nanocrystals (NCs), the material is also of interest for biological and physical applications. Unfortunately, as with most phosphors, with the reduction in size comes a large reduction of the photoluminescence quantum yield (PLQY), which is typically associated with an increase in surface-related PL quenching. Here, we report the synthesis of bipyramidal Yb:YLF NCs with a short axis of ∼60 nm. We systematically study and remove all sources of PL quenching in these NCs. By chemically removing all traces of water from the reaction mixture, we obtain NCs that exhibit a near-unity PLQY for an Yb ³⁺ concentration below 20%. At higher Yb ³⁺ concentrations, efficient concentration quenching occurs. The surface PL quenching is mitigated by growing an undoped YLF shell around the NC core, resulting in near-unity PLQY values even for fully Yb ³⁺-based LiYbF ₄ cores. This unambiguously shows that the only remaining quenching sites in core-only Yb:YLF NCs reside on the surface and that concentration quenching is due to energy transfer to the surface. Monte Carlo simulations can reproduce the concentration dependence of the PLQY. Surprisingly, Förster resonance energy transfer does not give satisfactory agreement with the experimental data, whereas nearest-neighbor energy transfer does. This work demonstrates that Yb ³⁺-based nanophosphors can be synthesized with a quality close to that of bulk single crystals. The high Yb ³⁺ concentration in the LiYbF ₄/LiYF ₄ core/shell nanocrystals increases the weak Yb ³⁺ absorption, making these materials highly promising for fundamental studies and increasing their effectiveness in bioapplications and optical refrigeration.

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Due to recent development in detector technology, photon-counting computed tomography (PCCT) has become a rapidly emerging medical imaging technology. Current PCCT systems rely on the direct conversion of X-ray photons into charge pulses, using CdTe, CZT, or Si semiconductor detectors. Indirect detection using ultrafast scintillators coupled to silicon photomultipliers (SiPM) offers a potentially more straightforward and cost-effective alternative. In this work a new 2D perovskite scintillator, benzylamonium lead bromide (BZA)₂PbBr₄, is experimentally characterised as function of temperature. The material exhibits a 4.2 ns decay time under X-ray excitation at room temperature and a light yield of 3700 photons/MeV. The simulation tool developed by Van der Sar et al. was used to model the pulse trains produced by a SiPM-based (BZA)₂PbBr₄ detector. The fast decay time of (BZA)₂PbBr₄ results in outstanding count-rate performance as well as very low statistical fluctuations in the simulated pulses. These features of (BZA)₂PbBr₄, combined with its cost-effective synthesis make (BZA)₂PbBr₄ very promising for PCCT.

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Currently only Eu²⁺-based scintillators have approached the light yield needed to improve the 2% energy resolution at 662 keV of LaBr₃:Ce³⁺,Sr²⁺. Their major limitation, however, is the significant self-absorption due to Eu²⁺. CsCu₂I₃ is an interesting new small band gap scintillator. It is nonhygroscopic and nontoxic, melts congruently, and has an extremely low afterglow, a density of 5.01 g/cm³, and an effective atomic number of 50.6. It shows self-trapped exciton emission at room temperature. The large Stokes shift of this emission ensures that this material is not sensitive to self-absorption, tackling one of the major problems of Eu²⁺-based scintillators. An avalanche photo diode, whose optimal detection efficiency matches the 570 nm mean emission wavelength of CsCu₂I₃, was used to measure pulse height spectra. From the latter, a light yield of 36 000 photons/MeV and energy resolution of 4.82% were obtained. The scintillation proportionality of CsCu₂I₃ was found to be on par with that of SrI₂:Eu²⁺. Based on temperature-dependent emission and decay measurements, it was demonstrated that CsCu₂I₃ emission is already about 50% quenched at room temperature. Using temperature-dependent pulse height measurements, it is shown that the light yield can be increased up to 60 000 photons/MeV by cooling to 200 K, experimentally demonstrating the scintillation potential of CsCu₂I₃.

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In this work the scintillation properties of PEA₂PbBr₄ are studied as function of temperature, accessing the potential use of these materials for low temperature applications. The scintillation properties and mechanism have been studied using a combination of temperature dependent photoluminescence emission and excitation, X-ray excited emission and decay measurements. At room temperature the X-ray excited emission is dominated by the 442 nm emission with a lifetime of 35.2 ns. Under UV-Vis photon excitation an additional emission peak is observed at 412 nm. At 10 K, both X-ray and UV-Vis photon excited emission spectra show a narrow emission peak at 412 nm and a broad emission band centred around 525 nm with a lifetime of 1.53 ns (24%) and 154 ns (76%) respectively. The exact nature of the observed emission peaks is not known. For this reason two potential mechanisms explaining the difference between UV-Vis photon and X-ray excitation and their temperature dependent emissions are explored. The total spectral intensity decreases to 72% of the intensity at room temperature at 10 K. It is suggested that the observed negative thermal quenching behaviour results from a combination of more self absorption and a higher degree of self trapped exciton formation under X-ray excitation. Based on the observed fast decay component at 10 K and light yield of 9400 photons per MeV at room temperature, showing only a 28% decrease at 10 K, could make this material potentially interesting for low temperature and fast timing applications.

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