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The development of hybrid nanoscintillators is hunted for the implementation of modern detection technologies, like in high energy physics, homeland security, radioactive gas sensing, and medical imaging, as well as of the established therapies in radiation oncology, such as in X-ray activated photodynamic therapy. Engineering of the physico-chemical properties of nanoparticles (NPs) enables the manufacture of hybrids in which the conjugation of inorganic/organic components leads to increased multifunctionality and performance. However, the optimization of the properties of nanoparticles in combination with the use of ionizing radiation is not trivial: a complete knowledge on the structure, composition, physico-chemical features, and scintillation property relationships in hybrid nanomaterials is pivotal for any applications exploiting X-rays. In this paper, the design of hybrid nanoscintillators based on ZnO grown onto porous SiO2 substrates (ZnO/SiO2) has been performed in the view to create nanosystems potentially suitable in X-ray activated photodynamic therapy. Indeed, cytotoxic porphyrin dyes with increasing concentrations have been anchored on ZnO/SiO2 nanoparticles through amino-silane moieties. Chemical and structural analyses correlated with photoluminescence reveal that radiative energy transfer between ZnO and porphyrins is the principal mechanism prompting the excitation of photosensitizers. The use of soft X-ray excitation results in a further sensitization of the porphyrin emission, due to augmented energy deposition promoted by ZnO in the surroundings of the chemically bound porphyrin. This finding unveils the cruciality of the design of hybrid nanoparticles in ruling the efficacy of the interaction between ionizing radiation and inorganic/organic moieties, and thus of the final nanomaterial performances towards the foreseen application.

The coupling of ZnO-based nanomaterials with organic photosensitizers (PS) is potentially interesting for cancer treatment under X-ray. In these conditions, ZnO nanoparticles (NPs) convert the X-ray into UV-Vis emission, promoting the PS excitation and producing reactive oxygen species (ROS). Main advantages for in vivo applications are ZnO photostability and biocompatibility, even if its efficient coupling with different PS (typically porphyrin) is still a controversial issue, as both a high ZnO luminescence yield and a good overlapping of ZnO emission-PS absorption spectra are necessary, along with a suitable energy transfer between ZnO and PS. In this perspective, the aim is the investigation of the optical properties of an ad-hoc system composed of porphyrin functionalized ZnO NPs anchored on SiO2 NPs (ZnO/SiO2). The goal is the understanding of the optimal conditions for a good energy transfer efficiency of ZnO-porphyrin structures, including the role of ZnO-PS proximity, to promote their application in anti-cancer therapies and imaging with ionizing radiations. First, amorphous ZnO NPs of 5-6 nm were anchored onto SiO2 NPs (~80 nm); then, ZnO/SiO2 was functionalized with different porphyrin contents (tetrakis(4-carboxyphenyl)porphyrin, TCPP, 0.3 – 3.0 wt%) by exploiting a silane grafting agent (3-aminopropyl)triethoxysilane. The structural characterization demonstrated that increasing TCPP amounts were bonded to SiO2 depending on the TCPP loading. The optical properties were preliminary tested in dimethylformamide, used as solvent reaction for TCPP anchoring on SiO2. The Photoluminescence Analysis (PL) revealed a high luminescence of ZnO NPs and the occurrence of a radiative energy transfer between ZnO and TCPP, that was not visible in a mechanical mixing of ZnO and TCCP, highlighting their optical interaction upon functionalization. Besides, TCPP emission was hugely enhanced under X-ray in the Radioluminescence (RL), whereas no enhancement was detectable in t

Lead halide perovskites (LHP) are rapidly emerging as efficient, low-cost, solution-processable scintillators for radiation detection. Carrier trapping is arguably the most critical limitation to the scintillation performance. Nonetheless, no clear picture of the trapping and detrapping mechanisms to/from shallow and deep trap states involved in the scintillation process has been reported to date, as well as on the role of the material dimensionality. Here, this issue is addressed by performing, for the first time, a comprehensive study using radioluminescence and photoluminescence measurements side-by-side to thermally-stimulated luminescence (TSL) and afterglow experiments on CsPbBr3 with increasing dimensionality, namely nanocubes, nanowires, nanosheets, and bulk crystals. All systems are found to be affected by shallow defects resulting in delayed intragap emission following detrapping via a-thermal tunneling. TSL further reveals the existence of additional temperature-activated detrapping pathways from deeper trap states, whose effect grows with the material dimensionality, becoming the dominant process in bulk crystals. These results highlight that, compared to massive solids where the suppression of both deep and shallow defects is critical, low dimensional nanostructures are more promising active materials for LHP scintillators, provided that their integration in functional devices meets efficient surface engineering.

We report here the synthesis of undoped and Cu-doped Cs2ZnCl4 nanocrystals (NCs) in which we could tune the concentration of Cu from 0.7 to 7.5%. Cs2ZnCl4 has a wide band gap (4.8 eV), and its crystal structure is composed of isolated ZnCl4 tetrahedra surrounded by Cs+ cations. According to our electron paramagnetic resonance analysis, in 0.7 and 2.1% Cu-doped NCs the Cu ions were present in the +1 oxidation state only, while in NCs at higher Cu concentrations we could detect Cu(II) ions (isovalently substituting the Zn(II) ions). The undoped Cs2ZnCl4 NCs were non emissive, while the Cu-doped samples had a bright intragap photoluminescence (PL) at similar to 2.6 eV mediated by band-edge absorption. Interestingly, the PL quantum yield was maximum (similar to 55%) for the samples with a low Cu concentration ([Cu] <= 2.1%), and it systematically decreased when further increasing the concentration of Cu, reaching 15% for the NCs with the highest doping level ([Cu] = 7.5%). The same (similar to 2.55 eV) emission band was detected under X-ray excitation. Our density functional theory calculations indicated that the PL emission could be ascribed only to Cu(I) ions: these ions promote the formation of trapped excitons, through which an efficient emission takes place. Overall, these Cu-doped Cs2ZnCl4 NCs, with their high photo- and radio-luminescence emission in the blue spectral region that is free from reabsorption, are particularly suitable for applications in ionizing radiation detection.