Scintillation Properties of CsPbBr3 Nanocrystals Prepared by Ligand-Assisted Reprecipitation and Dual Effect of Polyacrylate Encapsulation toward Scalable Ultrafast Radiation Detectors.

Lead halide perovskite nanocrystals (LHP-NCs) embedded in polymeric hosts are gaining attention as scalable and low-cost scintillation detectors for technologically relevant applications. Despite rapid progress, little is currently known about the scintillation properties and stability of LHP-NCs prepared by the ligand assisted reprecipitation (LARP) method, which allows mass scalability at room temperature unmatched by any other type of nanostructure, and the implications of incorporating LHP-NCs into polyacrylate hosts are still largely debated. Here, we show that LARP-synthesized CsPbBr3 NCs are comparable to particles from hot-injection routes and unravel the dual effect of polyacrylate incorporation, where the partial degradation of LHP-NCs luminescence is counterbalanced by the passivation of electron-poor defects by the host acrylic groups. Experiments on NCs with tailored surface defects show that the balance between such antithetical effects of polymer embedding is determined by the surface defect density of the NCs and provide guidelines for further material optimization.

Ultrafast and Radiation-Hard Lead Halide Perovskite Nanocomposite Scintillators.

The use of scintillators for the detection of ionizing radiation is a critical aspect in many fields, including medicine, nuclear monitoring, and homeland security. Recently, lead halide perovskite nanocrystals (LHP-NCs) have emerged as promising scintillator materials. However, the difficulty of affordably upscaling synthesis to the multigram level and embedding NCs in optical-grade nanocomposites without compromising their optical properties still limits their widespread use. In addition, fundamental aspects of the scintillation mechanisms are not fully understood, leaving the scientific community without suitable fabrication protocols and rational guidelines for the full exploitation of their potential. In this work, we realize large polyacrylate nanocomposite scintillators based on CsPbBr3 NCs, which are synthesized via a novel room temperature, low waste turbo-emulsification approach, followed by their in situ transformation during the mass polymerization process. The interaction between NCs and polymer chains strengthens the scintillator structure, homogenizes the particle size distribution and passivates NC defects, resulting in nanocomposite prototypes with luminescence efficiency >90%, exceptional radiation hardness, 4800 ph/MeV scintillation yield even at low NC loading, and ultrafast response time, with over 30% of scintillation occurring in the first 80 ps, promising for fast-time applications in precision medicine and high-energy physics. Ultrafast radioluminescence and optical spectroscopy experiments using pulsed synchrotron light further disambiguate the origin of the scintillation kinetics as the result of charged-exciton and multiexciton recombination formed under ionizing excitation. This highlights the role of nonradiative Auger decay, whose potential impact on fast timing applications we anticipate via a kinetic model.

Optical and Scintillation Properties of Record-Efficiency CdTe Nanoplatelets toward Radiation Detection Applications.

Colloidal CdTe nanoplatelets featuring a large absorption coefficient and ultrafast tunable luminescence coupled with heavy-metal-based composition present themselves as highly desirable candidates for radiation detection technologies. Historically, however, these nanoplatelets have suffered from poor emission efficiency, hindering progress in exploring their technological potential. Here, we report the synthesis of CdTe nanoplatelets possessing a record emission efficiency of 9%. This enables us to investigate their fundamental photophysics using ultrafast transient absorption, temperature-controlled photoluminescence, and radioluminescence measurements, elucidating the origins of exciton- and defect-related phenomena under both optical and ionizing excitation. For the first time in CdTe nanoplatelets, we report the cumulative effects of a giant oscillator strength transition and exciton fine structure. Simultaneously, thermally stimulated luminescence measurements reveal the presence of both shallow and deep trap states and allow us to disclose the trapping and detrapping dynamics and their influence on the scintillation properties.

Cu+ → Mn2+ Energy Transfer in Cu, Mn Coalloyed Cs3ZnCl5 Colloidal Nanocrystals.

In this work, we report the hot-injection synthesis of Cs3ZnCl5 colloidal nanocrystals (NCs) with tunable amounts of Cu+ and Mn2+ substituent cations. All the samples had a rodlike morphology, with a diameter of ∼14 nm and a length of ∼30-100 nm. Alloying did not alter the crystal structure of the host Cs3ZnCl5 NCs, and Cu ions were mainly introduced in the oxidation state +1 according to X-ray photoelectron and electron paramagnetic resonance spectroscopies. The spectroscopic analysis of unalloyed, Cu-alloyed, Mn-alloyed, and Cu, Mn coalloyed NCs indicated that (i) the Cs3ZnCl5 NCs have a large band gap of ∼5.35 eV; (ii) Cu(I) aliovalent alloying leads to an absorption shoulder/peak at ∼4.8 eV and cyan photoluminescence (PL) peaked at 2.50 eV; (iii) Mn(II) isovalent alloying leads to weak Mn PL, which intensifies remarkably in the coalloyed samples, prompted by an energy transfer (ET) process between the Cu and Mn centers, favored by the overlap between the lowest (6A1 → 4T1) transition for tetrahedrally coordinated Mn2+ and the PL profile from Cu(I) species in the Cs3ZnCl5 NCs. The efficiency of this ET process reaches a value of 61% for the sample with the highest extent of Mn alloying. The PL quantum yield (QY) values in these Cu, Mn coalloyed NCs are lower at higher Mn contents. The analysis of the Mn PL dynamics in these samples indicates that this PL drop stems from inter-Mn exciton migration, which increases the likelihood of trapping in defect sites, in agreement with previous studies.

Optical and Magneto-Optical Properties of Donor-Bound Excitons in Vacancy-Engineered Colloidal Nanocrystals.

Controlled insertion of electronic states within the band gap of semiconductor nanocrystals (NCs) is a powerful tool for tuning their physical properties. One compelling example is II-VI NCs incorporating heterovalent coinage metals in which hole capture produces acceptor-bound excitons. To date, the opposite donor-bound exciton scheme has not been realized because of the unavailability of suitable donor dopants. Here, we produce a model system for donor-bound excitons in CdSeS NCs engineered with sulfur vacancies (VS) that introduce a donor state below the conduction band (CB), resulting in long-lived intragap luminescence. VS-localized electrons are almost unaffected by trapping, and suppression of thermal quenching boosts the emission efficiency to 85%. Magneto-optical measurements indicate that the VS are not magnetically coupled to the NC bands and that the polarization properties are determined by the spin of the valence-band photohole, whose spin flip is massively slowed down due to suppressed exchange interaction with the donor-localized electron.

Sb-Doped Metal Halide Nanocrystals: A 0D versus 3D Comparison.

We synthesize colloidal nanocrystals (NCs) of Rb3InCl6, composed of isolated metal halide octahedra ("0D"), and of Cs2NaInCl6 and Cs2KInCl6 double perovskites, where all octahedra share corners and are interconnected ("3D"), with the aim to elucidate and compare their optical features once doped with Sb3+ ions. Our optical and computational analyses evidence that the photoluminescence quantum yield (PLQY) of all these systems is consistently lower than that of the corresponding bulk materials due to the presence of deep surface traps from under-coordinated halide ions. Also, Sb-doped "0D" Rb3InCl6 NCs exhibit a higher PLQY than Sb-doped "3D" Cs2NaInCl6 and Cs2KInCl6 NCs, most likely because excitons responsible for the PL emission migrate to the surface faster in 3D NCs than in 0D NCs. We also observe that all these systems feature a large Stokes shift (varying from system to system), a feature that should be of interest for applications in photon management and scintillation technologies. Scintillation properties are evaluated via radioluminescence experiments, and re-absorption-free waveguiding performance in large-area plastic scintillators is assessed using Monte Carlo ray-tracing simulations.

Compositional Tuning of Carrier Dynamics in Cs2Na1-x Ag x BiCl6 Double-Perovskite Nanocrystals.

We devised a hot-injection synthesis to prepare colloidal double-perovskite Cs2NaBiCl6 nanocrystals (NCs). We also examined the effects of replacing Na+ with Ag+ cations by preparing and characterizing Cs2Na1-x Ag x BiCl6 alloy NCs with x ranging from 0 to 1. Whereas Cs2NaBiCl6 NCs were not emissive, Cs2Na1-x Ag x BiCl6 NCs featured a broad photoluminescence band at ∼690 nm, Stokes-shifted from the respective absorption by ≥1.5 eV. The emission efficiency was maximized for low Ag+ amounts, reaching ∼3% for the Cs2Na0.95Ag0.05BiCl6 composition. Density functional theory calculations coupled with spectroscopic investigations revealed that Cs2Na1-x Ag x BiCl6 NCs are characterized by a complex photophysics stemming from the interplay of (i) radiative recombination via trapped excitons localized in spatially connected AgCl6-BiCl6 octahedra; (ii) surface traps, located on undercoordinated surface Bi centers, behaving as phonon-assisted nonradiative decay channels; and (iii) a thermal equilibrium between trapping and detrapping processes. These results offer insights into developing double-perovskite NCs with enhanced optoelectronic efficiency.

High Photon Upconversion Efficiency with Hybrid Triplet Sensitizers by Ultrafast Hole-Routing in Electronic-Doped Nanocrystals.

Low-power photon upconversion (UC) based on sensitized triplet-triplet annihilation (sTTA) is considered as the most promising upward wavelength-shifting technique to enhance the light-harvesting capability of solar devices. Colloidal nanocrystals (NCs) with conjugated organic ligands have been recently proposed to extend the limited light-harvesting capability of molecular absorbers. Key to their functioning is efficient energy transfer (ET) from the NC to the triplet state of the ligands that sensitize free annihilator moieties responsible for the upconverted luminescence. The ET efficiency is typically limited by parasitic processes, above all nonradiative hole-transfer to the ligand highest occupied molecular orbital (HOMO). Here, a new exciton-manipulation approach is demonstrated that enables loss-free ET by electronically doping CdSe NCs with gold impurities that introduce a hole-accepting intragap state above the HOMO energy of 9-anthracene acid ligands. Upon photoexcitation, the NC photoholes are rapidly routed to the Au-level, producing a long-lived bound exciton in perfect resonance with the ligand triplet. This hinders hole-transfer leading to ≈100% efficient ET that translates into an upconversion quantum yield as high as ≈12% (≈24% in the normalized definition), which is the highest performance for NC-based upconverters based on sTTA to date and approaches the record efficiency of optimized organic systems.

Bright Blue Emitting Cu-Doped Cs2ZnCl4 Colloidal Nanocrystals.

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 ∼2.6 eV mediated by band-edge absorption. Interestingly, the PL quantum yield was maximum (∼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 (∼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.