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Light-emitting diodes based on perovskite nanocrystals (PNCs-LEDs) have gained great interest for next-generation display and lighting technologies prized for their color purity, high brightness, and luminous efficiency which approach the intrinsic limit imposed by light extraction from the device structure. Although the time is ripe for the development of effective light outcoupling strategies to further boost the device performance, this technologically relevant aspect of PNC-LEDs is still without a definitive solution. Here, following theoretical guidelines and without the integration of complex photonic structures, we realize stable PNC-LEDs with external quantum efficiency (EQE) as high as 26.7%. Key to such performance is channeling the recombination zone in PNC emissive layers as thin as 10 nm, which we achieve by finely balancing charge transport using CsPbBr3 PNCs resurfaced with a nickel oxide layer. The ultrathin approach is general and, in principle, applicable to other perovskite nanostructures for fabricating highly efficient, color-tunable transparent LEDs.

Cesium lead halide perovskite nanocrystals of general formula CsPbX3 are having tremendous impact on a vast array of technologies requiring strong and tunable luminescence across the visible range and solutions processing. The development of plastic scintillators is just one of the many relevant applications. The syntheses are relatively simple but generally unsuitable to produce a large amount of material of reproducible quality required when moving from proof-of-concept scale to industrial applications. Wastes, particularly large amounts of lead-contaminated toxic and flammable organic solvents, are also an open issue. We describe a simple and reproducible procedure enabling the synthesis of luminescent CsPbX3 nanobricks of constant quality on a scale going from 0.12 to 8 g in a single batch. We also show complete recycling of the reaction wastes, leading to dramatically improved efficiency and sustainability.

Micro light-emitting diodes (μ-LEDs) coupled to color conversion phosphors are among the most promising technologies for future display and artificial light sources. However, current emitters suffer from excessively large particle sizes, preventing micron-scale processability, and/or low stability that hampers the device lifetime. Here, we demonstrate down-conversion μ-LED phosphors based on CsPbBr3 perovskite nanocrystals directly grown inside perfectly sealed mesoporous silica nanospheres (NSs). Key for this advancement is a high-throughput calcination procedure in the presence of K2CO3 as selective pore sealing agent, which simultaneously produces the CsPbBr3 nanocrystals, boosts their emission efficiency to >87%, and perfectly isolates them from the outer environment without causing inter-particle cross-linking or aggregation. This results in size-homogeneous, finely solution-dispersible, ultra-stable, and highly emissive CsPbBr3-SiO2 NSs that fit the technological requirements of photolithographic inks for highly uniform μ-LED color conversion patterns with pixels smaller than 20 μm.

Fluorescent concentrators (FCs) have been recently proposed as optical condensers for visible light communications (VLC) and optical wireless communication (OWC) receivers, with advantages over conventional optical stages in terms of optical gain and field of view (FoV). However, the use of FC-based receivers in real-world scenarios is hampered by the need for large resilience of the involved chromophores to sunlight exposure, and availability of large-area FC substrates with suitable optochemical properties. This paper presents an innovative OWC system, based on a high-power blue LED and a large-area FC-based on CuInS2 quantum dots (Q-Dots) as receiving optical stage. A thorough characterization of the FC material in terms of conversion efficiency, temporal response, and FoV is provided, along with a full set of outdoor measurements. The combination of the Q-Dots fluorophores chemico-physical properties with the strong DC rejection granted by the design receiver stage allows error-free VLC link distances up to 60 m and baud rates up to 1 Mb/s. This work represents the first demonstration of long-range VLC links under strong solar irradiance using large-area FC antennas and paves the way to deployment of long-range free-space optical links with minimal susceptibility to misalignments and pointing instabilities between receiver and transmitter.

We elucidate here the nature of the emissive states in Rb7Sb3Cl16 nanocrystals (NCs) for which we report a synthesis. These NCs have a crystal structure comprising both isolated [SbCl6]3- octahedra and isolated [Sb2Cl10]4- dimers of octahedra. The optical properties of Rb7Sb3Cl16 NCs are compared with those of Sb-doped Rb3InCl6 NCs, the latter containing only isolated [SbCl6]3- octahedra. The remarkably similar behaviors of the two systems indicate that the optical emission in both materials originates from the isolated octahedra. Density functional theory calculations suggest that the [SbCl6]3- octahedra are optically active in emission because the local arrangement of the Rb+ ions around the octahedra limits the elongation of the Sb-Cl bonds upon excitation, helping to confine the self-trapped exciton in them. Conversely, in the [Sb2Cl10]4- dimers the constraining effect of the surrounding Rb+ ions is less marked and the Sb-Cl bonds fully break upon photoexcitation, opening up an efficient nonradiative channel for the self-trapped excitons.

The family of metal halide (MH) nanocrystal materials is still vastly unexplored and unlocking their full potential is just at the beginning. The understanding and, therefore, the optimization of the properties of these nanoscale systems passes through a series of experimental characterization techniques that span compositional analysis, resolution of unknown (nano)crystal phases, determination of the nanocrystal facets, assessment of ligands bound to the surface, and analysis of the optical properties. All of these characterizations, in turn, require specific advanced tools. The data collected are complemented by computational models to attain a complete picture of a given system. Here, we highlight the best practices for the application of these techniques, also based on the expertise developed in our groups.

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.

The thermal quenching of light emission is a critical bottleneck that hampers the real-world application of lead halide perovskite nanocrystals in both electroluminescent and down-conversion light-emitting diodes. Here, we report CsPbBr3 perovskite nanocrystals with a temperature-independent emission efficiency of near unity and constant decay kinetics up to a temperature of 373 K. This unprecedented regime is obtained by a fluoride post-synthesis treatment that produces fluorine-rich surfaces with a wider energy gap than the inner nanocrystal core, yielding suppressed carrier trapping, improved thermal stability and efficient charge injection. Light-emitting diodes incorporating these fluoride-treated perovskite nanocrystals show a low turn-on voltage and spectrally pure green electroluminescence with an external quantum efficiency as high as 19.3% at 350 cd m−2. Importantly, nearly 80% of the room-temperature external quantum efficiency is preserved at 343 K, in contrast to the dramatic drop commonly observed for standard CsPbBr3 perovskite nanocrystal light-emitting diodes. These results provide a promising pathway for high-performance, practical light-emitting diodes based on perovskite nanostructures. Fluoride-treated CsPbBr3 nanocrystals emit light with near unity efficiency at temperatures of up to 373 K.

In this work, we report the hot-injection synthesis of Cs

Summary Surface vacancy engineering played a significant role in tailoring the structure and improving the performance of semiconductor nanocrystals (SNCs). Developing controllable vacancy engineering strategies to overcome kinetic energy barriers in multi-step reactions is anticipated to explore further synthesis mechanisms and functional nanomaterials. Herein, we exploited an effective surface-vacancy-engineering-initialized cation exchange (SVEICE) strategy to realize energy-unfavored cation exchange reactions from ternary CuInX2 (X = S, Se) to Cu, In dual-doped binary CdX, or ZnX SNCs, unprecedentedly. The sequential and selective creation of Cu and In vacancies on multi-component SNC surface is critical to break through kinetic energy barriers. The emission of dual-doped CdS:Cu/In SNCs crossed visible-NIR region due to the radiative transition from doped In level to Cu-doped e- or t-level, and the radiative recombination process could also be tailored by this strategy. Further energy analysis and experiments confirmed its versatility.

Luminescent solar concentrators (LSCs) have recently emerged as valuable candidates for the realization of aesthetically pleasing solar windows for near-zero-energy consumption buildings. The growing demand by the building-integrated photovoltaic sector is urging the development of sustainable production methods that minimize the use of polluting organic solvents and hazardous materials, while still enabling industrial-grade LSCs. Here, we introduce a new class of benzothieno-benzothiophene (BTBT) derivatives as highly efficient reabsorption-free emitters for transparent LSCs featuring high stability and a solvent-free chemical access with sustainability factor as low as 21, 10 to 50 times lower than conventional LSC emitters. By embedding our BTBT emitters in optical-grade polymeric waveguides, we produced large-area (40 cm × 40 cm) LSCs with optical power efficiency as high as 3% (corresponding to an optical quantum efficiency of 54%). These results represent an important advancement toward sustainable solar glazing systems for green architecture.The growing demand for building-integrated photovoltaic technologies for near-zero-energy buildings is motivating the scientific community to develop devices that meet the functional, energetic, and aesthetic needs for sustainable architecture. Luminescent solar concentrators (LSCs) are emerging as valuable solutions to realize aesthetically pleasing semitransparent photovoltaic windows capable of converting urban buildings into energy generators. In this work, we report on efficient, transparent LSCs based on a novel class of reabsorption-free derivatives synthesized through a solvent-free route that massively improves the sustainability factor with respect to the state of the art. Optical-grade polymeric LSCs are produced via industrial methods with an optical power efficiency as high as 3% despite their transparency in the visible region. These results represent an important step forward for sustainable solar glazing systems for environmentally friendly architecture. Efficient and aesthetically pleasing solar technologies, such as LSC photovoltaic windows, are becoming essential for the widespread of zero-energy buildings. The more the LSC technology gains appeal, the higher the need becomes for efficient and sustainable materials and production routes. Through a new mechanochemical route, we produce efficient, reabsorption-free LSC emitters with a massively increased sustainability factor. The integration of such derivatives into industrial-grade LSCs leads to an optical efficiency of 3% for large-area devices.

Colloidal semiconductor nanocrystals (NCs) and, recently, nanoplatelets (NPLs), owing to their efficient and narrow-band luminescence, are considered as frontier materials for light-emitting diode (LED) technology. NC-LEDs typically incorporate interfacial layers as charge regulators to ensure charge balancing and high performance. In this Letter, we show the prolongation of the lifetime of multilayer solution-processed NC-LEDs by combining a self-doped conductive conjugated polyelectrolyte and exfoliated molybdenum disulfide (MoS2) flakes as an alternative to PEDOT:PSS. The ink features a neutral pH and a tunable hydrophobicity that mainly results in a remarkable stability of LEDs, using CdSe/CdZnS NPLs.

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.

Fair and meaningful device per- formance comparison among luminescent solar concentrator- photovoltaic (LSC-PV) reports cannot be realized without a gen- eral consensus on reporting stan- dards in LSC-PV research. There- fore, it is imperative to adopt standardized characterization protocols for these emerging types of PV devices that are consistent with other PV devices. This commentary highlights several common limitations in LSC literature and summarizes the best practices moving for- ward to harmonize with standard PV reporting, considering the greater nuances present with LSC-PV. Based on these prac- tices, a checklist of actionable items is provided to help stan- dardize the characterization/re- porting protocols and offer a set of baseline expectations for au- thors, reviewers, and editors. The general consensus combined with the checklist will ultimately guide LSC-PV research towards reliable and meaningful ad- vances.

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.

Plastic scintillators are gaining attention as alternatives to inorganic scintillator crystals owing to their low fabrication cost, customable shape/size, and substantially lighter weight that make them suitable for various radiation detection technologies. These include scintillation panels for national security and industrial monitoring, radiation screens for medical diagnostics, and calorimeters for high energy physics. Because of their low density, plastic scintillators are typically doped with high atomic number (Z) sensitizers that enhance the interaction probability with ionizing radiation and excite molecular emitters. Although effective, such a two-component design suffers from incomplete sensitization, intrinsically limited efficiency due to multiple radiative steps with non-unity quantum yield, detrimental phase segregation effects and the fragility of organic emitters to ionizing radiation. In this work, an alternative single-component scheme is proposed based on high-Z reabsorption-free CdZnS/ZnS semiconductor nanocrystals (NCs) doped with manganese embedded in a polyvinyltoluene (PVT) waveguide. Optical-grade nanocomposites free from optical reabsorption of the scintillation light and with performance comparable to commercial products are obtained through a post-synthesis resurfacing procedure that maximizes the compatibility between the NCs and PVT and preserves their optical properties upon curing.

Radiation detection is of utmost importance in fundamental scientific research, as well as medical diagnostics, homeland security, environmental monitoring and industrial control. Lead halide perovskites (LHPs) are attracting growing attention as high-atomic-number materials for next-generation scintillators and photoconductors for ionizing radiation detection. To unlock their full potential as reliable and cost-effective alternatives to conventional materials, it is necessary for LHPs to conjugate high scintillation yields with emission stability under high doses of ionizing radiation. To date, no definitive solution has been devised to optimize the scintillation efficiency and kinetics of LHPs and nothing is known of their radiation hardness for doses above a few kilograys, to the best of our knowledge. Here we demonstrate that CsPbBr3 nanocrystals exhibit exceptional radiation hardness for γ-radiation doses as high as 1 MGy. Spectroscopic and radiometric experiments highlight that despite their defect tolerance, standard CsPbBr3 nanocrystals suffer from electron trapping in dense surface defects that are eliminated by post-synthesis fluorination. This results in >500% enhancement in scintillation efficiency, which becomes comparable to commercial scintillators, and still retaining exceptional levels of radiation hardness. These results have important implications for the widespread use of LHPs in ultrastable and efficient radiation detectors.

We report the composition-dependent optical properties of Bi-doped Cs2Ag1-xNaxInCl6 nanocrystals (NCs) having a double perovskite crystal structure. Their photoluminescence (PL) was characterized by a large Stokes shift, and the PL quantum yield increased with the amount of Na up to ∼22% for the Cs2Ag0.4Na0.6InCl6 stoichiometry. The presence of Bi3+ dopants was crucial to achieve high PL quantum yields (PLQYs) as nondoped NC systems were not emissive. Density functional theory calculations revealed that the substitution of Ag+ with Na+ leads to localization of AgCl6 energy levels above the valence band maximum, whereas doping with Bi3+ creates BiCl6 states below the conduction band minimum. As such, the PL emission stems from trapped emission between states localized in the BiCl6 and AgCl6 octahedra, respectively. Our findings indicated that both the partial replacement of Ag+ with Na+ ions and doping with Bi3+ cations are essential in order to optimize the PL emission of these systems.

"Charge engineering" of semiconductor nanocrystals (NCs) through so-called electronic impurity doping is a long-standing challenge in colloidal chemistry and holds promise for ground-breaking advancements in many optoelectronic, photonic, and spin-based nanotechnologies. To date, our knowledge is limited to a few paradigmatic studies on a small number of model compounds and doping conditions, with important electronic dopants still unexplored in nanoscale systems. Equally importantly, fine-tuning of charge engineered NCs is hampered by the statistical limitations of traditional approaches. The resulting intrinsic doping inhomogeneity restricts fundamental studies to statistically averaged behaviors and complicates the realization of advanced device concepts based on their advantageous functionalities. Here we aim to address these issues by realizing the first example of II-VI NCs electronically doped with an exact number of heterovalent gold atoms, a known p-type acceptor impurity in bulk chalcogenides. Single-dopant accuracy across entire NC ensembles is obtained through a novel non-injection synthesis employing ligand-exchanged gold clusters as "quantized" dopant sources to seed the nucleation of CdSe NCs in organic media. Structural, spectroscopic, and magneto-optical investigations trace a comprehensive picture of the physical processes resulting from the exact doping level of the NCs. Gold atoms, doped here for the first time into II-VI NCs, are found to incorporate as nonmagnetic Au + species activating intense size-tunable intragap photoluminescence and artificially offsetting the hole occupancy of valence band states. Fundamentally, the transient conversion of Au + to paramagnetic Au 2+ (5d 9 configuration) under optical excitation results in strong photoinduced magnetism and diluted magnetic semiconductor behavior revealing the contribution of individual paramagnetic impurities to the macroscopic magnetism of the NCs. Altogether, our results demonstrate a new chemical approach toward NCs with physical functionalities tailored to the single impurity level and offer a versatile platform for future investigations and device exploitation of individual and collective impurity processes in quantum confined structures.

Luminescent solar concentrators (LSCs) are rapidly gaining momentum in building integrated photovoltaics. The use of cycloparaphenylenes (CPPs) as large Stokes shift emitters enables the preparation of nearly transparent, large area LSC devices that remain unaffected by reabsorption losses.

A wide variety of materials with nanometre dimensions are increasingly explored for photonic applications. Among them, semiconductor nanocrystals (NCs) are very promising for a variety of uses, including light emission devices (LEDs), lasers, detectors, photovoltaic cells, biological labelling and sensing [1]. Key advantage of NCs is the possibility to tailor their optical response by controlling the electronic structure (“wave function engineering”) through the choice of composition, size and shape. Significant and interesting results have been obtained with heterostructured and doped NCs. Beyond single wavelength tuneable band-edge emission, other regimes have been demonstrated such as intragap emission, simultaneous emission on two different wavelengths, amplified spontaneous emission and laser emission. The luminescent properties are governed by exciton decay, which can proceed through radiative or nonradiative pathways, following different routes. The study of exciton dynamics can allow elucidating the processes connected to single or dual emission and to optical gain. This, in turn, can lead to the identification of the functional and structural characteristics that are responsible for these behaviors. Exciton relaxation occurs on picosecond timescales, so ultrafast optical techniques are required to perform these studies. In this talk, we present studies carried out by ultrafast pump-probe spectroscopy technique, with 100-fs time resolution, on CdSe/CdS and PbS/CdS heterostructured NCs, with different geometries (core/shell, dot-in-rod, dot-in-bulk, with sharp or graded interface) [2-6] and CdSeS and CdZnSe doped NCs [7,8]. These NCs are optically active in the visible and near-infrared spectral region, show single and dual colour photoluminescence emission, optical gain, laser emission and intragap emission [2-9]. The analysis of the experimental data allowed us to unravel the decay processes: the initials take place in a few ps, leading to the ultimate emitting state whose lifetime can extend to hundreds of ps to few ns, allowing for efficient luminescence and optical gain. Our data on heterostructures allowed us to clarify the role of the volume and of the shape of the outer component and the effect of the interface [2-4]. We found that dual emission is possible for both thick and thin quantum-confined shells, and for different interfaces. We studied the decoupling of excitons lying in the two different component of the NC (core exciton and shell exciton) and we revealed the evolution of the exciton barrier known as dynamic hole-blockade effect. We showed that these phenomena are strictly connected to dual emission and optical gain and we identified the condition for their maximum efficiency, in term of band alignment and band transitions. Our results provide a comprehensive understanding of the physical phenomena governing dual-emission mechanisms, suppression of Auger recombination, optical gain and laser emission in heterostructured NCs. Experiments on CdZnSe NCs doped with Mn and on CdSeS NCs engineered with sulfur vacancies, enabled us to disclose donor and acceptor localized states in the band gap. We observed the carrier dynamics responsible for intragap emission which is associated to the emergence of a transient Mn3+ state [7], in the first case, and to a donor state below the conduction band introduced by sulfur vacancies [8], in the latter case. In conclusion, the study of the exciton dynamics in different NCs allowed us to elucidate the relation between structural-morphological characteristics (shape, volume, and interface) and unconventional emission capabilities (dual emission and optical gain) in heterostructures and the photophysics of electronic states introduced by doping. This knowledge is very important to control NC functionalities toward new multilevel electronic or photonic schemes and in applications such as lasers [9], photoelectrochemical (PEC) cell [10], white light emission [11], ratiometric sensing [12]. [1] P. V. Kamat and G. D. Scholes, J. Phys. Chem. Lett. 7, 584 (2016) [2] G. Sirigu et al., Phys. Rev. B 96, 155303 (2017) [3] V. Pinchetti et al., ACS Nano 10, 6877-6887 (2016) [4] H. Zhao et al., Nanoscale 8, 4217-4226 (2016) [5] M. Zavelani-Rossi et al., Nano Lett. 10, 3142-3150 (2010) [6] R. Krahne et al., Appl. Phys. Lett. 98, 063105 (2011) [7] K. Gahlot et al., ACS Energy Lett. 4, 729−735 (2019) [8] F. Carulli et al., Nano Lett. 21, 6211−6219 (2021) [9] M. Zavelani-Rossi et al., Laser & Photonics Reviews 6, 678-683 (2012) [10] L. Jin et al., Nano Energy 30, 531-541 (2016) [11] S. Sapra et al., Adv. Mater. 19, 569 (2007) [12] J. Liu et al., ACS Photonics, 2479 (2019)

Colloidal semiconductor nanoplatelets (NPLs) are a subgroup of quantum confined materials that have recently emerged as promising active materials for solution processed light-emitting diodes (LEDs) thanks to their peculiar structural and electronic properties as well as their reduced dimensionality. Nowadays, the conventional structure for NPL-based LEDs makes use of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) as a hole transporting layer (HTL). This is a well-known conjugated conductive polymer because it leads to high LED efficiency, though it has limited stability in air due to its intrinsic acidity and hygroscopicity. Here, we develop a nanocomposite aqueous ink, obtained by blending commercial PEDOT:PSS with water-based, stable and highly concentrated molybdenum disulfide (MoS2) nanosheets, obtained via liquid phase exfoliation (LPE), which is suitable as a HTL for solution processed NPL-based LEDs. We demonstrate that the MoS2 additive effectively works as a performance booster in unpackaged devices, thereby prolonging the lifetime up to 1000 hours under ambient conditions. Moreover, the addition of MoS2 induces a modification of the anode interface properties, including a change in the work function and a significant enhancement of the permittivity of the HTL.

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.

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.

Luminescent solar concentrators (LSC) allow to obtain renewable energy from building integrated photovoltaic systems. As promising efficient and long-term stable LSC fluorophores semiconductor nanocrystals like quantum dots (QDs) with size and composition tunable optoelectronic properties have recently emerged. The most popular II/VI or IV/VI semiconductor QDs contain, however, potentially hazardous cadmium or lead ions, which is a bottleneck for commercial applications. A simple aqueous based, microwave-assisted synthesis for environmentally friendly and highly emissive AgInS2/ZnS QDs is developed using 3-mercaptopropionic acid (MPA) and glutathione (GSH) and their incorporation into polylaurylmethacrylate (PLMA) polymer slabs integrable in LSC devices (10.4 × 10.4 × 0.2 cm3, G = 12.98). With this simple approach, optical power efficiencies (OPE) of 3.8% and 3.6% and optical quantum efficiencies (OQE) of 24.1% and 27.4% are obtained, which are among the highest values yet reported. German Research Council European Union's Horizon 2020 Marie Sklodowska‐Curie Deutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659

In the Deep Underground Neutrino Experiment (DUNE), the VUV LAr luminescence is collected by light trap devices named X-Arapuca, sizing ∼ (480 × 93) mm2. Six thousand of these units will be deployed in the first DUNE ten kiloton far detector module. In this work we present the first characterisation of the photon detection efficiency of an X-Arapuca device sizing ∼(200 × 75) mm2 via a complete and accurate set of measurements along the cell longitudinal axis with a movable 241Am source. The MPPCs photosensors are readout by a cryogenic trans-impedance amplifier to enhance the single photoelectron sensitivity and improve the signal-to-noise while ganging 8 MPPC for a total surface of 288 mm2. Moreover, we developed a new photon downshifting polymeric material, by which the X-Arapuca photon detection efficiency was enhanced of about +50% with respect to the baseline off-shell product deployed in the standard device configuration. The achieved results are compared to previous measurements on a half size X-Arapuca device, with a fixed source facing the center, with no cold amplification stage, and discussed in view of the DUNE full size optical cell construction for both the horizontal and the vertical drift configurations of the DUNE TPC design and in view of liquid Argon doping by ppms of Xe. Other particle physics projects adopting Liquid Argon as target or active veto, such as Dark Side and LEGEND or the DUNE Near Detector, may take advantage of this novel wavelength shifting material.

We report the synthesis of colloidal CsPbX3-Pb4S3Br2 (X=Cl, Br, I) nanocrystal heterostructures, providing an example of a sharp and atomically resolved epitaxial interface between a metal halide perovskite and a non-perovskite lattice. The CsPbBr3-Pb4S3Br2 nanocrystals are prepared by a two-step direct synthesis, using pre-formed sub-nm CsPbBr3 clusters. Density functional theory calculations indicate the creation of a quasi-type II alignment at the heterointerface, as well as the formation of localized trap states, respectively promoting ultrafast separation of photogenerated excitons and carrier trapping, as confirmed by spectroscopic experiments. Post-synthesis reaction with either Cl- or I- ions delivers the corresponding CsPbCl3-Pb4S3Br2 and CsPbI3-Pb4S3Br2 heterostructures, thus enabling anion exchange only in the perovskite domain. An increased structural rigidity is conferred to the perovskite lattice when it is interfaced with the chalcohalide lattice. This is attested by the improved stability of the metastable g phase (or “black” phase) of CsPbI3 in the CsPbI3-Pb4S3Br2 heterostructure.

Ternary I-III-VI 2 nanocrystals (NCs), such as AgInS 2 and CuInS 2 , are garnering interest as heavy-metal-free materials for photovoltaics, luminescent solar concentrators, LEDs, and bioimaging. The origin of the emission and absorption properties in this class of NCs is still a subject of debate. Recent theoretical and experimental studies revealed that the characteristic Stokes-shifted and long-lived luminescence of stoichiometric CuInS 2 NCs arises from the detailed structure of the valence band featuring two sublevels with different parity. The same valence band substructure is predicted to occur in AgInS 2 NCs, yet no experimental confirmation is available to date. Here, we use complementary spectroscopic, spectro-electrochemical, and magneto-optical investigations as a function of temperature to investigate the band structure and the excitonic recombination mechanisms in stoichiometric AgInS 2 NCs. Transient transmission measurements reveal the signatures of two subbands with opposite parity, and photoluminescence studies at cryogenic temperatures evidence a dark state emission due to enhanced exchange interaction, consistent with the behavior of stoichiometric CuInS 2 NCs. Lowering the temperature as well as applying reducing electrochemical potentials further suppress electron trapping, which represents the main nonradiative channel for exciton decay, leading to nearly 100% emission efficiency.

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]

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.

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%. According to 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. The undoped Cs2ZnCl4 NCs were non emissive, while the Cu-doped samples had a bright intra-gap photoluminescence (PL) at 2.6eV mediated by band-edge absorption. The PL quantum yield was maximum (~55%) for the samples with low Cu concentration (≤ 2.1%) and it systematically decreased when further increasing the concentration of Cu, reaching 15% for the NCs with the highest doping level (7.5%). Density functional theory calculations indicated that the PL emission could be ascribed only to Cu(I) ions: these ions introduce intra-gap states that promote the formation of self-trapped excitons, through which an efficient emission takes place.