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Energy sustainability and interconnectivity are the two main pillars on which cutting-edge architecture is based and require the realization of energy and intelligent devices that can be fully integrated into buildings, capable of meeting stringent regulatory requirements and operating in real-world conditions. Luminescent solar concentrators, particularly those based on near-infrared emitting reabsorption-free quantum dots, are considered good candidates for the realization of semi-transparent photovoltaic glazing, but despite important advances in optical property engineering strategies, studies of finished devices suitable for real-world operation are still lacking. In this paper, the first example of a fully assembled quantum dot luminescent solar concentrator-based photovoltaic glazing is demonstrated that meets all international standards for photovoltaic and building elements. It is also shown that these devices are capable of functioning as efficient Visible Light Communication (VLC) receivers even under full sunlight, thus combining energy and wireless connectivity functions in a realistic solution for smart, sustainable buildings.

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.

In recent years, the field of radiation detection has witnessed a paradigm shift with the emergence of plastic scintillators incorporating perovskite nanocrystals (PNCs). This innovative class of scintillators not only capitalizes on the superior luminescent properties of PNCs but also harnesses the flexibility and processability of polymers. This review explores the intricate landscape of synthesizing and fabricating scintillating PNCs and nanocomposites, delving into the methods employed in their production. From solution-based methods to innovative solid-state approaches, the synthesis of PNCs for scintillators application is explored comprehensively. Furthermore, embedding strategies within polymeric matrices are scrutinized, shedding light on the various techniques utilized to achieve optimal dispersion and compatibility. The evaluation of the final nanocomposites is finally discussed, with a particular emphasis on their scintillating performance and radiation hardness. Through a meticulous exploration of synthesis methodologies, embedding techniques, and performance assessments, this Review aims to provide a multilayered understanding of the state-of-the-art in PNC-based nanoscintillators

We report a colloidal synthesis of blue emissive, stable cube-shaped CsPbBr3 quantum dots (QDs) in the strong quantum confinement regime via dissolution–recrystallization starting from pre-syntesized (KxCs1–x)4PbBr6 nanocrystals which are then reacted with PbBr2. This is markedly different from the known case of Cs4PbBr6 nanocrystals that react within seconds with PbBr2 and get transformed into much larger, green emitting CsPbBr3 nanocrystals. Here, instead, the conversion of (KxCs1–x)4PbBr6 nanocrystals to CsPbBr3 QDs occurs in a time span of hours, and tuning of the QD size is achieved by adjusting the concentration of the precursors. The QDs exhibit excitonic features in optical absorption that are tunable in the 420–452 nm range, accompanied by blue photoluminescence with quantum yield around 60%. Detailed spectroscopic investigations in both the single and multiexciton regime reveal the exciton fine structure and the effect of Auger recombination of these CsPbBr3 QDs, confirming theoretical predictions for this system.

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.

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.

Simultaneously achieving both broad absorption and sharp emission in the near-infrared (NIR) is challenging. Coupling of an efficient absorber such as lead halide perovskites to lanthanide emissive species is a promising way to meet the demands for visible-to-NIR spectral conversion. However, lead-based perovskite sensitizers suffer from relatively narrow absorption in the visible range, poor stability, and toxicity. Herein, we introduce a downshifting configuration based on lead-free cesium manganese bromide nanocrystals acting as broad visible absorbers coupled to sharp emission in the NIR-I and NIR-II spectral regions. To achieve this, we synthesized CsMnBr3 and Cs3MnBr5 nanocrystals and attempted to dope them with a series of lanthanides, achieving success only with CsMnBr3. The correlation of the lanthanide emission to the CsMnBr3 visible absorption was confirmed with steady-state excitation spectra and time-resolved photoluminescence measurements, whereas the mechanism of downconversion from the CsMnBr3 matrix to the lanthanides was understood by density functional theory calculations. This study shows that lead-free metal halides with an appropriate phase are effective sensitizers for lanthanides and offer a route to efficient downshifting applications.

Colloidal chemistry grants access to a wealth of materials through simple and mild reactions. However, even few elements can combine in a variety of stoichiometries and structures, potentially resulting in impurities or even wrong products. Similar issues have been long addressed in organic chemistry by using reaction-directing groups, that are added to a substrate to promote a specific product and are later removed. Inspired by such approach, we demonstrate the use of CsPbCl3 perovskite nanocrystals to drive the phase-selective synthesis of two yet unexplored lead sulfochlorides: Pb3S2Cl2 and Pb4S3Cl2. When homogeneously nucleated in solution, lead sulfochlorides form Pb3S2Cl2 nanocrystals. Conversely, the presence of CsPbCl3 triggers the formation of Pb4S3Cl2/CsPbCl3 epitaxial heterostructures. The phase selectivity is guaranteed by the continuity of the cationic subnetwork across the interface, a condition not met in a hypothetical Pb3S2Cl2/CsPbCl3 heterostructure. The perovskite domain is then etched, delivering phase-pure Pb4S3Cl2 nanocrystals that could not be synthesized directly.

Antimony-based 0-dimensional metal halides (0D-MHs) are attracting attention owing to their bright Stokes-shifted luminescence due to self-trapped excitons (STEs). One unexplored motif to expand their functionalities is to dope them with optically and/or magnetically active dopants that participate in energy-transfer schemes involving STEs. We investigated the photophysical and magnetic properties of Rb7Sb3Cl16nanocrystals doped with Mn2+ions, which introduce strong magnetism and activate their characteristic intra-d luminescence. By controlling the doping level, we optimize the STE → Mn2+energy transfer and tune the magnetic character of the NCs. Particles lightly doped with isolated Mn2+centers exhibit paramagnetic character and temperature-independent luminescence. By contrast, highly doped NCs show a clear transition to antiferromagnetic behavior at cryogenic temperatures similar to the behavior of low-dimensional manganese halides, accompanied by enhanced Mn emission due to suppressed exciton migration among the dopant subnetwork, thus pointing to an intimate link between the optical and magnetic properties also in Sb-based 0D-MHs.

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.

Luminescent solar concentrators (LSCs) are all-photonic, semitransparent solar devices with great potential in the emerging fields of building-integrated photovoltaics and agrivoltaics. Over the past decade, particularly with the advent of quantum dot (QD) LSCs, tremendous progress has been made in terms of photovoltaic efficiency and device size by increasing solar spectral coverage and suppressing reabsorption losses. Despite these advances in LSC design, the effects of environmental conditions such as rain, dust, and dirt deposits, which are ubiquitous in both urban and agricultural environments, on LSC performance have been largely overlooked. Here, we address these issues by systematically investigating the environmental effects on the solar harvesting and waveguiding capability of state-of-the-art QD-LSCs, namely, the presence of airborne pollutants (dust), water droplets, and dried deposits. Our results show that dust is unexpectedly insignificant for the waveguiding of the concentrated luminescence and only reduces the LSC efficiency through a shadowing effect when deposited on the outer surface, while dust accumulation on the inner LSC side increases the output power due to backscattering of transmitted sunlight. Water droplets, on the other hand, do not dim the incident sunlight, but are detrimental to waveguiding by forming an optical interface with the LSC. Finally, dried deposits, which mimic the evaporation residues of heavy rain or humidity, have the worst effect of all, combining shading and waveguide losses. These results are relevant for the design of application-specific surface functionalization/protection strategies real LSC modules.

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.

The search for efficient, re-absorption-free scintillators has recently focused the attention on antimony-based halides, which exhibit largely Stokes shifted luminescence due to radiative recombination of excitons self-trapped (STE) in strongly Jahn–Teller distorted Sb3+ color centers. Here, the synthesis of a hybrid structure is reported with chemical formula (C13H14N3)3SbCl6 consisting of spatially isolated [SbCl6]3− octahedra separated by organic N,N'-diphenylguanidinium (Gua) molecules. The optical properties of this material are mainly determined by the inorganic component and are characterized by a pronounced Stokes shift of ≈1.3 eV and a room-temperature photoluminescence (PL) efficiency of up to 85%. Remarkably, highly efficient radioluminescence (RL) is observed with scintillation light yields of ≈2000 ph MeV−1 using both soft X-rays and a 124 keV gamma source. Temperature-dependent PL and RL measurements confirm the minor role of non-radiative channels, which are completely suppressed below 100 K. Thermally stimulated luminescence measurements suggest that the traps in Gua3SbCl6 crystals have a significantly large energy depth distribution below the absorbing state.

Multicomponent systems consisting of lead halide perovskite nanocrystals (CsPbX3-NCs, X = Br, I) grown inside mesoporous silica nanospheres (NSs) with selectively sealed pores combine intense scintillation and strong interaction with ionizing radiation of CsPbX3 NCs with the chemical robustness in aqueous environment of silica particles, offering potentially promising candidates for enhanced radiotherapy and radio-imaging strategies. We demonstrate that CsPbX3 NCs boost the generation of singlet oxygen species (1O2) in water under X-ray irradiation and that the encapsulation into sealed SiO2 NSs guarantees perfect preservation of the inner NCs after prolonged storage in harsh conditions. We find that the 1O2 production is triggered by the electromagnetic shower released by the CsPbX3 NCs with a striking correlation with the halide composition (I3 > I3-xBrx > Br3). This opens the possibility of designing multifunctional radio-sensitizers able to reduce the local delivered dose and the undesired collateral effects in the surrounding healthy tissues by improving a localized cytotoxic effect of therapeutic treatments and concomitantly enabling optical diagnostics by radio imaging.

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.

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.

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.

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.

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 s

We employed oleylphosphonic acid (OLPA) for the synthesis of CsPbBr3 nanocrystals (NCs). Compared to phosphonic acids with linear alkyl chains, OLPA features a higher solubility in apolar solvents, allowing us to work at lower synthesis temperatures (100 °C), which in turn offer a good control over the NCs size. This can be reduced down to 5.0 nm, giving access to the strong quantum confinement regime. OLPA-based NCs form stable colloidal solutions at very low concentrations (∼1 nM), even when exposed to air. Such stability stems from the high solubility of OLPA in apolar solvents, which enables these molecules to reversibly bind/unbind to/from the NCs, preventing the NCs aggregation/precipitation. Small NCs feature efficient, blue-shifted emission and an ultraslow emission kinetics at cryogenic temperature, in striking difference to the fast decay of larger particles, suggesting that size-related exciton structure and/or trapping-detrapping dynamics determine the thermal equilibrium between coexisting radiative processes.

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.

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.

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.

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.

The realization of perovskite nanostructures featuring high emission efficiency and a wide Stokes shift is proving difficult, limiting their impact on luminescent solar concentration technology. Now, engineered exciton routing within multilayered perovskite nanoplatelets may open a path towards high-performing, low-loss devices.

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.

Lead halide perovskites, owing to their flexible, scalable chemistry and promising physical properties are attracting increasing attention for solution-processed optoelectronic and photonic technologies. Despite their well-known 'defect tolerant' electronic structure, studies highlighted the active role of shallow and deep defect states, as well as of oxidative environmental conditions, on the optical and electrical behavior of perovskite nanocubes, films and single bulk crystals. To date, however, no in-depth systematic study of the surface trap-mediated processes in perovskite materials of different dimensionality has been conducted. In this work, we aim to bridge this gap by using O 2 as a molecular probe for the effects of surface states on the exciton recombination processes of nanocubes (NCs), nanowires (NWs), nanosheets (NSs) and bulk single crystals (SCs) of CsPbBr 3 perovskite. Continuous wave and time-resolved photoluminescence (PL) experiments in a controlled O 2 atmosphere reveal the opposite optical response of NCs with respect to higher dimensional perovskites directly deriving from the different nature of the material surfaces. Specifically, O 2 passivates surface hole-traps in NWs, NSs and SCs, leading to PL brightening with unaltered recombination dynamics. Conversely, NCs appear to be free from such surface hole-traps and exposure to O 2 leads to direct extraction of photogenerated electrons that competes with radiative exciton recombination, leading to dimmed PL efficiency in atmospheric conditions. This opposite oxygen PL response demystifies the critical role of surface passivation in perovskite NCs in stark contrast to higher dimensional nanostructures and single crystals.

"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 n

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 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.

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.