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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.

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.

One major concern toward the performance and stability of halide perovskite-based optoelectronic devices is the formation of metallic lead that promotes nonradiative recombination of charge carriers. The origin of metallic lead formation is being disputed whether it occurs during the perovskite synthesis or only after light, electron, or X-ray beam irradiation or thermal annealing. Here, we show that the quantity of metallic lead detected in perovskite crystals depends on the concentration and composition of the precursor solution. Through a controlled crystallization process, we grew black-colored mixed dimethylammonium (DMA)/methylammonium (MA) lead tribromide crystals. The black color is suggested to be due to the presence of small lead clusters. Despite the unexpected black coloring, the crystals show higher crystallinity and less defect density with respect to the standard yellow-colored DMA/MAPbBr3 crystals, as indicated by X-ray rocking curve and dark current measurements, respectively. While the formation of metallic lead could still be induced by external factors, the precursor solution composition and concentration can facilitate the formation of metallic lead during the crystallization process. Our results indicate that additional research is required to fully understand the perovskite precursor solution chemistry.

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.

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.

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.

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.

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.

Lead halide perovskite nanocrystals have drawn attention as active light-absorbing or -emitting materials for opto-electronic applications due to their facile synthesis, intrinsic defect tolerance, and color-pure emission ranging over the entire visible spectrum. To optimize their application in, e.g., solar cells and light-emitting diodes, it is desirable to gain control over electronic doping of these materials. However, predominantly due to the intrinsic instability of perovskites, successful electronic doping has remained elusive. Using spectro-electrochemistry and electrochemical transistor measurements, we demonstrate here that CsPbBr3 nanocrystals can be successfully and reversibly p-doped via electrochemical hole injection. From an applied potential of ∼0.9 V vs NHE, the emission quenches, the band edge absorbance bleaches, and the electronic conductivity quickly increases, demonstrating the successful injection of holes into the valence band of the CsPbBr3 nanocrystals., ChemE/Opto-electronic Materials

Both mild and severe epilepsies are influenced by variants in the same genes, yet an explanation for the resulting phenotypic variation is unknown. As part of the ongoing Epi25 Collaboration, we performed a whole-exome sequencing analysis of 13,487 epilepsy-affected individuals and 15,678 control individuals. While prior Epi25 studies focused on gene-based collapsing analyses, we asked how the pattern of variation within genes differs by epilepsy type. Specifically, we compared the genetic architectures of severe developmental and epileptic encephalopathies (DEEs) and two generally less severe epilepsies, genetic generalized epilepsy and non-acquired focal epilepsy (NAFE). Our gene-based rare variant collapsing analysis used geographic ancestry-based clustering that included broader ancestries than previously possible and revealed novel associations. Using the missense intolerance ratio (MTR), we found that variants in DEE-affected individuals are in significantly more intolerant genic sub-regions than those in NAFE-affected individuals. Only previously reported pathogenic variants absent in available genomic datasets showed a significant burden in epilepsy-affected individuals compared with control individuals, and the ultra-rare pathogenic variants associated with DEE were located in more intolerant genic sub-regions than variants associated with non-DEE epilepsies. MTR filtering improved the yield of ultra-rare pathogenic variants in affected individuals compared with control individuals. Finally, analysis of variants in genes without a disease association revealed a significant burden of loss-of-function variants in the genes most intolerant to such variation, indicating additional epilepsy-risk genes yet to be discovered. Taken together, our study suggests that genic and sub-genic intolerance are critical characteristics for interpreting the effects of variation in genes that influence epilepsy.

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.

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.

Ternary I-III-VI2 nanocrystals (NCs), such as AgInS2 and CuInS2, 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 CuInS2 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 AgInS2 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 AgInS2 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 CuInS2 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 show here the first colloidal synthesis of double perovskite Cs2AgInCl6 nanocrystals (NCs) with a control over their size distribution. In our approach, metal carboxylate precursors and ligands (oleylamine and oleic acid) are dissolved in diphenyl ether and reacted at 105 °C with benzoyl chloride. The resulting Cs2AgInCl6 NCs exhibit the expected double perovskite crystal structure, are stable under air, and show a broad spectrum white photoluminescence (PL) with quantum yield of ∼1.6 ± 1%. The optical properties of these NCs were improved by synthesizing Mn-doped Cs2AgInCl6 NCs through the simple addition of Mn-acetate to the reaction mixture. The NC products were characterized by the same double perovskite crystal structure, and Mn doping levels up to 1.5%, as confirmed by elemental analyses. The effective incorporation of Mn ions inside Cs2AgInCl6 NCs was also proved by means of electron spin resonance spectroscopy. A bright orange emission characterized our Mn-doped Cs2AgInCl6 NCs with a PL quantum yield as high as ∼16 ± 4%.