Perovskite-Like Liquid-Crystalline Materials Based on Polyfluorinated Imidazolium Cations.

Hybrid Organic-Inorganic Halide Perovskites (HOIHPs) represent an emerging class of semiconducting materials, widely employed in a variety of optoelectronic applications. Despite their skyrocket growth in the last decade, a detailed understanding on their structure-property relationships is still missing. In this communication, we report two unprecedented perovskite-like materials based on polyfluorinated imidazolium cations. The two materials show thermotropic liquid crystalline behavior resulting in the emergence of stable mesophases. The manifold intermolecular F ⋅ ⋅ ⋅ F interactions are shown to be meaningful for the stabilization of both the solid- and liquid-crystalline orders of these perovskite-like materials. Moreover, the structure of the incorporated imidazolium cation was found to tune the properties of the liquid crystalline phase. Collectively, these results may pave the way for the design of a new class of halide perovskite-based soft materials.

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

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

Facet-Defect Tolerant Bi-Doped Cs2AgxNa1-xInCl6 Nanoplatelets with a Near-Unity Photoluminescence Quantum Yield.

We report the colloidal synthesis of Bi-doped Cs2AgxNa1-xInCl6 double perovskite nanoplatelets (NPLs) exhibiting a near-unity photoluminescence quantum yield (PLQY), a record emission efficiency for nanoscale lead-free metal halides. A combination of optical spectroscopies revealed that nonradiative decay processes in the NPL were suppressed, indicating a well-passivated surface. By comparison, nanocubes with the same composition and surface ligands as the NPLs had a PLQY of only 40%. According to our calculations, the type of trap states arising from the presence of surface defects depends on their specific location: defects located on the facets of nanocubes generate only shallow traps, while those at the edges result in deep traps. In NPLs, due to their extended basal facets, most of the surface defects are facet defects. This so-called facet-defect tolerant behavior of double perovskites explains the more efficient optical emission of NPLs compared to that of nanocubes.

Ultrafast and Radiation-Hard Lead Halide Perovskite Nanocomposite Scintillators.

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

Environmental Effects on the Performance of Quantum Dot Luminescent Solar Concentrators.

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.

Fluorine Passivation Inhibits "Particle Talking" Behaviors under Thermal and Electrical Conditions of Pure Blue Mixed Halide Perovskite Nanocrystals.

Owing to outstanding optoelectronic properties, lead halide perovskite nanocrystals (PNCs) are considered promising emitters for next-generation displays. However, the development of pure blue (460-470 nm) perovskite nanocrystal light-emitting diodes (PNC-LEDs), which correspond to the requirements of Rec. 2020 standard, lag far behind that of their green and red counterparts. Here, pure blue CsPb(Br/Cl)3 nanocrystals with remarkable optical performance are demonstrated by a facile fluorine passivation strategy. Prominently, the fluorine passivation on halide vacancies and strong bonding of Pb-F intensely enhance crystal structure stability and inhibit "particle talking" behaviors under both thermal and electrical conditions. Fluorine-based PNCs with high resistance of luminescence thermal quenching retain 70% of photoluminescent intensity when heated to 343 K, which can be attributed to the elevated activation energy for carrier trapping and unchanged grain size. Fluorine-based PNC-LEDs also exhibit stable pure blue electroluminescence (EL) emission with sevenfold promoted luminance and external quantum efficiencies (EQEs), where the suppression of ion migration is further evidenced by a lateral structure device with applied polarizing potential.

Stable Sn-Based Hybrid Perovskite-Related Structures with Tunable Color Coordinates via Organic Cations in Low-Temperature Synthesis.

Organic-inorganic Pb-free layered perovskites are efficient broadband emitters and thus are promising materials for lighting applications. However, their synthetic protocols require a controlled atmosphere, high temperature, and long preparation time. This hinders the potential tunability of their emission through organic cations, as is instead common practice in Pb-based structures. Here, we present a set of Sn-Br layered perovskite-related structures that display different chromaticity coordinates and photoluminescence quantum yield (PLQY) up to 80%, depending on the choice of the organic monocation. We first develop a synthetic protocol that is performed under air and at 4 °C, requiring only a few steps. X-ray and 3D electron diffraction analyses show that the structures exhibit diverse octahedra connectivity (disconnected and face-sharing) and thus optical properties, while preserving the organic-inorganic layer intercalation. These results provide key insight into a previously underexplored strategy to tune the color coordinates of Pb-free layered perovskites through organic cations with complex molecular configurations.

Multigram-Scale Synthesis of Luminescent Cesium Lead Halide Perovskite Nanobricks for Plastic Scintillators.

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.

Silica-Encapsulated Perovskite Nanocrystals for X-ray-Activated Singlet Oxygen Production and Radiotherapy Application.

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-x Br x > 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.

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

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

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

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

Halide perovskites as disposable epitaxial templates for the phase-selective synthesis of lead sulfochloride nanocrystals.

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.

Cesium Manganese Bromide Nanocrystal Sensitizers for Broadband Vis-to-NIR Downshifting.

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.

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

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

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

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

Hybrid MoS2/PEDOT:PSS transporting layers for interface engineering of nanoplatelet-based light-emitting diodes.

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.

Halide Perovskite-Lead Chalcohalide Nanocrystal Heterostructures.

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 preformed subnanometer 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, promoting ultrafast separation of photogenerated excitons and carrier trapping, as confirmed by spectroscopic experiments. Postsynthesis 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 γ phase (or "black" phase) of CsPbI3 in the CsPbI3-Pb4S3Br2 heterostructure.

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

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

Stable and Size Tunable CsPbBr3 Nanocrystals Synthesized with Oleylphosphonic Acid.

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.

Luminescent Colloidal InSb Quantum Dots from In Situ Generated Single-Source Precursor.

Despite recent advances, the synthesis of colloidal InSb quantum dots (QDs) remains underdeveloped, mostly due to the lack of suitable precursors. In this work, we use Lewis acid-base interactions between Sb(III) and In(III) species formed at room temperature in situ from commercially available compounds (viz., InCl3, Sb[NMe2]3 and a primary alkylamine) to obtain InSb adduct complexes. These complexes are successfully used as precursors for the synthesis of colloidal InSb QDs ranging from 2.8 to 18.2 nm in diameter by fast coreduction at sufficiently high temperatures (≥230 °C). Our findings allow us to propose a formation mechanism for the QDs synthesized in our work, which is based on a nonclassical nucleation event, followed by aggregative growth. This yields ensembles with multimodal size distributions, which can be fractionated in subensembles with relatively narrow polydispersity by postsynthetic size fractionation. InSb QDs with diameters below 7.0 nm have the zinc blende crystal structure, while ensembles of larger QDs (≥10 nm) consist of a mixture of wurtzite and zinc blende QDs. The QDs exhibit photoluminescence with small Stokes shifts and short radiative lifetimes, implying that the emission is due to band-edge recombination and that the direct nature of the bandgap of bulk InSb is preserved in InSb QDs. Finally, we constructed a sizing curve correlating the peak position of the lowest energy absorption transition with the QD diameters, which shows that the band gap of colloidal InSb QDs increases with size reduction following a 1/d dependence.