Sensitized Triplet-Triplet Annihilation in Nanostructured Polymeric Scintillators Allows for Pulse Shape Discrimination.

Scintillating materials emit light when exposed to ionizing radiation or particles and are used for the detection of nuclear threats, medical imaging, high-energy physics, and other usages. For some of these applications, it is vital to distinguish neutrons and charged particles from γ-rays. This is achievable by pulse shape discrimination (PSD), a time-gated technique, which exploits that the scintillation kinetics can depend on the nature of the incident radiation. However, it proves difficult to realize efficient PSD with plastic scintillators, which have several advantages over liquid or crystalline scintillating materials, including mechanical robustness and shapeability. It is shown here that sensitive and rapid PSD is possible with nanostructured polymer scintillators that consist of a solid polymer matrix and liquid nanodomains in which an organic dye capable of triplet-triplet annihilation (TTA) is dissolved. The liquid nature of the nanodomains renders TTA highly efficient so that delayed fluorescence can occur at low energy density. The nanostructured polymer scintillators allow discriminating α particles, neutrons, and γ-rays with a time response that is better than that of commercial scintillators. Exploiting that the liquid nanodomains can facilitate energy transfer processes otherwise difficult to realize in solid polymers, an auxiliary triplet sensitizer is incorporated. This approach further increases the scintillator's sensitivity toward α particles and neutrons and other high-energy processes where localized interactions are involved.

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.

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.

Bypassing the statistical limit of singlet generation in sensitized upconversion using fluorinated conjugated systems.

The photon upconversion based on triplet-triplet annihilation (TTA) is a mechanism that converts the absorbed low-energy electromagnetic radiation into higher energy photons also at extremely low excitation intensities, but its use in actual technologies is still hindered by the limited availability of efficient annihilator moieties. We present here the results obtained by the synthesis and application of two new fluorinated chromophores based on phenazine and acridine structures, respectively. Both compounds show upconverted emission demonstrating their ability as TTA annihilator. More interesting, the acridine-based chromophore shows an excellent TTA yield that overcomes the one of some of best model systems. By correlating the experimental data and the quantum mechanical modeling of the investigated compound, we propose an alternative efficient pathway for the generation of the upconverted emissive states involving the peculiar high-energy triplet levels of the dye, thus suggesting a new development strategy for TTA annihilators based on the fine tuning of their high-energy excited states properties.

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

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

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

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

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

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

Photon upconversion in multicomponent systems: Role of back energy transfer.

Photon upconversion based on sensitized triplet-triplet annihilation in bi-component systems is a multistep process that involves a triplet-triplet energy transfer (ET) from a donor to an acceptor moiety. This is aimed at sensitizing the population of annihilating optically dark triplets that generates the high energy photoluminescence. A large resonance between the involved triplets is usually recommended because it increases the energy gain between absorbed and emitted upconverted photons. However, it also enables efficient back-ET from acceptor to donor triplets, with potential detrimental consequences on the system performance. Here, we analyze a model system, where the energy difference between donor and acceptor triplets is lower than kBT at room temperature by means of time resolved and steady state photoluminescence spectroscopy, and develop a kinetic model, which describes the iterative loop that transfers the triplet exciton between the donor and acceptor molecules. In such a way, we obtained the guidelines for the optimization of the system composition required to overcome the back-ET effect and maximize the upconversion quantum yield.

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

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

Dual-Emitting Dot-in-Bulk CdSe/CdS Nanocrystals with Highly Emissive Core- and Shell-Based Trions Sharing the Same Resident Electron.

Colloidal CdSe nanocrystals (NCs) overcoated with an ultrathick CdS shell, also known as dot-in-bulk (DiB) structures, can support two types of excitons, one of which is core-localized and the other, shell-localized. In the case of weak "sub-single-exciton" pumping, emission alternates between the core- and shell-related channels, which leads to two-color light. This property makes these structures uniquely suited for a variety of photonic applications as well as ideal model systems for realizing complex excitonic quasi-particles that do not occur in conventional core/shell NCs. Here, we show that the DiB design can enable an unusual regime in which the same long-lived resident electron can endow trionlike characteristics to either of the two excitons of the DiB NC (core- or shell-based). These two spectrally distinct trion states are apparent in the measured photoluminescence (PL) and spin dynamics of core and shell excitons conducted over a wide range of temperatures and applied magnetic fields. Low-temperature PL measurements indicate that core- and shell-based trions are characterized by a nearly ideal (∼100%) emission quantum yield, suggesting the strong suppression of Auger recombination for both types of excitations. Polarization-resolved PL experiments in magnetic fields of up to 60 T reveal that the core- and the shell-localized trions exhibit remarkably similar spin dynamics, which in both cases are controlled by spin-flip processes involving a heavy hole.

Engineering Porous Emitting Framework Nanoparticles with Integrated Sensitizers for Low-Power Photon Upconversion by Triplet Fusion.

The conversion of low-energy light into photons of higher energy based on sensitized triplet-triplet annihilation (sTTA) upconversion is emerging as the most promising wavelength-shifting methodology because it operates efficiently at excitation powers as low as the solar irradiance. However, the production of solid-state upconverters suited for direct integration in devices is still an ongoing challenge owing to the difficulties concerning the organization of two complementary moieties, the triplet sensitizer, and the annihilator, which must interact efficiently. This problem is solved by fabricating porous fluorescent nanoparticles wherein the emitters are integrated into robust covalent architectures. These emitting porous aromatic framework (ePAF) nanoparticles allow intimate interaction with the included metallo-porphyrin as triplet sensitizers. Remarkably, the high concentration of framed chromophores ensures hopping-mediated triplet diffusion required for TTA, yet the low density of the framework promotes their high optical features without quenching effects, typical of the solid state. A green-to-blue photon upconversion yield as high as 15% is achieved: a record performance among annihilators in a condensed phase. Furthermore, the engineered ePAF architecture containing covalently linked sensitizers produces full-fledge solid-state bicomponent particles that behave as autonomous nanodevices.

Triplet-triplet annihilation based photon up-conversion in hybrid molecule-semiconductor nanocrystal systems.

Photon up-conversion based on triplet-triplet annihilation (TTA) exploits the annihilation of optically dark triplets of an organic emitter to produce high-energy singlets that generate high energy emission. In recently proposed hybrid systems, the annihilating triplets are indirectly sensitized by light-harvesting semiconductor colloidal nanocrystals via energy transfer from their capping ligands (h-sTTA). Here, we discuss quantitatively the performance of the h-sTTA up-conversion mechanism in a reference nanocrystal/organic emitter pair, by introducing a kinetic model that points out the relationship between the up-conversion yield and the excitation intensity. This model highlights the fundamental properties of the employed moieties that mostly affect the conversion efficiency. We derive a new expression for the excitation threshold specific for h-sTTA up-conversion, which allows us to estimate a priori the material performances from a few key parameters and to point out the most severe bottlenecks. The obtained results demonstrate that the up-conversion yield is mainly limited by ultrafast non-radiative recombinations of the optical excitons created on nanocrystals, which are competitive to the sensitization channel for emitter triplets in solution. Our results suggest that the quenching partially arises from charge transfer interactions between nanocrystals and surface ligands. Improved ligand design and optimized surface functionalization strategies are required to avoid energy losses and enhance the up-conversion performance, thus promoting the application of h-sTTA up-conversion materials in solar technologies.

O2 as a molecular probe for nonradiative surface defects in CsPbBr3 perovskite nanostructures and single crystals.

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 O2 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 CsPbBr3 perovskite. Continuous wave and time-resolved photoluminescence (PL) experiments in a controlled O2 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, O2 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 O2 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.

Quantized Electronic Doping towards Atomically Controlled "Charge-Engineered" Semiconductor Nanocrystals.

"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 Au2+ (5d9 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.

Towards hydrophobic carminic acid derivatives and their incorporation in polyacrylates.

Carminic acid, a natural hydrophilic dye extensively used in the food and cosmetic industries, is converted in hydrophobic dyes by acetylation or pivaloylation. These derivatives are successfully used as biocolourants for rubber objects. In this paper, spectroscopic properties of the carminic acid derivatives in dimethyl sulfoxide and in polybutylacrylate are studied by means of photoluminescence and time-resolved photoluminescence decays, revealing a hypsochromic effect due to the presence of bulky substituents as the acetyl or pivaloyl groups. Molecular mechanics and density functional theory calculations confirm the disruption of planarity between the sugar ring and the anthraquinoid system determined by the esterification.

Efficient Solution-Processed Nanoplatelet-Based Light-Emitting Diodes with High Operational Stability in Air.

Colloidal nanoplatelets (NPLs), owing to their efficient and narrow-band luminescence, are considered as promising candidates for solution-processable light-emitting diodes (LEDs) with ultrahigh color purity. To date, however, the record efficiencies of NPL-LEDs are significantly lower than those of more-investigated devices based on spherical nanocrystals. This is particularly true for red-emitting NPL-LEDs, the best-reported external quantum efficiency (EQE) of which is limited to 0.63% (EQE = 5% for green NPL-LEDs). Here, we address this issue by introducing a charge-regulating layer of a polar and polyelectrolytic polymer specifically engineered with complementary trimethylammonium and phosphonate functionalities that provide high solubility in orthogonal polar media with respect to the NPL active layer, compatibility with the metal cathode, and the ability to control electron injection through the formation of a polarized interface under bias. Through this synergic approach, we achieve EQE = 5.73% at 658 nm (color saturation 98%) in completely solution processed LEDs. Remarkably, exposure to air increases the EQE to 8.39%, exceeding the best reports of red NPL-LEDs by over 1 order of magnitude and setting a new global record for quantum-dot LEDs of any color embedding solution-deposited organic interlayers. Considering the emission quantum yield of the NPLs (40 ± 5%), this value corresponds to a near-unity internal quantum efficiency. Notably, our devices show exceptional operational stability for over 5 h of continuous drive in air with no encapsulation, thus confirming the potential of NPLs for efficient, high-stability, saturated LEDs.

Bottom-up Synthesis and Self-Assembly of Copper Clusters into Permanent Excimer Supramolecular Nanostructures.

Metal clusters with appropriate molecular ligands have been shown to be suitable subnanometer building blocks for supramolecular architectures with controlled secondary interactions, providing access to physical regimes not achievable with conventional intermolecular motifs. An example is the excimer photophysics exhibited by individual cluster-based superstructures produced by top-down etching of gold nanoparticles. Now, a supramolecular architecture of copper clusters is presented with controlled optical properties and efficient non-resonant luminescence produced via a novel bottom-up synthesis using mild green reductants followed by a ligand exchange reaction and spontaneous supramolecular assembly. Spectroscopic experiments confirm the formation of the intercluster network and reveal the permanent nature of their excimer-like behavior, thus extending the potential impact and applicability of metal cluster superstructures as efficient and stable non-resonant single-particle emitters.

Cascade sensitization of triplet-triplet annihilation based photon upconversion at sub-solar irradiance.

In triplet-triplet annihilation based upconversion, high-energy photons are generated through the annihilation of fluorophore triplets, populated via energy transfer from a light-harvesting sensitizer. However, the absorption band of common sensitizers is narrow, limiting the fraction of recoverable photons. We overcome this issue using a third chromophore as an additional light-harvester in the transparency window between the upconverted luminescence and the sensitizer absorption. The third component transfers the extra-collected energy to sensitizers, realizing a cascade-sensitized upconversion that shows a 20% increment of the high-energy photon output and a conversion yield of 10% at solar irradiance.

Excitonic pathway to photoinduced magnetism in colloidal nanocrystals with nonmagnetic dopants.

Electronic doping of colloidal semiconductor nanostructures holds promise for future device concepts in optoelectronic and spin-based technologies. Ag+ is an emerging electronic dopant in III-V and II-VI nanostructures, introducing intragap electronic states optically coupled to the host conduction band. With its full 4d shell Ag+ is nonmagnetic, and the dopant-related luminescence is ascribed to decay of the conduction-band electron following transfer of the photoexcited hole to Ag+. This optical activation process and the associated modification of the electronic configuration of Ag+ remain unclear. Here, we trace a comprehensive picture of the excitonic process in Ag-doped CdSe nanocrystals and demonstrate that, in contrast to expectations, capture of the photohole leads to conversion of Ag+ to paramagnetic Ag2+. The process of exciton recombination is thus inextricably tied to photoinduced magnetism. Accordingly, we observe strong optically activated magnetism and diluted magnetic semiconductor behaviour, demonstrating that optically switchable magnetic nanomaterials can be obtained by exploiting excitonic processes involving nonmagnetic impurities.