Trial of Cinpanemab in Early Parkinson's Disease.

BACKGROUND: Aggregated α-synuclein plays an important role in Parkinson's disease pathogenesis. Cinpanemab, a human-derived monoclonal antibody that binds to α-synuclein, is being evaluated as a disease-modifying treatment for Parkinson's disease. METHODS: In a 52-week, multicenter, double-blind, phase 2 trial, we randomly assigned, in a 2:1:2:2 ratio, participants with early Parkinson's disease to receive intravenous infusions of placebo (control) or cinpanemab at a dose of 250 mg, 1250 mg, or 3500 mg every 4 weeks, followed by an active-treatment dose-blinded extension period for up to 112 weeks. The primary end points were the changes from baseline in the Movement Disorder Society-sponsored revision of the Unified Parkinson's Disease Rating Scale (MDS-UPDRS) total score (range, 0 to 236, with higher scores indicating worse performance) at weeks 52 and 72. Secondary end points included MDS-UPDRS subscale scores and striatal binding as assessed on dopamine transporter single-photon-emission computed tomography (DaT-SPECT). RESULTS: Of the 357 enrolled participants, 100 were assigned to the control group, 55 to the 250-mg cinpanemab group, 102 to the 1250-mg group, and 100 to the 3500-mg group. The trial was stopped after the week 72 interim analysis owing to lack of efficacy. The change to week 52 in the MDS-UPDRS score was 10.8 points in the control group, 10.5 points in the 250-mg group, 11.3 points in the 1250-mg group, and 10.9 points in the 3500-mg group (adjusted mean difference vs. control, -0.3 points [95% confidence interval {CI}, -4.9 to 4.3], P = 0.90; 0.5 points [95% CI, -3.3 to 4.3], P = 0.80; and 0.1 point [95% CI, -3.8 to 4.0], P = 0.97, respectively). The adjusted mean difference at 72 weeks between participants who received cinpanemab through 72 weeks and the pooled group of those who started cinpanemab at 52 weeks was -0.9 points (95% CI, -5.6 to 3.8) for the 250-mg dose, 0.6 points (95% CI, -3.3 to 4.4) for the 1250-mg dose, and -0.8 points (95% CI, -4.6 to 3.0) for the 3500-mg dose. Results for secondary end points were similar to those for the primary end points. DaT-SPECT imaging at week 52 showed no differences between the control group and any cinpanemab group. The most common adverse events with cinpanemab were headache, nasopharyngitis, and falls. CONCLUSIONS: In participants with early Parkinson's disease, the effects of cinpanemab on clinical measures of disease progression and changes in DaT-SPECT imaging did not differ from those of placebo over a 52-week period. (Funded by Biogen; SPARK ClinicalTrials.gov number, NCT03318523.).

Ligand-Directed Self-Assembly of Organic-Semiconductor/Quantum-Dot Blend Films Enables Efficient Triplet Exciton-Photon Conversion.

Blends comprising organic semiconductors and inorganic quantum dots (QDs) are relevant for many optoelectronic applications and devices. However, the individual components in organic-QD blends have a strong tendency to aggregate and phase-separate during film processing, compromising both their structural and electronic properties. Here, we demonstrate a QD surface engineering approach using electronically active, highly soluble semiconductor ligands that are matched to the organic semiconductor host material to achieve well-dispersed inorganic-organic blend films, as characterized by X-ray and neutron scattering, and electron microscopies. This approach preserves the electronic properties of the organic and QD phases and also creates an optimized interface between them. We exemplify this in two emerging applications, singlet-fission-based photon multiplication (SF-PM) and triplet-triplet annihilation-based photon upconversion (TTA-UC). Steady-state and time-resolved optical spectroscopy shows that triplet excitons can be transferred with near unity efficiently across the organic-inorganic interface, while the organic films maintain efficient SF (190% yield) in the organic phase. By changing the relative energy between organic and inorganic components, yellow upconverted emission is observed upon 790 nm NIR excitation. Overall, we provide a highly versatile approach to overcome longstanding challenges in the blending of organic semiconductors with QDs that have relevance for many optical and optoelectronic applications.

Ultrafast exciton transport at early times in quantum dot solids.

Quantum dot (QD) solids are an emerging platform for developing a range of optoelectronic devices. Thus, understanding exciton dynamics is essential towards developing and optimizing QD devices. Here, using transient absorption microscopy, we reveal the initial exciton dynamics in QDs with femtosecond timescales. We observe high exciton diffusivity (~102 cm2 s-1) in lead chalcogenide QDs within the first few hundred femtoseconds after photoexcitation followed by a transition to a slower regime (~10-1-1 cm2 s-1). QD solids with larger interdot distances exhibit higher initial diffusivity and a delayed transition to the slower regime, while higher QD packing density and heterogeneity accelerate this transition. The fast transport regime occurs only in materials with exciton Bohr radii much larger than the QD sizes, suggesting the transport of delocalized excitons in this regime and a transition to slower transport governed by exciton localization. These findings suggest routes to control the optoelectronic properties of QD solids.

Efficient Energy Funneling in Spatially Tailored Segmented Conjugated Block Copolymer Nanofiber-Quantum Dot or Rod Conjugates.

Hybrid systems composed of conjugated polymers and inorganic semiconductor nanocrystals such as quantum dots (QDs) and nanorods (QRs) represent highly desirable multifunctional materials for applications from energy harvesting to light emission and sensing. Herein, we describe energy transfer studies between low-dispersity segmented conjugated polymer micellar nanofibers integrated with quantum dots that are spatially confined to discrete regions in the hybrid assembly via noncovalent interactions. The nanofibers were prepared from diblock copolymers with a crystallizable poly(di-n-hexylfluorene) (PDHF) core-forming block and different corona-forming blocks using the seeded-growth "living" crystallization-driven self-assembly method. The highly ordered crystalline PDHF core in the fibers functions as a donor and permits long-range exciton transport (>200 nm). Energy can therefore be funneled through the fiber core to QDs and QRs that function as acceptor materials and which are noncovalently bound to spatially defined coronal regions of poly(2-vinylpyridine) (P2VP) or quaternized polyfluorene (QPF). Using steady-state and time-resolved spectroscopy, we demonstrate that efficient energy transfer (over 70%) occurs from the crystalline PDHF donor core to the acceptor CdSe QRs attached at the fiber termini. The emission of the PDHF donor in the hybrid conjugate was extensively quenched (by 84%), and a subsequent 4-fold enhancement of the QR emission in solution was observed. These results indicate that the conjugates prepared in this work show promise for potential applications in fields such as light-emitting diodes, photovoltaics, chemical sensors, and photocatalysis.

Controlling the structures of organic semiconductor-quantum dot nanocomposites through ligand shell chemistry.

Nanocrystal quantum dots (QD) functionalised with active organic ligands hold significant promise as solar energy conversion materials, capable of multiexcitonic processes that could improve the efficiencies of single-junction photovoltaic devices. Small-angle X-ray and neutron scattering (SAXS and SANS) were used to characterize the structure of lead sulphide QDs post ligand-exchange with model acene-carboxylic acid ligands (benzoic acid, hydrocinnamic acid and naphthoic acid). Results demonstrate that hydrocinnamic acid and naphthoic acid ligated QDs form monolayer ligand shells, whilst benzoic acid ligated QDs possess ligand shells thicker than a monolayer. Further, the formation of a range of nanocomposite materials through the self-assembly of such acene-ligated QDs with an organic small-molecule semiconductor [5,12-bis((triisopropylsilyl)ethynyl)tetracene (TIPS-Tc)] is investigated. These materials are representative of a wider set of functional solar energy materials; here the focus is on structural studies, and their optoelectronic function is not investigated. As TIPS-Tc concentrations are increased, approaching the solubility limit, SANS data show that QD fractal-like features form, with structures possibly consistent with a diffusion limited aggregation mechanism. These, it is likely, act as heterogeneous nucleation agents for TIPS-Tc crystallization, generating agglomerates containing both QDs and TIPS-Tc. Within the TIPS-Tc crystals there seem to be three distinct QD morphologies: (i) at the crystallite centre (fractal-like QD aggregates acting as nucleating agents), (ii) trapped within the growing crystallite (giving rise to QD features ordered as sticky hard spheres), and (iii) a population of aggregate QDs at the periphery of the crystalline interface that were expelled from the growing TIPS-Tc crystal. Exposure of the QD:TIPS-Tc crystals to DMF vapour, a solvent known to be able to strip ligands from QDs, alters the spacing between PbS-hydrocinnamic acid and PbS-naphthoic acid ligated QD aggregate features. In contrast, for PbS-benzoic acid ligated QDs, DMF vapour exposure promotes the formation of ordered QD colloidal crystal type phases. This work thus demonstrates how different QD ligand chemistries control the interactions between QDs and an organic small molecule, leading to widely differing self-assembly processes. It highlights the unique capabilities of multiscale X-ray and neutron scattering in characterising such composite materials.

All-Optical Detection of Neuronal Membrane Depolarization in Live Cells Using Colloidal Quantum Dots.

Luminescent semiconductor quantum dots (QDs) have recently been suggested as novel probes for imaging and sensing cell membrane voltages. However, a key bottleneck for their development is a lack of techniques to assess QD responses to voltages generated in the aqueous electrolytic environments typical of biological systems. Even more generally, there have been relatively few efforts to assess the response of QDs to voltage changes in live cells. Here, we develop a platform for monitoring the photoluminescence (PL) response of QDs under AC and DC voltage changes within aqueous ionic environments. We evaluate both traditional CdSe/CdS and more biologically compatible InP/ZnS QDs at a range of ion concentrations to establish their PL/voltage characteristics on chip. Wide-field, few-particle PL measurements with neuronal cells show the QDs can be used to track local voltage changes with greater sensitivity (ΔPL up to twice as large) than state-of-the-art calcium imaging dyes, making them particularly appealing for tracking subthreshold events. Additional physiological observation studies showed that while CdSe/CdS dots have greater PL responses on membrane depolarization, their lower cytotoxicity makes InP/ZnS far more suitable for voltage sensing in living systems. Our results provide a methodology for the rational development of QD voltage sensors and highlight their potential for imaging changes in cell membrane voltage.

Enhancing Photoluminescence and Mobilities in WS2 Monolayers with Oleic Acid Ligands.

Many potential applications of monolayer transition metal dichalcogenides (TMDs) require both high photoluminescence (PL) yield and high electrical mobilities. However, the PL yield of as prepared TMD monolayers is low and believed to be limited by defect sites and uncontrolled doping. This has led to a large effort to develop chemical passivation methods to improve PL and mobilities. The most successful of these treatments is based on the nonoxidizing organic "superacid" bis(trifluoromethane)sulfonimide (TFSI) which has been shown to yield bright monolayers of molybdenum disulfide (MoS2) and tungsten disulfide (WS2) but with trap-limited PL dynamics and no significant improvements in field effect mobilities. Here, using steady-state and time-resolved PL microscopy we demonstrate that treatment of WS2 monolayers with oleic acid (OA) can greatly enhance the PL yield, resulting in bright neutral exciton emission comparable to TFSI treated monolayers. At high excitation densities, the OA treatment allows for bright trion emission, which has not been demonstrated with previous chemical treatments. We show that unlike the TFSI treatment, the OA yields PL dynamics that are largely trap free. In addition, field effect transistors show an increase in mobilities with the OA treatment. These results suggest that OA serves to passivate defect sites in the WS2 monolayers in a manner akin to the passivation of colloidal quantum dots with OA ligands. Our results open up a new pathway to passivate and tune defects in monolayer TMDs using simple "wet" chemistry techniques, allowing for trap-free electronic properties and bright neutral exciton and trion emission.

Engineering Molecular Ligand Shells on Quantum Dots for Quantitative Harvesting of Triplet Excitons Generated by Singlet Fission.

Singlet fission is an exciton multiplication process in organic molecules in which a photogenerated spin-singlet exciton is rapidly and efficiently converted to two spin-triplet excitons. This process offers a mechanism to break the Shockley-Queisser limit by overcoming the thermalization losses inherent to all single-junction photovoltaics. One of the most promising methods to harness the singlet fission process is via the efficient extraction of the dark triplet excitons into quantum dots (QDs) where they can recombine radiatively, thereby converting high-energy photons to pairs of low-energy photons, which can then be captured in traditional inorganic PVs such as Si. Such a singlet fission photon multiplication (SF-PM) process could increase the efficiency of the best Si cells from 26.7% to 32.5%, breaking the Shockley-Queisser limit. However, there has been no demonstration of such a singlet fission photon multiplication (SF-PM) process in a bulk system to date. Here, we demonstrate a solution-based bulk SF-PM system based on the singlet fission material TIPS-Tc combined with PbS QDs. Using a range of steady-state and time-resolved measurements combined with analytical modeling we study the dynamics and mechanism of the triplet harvesting process. We show that the system absorbs >95% of incident photons within the singlet fission material to form singlet excitons, which then undergo efficient singlet fission in the solution phase (135 ± 5%) before quantitative harvesting of the triplet excitons (95 ± 5%) via a low concentration of QD acceptors, followed by the emission of IR photons. We find that in order to achieve efficient triplet harvesting it is critical to engineer the surface of the QD with a triplet transfer ligand and that bimolecular decay of triplets is potentially a major loss pathway which can be controlled via tuning the concentration of QD acceptors. We demonstrate that the photon multiplication efficiency is maintained up to solar fluence. Our results establish the solution-based SF-PM system as a simple and highly tunable platform to understand the dynamics of a triplet energy transfer process between organic semiconductors and QDs, one that can provide clear design rules for new materials.

Multimodal Continual Learning for Process Monitoring: A Novel Weighted Canonical Correlation Analysis With Attention Mechanism.

Aimed at sequential dynamic modes, a novel multimodal weighted canonical correlation analysis using an attention (MWCCA-A) mechanism is introduced to derive a single model for process monitoring, by integrating two ideas of replay and regularization in continual learning. Under the assumption that data are received sequentially, subsets of data from past modes with dynamic features are selected and stored as replay data, which are utilized together with the current mode data for continual model parameter estimation. The weighted canonical correlation analysis (WCCA) is introduced to achieve appropriate weightings of past modes' replay data so that the latent variables are extracted by maximizing the weighted correlation with its prediction via the attention mechanism. Specifically, replay data weightings are obtained via the probability density estimation from each mode. This is also beneficial in overcoming data imbalance among multiple modes and consolidating the significant features of past modes further. Alternatively, the proposed model also regularizes parameters based on its previous modes' importance, which is measured by synaptic intelligence (SI). Meanwhile, the objective is decoupled into a regularization-related part and a replay-related part, to overcome the potentially unstable optimization trajectory of SI-based continual learning. In comparison with several multimode monitoring methods, the effectiveness of the proposed MWCCA-A approach is demonstrated by a continuous stirred tank heater (CSTH), Tennessee Eastman process (TEP), and a practical coal pulverizing system.

Spatially Resolved Optical Efficiency Measurements of Luminescent Solar Concentrators.

Luminescent solar concentrators (LSCs) are able to concentrate both direct and diffuse solar radiation, and this ability has led to great interest in using them to improve solar energy capture when coupled to traditional photovoltaics (PV). In principle, a large-area LSC could concentrate light onto a much smaller area of PV, thus reducing costs or enabling new architectures. However, LSCs suffer from various optical losses which are hard to quantify using simple measurements of power conversion efficiency. Here, we show that spatially resolved photoluminescence quantum efficiency measurements on large-area LSCs can be used to resolve various loss processes such as out-coupling, self-absorption via emitters, and self-absorption from the LSC matrix. Further, these measurements allow for the extrapolation of device performance to arbitrarily large LSCs. Our results provide insight into the optimization of optical properties and guide the design of future LSCs for improved solar energy capture.

Insights into the kinetics and self-assembly order of small-molecule organic semiconductor/quantum dot blends during blade coating.

Organic-inorganic nanocomposite films formed from blends of small-molecule organic semiconductors and colloidal quantum dots are attractive candidates for high efficiency, low-cost solar energy harvesting devices. Understanding and controlling the self-assembly of the resulting organic-inorganic nanocomposite films is crucial in optimising device performance, not only at a lab-scale but for large-scale, high-throughput printing and coating methods. Here, in situ grazing incidence X-ray scattering (GIXS) gives direct insights into how small-molecule organic semiconductors and colloidal quantum dots self-assemble during blade coating. Results show that for two blends separated only by a small difference in the structure of the small molecule forming the organic phase, crystallisation may proceed down two distinct routes. It either occurs spontaneously or is mediated by the formation of quantum dot aggregates. Irrespective of the initial crystallisation route, the small-molecule crystallisation acts to exclude the quantum dot inclusions from the growing crystalline matrix phase. These results provide important fundamental understanding of structure formation in nanocomposite films of organic small molecules and colloidal quantum dots prepared via solution processing routes. It highlights the fundamental difference to structural evolution which can be made by seemingly small changes in system composition. It provides routes for the structural design and optimisation of solution-processed nanocomposites that are compatible with the large-scale deposition manufacturing techniques that are crucial in driving their wider adoption in energy harvesting applications.

Understanding the Photoluminescence Quenching of Liquid Exfoliated WS2 Monolayers.

Monolayer transition metal dichalcogenides (TMDs) are being investigated as active materials in optoelectronic devices due to their strong excitonic effects. While mechanical exfoliation (ME) of monolayer TMDs is limited to small areas, these materials can also be exfoliated from their parent layered materials via high-volume liquid phase exfoliation (LPE). However, it is currently considered that LPE-synthesized materials show poor optoelectronic performance compared to ME materials, such as poor photoluminescence quantum efficiencies (PLQEs). Here we evaluate the photophysical properties of monolayer-enriched LPE WS2 dispersions via steady-state and time-resolved optical spectroscopy and benchmark these materials against untreated and chemically treated ME WS2 monolayers. We show that the LPE materials show features of high-quality semiconducting materials such as very small Stokes shift, smaller photoluminescence line widths, and longer exciton lifetimes than ME WS2. We reveal that the energy transfer between the direct-gap monolayers and in-direct gap few-layers in LPE WS2 dispersions is a major reason for their quenched PL. Our results suggest that LPE TMDs are not inherently highly defective and could have a high potential for optoelectronic device applications if improved strategies to purify the LPE materials and reduce aggregation could be implemented.

Triplet transfer from PbS quantum dots to tetracene ligands: is faster always better?

Quantum dot-organic semiconductor hybrid materials are gaining increasing attention as spin mixers for applications ranging from solar harvesting to spin memories. Triplet energy transfer between the inorganic quantum dot (QD) and organic semiconductor is a key step to understand in order to develop these applications. Here we report on the triplet energy transfer from PbS QDs to four energetically and structurally similar tetracene ligands. Even with similar ligands we find that the triplet energy transfer dynamics can vary significantly. For TIPS-tetracene derivatives with carboxylic acid, acetic acid and methanethiol anchoring groups on the short pro-cata side we find that triplet transfer occurs through a stepwise process, mediated via a surface state, whereas for monosubstituted TIPS-tetracene derivative 5-(4-benzoic acid)-12-triisopropylsilylethynyl tetracene (BAT) triplet transfer occurs directly, albeit slower, via a Dexter exchange mechanism. Even though triplet transfer is slower with BAT the overall yield is greater, as determined from upconverted emission using rubrene emitters. This work highlights that the surface-mediated transfer mechanism is plagued with parasitic loss pathways and that materials with direct Dexter-like triplet transfer are preferred for high-efficiency applications.

Strong absorption and ultrafast localisation in NaBiS2 nanocrystals with slow charge-carrier recombination.

I-V-VI2 ternary chalcogenides are gaining attention as earth-abundant, nontoxic, and air-stable absorbers for photovoltaic applications. However, the semiconductors explored thus far have slowly-rising absorption onsets, and their charge-carrier transport is not well understood yet. Herein, we investigate cation-disordered NaBiS2 nanocrystals, which have a steep absorption onset, with absorption coefficients reaching >105 cm-1 just above its pseudo-direct bandgap of 1.4 eV. Surprisingly, we also observe an ultrafast (picosecond-time scale) photoconductivity decay and long-lived charge-carrier population persisting for over one microsecond in NaBiS2 nanocrystals. These unusual features arise because of the localised, non-bonding S p character of the upper valence band, which leads to a high density of electronic states at the band edges, ultrafast localisation of spatially-separated electrons and holes, as well as the slow decay of trapped holes. This work reveals the critical role of cation disorder in these systems on both absorption characteristics and charge-carrier kinetics.

Mechanistic insight into the chemical treatments of monolayer transition metal disulfides for photoluminescence enhancement.

There is a growing interest in obtaining high quality monolayer transition metal disulfides for optoelectronic applications. Surface treatments using a range of chemicals have proven effective to improve the photoluminescence yield of these materials. However, the underlying mechanism for the photoluminescence enhancement is not clear, which prevents a rational design of passivation strategies. Here, a simple and effective approach to significantly enhance the photoluminescence is demonstrated by using a family of cation donors, which we show to be much more effective than commonly used p-dopants. We develop a detailed mechanistic picture for the action of these cation donors and demonstrate that one of them, bis(trifluoromethane)sulfonimide lithium salt (Li-TFSI), enhances the photoluminescence of both MoS2 and WS2 to a level double that of the currently best performing super-acid trifluoromethanesulfonimide (H-TFSI) treatment. In addition, the ionic salts used in our treatments are compatible with greener solvents and are easier to handle than super-acids, providing the possibility of performing treatments during device fabrication. This work sets up rational selection rules for ionic chemicals to passivate transition metal disulfides and increases their potential in practical optoelectronic applications.

Giant photoluminescence enhancement in MoSe2 monolayers treated with oleic acid ligands.

The inherently low photoluminescence (PL) yields in the as prepared transition metal dichalcogenide (TMD) monolayers are broadly accepted to be the result of atomic vacancies (i.e., defects) and uncontrolled doping, which give rise to non-radiative exciton decay pathways. To date, a number of chemical passivation schemes have been successfully developed to improve PL in sulphur based TMDs i.e., molybdenum disulphide (MoS2) and tungsten disulphide (WS2) monolayers. Studies on solution based chemical passivation schemes for improving PL yields in selenium (Se) based TMDs are however lacking in comparison. Here, we demonstrate that treatment with oleic acid (OA) provides a simple wet chemical passivation method for monolayer MoSe2, enhancing PL yields by an average of 58-fold, while also improving spectral uniformity across the material and reducing the emission linewidth. Excitation intensity dependent PL reveals trap-free PL dynamics dominated by neutral exciton recombination. Time-resolved PL (TRPL) studies reveal significantly increased PL lifetimes, with pump intensity dependent TRPL measurements also confirming trap free PL dynamics in OA treated MoSe2. Field effect transistors show reduced charge trap density and improved on-off ratios after treatment with OA. These results indicate defect passivation by OA, which we hypothesise as ligands passivating chalcogen defects through oleate coordination to Mo dangling bonds. Importantly, this work combined with our previous study on OA treated WS2, verifies OA treatment as a simple solution-based chemical passivation protocol for improving PL yields and electronic characteristics in both selenide and sulphide TMDs - a property that has not been reported previously for other solution-based passivation schemes.

Rational Passivation of Sulfur Vacancy Defects in Two-Dimensional Transition Metal Dichalcogenides.

Structural defects vary the optoelectronic properties of monolayer transition metal dichalcogenides, leading to concerted efforts to control defect type and density via materials growth or postgrowth passivation. Here, we explore a simple chemical treatment that allows on-off switching of low-lying, defect-localized exciton states, leading to tunable emission properties. Using steady-state and ultrafast optical spectroscopy, supported by ab initio calculations, we show that passivation of sulfur vacancy defects, which act as exciton traps in monolayer MoS2 and WS2, allows for controllable and improved mobilities and an increase in photoluminescence up to 275-fold, more than twice the value achieved by other chemical treatments. Our findings suggest a route for simple and rational defect engineering strategies for tunable and switchable electronic and excitonic properties through passivation.

Directed Energy Transfer from Monolayer WS2 to Near-Infrared Emitting PbS-CdS Quantum Dots.

Heterostructures of two-dimensional (2D) transition metal dichalcogenides (TMDs) and inorganic semiconducting zero-dimensional (0D) quantum dots (QDs) offer useful charge and energy transfer pathways, which could form the basis of future optoelectronic devices. To date, most have focused on charge transfer and energy transfer from QDs to TMDs, that is, from 0D to 2D. Here, we present a study of the energy transfer process from a 2D to 0D material, specifically exploring energy transfer from monolayer tungsten disulfide (WS2) to near-infrared emitting lead sulfide-cadmium sulfide (PbS-CdS) QDs. The high absorption cross section of WS2 in the visible region combined with the potentially high photoluminescence (PL) efficiency of PbS QD systems makes this an interesting donor-acceptor system that can effectively use the WS2 as an antenna and the QD as a tunable emitter, in this case, downshifting the emission energy over hundreds of millielectron volts. We study the energy transfer process using photoluminescence excitation and PL microscopy and show that 58% of the QD PL arises due to energy transfer from the WS2. Time-resolved photoluminescence microscopy studies show that the energy transfer process is faster than the intrinsic PL quenching by trap states in the WS2, thus allowing for efficient energy transfer. Our results establish that QDs could be used as tunable and high PL efficiency emitters to modify the emission properties of TMDs. Such TMD-QD heterostructures could have applications in light-emitting technologies or artificial light-harvesting systems or be used to read out the state of TMD devices optically in various logic and computing applications.

Thiol-Anchored TIPS-Tetracene Ligands with Quantitative Triplet Energy Transfer to PbS Quantum Dots and Improved Thermal Stability.

Triplet energy transfer between inorganic quantum dots (QDs) and organic materials plays a fundamental role in many optoelectronic applications based on these nanocomposites. Attaching organic molecules to the QD as transmitter ligands has been shown to facilitate transfer both to and from QDs. Here we show that the often disregarded thiol anchoring group can achieve quantitative triplet energy transfer yields in a PbS QD system with 6,11-bis[(triisopropylsilyl)ethynyl]tetracene-2-methylthiol (TET-SH) ligands. We demonstrate efficient triplet transfer in a singlet fission-based photon multiplication system with 5,12-bis[(triisopropylsilyl)ethynyl]tetracene generating triplets in solution that transfer to the PbS QDs via the thiol ligand TET-SH. Importantly, we demonstrate the increased thermal stability of the PbS/TET-SH system, compared to the traditional carboxylic acid counterpart, allowing for higher photoluminescence quantum yields.