Distribution control enables efficient reduced-dimensional perovskite LEDs.

Light-emitting diodes (LEDs) based on perovskite quantum dots have shown external quantum efficiencies (EQEs) of over 23% and narrowband emission, but suffer from limited operating stability1. Reduced-dimensional perovskites (RDPs) consisting of quantum wells (QWs) separated by organic intercalating cations show high exciton binding energies and have the potential to increase the stability and the photoluminescence quantum yield2,3. However, until now, RDP-based LEDs have exhibited lower EQEs and inferior colour purities4-6. We posit that the presence of variably confined QWs may contribute to non-radiative recombination losses and broadened emission. Here we report bright RDPs with a more monodispersed QW thickness distribution, achieved through the use of a bifunctional molecular additive that simultaneously controls the RDP polydispersity while passivating the perovskite QW surfaces. We synthesize a fluorinated triphenylphosphine oxide additive that hydrogen bonds with the organic cations, controlling their diffusion during RDP film deposition and suppressing the formation of low-thickness QWs. The phosphine oxide moiety passivates the perovskite grain boundaries via coordination bonding with unsaturated sites, which suppresses defect formation. This results in compact, smooth and uniform RDP thin films with narrowband emission and high photoluminescence quantum yield. This enables LEDs with an EQE of 25.6% with an average of 22.1 ±1.2% over 40 devices, and an operating half-life of two hours at an initial luminance of 7,200 candela per metre squared, indicating tenfold-enhanced operating stability relative to the best-known perovskite LEDs with an EQE exceeding 20%1,4-6.

Effect of Tranexamic Acid on Intra- and Postoperative Bleeding in Eyelid Surgery: A Prospective, Randomized, Multicenter, Double-Masked, Control Trial.

PURPOSE: Pilot studies suggest that waiting 15 minutes after a subcutaneous tranexamic acid injection is associated with decreased intraoperative bleeding and postoperative ecchymosis in eyelid surgery. The outcomes of commencing eyelid surgery immediately after injection without a waiting period remain unexplored. METHODS: This prospective, randomized, multicenter, double-masked, controlled study examined bilateral symmetric upper and/or lower lid blepharoplasty or ptosis repair. Patients received tranexamic acid in 1 eyelid and control in the contralateral eyelid. The surgeon recorded the side with more intraoperative bleeding. Two masked graders evaluated periocular ecchymosis at postoperative day 0 and postoperative week 1 (POW 1) with a 5-point scale. At POW 1, patients reported subjective grading of bruising as increased on 1 side or similar on both sides. Results were analyzed with Wilcoxon signed-rank and sign tests. RESULTS: Of 130 patients, there was less eyelid ecchymosis on the tranexamic side at postoperative day 0 ( p = 0.001) and POW 1 ( p < 0.001). By surgery type, the 69 levator advancement surgeries had significantly less ecchymosis at postoperative day 0 ( p < 0.001) and POW 1 ( p = 0.001), while upper eyelid blepharoplasty, combined upper and lower lid blepharoplasty, and conjunctivomullerectomy trended toward significance. Of 68 patients reporting a POW 1 grading, 69% reported less bruising on the tranexamic side ( p < 0.001). Intraoperative bleeding was not significantly different between sides ( p = 0.930). CONCLUSIONS: Without a postinjection waiting period, subcutaneous tranexamic acid for eyelid surgery significantly decreased postoperative ecchymosis on postoperative day 0 and POW 1 but did not affect intraoperative bleeding. Subcutaneous tranexamic acid was not associated with any complications.

Micron Thick Colloidal Quantum Dot Solids.

Shortwave infrared colloidal quantum dots (SWIR-CQDs) are semiconductors capable of harvesting across the AM1.5G solar spectrum. Today's SWIR-CQD solar cells rely on spin-coating; however, these films exhibit cracking once thickness exceeds ∼500 nm. We posited that a blade-coating strategy could enable thick QD films. We developed a ligand exchange with an additional resolvation step that enabled the dispersion of SWIR-CQDs. We then engineered a quaternary ink that combined high-viscosity solvents with short QD stabilizing ligands. This ink, blade-coated over a mild heating bed, formed micron-thick SWIR-CQD films. These SWIR-CQD solar cells achieved short-circuit current densities (Jsc) that reach 39 mA cm-2, corresponding to the harvest of 60% of total photons incident under AM1.5G illumination. External quantum efficiency measurements reveal both the first exciton peak and the closest Fabry-Perot resonance peak reaching approximately 80%-this is the highest unbiased EQE reported beyond 1400 nm in a solution-processed semiconductor.

All-Inorganic Quantum-Dot LEDs Based on a Phase-Stabilized α-CsPbI3 Perovskite.

The all-inorganic nature of CsPbI3 perovskites allows to enhance stability in perovskite devices. Research efforts have led to improved stability of the black phase in CsPbI3 films; however, these strategies-including strain and doping-are based on organic-ligand-capped perovskites, which prevent perovskites from forming the close-packed quantum dot (QD) solids necessary to achieve high charge and thermal transport. We developed an inorganic ligand exchange that leads to CsPbI3 QD films with superior phase stability and increased thermal transport. The atomic-ligand-exchanged QD films, once mechanically coupled, exhibit improved phase stability, and we link this to distributing strain across the film. Operando measurements of the temperature of the LEDs indicate that KI-exchanged QD films exhibit increased thermal transport compared to controls that rely on organic ligands. The LEDs exhibit a maximum EQE of 23 % with an electroluminescence emission centered at 640 nm (FWHM: ≈31 nm). These red LEDs provide an operating half-lifetime of 10 h (luminance of 200 cd m-2 ) and an operating stability that is 6× higher than that of control devices.

Chloride Insertion-Immobilization Enables Bright, Narrowband, and Stable Blue-Emitting Perovskite Diodes.

Metal halide perovskites show promise for light-emitting diodes (LEDs) owing to their facile manufacture and excellent optoelectronic performance, including high color purity and spectral stability, especially in the green region. However, for blue perovskite LEDs, the emission spectrum line width is broadened to over 25 nm by the coexistence of multiple reduced-dimensional perovskite domains, and the spectral stability is poor, with an undesirable shift (over 7 nm) toward longer wavelengths under operating conditions, degradation that occurs due to phase separation when mixed halides are employed. Here we demonstrate chloride insertion-immobilization, a strategy that enables blue perovskite LEDs, the first to exhibit narrowband (line width of 18 nm) and spectrally stable (no wavelength shift) performance. We prepare bromide-based perovskites and then employ organic chlorides for dynamic treatment, inserting and in situ immobilizing chlorides to blue-shift and stabilize the emission. We achieve sky-blue LEDs with a record luminance over 5100 cd/m2 at 489 nm, and an operating half-life of 51 min at 1500 cd/m2. By device structure optimization, we further realize an improved EQE of 5.2% at 479 nm and an operating half-life of 90 min at 100 cd/m2.

Anchored Ligands Facilitate Efficient B-Site Doping in Metal Halide Perovskites.

Metal halide perovskites exhibit outstanding optoelectronic properties: superior charge carrier mobilities, low densities of deep trap states, high photoluminescence quantum yield, and wide color tunability. The introduction of dopant ions provides pathways to manipulate the electronic and chemical features of perovskites. In metal halide perovskites ABX3, where A is a monovalent cation (e.g., methylammonium (MA+), Cs+), B is the divalent metal ion(s) (e.g., Pb2+, Sn2+), and X is the halide group (e.g., Cl-, Br-, or I-), the isovalent exchange of A- and X-site ions has been widely accomplished; in contrast, strategies to exchange B-site cations are underexamined. The activation energies for vacancy-mediated diffusion of B-site cations are much higher than those for A- and X-sites, leading to slow doping processes and low doping ratios. Herein we demonstrate a new method that exchanges B-site cations in perovskites. We design a series of metal carboxylate solutions that anchor on the perovskite surface, allowing fast and efficient doping of B-sites with both homovalent and heterovalent cations (e.g., Sn2+, Zn2+, Bi3+) at room temperature. The doping process in the reduced-dimensional perovskites is complete within 1 min, whereas a similar reaction only leads to the surface attachment of dopant ions in three-dimensional structures. We offer a model based on ammonium extraction and surface ion-pair substitution.

Picosecond Charge Transfer and Long Carrier Diffusion Lengths in Colloidal Quantum Dot Solids.

Quantum dots (QDs) are promising candidates for solution-processed thin-film optoelectronic devices. Both the diffusion length and the mobility of photoexcited charge carriers in QD solids are critical determinants of solar cell performance; yet various techniques offer diverse values of these key parameters even in notionally similar films. Here we report diffusion lengths and interdot charge transfer rates using a 3D donor/acceptor technique that directly monitors the rate at which photoexcitations reach small-bandgap dot inclusions having a known spacing within a larger-bandgap QD matrix. Instead of relying on photoluminescence (which can be weak in strongly coupled QD solids), we use ultrafast transient absorption spectroscopy, a method where sensitivity is undiminished by exciton dissociation. We measure record diffusion lengths of ∼300 nm in metal halide exchanged PbS QD solids that have led to power conversion efficiencies of 12%, and determine 8 ps interdot hopping of carriers following photoexcitation, among the fastest rates reported for PbS QD solids. We also find that QD solids composed of smaller QDs ( d = ∼3.2 nm) exhibit 5 times faster interdot charge transfer rates and 10 times lower trap state densities compared to larger ( d = ∼5.5 nm) QDs.

Acid-Assisted Ligand Exchange Enhances Coupling in Colloidal Quantum Dot Solids.

Colloidal quantum dots (CQDs) are promising solution-processed infrared-absorbing materials for optoelectronics. In these applications, it is crucial to replace the electrically insulating ligands used in synthesis to form strongly coupled quantum dot solids. Recently, solution-phase ligand-exchange strategies have been reported that minimize the density of defects and the polydispersity of CQDs; however, we find herein that the new ligands exhibit insufficient chemical reactivity to remove original oleic acid ligands completely. This leads to low CQD packing and correspondingly low electronic performance. Here we report an acid-assisted solution-phase ligand-exchange strategy that, by enabling efficient removal of the original ligands, enables the synthesis of densified CQD arrays. Our use of hydroiodic acid simultaneously facilitates high CQD packing via proton donation and CQD passivation through iodine. We demonstrate highly packed CQD films with a 2.5 times increased carrier mobility compared with prior exchanges. The resulting devices achieve the highest infrared photon-to-electron conversion efficiencies (>50%) reported in the spectral range of 0.8 to 1.1 eV.

Origins of Stokes Shift in PbS Nanocrystals.

Stokes shift, an energy difference between the excitonic absorption and emission, is a property of colloidal quantum dots (CQDs) typically ascribed to splitting between dark and bright excitons. In some materials, e.g., PbS, CuInS2, and CdHgTe, a Stokes shift of up to 200 meV is observed, substantially larger than the estimates of dark-bright state splitting or vibronic relaxations. The shift origin remains highly debated because contradictory signatures of both surface and bulk character were reported for the Stokes-shifted electronic state. Here, we show that the energy transfer among CQDs in a polydispersed ensemble in solution suffices to explain the excess Stokes shift. This energy transfer is primarily due to CQD aggregation and can be substantially eliminated by extreme dilution, higher-viscosity solvent, or better-dispersed colloids. Our findings highlight that ensemble polydispersity remains the primary source of the Stokes shift in CQDs in solution, propagating into the Stokes shift in films and the open-circuit voltage deficit in CQD solar cells. Improved synthetic control can bring notable advancements in CQD photovoltaics, and the Stokes shift continues to provide a sensitive and significant metric to monitor ensemble size distribution.

Tailoring the Energy Landscape in Quasi-2D Halide Perovskites Enables Efficient Green-Light Emission.

Organo-metal halide perovskites are a promising platform for optoelectronic applications in view of their excellent charge-transport and bandgap tunability. However, their low photoluminescence quantum efficiencies, especially in low-excitation regimes, limit their efficiency for light emission. Consequently, perovskite light-emitting devices are operated under high injection, a regime under which the materials have so far been unstable. Here we show that, by concentrating photoexcited states into a small subpopulation of radiative domains, one can achieve a high quantum yield, even at low excitation intensities. We tailor the composition of quasi-2D perovskites to direct the energy transfer into the lowest-bandgap minority phase and to do so faster than it is lost to nonradiative centers. The new material exhibits 60% photoluminescence quantum yield at excitation intensities as low as 1.8 mW/cm2, yielding a ratio of quantum yield to excitation intensity of 0.3 cm2/mW; this represents a decrease of 2 orders of magnitude in the excitation power required to reach high efficiency compared with the best prior reports. Using this strategy, we report light-emitting diodes with external quantum efficiencies of 7.4% and a high luminescence of 8400 cd/m2.

Pure Cubic-Phase Hybrid Iodobismuthates AgBi2 I7 for Thin-Film Photovoltaics.

Bismuth-based hybrid perovskites are candidates for lead-free and air-stable photovoltaics, but poor surface morphologies and a high band-gap energy have previously limited these hybrid perovskites. A new materials processing strategy to produce enhanced bismuth-based thin-film photovoltaic absorbers by incorporation of monovalent silver cations into iodobismuthates is presented. Solution-processed AgBi2 I7 thin films are prepared by spin-coating silver and bismuth precursors dissolved in n-butylamine and annealing under an N2 atmosphere. X-ray diffraction analysis reveals the pure cubic structure (Fd3m) with lattice parameters of a=b=c=12.223 Å. The resultant AgBi2 I7 thin films exhibit dense and pinhole-free surface morphologies with grains ranging in size from 200-800 nm and a low band gap of 1.87 eV suitable for photovoltaic applications. Initial studies produce solar power conversion efficiencies of 1.22 % and excellent stability over at least 10 days under ambient conditions.

Postoperative Complications of True Dropless Cataract Surgery versus Standard Topical Drops.

Purpose Compare postoperative outcomes in cataract surgery between eyes with standard drop regimen versus dropless protocol by residents. Design Retrospective cohort study between April 1, 2018 and March 31, 2020. Methods The study was performed at Lyndon B. Johnson General Hospital in Houston, Harris County, Texas. A total of 547 eyes (234 dropless vs. 313 standard) with phacoemulsification cataract surgery and minimum of 1-month follow-up with best-corrected visual acuity (BCVA) were included. Dropless received 40 mg sub-Tenon's triamcinolone and intracameral moxifloxacin. Patients were followed at postoperative day 1 (POD1), week 1 (POW1), and month 1 (POM1). Postoperative rate of BCVA better than 20/40 (Good vision) and rate of complications were compared between groups. Results Good vision on POM1 in dropless (77.8%) was noninferior to standard (75.1%, p = 0.80). Complication rate in dropless (28.6%) was noninferior to standard (24.0%, p = 0.13). Intraocular pressure (IOP) elevation on POD1 ( p = 0.041) and anterior chamber (AC) cells on POW1 and POM1 ( p < 0.001) were more frequent in dropless. Mean spherical equivalent at POM1 was better in dropless (-0.37 D [±0.81 D]) compared with standard (-0.61D [±0.77 D], p = 0.001). Early posterior capsular opacification (early PCO) was more frequent in dropless ( p = 0.042). Conclusions Postoperative rate of BCVA better than 20/40 and rate of postoperative complications were noninferior, although dropless had higher rates of AC inflammation, IOP elevation, and early PCO.

Associations of Incomplete SARS-CoV-2 Vaccination among Patients with Unstable Housing in Houston.

Vaccination is a safe and effective way to protect against SARS-CoV-2. Two of the three authorized SARS-CoV-2 vaccines require two doses, presenting logistical challenges. Those with unstable housing face barriers that amplify these challenges. In this study, we utilized a database maintained by Healthcare for the Homeless-Houston to determine the rates of partial vaccination among those with unstable housing in Houston (n=294). We then performed post-hoc analyses to identify predictors of partial vaccination. Our key finding was that 30% of those with unstable housing missed their second dose, a proportion far higher than the national average. Those with permanent supportive housing and those who had a Harris County Gold Card (financial assistance for health care costs) were more likely to return for dose two, while those who were younger, living on the streets, or staying in a temporary homeless shelter were more likely to miss the second dose.

Non-traumatic open globe injuries: presenting characteristics and visual outcomes.

PURPOSE: To describe clinical characteristics and visual outcomes of non-traumatic open globe injuries. SETTING: A level 1 trauma centre in a large urban medical centre. DESIGN: Retrospective study. METHODS: Charts of non-traumatic open globe patients admitted to MHH-TMC from 1/2010 to 3/2015 were reviewed for demographics, cause, clinical characteristics, visual acuity (VA) and enucleation. RESULTS: Thirty eyes were included: 15 (50%) were males with a mean age of 47 (±28) years. All presented with zone 1 injury. Twenty-five (83%) had a perforated corneal ulcer. Presenting VA was count fingers (n = 3, 10%) to NLP (n = 6, 20%). Twenty-four (80%) involved infection, 5 (17%) congenital, 3 (10%) chemical burn and 2 (7%) neurotrophic. Conjunctival injection (n = 22, 77%), corneal opacification (n = 20, 71%) and relative afferent pupillary defect (n = 9, 44%) were common. After treatment, 23 (88%) were worse than 6/60 (20/200), 9 (35%) were NLP and 8 (27%) required enucleation. CONCLUSIONS: Often non-traumatic open globe injuries are zone 1 and due to perforated infectious ulcers. Compared to previously reported traumatic injuries, these have higher rates of enucleation (27% vs 8%) and poorer final VA (88% vs 68% worse than 6/60 20/200).

Where Do I Fit In? A Perspective on Challenges Faced by Asian American Medical Students.

Asian American medical students (AAMSs) face significant bias in the medical learning environment and are more likely than White students to perceive their school climate negatively. Little is known about the factors that contribute to AAMSs' negative experiences. This perspective aims to describe AAMSs' experiences with diversity and inclusion efforts using survey data from a midwest regional conference, Asians in Medicine: A Conference on Advocacy and Allyship. AAMS respondents reported feeling excluded from diversity and inclusion efforts and conference participants advocated for institutional culture and climate assessments stratified by race and disaggregated into Asian subgroups.

Over the Horizon: The Present and Future of Endovascular Neural Recording and Stimulation.

The past decade has witnessed an explosion in applications for neural recording and stimulation in the treatment of clinical disorders. Neuromodulatory approaches are now a mainstay of care for essential tremor and Parkinson's disease, and are expanding rapidly into a wide range of other neurological and psychiatric diseases. In parallel, advancements in endovascular approaches to cerebrovascular diseases have resulted in minimally invasive techniques that deliver devices to neural tissue in the central and peripheral nervous systems, with significantly improved safety and efficacy. In this review, we discuss the history of endovascular neural recording and stimulation, its current progress, and applications for neurological disease.

Color-pure red light-emitting diodes based on two-dimensional lead-free perovskites.

It remains a central challenge to the information display community to develop red light-emitting diodes (LEDs) that meet demanding color coordinate requirements for wide color gamut displays. Here, we report high-efficiency, lead-free (PEA)2SnI4 perovskite LEDs (PeLEDs) with color coordinates (0.708, 0.292) that fulfill the Rec. 2100 specification for red emitters. Using valeric acid (VA)-which we show to be strongly coordinated to Sn2+-we slow the crystallization rate of the perovskite, improving the film morphology. The incorporation of VA also protects tin from undesired oxidation during the film-forming process. The improved films and the reduced Sn4+ content enable PeLEDs with an external quantum efficiency of 5% and an operating half-life exceeding 15 hours at an initial brightness of 20 cd/m2 This work illustrates the potential of Cd- and Pb-free PeLEDs for display technology.

Chelating-agent-assisted control of CsPbBr3 quantum well growth enables stable blue perovskite emitters.

Metal halide perovskites have emerged as promising candidates for solution-processed blue light-emitting diodes (LEDs). However, halide phase segregation - and the resultant spectral shift - at LED operating voltages hinders their application. Here we report true-blue LEDs employing quasi-two-dimensional cesium lead bromide with a narrow size distribution of quantum wells, achieved through the incorporation of a chelating additive. Ultrafast transient absorption spectroscopy measurements reveal that the chelating agent helps to control the quantum well thickness distribution. Density functional theory calculations show that the chelating molecule destabilizes the lead species on the quantum well surface and that this in turn suppresses the growth of thicker quantum wells. Treatment with γ-aminobutyric acid passivates electronic traps and enables films to withstand 100 °C for 24 h without changes to their emission spectrum. LEDs incorporating γ-aminobutyric acid-treated perovskites exhibit blue emission with Commission Internationale de l'Éclairage coordinates of (0.12, 0.14) at an external quantum efficiency of 6.3%.

Bipolar-shell resurfacing for blue LEDs based on strongly confined perovskite quantum dots.

Colloidal quantum dot (QD) solids are emerging semiconductors that have been actively explored in fundamental studies of charge transport1 and for applications in optoelectronics2. Forming high-quality QD solids-necessary for device fabrication-requires substitution of the long organic ligands used for synthesis with short ligands that provide increased QD coupling and improved charge transport3. However, in perovskite QDs, the polar solvents used to carry out the ligand exchange decompose the highly ionic perovskites4. Here we report perovskite QD resurfacing to achieve a bipolar shell consisting of an inner anion shell, and an outer shell comprised of cations and polar solvent molecules. The outer shell is electrostatically adsorbed to the negatively charged inner shell. This approach produces strongly confined perovskite QD solids that feature improved carrier mobility (≥0.01 cm2 V-1 s-1) and reduced trap density relative to previously reported low-dimensional perovskites. Blue-emitting QD films exhibit photoluminescence quantum yields exceeding 90%. By exploiting the improved mobility, we have been able to fabricate CsPbBr3 QD-based efficient blue and green light-emitting diodes. Blue devices with reduced trap density have an external quantum efficiency of 12.3%; the green devices achieve an external quantum efficiency of 22%.