Revealing Two Distinct Formation Pathways of 2D Wurtzite-CdSe Nanocrystals Using In Situ X-Ray Scattering.

Understanding the mechanism underlying the formation of quantum-sized semiconductor nanocrystals is crucial for controlling their synthesis for a wide array of applications. However, most studies of 2D CdSe nanocrystals have relied predominantly on ex situ analyses, obscuring key intermediate stages and raising fundamental questions regarding their lateral shapes. Herein, the formation pathways of two distinct quantum-sized 2D wurtzite-CdSe nanocrystals - nanoribbons and nanosheets - by employing a comprehensive approach, combining in situ small-angle X-ray scattering techniques with various ex situ characterization methods is studied. Although both nanostructures share the same thickness of ≈1.4 nm, they display contrasting lateral dimensions. The findings reveal the pivotal role of Se precursor reactivity in determining two distinct synthesis pathways. Specifically, highly reactive precursors promote the formation of the nanocluster-lamellar assemblies, leading to the synthesis of 2D nanoribbons with elongated shapes. In contrast, mild precursors produce nanosheets from a tiny seed of 2D nuclei, and the lateral growth is regulated by chloride ions, rather than relying on nanocluster-lamellar assemblies or Cd(halide)2 -alkylamine templates, resulting in 2D nanocrystals with relatively shorter lengths. These findings significantly advance the understanding of the growth mechanism governing quantum-sized 2D semiconductor nanocrystals and offer valuable guidelines for their rational synthesis.

Recent Advances in Patterning Strategies for Full-Color Perovskite Light-Emitting Diodes.

Metal halide perovskites have emerged as promising light-emitting materials for next-generation displays owing to their remarkable material characteristics including broad color tunability, pure color emission with remarkably narrow bandwidths, high quantum yield, and solution processability. Despite recent advances have pushed the luminance efficiency of monochromic perovskite light-emitting diodes (PeLEDs) to their theoretical limits, their current fabrication using the spin-coating process poses limitations for fabrication of full-color displays. To integrate PeLEDs into full-color display panels, it is crucial to pattern red-green-blue (RGB) perovskite pixels, while mitigating issues such as cross-contamination and reductions in luminous efficiency. Herein, we present state-of-the-art patterning technologies for the development of full-color PeLEDs. First, we highlight recent advances in the development of efficient PeLEDs. Second, we discuss various patterning techniques of MPHs (i.e., photolithography, inkjet printing, electron beam lithography and laser-assisted lithography, electrohydrodynamic jet printing, thermal evaporation, and transfer printing) for fabrication of RGB pixelated displays. These patterning techniques can be classified into two distinct approaches: in situ crystallization patterning using perovskite precursors and patterning of colloidal perovskite nanocrystals. This review highlights advancements and limitations in patterning techniques for PeLEDs, paving the way for integrating PeLEDs into full-color panels.

Ultrathin Self-Powered Heavy-Metal-Free Cu-In-Se Quantum Dot Photodetectors for Wearable Health Monitoring.

Mechanically deformable photodetectors (PDs) are key device components for wearable health monitoring systems based on photoplethysmography (PPG). Achieving high detectivity, fast response time, and an ultrathin form factor in the PD is highly needed for next-generation wearable PPG systems. Self-powered operation without a bulky power-supply unit is also beneficial for point-of-care application. Here, we propose ultrathin self-powered PDs using heavy-metal-free Cu-In-Se quantum dots (QDs), which enable high-performance wearable PPG systems. Although the light-absorbing QD layer is extremely thin (∼40 nm), the developed PD exhibits excellent performance (specific detectivity: 2.10 × 1012 Jones, linear dynamic range: 102 dB, and spectral range: 250-1050 nm at zero bias), which is comparable to that of conventional rigid QD-PDs employing thick Pb-chalcogenide QD layers. This is attributed to material and device strategies─materials that include Cu-In-Se QDs, a MoS2-nanosheet-blended poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) hole transport layer, a ZnO nanoparticle electron transport layer, Ag and ITO electrodes, and an ultrathin form factor (∼120 nm except the electrodes) that enable excellent mechanical deformability. These allow the successful application of QD-PDs to a wearable system for real-time PPG monitoring, expanding their potential in the field of mobile bioelectronics.

Moisture-Induced Degradation of Quantum-Sized Semiconductor Nanocrystals through Amorphous Intermediates.

Elucidating the water-induced degradation mechanism of quantum-sized semiconductor nanocrystals is an important prerequisite for their practical application because they are vulnerable to moisture compared to their bulk counterparts. In-situ liquid-phase transmission electron microscopy is a desired method for studying nanocrystal degradation, and it has recently gained technical advancement. Herein, the moisture-induced degradation of semiconductor nanocrystals is investigated using graphene double-liquid-layer cells that can control the initiation of reactions. Crystalline and noncrystalline domains of quantum-sized CdS nanorods are clearly distinguished during their decomposition with atomic-scale imaging capability of the developed liquid cells. The results reveal that the decomposition process is mediated by the involvement of the amorphous-phase formation, which is different from conventional nanocrystal etching. The reaction can proceed without the electron beam, suggesting that the amorphous-phase-mediated decomposition is induced by water. Our study discloses unexplored aspects of moisture-induced deformation pathways of semiconductor nanocrystals, involving amorphous intermediates.

Thermal Effect on Photoelectrochemical Water Splitting Toward Highly Solar to Hydrogen Efficiency.

Photoelectrochemical (PEC) hydrogen production is an emerging technology that uses renewable solar light aimed to establish a sustainable carbon-neutral society. The barriers to commercialization are low efficiency and high cost. To date, researchers have focused on materials and systems. However, recent studies have been conducted to utilize thermal effects in PEC hydrogen production. This Review provides a fresh perspective to utilize the thermal effects for PEC performance enhancement while delineating the underlying principles and equations associated with efficiency. The fundamentals of the thermal effect on the PEC system are summarized from various perspectives: kinetics, thermodynamics, and empirical equations. Based on this, materials are classified as plasmonic metals, quantum dot-based semiconductors, and photothermal organic materials, which have an inherent response to photothermal irradiation. Finally, the economic viability and challenges of these strategies for PEC are explained, which can pave the way for the future progress in the field.

Direct Observation of Off-Stoichiometry-Induced Phase Transformation of 2D CdSe Quantum Nanosheets.

Crystal structures determine material properties, suggesting that crystal phase transformations have the potential for application in a variety of systems and devices. Phase transitions are more likely to occur in smaller crystals; however, in quantum-sized semiconductor nanocrystals, the microscopic mechanisms by which phase transitions occur are not well understood. Herein, the phase transformation of 2D CdSe quantum nanosheets caused by off-stoichiometry is revealed, and the progress of the transformation is directly observed by in situ transmission electron microscopy. The initial hexagonal wurtzite-CdSe nanosheets with atomically uniform thickness are transformed into cubic zinc blende-CdSe nanosheets. A combined experimental and theoretical study reveals that electron-beam irradiation can change the stoichiometry of the nanosheets, thereby triggering phase transformation. The loss of Se atoms induces the reconstruction of surface atoms, driving the transformation from wurtzite-CdSe(11 2 ¯ $\bar{2}$ 0) to zinc blende-CdSe(001) 2D nanocrystals. Furthermore, during the phase transformation, unconventional dynamic phenomena occur, including domain separation. This study contributes to the fundamental understanding of the phase transformations in 2D quantum-sized semiconductor nanocrystals.

Quantum Dots, Passivation Layer and Cocatalysts for Enhanced Photoelectrochemical Hydrogen Production.

Solar-driven photoelectrochemical (PEC) hydrogen production is one potential pathway to establish a carbon-neutral society. Nowadays, quantum dots (QDs)-sensitized semiconductors have emerged as promising materials for PEC hydrogen production due to their tunable bandgap by size or morphology control, displaying excellent optical and electrical properties. Nevertheless, they still suffer from anodic corrosion during long-term cycling, offering poor stability. This Review discussed advancements to improve long-term stability of QDs particularly in terms of cocatalysts and passivation layers. The working principle of PEC cells was reviewed, along with all important configurations adopted over recent years. The equations to assess PEC performance were also described. A greater emphasized was placed on QDs and incorporation of cocatalysts or passivation layers that could enhance the PEC performance by influencing the charge transfer and surface recombination processes.

Temporary postoperative myocardial injury and long-term survival in liver transplant patients with coronary artery disease.

BACKGROUND: Coronary artery disease (CAD) is increasing worldwide due to the aging population and cardiometabolic syndrome. However, the extent of postoperative myocardial injury, the most common cause of death during the 30 days after noncardiac surgery, remains unclear with respect to liver transplant (LT) patients with CAD. We examined the link between post-LT high sensitivity cardiac troponin I (hs_cTnI) and long-term survival according to liver disease severity. METHODS: Consecutive patients who underwent LT (n = 3,220) from 2010 to 2020 were evaluated retrospectively. CAD was defined as a history of coronary artery bypass surgery or percutaneous intervention, or previous myocardial infarction. Peak hs_cTnI levels within 30 days post-transplant were compared in patients with and without CAD. The primary endpoint was defined as an all-cause mortality at 12 years following LT. Secondary endpoints include peak hs_cTnI level within post-transplant 30 days and 30-day mortality. Survival analysis was performed using the Kaplan-Meier method. RESULTS: CAD patients (n = 264, 8.2%) had higher peak hs_cTnI levels within 30 days post-LT than those without CAD (median [interquartile]: 0.068 [0.030-0.154] vs. 0.087 [0.037-0.203] ng/ml, respectively; P = 0.004); however, the mortality rate was comparable (14.7% vs. 14.8%, respectively, P = 0.999), at 12 years, and 1.9% vs. 1.1% (P = 0.522) at 30 days, respectively, at 30 days. Subgroup analysis with stratified liver disease severity identified a similar risk of long-term mortality. CONCLUSIONS: Although the peak hs_cTnI level within 30 days was higher in revascularized or treated CAD patients after LT compared those without CAD, long-term mortality rates at 12 years and 30-day mortality rate were comparable.

C-reactive protein-to-albumin ratio is a predictor of 1-year mortality following liver transplantation.

BACKGROUND: Considering the importance of the inflammatory status of recipients on outcomes following liver transplantation (LT), we investigated the association between C-reactive protein-to-albumin ratio (CAR) and one-year mortality following LT and compared it with other parameters reflecting patients' underlying inflammatory status. METHODS: A total of 3,614 consecutive adult LT recipients were retrospectively evaluated. Prognostic parameters were analyzed using area under the receiver operating characteristic curve (AUROC) analysis, and subsequent cutoffs were derived. For survival analysis, Cox proportional hazards and Kaplan-Meier analyses were performed. RESULTS: The AUROC for CAR to predict one-year mortality after LT was 0.68 (0.65-0.72), which was the highest compared with other inflammatory parameters, with the best cutoff of 0.34. A CAR ≥ 0.34 was associated with a significantly higher one-year mortality rate (13.3% vs. 5.8 %, log-rank P < 0.001) and overall mortality rate (24.5% vs. 12.9%, log-rank P = 0.039). A CAR ≥ 0.34 was an independent predictor of one-year mortality (hazard ratio, 1.40 [1.03-1.90], P = 0.031) and overall mortality (hazard ratio 1.39 [1.13-1.71], P = 0.002) after multivariable adjustment. CONCLUSIONS: Preoperative CAR (≥ 0.34) was independently associated with a higher risk of one-year and overall mortality after LT. This may suggest that CAR, a simple and readily available biomarker, maybe a practical index that may assist in the risk stratification of liver transplantation outcomes.

Ultrahigh-resolution full-color perovskite nanocrystal patterning for ultrathin skin-attachable displays.

High-definition red/green/blue (RGB) pixels and deformable form factors are essential for the next-generation advanced displays. Here, we present ultrahigh-resolution full-color perovskite nanocrystal (PeNC) patterning for ultrathin wearable displays. Double-layer transfer printing of the PeNC and organic charge transport layers is developed, which prevents internal cracking of the PeNC film during the transfer printing process. This results in RGB pixelated PeNC patterns of 2550 pixels per inch (PPI) and monochromic patterns of 33,000 line pairs per inch with 100% transfer yield. The perovskite light-emitting diodes (PeLEDs) with transfer-printed active layers exhibit outstanding electroluminescence characteristics with remarkable external quantum efficiencies (15.3, 14.8, and 2.5% for red, green, and blue, respectively), which are high compared to the printed PeLEDs reported to date. Furthermore, double-layer transfer printing enables the fabrication of ultrathin multicolor PeLEDs that can operate on curvilinear surfaces, including human skin, under various mechanical deformations. These results highlight that PeLEDs are promising for high-definition full-color wearable displays.

Integration of synaptic phototransistors and quantum dot light-emitting diodes for visualization and recognition of UV patterns.

Synaptic photodetectors exhibit photon-triggered synaptic plasticity, which thus can improve the image recognition rate by enhancing the image contrast. However, still, the visualization and recognition of invisible ultraviolet (UV) patterns are challenging, owing to intense background noise. Here, inspired by all-or-none potentiation of synapse, we develop an integrated device of synaptic phototransistors (SPTrs) and quantum dot light-emitting diodes (QLEDs), facilitating noise reduction and visualization of UV patterns through on-device preprocessing. The SPTrs convert noisy UV inputs into a weighted photocurrent, which is applied to the QLEDs as a voltage input through an external current-voltage-converting circuit. The threshold switching characteristics of the QLEDs result in amplified current and visible illumination by the suprathreshold input voltage or nearly zero current and no visible illumination by the input voltage below the threshold. The preprocessing of image data with the SPTr-QLED can amplify the image contrast, which is helpful for high-accuracy image recognition.

Effects of Mono- and Bifunctional Surface Ligands of Cu-In-Se Quantum Dots on Photoelectrochemical Hydrogen Production.

Semiconductor nanocrystal quantum dots (QDs) are promising materials for solar energy conversion because of their bandgap tunability, high absorption coefficient, and improved hot-carrier generation. CuInSe2 (CISe)-based QDs have attracted attention because of their low toxicity and wide light-absorption range, spanning visible to near-infrared light. In this work, we study the effects of the surface ligands of colloidal CISe QDs on the photoelectrochemical characteristics of QD-photoanodes. Colloidal CISe QDs with mono- and bifunctional surface ligands are prepared and used in the fabrication of type-II heterojunction photoanodes by adsorbing QDs on mesoporous TiO2. QDs with monofunctional ligands are directly attached on TiO2 through partial ligand detachment, which is beneficial for electron transfer between QDs and TiO2. In contrast, bifunctional ligands bridge QDs and TiO2, increasing the amount of QD adsorption. Finally, photoanodes fabricated with oleylamine-passivated QDs show a current density of ~8.2 mA/cm2, while those fabricated with mercaptopropionic-acid-passivated QDs demonstrate a current density of ~6.7 mA/cm2 (at 0.6 VRHE under one sun illumination). Our study provides important information for the preparation of QD photoelectrodes for efficient photoelectrochemical hydrogen generation.

Rapid one-pot synthesis of magnetically separable Fe3O4-Pd nanocatalysts: a highly reusable catalyst for the Suzuki-Miyaura coupling reaction.

Heterogeneous catalysts comprising noble metals and magnetic materials allow a straightforward separation from a reaction using an external magnet and are recovered easily. In this study, we synthesized magnetic Fe3O4-Pdn hybrid heterogeneous catalysts via a rapid one-pot aqueous-phase method. The synthesized Fe3O4-Pd NPs dispersed well with small size (∼50 nm), maintaining high magnetic responsiveness, and showed high reactivity and reusability for the Suzuki-Miyaura coupling reaction between aryl halides and phenylboronic acid. The synthesized Fe3O4-Pd50 catalyst could be recycled at least ten times with no significant loss of catalytic activity by external magnet separation.

Materials and design strategies for stretchable electroluminescent devices.

Stretchable displays have recently received increasing attention as input and/or output interfaces for next-generation human-friendly electronic systems. Stretchable electroluminescent (EL) devices are a core component of stretchable displays, and they can be classified into two types, structurally stretchable EL devices and intrinsically stretchable EL devices, according to the mechanism for achieving their stretchability. We herein present recent advances in materials and design strategies for stretchable EL devices. First, stretchable devices based on ultrathin EL devices are introduced. Ultrathin EL devices are mechanically flexible like thin paper, and they can become stretchable through various structural engineering methods, such as inducing a buckled structure, employing interconnects with stretchable geometries, and applying origami/kirigami techniques. Secondly, intrinsically stretchable EL devices can be fabricated by using inherently stretchable electronic materials. For example, light-emitting electrochemical cells and EL devices with a simpler structure using alternating current have been developed. Furthermore, novel stretchable semiconductor materials have been presented for the development of intrinsically stretchable light-emitting diodes. After discussing these two types of stretchable EL devices, we briefly discuss applications of deformable EL devices and conclude the review.

Nonvolatile Control of Metal-Insulator Transition in VO2 by Ferroelectric Gating.

Controlling phase transitions in correlated materials yields emergent functional properties, providing new aspects to future electronics and a fundamental understanding of condensed matter systems. With vanadium dioxide (VO2 ), a representative correlated material, an approach to control a metal-insulator transition (MIT) behavior is developed by employing a heteroepitaxial structure with a ferroelectric BiFeO3 (BFO) layer to modulate the interaction of correlated electrons. Owing to the defect-alleviated interfaces, the enhanced coupling between the correlated electrons and ferroelectric polarization is successfully demonstrated by showing a nonvolatile control of MIT of VO2 at room temperature. The ferroelectrically-tunable MIT can be realized through the Mott transistor (VO2 /BFO/SrRuO3 ) with a remanent polarization of 80 µC cm-2 , leading to a nonvolatile MIT behavior through the reversible electrical conductance with a large on/off ratio (≈102 ), long retention time (≈104 s), and high endurance (≈103 cycles). Furthermore, the structural phase transition of VO2 is corroborated by ferroelectric polarization through in situ Raman mapping analysis. This study provides novel design principles for heteroepitaxial correlated materials and innovative insight to modulate multifunctional properties.

Dynamics of Polymer Nanocapsule Buckling and Collapse Revealed by In Situ Liquid-Phase TEM.

Nanocapsules are hollow nanoscale shells that have applications in drug delivery, batteries, self-healing materials, and as model systems for naturally occurring shell geometries. In many applications, nanocapsules are designed to release their cargo as they buckle and collapse, but the details of this transient buckling process have not been directly observed. Here, we use in situ liquid-phase transmission electron microscopy to record the electron-irradiation-induced buckling in spherical 60-187 nm polymer capsules with ∼3.5 nm walls. We observe in real time the release of aqueous cargo from these nanocapsules and their buckling into morphologies with single or multiple indentations. The in situ buckling of nanoscale capsules is compared to ex situ measurements of collapsed and micrometer-sized capsules and to Monte Carlo (MC) simulations. The shape and dynamics of the collapsing nanocapsules are consistent with MC simulations, which reveal that the excessive wrinkling of nanocapsules with ultrathin walls results from their large Föppl-von Kármán numbers around 105. Our experiments suggest design rules for nanocapsules with the desired buckling response based on parameters such as capsule radius, wall thickness, and collapse rate.

Global biosphere primary productivity changes during the past eight glacial cycles.

Global biosphere productivity is the largest uptake flux of atmospheric carbon dioxide (CO2), and it plays an important role in past and future carbon cycles. However, global estimation of biosphere productivity remains a challenge. Using the ancient air enclosed in polar ice cores, we present the first 800,000-year record of triple isotopic ratios of atmospheric oxygen, which reflects past global biosphere productivity. We observe that global biosphere productivity in the past eight glacial intervals was lower than that in the preindustrial era and that, in most cases, it starts to increase millennia before deglaciations. Both variations occur concomitantly with CO2 changes, implying a dominant control of CO2 on global biosphere productivity that supports a pervasive negative feedback under the glacial climate.

Bendable BiVO4-Based Photoanodes on a Metal Substrate Realized through Template Engineering for Photoelectrochemical Water Splitting.

Unlike planar photoelectrodes, bendable and malleable photoelectrodes extend their application to mechanical flexibility beyond conventional rigid structures, which have garnered new attention in the field of photoelectrochemical water splitting. A bendable metal (Hastelloy), which has both bendability and compatibility with various oxide layers, allows high-temperature processes for crystallization; therefore it is far superior as a substrate than a conventional flexible polymer. In this study, we fabricate bendable BiVO4 crystalline thin films on the metal substrates by employing template layers (SrRuO3/SrTiO3) to reduce the structural misfits between BiVO4 and the substrate. The crystallinities were verified through X-ray diffraction and transmission electron microscopy, and photocatalytic performances were examined. The crystallinity of BiVO4 was significantly improved by utilizing similar lattice constants and affinities between BiVO4 and the oxide template layers. We also formed a type II heterojunction by adding a WO3 layer which complements the charge separation and charge transfer as a photoanode. The photocurrent densities of tensile-bent BiVO4/WO3 thin films with a bending radius of 10 mm are comparable to those of pristine BiVO4/WO3 thin film in various aqueous electrolytes. Moreover, photostability tests showed that the tensile-bent crystalline photoanodes retained 90% of their initial photocurrent density after 24 h, which proved their exceptional durability. Our work demonstrates that the bendable photoelectrodes with crystallinity hold great potential in terms of device structure for solar-driven water splitting.

Toward Full-Color Electroluminescent Quantum Dot Displays.

Colloidal quantum dots (QDs) exhibit unique characteristics such as facile color tunability, pure color emission with extremely narrow bandwidths, high luminescence efficiency, and high photostability. In addition, quantum dot light-emitting diodes (QLEDs) feature bright electroluminescence, low turn-on voltage, and ultrathin form factor, making them a promising candidate for next-generation displays. To achieve the overarching goal of the full-color display based on the electroluminescence of QDs, however it is essential to enhance the performance of QLEDs further for each color (e.g., red, green, and blue; RGB) and develop novel techniques for patterning RGB QD pixels without cross-contamination. Here, we present state-of-the-art material, process, and device technologies for full-color QLED-based displays. First, we highlight recent advances in the development of efficient red-, green-, and blue-monochromatic QLEDs. In particular, we focus on the progress of heavy-metal-free QLEDs. Then, we describe patterning techniques for individual RGB QDs to fabricate pixelated displays. Finally, we briefly summarize applications of such QLEDs, presenting the possibility of full-color QLED-based displays.

Hybrid nanocapsules for in situ TEM imaging of gas evolution reactions in confined liquids.

Liquid cell transmission electron microscopy (TEM) enables the direct observation of dynamic physical and chemical processes in liquids at the nanoscale. Quantitative investigations into reactions with fast kinetics and/or multiple reagents will benefit from further advances in liquid cell design that facilitate rapid in situ mixing and precise control over reagent volumes and concentrations. This work reports the development of inorganic-organic nanocapsules for high-resolution TEM imaging of nanoscale reactions in liquids with well-defined zeptoliter volumes. These hybrid nanocapsules, with 48 nm average diameter, consist of a thin layer of gold coating a lipid vesicle. As a model reaction, the nucleation, growth, and diffusion of nanobubbles generated by the radiolysis of water is investigated inside the nanocapsules. When the nanobubbles are sufficiently small (10-25 nm diameter), they are mobile in the nanocapsules, but their movement deviates from Brownian motion, which may result from geometric confinement by the nanocapsules. Gases and fluids can be transported between two nanocapsules when they fuse, demonstrating in situ mixing without using complex microfluidic schemes. The ability to synthesize nanocapsules with controlled sizes and to monitor dynamics simultaneously inside multiple nanocapsules provides opportunities to investigate nanoscale processes such as single nanoparticle synthesis in confined volumes and biological processes such as biomineralization and membrane dynamics.