Thermodynamic Origin-Based In Situ Electrochemical Construction of Reversible p-n Heterojunctions for Optimal Stability in Potassium Ion Storage.

Heterojunctions in electrode materials offer diverse improvements during the cycling process of energy storage devices, such as volume change buffering, accelerated ion/electron transfer, and better electrode structure integrity, however, obtaining optimal heterostructures with nanoscale domains remains challenging within constrained materials. A novel in situ electrochemical method is introduced to develop a reversible CuSe/PSe p-n heterojunction (CPS-h) from Cu3PSe4 as starting material, targeting maximum stability in potassium ion storage. The CPS-h formation is thermodynamically favorable, characterized by its superior reversibility, minimized diffusion barriers, and enhanced conversion post K+ interaction. Within CPS-h, the synergy of the intrinsic electric field and P-Se bonds enhance electrode stability, effectively countering the Se shuttling phenomenon. The specific orientation between CuSe and PSe leads to a 35° lattice mismatch generates large space at the interface, promoting efficient K ion migration. The Mott-Schottky analysis validates the consistent reversibility of CPS-h, underlining its electrochemical reliability. Notably, CPS-h demonstrates a negligible 0.005% capacity reduction over 10,000 half-cell cycles and remains stable through 2,000 and 4,000 cycles in full cells and hybrid capacitors, respectively. This study emphasizes the pivotal role of electrochemical dynamics in formulating highly stable p-n heterojunctions, representing a significant advancement in potassium-ion battery (PIB) electrode engineering.

Highly Efficient MAPbI3 -Based Quantum Dots Exhibiting Unusual Nonblinking Single Photon Emission at Room Temperature.

Highly emissive semiconductor nanocrystals, or so-called quantum dots (QDs) possess a variety of applications from displays and biology labeling, to quantum communication and modern security. Though ensembles of QDs have already shown very high photoluminescent quantum yields (PLQYs) and have been widely utilized in current optoelectronic products, QDs that exhibit high absorption cross-section, high emission intensity, and, most important, nonblinking behavior at single-dot level have long been desired and not yet realized at room temperature. In this work, infrared-emissive MAPbI3 -based halide perovskite QDs is demonstrated. These QDs not only show a ≈100% PLQY at the ensemble level but also, surprisingly, at the single-dot level, display an extra-large absorption cross-section up to 1.80 × 10-12 cm2 and non-blinking single photon emission with a high single photon purity of 95.3%, a unique property that is extremely rare among all types of quantum emitters operated at room temperature. An in-depth analysis indicates that neither trion formation nor band-edge carrier trapping is observed in MAPbI3 QDs, resulting in the suppression of intensity blinking and lifetime blinking. Fluence-dependent transient absorption measurements reveal that the coexistence of non-blinking behavior and high single photon purity in these perovskite QDs results from a significant repulsive exciton-exciton interaction, which suppresses the formation of biexciton, and thus greatly reduces photocharging. The robustness of these QDs is confirmed by their excellent stability under continuous 1 h electron irradiation in high-resolution transmission electron microscope inspection. It is believed that these results mark an important milestone in realizing nonblinking single photon emission in semiconductor QDs.

Harnessing 2D Ruddlesden-Popper Perovskite with Polar Organic Cation for Ultrasensitive Multibit Nonvolatile Transistor-Type Photomemristors.

Photomemristors have been regarded as one of the most promising candidates for next-generation hardware-based neuromorphic computing due to their potentials of fast data transmission and low power consumption. However, intriguingly, so far, photomemristors seldom display truly nonvolatile memory characteristics with high light sensitivity. Herein, we demonstrate ultrasensitive photomemristors utilizing two-dimensional (2D) Ruddlesden-Popper (RP) perovskites with a highly polar donor-acceptor-type push-pull organic cation, 4-(5-(2-aminoethyl)thiophen-2-yl)benzonitrile+ (EATPCN+), as charge-trapping layers. High linearity and almost zero-decay retention are observed in (EATPCN)2PbI4 devices, which are very distinct from that of the traditional 2D RP perovskite devices consisting of nonpolar organic cations, such as phenethylamine+ (PEA+) and octylamine+ (OA+), and traditional 3D perovskite devices consisting of methylamine+ (MA+). The 2-fold advantages, including desirable spatial crystal arrangement and engineered energetic band alignment, clarify the mechanism of superior performance in (EATPCN)2PbI4 devices. The optimized (EATPCN)2PbI4 photomemristor also shows a memory window of 87.9 V and an on/off ratio of 106 with a retention time of at least 2.4 × 105 s and remains unchanged after >105 writing-reading-erasing-reading endurance cycles. Very low energy consumptions of 1.12 and 6 fJ for both light stimulation and the reading process of each status update are also demonstrated. The extremely low power consumption and high photoresponsivity were simultaneously achieved. The high photosensitivity surpasses that of a state-of-the-art commercial pulse energy meter by several orders of magnitude. With their outstanding linearity and retention, rabbit images have been rebuilt by (EATPCN)2PbI4 photomemristors, which truthfully render the image without fading over time. Finally, by utilizing the powerful ∼8 bits of nonvolatile potentiation and depression levels of (EATPCN)2PbI4 photomemristors, the accuracies of the recognition tasks of CIFAR-10 image classification and MNIST handwritten digit classification have reached 89% and 94.8%, respectively. This study represents the first report of utilizing a functional donor-acceptor type of organic cation in 2D RP perovskites for high-performance photomemristors with characteristics that are not found in current halide perovskites.

Unleashing the Power of 2D MoS2: In Situ TEM Study of Its Potential as Diffusion Barriers in Ru Interconnects.

This study presents the utilization of MoS2 as a diffusion barrier for metal interconnects, in situ transmission electron microscopy (TEM) observations are employed for comprehensive understanding. The diffusion-blocking ability of MoS2 is discussed by the diffusion and phase transformation between Ru and Si via TEM diffraction and imaging. When the sample is heated to a high temperature such that MoS2 loses the ability to block the diffusion, Si diffuses through the MoS2 into the Ru layer, leading to the formation of Ru2Si3. Both multilayer and monolayer (1L) MoS2 exhibit exceptional diffusion-blocking ability up to 800 °C. Furthermore, plasma-treated 1L-MoS2 shows a slightly low diffusion-blocking temperature of 750 °C, while the dangling bonds in MoS2 improve the interfacial adhesion. These findings suggest that MoS2 holds great potential as a diffusion barrier for metal interconnects.

Toward controllable and predictable synthesis of high-entropy alloy nanocrystals.

High-entropy alloy (HEA) nanocrystals have attracted extensive attention in catalysis. However, there are no effective strategies for synthesizing them in a controllable and predictable manner. With quinary HEA nanocrystals made of platinum-group metals as an example, we demonstrate that their structures with spatial compositions can be predicted by quantitatively knowing the reduction kinetics of metal precursors and entropy of mixing in the nanocrystals under dropwise addition of the mixing five-metal precursor solution. The time to reach a steady state for each precursor plays a pivotal role in determining the structures of HEA nanocrystals with homogeneous alloy and core-shell features. Compared to the commercial platinum/carbon and phase-separated counterparts, the dendritic HEA nanocrystals with a defect-rich surface show substantial enhancement in catalytic activity and durability toward both hydrogen evolution and oxidation. This quantitative study will lead to a paradigm shift in the design of HEA nanocrystals, pushing away from the trial-and-error approach.

Probing the sublimation kinetics of Ag, Ag@TiO2, and Ag@C nanoparticles.

In this study, we used an in situ transmission electron microscopy (TEM) heating system to investigate the sublimation-induced morphological changes of cubic Ag nanoparticles (NPs) and Ag-based core-shell structures and the influence of shell coverage on the thermal stability. In contrast to previous research performed with small Ag nanoparticles (<30 nm), here we found that large-particle Ag NPs (>50 nm) underwent a three-stage sublimation-induced morphological change at 800 °C, in the sequence uniform (I)-nonuniform (II)-uniform (III) sublimation. The (110) and (100) planes were the main sublimation planes during stages I and II. When the reaction reached stage III, the sublimation rate decreased as a result of an increase in the sublimation energy barrier. For core-shell NPs, the sublimation process began with stage II. For Ag NPs presenting TiO2 shells, the sublimation process was initiated at a relatively low temperature (700-750 °C) because of a local heating effect; for Ag NPs with carbon shells, the reaction was suppressed through surface atom passivation, thereby enhancing the thermal stability.

Vacuum-Deposited Inorganic Perovskite Light-Emitting Diodes with External Quantum Efficiency Exceeding 10% via Composition and Crystallinity Manipulation of Emission Layer under High Vacuum.

Although vacuum-deposited metal halide perovskite light-emitting diodes (PeLEDs) have great promise for use in large-area high-color-gamut displays, the efficiency of vacuum-sublimed PeLEDs currently lags that of solution-processed counterparts. In this study, highly efficient vacuum-deposited PeLEDs are prepared through a process of optimizing the stoichiometric ratio of the sublimed precursors under high vacuum and incorporating ultrathin under- and upper-layers for the perovskite emission layer (EML). In contrast to the situation in most vacuum-deposited organic light-emitting devices, the properties of these perovskite EMLs are highly influenced by the presence and nature of the upper- and presublimed materials, thereby allowing us to enhance the performance of the resulting devices. By eliminating Pb° formation and passivating defects in the perovskite EMLs, the PeLEDs achieve an outstanding external quantum efficiency (EQE) of 10.9% when applying a very smooth and flat geometry; it reaches an extraordinarily high value of 21.1% when integrating a light out-coupling structure, breaking through the 10% EQE milestone of vacuum-deposited PeLEDs.

Enhanced Piezocatalytic Activity in Bi1/2Na1/2TiO3 for Water Splitting by Oxygen Vacancy Engineering.

Piezoelectric materials have demonstrated applicability in clean energy production and environmental wastewater remediation through their ability to initiate a number of catalytic reactions. In this study, we used a conventional sol-gel method to synthesize lead-free rhombohedral R3c bismuth sodium titanate (BNT) particles of various sizes. When used as a piezocatalyst to generate H2 through water splitting, the BNT samples provided high production rates (up to 506.70 µmol g-1 h-1). These piezocatalysts also degraded the organic pollutant methylene blue (MB, 20 mg L-1) with high efficiency (up to k = 0.039 min-1), suggesting their potential to treat polluted water. Finally, we found that the piezopotential caused band tilting in the semiconductor and aided charge transfer such that recombination was suppressed and the rate of H2 production increased. The mechanism of piezoelectric catalysis involved oxygen vacancies, the size of the catalyst, and the internal electric field playing important roles to enhance electron-hole separation, which further enhanced the catalysis reactions.

Improved Mass-Transfer Enhances Photo-Driven Dye Degradation and H2 Evolution over a Few-Layer WS2/ZnO Heterostructure.

In this study, we observed the enhanced photocatalytic activity of a few-layer WS2/ZnO (WZ) heterostructure toward dye degradation and H2 production. The few-layer WS2 acted as a co-catalyst that separated photogenerated electron/hole pairs and provided active sites for reactions, leading to the rate of photocatalytic H2 production of WZ being 35% greater than that over the bare ZnO nanoparticles. Moreover, vortex-stirring accelerated the mass-transfer of the reactants, leading to the efficiency of dye photodegradation being 3 times higher than that obtained without high-speed stirring. We observed a similar effect for H2 production, with greater photocatalytic performance arising from the increased mass-transfer of H2 from the catalyst surface to the atmosphere.

In situ TEM observations of void movement in Ag nanowires affecting the electrical properties under biasing.

In this study we investigated the electromigration (EM) of metal electrodes and the effect of stacking faults on the EM in Ag nanowires (NWs). We used the galvanic replacement method to synthesize these NWs by controlling the concentration of silver nitrate. In situ transmission electron microscopy (TEM) revealed the presence of both intrinsic and extrinsic stacking faults in the Ag NWs. We found that planar defects increased the lifetime of the devices with an intrinsic change in the material properties. Our EM measurements involved examinations of the change in electrical resistance (arising from void formation in the NW as a result of electromigration) as well as direct visual observation of the shape (using in situ TEM).

Organic Lead Halide Nanocrystals Providing an Ultra-Wide Color Gamut with Almost-Unity Photoluminescence Quantum Yield.

The most attractive aspect of perovskite nanocrystals (NCs) for optoelectronic applications is their widely tunable emission wavelength, but it has been quite challenging to tune it without sacrificing the photoluminescence quantum yield (PLQY). In this work, we report a facile ligand-optimized ion-exchange (LOIE) method to convert room-temperature spray-synthesized, perovskite parent NCs that emit a saturated green color to NCs capable of emitting colors across the entire visible spectrum. These NCs exhibited exceptionally stable and high PLQYs, particularly for the pure blue (96%) and red (93%) primary colors that are indispensable for display applications. Surprisingly, the blue- and red-emissive NCs obtained using the LOIE method preserved the cubic shape and cubic phase structure that they inherited from their parent NCs, while exhibiting high crystallinity and high color-purity. Together with the parent green-emissive NCs, the obtained blue- and red-emissive NCs provided a very wide color gamut, corresponding to a Digital Cinema Initiatives-P3 of 140% or an International Telecommunication Union Recommendation BT.2020 of 102%. With the superior optical merits of these LOIE-manipulated NCs, a corresponding color conversion luminescence device provided a high external quantum efficiency (10.5%) and extremely high brightness (970 000 cd/m2). This study provides a valid route toward highly stable, extremely emissive, and panchromatic perovskite NCs with potential use in a variety of future optoelectronic applications.

An Ultrasensitive Gateless Photodetector Based on the 2D Bilayer MoS2-1D Si Nanowire-0D Ag Nanoparticle Hybrid Structure.

Atomically thin transition metal dichalcogenides (TMDC) have received much attention due to their wide variety of optical and electronic properties. Among various TMDC materials, molybdenum disulfide (MoS2) has been intensely studied owing to its potential applications in nanoelectronics and optoelectronics. However, two-dimensional MoS2 photodetectors suffer from low responsivity due to low optical cross section. Combining MoS2 with plasmonic nanostructures can drastically increase scattering cross section and enhance local light-matter interaction. Moreover, suspended MoS2 has been shown to exhibit higher photoluminescence intensity and strong photogating effect, which can be employed in photodetectors. Herein, we propose an approach to utilize plasmonic nanostructures and physical suspension for 2D MoS2 photosensing enhancement by hybridizing 2D bilayer MoS2, 1D silicon nanowires, and 0D silver nanoparticles. The hybrid structure shows a gateless responsivity of 402.4 A/W at a wavelength of 532 nm, which represents the highest value among the ever reported gateless plasmonic MoS2 photodetector. The great responsivity and large active area results in an exceptional detectivity of 2.34 × 1012 Jones. This study provides a new approach for designing high-performance 2D TMDC-based optoelectronic devices.

ZnO Nanowires on Single-Crystalline Aluminum Film Coupled with an Insulating WO3 Interlayer Manifesting Low Threshold SPP Laser Operation.

ZnO nanowire-based surface plasmon polariton (SPP) nanolasers with metal-insulator-semiconductor hierarchical nanostructures have emerged as potential candidates for integrated photonic applications. In the present study, we demonstrated an SPP nanolaser consisting of ZnO nanowires coupled with a single-crystalline aluminum (Al) film and a WO3 dielectric interlayer. High-quality ZnO nanowires were prepared using a vapor phase transport and condensation deposition process via catalyzed growth. Subsequently, prepared ZnO nanowires were transferred onto a single-crystalline Al film grown by molecular beam epitaxy (MBE). Meanwhile, a WO3 dielectric interlayer was deposited between the ZnO nanowires and Al film, via e-beam technique, to prevent the optical loss from dominating the metallic region. The metal-oxide-semiconductor (MOS) structured SPP laser, with an optimal WO3 insulating layer thickness of 3.6 nm, demonstrated an ultra-low threshold laser operation (lasing threshold of 0.79 MW cm-2). This threshold value was nearly eight times lower than that previously reported in similar ZnO/Al2O3/Al plasmonic lasers, which were ≈2.4 and ≈3 times suppressed compared to the SPP laser, with WO3 insulating layer thicknesses of 5 nm and 8 nm, respectively. Such suppression of the lasing threshold is attributed to the WO3 insulating layer, which mediated the strong confinement of the optical field in the subwavelength regime.

Intelligent Identification of MoS2 Nanostructures with Hyperspectral Imaging by 3D-CNN.

Increasing attention has been paid to two-dimensional (2D) materials because of their superior performance and wafer-level synthesis methods. However, the large-area characterization, precision, intelligent automation, and high-efficiency detection of nanostructures for 2D materials have not yet reached an industrial level. Therefore, we use big data analysis and deep learning methods to develop a set of visible-light hyperspectral imaging technologies successfully for the automatic identification of few-layers MoS2. For the classification algorithm, we propose deep neural network, one-dimensional (1D) convolutional neural network, and three-dimensional (3D) convolutional neural network (3D-CNN) models to explore the correlation between the accuracy of model recognition and the optical characteristics of few-layers MoS2. The experimental results show that the 3D-CNN has better generalization capability than other classification models, and this model is applicable to the feature input of the spatial and spectral domains. Such a difference consists in previous versions of the present study without specific substrate, and images of different dynamic ranges on a section of the sample may be administered via the automatic shutter aperture. Therefore, adjusting the imaging quality under the same color contrast conditions is unnecessary, and the process of the conventional image is not used to achieve the maximum field of view recognition range of ~1.92 mm2. The image resolution can reach ~100 nm and the detection time is 3 min per one image.

Surfactant-free synthesis of ultralong silver nanowires for durable transparent conducting electrodes.

The present study employed the surfactant-free growth of ultralong (∼50 µm) silver nanowires (AgNWs) with a high aspect ratio (more than 1000) by galvanic replacement. AgNW conducting films were fabricated as electrodes using drop-casting. The AgNW film had 90% transmittance to 550 nm light with a sheet resistance of 232 Ω sq-1. Further, the flexibility test of the transparent flexible AgNW/MoS2 device array indicated that the variation of the current was within 5% when a strain of 0.5% was applied to the device; additionally, the device showed a 13% decrease in current after experiencing 50 000 bending cycles. This study indicated that the ultralong AgNWs synthesized using galvanic replacement have potential for applications as transparent and flexible electrodes.

Layer-Dependent and In-Plane Anisotropic Properties of Low-Temperature Synthesized Few-Layer PdSe2 Single Crystals.

Palladium diselenide (PdSe2), a peculiar noble metal dichalcogenide, has emerged as a new two-dimensional material with high predicted carrier mobility and a widely tunable band gap for device applications. The inherent in-plane anisotropy endowed by the pentagonal structure further renders PdSe2 promising for novel electronic, photonic, and thermoelectric applications. However, the direct synthesis of few-layer PdSe2 is still challenging and rarely reported. Here, we demonstrate that few-layer, single-crystal PdSe2 flakes can be synthesized at a relatively low growth temperature (300 °C) on sapphire substrates using low-pressure chemical vapor deposition (CVD). The well-defined rectangular domain shape and precisely determined layer number of the CVD-grown PdSe2 enable us to investigate their layer-dependent and in-plane anisotropic properties. The experimentally determined layer-dependent band gap shrinkage combined with first-principle calculations suggest that the interlayer interaction is weaker in few-layer PdSe2 in comparison with that in bulk crystals. Field-effect transistors based on the CVD-grown PdSe2 also show performances comparable to those based on exfoliated samples. The low-temperature synthesis method reported here provides a feasible approach to fabricate high-quality few-layer PdSe2 for device applications.

Photosynthesis-inspired H2 generation using a chlorophyll-loaded liposomal nanoplatform to detect and scavenge excess ROS.

A disturbance of reactive oxygen species (ROS) homeostasis may cause the pathogenesis of many diseases. Inspired by natural photosynthesis, this work proposes a photo-driven H2-evolving liposomal nanoplatform (Lip NP) that comprises an upconversion nanoparticle (UCNP) that is conjugated with gold nanoparticles (AuNPs) via a ROS-responsive linker, which is encapsulated inside the liposomal system in which the lipid bilayer embeds chlorophyll a (Chla). The UCNP functions as a transducer, converting NIR light into upconversion luminescence for simultaneous imaging and therapy in situ. Functioning as light-harvesting antennas, AuNPs are used to detect the local concentration of ROS for FRET biosensing, while the Chla activates the photosynthesis of H2 gas to scavenge local excess ROS. The results thus obtained indicate the potential of using the Lip NPs in the analysis of biological tissues, restoring their ROS homeostasis, possibly preventing the initiation and progression of diseases.

Probing the photovoltaic properties of Ga-doped CdS-Cu2S core-shell heterostructured nanowire devices.

In this study Ga-doped cadmium sulfide (CdS) nanowires (NWs) were grown through chemical vapor deposition. The carrier conductivities of the CdS NWs improved after the incorporation of Ga; moreover, the conductivities of the CdS NWs increased upon increasing the amount of the Ga source. Using a cation exchange method, these CdS NWs served as the source material for the preparation of Cu2S-CdS p-n heterostructured NWs. The short-circuit current, open-circuit voltage, fill factor, and power conversion efficiency of the best-performing Cu2S-CdS NW photovoltaic device were 0.152 nA, 0.245 V, 44.5%, and 0.405%, respectively, when illuminated under AM 1.5 solar light. This study demonstrates the possibility of modulating not only the properties of CdS NWs through the incorporation of dopant Ga atoms but also the photovoltaic properties of Cu2S-CdS p-n heterostructured NW devices, paving the way for the exploitation of nanostructures within optoelectronics.

Early identification of esophageal squamous neoplasm by hyperspectral endoscopic imaging.

Esophageal squamous neoplasm presents a spectrum of different diatheses. A precise assessment for individualized treatment depends on the accuracy of the initial diagnosis. Detection relies on comprehensive and accurate white-light, iodine staining, and narrow-band imaging endoscopy. These methods have limitations in addition to its invasive nature and the potential risks related to the method. These limitations include difficulties in precise tumor delineation to enable complete resection, inflammation and malignancy differentiation, and stage determination. The resolution of these problems depends on the surgeon's ability and experience with available technology for visualization and resection. We proposed a method for identifying early esophageal cancerous lesion by endoscopy and hyperspectral endoscopic imaging. Experimental result shows the characteristic spectrum of a normal esophagus, precancerous lesion, canceration, and intraepithelial papillary capillary loop can be identified through principal component score chart. The narrow-band imaging (NBI) image shows remarkable spectral characteristic distribution, and the sensitivity and specificity of the proposed method are higher than those of other methods by ~0.8 and ~0.88, respectively. The proposed method enables the accurate visualization of target organs, it may be useful to capsule endoscope and telemedicine, which requires highly precise images for diagnosis.

Efficient Self-Driven Photodetectors Featuring a Mixed-Dimensional van der Waals Heterojunction Formed from a CdS Nanowire and a MoTe2 Flake.

Heterojunctions formed from low-dimensional materials can result in photovoltaic and photodetection devices displaying exceptional physical properties and excellent performance. Herein, a mixed-dimensional van der Waals (vdW) heterojunction comprising a 1D n-type Ga-doped CdS nanowire and a 2D p-type MoTe2 flake is demonstrated; the corresponding photovoltaic device exhibits an outstanding conversion efficiency of 15.01% under illumination with white light at 650 µW cm-2 . A potential difference of 80 meV measured, using Kelvin probe force microscopy, at the CdS-MoTe2 interface confirms the separation and accumulation of photoexcited carriers upon illumination. Moreover, the photodetection characteristics of the vdW heterojunction device at zero bias reveal a rapid response time (<50 ms) and a photoresponsivity that are linearly proportional to the power density of the light. Interestingly, the response of the vdW heterojunction device is negligible when illuminated at 580 nm; this exceptional behavior is presumably due to the rapid rate of recombination of the photoexcited carriers of MoTe2 . Such mixed-dimensional vdW heterojunctions appear to be novel design elements for efficient photovoltaic and self-driven photodetection devices.