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.

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.

Time-evolution of the electrical characteristics of MoS2 field-effect transistors after electron beam irradiation.

As the feature sizes of devices decrease to the nanoscale, electron microscopy and lithography will become increasingly essential techniques for fabrication and inspection. In this study, we probed the memory effects of MoS2 field-effect transistors (FETs) subjected to electron beam (e-beam) irradiation; after fabricating the devices on 300 nm SiO2/Si substrates, we irradiated the MoS2 FETs with various doses of irradiation from a 30 kV e-beam. The threshold voltage shifted to the negative side and the mobility increased-a so-called memory effect-upon increasing the e-beam dose. These changes resulted from positively charged oxide traps, formed upon e-beam irradiation, in the gate oxide layer. Interestingly, the electrical characteristics of the MoS2 FETs after e-beam irradiation continued to change upon aging: the threshold voltage shifted toward the positive side and the mobility decreased, suggesting that the dominant mechanism changed from the presence of positively charged oxide traps to the presence of negatively charged interface traps. Notably, the threshold voltage shifts of the MoS2 FETs could be retained for one or two days. This behavior should be useful for preparing property-adjustable nanodevices, with particular potential for applications in multi-level memory devices.

Nano-structure ZnO/Cu2O photoelectrochemical and self-powered biosensor for esophageal cancer cell detection.

The p-n heterojunction photoelectrochemical biosensor, which comprises a p-type Cu2O film formed by electrochemical deposition and n-type ZnO nanorods formed by the hydrothermal method, is prone to photoelectrochemical reactions and self-powered. Four types of human esophageal cancer cells (ECCs) were detected by this biosensor without requiring an extra bias voltage. The measured photocurrent values of high invasion capacity cancer cells was consistently 2 times higher than those measured by a slight invasion capacity cancer cells. The response time, which was about 0.5 s, allowed repeated measurement.

All-reflective RGB LED flashlight design for effective color mixing.

Red, green, and blue (RGB) light-emitting diode (LED) is a narrow-band light source that can improve visual contrast, and thus, can be used for special illumination. In this study, three RGB LEDs, each provided with two reflective mirrors, are used to design an all-reflective color temperature-adjustable LED flashlight. The LED flashlight features an adjustable color temperature ranging from 2000 K to 6500 K, a uniformity of illuminance of 0.68, an average difference of uniformity of approximately 25%, and a color uniformity of 0.0042.

Selective growth of ZnO nanorods on hydrophobic Si nanorod arrays.

In this paper we describe the selective growth of ZnO nanorods (NRs) on top of hydrophobic Si NR arrays. The periodic Si NR arrays, prepared through electroless chemical etching and HF treatment, functioned as hydrophobic substrates. Droplets containing ZnO seeds could be positioned on the Si NR arrays, causing the ZnO seeds to deposit selectively upon them, with n-ZnO NR/p-Si NR array heterojunctions ultimately forming after hydrothermal growth of ZnO NRs. Because of compensation for the difference in refractive index between air and the Si substrate, the n-ZnO NR/p-Si NR arrays exhibited excellent absorption ability in the visible range. Devices based on these n-ZnO NR/p-Si NR array heterojunctions displayed not only rectifying behavior but also photovoltaic effects when illuminated with UV light. The low temperature and low cost of this fabrication process suggest that the selective growth of n-ZnO NRs on p-Si NR arrays might allow such structures to have diverse applications in optoelectronics.

Complete replacement of metal in metal oxide nanowires via atomic diffusion: In/ZnO case study.

Atomic diffusion is a fundamental process that dictates material science and engineering. Direct visualization of atomic diffusion process in ultrahigh vacuum in situ TEM could comprehend the fundamental information about metal-semiconductor interface dynamics, phase transitions, and different nanostructure growth phenomenon. Here, we demonstrate the in situ TEM observations of the complete replacement of ZnO nanowire by indium with different growth directions. In situ TEM analyses reveal that the diffusion processes strongly depend and are dominated by the interface dynamics between indium and ZnO. The diffusion exhibited a distinct ledge migration by surface diffusion at [001]-ZnO while continuous migration with slight/no ledges by inner diffusion at [100]-ZnO. The process is explained based on thermodynamic evaluation and growth kinetics. The results present the potential possibilities to completely replace metal-oxide semiconductors with metal nanowires without oxidation and form crystalline metal nanowires with precise epitaxial metal-semiconductor atomic interface. Formation of such single crystalline metal nanowire without oxidation by diffusion to the metal oxide is unique and is crucial in nanodevice performances, which is rather challenging from a manufacturing perspective of 1D nanodevices.

All-color plasmonic nanolasers with ultralow thresholds: autotuning mechanism for single-mode lasing.

We report on the first demonstration of broadband tunable, single-mode plasmonic nanolasers (spasers) emitting in the full visible spectrum. These nanolasers are based on a single metal-oxide-semiconductor nanostructure platform comprising of InGaN/GaN semiconductor nanorods supported on an Al2O3-capped epitaxial Ag film. In particular, all-color lasing in subdiffraction plasmonic resonators is achieved via a novel mechanism based on a property of weak size dependence inherent in spasers. Moreover, we have successfully reduced the continuous-wave (CW) lasing thresholds to ultrasmall values for all three primary colors and have clearly demonstrated the possibility of "thresholdless" lasing for the blue plasmonic nanolaser.

Low-frequency electrical fluctuations in metal-nanowire-metal phototransistors.

Using low-frequency noise spectroscopy to explore the physical origins of electrical fluctuations in ZnO nanowire (NW) phototransistors featuring a metal-NW-metal configuration, we have found that bulk mobility scatterings gave rise to electrical fluctuations in the low-gate voltage (V G) regime, providing values of Hooge's constant in the ranges 6.0-9.6 × 10(-3) and 1.9-2.2 × 10(-1) in the dark and under UV excitation, respectively. When moving into the higher V G regime, we assign the electrical fluctuations to an interaction process involving trapping and detrapping of channel carriers by charge traps located near the NW-dielectric interface, suggesting that the mechanism of the electrical fluctuation transitioned from bulk NW-dominated to NW/dielectric interface-dominated regimes. We have also addressed the effective density of interface traps responsible for the electrical fluctuations in the high-V G region. This report provides physical insight into the origins of electrical fluctuations in NW phototransistors.

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.

A catalyst family of high-entropy alloy atomic layers with square atomic arrangements comprising iron- and platinum-group metals.

We report a catalyst family of high-entropy alloy (HEA) atomic layers having three elements from iron-group metals (IGMs) and two elements from platinum-group metals (PGMs). Ten distinct quinary compositions of IGM-PGM-HEA with precisely controlled square atomic arrangements are used to explore their impact on hydrogen evolution reaction (HER) and hydrogen oxidation reaction (HOR). The PtRuFeCoNi atomic layers perform enhanced catalytic activity and durability toward HER and HOR when benchmarked against the other IGM-PGM-HEA and commercial Pt/C catalysts. Operando synchrotron x-ray absorption spectroscopy and density functional theory simulations confirm the cocktail effect arising from the multielement composition. This effect optimizes hydrogen-adsorption free energy and contributes to the remarkable catalytic activity observed in PtRuFeCoNi. In situ electron microscopy captures the phase transformation of metastable PtRuFeCoNi during the annealing process. They transform from random atomic mixing (25°C), to ordered L10 (300°C) and L12 (400°C) intermetallic, and finally phase-separated states (500°C).

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.

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.

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.

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.

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.

Superior field emissions from boron-doped nanocrystalline diamond compared to boron-doped microcrystalline diamond.

Boron-doped microcrystalline diamond (BMD) and nanocrystalline diamond (BND) thin films were grown on Si substrates by microwave-assisted chemical vapor deposition, and their field emission properties were evaluated. BND exhibited a lower turn-on field and higher field enhancement factor than BMD. Furthermore, in a long-term emission stability test, BND showed only a 4% increase in the current density after 12 h of emission, whereas the current density of BMD decreased by - 59%. These results indicate that BND is a more stable and viable current emitter than BMD.

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.

An ordered Si nanowire with NiSi2 tip arrays as excellent field emitters.

A method was developed to grow ordered silicon nanowire with NiSi(2) tip arrays by reacting nickel thin films on silica-coated ordered Si nanowire (NW) arrays. The coating of thin silica shell on Si NW arrays has the effect of limiting the diffusion of nickel during the silicidation process to achieve the single crystalline NiSi(2) NWs. In the meantime, it relieves the distortion of the NWs caused by the strain associated with formation of NiSi(2) to maintain the straightness of the nanowire and the ordering of the arrays. Other nickel silicide phases such as Ni(2)Si and NiSi were obtained if the silicidation processes were conducted on the ordered Si NWs without a thin silica shell. Excellent field emission properties were found for NiSi(2)/Si NW arrays with a turn on field of 0.82 V µm(-1) and a threshold field of 1.39 V µm(-1). The field enhancement factor was calculated to be about 2440. The stability test showed a fluctuation of about 7% with an applied field of 2.6 V µm(-1) for a period of 24 h. The excellent field emission characteristics are attributed to the well-aligned and highly ordered arrangement of the single crystalline NiSi(2)/Si heterostructure field emitters. In contrast to other growth methods, the present growth of ordered nickel silicide/Si NWs on silicon is compatible with silicon nanoelectronics device processes, and also provides a facile route to grow other well-aligned metal silicide NW arrays. The advantages will facilitate its applications as field emission devices.