Resonantly hybridized excitons in moiré superlattices in van der Waals heterostructures.

Atomically thin layers of two-dimensional materials can be assembled in vertical stacks that are held together by relatively weak van der Waals forces, enabling coupling between monolayer crystals with incommensurate lattices and arbitrary mutual rotation1,2. Consequently, an overarching periodicity emerges in the local atomic registry of the constituent crystal structures, which is known as a moiré superlattice3. In graphene/hexagonal boron nitride structures4, the presence of a moiré superlattice can lead to the observation of electronic minibands5-7, whereas in twisted graphene bilayers its effects are enhanced by interlayer resonant conditions, resulting in a superconductor-insulator transition at magic twist angles8. Here, using semiconducting heterostructures assembled from incommensurate molybdenum diselenide (MoSe2) and tungsten disulfide (WS2) monolayers, we demonstrate that excitonic bands can hybridize, resulting in a resonant enhancement of moiré superlattice effects. MoSe2 and WS2 were chosen for the near-degeneracy of their conduction-band edges, in order to promote the hybridization of intra- and interlayer excitons. Hybridization manifests through a pronounced exciton energy shift as a periodic function of the interlayer rotation angle, which occurs as hybridized excitons are formed by holes that reside in MoSe2 binding to a twist-dependent superposition of electron states in the adjacent monolayers. For heterostructures in which the monolayer pairs are nearly aligned, resonant mixing of the electron states leads to pronounced effects of the geometrical moiré pattern of the heterostructure on the dispersion and optical spectra of the hybridized excitons. Our findings underpin strategies for band-structure engineering in semiconductor devices based on van der Waals heterostructures9.

Author Correction: Resonantly hybridized excitons in moiré superlattices in van der Waals heterostructures.

An Amendment to this paper has been published and can be accessed via a link at the top of the paper.

Evolution of Local Structural Motifs in Colloidal Quantum Dot Semiconductor Nanocrystals Leading to Nanofaceting.

Colloidal nanocrystals (NCs) have shown remarkable promise for optoelectronics, energy harvesting, photonics, and biomedical imaging. In addition to optimizing quantum confinement, the current challenge is to obtain a better understanding of the critical processing steps and their influence on the evolution of structural motifs. Computational simulations and electron microscopy presented in this work show that nanofaceting can occur during nanocrystal synthesis from a Pb-poor environment in a polar solvent. This could explain the curved interfaces and the olivelike-shaped NCs observed experimentally when these conditions are employed. Furthermore, the wettability of the PbS NCs solid film can be further modified via stoichiometry control, which impacts the interface band bending and, therefore, processes such as multiple junction deposition and interparticle epitaxial growth. Our results suggest that nanofaceting in NCs can become an inherent advantage when used to modulate band structures beyond what is traditionally possible in bulk crystals.

Pre-Anodized Graphite Pencil Electrode Coated with a Poly(Thionine) Film for Simultaneous Sensing of 3-Nitrophenol and 4-Nitrophenol in Environmental Water Samples.

A very simple, as well as sensitive and selective, sensing protocol was developed on a pre-anodized graphite pencil electrode surface coated using poly(thionine) (APGE/PTH). The poly(thionine) coated graphite pencil was then used for simultaneous sensing of 3-nitrophenol (3-NP) and 4-nitrophenol (4-NP). The poly(thionine) coated electrode exhibited an enhanced electrocatalytic property towards nitrophenol (3-NP and 4-NP) reduction. Redox peak potential and current of both nitrophenols were found well resolved and their simultaneous analysis was studied. Under optimized experimental conditions, APGE/PTH showed a long linear concentration range from 20 to 230 nM and 15 nM to 280 nM with a calculated limit of detection (LOD) of 4.5 and 4 nM and a sensitivity of 22.45 µA/nM and 27.12 µA/nM for 3-NP and 4-NP, respectively. Real sample analysis using the prepared sensor was tested with different environmental water samples and the sensors exhibited excellent recovery results in the range from 98.16 to 103.43%. Finally, the sensor exposed an promising selectivity, stability, and reproducibility towards sensing of 3-NP and 4-NP.

Plasmonic Core-Shell-Satellites with Abundant Electromagnetic Hotspots for Highly Sensitive and Reproducible SERS Detection.

In this work, we develop a Ag@Al2O3@Ag plasmonic core-shell-satellite (PCSS) to achieve highly sensitive and reproducible surface-enhanced Raman spectroscopy (SERS) detection of probe molecules. To fabricate PCSS nanostructures, we employ a simple hierarchical dewetting process of Ag films coupled with an atomic layer deposition (ALD) method for the Al2O3 shell. Compared to bare Ag nanoparticles, several advantages of fabricating PCSS nanostructures are discovered, including high surface roughness, high density of nanogaps between Ag core and Ag satellites, and nanogaps between adjacent Ag satellites. Finite-difference time-domain (FDTD) simulations of the PCSS nanostructure confirm an enhancement in the electromagnetic field intensity (hotspots) in the nanogap between the Ag core and the satellite generated by the Al2O3 shell, due to the strong core-satellite plasmonic coupling. The as-prepared PCSS-based SERS substrate demonstrates an enhancement factor (EF) of 1.7 × 107 and relative standard deviation (RSD) of ~7%, endowing our SERS platform with highly sensitive and reproducible detection of R6G molecules. We think that this method provides a simple approach for the fabrication of PCSS by a solid-state technique and a basis for developing a highly SERS-active substrate for practical applications.

Field effect transistors and phototransistors based upon p-type solution-processed PbS nanowires.

We demonstrate the fabrication of solution processed highly crystalline p-type PbS nanowires via the oriented attachment of nanoparticles. The analysis of single nanowire field effect transistor (FET) devices revealed a hole conduction behaviour with average mobilities greater than 30 cm2 V-1 s-1, which is an order of magnitude higher than that reported to date for p-type PbS colloidal nanowires. We have investigated the response of the FETs to near-infrared light excitation and show herein that the nanowires exhibited gate-dependent photo-conductivities, enabling us to tune the device performances. The responsivity was found to be greater than 104 A W-1 together with a detectivity of 1013 Jones, which benefits from a photogating effect occurring at negative gate voltages. These encouraging detection parameters are accompanied by relatively short switching times of 15 ms at positive gate voltages, resulting from a combination of the standard photoconduction and the high crystallinity of the nanowires. Collectively, these results indicate that solution-processed PbS nanowires are promising nanomaterials for infrared photodetectors as well as p-type nanowire FETs.

Imaging of Interlayer Coupling in van der Waals Heterostructures Using a Bright-Field Optical Microscope.

Vertically stacked atomic layers from different layered crystals can be held together by van der Waals forces, which can be used for building novel heterostructures, offering a platform for developing a new generation of atomically thin, transparent, and flexible devices. The performance of these devices is critically dependent on the layer thickness and the interlayer electronic coupling, influencing the hybridization of the electronic states as well as charge and energy transfer between the layers. The electronic coupling is affected by the relative orientation of the layers as well as by the cleanliness of their interfaces. Here, we demonstrate an efficient method for monitoring interlayer coupling in heterostructures made from transition metal dichalcogenides using photoluminescence imaging in a bright-field optical microscope. The color and brightness in such images are used here to identify mono- and few-layer crystals and to track changes in the interlayer coupling and the emergence of interlayer excitons after thermal annealing in heterobilayers composed of mechanically exfoliated flakes and as a function of the twist angle in atomic layers grown by chemical vapor deposition. Material and crystal thickness sensitivity of the presented imaging technique makes it a powerful tool for characterization of van der Waals heterostructures assembled by a wide variety of methods, using combinations of materials obtained through mechanical or chemical exfoliation and crystal growth.

Strain-Mediated Interlayer Coupling Effects on the Excitonic Behaviors in an Epitaxially Grown MoS2/WS2 van der Waals Heterobilayer.

van der Waals heterostructures composed of two different monolayer crystals have recently attracted attention as a powerful and versatile platform for studying fundamental physics, as well as having great potential in future functional devices because of the diversity in the band alignments and the unique interlayer coupling that occurs at the heterojunction interface. However, despite these attractive features, a fundamental understanding of the underlying physics accounting for the effect of interlayer coupling on the interactions between electrons, photons, and phonons in the stacked heterobilayer is still lacking. Here, we demonstrate a detailed analysis of the strain-dependent excitonic behavior of an epitaxially grown MoS2/WS2 vertical heterostructure under uniaxial tensile and compressive strain that enables the interlayer interactions to be modulated along with the electronic band structure. We find that the strain-modulated interlayer coupling directly affects the characteristic combined vibrational and excitonic properties of each monolayer in the heterobilayer. It is further revealed that the relative photoluminescence intensity ratio of WS2 to MoS2 in our heterobilayer increases monotonically with tensile strain and decreases with compressive strain. We attribute the strain-dependent emission behavior of the heterobilayer to the modulation of the band structure for each monolayer, which is dictated by the alterations in the band gap transitions. These findings present an important pathway toward designing heterostructures and flexible devices.

Defect-mediated modulation of optical properties in vertically aligned ZnO nanowires via substrate-assisted Ga incorporation.

We report the defect-mediated modulation of optical properties in vertically aligned ZnO nanowires via a substrate-assisted Ga incorporation method. We find that Ga atoms were incorporated into a ZnO lattice via the diffusion of liquid Ga droplets from a GaAs substrate in which as-grown ZnO nanowires were placed face down on the GaAs substrate and annealed at 650 °C. Based on structural and compositional characterization, it was confirmed that the substrate-assisted incorporation of Ga can induce a high defect density in vertically aligned ZnO nanowires grown on a Si substrate. In addition, distinct differences in optical properties between as-grown and Ga-incorporated ZnO nanowires were found and discussed in terms of defect-mediated modifications of energy band states, which were associated with the generation and recombination of photoexcited carriers. Furthermore, it was clearly observed that for Ga-incorporated ZnO nanowires, the photocurrent rise and decay processes were slower and the photocurrents under UV illumination were significantly higher compared with as-grown nanowires.

Tunable threshold voltage of an n-type Si nanowire ferroelectric-gate field effect transistor for high-performance nonvolatile memory applications.

We successfully fabricated ferroelectric-gate field effect transistor (FEFET)-based nonvolatile memory devices using an n-type Si nanowire coated with omega-shaped-gate organic ferroelectric poly(vinylidene fluoride-trifluoroethylene) via a low-temperature fabrication process. Our FEFET memory devices with controllable threshold voltage via adjustment of the doping concentration exhibit excellent memory characteristics with ultra-low ON state power dissipation (≤3 nW), a large modulation in channel conductance between the ON and OFF states exceeding 10(5), a long retention time of over 3 × 10(4) s and a high endurance of over 10(5) programming cycles whilst maintaining an I ON/I OFF ratio higher than 10(3). This result may be promising for next-generation nonvolatile memory on flexible substrate applications.

Iron-nitrogen-doped mesoporous tungsten carbide nanostructures as oxygen reduction electrocatalysts.

Since Pt-based catalysts have the disadvantages of high cost, large overpotential loss, and limited long-term stability, there have been various promising alternatives to Pt-based catalysts to improve the catalytic activity towards the oxygen reduction reaction (ORR). We have synthesized iron-nitrogen-doped mesoporous tungsten carbide catalysts (WC-m-FT) by pyrolysis of well-ordered mesoporous tungsten carbides with iron porphyrin. WC-m-FT exhibits excellent ORR catalytic activity in an alkaline medium, i.e. a high electron-transfer number as well as superior stability and methanol tolerance. The improved activity and stability of WC-m-FT are ascribed to iron-containing catalytic active sites surrounded by nitrogen species and the well-defined mesoporous tungsten carbide structure.

Hydrogen-induced morphotropic phase transformation of single-crystalline vanadium dioxide nanobeams.

We report a morphotropic phase transformation in vanadium dioxide (VO2) nanobeams annealed in a high-pressure hydrogen gas, which leads to the stabilization of metallic phases. Structural analyses show that the annealed VO2 nanobeams are hexagonal-close-packed structures with roughened surfaces at room temperature, unlike as-grown VO2 nanobeams with the monoclinic structure and with clean surfaces. Quantitative chemical examination reveals that the hydrogen significantly reduces oxygen in the nanobeams with characteristic nonlinear reduction kinetics which depend on the annealing time. Surprisingly, the work function and the electrical resistance of the reduced nanobeams follow a similar trend to the compositional variation due mainly to the oxygen-deficiency-related defects formed at the roughened surfaces. The electronic transport characteristics indicate that the reduced nanobeams are metallic over a large range of temperatures (room temperature to 383 K). Our results demonstrate the interplay between oxygen deficiency and structural/electronic phase transitions, with implications for engineering electronic properties in vanadium oxide systems.

Hierarchically Interconnected 3D Catalyst Structure of Porous Multi-Metal Oxide Nanofibers for High-Performance Li-O2 Batteries.

Non-aqueous lithium-oxygen batteries (LOBs) have emerged as a promising candidate due to their high theoretical energy density and eco-friendly cathode reaction materials. However, LOBs still suffer from high overpotential and poor cycling stability resulting from difficulties in the decomposition of discharge reaction Li2 O2 products. Here, a 3D open network catalyst structure is proposed based on highly-thin and porous multi-metal oxide nanofibers (MMONFs) developed by a facile electrospinning approach coupled with a heat treatment process. The developed hierarchically interconnected 3D porous MMONFs catalyst structure with high specific surface area and porosity shows the enhanced electrochemical reaction kinetics associated with Li2 O2 formation and decomposition on the cathode surface during the charge and discharge processes. The uniquely assembled cathode materials with MMONFs exhibit excellent electrochemical performance with energy efficiency of 82% at a current density of 50 mA g-1 and a long-term cycling stability over 100 cycles at 200 mA g-1 with a cut-off capacity of 500 mAh g-1 . Moreover, the optimized cathode materials exhibit a remarkable energy density of 1013 Wh kg-1 at the 100th discharge and charge cycle, which is nearly four times higher than that of C/NMC721, which has the highest energy density among the cathode materials currently used in electric vehicles.

Stabilization of Lattice Oxygen Evolution Reactions in Oxophilic Ce-Mediated Bi/BiCeO1.8H Electrocatalysts for Efficient Anion Exchange Membrane Water Electrolyzers.

The lattice oxygen mechanism (LOM) offers an efficient reaction pathway for oxygen evolution reactions (OERs) in energy storage and conversion systems. Owing to the involvement of active lattice oxygen enhancing electrochemical activity, addressing the structural and electrochemical stabilities of LOM materials is crucial. Herein, a heterostructure (Bi/BiCeO1.8H) containing abundant under-coordinated oxygen atoms having oxygen nonbonding states is synthesized by a simple electrochemical deposition method. Given the difference in reduction potentials between Bi and Ce, partially reduced Bi nanoparticles and surrounding under-coordinated oxygen atoms are generated in BiCeO1.8H. It is found that the lattice oxygen can be activated as a reactant of the OER when the valence state of Bi increases to Bi5+, leading to increased metal-oxygen covalency and that the oxophilic Ce3+/4+ redox couple can maintain the Bi nanoparticles and surrounding under-coordinated oxygen atoms by preventing over-oxidation of Bi. The anion exchange membrane water electrolyzer with Bi/BiCeO1.8H exhibits a low cell voltage of 1.79 V even at a high practical current density of 1.0 A cm-2. Furthermore, the cell performance remains significantly stable over 100 h with only a 2.2% increase in the initial cell voltage, demonstrating sustainable lattice oxygen redox.

Strain effects in a single ZnO microwire with wavy configurations.

We investigate strain-induced optical modulation in a ZnO microwire with wavy geometries induced by mechanical strains. Curved sections of the wavy ZnO microwire show red-/blue-shifts of near-band-edge emission and broadening of full width at half maximum in cathodoluminescence spectra along the length of the wavy ZnO microwire, compared with straight sections. The observed variations indicate that local strains in the wavy ZnO microwire lead to strain-dependent local changes of its energy band structure. The local bending curvature calculations using a geometric model also provide correlation between the shift of the near-band-edge emission peaks and the bending strain.

Luminance behavior of lithium-doped ZnO nanowires with p-type conduction characteristics.

The present study describes the room-temperature cathodeluminescence (CL) and temperature-dependent photoluminescence (PL) properties of p-type lithium (Li)-doped zinc oxide (ZnO) nanowires (NWs) grown by hydrothermal doping and post-annealing processes. A ZnO thin film was used as a seed layer in NW growth. The emission wavelengths and intensities of undoped ZnO NWs and p-type Li-doped ZnO NWs were analyzed for comparison. CL and PL observations of post-annealed p-type Li-doped ZnO NWs clearly exhibited a dominant sharp band-edge emission. Finally, a n-type ZnO thin film/p-type annealed Li-doped ZnO NW homojunction diode was prepared to confirm the p-type conduction of annealed Li-doped ZnO NWs as well as the structural properties measured by transmission electron microscopy.

p-Type polymer-hybridized high-performance piezoelectric nanogenerators.

Enhancing the output power of a nanogenerator is essential in applications as a sustainable power source for wireless sensors and microelectronics. We report here a novel approach that greatly enhances piezoelectric power generation by introducing a p-type polymer layer on a piezoelectric semiconducting thin film. Holes at the film surface greatly reduce the piezoelectric potential screening effect caused by free electrons in a piezoelectric semiconducting material. Furthermore, additional carriers from a conducting polymer and a shift in the Fermi level help in increasing the power output. Poly(3-hexylthiophene) (P3HT) was used as a p-type polymer on piezoelectric semiconducting zinc oxide (ZnO) thin film, and phenyl-C(61)-butyric acid methyl ester (PCBM) was added to P3HT to improve carrier transport. The ZnO/P3HT:PCBM-assembled piezoelectric power generator demonstrated 18-fold enhancement in the output voltage and tripled the current, relative to a power generator with ZnO only at a strain of 0.068%. The overall output power density exceeded 0.88 W/cm(3), and the average power conversion efficiency was up to 18%. This high power generation enabled red, green, and blue light-emitting diodes to turn on after only tens of times bending the generator. This approach offers a breakthrough in realizing a high-performance flexible piezoelectric energy harvester for self-powered electronics.

2D Nanostructures for Optoelectronic and Green Energy Devices.

Two-dimensional (2D) materials and nanostructures have gathered significant attention due to their excellent mechanical properties [...].

Mechanochemically interlocked cubane copper complex interface for WOLED.

In the rapid development of organic light-emitting diodes (OLEDs), phosphorescent transition metal complexes have played a crucial role as the most promising candidates for next generation display and lighting applications. However, most devices are fabricated using iridium and platinum-based complexes which are expensive and available in very limited quantities, whereas using relatively abundant organometallic complexes for fabrication results mostly in inefficient performance results. To overcome these issues, we have synthesized tetra copper iodide with tetra triphenyl cage like structure (denoted as CIPh) as an emerging class of luminescent material by mechanochemical grinding followed by thermal treatment for application in white OLED. The CIPh complex exhibits considerable quantum yield and a millisecond decay lifetime. Phosphorescent OLEDs were fabricated using CIPh complex as emitter shows a remarkable performance with external quantum efficiency and current efficiency of 5.28 % and 22.76 cd/A, with a high brightness of 4200 cd m-2, respectively. White OLEDs were also fabricated with a fluorescent blue and phosphorescent red emitted with (CIPh) as green emitter and achieved an impressive CRI of 82 with an EQE of over 3 %. This is the first ever attempt at fabricating WOLEDs using organocopper complex.

Truly form-factor-free industrially scalable system integration for electronic textile architectures with multifunctional fiber devices.

An integrated textile electronic system is reported here, enabling a truly free form factor system via textile manufacturing integration of fiber-based electronic components. Intelligent and smart systems require freedom of form factor, unrestricted design, and unlimited scale. Initial attempts to develop conductive fibers and textile electronics failed to achieve reliable integration and performance required for industrial-scale manufacturing of technical textiles by standard weaving technologies. Here, we present a textile electronic system with functional one-dimensional devices, including fiber photodetectors (as an input device), fiber supercapacitors (as an energy storage device), fiber field-effect transistors (as an electronic driving device), and fiber quantum dot light-emitting diodes (as an output device). As a proof of concept applicable to smart homes, a textile electronic system composed of multiple functional fiber components is demonstrated, enabling luminance modulation and letter indication depending on sunlight intensity.