Interlayer Charge Transfer Induced Electrical Behavior Transition in 1D AgI@sSWCNT van der Waals Heterostructures.

The emergence of one-dimensional van der Waals heterostructures (1D vdWHs) opens up potential fields with unique properties, but precise synthesis remains a challenge. The utilization of mixed conductive types of carbon nanotubes as templates has imposed restrictions on the investigation of the electrical behavior and interlayer interaction of 1D vdWHs. In this study, we efficiently encapsulated silver iodide in high-purity semiconducting single-walled carbon nanotubes (sSWCNTs), forming 1D AgI@sSWCNT vdWHs. We characterized the semiconductor-metal transition and increased the carrier concentration of individual AgI@sSWCNTs via sensitive dielectric force microscopy and confirmed the results through electrical device tests. The electrical behavior transition was attributed to an interlayer charge transfer, as demonstrated by Kelvin probe force microscopy. Furthermore, we showed that this method of synthesizing 1D heterostructures can be extended to other metal halides. This work opens the door for the further exploration of the electrical properties of 1D vdWHs.

Non-epitaxial growth of highly oriented transition metal dichalcogenides with density-controlled twin boundaries.

Twin boundaries (TBs) in transition metal dichalcogenides (TMDs) constitute distinctive one-dimensional electronic systems, exhibiting intriguing physical and chemical properties that have garnered significant attention in the fields of quantum physics and electrocatalysis. However, the controlled manipulation of TBs in terms of density and specific atomic configurations remains a formidable challenge. In this study, we present a non-epitaxial growth approach that enables the controlled and large-scale fabrication of homogeneous catalytically active TBs in monolayer TMDs on arbitrary substrates. Notably, the density achieved using this strategy is six times higher than that observed in convention chemical vapor deposition (CVD)-grown samples. Through rigorous experimental analysis and multigrain Wulff construction simulations, we elucidate the role of regulating the metal source diffusion process, which serves as the key factor for inducing the self-oriented growth of TMD grains and the formation of unified TBs. Furthermore, we demonstrate that this novel growth mode can be readily incorporated into the conventional CVD growth method by making a simple modification of the growth temperature profile, thereby offering a universal approach for engineering of grain boundaries in two-dimensional materials.

Identifying spatial domains of spatially resolved transcriptomics via multi-view graph convolutional networks.

MOTIVATION: Recent advances in spatially resolved transcriptomics (ST) technologies enable the measurement of gene expression profiles while preserving cellular spatial context. Linking gene expression of cells with their spatial distribution is essential for better understanding of tissue microenvironment and biological progress. However, effectively combining gene expression data with spatial information to identify spatial domains remains challenging. RESULTS: To deal with the above issue, in this paper, we propose a novel unsupervised learning framework named STMGCN for identifying spatial domains using multi-view graph convolution networks (MGCNs). Specifically, to fully exploit spatial information, we first construct multiple neighbor graphs (views) with different similarity measures based on the spatial coordinates. Then, STMGCN learns multiple view-specific embeddings by combining gene expressions with each neighbor graph through graph convolution networks. Finally, to capture the importance of different graphs, we further introduce an attention mechanism to adaptively fuse view-specific embeddings and thus derive the final spot embedding. STMGCN allows for the effective utilization of spatial context to enhance the expressive power of the latent embeddings with multiple graph convolutions. We apply STMGCN on two simulation datasets and five real spatial transcriptomics datasets with different resolutions across distinct platforms. The experimental results demonstrate that STMGCN obtains competitive results in spatial domain identification compared with five state-of-the-art methods, including spatial and non-spatial alternatives. Besides, STMGCN can detect spatially variable genes with enriched expression patterns in the identified domains. Overall, STMGCN is a powerful and efficient computational framework for identifying spatial domains in spatial transcriptomics data.

Colloid driven low supersaturation crystallization for atomically thin Bismuth halide perovskite.

It is challenging to grow atomically thin non-van der Waals perovskite due to the strong electronic coupling between adjacent layers. Here, we present a colloid-driven low supersaturation crystallization strategy to grow atomically thin Cs3Bi2Br9. The colloid solution drives low-concentration solute in a supersaturation state, contributing to initial heterogeneous nucleation. Simultaneously, the colloids provide a stable precursor source in the low-concentration solute. The surfactant is absorbed in specific crystal nucleation facet resulting in the anisotropic growth of planar dominance. Ionic perovskite Cs3Bi2Br9 is readily grown from monolayered to six-layered Cs3Bi2Br9 corresponding to thicknesses of 0.7, 1.6, 2.7, 3.6, 4.6 and 5.7 nm. The atomically thin Cs3Bi2Br9 presents layer-dependent nonlinear optical performance and stacking-induced second harmonic generation. This work provides a concept for growing atomically thin halide perovskite with non-van der Waal structures and demonstrates potential application for atomically thin single crystals' growth with strong electronic coupling between adjacent layers.

On-skin biosensors for noninvasive monitoring of postoperative free flaps and replanted digits.

Severe soft tissue defects and amputated digits are clinically common injuries. Primary treatments include surgical free flap transfer and digit replantation, but these can fail because of vascular compromise. Postoperative monitoring is therefore crucial for timely detection of vessel obstruction and survival of replanted digits and free flaps. However, current postoperative clinical monitoring methods are labor intensive and highly dependent on the experience of nurses and surgeons. Here, we developed on-skin biosensors for noninvasive and wireless postoperative monitoring based on pulse oximetry. The on-skin biosensor was made of polydimethylsiloxane with gradient cross-linking to create a self-adhesive and mechanically robust substrate that interfaces with skin. The substrate was shown to exhibit appropriate adhesion on one side for both high-fidelity measurements of the sensor and low risk of peeling injury to delicate tissues. The other side demonstrated mechanical integrity to facilitate flexible hybrid integration of the sensor. Validation studies using a model of vascular obstruction in rats demonstrated the effectiveness of the sensor in vivo. Clinical studies indicated that the on-skin biosensor was accurate and more responsive than current clinical monitoring methods in identifying microvascular conditions. Comparisons with existing monitoring techniques, including laser Doppler flowmetry and micro-lightguide spectrophotometry, further verified the sensor's accuracy and ability to identify both arterial and venous insufficiency. These findings suggest that this on-skin biosensor may improve postoperative outcomes in free flap and replanted digit surgeries by providing sensitive and unbiased data directly from the surgical site that can be remotely monitored.

Non-Bonding Interaction of Neighboring Fe and Ni Single-Atom Pairs on MOF-Derived N-Doped Carbon for Enhanced CO2 Electroreduction.

Single-atom catalysts (SACs), featuring high atom utilization, have captured widespread interests in diverse applications. However, the single-atom sites in SACs are generally recognized as independent units and the interplay of adjacent sites is largely overlooked. Herein, by the direct pyrolysis of MOFs assembled with Fe and Ni-doped ZnO nanoparticles, a novel Fe1-Ni1-N-C catalyst, with neighboring Fe and Ni single-atom pairs decorated on nitrogen-doped carbon support, has been precisely constructed. Thanks to the synergism of neighboring Fe and Ni single-atom pairs, Fe1-Ni1-N-C presents significantly boosted performances for electrocatalytic reduction of CO2, far surpassing Fe1-N-C and Ni1-N-C with separate Fe or Ni single atoms. Additionally, the Fe1-Ni1-N-C also exhibits superior performance with excellent CO selectivity and durability in Zn-CO2 battery. Theoretical simulations reveal that, in Fe1-Ni1-N-C, single Fe atoms can be highly activated by adjacent single-atom Ni via non-bonding interaction, significantly facilitating the formation of COOH* intermediate and thereby accelerating the overall CO2 reduction. This work supplies a general strategy to construct single-atom catalysts containing multiple metal species and reveals the vital importance of the communitive effect between adjacent single atoms toward improved catalysis.

Immobilized Precursor Particle Driven Growth of Centimeter-Sized MoTe2 Monolayer.

Molybdenum ditelluride (MoTe2) has attracted ever-growing attention in recent years due to its novel characteristics in spintronics and phase-engineering, and an efficient and convenient method to achieve large-area high-quality film is an essential step toward electronic applications. However, the growth of large-area monolayer MoTe2 is challenging. Here, for the first time, we achieve the growth of a centimeter-sized monoclinic MoTe2 monolayer and manifest the mechanism of immobilized precursor particle driven growth. Microscopic characterizations reveal an obvious trend of immobilized precursor particles being consumed by the monolayer and continuing to provide a source for the growth of the monolayer. Time-of-flight secondary ion mass spectrometry verifies the attachment of hydroxide ions on the surface of the MoTe2 monolayer, thereby realizing the inhibition of crystal growth along the [001] zone axis and the continuous growth of the MoTe2 monolayer. The first-principles DFT calculations prove the mechanism of immobilized precursor particles and the absorption of hydroxide ions on the MoTe2 monolayer. The as-grown MoTe2 monolayer exhibits a surface roughness of 0.19 nm and average conductivity of 1.5 × 10-5 S/m, which prove the smoothness and uniformity of the MoTe2 monolayer. Temperature-dependent electrical measurements together with the transfer characteristic curves further demonstrate the typical semimetallic properties of monoclinic MoTe2. Our research elaborates the microscopic process of immobilized precursor particles to grow large-area MoTe2 monolayer and provides a new thinking about the growth of many other two-dimensional materials.

The Photodetectors Based on Lateral Monolayer MoS2/WS2 Heterojunctions.

Monolayer transition metal dichalcogenides (TMDs) show promising potential for next-generation optoelectronics due to excellent light capturing and photodetection capabilities. Photodetectors, as important components of sensing, imaging and communication systems, are able to perceive and convert optical signals to electrical signals. Herein, the large-area and high-quality lateral monolayer MoS2/WS2 heterojunctions were synthesized via the one-step liquid-phase chemical vapor deposition approach. Systematic characterization measurements have verified good uniformity and sharp interfaces of the channel materials. As a result, the photodetectors enhanced by the photogating effect can deliver competitive performance, including responsivity of ~ 567.6 A/W and detectivity of ~ 7.17 × 1011 Jones. In addition, the 1/f noise obtained from the current power spectrum is not conductive to the development of photodetectors, which is considered as originating from charge carrier trapping/detrapping. Therefore, this work may contribute to efficient optoelectronic devices based on lateral monolayer TMD heterostructures.

One-Pot Selective Epitaxial Growth of Large WS2/MoS2 Lateral and Vertical Heterostructures.

Controllable nucleation sites play a key role in the selective growth of heterostructures. Here, we are the first to report a one-pot strategy to realize the confined and selective growth of large MoS2/WS2 lateral and vertical heterostructures. A hydroxide-assisted process is introduced to control the nucleation sites, thereby realizing the optional formation of lateral and vertical heterostructures. Time-of-flight secondary ion mass spectrometry verifies the critical role of hydroxide groups toward the controllable growth of these heterostructures. The size of the as-grown MoS2/WS2 lateral heterostructures can be as large as 1 mm, which is the largest lateral size reported thus far. The obtained MoS2/WS2 heterostructures have a high carrier mobility of ∼58 cm2 V-1 s-1, and the maximum on/off current ratio is >108. This approach provides not only a pathway for the selective growth of large MoS2/WS2 lateral and vertical heterostructures but also a fundamental understanding of surface chemistry for controlling the selective growth of transition-metal dichalcogenide heterostructures.

An ultrathin MoSe2 photodetector with near-perfect absorption.

An ultrathin near-perfect MoSe2 absorber working in the visible regime is demonstrated theoretically and experimentally, and it consists of a MoSe2/Au bi-layer film. The polymer-assisted deposition method is used to synthesize MoSe2 films, which can reduce the roughness and thus improve the film absorption. Simulation results show that the absorption of the absorber with 22 nm MoSe2 reaches to larger than 90% between 628.5 nm and 718 nm with a peak value up to 99.5% at 686 nm. Moreover, the measured absorption also shows near-perfect absorption of this simple absorber. Finally, an ultrathin photodetector is fabricated based on this perfect absorber and shows on/off reproducibility and remarkable photocurrent, which is three orders of magnitude higher than the dark current.

Spatially Bandgap-Graded MoS2(1-x)Se2x Homojunctions for Self-Powered Visible-Near-Infrared Phototransistors.

Ternary transition metal dichalcogenide alloys with spatially graded bandgaps are an emerging class of two-dimensional materials with unique features, which opens up new potential for device applications. Here, visible-near-infrared and self-powered phototransistors based on spatially bandgap-graded MoS2(1-x)Se2x alloys, synthesized by a simple and controllable chemical solution deposition method, are reported. The graded bandgaps, arising from the spatial grading of Se composition and thickness within a single domain, are tuned from 1.83 to 1.73 eV, leading to the formation of a homojunction with a built-in electric field. Consequently, a strong and sensitive gate-modulated photovoltaic effect is demonstrated, enabling the homojunction phototransistors at zero bias to deliver a photoresponsivity of 311 mA W-1, a specific detectivity up to ~ 1011 Jones, and an on/off ratio up to ~ 104. Remarkably, when illuminated by the lights ranging from 405 to 808 nm, the biased devices yield a champion photoresponsivity of 191.5 A W-1, a specific detectivity up to ~ 1012 Jones, a photoconductive gain of 106-107, and a photoresponsive time in the order of ~ 50 ms. These results provide a simple and competitive solution to the bandgap engineering of two-dimensional materials for device applications without the need for p-n junctions.

MoS2-OH Bilayer-Mediated Growth of Inch-Sized Monolayer MoS2 on Arbitrary Substrates.

Due to remarkable electronic property, optical transparency, and mechanical flexibility, monolayer molybdenum disulfide (MoS2) has been demonstrated to be promising for electronic and optoelectronic devices. To date, the growth of high-quality and large-scale monolayer MoS2 has been one of the main challenges for practical applications. Here we present a MoS2-OH bilayer-mediated method that can fabricate inch-sized monolayer MoS2 on arbitrary substrates. This approach relies on a layer of hydroxide groups (-OH) that are preferentially attached to the (001) surface of MoS2 to form a MoS2-OH bilayer structure for growth of large-area monolayer MoS2 during the growth process. Specifically, the hydroxide layer impedes vertical growth of MoS2 layers along the [001] zone axis, promoting the monolayer growth of MoS2, constrains growth of the MoS2 monolayer only in the lateral direction into larger area, and effectively reduces sulfur vacancies and defects according to density functional theory calculations. Finally, the hydroxide groups advantageously prevent the MoS2 from interface oxidation in air, rendering high-quality MoS2 monolayers with carrier mobility up to ∼30 cm2 V-1 s-1. Using this approach, inch-sized uniform monolayer MoS2 has been fabricated on the sapphire and mica and high-quality monolayer MoS2 of single-crystalline domains exceeding 200 µm has been grown on various substrates including amorphous SiO2 and quartz and crystalline Si, SiC, Si3N4, and graphene This method provides a new opportunity for the monolayer growth of other two-dimensional transition metal dichalcogenides such as WS2 and MoSe2.

High Detectivity and Transparent Few-Layer MoS2 /Glassy-Graphene Heterostructure Photodetectors.

Layered van der Waals heterostructures have attracted considerable attention recently, due to their unique properties both inherited from individual two-dimensional (2D) components and imparted from their interactions. Here, a novel few-layer MoS2 /glassy-graphene heterostructure, synthesized by a layer-by-layer transfer technique, and its application as transparent photodetectors are reported for the first time. Instead of a traditional Schottky junction, coherent ohmic contact is formed at the interface between the MoS2 and the glassy-graphene nanosheets. The device exhibits pronounced wavelength selectivity as illuminated by monochromatic lights. A responsivity of 12.3 mA W-1 and detectivity of 1.8 × 1010 Jones are obtained from the photodetector under 532 nm light illumination. Density functional theory calculations reveal the impact of specific carbon atomic arrangement in the glassy-graphene on the electronic band structure. It is demonstrated that the band alignment of the layered heterostructures can be manipulated by lattice engineering of 2D nanosheets to enhance optoelectronic performance.

High-performance oxygen reduction catalyst derived from porous, nitrogen-doped carbon nanosheets.

A facile, self-foaming strategy is reported to synthesize porous, nitrogen-doped carbon nanosheets (N-CNSs) as a metal-free electrocatalyst for oxygen reduction reaction (ORR). Benefiting from the synergistic functions of N-induced active sites, a highly specific surface area and continuous structure, the optimal N-CNS catalyst exhibits Pt-like ORR activity (positive onset potential of ∼0 V versus Ag/AgCl and limiting current density of 5 mA cm(-2)) through a four-electron transfer process in alkaline media with excellent cycle stability and methanol tolerance. This work not only provides a promising metal-free ORR catalyst but also opens up a new path for designing carbon-based materials towards broad applications.

Neutral Mononuclear Copper(I) Complexes: Synthesis, Crystal Structures, and Photophysical Properties.

Neutral green-emitting four-coordinate Cu(I) complexes with general formula POPCu(NN), where POP = bis[2-(diphenylphosphino)phenyl]ether and NN = substituted 2-pyridine-1,2,4-triazole ligands, were synthesized. The crystal structures of (POPCuMeCN)(+)(PF6)(-) (1), POPCuPhPtp (2a, PhPtp = 2-(5-phenyl-2H-[1,2,4]triazol-3-yl)-pyridine), and POPCu(3,5-2FPhPtp) (2d, 3,5-2FPhPtp = 2-(5-(3,5-difluorophenyl)-2H-1,2,4-triazol-3-yl)pyridine) were determined by single-crystal X-ray diffraction analysis. The electronic and photophysical properties of the complexes were examined by UV-vis, steady-state, and time-resolved spectroscopy. At room temperature, weak emission was observed in solution, while in the solid state, all complexes exhibit intense green emission with quantum yield up to 0.54. The electronic and photophysical properties were further supported by calculation performed at the (time-dependent) density functional theory level. One of the complexes was also tested as dopant in electroluminescent devices.