Ultrathin Materials Research Articles

Highly conductive Ti3C2 MXene-supported CoAl-layered double hydroxide nanosheets for ultrasensitive electrochemical detection of organophosphate pesticide fenitrothion.

A novel electrochemical method is presented for ultrasensitive detection of the organophosphate pesticide (OPP) fenitrothion by using Ti3C2 MXene/CoAl-LDH nanocomposite as the electrode modifier. The Ti3C2 MXene/CoAl-LDH nanocomposite is synthesized by growing CoAl-LDH in situ on MXene nanosheets. The combination of two ultrathin 2D materials provides more active sites, larger specific surface area, superior adsorption properties, and better electrical conductivity, which leads to rapid electron-transfer and mass-transfer between the substrate electrode and analytes when it is acted as the electrochemical sensing material. In addition, through the chelation of phosphate groups with the Ti defect sites enriched in MXene, OPP is adsorbed on the electrode. Consequently, the corresponding modified electrode gives rise to a wide linear response range of 0.03 ~ 120μmol/L for the differential pulse voltammetry detection of fenitrothion with a low detection limit of 5.8nmol/L (3σ). The method offers good repeatability, stability, selectivity, and practicability for real samples. This strategy provides a reference platform for the electrochemical monitoring of trace OPPs residue by using MXene/LDH-based nanocomposites.

Broadband absorptive metamaterials enhanced by magnetic rubber to broaden bandwidth

A method to extend the operational bandwidth of metal-dielectric-metal (MDM) type absorptive metamaterials is proposed. An ultrathin, five-band absorptive metamaterial with wide-angle absorption and polarization sensitivity in the X-band is designed. The total absorption bandwidth across the five bands, with reflection losses below −10 dB (absorption rate greater than 90 %), is nearly 1 GHz. The physical mechanisms of absorption are analyzed through the distributions of surface current, electric field, and magnetic field. Samples were fabricated and tested, and the results were consistent with the simulation outcomes. To enhance the bandwidth of the absorptive metamaterial and its application prospects, magnetic materials such as barium ferrite and carbonyl iron were introduced into a rubber vulcanization layer, which was then combined with the ultrathin absorptive material to create a novel absorptive material. When the magnetic material content in the rubber layer was 50 wt%, the frequency range with reflection losses below −10 dB increased by approximately nine times, covering 69.5 % of the C-Ku band. This significantly broadens the bandwidth of the pure MDM-type absorptive metamaterial, providing a feasible solution for the design of broadband ultrathin absorptive materials.

Ultralight Hierarchical Fe3O4/MoS2/rGO/Ti3C2Tx MXene Composite Aerogels for High-Efficiency Electromagnetic Wave Absorption.

Aerogel-based composites, renowned for their three-dimensional (3D) network architecture, are gaining increasing attention as lightweight electromagnetic (EM) wave absorbers. However, attaining high reflection loss, broad effective absorption bandwidth (EAB), and ultrathin thickness concurrently presents a formidable challenge, owing to the stringent demands for precise structural regulation and incorporation of magnetic/dielectric multicomponents with synergistic loss mechanisms within the 3D networks. In this study, we successfully synthesized a 3D hierarchical porous Fe3O4/MoS2/rGO/Ti3C2Tx MXene (FMGM) composite aerogel via directional freezing and subsequent heat treatment processes. Owing to their ingenious structure and multicomponent design, the FMGM aerogels, featured with abundant heterogeneous interface structure and magnetic/dielectric synergism, show exceptional impedance matching characteristics and diverse EM wave absorption mechanisms. After optimization, the prepared ultralight (6.4 mg cm-3) FMGM-2 aerogel exhibits outstanding EM wave absorption performance, achieving a minimal reflection loss of -66.92 dB at a thickness of 3.61 mm and an EAB of 6.08 GHz corresponding to the thickness of 2.3 mm, outperforming most of the previously reported aerogel-based absorbing materials. This research presents an effective strategy for fabricating lightweight, ultrathin, highly efficient, and broad band EM wave absorption materials.

Ultra strong, tough and extreme environments resistant PBO papers with a nacre-like structure constructed by synergistic electrostatic interaction and interlayer entanglement

In extreme environments, it is difficult to balance the strength and toughness of ultra-thin film materials. To address this problem, we propose a promising strategy to build ultra strong, tough and extreme environments resistant Poly(p-phenylene-2,6-benzobisoxazole) (PBO) papers with a nacre-like structure constructed by synergistic electrostatic interaction and interlayer entanglement through the sol–gel-film method and hot press orientation. Highly interconnected PBO nanofibres （PNFs） with positive charges are tightly wound around the anisotropic graphene oxide (GO) nanosheets with negative charges through strong electrostatic interaction, forming a nacre like microstructure. The addition of Fe (Ⅲ) can form a coordination bond with the amino group on PNFs. Chemical crosslinking and hydrogen bonding synergize with interlayer entanglement effect among different PNFs，which can effectively dissipate interlayer energy and alleviate the conflict between strength and toughness. The resultant tensile strength and toughness are as high as 338.3 MPa and 16.04 MJ/m3，which are 197.7 % and 425.4 % of those of the intrinsic PBO paper, respectively. Additionally, after 5000 folding-unfolding cycles, the tensile strength retention and toughness retention of the PBO/GO/Fe (PGFe) paper were still 85.4 % and 71.9 %, respectively. Moreover, the paper exhibits excellent tolerance to extreme temperature environments and showed extremely strong chemical stability.

Analysis and EOT Scaling on Top‐ and Double‐Gate 2D CVD‐Grown Monolayer MoS2 FETs

Abstract2D layered semiconductors have attracted considerable attention for beyond‐Si complementary metal‐oxide‐semiconductor (CMOS) technologies. They can be prepared into ultrathin channel materials toward ultrascaled device architectures, including double‐gate field‐effect‐transistors (DGFETs). This work presents an experimental analysis of DGFETs constructed from chemical vapor deposition (CVD)‐grown monolayer (1L) molybdenum disulfide (MoS2) with atomic layer deposition (ALD) of hafnium oxide (HfO2) high‐k gate dielectrics (top and bottom). This extends beyond previous studies of DGFETs based mostly on exfoliated (few‐nm thick) MoS2 flakes, and advances toward large‐area wafer‐scale processing. Here, significant improvements in performance are obtained with DGFETs (i.e., improvements in ON/OFF ratio, ON‐state current, sub‐threshold swing, etc.) compared to single top‐gate FETs. In addition to multi‐gate device architectures (e.g., DGFETs), the scaling of the equivalent oxide thickness (EOT) is crucial toward improved electrostatics required for next‐generation transistors. However, the impact of EOT scaling on the characteristics of CVD‐grown MoS2 DGFETs remains largely unexplored. Thus, this work studies the impact of EOT scaling on subthreshold swing (SS) and gate hysteresis using current–voltage (I–V) measurements with varying sweep rates. The experimental analysis and results elucidate the basic mechanisms responsible for improvements in CVD‐grown 1L‐MoS2 DGFETs compared to standard top‐gate FETs.

Atomically Thin Kagome-Structured Co9Te16 Achieved through Self-Intercalation and Its Flat Band Visualization.

Kagome materials have recently garnered substantial attention due to the intrinsic flat band feature and the stimulated magnetic and spin-related many-body physics. In contrast to their bulk counterparts, two-dimensional (2D) kagome materials feature more distinct kagome bands, beneficial for exploring novel quantum phenomena. Herein, we report the direct synthesis of an ultrathin kagome-structured Co-telluride (Co9Te16) via a molecular beam epitaxy (MBE) route and clarify its formation mechanism from the Co-intercalation in the 1T-CoTe2 layers. More significantly, we unveil the flat band states in the ultrathin Co9Te16 and identify the real-space localization of the flat band states by in situ scanning tunneling microscopy/spectroscopy (STM/STS) combined with first-principles calculations. A ferrimagnetic order is also predicted in kagome-Co9Te16. This work should provide a novel route for the direct synthesis of ultrathin kagome materials via a metal self-intercalation route, which should shed light on the exploration of the intriguing flat band physics in the related systems.

Synthesis of Large-Sized van der Waals Layered MoO3 Single Crystals with Improved Dielectric Performance.

The applications of two-dimensional semiconductors strictly require the reliable integration of ultrathin high-κ dielectric materials on the semiconductor surface to enable fine gate control and low power consumption. As layered oxide materials, MoO3 can be potentially used as a high-κ two-dimensional material with a larger bandgap and high electron affinity. In this work, relying on the oxidization of molybdenum chlorides, we have synthesized α-MoO3 single crystals, which can be easily exfoliated into flakes with thicknesses of a few nanometers and sizes of hundreds of micrometers and fine thermal stability. Based on measurement results of conventional metal/insulator/metal devices and graphene based dual-gate devices, the as-received MoO3 nanosheets exhibit improved dielectric performance, including high dielectric constants and competitive breakdown field strength. Our work demonstrates that MoO3 with improved crystalline quality is a promising candidate for dielectric materials with a large gate capacitance in future electronics based on two-dimensional materials.

Deformation state of a graphene sheet within the framework of the continuum moment-membrane theory of elasticity

The paper proposes an approach to finding the stress-strain state (SSS) of structures containing graphene, a novel nanomaterial that has currently found а wide range of practical applications in nanoelectromechanical systems. Graphene is a 2D basic building block for other carbon structures such as membranes, sheets, nanotubes, etc. To describe the SSS of a graphene sheet, the phenomenological continuum moment-membrane theory of plates is used, from which, due to the fact that graphene is an ultrathin material, the concept of thickness is excluded. The physical elasticity relationships of a graphene sheet are expressed through its rigidity characteristics, determined using the harmonic potential of interatomic interactions in carbon. A differential formulation and the corresponding variational formulation are given for the problem of static deformation and determination of the natural frequencies and modes of vibration of a graphene sheet. The variational formulation is based on the Lagrange principle and is implemented numerically using the finite element method. Finite element relations are constructed taking into account moment effects of the behavior of a graphene sheet. For approximation, a 4-node rectangular finite element is used. Numerical solutions to several problems of static deformation of a graphene sheet under conditions of a plane stress state and transverse bending are presented, and the analysis of its natural vibrations is also performed. Good convergence of numerical simulation results in all considered problems is demonstrated. The obtained numerical solutions are essential in designing and calculating resonators in which ultrathin nanostructures are used. The establishment of the fact that a graphene sheet has a high intrinsic frequency falling in the GHz region (for example, quartz resonators are characterized by megahertz frequencies) opens up new prospects for using graphene itself as an ultrasensitive nanomechanical resonator for detecting small masses and ultrasmall displacements.

Giant and controllable nonlinear magneto-optical effects in two-dimensional magnets

The interplay of polarization and magnetism in materials with light can create rich nonlinear magneto-optical (NLMO) effects, and the recent discovery of two-dimensional (2D) van der Waals magnets provides remarkable control over NLMO effects due to their superb tunability. Here, based on first-principles calculations, we reported giant NLMO effects in CrI3-based 2D magnets, including a dramatic change of second-harmonics generation (SHG) polarization direction (90°) and intensity (on/off switch) under magnetization reversal and a 100% SHG circular dichroism effect. We further revealed that these effects could not only be used to design ultra-thin multifunctional optical devices but also to detect subtle magnetic orderings. Remarkably, we analytically derived conditions to achieve giant NLMO effects and proposed general strategies to realize them in 2D magnets. Our work not only uncovers a series of intriguing NLMO phenomena but also paves the way for both fundamental research and device applications of ultra-thin NLMO materials.

Sustainable high-strength and dimensionally stable composites through in situ regulation and reconstitution of bamboo-derived lignin and hemicellulose contents

The development of modern construction and transportation industries demands increasingly high requirements for thin, lightweight, high-strength, and highly tough composite materials, such as metal carbides and concrete. Bamboo is a green, low-carbon, fast-growing, renewable, and biodegradable material with high strength and toughness. However, the density of its inner layer is low due to the functional gradient (the volume fraction of vascular bundles decreases from the outer layer to the inner layer), resulting in low performance, high compressibility, and significant amounts of bamboo waste. We utilized chemical and mechanical treatments of bamboo's low-density, low-strength inner layers to create lightweight, ultra-thin, high-strength, and high-toughness composites. The treatment included the partial removal of lignin and hemicellulose to alter the chemical components, followed by mechanical drying and hot pressing. The treated bamboo had 100.8 % higher tensile strength (150.35 MPa), 47.7 % higher flexural strength (97.67 MPa), and 132.0 % higher water resistance and was approximately 68.9 % thinner than the natural bamboo. The excellent physical and mechanical properties of the treated bamboo are attributed to the contraction of parenchyma cells during delignification, the interlocking due to the collapse of parenchyma cells during mechanical drying, and an increase in the density of hydrogen bonds between cellulose molecular chains during hot pressing. Our research provides a new strategy for obtaining sustainable, ultra-thin, lightweight, high-strength, and high-toughness composite materials from bamboo for construction and transportation applications.

Ligin-derived graphene-like ultrathin carbon materials for ORR catalysis

Low-cost nitrogen-doped carbon materials with graphene-like structures were designed and prepared from extensive renewable biomass waste lignin. The obtained carbon materials exhibited well-designed ultrathin two-dimensional structures with high specific area and mesoporous characteristics. Benefiting from the well-designed structures with extensive catalytic active sites and efficient mass transfer and diffusion, as well as the modified electronic characteristics from nitrogen doping, the lignin-derived carbon materials exhibited pronounced ORR catalytic activity and methanol tolerance. Considering these, the lignin-derived carbon materials hold great application potentials as ORR catalysts and catalyst supports.

Opinions on the Development of Ultrahigh Permeation Membranes

In this work, recent progresses made in the development of membranes with ultrahigh permeation rate for reverse osmosis (RO) and membrane distillation (MD) are briefly summarized and the future prospect of those membranes is discussed. In fabrication of ultrahigh permeation RO membranes, carbon nanotube, aquaporin, graphene and fluorous oligoamide nanorings were used and in all of them several orders of magnitude higher fluxes than the conventional commercial membranes were achieved. Ultrahigh MD membranes were fabricated mostly from carbonaceous materials also with several orders of magnitude higher fluxes than conventional commercial membranes, except for those made of ultrathin polymeric material, which demonstrated a high flux at a low transmembrane temperature difference. Despite these remarkable achievements, it was concluded that many challenges would be encountered to produce a sufficient amount of water by the so-called membrane chips.

High-performance ferroelectric field-effect transistors with ultra-thin indium tin oxide channels for flexible and transparent electronics

With the development of wearable devices and hafnium-based ferroelectrics (FE), there is an increasing demand for high-performance flexible ferroelectric memories. However, developing ferroelectric memories that simultaneously exhibit good flexibility and significant performance has proven challenging. Here, we developed a high-performance flexible field-effect transistor (FeFET) device with a thermal budget of less than 400 °C by integrating Zr-doped HfO2 (HZO) and ultra-thin indium tin oxide (ITO). The proposed FeFET has a large memory window (MW) of 2.78 V, a high current on/off ratio (ION/IOFF) of over 108, and high endurance up to 2×107 cycles. In addition, the FeFETs under different bending conditions exhibit excellent neuromorphic properties. The device exhibits excellent bending reliability over 5×105 pulse cycles at a bending radius of 5 mm. The efficient integration of hafnium-based ferroelectric materials with promising ultrathin channel materials (ITO) offers unique opportunities to enable high-performance back-end-of-line (BEOL) compatible wearable FeFETs for edge intelligence applications.

Fabrication of Liquid-Metal Printed 2D Tin Oxide Nanosheets for Optoelectronic Applications

Liquid-metal printed processes have been recently developed as a novel strategy to grow ultrathin 2D oxide materials, which are transferred from liquid-metal surfaces to substrates. In this study, we fabricated liquid-metal printing 2D tin oxide (SnO) nanosheets on SiO2/Si and glass substrates. A large lateral-sized 2D SnO nanosheets of >100 µm and a thickness of approximately 6.3 nm was fabricated. The 2D SnO nanosheets exhibited a strong optical absorption in the ultraviolet and violet region and its bandgap was estimated to be approximately 2.9 eV. The 2D SnO nanosheets on glass substrates with patterned gold electrodes generated a photocurrent under ultraviolet (UV) light irradiation, demonstrating a potential for optoelectronic applications such as UV detectors.

High-Throughput and Scalable Exfoliation of Large-Sized Ultrathin 2D Materials by Ball-Milling in Supercritical Carbon Dioxide.

The 2D materials exhibit numerous technological applications, but their scalable production is a core challenge. Herein, ball milling exfoliation in supercritical carbon dioxide (scCO2) and polystyrene (PS) is demonstrated to completely exfoliate hexagonal boron nitride nanosheets (BNNSs), graphene, molybdenum disulfide (MoS2), and tungsten disulfide (WS2). The exfoliation yield of 91%, 93%, 92%, and 92% and average aspect ratios of 743, 565, 564, and 502 for BNNSs, graphene, MoS2, and WS2, respectively, are achieved. Integrating exfoliated BNNSS in the polystyrene matrix, 3768 % thermal conductivity in the axial direction and 316% in the cross-plane direction at 12wt.% loading is increased. Also, the in-plane and cross-plane electrical conductivity of 6.3×10-4Sm-1 and 6.6×10-3Sm-1, respectively, and the electromagnetic interference (EMI) of 63.3 dB is achieved by exfoliated graphene nanosheets based composite. High thermal and electrical conductivities and EMI shielding are attributed to the high aspect ratio and ultrathin morphology of the exfoliated nanosheets, which exert high charge mobility and form better the percolation network in the composite films due to their high surface area. The process demonstrate herein can produce substantial quantities of diverse 2D nanosheets for widespread commercial utilization.

Scalable Synthesis of High-Quality Ultrathin Ferroelectric Magnesium Molybdenum Oxide.

The development of ultrathin, stable ferroelectric materials is crucial for advancing high-density, low-power electronic devices. Nonetheless, ultrathin ferroelectric materials are rare due to the critical size effect. Here, a novel ferroelectric material, magnesium molybdenum oxide (Mg2Mo3O8) is presented. High-quality ultrathin Mg2Mo3O8 crystals are synthesized using chemical vapor deposition (CVD). Ultrathin Mg2Mo3O8 has a wide bandgap (≈4.4eV) and nonlinear optical response. Mg2Mo3O8 crystals of varying thicknesses exhibit out-of-plane ferroelectric properties at room temperature, with ferroelectricity retained even at a 2nm thickness. The Mg2Mo3O8 exhibits a relatively large remanent polarization ranging from 33 to 52µCcm- 2, which is tunable by changing its thickness. Notably, Mg2Mo3O8 possesses a high Curie temperature (>980°C) across various thicknesses. Moreover, the as-grown Mg2Mo3O8 crystals display remarkable stability under harsh environments. This work introduces nolanites-type crystal into ultrathin ferroelectrics. The scalable synthesis of stable ultrathin ferroelectric Mg2Mo3O8 expands the scope of ferroelectric materials and may prosper applications of ferroelectrics.

Surface plasmon resonance-enhanced photoelectrochemical immunoassay with Cu-doped porous Bi2WO6 nanosheets

The development of rapid screening sensing platforms to improve pre-screening mechanisms in community healthcare is necessary to meet the significant need for portable testing in biomarker diagnostics. Here, we designed a portable smartphone-based photoelectrochemical (PEC) immunoassay for carcinoembryonic antigen (CEA) detection using Cu-doped ultrathin porous Bi2WO6 (CuBWO) nanosheets as the photoactive material. The CuBWO nanosheets exhibit a fast photocurrent response and excellent electrical transmission rate under UV light due to their surface plasmon resonance effect (SPR). The method uses glucose oxidase-labeled secondary antibody as a signal indicator for sandwich-type immune conjugation. In the presence of the target CEA, the electrons and holes generated at the surface of the photo-excited ultrathin porous CuBWO were rapidly consumed by the production of H2O2 from glucose oxidase oxidizing glucose, resulting in a weakened photocurrent signal. The photocurrent intensity increased logarithmically and linearly with increasing CEA concentration (0.02–50 ng mL−1), with a detection limit of 15.0 pg mL−1 (S/N = 3). The system provides a broader idea for inferring the electron-hole transport mechanism in ultrathin porous nanosheet layer materials and developing efficient PEC sensors.

Universal Vapor‐Phase Synthesis of Large‐Scale Ultrathin Perovskites with Superior Stability for Photodetectors and Image Sensors

AbstractUltrathin halide perovskites have drawn tremendous attention in nano‐/micro‐optoelectronic devices due to their fascinating performance and capability for chip integration. Unfortunately, it is highly challenging to obtain large‐scale and chronically stable ultrathin halide perovskites for practical application. Herein, the universal low‐temperature vapor‐phase synthesis of ultrathin perovskite family materials with thickness down to 2D level and lateral size up to 1.5 cm × 1.5 cm is reported by developing a self‐limiting chemical vapor deposition strategy. The perovskite products are found to exhibit superior stability over 180 days under an air environment. The resultant photodetectors demonstrate charming optoelectronic properties such as superior responsivity (3.7 × 103 A W−1), ultrafast response time (<10 µs), and outstanding low‐level light image sensing capability. This universal perovskite synthesis strategy offers great potential for practical applications of halide perovskites in future nano‐/micro‐optoelectronic devices.

Ultra-thin double-layered hexagonal CuI: strain tunable properties and robust semiconducting behavior.

In this study, the freestanding form of ultra-thin CuI crystals, which have recently been synthesized experimentally, and their strain-dependent properties are investigated by means of density functional theory calculations. Structural optimizations show that CuI crystallizes in a double-layered hexagonal crystal (DLHC) structure. While phonon calculations predict that DLHC CuI crystals are dynamically stable, subsequent vibrational spectrum analyzes reveal that this structure has four unique Raman-active modes, allowing it to be easily distinguished from similar ultra-thin two-dimensional materials. Electronically, DLHC CuI is found to be a semiconductor with a direct band gap of 3.24 eV which is larger than that of its wurtzite and zincblende phases. Furthermore, it is found that in both armchair (AC) and zigzag (ZZ) orientations the elastic instabilities occur over the high strain strengths indicating the soft nature of CuI layer. In addition, the stress-strain curve along the AC direction reveal that DLHC CuI undergoes a structural phase transition between the 4% and 5% tensile uniaxial strains as indicated by a sudden drop of the stress in the lattice. Moreover, the phonon band dispersions show that the phononic instability occurs at much smaller strain along the ZZ direction than that of along the AC direction. Furthermore, the external strain direction can be deduced from the predicted Raman spectra through the splitting rates of the doubly degenerate in-plane vibrations. The mobility of the hole carriers display highly anisotropic characteristic as the applied strain reaches 5% along the AC direction. Due to its anomalous strain-dependent electronic features and elastically soft nature, DLHC of CuI is a potential candidate for future electro-mechanical applications.

2D CuInP2Se6 in High‐Sensitivity UV‐vis And X‐Ray Detection

AbstractMetal thio(seleno)phosphates are renowned for their multifaceted physical characteristics and versatile applications, particularly in optoelectronics. In detection applications, a low and stable dark current is crucial, enhancing the sensitivity and signal‐to‐noise ratio of detectors. Herein, a van der Waals layered material has synthesized, CuInP2Se6. Despite its nanometric scale, 2D CuInP2Se6 detector transcends the conventional absorption inefficiencies tied to ultrathin materials. It delivers exceptional ultraviolet–visible detection, characterized by an ultralow, stable dark current of 150 fA, and a noise power density of 27.7 fA Hz−1/2 at room temperature. The in‐depth investigation reveals a responsivity of 4.47 A W−1, an external quantum efficiency of 1369%, a special detectivity of 1.44 × 1013 Jones, and a rapid response speed of 280 µs, positioning it at the pinnacle of 2D photodetector performance. The CuInP2Se6’s ultralow, stable dark current paves the way for X‐ray detection, achieving an unprecedented sensitivity of 1.32 × 105 µC Gyair−1 cm−2 and a low detection limit of 0.15 µGyair s−1. Furthermore, 2D CuInP2Se6 detector exhibits a remarkable image‐sensing capability, adeptly capturing intricate patterns with high resolution. This discovery indicates its promise in revolutionizing integrated micro/nano optoelectronic devices, opening avenues for advancements in light and X‐ray detection and imaging technologies.