2D Materials Research Articles

Current-induced spin polarization and spin Hall effect in III-V compounds two-dimensional materials

Current-induced spin polarization and spin Hall effect in III-V compounds two-dimensional materials

Precision 4D Printing of Multifunctional Olive Oil‐Based Acrylate Photo‐resin for Biomedical Applications

AbstractSince the advent of 3D printing technology, a significant effort has been made to develop new 3D printable materials. Despite the recent progress in the field of 3D printing, the limited availability of photoactive resins has motivated continuous research endeavors to develop novel photoresins with multifunctional capabilities. Herein a biobased photoresin derived is reported from modified olive oil, designed for high‐resolution solvent‐free 4D printing with multifunctional capabilities. The physicochemical properties of the printed polymers are fine‐tuned using acrylic acid as a diluent cum comonomer. The mechanical properties of the printed polymers are similar to various soft tissues, such as ligaments, articular cartilage, and soft collagenous bone, showcasing its potential for soft tissue engineering applications. While the excellent temperature‐responsive shape memory 4D attributes coupled with exceptional antimicrobial properties toward gram‐negative and gram‐positive bacteria highlight the multifunctional nature of the printed polymers. Moreover, the printed polymers exhibited outstanding hemocompatibility and good cytocompatibility toward mouse fibroblast cells, suggesting their potential soft tissue engineering applications. In sum, the newly developed biobased resin can be employed to minimize the environmental impact of additive manufacturing while being competitive with existing fossil‐based photoresins, thereby meeting the growing demand for advanced photoresins with superior high‐resolution printing and smart properties for biomedical applications.

Robust Plasma-Assisted Growth of 2D Janus Transition Metal Dichalcogenides and Their Enhanced Photoluminescent Properties.

Janus transition metal dichalcogenides (TMDs) are a novel class of 2D materials with unique mirror asymmetry. Plasma-assisted synthesis at room temperature is favored for producing Janus TMDs due to its energy efficiency and prevention of alloying. However, current methods require stringent control over growth conditions, risking defects or unintended materials. A robust plasma-assisted (RPA) synthesis strategy is introduced, incorporating a built-in tube with a suitable inner diameter into the plasma-assisted system. This innovation creates a mild, uniform plasma atmosphere, allowing for broader variations in growth parameters without significantly affecting Janus MoSSe's morphology and characteristics. This approach simplifies the synthesis process and enhances the success rate of Janus TMD production. Additionally, methods are explored to enhance the photoluminescence (PL) of Janus MoSSe. Releasing MoSSe from the growth substrate and annealing it removes strain and unintentional doping, improving PL performance. MoSSe on hexagonal boron nitride (h-BN) flakes after annealing shows a 32-fold increase in PL intensity. Bis(trifluoromethane) sulfonimide (TFSI) treatment of MoSSe results in a remarkable 70-fold increase in PL intensity, a 2.5-fold extension in exciton lifetime, and quantum yield (QY) reaching up to ≈31.2%. These findings provide critical insights for optimizing the luminescence properties of 2D Janus materials, advancing Janus optoelectronics.

Unusual Anomalous Hall Effect in Two-Dimensional Ferromagnetic Cr7Te8

Two-dimensional (2D) materials with inherent magnetism have attracted considerable attention in the fields of spintronics and condensed matter physics. The anomalous Hall effect (AHE) offers a theoretical foundation for understanding the origins of 2D ferromagnetism (2D-FM) and offers a valuable opportunity for applications in topological electronics. Here, we present uniform and large-size 2D Cr7Te8 nanosheets with varying thicknesses grown using the chemical vapor deposition (CVD) method. The 2D Cr7Te8 nanosheets with robust perpendicular magnetic anisotropy, even a few layers deep, exhibit a Curie temperature (TC) ranging from 180 to 270 K according to the varying thickness of Cr7Te8. Moreover, we observed a temperature-induced reversal in the sign of the anomalous Hall resistance, correlating with changes in the intrinsic Berry curvature. Additionally, the topological Hall effect (THE) observed at low temperatures suggests the presence of non-trivial spin chirality. Our findings about topologically non-trivial magnetic spin states in 2D ferromagnets provide a promising opportunity for new designs in magnetic memory spintronics.

High-Performance Ultra-Broadband Photodetector Based on Fe3O4/CrSiTe3 Heterostructures.

Photodetectors based on advanced materials with a broad spectral photoresponse, high sensitivity, huge integration ability, room-temperature operation, and stable environmental stability are highly desired for diversified applications of imaging, sensing, and communication. Herein, a high-performance ultra-broadband photodetector based on an ultrathin two-dimensional (2D) Fe3O4 nanoflake heterostructure with high sensitivity was designed. The photodetector response light was from visible 405 nm to long-wave infrared (LWIR) 10.6 μm in ambient air. The competitive performances, including a high photoresponsivity (R) of 182.8 A W-1, fast speed with the rise time τr = 8.8 μs, and decay time τd = 4.1 μs, were demonstrated in the visible range. Notably, the device exhibits an excellent uncooled LWIR detection ability, with a high R of 1.4 A W-1 realized at a 1.5 V bias. In the full spectral range, the noise equivalent power is lower than 0.79 pW Hz-1/2, and specific detectivity (D*) is higher than 4.9 × 108 cm Hz1/2 W-1 in ambient air. This work provides alternative ultrathin 2D materials for future infrared optoelectronic devices.

Spin-orbit proximity in MoS2/bilayer graphene heterostructures

Van der Waals heterostructures provide a versatile platform for tailoring electronic properties through the integration of two-dimensional materials. Among these combinations, the interaction between bilayer graphene and transition metal dichalcogenides (TMDs) stands out due to its potential for inducing spin–orbit coupling (SOC) in graphene. Future devices concepts require the understanding of the precise nature of SOC in TMD/bilayer graphene heterostructures and its influence on electronic transport phenomena. Here, we experimentally confirm the presence of two distinct types of SOC – Ising (ΔI = 1.55 meV) and Rashba (ΔR = 2.5 meV) – in bilayer graphene when interfaced with molybdenum disulfide. Furthermore, we reveal a non-monotonic trend in conductivity with respect to the electric displacement field at charge neutrality. This phenomenon is ascribed to the existence of single-particle gaps induced by the Ising SOC, which can be closed by a critical displacement field. Our findings also unveil sharp peaks in the magnetoconductivity around the critical displacement field, challenging existing theoretical models.

Machine Learnable Language for the Chemical Space of Nanopores Enables Structure-Property Relationships in Nanoporous 2D Materials.

The synthesis of nanoporous two-dimensional (2D) materials has revolutionized fields such as membrane separations, DNA sequencing, and osmotic power harvesting. Nanopores in 2D materials significantly modulate their optoelectronic, magnetic, and barrier properties. However, the large number of possible nanopore isomers makes their study onerous, while the lack of machine-learnable representations stymies progress toward structure-property relationships. Here, we develop a language for nanopores in 2D materials, called STring Representation Of Nanopore Geometry (STRONG), that opens the field of 2D nanopore informatics. We show that STRONGs are naturally suited for machine learning via recurrent neural networks, predicting formation energies/times of arbitrary nanopores and transport barriers for CO2, N2, and O2 gas molecules, enabling structure-property relationships. The machine learning models enable the discovery of specific nanopore topologies to separate CO2/N2, O2/CO2, and O2/N2 gas mixtures with high selectivity ratios. We also enable the rapid enumeration of unique configurations of stable, functionalized nanopores in 2D materials via STRONGs, allowing systematic searching of the vast chemical space of nanopores. Using the STRONGs approach, we find that a mix of hydrogen and quinone functionalization results in the most stable functionalized nanopore configuration in graphene, a discovery made feasible by expedited chemical space exploration. Additionally, we also unravel the STRONGs approach as ∼1000 times faster than graph theory algorithms to distinguish nanopore shapes. These advances in the language-based representation of 2D nanopores will accelerate the tailored design of nanoporous materials.

Double-pentagon silicon chains in a quasi-1D Si/Ag(001) surface alloy

Silicon surface alloys and silicide nanolayers are highly important as contact materials in integrated circuit devices. Here we demonstrate that the submonolayer Si/Ag(001) surface reconstruction, reported to exhibit interesting topological properties, comprises a quasi-one-dimensional Si-Ag surface alloy based on chains of planar double-pentagon Si moieties. This geometry is determined using a combination of density functional theory calculations, scanning tunnelling microscopy, and grazing incidence x-ray diffraction simulations, and yields an electronic structure in excellent agreement with photoemission measurements. This work provides further evidence of pentagonal geometries in 2D materials and heterostructures and elucidates the importance of surface alloying in stabilizing their formation.

Tilted Dirac cones in two-dimensional materials: Impact on electron transmission and pseudospin dynamics

Tilted Dirac cones in two-dimensional materials: Impact on electron transmission and pseudospin dynamics

New Two-Dimensional Materials Obtained by Functionalization of Boron Graphdiyne Layers with Nickel

The decoration of hexagonal boron graphdiyne (BGDY) layers with Ni atoms has been investigated by density functional calculations. For one, two, and three Ni atoms per hexagon, the BGDY structure is approximately maintained. Decoration with six Ni atoms per hexagon leads to the formation of a novel, very stable two-dimensional material in which the hexagonal structure of BGDY is substantially distorted. The Ni-doped materials have a semiconductor character, and the electronic band gap width can be tailored by varying the amount of adsorbed Ni. BGDY-2Ni, BGDY-3Ni, and BGDY-6Ni have electronic band gaps promising for infrared detectors. This work shows that computer simulation helps to discover new materials by the functionalization of layered carbon materials with metal atoms.

Transferable Percolated Particle Monolayers Derived from Marangoni Flows for Thermally Conductive Dielectric Coatings.

Thermal management is becoming one of the most significant design and size limitations for high power density electronics, including motherboards, power converters, and phased array antennas for 5G communications. There are few options for conducting heat away with dielectric materials that avoid shortening or distorting the performance of these electronics. Certain highly thermally conductive 2D and 3D materials, including hexagonal boron nitride and diamond, offer ideal material properties to address these issues but are extremely challenging to process. This work studies highly oriented single-particle thick films of hexagonal boron nitride, manufactured through a modified Langmuir-Blodgett process and densified further using the Marangoni effect to attain remarkable thermal conductivity enhancement with minimal coating thickness. High loadings of hexagonal boron nitride (∼60 vol %) in dense, castable films are also produced to compare thermal spreading ability in a comparatively simpler but less-coordinated percolated system to the highly percolated particle monolayers. These procedures were applied to glass fiber reinforced polymers used in aerospace and radome applications as well as to a single-board computer to demonstrate enhanced thermal management.

Ultra-sensitivity of surface plasmon resonance sensor using halide perovskite FASnI3 and 2D materials on Cu thin films

This paper studies a novel surface plasmon resonance (SPR) biosensor using a BK7 glass prism, a copper (Cu) metal plasmonic layer, which combine a halide perovskite (FASnI3) with two-dimensional (2D) materials such as phosphorus black, graphene and TMDC (MoS2, MoSe2, WS2, WSe2) for the detection of breast cancer cells. We have optimized the thickness of each layer in order to obtain maximum sensitivity. A numerical study mainly uses the transfer matrix principle, while the attenuation total reflection method involves examining the reflection properties. The evaluation of SPR biosensor configurations serves to obtain optimal performance. The simulation results indicate that the integration of halide perovskite (FASnI3) and 2D materials into the BK7/Cu/medium sensing structure significantly improves the sensitivity and figure of merit (ZT). The outstanding results in terms of sensor performance characteristics are observed in the BK7/Cu (48 nm)/FASnI3 (5 nm)/BP (0.53 nm) configuration. The figure of merit and sensitivity estimated at 123.11 RIU−1 and 459.28°/RIU, with a notable improvement of 338.45 %.

Strain-Engineered Ferroelectricity in 2H Bilayer MoS2.

The exploration of two-dimensional (2D) materials exhibiting out-of-plane ferroelectric and piezoelectric properties through interlayer twist/translation or strain, known as sliding ferroelectricity, has become a focal point in the quest for low-power electronic devices, capitalizing on weak van der Waals interactions. Herein, we delve into the behavior of strained bilayer molybdenum disulfide (2L-MoS2) transferred onto a nanocone-patterned substrate. An intriguing observation is the emergence of unexpected vertical ferroelectricity in MoS2, irrespective of whether it was prepared using chemical vapor deposition or mechanical exfoliation from the bulk crystal. Such an observation underscores the versatility and reproducibility of the emerging ferroelectricity across different preparation methods. Furthermore, the piezoelectric coefficients recorded are exceptionally high, with the values of 37.54 and 24.80 pm V-1 for monolayer and bilayer MoS2, respectively, outperforming most currently discovered 2D piezoelectrics. The presence of room-temperature out-of-plane ferroelectricity in strained 2L-MoS2 is confirmed through first-principles calculations and piezoresponse force microscopy. This ferroelectric behavior can be attributed to the symmetry breaking and interlayer sliding within the strained 2L-MoS2 structure. Our findings not only deepen the understanding of ferroelectricity in 2D materials but also offer insights for the design of 2D ferroelectrics, thereby enabling diverse functionalities and applications in ferroelectricity.

Tailoring the Electronic Structure and Properties of Graphdiyne by Cyano Groups.

Two-dimensional (2D) materials, such as 2D carbon-based systems, have been recently the subject of intense studies, thanks to their optoelectronic properties and promising electronic performances. 2D carbon-based materials such as graphdiyne (GDY) represent an optimal platform for tuning the optoelectronic properties via precise chemical functionalization. Here, we report a synthetic strategy to precisely introduce cyano groups into the 2D GDY backbone in order to tune the electronic properties of GDY. Three kinds of cyano-modified GDY have been synthesized, namely, bearing one cyano group (CNGDY), two CN in meta (m-CNGDY), and two in para (p-CNGDY) positions. A variety of experimental data as well as first-principles calculations allowed us to elucidate the role of the cyano groups in tuning the structural and functional properties of GDYs. We found that an increase in the number of cyano groups reduces the interlayer spacing between GDY layers, increases the lithium adsorption amount, as well as impacts the lithium diffusion rate, while changes in meta- or para-position impact the energy band gap.

Efficient CO2 Reduction Reaction on Cu-Decorated Biphenylene.

Developing efficient electrocatalysts for CO2 reduction into value-added products is crucial for a green economy. Inspired by the recent experimental synthesis of biphenylene (BPH) and the excellent catalytic activity of copper dispersed on two-dimensional (2D) materials, we chose to systematically investigate the pristine, defective, and Cu-decorated BPH for the electrocatalytic CO2 reduction to value-added hydrocarbons. It is observed that the CO2 molecules bind weakly to the pristine BPH, indicating their chemical inertness. Carbon single-vacancy defects facilitate CO2 adsorption with a strong binding energy (Eb) of -3.23 eV, detrimental to the CO2 reduction reaction (CRR) mechanism. We have further investigated the binding energy and kinetic stability of Cu-decorated BPH as a single-atom-catalyst (SAC). The molecular dynamics simulations confirm the kinetic stability, revealing that the Cu-atom avoids agglomeration under low metal dispersal conditions. The CO2 molecule gets adsorbed horizontally on the Cu-BPH surface with a ΔEb of -0.52 eV. The CRR mechanism is investigated using two pathways beginning with two different initial states, formate (*OCOH) and carboxylic (*COOH). The formate pathway confirms the conversion of *OCOH to *HCOOH with the rate-limiting potential (UL) of 0.39 eV for the production of HCOOH, while for the carboxylic pathway, the conversion of *COH to *CHOH has a UL of 0.32 eV, eventually producing CH3OH. Our findings highlight the role of Cu-BPH as an efficient SAC for CO2 catalytic activity to C1 products, as compared to the state-of-the-art Cu, and holds promise as an electrocatalyst for CRR.

Ti3C2Tx-UHMWPE Nanocomposites-Towards an Enhanced Wear-Resistance of Biomedical Implants.

There is an urgent need to enhance the mechanical and biotribological performance of polymeric materials utilized in biomedical devices such as load-bearing artificial joints, notably ultrahigh molecular weight polyethylene (UHMWPE). While two-dimensional (2D) materials like graphene, graphene oxide (GO), reduced GO, or hexagonal boron nitride (h-BN) have shown promise as reinforcement phases in polymer matrix composites (PMCs), the potential of MXenes, known for their chemical inertness, mechanical robustness, and wear-resistance, remains largely unexplored in biotribology. This study aims to address this gap by fabricating Ti3C2Tx-UHMWPE nanocomposites using compression molding. Primary objectives include enhancements in mechanical properties, biocompatibility, and biotribological performance, particularly in terms of friction and wear resistance in cobalt chromium alloy pin-on-UHMWPE disk experiments lubricated by artificial synovial fluid. Thereby, no substantial changes in the indentation hardness or the elastic modulus are observed, while the analysis of the resulting wettability and surface tension as well as indirect and direct invitro evaluation do not point towards cytotoxicity. Most importantly, Ti3C2Tx-reinforced PMCs substantially reduce friction and wear by up to 19% and 44%, respectively, which was attributed to the formation of an easy-to-shear transfer film.

Layer-by-layer assembling boron nitride/polyethyleneimine/MXene hierarchical sandwich structure onto basalt fibers for high-performance epoxy composites

Interfacial adhesion directly affects the mechanical properties of basalt fiber (BF)-reinforced polymer composites. To construct a more superior interphase between BFs and epoxy resin (EP) than a weak interphase of the unmodified BF/EP, we propose a hierarchical sandwich structure consisting of sodium hydroxide–activated boron nitride (BNOH), polyethyleneimine (PEI), and MXene (MX, Ti3C2Tx) through facile layer-by-layer self-assembly. The fabricated BNOH/P/MX sandwich structure (P denoting “PEI”) can synergistically improve the interface adhesion by enhancing the mechanical interlocking and chemical bonding of the composites. When the composites reinforced by BF–BNOH/P/MX subject to the external loading, flexible PEI molecules allow two-dimensional (2D) rigid BNOH and MX nanosheets to slip at the interface by uncurling the molecular chains, dissipating a great amount of energy during the fracture progress. Meanwhile, the hierarchical BNOH/P/MX sandwich structure acts as an excellent interface and possesses multistage gradient modulus and wider thickness, uniformly and efficiently transferring the stress from the EP matrix to BFs. The interfacial shear strength, impact strength, and fracture toughness of BF–BNOH/P/MX-reinforced EP composite are substantially improved by 45.9 %, 60.6 %, and 148.9 %, respectively, compared with bare BF–based composites. This study can provide valuable references and inspirations for designing and constructing high-quality interfaces for high-strength and high-toughness BF structural materials, taking advantage of 2D materials.

Mechanism of Thermodynamically Rationalized Selective Growth of a Two-Dimensional Ternary Ferromagnet on Insulating Substrates.

Two-dimensional (2D) semiconducting ferromagnet Fe3GeTe2 holds great promise for advanced spintronic applications because of its gate-tunable ferromagnetic ordering at room temperature, whereas the controllable growth of large-area single crystals remains very challenging due to its ternary nature and variable stoichiometry inducing many competitive phases. Here, we theoretically probe the mechanism of selective growth of monolayer Fe3GeTe2 on various epitaxial substrates. Thermodynamic analysis shows that the corresponding phase-pure chemical potential windows for the selective growth of Fe3GeTe2 can be reasonably attained in ternary phase space on insulating and chemically inert c-plane sapphire and Ga2O3(0001) substrates by properly modulating the interfacial interaction and employing suitable feedstocks to avoid competitive growth of possible impurity phases with different stoichiometry ratios. It is also revealed that both the weak edge-substrate interaction and interlayer coupling of Fe3GeTe2 together lead to a surface-dominated nucleation behavior and, thereby, energetically favor lateral growth of the monolayer rather than vertical growth of the multilayer. Importantly, straight protocols for the experimentally selective growth of phase-pure ternary Fe3GeTe2 are also provided by establishing the relationship between the feedstock chemical potential and growth parameters on a thermochemical basis. Our insightful study can also be reasonably extended to guide future experimental design for the selective growth of other multicomponent 2D materials.

Entropy Engineering of 2D Materials.

Entropy, a measure of disorder or uncertainty in the thermodynamics system, has been widely used to confer desirable functions to alloys and ceramics. The incorporation of three or more principal elements into a single sublattice increases the entropy to medium and high levels, imparting these materials a mélange of advanced mechanical and catalytic properties. In particular, when scaling down the dimensionality of crystals from bulk to the 2D space, the interplay between entropy stabilization and quantum confinement offers enticing opportunities for exploring new fundamental science and applications, since the structural ordering, phase stability, and local electronic states of these distorted 2D materials get significantly reshaped. During the last few years, the large family of high-entropy 2D materials is rapidly expanding to host MXenes, hydrotalcites, chalcogenides, metal-organic frameworks (MOFs), and many other uncharted members. Here, the recent advances in this dynamic field are reviewed, elucidating the influence of entropy on the fundamental properties and underlying elementary mechanisms of 2D materials. In particular, their structure-property relationships resulting from theoretical predictions and experimental findings are discussed. Furthermore, an outlook on the key challenges and opportunities of such an emerging field of 2D materials is also provided.

Preparation of interconnected tin oxide nanoparticles on multi-layered MXene for lithium storage anodes

MXenes, a novel class of two-dimensional (2D) materials known for their excellent electronic conductivity and hydrophilicity, have emerged as promising candidates for lithium-ion battery anodes. This study presents a simple wet-chemical method for depositing interconnected SnO2 nanoparticles (NPs) onto MXene sheets. The SnO2 NPs act as both a high-capacity energy source and a spacer to prevent MXene sheets from restacking. The highly conductive MXene facilitates rapid electron and lithium-ion transport and mitigates the volume changes of SnO₂ during the lithiation/delithiation process by confining the SnO₂ NPs between the MXene layers. This composite anode, SnO2@MXene, leverages the high capacity of SnO2 and the structural and mechanical stability MXene provides. The SnO2@MXene anode exhibits superior electrochemical performance, with a high specific capacity of 678 mAh g− 1 at a current rate of 2.0 A g− 1 over 500 cycles, outperforming pristine MXenes and SnO2 nanoparticles.