Strong and Tunable Electrical Anisotropy in Type‐II Weyl Semimetal Candidate WP2 with Broken Inversion Symmetry

A transition metal diphosphide, WP₂, is a candidate for type‐II Weyl semimetals (WSMs) in which spatial inversion symmetry is broken and Lorentz invariance is violated. As one of the prerequisites for the presence of the WSM state in WP₂, spatial inversion symmetry breaking in this compound has rarely been investigated. Furthermore, the anisotropy of the WP₂ electrical properties and whether its electrical anisotropy can be tuned remain elusive. Angle‐resolved polarized Raman spectroscopy, electrical transport, optical spectroscopy, and first‐principle studies of WP₂ are reported. The energies of the observed Raman‐active phonons and the angle dependences of the detected phonon intensities are consistent with results obtained by first‐principle calculations and analysis of the proposed crystal symmetry without spatial inversion, showing that spatial inversion symmetry is broken in WP₂. Moreover, the measured ratio (R_c /R_a ) between the crystalline c‐axis and a‐axis electrical resistivities exhibits a weak dependence on temperature (T) in the temperature range from 100 to 250 K, but increases abruptly at T ≤ 100 K, and then reaches the value of ≈8.0 at T = 10 K, which is by far the strongest in‐plane electrical resistivity anisotropy among the reported type‐II WSM candidates with comparable carrier concentrations. Optical spectroscopy study, together with the first‐principle calculations on the electronic band structure, reveals that the abrupt enhancement of the electrical resistivity anisotropy at T ≤ 100 K mainly arises from a sharp increase in the scattering rate anisotropy at low temperatures. More interestingly, the R_c /R_a of WP₂ at T = 10 K can be tuned from 8.0 to 10.6 as the magnetic field increases from 0 to 9 T. The so‐far‐strongest and magnetic‐field‐tunable electrical resistivity anisotropy found in WP₂ can serve as a degree of freedom for tuning the electrical properties of type‐II WSMs, which paves the way for the development of novel electronic applications based on type‐II WSMs.     

2D GeP: An Unexploited Low‐Symmetry Semiconductor with Strong In‐Plane Anisotropy

Germanium phosphide (GeP), a new member of the Group IV–Group V compounds, is introduced into the fast growing 2D family with experimental and theoretical demonstration of strong anisotropic physical properties. The indirect band gap of GeP can be drastically tuned from 1.68 eV for monolayer to 0.51 eV for bulk, with highly anisotropic dispersions of band structures. Thin GeP shows strong anisotropy of phonon vibrations. Moreover, photodetectors based on GeP flakes show highly anisotropic behavior with anisotropic factors of 1.52 and 1.83 for conductance and photoresponsivity, respectively. This work lays the foundation and ignites future research interests in Group IV–Group V compound 2D materials.     

Anisotropic Broadband Photoresponse of Layered Type‐II Weyl Semimetal MoTe2

Photodetectors based on Weyl semimetal promise extreme performance in terms of highly sensitive, broadband and self‐powered operation owing to its extraordinary material properties. Layered Type‐II Weyl semimetal that break Lorentz invariance can be further integrated with other two‐dimensional materials to form van der Waals heterostructures and realize multiple functionalities inheriting the advantages of other two‐dimensional materials. Herein, we report the realization of a broadband self‐powered photodetector based on Type‐II Weyl semimetal T_d‐MoTe₂. The prototype metal–MoTe₂–metal photodetector exhibits a responsivity of 0.40 mA W^?1 and specific directivity of 1.07 × 10⁸ Jones with 43 μs response time at 532 nm. Broadband responses from 532 nm to 10.6 μm are experimentally tested with a potential detection range extendable to far‐infrared and terahertz. Furthermore, we identify the response of the detector is polarization angle sensitive due to the anisotropic response of MoTe₂. The anisotropy is found to be wavelength dependent, and the degree of anisotropy increases as the excitation wavelength gets closer to the Weyl nodes. In addition, with power and temperature dependent photoresponse measurements, the photocurrent generation mechanisms are investigated. Our results suggest this emerging class of materials can be harnessed for broadband angle sensitive, self‐powered photodetection with decent responsivities.     

In‐Plane Anisotropic Thermal Conductivity of Few‐Layered Transition Metal Dichalcogenide Td‐WTe2

2D Td‐WTe₂ has attracted increasing attention due to its promising applications in spintronic, field‐effect chiral, and high‐efficiency thermoelectric devices. It is known that thermal conductivity plays a crucial role in condensed matter devices, especially in 2D systems where phonons, electrons, and magnons are highly confined and coupled. This work reports the first experimental evidence of in‐plane anisotropic thermal conductivities in suspended Td‐WTe₂ samples of different thicknesses, and is also the first demonstration of such anisotropy in 2D transition metal dichalcogenides. The results reveal an obvious anisotropy in the thermal conductivities between the zigzag and armchair axes. The theoretical calculation implies that the in‐plane anisotropy is attributed to the different mean free paths along the two orientations. As thickness decreases, the phonon‐boundary scattering increases faster along the armchair direction, resulting in stronger anisotropy. The findings here are crucial for developing efficient thermal management schemes when engineering thermal‐related applications of a 2D system.     

Band Structure Perfection and Superconductivity in Type‐II Dirac Semimetal Ir1−xPtxTe2

The discovery of a new type‐II Dirac semimetal in Ir_1?xPt_xTe₂ with optimized band structure is described. Pt dopants protect the crystal structure holding the Dirac cones and tune the Fermi level close to the Dirac point. The type‐II Dirac dispersion in Ir_1?xPt_xTe₂ is confirmed by angle‐resolved photoemission spectroscopy and first‐principles calculations. Superconductivity is also observed and persists when the Fermi level aligns with the Dirac points. Ir_1?xPt_xTe₂ is an ideal platform for further studies on the exotic properties and potential applications of type‐II DSMs, and opens up a new route for the investigation of the possible topological superconductivity and Majorana physics.     

Probing the Domain Architecture in 2D α‐Mo2C via Polarized Raman Spectroscopy

MXenes are emerging 2D materials with intriguing properties such as excellent stability and high conductivity. Here, a systematic study on the Raman spectra of 2D α‐Mo₂C (molybdenum carbide), a promising member in MXene family, is conducted. Six experimentally observed Raman modes from ultrathin α‐Mo₂C crystal are first assigned with the assistance of phonon dispersion calculated from density functional theory. Angle‐resolved polarized Raman spectroscopy indicates the anisotropy of α‐Mo₂C in the b–c plane. Raman spectroscopy is further used to study the unique domain structures of 2D α‐Mo₂C crystals grown by chemical vapor deposition. A Raman mapping investigation suggests that most of the α‐Mo₂C flakes contain multiple domains and the c‐axes of neighboring domains tend to form a 60° or 120° angle, due to the weak Mo? C bonds in this interstitial carbide and the low formation energy of the carbon chains along three equivalent directions. This study demonstrates that polarized Raman spectroscopy is a powerful and effective way to characterize the domain structures in α‐Mo₂C, which will facilitate the further exploration of the domain‐structure‐related properties and potential applications of α‐Mo₂C.     

In‐Plane Heterostructures Enable Internal Stress Assisted Strain Engineering in 2D Materials

Conventional methods to induce strain in 2D materials can hardly catch up with the sharp increase in requirements to design specific strain forms, such as the pseudomagnetic field proposed in graphene, funnel effect of excitons in MoS₂, and also the inverse funnel effect reported in black phosphorus. Therefore, a long‐standing challenge in 2D materials strain engineering is to find a feasible scheme that can be used to design given strain forms. In this article, combining the ability of experimentally synthetizing in‐plane heterostructures and elegant Eshelby inclusion theory, the possibility of designing strain fields in 2D materials to manipulate physical properties, which is called internal stress assisted strain engineering, is theoretically demonstrated. Particularly, through changing the inclusion's size, the stress or strain gradient can be controlled precisely, which is never achieved. By taking advantage of it, the pseudomagnetic field as well as the funnel effect can be accurately designed, which opens an avenue to practical applications for strain engineering in 2D materials.     

Controllable Synthesis of Atomically Thin Type‐II Weyl Semimetal WTe2 Nanosheets: An Advanced Electrode Material for All‐Solid‐State Flexible Supercapacitors

Compared with 2D S‐based and Se‐based transition metal dichalcogenides (TMDs), Te‐based TMDs display much better electrical conductivities, which will be beneficial to enhance the capacitances in supercapacitors. However, to date, the reports about the applications of Te‐based TMDs in supercapacitors are quite rare. Herein, the first supercapacitor example of the Te‐based TMD is reported: the type‐II Weyl semimetal 1Td WTe₂. It is demonstrated that single crystals of 1Td WTe₂ can be exfoliated into the nanosheets with 2–7 layers by liquid‐phase exfoliation, which are assembled into air‐stable films and further all‐solid‐state flexible supercapacitors. The resulting supercapacitors deliver a mass capacitance of 221 F g^?1 and a stack capacitance of 74 F cm^?3. Furthermore, they also show excellent volumetric energy and power densities of 0.01 Wh cm^?3 and 83.6 W cm^?3, respectively, superior to the commercial 4V/500 µAh Li thin‐film battery and the commercial 3V/300 µAh Al electrolytic capacitor, in association with outstanding mechanical flexibility and superior cycling stability (capacitance retention of ≈91% after 5500 cycles). These results indicate that the 1Td WTe₂ nanosheet is a promising flexible electrode material for high‐performance energy storage devices.     

Tailoring Structure,Composition, and Energy Storage Properties of MXenes from Selective Etching of In‐Plane,Chemically Ordered MAX Phases

The exploration of 2D solids is one of our time's generators of materials discoveries. A recent addition to the 2D world is MXenes that possses a rich chemistry due to the large parent family of MAX phases. Recently, a new type of atomic laminated phases (coined i‐MAX) is reported, in which two different transition metal atoms are ordered in the basal planes. Herein, these i‐MAX phases are used in a new route for tailoriong the MXene structure and composition. By employing different etching protocols to the parent i‐MAX phase (Mo_2/3Y_1/3)₂AlC, the resulting MXene can be either: i) (Mo_2/3Y_1/3)₂C with in‐plane elemental order through selective removal of Al atoms or ii) Mo_1.33C with ordered vacancies through selective removal of both Al and Y atoms. When (Mo_2/3Y_1/3)₂C (ideal stoichiometry) is used as an electrode in a supercapacitor—with KOH electrolyte—a volumetric capacitance exceeding 1500 F cm^?3 is obtained, which is 40% higher than that of its Mo_1.33C counterpart. With H₂SO₄, the trend is reversed, with the latter exhibiting the higher capacitance (≈1200 F cm^?3). This additional ability for structural tailoring will indubitably prove to be a powerful tool in property‐tailoring of 2D materials, as exemplified here for supercapacitors.     

In‐Plane Potential Gradient Induces Low Frictional Energy Dissipation during the Stick‐Slip Sliding on the Surfaces of 2D Materials

Understanding the nanoscale friction properties of 2D materials and further manipulating their friction behaviors is of great significance for the development of various micro/nanodevices. Recent studies, taking advantage of the close relationship between friction and surface charges, use an external out‐of‐plane electric field to control the interfacial friction. Nevertheless, friction increases with the application of the out‐of‐plane electric field in most cases. Here, an in‐plane potential gradient is applied for the investigation of the contribution of electric charges to friction on the surfaces of 2D materials. Experimental results show that the friction between an atomic force microscope tip and the flakes of 2D materials decreases with the application of the in‐plane potential gradient, and the higher the potential gradient, the greater the friction decrease. By comparing the in situ atomic‐level stick‐slip maps before and after the application of the in‐plane potential gradient, it is proposed that the promotion of low friction dissipative motion during the stick‐slip process owing to the presence of the potential gradient gives rise to the friction reduction. These results not only help to reveal the origin of friction, but also provide a novel way to manipulate friction through an electrically‐controlled sliding process.     

Epitaxial Growth of Rectangle Shape MoS2 with Highly Aligned Orientation on Twofold Symmetry a‐Plane Sapphire

Research on transition metal dichalcogenides (TMDs) has been accelerated by the development of large‐scale synthesis based on chemical vapor deposition (CVD) growth. However, in most cases, CVD‐grown TMDs are composed of randomly oriented grains, and thus contain many distorted grain boundaries (GBs), which seriously degrade their electrical and photoelectrical properties. Here, the epitaxial growth of highly aligned MoS₂ grains is reported on a twofold symmetry a‐plane sapphire substrate. The obtained MoS₂ grains have an unusual rectangle shape with perfect orientation alignment along the [1‐100] crystallographic direction of a‐plane sapphire. It is found that the growth temperature plays a key role in its orientation alignment and morphology evolution, and high temperature is beneficial to the initial MoS₂ seeds rotate to the favorable orientation configurations. In addition, the photoluminescence quenching of the well‐aligned MoS₂ grains indicates a strong MoS₂?substrate interaction which induces the anisotropic growth of MoS₂, and thus brings the formation of rectangle shape grains. Moreover, the well‐aligned MoS₂ grains splice together without GB formation, and thus that has negligible effect on its electrical transport properties. The progress achieved in this work could promote the controlled synthesis of large‐area TMDs single crystal film and the scalable fabrication of high‐performance electronic devices.     

Thickness‐Dependent In‐Plane Polarization and Structural Phase Transition in van der Waals Ferroelectric CuInP2S6

van der Waals (vdW) layered materials have rather weaker interlayer bonding than the intralayer bonding, therefore the exfoliation along the stacking direction enables the achievement of monolayer or few layers vdW materials with emerging novel physical properties and functionalities. The ferroelectricity in vdW materials recently attracts renewed interest for the potential use in high‐density storage devices. With the thickness becoming thinner, the competition between the surface energy, depolarization field, and interfacial chemical bonds may give rise to the modification of ferroelectricity and crystalline structure, which has limited investigations. In this work, combining the piezoresponse force microscope scanning, contact resonance imaging, the existence of the intrinsic in‐plane polarization in vdW ferroelectrics CuInP₂S₆ single crystals is reported, whereas below a critical thickness between 90 and 100 nm, the in‐plane polarization disappears. The Young's modulus also shows an abrupt stiffness at the critical thickness. Based on the density functional theory calculations, these behaviors are ascribed to a structural phase transition from monoclinic to trigonal structure, which is further verified by transmission electron microscope technique. These findings demonstrate the foundational importance of structural phase transition for enhancing the rich functionality and broad utility of vdW ferroelectrics.     

Eliminating Trap‐States and Functionalizing Vacancies in 2D Semiconductors by Electrochemistry

One major challenge that limits the applications of 2D semiconductors is the detrimental electronic trap states caused by vacancies. Here using grand‐canonical density functional theory calculations, a novel approach is demonstrated that uses aqueous electrochemistry to eliminate the trap states of the vacancies in 2D transition metal dichalcogenides while leaving the perfect part of the material intact. The success of this electrochemical approach is based on the selectivity control by the electrode potential and the isovalence between oxygen and chalcogen. Motivated by these results, electrochemical conditions are further identified to functionalize the vacancies by incorporating various single metal atoms, which can bring in magnetism, tune carrier concentration/polarity, and/or activate single‐atom catalysis, enabling a wide range of potential applications. These approaches may be generalized to other 2D materials. The results open up a new avenue for improving the properties and extending the applications of 2D materials.     

Giant Enhancements of Perpendicular Magnetic Anisotropy and Spin‐Orbit Torque by a MoS2 Layer

2D transition metal dichalcogenides have attracted much attention in the field of spintronics due to their rich spin‐dependent properties. The promise of highly compact and low‐energy‐consumption spin‐orbit torque (SOT) devices motivates the search for structures and materials that can satisfy the requirements of giant perpendicular magnetic anisotropy (PMA) and large SOT simultaneously in SOT‐based magnetic memory. Here, it is demonstrated that PMA and SOT in a heavy metal/transition metal ferromagnet structure, Pt/[Co/Ni]₂, can be greatly enhanced by introducing a molybdenum disulfide (MoS₂) underlayer. According to first‐principles calculation and X‐ray absorption spectroscopy (XAS), the enhancement of the PMA is ascribed to the modification of the orbital hybridization at the interface of Pt/Co due to MoS₂. The enhancement of SOT by the role played by MoS₂ is explained, which is strongly supported by the identical behavior of SOT and PMA as a function of Pt thickness. This work provides new possibilities to integrate 2D materials into promising spintronics devices.     

Geometric Imperfection Sensitivity of Curved Panels Under Combined Compression and In‐Plane Bending – A Study Using Adaptive Meshing and DIC

Abstract: The existence of geometric imperfections, either resulting from the use of manufacturing tolerances or because of damage in situ is known to have a detrimental effect on the buckling and post‐buckling behaviour of thin‐walled structures, which depending upon factors such as geometry and loading, can be significant. This paper presents an automated technique, based on the use of topography data obtained from optical measurement, for creating finite meshes representative of the geometry of real structures, which can be analysed to obtain accurate predictions of unstable behaviour. The technique incorporates an algorithm to allow mesh density to be varied across the specimen according to level of curvature thus ensuring the meshes generated are not only accurate but also computationally efficient by reducing the number of degrees of freedom where appropriate. The results of applying this technique to a series of curved panels subject to combined shear and in‐plane bending (an example of a component of an aero engine blade) are reported.     

Towards Eliminating the Displacement Bias Due to Out‐Of‐Plane Motion in 2D Inverse Problems: A Case of General Rigid‐Body Motion

This article reports an important development related to the inverse characterization of material constitutive parameters using 2D optical displacement field measurements. The out‐of‐plane motion of the specimen, which has traditionally been considered detrimental to the accuracy of these experiments, is generally of two types: (a) a global out‐of‐plane rigid‐body motion of the specimen relative to the camera and (b) out‐of‐plane deformations resulting from material heterogeneity or out‐of‐plane loads. In an earlier article, we proposed to partially relax the condition of no out‐of‐plane motion by allowing for (b) in 2D inverse procedures, in the context of finite element update method, and introduced a compensation strategy by redefining the cost function on the object plane of the acquisition system. The experimental errors due to (a) were assumed negligible. Here, we propose that the global rigid‐body motion (a) may also be recovered within the inverse procedures, hence completely waiving the condition of strictly in‐plane displacements for inverse problems. The recovery is achieved by identifying and including the possible modes of global rigid‐body motion within the cost function together with careful selection of test configuration. The effects of individual rigid‐body modes on the computed displacement fields are studied in detail and utilized as a guideline for selection of test configuration. The approach is fully demonstrated and validated by simulated as well as real experiments for determining elastic constants of isotropic and orthotropic materials using different experimental setups. Effects of improving the optimization routine, for cost function minimization, and experimental noise are also presented.     

Ordered Arrangement and Optical Properties of Silica‐Stabilized Gold Nanoparticle–PNIPAM Core–Satellite Clusters for Sensitive Raman Detection

Gold–polymer hybrid nanoparticles attract wide interest as building blocks for the engineering of photonic materials and plasmonic (active) metamaterials with unique optical properties. In particular, the coupling of the localized surface plasmon resonances of individual metal nanostructures in the presence of nanometric gaps can generate highly enhanced and confined electromagnetic fields, which are frequently exploited for metal‐enhanced light–matter interactions. The optical properties of plasmonic structures can be tuned over a wide range of properties by means of their geometry and the size of the inserted nanoparticles as well as by the degree of order upon assembly into 1D, 2D, or 3D structures. Here, the synthesis of silica‐stabilized gold–poly(N‐isopropylacrylamide) (SiO₂‐Au‐PNIPAM) core–satellite superclusters with a narrow size distribution and their incorporation into ordered self‐organized 3D assemblies are reported. Significant alterations of the plasmon resonance are found for different assembled structures as well as strongly enhanced Raman signatures are observed. In a series of experiments, the origin of the highly enhanced signals can be assigned to the interlock areas of adjacent SiO₂‐Au‐PNIPAM core–satellite clusters and their application for highly sensitive nanoparticle‐enhanced Raman spectroscopy is demonstrated.     

In Situ Growth of Pd Nanosheets on g‐C3N4 Nanosheets with Well‐Contacted Interface and Enhanced Catalytic Performance for 4‐Nitrophenol Reduction

Loading novel metal nanosheets onto nanosheet support can improve their catalytic performance, but the morphological incompatibility makes it difficult to construct a well‐contacted interface, which is of particular interest in supported catalysts. Herein, Pd nanosheets (Pd NSs) are supported onto graphitic carbon nitride nanosheets (CNNSs) with intimate face‐to‐face contact through an in situ growth method. This method overcomes the limitations of the morphological incompatibility and ensures the intimate interfacial contact between Pd NSs and CNNSs. The nitrogen‐rich nature of CNNSs endows Pd NSs with abundant anchoring sites, which optimizes the electronic structure and improves the chemical and morphological stability of Pd NSs. The supported Pd NSs demonstrate high dispersion and exhibit largely enhanced activity toward the reduction of 4‐nitrophenol. The concentration‐normalized rate constant is up to 3052 min^?1 g^?1 L, which is 5.4 times higher than that obtained by unsupported Pd NSs. No obvious deactivation is observed after six runs of the recycling experiments. It is believed that the supported novel metal nanosheets with the intimately contacted interface may show promising applications in catalysis.