Linear Dichroism and Nondestructive Crystalline Identification of Anisotropic Semimetal Few‐Layer MoTe2

Semimetal 1T′ MoTe₂ crystals have attracted tremendous attention owing to their anisotropic optical properties, Weyl semimetal, phase transition, and so on. However, the complex refractive indices (n‐ik) of the anisotropic semimetal 1T′ MoTe₂ still are not revealed yet, which is important to applications such as polarized wide spectrum detectors, polarized surface plasmonics, and nonlinear optics. Here, the linear dichroism of as‐grown trilayer 1T′ MoTe₂ single crystals is investigated. Trilayer 1T′ MoTe₂ shows obvious anisotropic optical absorption due to the intraband transition of d_z² orbits for Mo atoms and p_x orbits for Te atoms. The anisotropic complex refractive indices of few‐layer 1T′ MoTe₂ are experimentally obtained for the first time by using the Pinier equation analysis. Based on the linear dichroism of 1T′ MoTe₂, angle‐resolved polarized optical microscopy is developed to visualize the grain boundary and identify the crystal orientation of 1T′ MoTe₂ crystals, which is also an excellent tool toward the investigation of the optical absorption properties in the visible range for anisotropic 2D transition metal chalcogenides. This work provides a universal and nondestructive method to identify the crystal orientation of anisotropic 2D materials, which opens up an opportunity to investigate the optical application of anisotropic semimetal 2D materials.     

Efficient Self‐Driven Photodetectors Featuring a Mixed‐Dimensional van der Waals Heterojunction Formed from a CdS Nanowire and a MoTe2 Flake

Heterojunctions formed from low‐dimensional materials can result in photovoltaic and photodetection devices displaying exceptional physical properties and excellent performance. Herein, a mixed‐dimensional van der Waals (vdW) heterojunction comprising a 1D n‐type Ga‐doped CdS nanowire and a 2D p‐type MoTe₂ flake is demonstrated; the corresponding photovoltaic device exhibits an outstanding conversion efficiency of 15.01% under illumination with white light at 650 µW cm^?2. A potential difference of 80 meV measured, using Kelvin probe force microscopy, at the CdS–MoTe₂ interface confirms the separation and accumulation of photoexcited carriers upon illumination. Moreover, the photodetection characteristics of the vdW heterojunction device at zero bias reveal a rapid response time (<50 ms) and a photoresponsivity that are linearly proportional to the power density of the light. Interestingly, the response of the vdW heterojunction device is negligible when illuminated at 580 nm; this exceptional behavior is presumably due to the rapid rate of recombination of the photoexcited carriers of MoTe₂. Such mixed‐dimensional vdW heterojunctions appear to be novel design elements for efficient photovoltaic and self‐driven photodetection devices.     

Ultrahigh‐Performance Self‐Powered Flexible Double‐Twisted Fibrous Broadband Perovskite Photodetector

Self‐powered flexible photodetectors without an external power source can meet the demands of next‐generation portable and wearable nanodevices; however, the performance is far from satisfactory becuase of the limited match of flexible substrates and light‐sensitive materials with proper energy levels. Herein, a novel self‐powered flexible fiber‐shaped photodetector based on double‐twisted perovskite–TiO₂–carbon fiber and CuO–Cu₂O–Cu wire is designed and fabricated. The device shows an ultrahigh detectivity of 2.15 × 10¹³ Jones under the illumination of 800 nm light at zero bias. CuO–Cu₂O electron block bilayer extends response range of perovskite from 850 to 1050 nm and suppresses dark current down to 10^?11 A. The fast response speed of less than 200 ms is nearly invariable after dozens of cycles of bending at the extremely 90 bending angle, demonstrating excellent flexibility and bending stability. These parameters are comparable and even better than reported flexible and even rigid photodetectors. The present results suggest a promising strategy to design photodetectors with integrated function of self‐power, flexibility, and broadband response.     

Pressure‐Induced Phase Transition in Weyl Semimetallic WTe2

Tungsten ditelluride (WTe₂) is a semimetal with orthorhombic T_d phase that possesses some unique properties such as Weyl semimetal states, pressure‐induced superconductivity, and giant magnetoresistance. Here, the high‐pressure properties of WTe₂ single crystals are investigated by Raman microspectroscopy and ab initio calculations. WTe₂ shows strong plane‐parallel/plane‐vertical vibrational anisotropy, stemming from its intrinsic Raman tensor. Under pressure, the Raman peaks at ≈120 cm^?1 exhibit redshift, indicating structural instability of the orthorhombic T_d phase. WTe₂ undergoes a phase transition to a monoclinic T′ phase at 8 GPa, where the Weyl states vanish in the new T′ phase due to the presence of inversion symmetry. Such T_d to T′ phase transition provides a feasible method to achieve Weyl state switching in a single material without doping. The new T′ phase also coincides with the appearance of superconductivity reported in the literature.     

Zero‐Field Nernst Effect in a Ferromagnetic Kagome‐Lattice Weyl‐Semimetal Co3Sn2S2

The discovery of magnetic topological semimetals has recently attracted significant attention in the field of topology and thermoelectrics. In a thermoelectric device based on the Nernst geometry, an external magnet is required as an integral part. Reported is a zero‐field Nernst effect in a newly discovered hard‐ferromagnetic kagome‐lattice Weyl‐semimetal Co₃Sn₂S₂. A maximum Nernst thermopower of ≈3 µV K^?1 at 80 K in zero field is achieved in this magnetic Weyl‐semimetal. The results demonstrate the possibility of application of topological hard magnetic semimetals for low‐power thermoelectric devices based on the Nernst effect and are thus valuable for the comprehensive understanding of transport properties in this class of materials.     

Near‐Infrared Photodetectors Based on MoTe2/Graphene Heterostructure with High Responsivity and Flexibility

2D transition metal dichalcogenides (TMDCs) have attracted considerable attention due to their impressively high performance in optoelectronic devices. However, efficient infrared (IR) photodetection has been significantly hampered because the absorption wavelength range of most TMDCs lies in the visible spectrum. In this regard, semiconducting 2D MoTe₂ can be an alternative choice owing to its smaller band gap ≈1 eV from bulk to monolayer and high carrier mobility. Here, a MoTe₂/graphene heterostructure photodetector is demonstrated for efficient near‐infrared (NIR) light detection. The devices achieve a high responsivity of ≈970.82 A W^?1 (at 1064 nm) and broadband photodetection (visible‐1064 nm). Because of the effective photogating effect induced by electrons trapped in the localized states of MoTe₂, the devices demonstrate an extremely high photoconductive gain of 4.69 × 10⁸ and detectivity of 1.55 × 10¹¹ cm Hz^1/2 W^?1. Moreover, flexible devices based on the MoTe₂/graphene heterostructure on flexible substrate also retains a good photodetection ability after thousands of times bending test (1.2% tensile strain), with a high responsivity of ≈60 A W^?1 at 1064 nm at V _DS = 1 V, which provides a promising platform for highly efficient, flexible, and low cost broadband NIR photodetectors.     

A Simple Method for Synthesis of High‐Quality Millimeter‐Scale 1T′ Transition‐Metal Telluride and Near‐Field Nanooptical Properties

The controlled synthesis of MoTe₂ and WTe₂ is crucial for their fundamental research and potential electronic applications. Here, a simplified ambient‐pressure chemical vapor deposition (CVD) strategy is developed to synthesize high‐quality and large‐scale monolayer and few‐layer 1T′‐phase MoTe₂ (length ≈ 1 mm) and WTe₂ (length ≈ 350 µm) crystals by using ordinary salts (KCl or NaCl) as the growth promoter combining with low‐cost (NH₄)₆Mo₇O₂₄·4H₂O and hydrate (NH₄)₁₀W₁₂O₄₁·xH₂O as the Mo and W sources, respectively. Atomic force microscopy, X‐ray photoelectron spectroscopy, Raman spectroscopy, and transmission electron microscopy confirm the high‐quality nature and the atomic structure of the as‐grown 1T′ MoTe₂ and WTe₂ flakes. Variable‐temperature transport measurements exhibit their semimetal properties. Furthermore, near‐field nanooptical imaging studies are performed on the 1T′ MoTe₂ and WTe₂ flakes for the first time. The sub‐wavelength effects of 1T′‐phase MoTe₂ (λ_p ≈ 140 nm) and WTe₂ (λ_p ≈ 100 nm) are obtained. This approach paves the way for the growth of special transition‐metal dichalcogenides materials and boosts the future polaritonic research of 2D telluride compounds.     

High Performance Lithium‐Ion Batteries Using Layered 2H‐MoTe2 as Anode

The major challenges faced by candidate electrode materials in lithium‐ion batteries (LIBs) include their low electronic and ionic conductivities. 2D van der Waals materials with good electronic conductivity and weak interlayer interaction have been intensively studied in the electrochemical processes involving ion migrations. In particular, molybdenum ditelluride (MoTe₂) has emerged as a new material for energy storage applications. Though 2H‐MoTe₂ with hexagonal semiconducting phase is expected to facilitate more efficient ion insertion/deinsertion than the monoclinic semi‐metallic phase, its application as an anode in LIB has been elusive. Here, 2H‐MoTe₂, prepared by a solid‐state synthesis route, has been employed as an efficient anode with remarkable Li⁺ storage capacity. The as‐prepared 2H‐MoTe₂ electrodes exhibit an initial specific capacity of 432 mAh g^?1 and retain a high reversible specific capacity of 291 mAh g^?1 after 260 cycles at 1.0 A g^?1. Further, a full‐cell prototype is demonstrated by using 2H‐MoTe₂ anode with lithium cobalt oxide cathode, showing a high energy density of 454 Wh kg^?1 (based on the MoTe₂ mass) and capacity retention of 80% over 100 cycles. Synchrotron‐based in situ X‐ray absorption near‐edge structures have revealed the unique lithium reaction pathway and storage mechanism, which is supported by density functional theory based calculations.     

Novel 2D Layered Molybdenum Ditelluride Encapsulated in Few‐Layer Graphene as High‐Performance Anode for Lithium‐Ion Batteries

Molybdenum ditelluride nanosheets encapsulated in few‐layer graphene (MoTe₂/FLG) are synthesized by a simple heating method using Te and Mo powder and subsequent ball milling with graphite. The as‐prepared MoTe₂/FLG nanocomposites as anode materials for lithium‐ion batteries exhibit excellent electrochemical performance with a highly reversible capacity of 596.5 mAh g^?1 at 100 mA g^?1, a high rate capability (334.5 mAh g^?1 at 2 A g^?1), and superior cycling stability (capacity retention of 99.5% over 400 cycles at 0.5 A g^?1). Ex situ X‐ray diffraction and transmission electron microscopy are used to explore the lithium storage mechanism of MoTe₂. Moreover, the electrochemical performance of a MoTe₂/FLG//0.35Li₂MnO₃·0.65LiMn_0.5Ni_0.5O₂ full cell is investigated, which displays a reversible capacity of 499 mAh g^?1 (based on the MoTe₂/FLG mass) at 100 mA g^?1 and a capacity retention of 78% over 50 cycles, suggesting the promising application of MoTe₂/FLG for lithium‐ion storage. First‐principles calculations exhibit that the lowest diffusion barrier (0.18 eV) for lithium ions along pathway III in the MoTe₂ layered structure is beneficial for improving the Li intercalation/deintercalation property.     

Ultrahigh‐Sensitive Broadband Photodetectors Based on Dielectric Shielded MoTe2/Graphene/SnS2 p–g–n Junctions

2D atomic sheets of transition metal dichalcogenides (TMDs) have a tremendous potential for next‐generation optoelectronics since they can be stacked layer‐by‐layer to form van der Waals (vdW) heterostructures. This allows not only bypassing difficulties in heteroepitaxy of lattice‐mismatched semiconductors of desired functionalities but also providing a scheme to design new optoelectronics that can surpass the fundamental limitations on their conventional semiconductor counterparts. Herein, a novel 2D h‐BN/p‐MoTe₂/graphene/n‐SnS₂/h‐BN p–g–n junction, fabricated by a layer‐by‐layer dry transfer, demonstrates high‐sensitivity, broadband photodetection at room temperature. The combination of the MoTe₂ and SnS₂ of complementary bandgaps, and the graphene interlayer provides a unique vdW heterostructure with a vertical built‐in electric field for high‐efficiency broadband light absorption, exciton dissociation, and carrier transfer. The graphene interlayer plays a critical role in enhancing sensitivity and broadening the spectral range. An optimized device containing 5?7‐layer graphene has been achieved and shows an extraordinary responsivity exceeding 2600 A W^?1 with fast photoresponse and specific detectivity up to ≈10¹³ Jones in the ultraviolet–visible–near‐infrared spectrum. This result suggests that the vdW p–g–n junctions containing multiple photoactive TMDs can provide a viable approach toward future ultrahigh‐sensitivity and broadband photonic detectors.     

Homogeneous 2D MoTe2 p–n Junctions and CMOS Inverters formed by Atomic‐Layer‐Deposition‐Induced Doping

Recently, α‐MoTe₂, a 2D transition‐metal dichalcogenide (TMD), has shown outstanding properties, aiming at future electronic devices. Such TMD structures without surface dangling bonds make the 2D α‐MoTe₂ a more favorable candidate than conventional 3D Si on the scale of a few nanometers. The bandgap of thin α‐MoTe₂ appears close to that of Si and is quite smaller than those of other typical TMD semiconductors. Even though there have been a few attempts to control the charge‐carrier polarity of MoTe₂, functional devices such as p–n junction or complementary metal–oxide–semiconductor (CMOS) inverters have not been reported. Here, we demonstrate a 2D CMOS inverter and p–n junction diode in a single α‐MoTe₂ nanosheet by a straightforward selective doping technique. In a single α‐MoTe₂ flake, an initially p‐doped channel is selectively converted to an n‐doped region with high electron mobility of 18 cm² V^?1 s^?1 by atomic‐layer‐deposition‐induced H‐doping. The ultrathin CMOS inverter exhibits a high DC voltage gain of 29, an AC gain of 18 at 1 kHz, and a low static power consumption of a few nanowatts. The results show a great potential of α‐MoTe₂ for future electronic devices based on 2D semiconducting materials.     

A Self‐Powered and Flexible Organometallic Halide Perovskite Photodetector with Very High Detectivity

Flexible and self‐powered photodetectors (PDs) are highly desirable for applications in image sensing, smart building, and optical communications. In this paper, a self‐powered and flexible PD based on the methylammonium lead iodide (CH₃NH₃PBI₃) perovskite is demonstrated. Such a self‐powered PD can operate even with irregular motion such as human finger tapping, which enables it to work without a bulky external power source. In addition, with high‐quality CH₃NH₃PBI₃ perovskite thin film fabricated with solvent engineering, the PD exhibits an impressive detectivity of 1.22 × 10¹³ Jones. In the self‐powered voltage detection mode, it achieves a large responsivity of up to 79.4 V mW^?1 cm^?2 and a voltage response of up to ≈90%. Moreover, as the PD is made of flexible and transparent polymer films, it can operate under bending and functions at 360 ° of illumination. As a result, the self‐powered, flexible, 360 ° omnidirectional perovskite PD, featuring high detectivity and responsivity along with real‐world sensing capability, suggests a new direction for next‐generation optical communications, sensing, and imaging applications.     

Controllable P‐ and N‐Type Conversion of MoTe2 via Oxide Interfacial Layer for Logic Circuits

To realize basic electronic units such as complementary metal‐oxide‐semiconductor (CMOS) inverters and other logic circuits, the selective and controllable fabrication of p‐ and n‐type transistors with a low Schottky barrier height is highly desirable. Herein, an efficient and nondestructive technique of electron‐charge transfer doping by depositing a thin Al₂O₃ layer on chemical vapor deposition (CVD)‐grown 2H‐MoTe₂ is utilized to tune the doping from p‐ to n‐type. Moreover, a type‐controllable MoTe₂ transistor with a low Schottky barrier height is prepared. The selectively converted n‐type MoTe₂ transistor from the p‐channel exhibits a maximum on‐state current of 10 µA, with a higher electron mobility of 8.9 cm² V^?1 s^?1 at a drain voltage (V_ds) of 1 V with a low Schottky barrier height of 28.4 meV. To validate the aforementioned approach, a prototype homogeneous CMOS inverter is fabricated on a CVD‐grown 2H‐MoTe₂ single crystal. The proposed inverter exhibits a high DC voltage gain of 9.2 with good dynamic behavior up to a modulation frequency of 1 kHz. The proposed approach may have potential for realizing future 2D transition metal dichalcogenide‐based efficient and ultrafast electronic units with high‐density circuit components under a low‐dimensional regime.     

Nonlinear Saturable Absorption of Liquid‐Exfoliated Molybdenum/Tungsten Ditelluride Nanosheets

Molybdenum disulfide (MoS₂) and tungsten disulfide (WS₂), two representative transition metal dichalcogenide materials, have captured tremendous interest for their unique electronic, optical, and chemical properties. Compared with MoS₂ and WS₂, molybdenum ditelluride (MoTe₂) and tungsten ditelluride (WTe₂) possess similar lattice structures while having smaller bandgaps (less than 1 eV), which is particularly interesting for applications in the near‐infrared wavelength regime. Here, few‐layer MoTe₂/WTe₂ nanosheets are fabricated by a liquid exfoliation method using sodium deoxycholate bile salt as surfactant, and the nonlinear optical properties of the nanosheets are investigated. The results demonstrate that MoTe₂/WTe₂ nanosheets exhibit nonlinear saturable absorption property at 1.55 μm. Soliton mode‐locking operations are realized separately in erbium‐doped fiber lasers utilizing two types of MoTe₂/WTe₂‐based saturable absorbers, one of which is prepared by depositing the nanosheets on side polished fibers, while the other is fabricated by mixing the nanosheets with polyvinyl alcohol and then evaporating them on substrates. Numerous applications may benefit from the nonlinear saturable absorption features of MoTe₂/WTe₂ nanosheets, such as visible/near‐infrared pulsed laser, materials processing, optical sensors, and modulators.     

Phase Transition and Superconductivity Enhancement in Se‐Substituted MoTe2 Thin Films

Consecutively tailoring few‐layer transition metal dichalcogenides MX₂ from 2H to T_d phase may realize the long‐sought topological superconductivity in a single material system by incorporating superconductivity and the quantum spin Hall effect together. Here, this study demonstrates that a consecutive structural phase transition from T_d to 1T′ to 2H polytype can be realized by increasing the Se concentration in Se‐substituted MoTe₂ thin films. More importantly, the Se‐substitution is found to dramatically enhance the superconductivity of the MoTe₂ thin film, which is interpreted as the introduction of two‐band superconductivity. The chemical‐constituent‐induced phase transition offers a new strategy to study the s^+? superconductivity and the possible topological superconductivity, as well as to develop phase‐sensitive devices based on MX₂ materials.     

Self‐Powered Si/CdS Flexible Photodetector with Broadband Response from 325 to 1550 nm Based on Pyro‐phototronic Effect: An Approach for Photosensing below Bandgap Energy

Cadmium sulfide (CdS) has received widespread attention as the building block of optoelectronic devices due to its extraordinary optoelectronic properties, low work function, and excellent thermal and chemical stability. Here, a self‐powered flexible photodetector (PD) based on p‐Si/n‐CdS nanowires heterostructure is fabricated. By introducing the pyro‐phototronic effect derived from wurtzite structured CdS, the self‐powered PD shows a broadband response range, even beyond the bandgap limitation, from UV (325 nm) to near infrared (1550 nm) under zero bias with fast response speed. The light‐induced pyroelectric potential is utilized to modulate the optoelectronic processes and thus improve the photoresponse performance. Lasers with different wavelengths have different effects on the self‐powered PDs and corresponding working mechanisms are carefully investigated. Upon 325 nm laser illumination, the rise time and fall time of the self‐powered PD are 245 and 277 µs, respectively, which are faster than those of most previously reported CdS‐based nanostructure PDs. Meanwhile, the photoresponsivity R and specific detectivity D* regarding to the relative peak‐to‐peak current are both enhanced by 67.8 times, compared with those only based on the photovoltaic effect‐induced photocurrent. The self‐powered flexible PD with fast speed, stable, and broadband response is expected to have extensive applications in various environments.     

A Light Harvesting,Self‐Powered Monolith Tactile Sensor Based on Electric Field Induced Effects in MAPbI3 Perovskite

Organolead trihalide perovskite MAPbI₃ shows a distinctive combination of properties such as being ferroelectric and semiconducting, with ion migration effects under poling by electric fields. The combination of its ferroelectric and semiconducting nature is used to make a light harvesting, self‐powered tactile sensor. This sensor interfaces ZnO nanosheets as a pressure‐sensitive drain on the MAPbI₃ film and once poled is operational for at least 72 h with just light illumination. The sensor is monolithic in structure, has linear response till 76 kPa, and is able to operate continuously as the energy harvesting mechanism is decoupled from its pressure sensing mechanism. It has a sensitivity of 0.57 kPa^?1, which can be modulated by the strength of the poling field. The understanding of these effects in perovskite materials and their application in power source free devices are of significance to a wide array of fields where these materials are being researched and applied.     

Carrier‐Type Modulation and Mobility Improvement of Thin MoTe2

A systematic modulation of the carrier type in molybdenum ditelluride (MoTe₂) field‐effect transistors (FETs) is described, through rapid thermal annealing (RTA) under a controlled O₂ environment (p‐type modulation) and benzyl viologen (BV) doping (n‐type modulation). Al₂O₃ capping is then introduced to improve the carrier mobilities and device stability. MoTe₂ is found to be ultrasensitive to O₂ at elevated temperatures (250 °C). Charge carriers of MoTe₂ flakes annealed via RTA at various vacuum levels are tuned between predominantly pristine n‐type ambipolar, symmetric ambipolar, unipolar p‐type, and degenerate‐like p‐type. Changes in the MoTe₂‐transistor performance are confirmed to originate from the physical and chemical absorption and dissociation of O₂, especially at tellurium vacancy sites. The electron branch is modulated by varying the BV dopant concentrations and annealing conditions. Unipolar n‐type MoTe₂ FETs with a high on–off ratio exceeding 10⁶ are achieved under optimized doping conditions. By introducing Al₂O₃ capping, carrier field effect mobilities (41 for holes and 80 cm² V^?1 s^?1 for electrons) and device stability are improved due to the reduced trap densities and isolation from ambient air. Lateral MoTe₂ p–n diodes with an ideality factor of 1.2 are fabricated using the p‐ and n‐type doping technique to test the superb potential of the doping method in functional electronic device applications.     

Raman Signatures of Broken Inversion Symmetry and In‐Plane Anisotropy in Type‐II Weyl Semimetal Candidate TaIrTe4

The layered ternary compound TaIrTe₄ is an important candidate to host the recently predicted type‐II Weyl fermions. However, a direct and definitive proof of the absence of inversion symmetry in this material, a prerequisite for the existence of Weyl Fermions, has so far remained evasive. Herein, an unambiguous identification of the broken inversion symmetry in TaIrTe₄ is established using angle‐resolved polarized Raman spectroscopy. Combining with high‐resolution transmission electron microscopy, an efficient and nondestructive recipe to determine the exact crystallographic orientation of TaIrTe₄ crystals is demonstrated. Such technique could be extended to the fast identification and characterization of other type‐II Weyl fermions candidates. A surprisingly strong in‐plane electrical anisotropy in TaIrTe₄ thin flakes is also revealed, up to 200% at 10 K, which is the strongest known electrical anisotropy for materials with comparable carrier density, notably in such good metals as copper and silver.     

Symmetry‐Reduction Enhanced Polarization‐Sensitive Photodetection in Core–Shell SbI3/Sb2O3 van der Waals Heterostructure

Structural symmetry is a simple way to quantify the anisotropic properties of materials toward unique device applications including anisotropic transportation and polarization‐sensitive photodetection. The enhancement of anisotropy can be achieved by artificial symmetry‐reduction design. A core–shell SbI₃/Sb₂O₃ nanowire, a heterostructure bonded by van der Waals forces, is introduced as an example of enhancing the performance of polarization‐sensitive photodetectors via symmetry reduction. The structural, vibrational, and optical anisotropies of such core–shell nanostructures are systematically investigated. It is found that the anisotropic absorbance of a core–shell nanowire is obviously higher than that of two single compounds from both theoretical and experimental investigations. Anisotropic photocurrents of the polarization‐sensitive photodetectors based on these core–shell SbI₃/Sb₂O₃ van der Waals nanowires are measured ranging from ultraviolet (UV) to visible light (360–532 nm). Compared with other van der Waals 1D materials, low anisotropy ratio (I_max/I_min) is measured based on SbI₃ but a device based on this core–shell nanowire possesses a relatively high anisotropy ratio of ≈3.14 under 450 nm polarized light. This work shows that the low‐symmetrical core–shell van der Waals heterostructure has large potential to be applied in wide range polarization‐sensitive photodetectors.