Metastable Polymorphic Phases in Monolayer TaTe2

Polymorphic phases and collective phenomena—such as charge density waves (CDWs)—in transition metal dichalcogenides (TMDs) dictate the physical and electronic properties of the material. Most TMDs naturally occur in a single given phase, but the fine-tuning of growth conditions via methods such as molecular beam epitaxy (MBE) allows to unlock otherwise inaccessible polymorphic structures. Exploring and understanding the morphological and electronic properties of new phases of TMDs is an essential step to enable their exploitation in technological applications. Here, scanning tunneling microscopy (STM) is used to map MBE-grown monolayer (ML) TaTe₂. This work reports the first observation of the 1H polymorphic phase, coexisting with the 1T, and demonstrates that their relative coverage can be controlled by adjusting synthesis parameters. Several superperiodic structures, compatible with CDWs, are observed to coexist on the 1T phase. Finally, this work provides theoretical insight on the delicate balance between Te…Te and Ta–Ta interactions that dictates the stability of the different phases. The findings demonstrate that TaTe₂ is an ideal platform to investigate competing interactions, and indicate that accurate tuning of growth conditions is key to accessing metastable states in TMDs.     

Field-Induced CDW Phases in a Quasi-One-Dimensional Organic Conductor, HMTSF-TCNQ Under Pressure of 1 GPa in Magnetic Field of 31 T

HMTSF-TCNQ is a quasi-one-dimensional organic conductor which undergoes CDW(charge density wave) transition at 30 K at ambient pressure, where HMTSF-TCNQ is hexamethylenetetraselena fulvalene-tetracyano quino dimethane. This CDW is suppressed by the pressure of 1 GPa. At this pressure, we found field-induced successive hysteretic transitions in magnetoresistance. This reminds us of the successive field-induced SDW (spin density wave) phases in TMTSF₂X salts. However, the field range of interest is 2–3 times higher than that of TMTSF₂X salts. Therefore, we need really high field to examine these properties. It is very likely that the field induced phases are of field induced CDW (FICDW), where quantum Hall effect and many interesting phenomena are expected like in the case of FISDW. Together with the magnetoresistance study up to the field of 31 Tesla and at temperatures down to 0.4 K in various magnetic field angles respective to the crystal axes, we examined the angular dependence of magnetoresistance oscillations(AMRO). It turned out that AMRO demonstrates clearly the occurrence of field-induced phase rather than the magneto-resistance by field sweep. Since the Hall resistance, R _xy in the field-induced phases showed stepwise plateau structure against the field sweep, and its strength was in the order of magnitude of h/e ² per molecular sheet, the Hall effect is very suggestive of quantum Hall effect.     

Visualizing the Anomalous Charge Density Wave States in Graphene/NbSe2 Heterostructures

Metallic layered transition metal dichalcogenides (TMDs) host collective many-body interactions, including the competing superconducting and charge density wave (CDW) states. Graphene is widely employed as a heteroepitaxial substrate for the growth of TMD layers and as an ohmic contact, where the graphene/TMD heterostructure is naturally formed. The presence of graphene can unpredictably influence the CDW order in 2D CDW conductors. This work reports the CDW transitions of 2H-NbSe₂ layers in graphene/NbSe₂ heterostructures. The evolution of Raman spectra demonstrates that the CDW phase transition temperatures (T_CDW) of NbSe₂ are dramatically decreased when capped by graphene. The induced anomalous short-range CDW state is confirmed by scanning tunneling microscopy measurements. The findings propose a new criterion to determine the T_CDW through monitoring the line shape of the A_1g mode. Meanwhile, the 2D band is also discovered as an indicator to observe the CDW transitions. First-principles calculations imply that interfacial electron doping suppresses the CDW states by impeding the lattice distortion of 2H-NbSe₂. The extraordinary random CDW lattice suggests deep insight into the formation mechanism of many collective electronic states and possesses great potential in modulating multifunctional devices.     

Lateral 2D WSe2 p–n Homojunction Formed by Efficient Charge-Carrier-Type Modulation for High-Performance Optoelectronics

As unique building blocks for next-generation optoelectronics, high-quality 2D p–n junctions based on semiconducting transition metal dichalcogenides (TMDs) have attracted wide interest, which are urgent to be exploited. Herein, a novel and facile electron doping of WSe₂ by cetyltrimethyl ammonium bromide (CTAB) is achieved for the first time to form a high-quality intramolecular p–n junction with superior optoelectronic properties. Efficient manipulation of charge carrier type and density in TMDs via electron transfer between Br⁻ in CTAB and TMDs is proposed theoretically by density functional theory (DFT) calculations. Compared with the intrinsic WSe₂ photodetector, the switching light ratio (I_light/I_dark) of the p–n junction device can be enhanced by 10³, and the temporal response is also dramatically improved. The device possesses a responsivity of 30 A W⁻¹, with a specific detectivity of over 10¹¹ Jones. In addition, the mechanism of charge transfer in CTAB-doped 2D WSe₂ and WS₂ are investigated by designing high-performance field effect transistors. Besides the scientific insight into the effective manipulation of 2D materials by chemical doping, this work presents a promising applicable approach toward next-generation photoelectronic devices with high efficiency.     

High Spin Hall Conductivity in Large-Area Type-II Dirac Semimetal PtTe2

Manipulation of magnetization by electric-current-induced spin–orbit torque (SOT) is of great importance for spintronic applications because of its merits in energy-efficient and high-speed operation. An ideal material for SOT applications should possess high charge-spin conversion efficiency and high electrical conductivity. Recently, transition metal dichalcogenides (TMDs) emerge as intriguing platforms for SOT study because of their controllability in spin–orbit coupling, conductivity, and energy band topology. Although TMDs show great potentials in SOT applications, the present study is restricted to the mechanically exfoliated samples with small sizes and relatively low conductivities. Here, a manufacturable recipe is developed to fabricate large-area thin films of PtTe₂, a type-II Dirac semimetal, to study their capability of generating SOT. Large SOT efficiency together with high conductivity results in a giant spin Hall conductivity of PtTe₂ thin films, which is the largest value among the presently reported TMDs. It is further demonstrated that the SOT from PtTe₂ layer can switch a perpendicularly magnetized CoTb layer efficiently. This work paves the way for employing PtTe₂-like TMDs for wafer-scale spintronic device applications.     

Chemical Growth of 1T‐TaS2 Monolayer and Thin Films: Robust Charge Density Wave Transitions and High Bolometric Responsivity

Ultrathin two‐dimensional (2D) charge density wave (CDW) materials, with sharp resistance change at the phase‐transition temperature, yet with ultrathin thickness, hold great potential for electrical device applications. However, chemical synthesis of high‐quality samples and observation of the CDW states down to the monolayer limit is still of great challenge. Chemical vapor deposition of 1T‐TaS₂ sheets on hexagonal boron nitride (h‐BN) with robust CDW states even down to the monolayer extreme is reported here. Further, based on the near commensurate CDW to incommensurate CDW phase transition with a high temperature coefficient of resistance (TCR), highly responsive room‐temperature bolometers are fabricated by suspending the as‐grown 1T‐TaS₂ sheets.     

Nanoscale Dynamics in Complex Materials by Resonant X-Ray Photon Correlation Spectroscopy (rXPCS)

Complex materials are characterized by a competition between multiple phases that coexist in a nanoscale phase separation scenario. In particular, there is a growing interest in understanding how the competition between charge density wave (CDW), the spin density wave (SDW), and the defects puddles promotes the material’s functionality at the macroscopic scale. For this reason, the finding of a new technique that could combine temporal and spatial resolution with bulk sensitivity is extremely important. A good solution could arrive by the use of a time-resolved scattering technique like X-ray photon correlation spectroscopy (XPCS). As example of possible application, we propose the study of CDW nanoscale dynamic, in a simple system like La _1.72Sr _0.28NiO ₄, using the combination of the resonant X-ray scattering (RXS) and XPCS. This could provide important information on the CDW nanoscale dynamic in complex material characterized by nanoscale phase separation.     

Magnetic Field Dependence of CDW Phases in (Per)2M(mnt)2 (M = Pt, Au)

Recently the authors discovered that the suppression of the charge density wave (CDW) ground states by high magnetic fields in the organic conductor series (Per)₂M(mnt)₂ is followed by additional high field, CDW-like phases. The purpose of this paper is to review these compounds and to consider the relevant parameters of the materials that describe the manner in which the CDW ground state may undergo new field induced changes above the Pauli limit.     

Evidence of Spin Frustration in a Vanadium Diselenide Monolayer Magnet

Monolayer VSe₂, featuring both charge density wave and magnetism phenomena, represents a unique van der Waals magnet in the family of metallic 2D transition‐metal dichalcogenides (2D‐TMDs). Herein, by means of in situ microscopy and spectroscopic techniques, including scanning tunneling microscopy/spectroscopy, synchrotron X‐ray and angle‐resolved photoemission, and X‐ray absorption, direct spectroscopic signatures are established, that identify the metallic 1T‐phase and vanadium 3d¹ electronic configuration in monolayer VSe₂ grown on graphite by molecular‐beam epitaxy. Element‐specific X‐ray magnetic circular dichroism, complemented with magnetic susceptibility measurements, further reveals monolayer VSe₂ as a frustrated magnet, with its spins exhibiting subtle correlations, albeit in the absence of a long‐range magnetic order down to 2 K and up to a 7 T magnetic field. This observation is attributed to the relative stability of the ferromagnetic and antiferromagnetic ground states, arising from its atomic‐scale structural features, such as rotational disorders and edges. The results of this study extend the current understanding of metallic 2D‐TMDs in the search for exotic low‐dimensional quantum phenomena, and stimulate further theoretical and experimental studies on van der Waals monolayer magnets.     

Phase Engineering of Transition Metal Dichalcogenides with Unprecedentedly High Phase Purity,Stability, and Scalability via Molten-Metal-Assisted Intercalation

The crystalline phase of layered transition metal dichalcogenides (TMDs) directly determines their material property. The most thermodynamically stable phase structures in TMDs are the semiconducting 2H and metastable metallic 1T phases. To overcome the low phase purity and instability of 1T-TMDs, which limits the utilization of their intrinsic properties, various synthesis strategies for 1T-TMDs have been proposed in phase-engineering studies. Herein, a facile and scalable synthesis of 1T-phase molybdenum disulfide (MoS₂) via the molten-metal-assisted intercalation (MMI) approach is introduced, which exploits the capillary action of molten potassium and the difference between the electron affinity of MoS₂ and the ionization potential of potassium. Highly reactive molten potassium metal can readily intercalate into the MoS₂ interlayers, inducing an efficient phase transition from the 2H to 1T crystal structure. The ionic bonding between the intercalated potassium and sulfur lowers the energy barrier of the 1T-phase transition, enhancing the phase stability of the 1T crystals. Owing to the high purity and stability of the 1T phase, the electrocatalytic performance for the hydrogen evolution reaction is significantly higher in 1T-MoS₂ (MMI) than in 2H-MoS₂ and even in 1T-MoS₂ synthesized using n-butyllithium.     

Synthesis of Ultrathin Metallic MTe2 (M = V,Nb, Ta) Single‐Crystalline Nanoplates

Two‐dimensional materials with intrinsic magnetism have recently drawn intense interest for both the fundamental studies and potential technological applications. However, the studies to date have been largely limited to mechanically exfoliated materials. Herein, an atmospheric pressure chemical vapor deposition route to ultrathin group VB metal telluride MTe₂ (M = V, Nb, Ta) nanoplates with thickness as thin as 3 nm is reported. It is shown that the resulting nanoplates can be systematically evolved from mostly thicker hexagonal domains to thinner triangular domains with an increasing flow rate of the carrier gas. X‐ray diffraction and transmission electron microscopy studies reveal MTe₂ (M = V, Nb, Ta) nanoplates are high‐quality single crystals. High‐resolution scanning transmission electron microscope imaging reveals the VTe₂ and NbTe₂ nanoplates adopt the hexagonal 1T phase and the TaTe₂ nanoplates show a monoclinic distorted 1T phase. Electronic transport studies show that MTe₂ single crystals exhibit metallic behavior. Magnetic measurements show that VTe₂ and NbTe₂ exhibit ferromagnetism and TaTe₂ shows paramagnetic behavior. The preparation of ultrathin few‐layered MTe₂ nanoplates will open up exciting opportunities for the burgeoning field of spintronics, sensors, and magneto‐optoelectronics.     

Large‐Area Atomic Layers of the Charge‐Density‐Wave Conductor TiSe2

Layered transition metal (Ti, Ta, Nb, etc.) dichalcogenides are important prototypes for the study of the collective charge density wave (CDW). Reducing the system dimensionality is expected to lead to novel properties, as exemplified by the discovery of enhanced CDW order in ultrathin TiSe₂. However, the syntheses of monolayer and large‐area 2D CDW conductors can currently only be achieved by molecular beam epitaxy under ultrahigh vacuum. This study reports the growth of monolayer crystals and up to 5 × 10⁵ µm² large films of the typical 2D CDW conductor—TiSe₂—by ambient‐pressure chemical vapor deposition. Atomic resolution scanning transmission electron microscopy indicates the as‐grown samples are highly crystalline 1T‐phase TiSe₂. Variable‐temperature Raman spectroscopy shows a CDW phase transition temperature of 212.5 K in few layer TiSe₂, indicative of high crystal quality. This work not only allows the exploration of many‐body state of TiSe₂ in 2D limit but also offers the possibility of utilizing large‐area TiSe₂ in ultrathin electronic devices.     

Single electron transistor fabricated with SOI wafer

The single electron transistor (SET) is the most sensitive device for measuring the charge of electron. It has been proposed by Kane that the SET can be used for readout of calculated results in Si-based quantum computer. We fabricated the SET with SOI substrate utilizing the suspended mask of SiO₂ and Si for the purpose of using it for readout of calculation in Si-Based quantum computer. By using only the above materials for the mask, high temperature processes including ion implantation and activation annealing could be possible and it was never achieved in conventional methods with the suspended mask with photoresist. First, the suspended mask with enough undercut in SOI was made by removing the box oxide of SOI wafer combining with pattern delineation by electron beam lithography, anisotropically reactive ion etching and isotropic wet etching. After forming the suspended mask, Al films were evaporated from two different angles to make an overlap just below the bridge, resulting in completing the SET in the undercut region possible to measure the electron spin. After making the Al/Al₂O₃/Al SET, we measured the I–V characteristic between source and drain at 1.8 K. The Coulomb blockade and the Coulomb oscillation were observed.     

Pseudogap and (An)isotropic Scattering in the Fluctuating Charge-Density Wave Phase of Cuprates

We present a general scenario for high-temperature superconducting cuprates, based on the presence of dynamical charge density waves (CDWs) and to the occurrence of a CDW quantum critical point, which occurs, e.g., at doping p ≈ 0.16 in YBa₂Cu₃O_{6 + δ} (YBCO). In this framework, the pseudogap temperature T ^? is interpreted in terms of a reduction of the density of states due to incipient CDW and, at lower temperature to the possible formation of incoherent superconducting pairs. The dynamically fluctuating character of CDW accounts for the different temperatures at which the CDW onset revealed by X-ray scattering (T _{o n s} (p)), and the static three-dimensional CDW ordering appear. We also investigate the anisotropic character of the CDW-mediated scattering. We find that this is strongly anisotropic only close to the CDW quantum critical point (QCP) at low temperature and very low energy. It rapidly becomes nearly isotropic and marginal-Fermi-liquid-like away from the CDW QCP and at finite (even rather small) energies. This may reconcile the interpretation of Hall measurements in terms of anisotropic CDW scattering (arXiv:1604.07852v1) with recent photoemission experiments Bok, J.M., et al. Sci. Adv. 2, e1501329 (2016).     

High-Temperature Superconductivity in a Hyperbolic Geometry of Complex Matter from Nanoscale to Mesoscopic Scale

While it was known that high-temperature superconductivity appears in cuprates showing complex multiscale phase separation due to inhomogeneous charge density wave (CDW) order, the spatial distribution of CDW domains remained an open question for a long time, because of the lack of experimental probes able to visualize their spatial distribution between atomic and macroscopic scale. Recently scanning micro-X-ray diffraction (S μXRD) revealed CDW crystalline electronic puddles with a complex fat-tailed spatial distribution of their size. In this work, we have determined and mapped the anisotropy of the CDW puddles in HgBa₂CuO₄ + y (Hg1201) single crystal. We discuss the emergence of high-temperature superconductivity in the interstitial space with hyperbolic geometry that opens a new paradigm for quantum coherence at high temperature where negative dielectric function and interference between different pathways can help to raise the critical temperature.     

Thermodynamic properties of VTe<Subscript>2</Subscript>

The methods of adiabatic and differential scanning calorimetry are used to measure the temperature dependence of the heat capacity. Thermodynamic functions are calculated for VTe₂. The Debye characteristic temperature is determined and the fractal dimension of crystalline vanadium ditelluride is calculated.     

Dirac Semimetal Heterostructures: 3D Cd3As2 on 2D Graphene

Dirac semimetal is an emerging class of quantum matters, ranging from 2D category, such as, graphene and surface states of topological insulator to 3D category, for instance, Cd₃As₂ and Na₃Bi. As 3D Dirac semimetals typically possess Fermi‐arc surface states, the 2D–3D Dirac van der Waals heterostructures should be promising for future electronics. Here, graphene–Cd₃As₂ heterostructures are fabricated through direct layer‐by‐layer stacking. The electronic coupling results in a notable interlayer charge transfer, which enables us to modulate the Fermi level of graphene through Cd₃As₂. A planar graphene p–n–p junction is achieved by selective modification, which demonstrates quantized conductance plateaus. Moreover, compared with the bare graphene device, the graphene–Cd₃As₂ hybrid device presents large nonlocal signals near the Dirac point due to the charge transfer from the spin‐polarized surface states in the adjacent Cd₃As₂. The results enrich the family of van der Waals heterostructure and should inspire more studies on the application of Dirac/Weyl semimetals in spintronics.     

Multioperation-Mode Light-Emitting Field-Effect Transistors Based on van der Waals Heterostructure

2D semiconductors have shown great potential for application to electrically tunable optoelectronics. Despite the strong excitonic photoluminescence (PL) of monolayer transition metal dichalcogenides (TMDs), their efficient electroluminescence (EL) has not been achieved due to the low efficiency of charge injection and electron–hole recombination. Here, multioperation-mode light-emitting field-effect transistors (LEFETs) consisting of a monolayer WSe₂ channel and graphene contacts coupled with two top gates for selective and balanced injection of charge carriers are demonstrated. Visibly observable EL is achieved with the high external quantum efficiency of ≈6% at room temperature due to efficient recombination of injected electrons and holes in a confined 2D channel. Further, electrical tunability of both the channel and contacts enables multioperation modes, such as antiambipolar, depletion,and unipolar regions, which can be utilized for polarity-tunable field-effect transistors and photodetectors. The work exhibits great potential for use in 2D semiconductor LEFETs for novel optoelectronics capable of high efficiency, multifunctions, and heterointegration.     

Superconductivity and Topological Numbers in the Hubbard Chain with Bond-Charge Interaction

We determine the quantum phase diagram of the Hubbard chain with electron-hole symmetric correlated hopping at 1/2- and 1/4-filling using geometric concepts and continuum limit field theory. The long distance behavior of various correlation functions show a very rich phase diagram with several insulating, metallic, and superconducting phases, which might be relevant to (TMTSF) ₂ X compounds. The closing of charge and spin gaps are accurately resolved as topological transitions (jumps in of Berry phases). The metallic or insulating character of each thermodynamic phase is obtained from the ground-state expectation value of a displacement operator in reciprocal space.     

Phase formation and properties of vanadium-modified Ni–Cr–B-Si–C laser-deposited coatings

A Ni–Cr–B-Si–C alloy powder was modified by addition of 2 and 5 wt% of vanadium to tackle the high cracking sensitivity of the original composition during laser deposition. The effects of vanadium on microstructure and phases were investigated by Scanning Electron Microscopy, Energy Dispersive Spectroscopy, and Transmission Electron Microscopy (TEM) and the changes in the hardness and cracking tendency of the deposits were evaluated. In comparison to the original composition, V-modified alloys produced deposits with lower hardness and moderately reduced cracking tendencies. Addition of vanadium transformed the nature and the morphology of the boride precipitates and added VC particles to the microstructure but did not induce a significant microstructural refinement. TEM characterizations confirmed that borides phases in the modified deposits consisted of alternating layers of CrB and (Cr_1?xV_x)B but the VC existed as independent particles which were formed on the boride precipitates. The final phase constitution of the modified alloys was dramatically influenced by the complete solid solubility between CrB and VB and the lack of solubility between Cr₇C₃ and VC. Addition of vanadium did not provide the phases which could act as nucleation sites to refine the microstructure of the deposits because VB had a tendency to dissolve in CrB and VC was formed at low temperatures on the boride phases. The outcomes of this study can be used to evaluate the effects of adding early transition metals such as vanadium on the microstructure and phase formations of the Ni–Cr–B-Si–C alloys.