A hybrid topological quantum state in an elemental solid.

Topology1-3 and interactions are foundational concepts in the modern understanding of quantum matter. Their nexus yields three important research directions: (1) the competition between distinct interactions, as in several intertwined phases, (2) the interplay between interactions and topology that drives the phenomena in twisted layered materials and topological magnets, and (3) the coalescence of several topological orders to generate distinct novel phases. The first two examples have grown into major areas of research, although the last example remains mostly unexplored, mainly because of the lack of a material platform for experimental studies. Here, using tunnelling microscopy, photoemission spectroscopy and a theoretical analysis, we unveil a 'hybrid' topological phase of matter in the simple elemental-solid arsenic. Through a unique bulk-surface-edge correspondence, we uncover that arsenic features a conjoined strong and higher-order topology that stabilizes a hybrid topological phase. Although momentum-space spectroscopy measurements show signs of topological surface states, real-space microscopy measurements unravel a unique geometry of topologically induced step-edge conduction channels revealed on various natural nanostructures on the surface. Using theoretical models, we show that the existence of gapless step-edge states in arsenic relies on the simultaneous presence of both a non-trivial strong Z2 invariant and a non-trivial higher-order topological invariant, which provide experimental evidence for hybrid topology. Our study highlights pathways for exploring the interplay of different band topologies and harnessing the associated topological conduction channels in engineered quantum or nano-devices.

An ultrafast symmetry switch in a Weyl semimetal.

Topological quantum materials exhibit fascinating properties1-3, with important applications for dissipationless electronics and fault-tolerant quantum computers4,5. Manipulating the topological invariants in these materials would allow the development of topological switching applications analogous to switching of transistors6. Lattice strain provides the most natural means of tuning these topological invariants because it directly modifies the electron-ion interactions and potentially alters the underlying crystalline symmetry on which the topological properties depend7-9. However, conventional means of applying strain through heteroepitaxial lattice mismatch10 and dislocations11 are not extendable to controllable time-varying protocols, which are required in transistors. Integration into a functional device requires the ability to go beyond the robust, topologically protected properties of materials and to manipulate the topology at high speeds. Here we use crystallographic measurements by relativistic electron diffraction to demonstrate that terahertz light pulses can be used to induce terahertz-frequency interlayer shear strain with large strain amplitude in the Weyl semimetal WTe2, leading to a topologically distinct metastable phase. Separate nonlinear optical measurements indicate that this transition is associated with a symmetry change to a centrosymmetric, topologically trivial phase. We further show that such shear strain provides an ultrafast, energy-efficient way of inducing robust, well separated Weyl points or of annihilating all Weyl points of opposite chirality. This work demonstrates possibilities for ultrafast manipulation of the topological properties of solids and for the development of a topological switch operating at terahertz frequencies.

Giant Tunability of Intersubband Transitions and Quantum Hall Quartets in Few-Layer InSe Quantum Wells.

A two-dimensional (2D) quantum electron system is characterized by quantized energy levels, or subbands, in the out-of-plane direction. Populating higher subbands and controlling the intersubband transitions have wide technological applications such as optical modulators and quantum cascade lasers. In conventional materials, however, the tunability of intersubband spacing is limited. Here we demonstrate electrostatic population and characterization of the second subband in few-layer InSe quantum wells, with giant tunability of its energy, population, and spin-orbit coupling strength, via the control of not only layer thickness but also the out-of-plane displacement field. A modulation of as much as 350% or over 250 meV is achievable, underscoring the promise of InSe for tunable infrared and THz sources, detectors, and modulators.

Giant Terahertz Birefringence in an Ultrathin Anisotropic Semimetal.

Manipulating the polarization of light at the nanoscale is key to the development of next-generation optoelectronic devices. This is typically done via waveplates using optically anisotropic crystals, with thicknesses on the order of the wavelength. Here, using a novel ultrafast electron-beam-based technique sensitive to transient near fields at THz frequencies, we observe a giant anisotropy in the linear optical response in the semimetal WTe2 and demonstrate that one can tune the THz polarization using a 50 nm thick film, acting as a broadband wave plate with thickness 3 orders of magnitude smaller than the wavelength. The observed circular deflections of the electron beam are consistent with simulations tracking the trajectory of the electron beam in the near field of the THz pulse. This finding offers a promising approach to enable atomically thin THz polarization control using anisotropic semimetals and defines new approaches for characterizing THz near-field optical response at far-subwavelength length scales.

One-pot growth of two-dimensional lateral heterostructures via sequential edge-epitaxy.

Two-dimensional heterojunctions of transition-metal dichalcogenides have great potential for application in low-power, high-performance and flexible electro-optical devices, such as tunnelling transistors, light-emitting diodes, photodetectors and photovoltaic cells. Although complex heterostructures have been fabricated via the van der Waals stacking of different two-dimensional materials, the in situ fabrication of high-quality lateral heterostructures with multiple junctions remains a challenge. Transition-metal-dichalcogenide lateral heterostructures have been synthesized via single-step, two-step or multi-step growth processes. However, these methods lack the flexibility to control, in situ, the growth of individual domains. In situ synthesis of multi-junction lateral heterostructures does not require multiple exchanges of sources or reactors, a limitation in previous approaches as it exposes the edges to ambient contamination, compromises the homogeneity of domain size in periodic structures, and results in long processing times. Here we report a one-pot synthetic approach, using a single heterogeneous solid source, for the continuous fabrication of lateral multi-junction heterostructures consisting of monolayers of transition-metal dichalcogenides. The sequential formation of heterojunctions is achieved solely by changing the composition of the reactive gas environment in the presence of water vapour. This enables selective control of the water-induced oxidation and volatilization of each transition-metal precursor, as well as its nucleation on the substrate, leading to sequential edge-epitaxy of distinct transition-metal dichalcogenides. Photoluminescence maps confirm the sequential spatial modulation of the bandgap, and atomic-resolution images reveal defect-free lateral connectivity between the different transition-metal-dichalcogenide domains within a single crystal structure. Electrical transport measurements revealed diode-like responses across the junctions. Our new approach offers greater flexibility and control than previous methods for continuous growth of transition-metal-dichalcogenide-based multi-junction lateral heterostructures. These findings could be extended to other families of two-dimensional materials, and establish a foundation for the development of complex and atomically thin in-plane superlattices, devices and integrated circuits.

Evidence of a room-temperature quantum spin Hall edge state in a higher-order topological insulator.

Room-temperature realization of macroscopic quantum phases is one of the major pursuits in fundamental physics1,2. The quantum spin Hall phase3-6 is a topological quantum phase that features a two-dimensional insulating bulk and a helical edge state. Here we use vector magnetic field and variable temperature based scanning tunnelling microscopy to provide micro-spectroscopic evidence for a room-temperature quantum spin Hall edge state on the surface of the higher-order topological insulator Bi4Br4. We find that the atomically resolved lattice exhibits a large insulating gap of over 200 meV, and an atomically sharp monolayer step edge hosts an in-gap gapless state, suggesting topological bulk-boundary correspondence. An external magnetic field can gap the edge state, consistent with the time-reversal symmetry protection inherent in the underlying band topology. We further identify the geometrical hybridization of such edge states, which not only supports the Z2 topology of the quantum spin Hall state but also visualizes the building blocks of the higher-order topological insulator phase. Our results further encourage the exploration of high-temperature transport quantization of the putative topological phase reported here.

Superconductivity enhancement in phase-engineered molybdenum carbide/disulfide vertical heterostructures.

Stacking layers of atomically thin transition-metal carbides and two-dimensional (2D) semiconducting transition-metal dichalcogenides, could lead to nontrivial superconductivity and other unprecedented phenomena yet to be studied. In this work, superconducting α-phase thin molybdenum carbide flakes were first synthesized, and a subsequent sulfurization treatment induced the formation of vertical heterolayer systems consisting of different phases of molybdenum carbide-ranging from α to γ' and γ phases-in conjunction with molybdenum sulfide layers. These transition-metal carbide/disulfide heterostructures exhibited critical superconducting temperatures as high as 6 K, higher than that of the starting single-phased α-Mo2C (4 K). We analyzed possible interface configurations to explain the observed moiré patterns resulting from the vertical heterostacks. Our density-functional theory (DFT) calculations indicate that epitaxial strain and moiré patterns lead to a higher interfacial density of states, which favors superconductivity. Such engineered heterostructures might allow the coupling of superconductivity to the topologically nontrivial surface states featured by transition-metal carbide phases composing these heterostructures potentially leading to unconventional superconductivity. Moreover, we envisage that our approach could also be generalized to other metal carbide and nitride systems that could exhibit high-temperature superconductivity.

Enhanced Superconductivity in Monolayer Td-MoTe2.

Crystalline two-dimensional (2D) superconductors (SCs) with low carrier density are an exciting new class of materials in which electrostatic gating can tune superconductivity, electronic interactions play a prominent role, and electrical transport properties may directly reflect the topology of the Fermi surface. Here, we report the dramatic enhancement of superconductivity with decreasing thickness in semimetallic Td-MoTe2, with critical temperature (Tc) increasing up to 7.6 K for monolayers, a 60-fold increase with respect to the bulk Tc. We show that monolayers possess a similar electronic structure and density of states (DOS) as the bulk, implying that electronic interactions play a strong role in the enhanced superconductivity. Reflecting the low carrier density, the critical temperature, magnetic field, and current density are all tunable by an applied gate voltage. The response to high in-plane magnetic fields is distinct from that of other 2D SCs and reflects the canted spin texture of the electron pockets.

Paramagnetic Molecular Semiconductors Combining Anisotropic Magnetic Ions with TCNQ Radical Anions.

We report the synthesis, magnetic properties, and transport properties of paramagnetic metal complexes, [Co(DMF)4(TCNQ)2](TCNQ)2 (1), [La(DMF)8(TCNQ)](TCNQ)5 (2), and [Nd(DMF)7(TCNQ)](TCNQ)5 (3) (DMF = N,N-dimethylformamide, TCNQ = 7,7,8,8-tetracyanoquinodimethane). All three compounds contain fractionally charged TCNQδ- anions (0 < δ < 1) and mononuclear complex cations in which the coordination environment of a metal center includes several DMF molecules and one or two terminally coordinated TCNQδ- anions. The coordinated TCNQδ- anions participate in π-π stacking interactions with noncoordinated TCNQδ- anions, forming columnar substructures that provide efficient charge-transporting pathways. As a result, temperature-dependent conductivity measurements demonstrate that all three compounds exhibit semiconducting behavior.

Approaching the Intrinsic Limit in Transition Metal Diselenides via Point Defect Control.

Two dimensional (2D) transition-metal dichalcogenide (TMD) based semiconductors have generated intense recent interest due to their novel optical and electronic properties and potential for applications. In this work, we characterize the atomic and electronic nature of intrinsic point defects found in single crystals of these materials synthesized by two different methods, chemical vapor transport and self-flux growth. Using a combination of scanning tunneling microscopy (STM) and scanning transmission electron microscopy (STEM), we show that the two major intrinsic defects in these materials are metal vacancies and chalcogen antisites. We show that by control of the synthetic conditions, we can reduce the defect concentration from above 1013/cm2 to below 1011/cm2. Because these point defects act as centers for nonradiative recombination of excitons, this improvement in material quality leads to a hundred-fold increase in the radiative recombination efficiency.

Antiferroelectric Phase Transition in a Proton-Transfer Salt of Squaric Acid and 2,3-Dimethylpyrazine.

A proton-transfer reaction between squaric acid (H2sq) and 2,3-dimethylpyrazine (2,3-Me2pyz) results in crystallization of a new organic antiferroelectric (AFE), (2,3-Me2pyzH+)(Hsq-)·H2O (1), which possesses a layered structure. The structure of each layer can be described as partitioned into strips lined with methyl groups of the Me2pyzH+ cations and strips featuring extensive hydrogen bonding between the Hsq- anions and water molecules. Variable-temperature dielectric measurements and crystal structures determined through a combination of single-crystal X-ray and neutron diffraction reveal an AFE ordering at 104 K. The phase transition is driven by ordering of protons within the hydrogen-bonded strips. Considering the extent of proton transfer, the paraelectric (PE) state can be formulated as (2,3-Me2pyzH+)2(Hsq23-)(H5O2+), whereas the AFE phase can be described as (2,3-Me2pyzH+)(Hsq-)(H2O). The structural transition caused by the localization of protons results in the change in color from yellow in the PE state to colorless in the AFE state. The occurrence and mechanism of the AFE phase transition have been also confirmed by heat capacity measurements and variable-temperature infrared and Raman spectroscopy. This work demonstrates a potentially promising approach to the design of new electrically ordered materials by engineering molecule-based crystal structures in which hydrogen-bonding interactions are intentionally partitioned into quasi-one-dimensional regions.

Giant Anisotropic Magnetoresistance due to Purely Orbital Rearrangement in the Quadrupolar Heavy Fermion Superconductor PrV_{2}Al_{20}.

We report the discovery of giant and anisotropic magnetoresistance due to the orbital rearrangement in a non magnetic correlated metal. In particular, we measured the magnetoresistance under fields up to 31.4 T in the cubic Pr-based heavy fermion superconductor PrV_{2}Al_{20} with a non magnetic Γ_{3} doublet ground state, exhibiting antiferroquadrupole ordering below 0.7 K. For the [100] direction, we find that the high-field phase appears between 12 and 25 T, accompanied by a large jump at 12 T in the magnetoresistance (ΔMR∼100%) and in the anisotropic magnetoresistivity ratio by ∼20%. These observations indicate that the strong hybridization between the conduction electrons and anisotropic quadrupole moments leads to the Fermi surface reconstruction upon crossing the field-induced antiferroquadrupole (orbital) rearrangement.

Cross-Plane Carrier Transport in Van der Waals Layered Materials.

The mechanisms of carrier transport in the cross-plane crystal orientation of transition metal dichalcogenides are examined. The study of in-plane electronic properties of these van der Waals compounds has been the main research focus in recent years. However, the distinctive physical anisotropies, short-channel physics, and tunability of cross layer interactions can make the study of their electronic properties along the out-of-plane crystal orientation valuable. Here, the out-of-plane carrier transport mechanisms in niobium diselenide and hafnium disulfide are explored as two broadly different representative materials. Temperature-dependent current-voltage measurements are preformed to examine the mechanisms involved. First principles simulations and a tunneling model are used to understand these results and quantify the barrier height and hopping distance properties. Using Raman spectroscopy, the thermal response of the chemical bonds is directly explored and the insight into the van der Waals gap properties is acquired. These results indicate that the distinct cross-plane carrier transport characteristics of the two materials are a result of material thermal properties and thermally mediated transport of carriers through the van der Waals gaps. Exploring the cross-plane electron transport, the exciting physics involved is unraveled and potential new avenues for the electronic applications of van der Waals layers are inspired.

Low temperature photoconductivity of few layer p-type tungsten diselenide (WSe2) field-effect transistors (FETs).

We report on the low-temperature photoconductive properties of few layer p-type tungsten diselenide (WSe2) field-effect transistors (FETs) synthesized using the chemical vapor transport method. Photoconductivity measurements show that these FETs display room temperature photo-responsivities of ∼7 mAW-1 when illuminated with a laser of wavelength λ = 658 nm with a power of 38 nW. The photo-responsivities of these FETs showed orders of magnitude improvement (up to ∼1.1 AW-1 with external quantum efficiencies reaching as high as ∼188%) upon application of a gate voltage (V G = -60 V). A temperature dependent (100 K < T < 300 K) photoconductivity study reveals a weak temperature dependence of responsivity for these WSe2 phototransistors. We demonstrate that it is possible to obtain stable photo-responsivities of ∼0.76 ± 0.2 AW-1 (with applied V G = -60 V), at low temperatures in these FETs. These findings indicate the possibility of developing WSe2-based FETs for highly robust, efficient, and swift photodetectors with a potential for optoelectronic applications over a broad range of temperatures.

Intricate Resonant Raman Response in Anisotropic ReS2.

The strong in-plane anisotropy of rhenium disulfide (ReS2) offers an additional physical parameter that can be tuned for advanced applications such as logic circuits, thin-film polarizers, and polarization-sensitive photodetectors. ReS2 also presents advantages for optoelectronics, as it is both a direct-gap semiconductor for few-layer thicknesses (unlike MoS2 or WS2) and stable in air (unlike black phosphorus). Raman spectroscopy is one of the most powerful characterization techniques to nondestructively and sensitively probe the fundamental photophysics of a 2D material. Here, we perform a thorough study of the resonant Raman response of the 18 first-order phonons in ReS2 at various layer thicknesses and crystal orientations. Remarkably, we discover that, as opposed to a general increase in intensity of all of the Raman modes at excitonic transitions, each of the 18 modes behave differently relative to each other as a function of laser excitation, layer thickness, and orientation in a manner that highlights the importance of electron-phonon coupling in ReS2. In addition, we correct an unrecognized error in the calculation of the optical interference enhancement of the Raman signal of transition metal dichalcogenides on SiO2/Si substrates that has propagated through various reports. For ReS2, this correction is critical to properly assessing the resonant Raman behavior. We also implemented a perturbation approach to calculate frequency-dependent Raman intensities based on first-principles and demonstrate that, despite the neglect of excitonic effects, useful trends in the Raman intensities of monolayer and bulk ReS2 at different laser energies can be accurately captured. Finally, the phonon dispersion calculated from first-principles is used to address the possible origins of unexplained peaks observed in the Raman spectra, such as infrared-active modes, defects, and second-order processes.

Metal to Insulator Quantum-Phase Transition in Few-Layered ReS2.

In ReS2, a layer-independent direct band gap of 1.5 eV implies a potential for its use in optoelectronic applications. ReS2 crystallizes in the 1T'-structure, which leads to anisotropic physical properties and whose concomitant electronic structure might host a nontrivial topology. Here, we report an overall evaluation of the anisotropic Raman response and the transport properties of few-layered ReS2 field-effect transistors. We find that ReS2 exfoliated on SiO2 behaves as an n-type semiconductor with an intrinsic carrier mobility surpassing µ(i) ∼ 30 cm(2)/(V s) at T = 300 K, which increases up to ∼350 cm(2)/(V s) at 2 K. Semiconducting behavior is observed at low electron densities n, but at high values of n the resistivity decreases by a factor of >7 upon cooling to 2 K and displays a metallic T(2)-dependence. This suggests that the band structure of 1T'-ReS2 is quite susceptible to an electric field applied perpendicularly to the layers. The electric-field induced metallic state observed in transition metal dichalcogenides was recently claimed to result from a percolation type of transition. Instead, through a scaling analysis of the conductivity as a function of T and n, we find that the metallic state of ReS2 results from a second-order metal-to-insulator transition driven by electronic correlations. This gate-induced metallic state offers an alternative to phase engineering for producing ohmic contacts and metallic interconnects in devices based on transition metal dichalcogenides.

Pronounced Photovoltaic Response from Multilayered Transition-Metal Dichalcogenides PN-Junctions.

Transition metal dichalcogenides (TMDs) are layered semiconductors with indirect band gaps comparable to Si. These compounds can be grown in large area, while their gap(s) can be tuned by changing their chemical composition or by applying a gate voltage. The experimental evidence collected so far points toward a strong interaction with light, which contrasts with the small photovoltaic efficiencies η ≤ 1% extracted from bulk crystals or exfoliated monolayers. Here, we evaluate the potential of these compounds by studying the photovoltaic response of electrostatically generated PN-junctions composed of approximately 10 atomic layers of MoSe2 stacked onto the dielectric h-BN. In addition to ideal diode-like response, we find that these junctions can yield, under AM-1.5 illumination, photovoltaic efficiencies η exceeding 14%, with fill factors of ~70%. Given the available strategies for increasing η such as gap tuning, improving the quality of the electrical contacts, or the fabrication of tandem cells, our study suggests a remarkable potential for photovoltaic applications based on TMDs.

Transition from slow Abrikosov to fast moving Josephson vortices in iron pnictide superconductors.

Iron pnictides are layered high T(c) superconductors with moderate material anisotropy and thus Abrikosov vortices are expected in the mixed state. Yet, we have discovered a distinct change in the nature of the vortices from Abrikosov-like to Josephson-like in the pnictide superconductor SmFeAs(O,F) with T(c)~48-50 K on cooling below a temperature T*~41-42 K, despite its moderate electronic anisotropy γ~4-6. This transition is hallmarked by a sharp drop in the critical current and accordingly a jump in the flux-flow voltage in a magnetic field precisely aligned along the FeAs layers, indicative of highly mobile vortices. T* coincides well with the temperature where the coherence length ξ(c) perpendicular to the layers matches half of the FeAs-layer spacing. For fields slightly out-of-plane (> 0.1°- 0.15°) the vortices are completely immobilized as well-pinned Abrikosov segments are introduced when the vortex crosses the FeAs layers. We interpret these findings as a transition from well-pinned, slow moving Abrikosov vortices at high temperatures to weakly pinned, fast flowing Josephson vortices at low temperatures. This vortex dynamics could become technologically relevant as superconducting applications will always operate deep in the Josephson regime.

Critical current oscillations in the intrinsic hybrid vortex state of SmFeAs(O,F).

In layered superconductors the order parameter may be modulated within the unit cell, leading to nontrivial modifications of the vortex core if the interlayer coherence length ξ(c)(T) is comparable to the interlayer spacing. In the iron pnictide SmFeAs(O,F) (T(c)≈50 K) this occurs below a crossover temperature T(⋆)≈41 K, which separates two regimes of vortices: anisotropic Abrikosov-like at high and Josephson-like at low temperatures. Yet in the transition region around T(⋆), hybrid vortices between these two characteristics appear. Only in this region around T(⋆) and for magnetic fields well aligned with the FeAs layers, we observe oscillations of the c-axis critical current j(c)(H) periodic in 1/sqrt[H] due to a delicate balance of intervortex forces and interaction with the layered potential. j(c)(H) shows pronounced maxima when a hexagonal vortex lattice is commensurate with the underlying crystal structure. The narrow temperature window in which oscillations are observed suggests a significant suppression of the order parameter between the superconducting layers in SmFeAs(O,F), despite its low coherence length anisotropy (γ(ξ)≈3-5).

Tunable electronics in large-area atomic layers of boron-nitrogen-carbon.

We report on the low-temperature electrical transport properties of large area boron and nitrogen codoped graphene layers (BNC). The temperature dependence of resistivity (5 K < T < 400 K) of BNC layers show semiconducting nature and display a band gap which increases with B and N content, in sharp contrast to large area graphene layers, which shows metallic behavior. Our investigations show that the amount of B dominates the semiconducting nature of the BNC layers. This experimental observations agree with the density functional theory (DFT) calculations performed on BNC structures similar in composition to the experimentally measured samples. In addition, the temperature dependence of the electrical conductivity of these samples displays two regimes: at higher temperatures, the doped samples display an Arrhenius-like temperature dependence thus indicating a well-defined band gap. At the lowest temperatures, the temperature dependence of the conductivity deviates from activated behavior and displays a conduction mechanism consistent with Mott's two-dimensional (2D) variable range hopping (2D-VRH). The ability to tune the electronic properties of thin layers of BNC by simply varying the concentration of B and N will provide a tremendous boost for obtaining materials with tunable electronic properties relevant to applications in solid state electronics.