Magnetism-Induced Band-Edge Shift as the Mechanism for Magnetoconductance in CrPS4 Transistors.

Transistors realized on the 2D antiferromagnetic semiconductor CrPS4 exhibit large magnetoconductance due to magnetic-field-induced changes in the magnetic state. The microscopic mechanism coupling the conductance and magnetic state is not understood. We identify it by analyzing the evolution of the parameters determining the transistor behavior─carrier mobility and threshold voltage─with temperature and magnetic field. For temperatures T near the Néel temperature TN, the magnetoconductance originates from a mobility increase due to the applied magnetic field that reduces spin fluctuation induced disorder. For T ≪ TN, instead, what changes is the threshold voltage, so that increasing the field at fixed gate voltage increases the density of accumulated electrons. The phenomenon is explained by a conduction band-edge shift correctly predicted by the ab initio calculations. Our results demonstrate that the band structure of CrPS4 depends on its magnetic state and reveal a mechanism for magnetoconductance that had not been identified earlier.

Multiple antiferromagnetic phases and magnetic anisotropy in exfoliated CrBr3 multilayers.

In twisted two-dimensional (2D) magnets, the stacking dependence of the magnetic exchange interaction can lead to regions of ferromagnetic and antiferromagnetic interlayer order, separated by non-collinear, skyrmion-like spin textures. Recent experimental searches for these textures have focused on CrI3, known to exhibit either ferromagnetic or antiferromagnetic interlayer order, depending on layer stacking. However, the very strong uniaxial anisotropy of CrI3 disfavors smooth non-collinear phases in twisted bilayers. Here, we report the experimental observation of three distinct magnetic phases-one ferromagnetic and two antiferromagnetic-in exfoliated CrBr3 multilayers, and reveal that the uniaxial anisotropy is significantly smaller than in CrI3. These results are obtained by magnetoconductance measurements on CrBr3 tunnel barriers and Raman spectroscopy, in conjunction with density functional theory calculations, which enable us to identify the stackings responsible for the different interlayer magnetic couplings. The detection of all locally stable magnetic states predicted to exist in CrBr3 and the excellent agreement found between theory and experiments, provide complete information on the stacking-dependent interlayer exchange energy and establish twisted bilayer CrBr3 as an ideal system to deterministically create non-collinear magnetic phases.

Electronic Structure of Few-Layer Black Phosphorus from µ-ARPES.

Black phosphorus (BP) stands out among two-dimensional (2D) semiconductors because of its high mobility and thickness dependent direct band gap. However, the quasiparticle band structure of ultrathin BP has remained inaccessible to experiment thus far. Here we use a recently developed laser-based microfocus angle resolved photoemission (µ-ARPES) system to establish the electronic structure of 2-9 layer BP from experiment. Our measurements unveil ladders of anisotropic, quantized subbands at energies that deviate from the scaling observed in conventional semiconductor quantum wells. We quantify the anisotropy of the effective masses and determine universal tight-binding parameters, which provide an accurate description of the electronic structure for all thicknesses.

Determining spin-orbit coupling in graphene by quasiparticle interference imaging.

Inducing and controlling spin-orbit coupling (SOC) in graphene is key to create topological states of matter, and for the realization of spintronic devices. Placing graphene onto a transition metal dichalcogenide is currently the most successful strategy to achieve this goal, but there is no consensus as to the nature and the magnitude of the induced SOC. Here, we show that the presence of backscattering in graphene-on-WSe2 heterostructures can be used to probe SOC and to determine its strength quantitatively, by imaging quasiparticle interference with a scanning tunneling microscope. A detailed theoretical analysis of the Fourier transform of quasiparticle interference images reveals that the induced SOC consists of a valley-Zeeman (λvZ ≈ 2 meV) and a Rashba (λR ≈ 15 meV) term, one order of magnitude larger than what theory predicts, but in excellent agreement with earlier transport experiments. The validity of our analysis is confirmed by measurements on a 30 degree twist angle heterostructure that exhibits no backscattering, as expected from symmetry considerations. Our results demonstrate a viable strategy to determine SOC quantitatively by imaging quasiparticle interference.

Gate-Controlled Magnetotransport and Electrostatic Modulation of Magnetism in 2D Magnetic Semiconductor CrPS4.

Using field-effect transistors (FETs) to explore atomically thin magnetic semiconductors with transport measurements is difficult, because the very narrow bands of most 2D magnetic semiconductors cause carrier localization, preventing transistor operation. Here, it is shown that exfoliated layers of CrPS4 -a 2D layered antiferromagnetic semiconductor whose bandwidth approaches 1 eV-allow the realization of FETs that operate properly down to cryogenic temperature. Using these devices, conductance measurements as a function of temperature and magnetic field are performed to determine the full magnetic phase diagram, which includes a spin-flop and a spin-flip phase. The magnetoconductance, which depends strongly on gate voltage, is determined. reaching values as high as 5000% near the threshold for electron conduction. The gate voltage also allows the magnetic states to be tuned, despite the relatively large thickness of the CrPS4 multilayers employed in the study. The results show the need to employ 2D magnetic semiconductors with sufficiently large bandwidth to realize properly functioning transistors, and identify a candidate material to realize a fully gate-tunable half-metallic conductor.

Full Control of Solid-State Electrolytes for Electrostatic Gating.

Ionic gating is a powerful technique to realize field-effect transistors (FETs) enabling experiments not possible otherwise. So far, ionic gating has relied on the use of top electrolyte gates, which pose experimental constraints and make device fabrication complex. Promising results obtained recently in FETs based on solid-state electrolytes remain plagued by spurious phenomena of unknown origin, preventing proper transistor operation, and causing limited control and reproducibility. Here, a class of solid-state electrolytes for gating (Lithium-ion conducting glass-ceramics, LICGCs) is explored, the processes responsible for the spurious phenomena and irreproducible behavior are identified, and properly functioning transistors exhibiting high density ambipolar operation with gate capacitance of ≈ 20   -   50 µ F c m - 2 \[20{\bm{ - }}50\;\mu F c{m^{{\bm{ - }}2}}\] (depending on the polarity of the accumulated charges) are demonstrated. Using 2D semiconducting transition-metal dichalcogenides, the ability to implement ionic-gate spectroscopy to determine the semiconducting bandgap, and to accumulate electron densities above 1014 cm-2 are demostrated, resulting in gate-induced superconductivity in MoS2 multilayers. As LICGCs are implemented in a back-gate configuration, they leave the surface of the material exposed, enabling the use of surface-sensitive techniques (such as scanning tunneling microscopy and photoemission spectroscopy) impossible so far in ionic-gated devices. They also allow double ionic gated devices providing independent control of charge density and electric field.

Band Gap Opening in Bilayer Graphene-CrCl3/CrBr3/CrI3 van der Waals Interfaces.

We report experimental investigations of transport through bilayer graphene (BLG)/chromium trihalide (CrX3; X = Cl, Br, I) van der Waals interfaces. In all cases, a large charge transfer from BLG to CrX3 takes place (reaching densities in excess of 1013 cm-2), and generates an electric field perpendicular to the interface that opens a band gap in BLG. We determine the gap from the activation energy of the conductivity and find excellent agreement with the latest theory accounting for the contribution of the σ bands to the BLG dielectric susceptibility. We further show that for BLG/CrCl3 and BLG/CrBr3 the band gap can be extracted from the gate voltage dependence of the low-temperature conductivity, and use this finding to refine the gap dependence on the magnetic field. Our results allow a quantitative comparison of the electronic properties of BLG with theoretical predictions and indicate that electrons occupying the CrX3 conduction band are correlated.

Quenching the bandgap of two-dimensional semiconductors with a perpendicular electric field.

Perpendicular electric fields can tune the electronic band structure of atomically thin semiconductors. In bilayer graphene, which is an intrinsic zero-gap semiconductor, a perpendicular electric field opens a finite bandgap. So far, however, the same principle could not be applied to control the properties of a broader class of 2D materials because the required electric fields are beyond reach in current devices. To overcome this limitation, we design double ionic gated transistors that enable the application of large electric fields of up to 3 V nm-1. Using such devices, we continuously suppress the bandgap of few-layer semiconducting transition metal dichalcogenides (that is, bilayer to heptalayer WSe2) from 1.6 V to zero. Our results illustrate an excellent level of control of the band structure of 2D semiconductors.

Light sources with bias tunable spectrum based on van der Waals interface transistors.

Light-emitting electronic devices are ubiquitous in key areas of current technology, such as data communications, solid-state lighting, displays, and optical interconnects. Controlling the spectrum of the emitted light electrically, by simply acting on the device bias conditions, is an important goal with potential technological repercussions. However, identifying a material platform enabling broad electrical tuning of the spectrum of electroluminescent devices remains challenging. Here, we propose light-emitting field-effect transistors based on van der Waals interfaces of atomically thin semiconductors as a promising class of devices to achieve this goal. We demonstrate that large spectral changes in room-temperature electroluminescence can be controlled both at the device assembly stage -by suitably selecting the material forming the interfaces- and on-chip, by changing the bias to modify the device operation point. Even though the precise relation between device bias and kinetics of the radiative transitions remains to be understood, our experiments show that the physical mechanism responsible for light emission is robust, making these devices compatible with simple large areas device production methods.

Quasi-1D Electronic Transport in a 2D Magnetic Semiconductor.

Electronic transport through exfoliated multilayers of CrSBr, a 2D semiconductor of interest because of its magnetic properties, is investigated. An extremely pronounced anisotropy manifesting itself in qualitative and quantitative differences of all quantities measured along the in-plane a and b crystallographic directions is found. In particular, a qualitatively different dependence of the conductivities σa and σb on temperature and gate voltage, accompanied by orders of magnitude differences in their values (σb /σa  ≈ 3 × 102  to 105 at low temperature and negative gate voltage) are observed, together with a different behavior of the longitudinal magnetoresistance in the two directions and the complete absence of the Hall effect in transverse resistance measurements. These observations appear not to be compatible with a description in terms of conventional band transport of a 2D doped semiconductor. The observed phenomenology-and unambiguous signatures of a 1D van Hove singularity detected in energy-resolved photocurrent measurements-indicate that electronic transport through CrSBr multilayers is better interpreted by considering the system as formed by weakly and incoherently coupled 1D wires, than by conventional 2D band transport. It is concluded that CrSBr is the first 2D semiconductor to show distinctly quasi-1D electronic transport properties.

Magnetization dependent tunneling conductance of ferromagnetic barriers.

Recent experiments on van der Waals antiferromagnets have shown that measuring the temperature (T) and magnetic field (H) dependence of the conductance allows their magnetic phase diagram to be mapped. Similarly, experiments on ferromagnetic CrBr3 barriers enabled the Curie temperature to be determined at H = 0, but a precise interpretation of the magnetoconductance data at H ≠ 0 is conceptually more complex, because at finite H there is no well-defined phase boundary. Here we perform systematic transport measurements on CrBr3 barriers and show that the tunneling magnetoconductance depends on H and T exclusively through the magnetization M(H, T) over the entire temperature range investigated. The phenomenon is reproduced by the spin-dependent Fowler-Nordheim model for tunneling, and is a direct manifestation of the spin splitting of the CrBr3 conduction band. Our analysis unveils a new approach to probe quantitatively different properties of atomically thin ferromagnetic insulators related to their magnetization by performing simple conductance measurements.

Design of van der Waals interfaces for broad-spectrum optoelectronics.

Van der Waals (vdW) interfaces based on 2D materials are promising for optoelectronics, as interlayer transitions between different compounds allow tailoring of the spectral response over a broad range. However, issues such as lattice mismatch or a small misalignment of the constituent layers can drastically suppress electron-photon coupling for these interlayer transitions. Here, we engineered type-II interfaces by assembling atomically thin crystals that have the bottom of the conduction band and the top of the valence band at the Γ point, and thus avoid any momentum mismatch. We found that these van der Waals interfaces exhibit radiative optical transitions irrespective of the lattice constant, the rotational and/or translational alignment of the two layers or whether the constituent materials are direct or indirect gap semiconductors. Being robust and of general validity, our results broaden the scope of future optoelectronics device applications based on two-dimensional materials.

Synthetic Semimetals with van der Waals Interfaces.

The assembly of suitably designed van der Waals (vdW) heterostructures represents a new approach to produce artificial systems with engineered electronic properties. Here, we apply this strategy to realize synthetic semimetals based on vdW interfaces formed by two different semiconductors. Guided by existing ab initio calculations, we select WSe2 and SnSe2 mono- and multilayers to assemble vdW interfaces and demonstrate the occurrence of semimetallicity by means of different transport experiments. Semimetallicity manifests itself in a finite minimum conductance upon sweeping the gate over a large range in ionic liquid gated devices, which also offer spectroscopic capabilities enabling the quantitative determination of the band overlap. The semimetallic state is additionally revealed in Hall effect measurements by the coexistence of electrons and holes, observed by either looking at the evolution of the Hall slope with sweeping the gate voltage or with lowering temperature. Finally, semimetallicity results in the low-temperature metallic conductivity of interfaces of two materials that are themselves insulating. These results demonstrate the possibility to implement a state of matter that had not yet been realized in vdW interfaces and represent a first step toward using these interfaces to engineer topological or excitonic insulating states.

Microfocus Laser-Angle-Resolved Photoemission on Encapsulated Mono-, Bi-, and Few-Layer 1T'-WTe2.

Two-dimensional crystals of semi-metallic van der Waals materials hold much potential for the realization of novel phases, as exemplified by the recent discoveries of a polar metal in few-layer 1T'-WTe2 and of a quantum spin Hall state in monolayers of the same material. Understanding these phases is particularly challenging because little is known from experiments about the momentum space electronic structure of ultrathin crystals. Here, we report direct electronic structure measurements of exfoliated mono-, bi-, and few-layer 1T'-WTe2 by laser-based microfocus angle-resolved photoemission. This is achieved by encapsulating with monolayer graphene a flake of WTe2 comprising regions of different thickness. Our data support the recent identification of a quantum spin Hall state in monolayer 1T'-WTe2 and reveal strong signatures of the broken inversion symmetry in the bilayer. We finally discuss the sensitivity of encapsulated samples to contaminants following exposure to ambient atmosphere.

Scanning Tunneling Microscopy of an Air Sensitive Dichalcogenide Through an Encapsulating Layer.

Many atomically thin exfoliated two-dimensional (2D) materials degrade when exposed to ambient conditions. They can be protected and investigated by means of transport and optical measurements if they are encapsulated between chemically inert single layers in the controlled atmosphere of a glovebox. Here, we demonstrate that the same encapsulation procedure is also compatible with scanning tunneling microscopy (STM) and spectroscopy (STS). To this end, we report a systematic STM/STS investigation of a model system consisting of an exfoliated 2H-NbSe2 crystal capped with a protective 2H-MoS2 monolayer. We observe different electronic coupling between MoS2 and NbSe2 from a strong coupling when their lattices are aligned within a few degrees to essentially no coupling for 30° misaligned layers. We show that STM always probes intrinsic NbSe2 properties such as the superconducting gap and charge density wave at low temperature when setting the tunneling bias inside the MoS2 band gap, irrespective of the relative angle between the NbSe2 and MoS2 lattices. This study demonstrates that encapsulation is fully compatible with STM/STS investigations of 2D materials.

Semiconducting van der Waals Interfaces as Artificial Semiconductors.

Recent technical progress demonstrates the possibility of stacking together virtually any combination of atomically thin crystals of van der Waals bonded compounds to form new types of heterostructures and interfaces. As a result, there is the need to understand at a quantitative level how the interfacial properties are determined by the properties of the constituent 2D materials. We address this problem by studying the transport and optoelectronic response of two different interfaces based on transition-metal dichalcogenide monolayers, namely WSe2-MoSe2 and WSe2-MoS2. By exploiting the spectroscopic capabilities of ionic liquid gated transistors, we show how the conduction and valence bands of the individual monolayers determine the bands of the interface, and we establish quantitatively (directly from the measurements) the energetic alignment of the bands in the different materials as well as the magnitude of the interfacial band gap. Photoluminescence and photocurrent measurements allow us to conclude that the band gap of the WSe2-MoSe2 interface is direct in k space, whereas the gap of WSe2/MoS2 is indirect. For WSe2/MoSe2, we detect the light emitted from the decay of interlayer excitons and determine experimentally their binding energy using the values of the interfacial band gap extracted from transport measurements. The technique that we employed to reach this conclusion demonstrates a rather-general strategy for characterizing quantitatively the interfacial properties in terms of the properties of the constituent atomic layers. The results presented here further illustrate how van der Waals interfaces of two distinct 2D semiconducting materials are composite systems that truly behave as artificial semiconductors, the properties of which can be deterministically defined by the selection of the appropriate constituent semiconducting monolayers.

Very large tunneling magnetoresistance in layered magnetic semiconductor CrI3.

Magnetic layered van der Waals crystals are an emerging class of materials giving access to new physical phenomena, as illustrated by the recent observation of 2D ferromagnetism in Cr2Ge2Te6 and CrI3. Of particular interest in semiconductors is the interplay between magnetism and transport, which has remained unexplored. Here we report magneto-transport measurements on exfoliated CrI3 crystals. We find that tunneling conduction in the direction perpendicular to the crystalline planes exhibits a magnetoresistance as large as 10,000%. The evolution of the magnetoresistance with magnetic field and temperature reveals that the phenomenon originates from multiple transitions to different magnetic states, whose possible microscopic nature is discussed on the basis of all existing experimental observations. This observed dependence of the conductance of a tunnel barrier on its magnetic state is a phenomenon that demonstrates the presence of a strong coupling between transport and magnetism in magnetic van der Waals semiconductors.

Direct Observation of a Long-Range Field Effect from Gate Tuning of Nonlocal Conductivity.

We report the direct observation of a long-range field effect in WTe_{2} devices, leading to large gate-induced changes of transport through crystals much thicker than the electrostatic screening length. The phenomenon-which manifests itself very differently from the conventional field effect-originates from the nonlocal nature of transport in the devices that are thinner than the carrier mean free path. We reproduce theoretically the gate dependence of the measured classical and quantum magnetotransport, and show that the phenomenon is caused by the gate tuning of the bulk carrier mobility by changing the scattering at the surface. Our results demonstrate experimentally the possibility to gate tune the electronic properties deep in the interior of conducting materials, avoiding limitations imposed by electrostatic screening.

Tuning magnetotransport in a compensated semimetal at the atomic scale.

Either in bulk form, or in atomically thin crystals, layered transition metal dichalcogenides continuously reveal new phenomena. The latest example is 1T'-WTe2, a semimetal found to exhibit the largest known magnetoresistance in the bulk, and predicted to become a topological insulator in strained monolayers. Here we show that reducing the thickness through exfoliation enables the electronic properties of WTe2 to be tuned, which allows us to identify the mechanisms responsible for the observed magnetotransport down to the atomic scale. The longitudinal resistance and the unconventional magnetic field dependence of the Hall resistance are reproduced quantitatively by a classical two-band model for crystals as thin as six monolayers, whereas a crossover to an Anderson insulator occurs for thinner crystals. Besides establishing the origin of the magnetoresistance of WTe2, our results represent a complete validation of the classical theory for two-band electron-hole transport, and indicate that atomically thin WTe2 layers remain gapless semimetals.