Logic-in-memory based on an atomically thin semiconductor.

The growing importance of applications based on machine learning is driving the need to develop dedicated, energy-efficient electronic hardware. Compared with von Neumann architectures, which have separate processing and storage units, brain-inspired in-memory computing uses the same basic device structure for logic operations and data storage1-3, thus promising to reduce the energy cost of data-centred computing substantially4. Although there is ample research focused on exploring new device architectures, the engineering of material platforms suitable for such device designs remains a challenge. Two-dimensional materials5,6 such as semiconducting molybdenum disulphide, MoS2, could be promising candidates for such platforms thanks to their exceptional electrical and mechanical properties7-9. Here we report our exploration of large-area MoS2 as an active channel material for developing logic-in-memory devices and circuits based on floating-gate field-effect transistors (FGFETs). The conductance of our FGFETs can be precisely and continuously tuned, allowing us to use them as building blocks for reconfigurable logic circuits in which logic operations can be directly performed using the memory elements. After demonstrating a programmable NOR gate, we show that this design can be simply extended to implement more complex programmable logic and a functionally complete set of operations. Our findings highlight the potential of atomically thin semiconductors for the development of next-generation low-power electronics.

Highly anisotropic spin transport in ultrathin black phosphorus.

In anisotropic crystals, the direction-dependent effective mass of carriers can have a profound impact on spin transport dynamics. The puckered crystal structure of black phosphorus leads to direction-dependent charge transport and optical response, suggesting that it is an ideal system for studying anisotropic spin transport. To this end, we fabricate and characterize high-mobility encapsulated ultrathin black-phosphorus-based spin valves in a four-terminal geometry. Our measurements show that in-plane spin lifetimes are strongly gate tunable and exceed one nanosecond. Through high out-of-plane magnetic fields, we observe a fivefold enhancement in the out-of-plane spin signal case compared to in-plane and estimate a colossal spin-lifetime anisotropy of ∼6. This finding is further confirmed by oblique Hanle measurements. Additionally, we estimate an in-plane spin-lifetime anisotropy ratio of up to 1.8. Our observation of strongly anisotropic spin transport along three orthogonal axes in this pristine material could be exploited to realize directionally tunable spin transport.

Room-temperature electrical control of exciton flux in a van der Waals heterostructure.

Devices that rely on the manipulation of excitons-bound pairs of electrons and holes-hold great promise for realizing efficient interconnects between optical data transmission and electrical processing systems. Although exciton-based transistor actions have been demonstrated successfully in bulk semiconductor-based coupled quantum wells1-3, the low temperature required for their operation limits their practical application. The recent emergence of two-dimensional semiconductors with large exciton binding energies4,5 may lead to excitonic devices and circuits that operate at room temperature. Whereas individual two-dimensional materials have short exciton diffusion lengths, the spatial separation of electrons and holes in different layers in heterostructures could help to overcome this limitation and enable room-temperature operation of mesoscale devices6-8. Here we report excitonic devices made of MoS2-WSe2 van der Waals heterostructures encapsulated in hexagonal boron nitride that demonstrate electrically controlled transistor actions at room temperature. The long-lived nature of the interlayer excitons in our device results in them diffusing over a distance of five micrometres. Within our device, we further demonstrate the ability to manipulate exciton dynamics by creating electrically reconfigurable confining and repulsive potentials for the exciton flux. Our results make a strong case for integrating two-dimensional materials in future excitonic devices to enable operation at room temperature.

van der Waals Bonded Co/h-BN Contacts to Ultrathin Black Phosphorus Devices.

Because of the chemical inertness of two dimensional (2D) hexagonal-boron nitride (h-BN), few atomic-layer h-BN is often used to encapsulate air-sensitive 2D crystals such as black phosphorus (BP). However, the effects of h-BN on Schottky barrier height, doping, and contact resistance are not well-known. Here, we investigate these effects by fabricating h-BN encapsulated BP transistors with cobalt (Co) contacts. In sharp contrast to directly Co contacted p-type BP devices, we observe strong n-type conduction upon insertion of the h-BN at the Co/BP interface. First-principles calculations show that this difference arises from the much larger interface dipole at the Co/h-BN interface compared to the Co/BP interface, which reduces the work function of the Co/h-BN contact. The Co/h-BN contacts exhibit low contact resistances (∼4.5 kΩ) and are Schottky barrier-free. This allows us to probe high electron mobilities (4,200 cm2/(V s)) and observe insulator-metal transitions even under two-terminal measurement geometry.

Van der Waals force: a dominant factor for reactivity of graphene.

Reactivity control of graphene is an important issue because chemical functionalization can modulate graphene's unique mechanical, optical, and electronic properties. Using systematic optical studies, we demonstrate that van der Waals interaction is the dominant factor for the chemical reactivity of graphene on two-dimensional (2D) heterostructures. A significant enhancement in the chemical stability of graphene is achieved by replacing the common SiO2 substrate with 2D crystals such as an additional graphene layer, WS2, MoS2, or h-BN. Our theoretical and experimental results show that its origin is a strong van der Waals interaction between the graphene layer and the 2D substrate. This results in a high resistive force on graphene toward geometric lattice deformation. We also demonstrate that the chemical reactivity of graphene can be controlled by the relative lattice orientation with respect to the substrates and thus can be used for a wide range of applications including hydrogen storage.

Electrical spectroscopy of defect states and their hybridization in monolayer MoS2.

Defects in solids are unavoidable and can create complex electronic states that can significantly influence the electrical and optical properties of semiconductors. With the rapid progress in the integration of 2D semiconductors in practical devices, it is imperative to understand and characterize the influence of defects in this class of materials. Here, we examine the electrical response of defect filling and emission using deep level transient spectroscopy (DLTS) and reveal defect states and their hybridization in a monolayer MOCVD-grown material deposited on CMOS-compatible substrates. Supported by aberration-corrected STEM imaging and theoretical calculations, we find that neighboring sulfur vacancy pairs introduce additional shallow trap states via hybridization of individual vacancy levels. Even though such vacancy pairs only represent ~10% of the total defect concentration, they can have a substantial influence on the off currents and switching slopes of field-effect transistors based on 2D semiconductors. Our technique, which can quantify the energy states of different defects and their interactions, allows rapid and nondestructive electrical characterization of defect states important for the defect engineering of 2D semiconductors.

Toward wafer scale fabrication of graphene based spin valve devices.

We demonstrate injection, transport, and detection of spins in spin valve arrays patterned in both copper based chemical vapor deposition (Cu-CVD) synthesized wafer scale single layer and bilayer graphene. We observe spin relaxation times comparable to those reported for exfoliated graphene samples demonstrating that chemical vapor deposition specific structural differences such as nanoripples do not limit spin transport in the present samples. Our observations make Cu-CVD graphene a promising material of choice for large scale spintronic applications.

Engineering Optically Active Defects in Hexagonal Boron Nitride Using Focused Ion Beam and Water.

Hexagonal boron nitride (hBN) has emerged as a promising material platform for nanophotonics and quantum sensing, hosting optically active defects with exceptional properties such as high brightness and large spectral tuning. However, precise control over deterministic spatial positioning of emitters in hBN remained elusive for a long time, limiting their proper correlative characterization and applications in hybrid devices. Recently, focused ion beam (FIB) systems proved to be useful to engineer several types of spatially defined emitters with various structural and photophysical properties. Here we systematically explore the physical processes leading to the creation of optically active defects in hBN using FIB and find that beam-substrate interaction plays a key role in the formation of defects. These findings are confirmed using transmission electron microscopy, which reveals local mechanical deterioration of the hBN layers and local amorphization of ion beam irradiated hBN. Additionally, we show that, upon exposure to water, amorphized hBN undergoes a structural and optical transition between two defect types with distinctive emission properties. Moreover, using super-resolution optical microscopy combined with atomic force microscopy, we pinpoint the exact location of emitters within the defect sites, confirming the role of defected edges as primary sources of fluorescent emission. This lays the foundation for FIB-assisted engineering of optically active defects in hBN with high spatial and spectral control for applications ranging from integrated photonics, to nanoscale sensing, and to nanofluidics.

Anomalous interfacial dynamics of single proton charges in binary aqueous solutions.

Our understanding of the dynamics of charge transfer between solid surfaces and liquid electrolytes has been hampered by the difficulties in obtaining interface, charge, and solvent-specific information at both high spatial and temporal resolution. Here, we measure at the single charge scale the dynamics of protons at the interface between an hBN crystal and binary mixtures of water and organic amphiphilic solvents (alcohols and acetone), evidencing a marked influence of solvation on interfacial dynamics. Applying single-molecule localization microscopy to emissive crystal defects, we observe correlated activation between adjacent ionizable surface defects, mediated by the transport of single excess protons along the solid/liquid interface. Solvent content has a nontrivial effect on interfacial dynamics, leading at intermediate water fraction to an increased surface diffusivity, as well as an increased affinity of the proton charges to the solid surface. Our measurements evidence the notable role of solvation on interfacial proton charge transport.

Probing magnetism in atomically thin semiconducting PtSe2.

Atomic-scale disorder in two-dimensional transition metal dichalcogenides is often accompanied by local magnetic moments, which can conceivably induce long-range magnetic ordering into intrinsically non-magnetic materials. Here, we demonstrate the signature of long-range magnetic orderings in defective mono- and bi-layer semiconducting PtSe2 by performing magnetoresistance measurements under both lateral and vertical measurement configurations. As the material is thinned down from bi- to mono-layer thickness, we observe a ferromagnetic-to-antiferromagnetic crossover, a behavior which is opposite to the one observed in the prototypical 2D magnet CrI3. Our first-principles calculations, supported by aberration-corrected transmission electron microscopy imaging of point defects, associate this transition to the interplay between the defect-induced magnetism and the interlayer interactions in PtSe2. Furthermore, we show that graphene can be effectively used to probe the magnetization of adjacent semiconducting PtSe2. Our findings in an ultimately scaled monolayer system lay the foundation for atom-by-atom engineering of magnetism in otherwise non-magnetic 2D materials.

Direct observation of water-mediated single-proton transport between hBN surface defects.

Aqueous proton transport at interfaces is ubiquitous and crucial for a number of fields, ranging from cellular transport and signalling, to catalysis and membrane science. However, due to their light mass, small size and high chemical reactivity, uncovering the surface transport of single protons at room temperature and in an aqueous environment has so far remained out-of-reach of conventional atomic-scale surface science techniques, such as scanning tunnelling microscopy. Here, we use single-molecule localization microscopy to resolve optically the transport of individual excess protons at the interface of hexagonal boron nitride crystals and aqueous solutions at room temperature. Single excess proton trajectories are revealed by the successive protonation and activation of optically active defects at the surface of the crystal. Our observations demonstrate, at the single-molecule scale, that the solid/water interface provides a preferential pathway for lateral proton transport, with broad implications for molecular charge transport at liquid interfaces.

Valley-polarized exciton currents in a van der Waals heterostructure.

Valleytronics is an appealing alternative to conventional charge-based electronics that aims at encoding data in the valley degree of freedom, that is, the information as to which extreme of the conduction or valence band carriers are occupying. The ability to create and control valley currents in solid-state devices could therefore enable new paradigms for information processing. Transition metal dichalcogenides (TMDCs) are a promising platform for valleytronics due to the presence of two inequivalent valleys with spin-valley locking1 and a direct bandgap2,3, which allows optical initialization and readout of the valley state4,5. Recent progress on the control of interlayer excitons in these materials6-8 could offer an effective way to realize optoelectronic devices based on the valley degree of freedom. Here, we show the generation and transport over mesoscopic distances of valley-polarized excitons in a device based on a type-II TMDC heterostructure. Engineering of the interlayer coupling results in enhanced diffusion of valley-polarized excitons, which can be controlled and switched electrically. Furthermore, using electrostatic traps, we can increase the exciton concentration by an order of magnitude, reaching densities in the order of 1012 cm-2, opening the route to achieving a coherent quantum state of valley-polarized excitons via Bose-Einstein condensation.

Polarization switching and electrical control of interlayer excitons in two-dimensional van der Waals heterostructures.

Long-lived interlayer excitons in van der Waals heterostructures based on transition metal dichalcogenides, together with unique spin-valley physics, make them promising for next-generation photonic and valleytronic devices. While the emission characteristics of interlayer excitons have been studied, efficient manipulation of their valley-state, a necessary requirement for information encoding, is still lacking. Here, we demonstrate comprehensive electrical control of interlayer excitons in a MoSe2/WSe2 heterostructure. Encapsulation of our well-aligned stack with hexagonal boron nitride (h-BN) allows us to resolve two separate narrow interlayer transitions with opposite helicities under circularly polarized excitation, either preserving or reversing the polarization of incoming light. By electrically controlling their relative intensities, we realize a polarization switch with tuneable emission intensity and wavelength. Finally, we demonstrate large Zeeman shifts of these two transitions upon application of an external magnetic field. These results are interpreted within the picture of moiré-induced brightening of forbidden optical transitions. The ability to control the polarization of interlayer excitons is a step forward towards the manipulation of the valley degree-of-freedom in realistic device applications.

Defect induced, layer-modulated magnetism in ultrathin metallic PtSe2.

Defects are ubiquitous in solids and often introduce new properties that are absent in pristine materials. One of the opportunities offered by these crystal imperfections is an extrinsically induced long-range magnetic ordering1, a long-time subject of theoretical investigations1-3. Intrinsic, two-dimensional (2D) magnetic materials4-7 are attracting increasing attention for their unique properties, which include layer-dependent magnetism4 and electric field modulation6. Yet, to induce magnetism into otherwise non-magnetic 2D materials remains a challenge. Here we investigate magneto-transport properties of ultrathin PtSe2 crystals and demonstrate an unexpected magnetism. Our electrical measurements show the existence of either ferromagnetic or antiferromagnetic ground-state orderings that depends on the number of layers in this ultrathin material. The change in the device resistance on the application of a ~25 mT magnetic field is as high as 400 Ω with a magnetoresistance value of 5%. Our first-principles calculations suggest that surface magnetism induced by the presence of Pt vacancies and the Ruderman-Kittel-Kasuya-Yosida (RKKY) exchange couplings across ultrathin films of PtSe2 are responsible for the observed layer-dependent magnetism. Given the existence of such unavoidable growth-related vacancies in 2D materials8,9, these findings can expand the range of 2D ferromagnets into materials that would otherwise be overlooked.

Thickness-modulated metal-to-semiconductor transformation in a transition metal dichalcogenide.

The possibility of tailoring physical properties by changing the number of layers in van der Waals crystals is one of the driving forces behind the emergence of two-dimensional materials. One example is bulk MoS2, which changes from an indirect gap semiconductor to a direct bandgap semiconductor in the monolayer form. Here, we show a much bigger tuning range with a complete switching from a metal to a semiconductor in atomically thin PtSe2 as its thickness is reduced. Crystals with a thickness of ~13 nm show metallic behavior with a contact resistance as low as 70 Ω·µm. As they are thinned down to 2.5 nm and below, we observe semiconducting behavior. In such thin crystals, we demonstrate ambipolar transport with a bandgap smaller than 2.2 eV and an on/off ratio of ~105. Our results demonstrate that PtSe2 possesses an unusual behavior among 2D materials, enabling novel applications in nano and optoelectronics.

Reconfigurable Diodes Based on Vertical WSe2 Transistors with van der Waals Bonded Contacts.

New device concepts can increase the functionality of scaled electronic devices, with reconfigurable diodes allowing the design of more compact logic gates being one of the examples. In recent years, there has been significant interest in creating reconfigurable diodes based on ultrathin transition metal dichalcogenide crystals due to their unique combination of gate-tunable charge carriers, high mobility, and sizeable band gap. Thanks to their large surface areas, these devices are constructed under planar geometry and the device characteristics are controlled by electrostatic gating through rather complex two independent local gates or ionic-liquid gating. In this work, similar reconfigurable diode action is demonstrated in a WSe2 transistor by only utilizing van der Waals bonded graphene and Co/h-BN contacts. Toward this, first the charge injection efficiencies into WSe2 by graphene and Co/h-BN contacts are characterized. While Co/h-BN contact results in nearly Schottky-barrier-free charge injection, graphene/WSe2 interface has an average barrier height of ≈80 meV. By taking the advantage of the electrostatic transparency of graphene and the different work-function values of graphene and Co/h-BN, vertical devices are constructed where different gate-tunable diode actions are demonstrated. This architecture reveals the opportunities for exploring new device concepts.

Resolving the spin splitting in the conduction band of monolayer MoS2.

Time-reversal symmetry and broken spin degeneracy enable the exploration of spin and valley quantum degrees of freedom in monolayer transition-metal dichalcogenides. While the strength of the large spin splitting in the valance band of these materials is now well-known, probing the 10-100 times smaller splitting in the conduction band poses significant challenges. Since it is easier to achieve n-type conduction in most of them, resolving the energy levels in the conduction band is crucial for the prospect of developing new spintronic and valleytronic devices. Here, we study quantum transport in high mobility monolayer MoS2 devices where we observe well-developed quantized conductance in multiples of e 2/h in zero magnetic field. We extract a sub-band spacing energy of 0.8 meV. The application of a magnetic field gradually increases the interband spacing due to the valley-Zeeman effect. Here, we extract a g-factor of ~2.16 in the conduction band of monolayer MoS2.

Optospintronics in Graphene via Proximity Coupling.

The observation of micrometer size spin relaxation makes graphene a promising material for applications in spintronics requiring long-distance spin communication. However, spin dependent scatterings at the contact/graphene interfaces affect the spin injection efficiencies and hence prevent the material from achieving its full potential. While this major issue could be eliminated by nondestructive direct optical spin injection schemes, graphene's intrinsically low spin-orbit coupling strength and optical absorption place an obstacle in their realization. We overcome this challenge by creating sharp artificial interfaces between graphene and WSe2 monolayers. Application of circularly polarized light activates the spin-polarized charge carriers in the WSe2 layer due to its spin-coupled valley-selective absorption. These carriers diffuse into the superjacent graphene layer, transport over a 3.5 µm distance, and are finally detected electrically using Co/h-BN contacts in a nonlocal geometry. Polarization-dependent measurements confirm the spin origin of the nonlocal signal. We also demonstrate that such signal is absent if graphene is contacted to bilayer WSe2 where the inversion symmetry is restored.

Air-stable transport in graphene-contacted, fully encapsulated ultrathin black phosphorus-based field-effect transistors.

The presence of direct bandgap and high mobility in semiconductor few-layer black phosphorus offers an attractive prospect for using this material in future two-dimensional electronic devices. However, creation of barrier-free contacts which is necessary to achieve high performance in black phosphorus-based devices is challenging and currently limits their potential for applications. Here, we characterize fully encapsulated ultrathin (down to bilayer) black phosphorus field effect transistors fabricated under inert gas conditions by utilizing graphene as source-drain electrodes and boron nitride as an encapsulation layer. The observation of a linear ISD-VSD behavior with negligible temperature dependence shows that graphene electrodes lead to barrier-free contacts, solving the issue of Schottky barrier limited transport in the technologically relevant two-terminal field-effect transistor geometry. Such one-atom-thick conformal source-drain electrodes also enable the black phosphorus surface to be sealed, to avoid rapid degradation, with the inert boron nitride encapsulating layer. This architecture, generally applicable for other sensitive two-dimensional crystals, results in air-stable, hysteresis-free transport characteristics.