Heterogeneous integration of single-crystalline complex-oxide membranes.

Complex-oxide materials exhibit a vast range of functional properties desirable for next-generation electronic, spintronic, magnetoelectric, neuromorphic, and energy conversion storage devices1-4. Their physical functionalities can be coupled by stacking layers of such materials to create heterostructures and can be further boosted by applying strain5-7. The predominant method for heterogeneous integration and application of strain has been through heteroepitaxy, which drastically limits the possible material combinations and the ability to integrate complex oxides with mature semiconductor technologies. Moreover, key physical properties of complex-oxide thin films, such as piezoelectricity and magnetostriction, are severely reduced by the substrate clamping effect. Here we demonstrate a universal mechanical exfoliation method of producing freestanding single-crystalline membranes made from a wide range of complex-oxide materials including perovskite, spinel and garnet crystal structures with varying crystallographic orientations. In addition, we create artificial heterostructures and hybridize their physical properties by directly stacking such freestanding membranes with different crystal structures and orientations, which is not possible using conventional methods. Our results establish a platform for stacking and coupling three-dimensional structures, akin to two-dimensional material-based heterostructures, for enhancing device functionalities8,9.

Electron ptychography of 2D materials to deep sub-ångström resolution.

Aberration-corrected optics have made electron microscopy at atomic resolution a widespread and often essential tool for characterizing nanoscale structures. Image resolution has traditionally been improved by increasing the numerical aperture of the lens (α) and the beam energy, with the state-of-the-art at 300 kiloelectronvolts just entering the deep sub-ångström (that is, less than 0.5 ångström) regime. Two-dimensional (2D) materials are imaged at lower beam energies to avoid displacement damage from large momenta transfers, limiting spatial resolution to about 1 ångström. Here, by combining an electron microscope pixel-array detector with the dynamic range necessary to record the complete distribution of transmitted electrons and full-field ptychography to recover phase information from the full phase space, we increase the spatial resolution well beyond the traditional numerical-aperture-limited resolution. At a beam energy of 80 kiloelectronvolts, our ptychographic reconstruction improves the image contrast of single-atom defects in MoS2 substantially, reaching an information limit close to 5α, which corresponds to an Abbe diffraction-limited resolution of 0.39 ångström, at the electron dose and imaging conditions for which conventional imaging methods reach only 0.98 ångström.

Layer-by-layer assembly of two-dimensional materials into wafer-scale heterostructures.

High-performance semiconductor films with vertical compositions that are designed to atomic-scale precision provide the foundation for modern integrated circuitry and novel materials discovery. One approach to realizing such films is sequential layer-by-layer assembly, whereby atomically thin two-dimensional building blocks are vertically stacked, and held together by van der Waals interactions. With this approach, graphene and transition-metal dichalcogenides-which represent one- and three-atom-thick two-dimensional building blocks, respectively-have been used to realize previously inaccessible heterostructures with interesting physical properties. However, no large-scale assembly method exists at present that maintains the intrinsic properties of these two-dimensional building blocks while producing pristine interlayer interfaces, thus limiting the layer-by-layer assembly method to small-scale proof-of-concept demonstrations. Here we report the generation of wafer-scale semiconductor films with a very high level of spatial uniformity and pristine interfaces. The vertical composition and properties of these films are designed at the atomic scale using layer-by-layer assembly of two-dimensional building blocks under vacuum. We fabricate several large-scale, high-quality heterostructure films and devices, including superlattice films with vertical compositions designed layer-by-layer, batch-fabricated tunnel device arrays with resistances that can be tuned over four orders of magnitude, band-engineered heterostructure tunnel diodes, and millimetre-scale ultrathin membranes and windows. The stacked films are detachable, suspendable and compatible with water or plastic surfaces, which will enable their integration with advanced optical and mechanical systems.

Resist-Free Lithography for Monolayer Transition Metal Dichalcogenides.

Photolithography and electron-beam lithography are the most common methods for making nanoscale devices from semiconductors. While these methods are robust for bulk materials, they disturb the electrical properties of two-dimensional (2D) materials, which are highly sensitive to chemicals used during lithography processes. Here, we report a resist-free lithography method, based on direct laser patterning and resist-free electrode transfer, which avoids unintentional modification to the 2D materials throughout the process. We successfully fabricate large arrays of field-effect transistors using MoS2 and WSe2 monolayers, the performance of which reflects the properties of the pristine materials. Furthermore, using these pristine devices as a reference, we reveal that among the various stages of a conventional lithography process, exposure to a solvent like acetone changes the electrical conductivity of MoS2 the most. This new approach will enable a rational design of reproducible processes for making large-scale integrated circuits based on 2D materials and other surface-sensitive materials.

Local Electronic Properties of Coherent Single-Layer WS2/WSe2 Lateral Heterostructures.

Lateral single-layer transition metal dichalcogenide (TMD) heterostructures are promising building blocks for future ultrathin devices. Recent advances in the growth of coherent heterostructures have improved the structural precision of lateral heterojunctions, but an understanding of the electronic effects of the chemical transition at the interface and associated strain is lacking. Here we present a scanning tunneling microscopy study of single-layer coherent TMD heterostructures with nearly uniform strain on each side of the heterojunction interface. We have characterized the local topography and electronic structure of single-layer WS2/WSe2 heterojunctions exhibiting ultrasharp coherent interfaces. Uniform built-in strain on each side of the interface arising from lattice mismatch results in a reduction of the bandgap of WS2. By mapping the tunneling differential conductance across the interface, we find type-II band alignment and an ultranarrow electronic transition region only ∼3 nm in width that arises from wave function mixing between the two materials.

Interfacial Electron-Phonon Coupling Constants Extracted from Intrinsic Replica Bands in Monolayer FeSe/SrTiO_{3}.

The observation of replica bands by angle-resolved photoemission spectroscopy has ignited interest in the study of electron-phonon coupling at low carrier densities, particularly in monolayer FeSe/SrTiO_{3}, where the appearance of replica bands has motivated theoretical work suggesting that the interfacial coupling of electrons in the FeSe layer to optical phonons in the SrTiO_{3} substrate might contribute to the enhanced superconducting pairing temperature. Alternatively, it has also been recently proposed that such replica bands might instead originate from extrinsic final state losses associated with the photoemission process. Here, we perform a quantitative examination of replica bands in monolayer FeSe/SrTiO_{3}, where we are able to conclusively demonstrate that the replica bands are indeed signatures of intrinsic electron-boson coupling, and not associated with final state effects. A detailed analysis of the energy splittings and relative peak intensities between the higher-order replicas, as well as other self-energy effects, allows us to determine that the interfacial electron-phonon coupling in the system corresponds to a value of λ=0.19±0.02, providing valuable insights into the enhancement of superconductivity in monolayer FeSe/SrTiO_{3}. The methodology employed here can also serve as a new and general approach for making more rigorous and quantitative comparisons to theoretical calculations of electron-phonon interactions and coupling constants.

High-mobility three-atom-thick semiconducting films with wafer-scale homogeneity.

The large-scale growth of semiconducting thin films forms the basis of modern electronics and optoelectronics. A decrease in film thickness to the ultimate limit of the atomic, sub-nanometre length scale, a difficult limit for traditional semiconductors (such as Si and GaAs), would bring wide benefits for applications in ultrathin and flexible electronics, photovoltaics and display technology. For this, transition-metal dichalcogenides (TMDs), which can form stable three-atom-thick monolayers, provide ideal semiconducting materials with high electrical carrier mobility, and their large-scale growth on insulating substrates would enable the batch fabrication of atomically thin high-performance transistors and photodetectors on a technologically relevant scale without film transfer. In addition, their unique electronic band structures provide novel ways of enhancing the functionalities of such devices, including the large excitonic effect, bandgap modulation, indirect-to-direct bandgap transition, piezoelectricity and valleytronics. However, the large-scale growth of monolayer TMD films with spatial homogeneity and high electrical performance remains an unsolved challenge. Here we report the preparation of high-mobility 4-inch wafer-scale films of monolayer molybdenum disulphide (MoS2) and tungsten disulphide, grown directly on insulating SiO2 substrates, with excellent spatial homogeneity over the entire films. They are grown with a newly developed, metal-organic chemical vapour deposition technique, and show high electrical performance, including an electron mobility of 30 cm(2) V(-1) s(-1) at room temperature and 114 cm(2) V(-1) s(-1) at 90 K for MoS2, with little dependence on position or channel length. With the use of these films we successfully demonstrate the wafer-scale batch fabrication of high-performance monolayer MoS2 field-effect transistors with a 99% device yield and the multi-level fabrication of vertically stacked transistor devices for three-dimensional circuitry. Our work is a step towards the realization of atomically thin integrated circuitry.

Tuning Electrical Conductance of MoS2 Monolayers through Substitutional Doping.

Tuning electrical conductivity of semiconducting materials through substitutional doping is crucial for fabricating functional devices. This, however, has not been fully realized in two-dimensional (2D) materials due to the difficulty of homogeneously controlling the dopant concentrations and the lack of systematic study of the net impact of substitutional dopants separate from that of the unintentional doping from the device fabrication processes. Here, we grow wafer-scale, continuous MoS2 monolayers with tunable concentrations of Nb and Re and fabricate devices using a polymer-free approach to study the direct electrical impact of substitutional dopants in MoS2 monolayers. In particular, the electrical conductivity of Nb doped MoS2 in the absence of electrostatic gating is reproducibly tuned over 7 orders of magnitude by controlling the Nb concentration. Our study further indicates that the dopant carriers do not fully ionize in the 2D limit, unlike in their three-dimensional analogues, which is explained by weaker charge screening and impurity band conduction. Moreover, we show that the dopants are stable, which enables the doped films to be processed as independent building blocks that can be used as electrodes for functional circuitry.

Strain Mapping of Two-Dimensional Heterostructures with Subpicometer Precision.

Next-generation, atomically thin devices require in-plane, one-dimensional heterojunctions to electrically connect different two-dimensional (2D) materials. However, the lattice mismatch between most 2D materials leads to unavoidable strain, dislocations, or ripples, which can strongly affect their mechanical, optical, and electronic properties. We have developed an approach to map 2D heterojunction lattice and strain profiles with subpicometer precision and the ability to identify dislocations and out-of-plane ripples. We collected diffraction patterns from a focused electron beam for each real-space scan position with a high-speed, high dynamic range, momentum-resolved detector-the electron microscope pixel array detector (EMPAD). The resulting four-dimensional (4D) phase space data sets contain the full spatially resolved lattice information on the sample. By using this technique on tungsten disulfide (WS2) and tungsten diselenide (WSe2) lateral heterostructures, we have mapped lattice distortions with 0.3 pm precision across multimicron fields of view and simultaneously observed the dislocations and ripples responsible for strain relaxation in 2D laterally epitaxial structures.

Absence of a Band Gap at the Interface of a Metal and Highly Doped Monolayer MoS2.

High quality electrical contact to semiconducting transition metal dichalcogenides (TMDCs) such as MoS2 is key to unlocking their unique electronic and optoelectronic properties for fundamental research and device applications. Despite extensive experimental and theoretical efforts reliable ohmic contact to doped TMDCs remains elusive and would benefit from a better understanding of the underlying physics of the metal-TMDC interface. Here we present measurements of the atomic-scale energy band diagram of junctions between various metals and heavily doped monolayer MoS2 using ultrahigh vacuum scanning tunneling microscopy (UHV-STM). Our measurements reveal that the electronic properties of these junctions are dominated by two-dimensional metal-induced gap states (MIGS). These MIGS are characterized by a spatially growing measured gap in the local density of states (L-DOS) of the MoS2 within 2 nm of the metal-semiconductor interface. Their decay lengths extend from a minimum of ∼0.55 nm near midgap to as long as 2 nm near the band edges and are nearly identical for Au, Pd, and graphite contacts, indicating that it is a universal property of the monolayer semiconductor. Our findings indicate that even in heavily doped semiconductors, the presence of MIGS sets the ultimate limit for electrical contact.

Long-Lived Hole Spin/Valley Polarization Probed by Kerr Rotation in Monolayer WSe2.

Time-resolved Kerr rotation and photoluminescence measurements are performed on MOCVD-grown monolayer tungsten diselenide (WSe2). We observe a surprisingly long-lived Kerr rotation signal (∼80 ns) at 10 K, which is attributed to spin/valley polarization of the resident holes. This polarization is robust to transverse magnetic field (up to 0.3 T). Wavelength-dependent measurements reveal that only excitation near the free exciton energy generates this long-lived spin/valley polarization.

Atomic-Scale Spectroscopy of Gated Monolayer MoS2.

The electronic properties of semiconducting monolayer transition-metal dichalcogenides can be tuned by electrostatic gate potentials. Here we report gate-tunable imaging and spectroscopy of monolayer MoS2 by atomic-resolution scanning tunneling microscopy/spectroscopy (STM/STS). Our measurements are performed on large-area samples grown by metal-organic chemical vapor deposition (MOCVD) techniques on a silicon oxide substrate. Topographic measurements of defect density indicate a sample quality comparable to single-crystal MoS2. From gate voltage dependent spectroscopic measurements, we determine that in-gap states exist in or near the MoS2 film at a density of 1.3 × 10(12) eV(-1) cm(-2). By combining the single-particle band gap measured by STS with optical measurements, we estimate an exciton binding energy of 230 meV on this substrate, in qualitative agreement with numerical simulation. Grain boundaries are observed in these polycrystalline samples, which are seen to not have strong electronic signatures in STM imaging.

Strong interlayer interactions in bilayer and trilayer moiré superlattices.

Moiré superlattices constructed from transition metal dichalcogenides have demonstrated a series of emergent phenomena, including moiré excitons, flat bands, and correlated insulating states. All of these phenomena depend crucially on the presence of strong moiré potentials, yet the properties of these moiré potentials, and the mechanisms by which they can be generated, remain largely open questions. Here, we use angle-resolved photoemission spectroscopy with submicron spatial resolution to investigate an aligned WS2/WSe2 moiré superlattice and graphene/WS2/WSe2 trilayer heterostructure. Our experiments reveal that the hybridization between moiré bands in WS2/WSe2 exhibits an unusually large momentum dependence, with the splitting between moiré bands at the Γ point more than an order of magnitude larger than that at K point. In addition, we discover that the same WS2/WSe2 superlattice can imprint an unexpectedly large moiré potential on a third, separate layer of graphene (g/WS2/WSe2), suggesting new avenues for engineering two-dimensional moiré superlattices.

Impact of 2D-3D Heterointerface on Remote Epitaxial Interaction through Graphene.

Remote epitaxy has drawn attention as it offers epitaxy of functional materials that can be released from the substrates with atomic precision, thus enabling production and heterointegration of flexible, transferrable, and stackable freestanding single-crystalline membranes. In addition, the remote interaction of atoms and adatoms through two-dimensional (2D) materials in remote epitaxy allows investigation and utilization of electrical/chemical/physical coupling of bulk (3D) materials via 2D materials (3D-2D-3D coupling). Here, we unveil the respective roles and impacts of the substrate material, graphene, substrate-graphene interface, and epitaxial material for electrostatic coupling of these materials, which governs cohesive ordering and can lead to single-crystal epitaxy in the overlying film. We show that simply coating a graphene layer on wafers does not guarantee successful implementation of remote epitaxy, since atomically precise control of the graphene-coated interface is required, and provides key considerations for maximizing the remote electrostatic interaction between the substrate and adatoms. This was enabled by exploring various material systems and processing conditions, and we demonstrate that the rules of remote epitaxy vary significantly depending on the ionicity of material systems as well as the graphene-substrate interface and the epitaxy environment. The general rule of thumb discovered here enables expanding 3D material libraries that can be stacked in freestanding form.

Imaging Polarity in Two Dimensional Materials by Breaking Friedel's Law.

Friedel's law guarantees an inversion-symmetric diffraction pattern for thin, light materials where a kinematic approximation or a single-scattering model holds. Typically, breaking Friedel symmetry is ascribed to multiple scattering events within thick, non-centrosymmetric crystals. However, two-dimensional (2D) materials such as a single monolayer of MoS2 can also violate Friedel's law, with unexpected contrast between conjugate Bragg peaks. We show analytically that retaining higher order terms in the power series expansion of the scattered wavefunction can describe the anomalous contrast between hkl and hkl¯peaks that occurs in 2D crystals with broken in-plane inversion symmetry. These higher-order terms describe multiple scattering paths starting from the same atom in an atomically thin material. Furthermore, 2D materials containing heavy elements, such as WS2, always act as strong phase objects, violating Friedel's law no matter how high the energy of the incident electron beam. Experimentally, this understanding can enhance diffraction-based techniques to provide rapid imaging of polarity, twin domains, in-plane rotations, or other polar textures in 2D materials.

Evidence for the Dominance of Carrier-Induced Band Gap Renormalization over Biexciton Formation in Cryogenic Ultrafast Experiments on MoS2 Monolayers.

Transition-metal dichalcogenides (TMDs) such as MoS2 display promising electrical and optical properties in the monolayer limit. Due to strong quantum confinement, TMDs provide an ideal environment for exploring excitonic physics using ultrafast spectroscopy. However, the interplay between collective excitation effects on single excitons such as band gap renormalization/exciton binding energy (BGR/EBE) change and multiexciton effects such biexciton formation remains poorly understood. Using two-dimensional electronic spectroscopy, we observe the dominance of single-exciton BGR/EBE signals over optically induced biexciton formation. We make this determination based on a lack of strong PIA features at T = 0 fs in the cryogenic spectra. By means of nodal line slope analysis, we determine that spectral diffusion occurs faster than BGR/EBE change, indicative of distinct processes. These results indicate that at higher sub-Mott limit fluences, collective effects on single excitons dominate biexciton formation.

Coherent, atomically thin transition-metal dichalcogenide superlattices with engineered strain.

Epitaxy forms the basis of modern electronics and optoelectronics. We report coherent atomically thin superlattices in which different transition metal dichalcogenide monolayers-despite large lattice mismatches-are repeated and laterally integrated without dislocations within the monolayer plane. Grown by an omnidirectional epitaxy, these superlattices display fully matched lattice constants across heterointerfaces while maintaining an isotropic lattice structure and triangular symmetry. This strong epitaxial strain is precisely engineered via the nanoscale supercell dimensions, thereby enabling broad tuning of the optical properties and producing photoluminescence peak shifts as large as 250 millielectron volts. We present theoretical models to explain this coherent growth and the energetic interplay governing the ripple formation in these strained monolayers. Such coherent superlattices provide building blocks with targeted functionalities at the atomically thin limit.

Atomically Thin Ohmic Edge Contacts Between Two-Dimensional Materials.

With the decrease of the dimensions of electronic devices, the role played by electrical contacts is ever increasing, eventually coming to dominate the overall device volume and total resistance. This is especially problematic for monolayers of semiconducting transition-metal dichalcogenides (TMDs), which are promising candidates for atomically thin electronics. Ideal electrical contacts to them would require the use of similarly thin electrode materials while maintaining low contact resistances. Here we report a scalable method to fabricate ohmic graphene edge contacts to two representative monolayer TMDs, MoS2 and WS2. The graphene and TMD layer are laterally connected with wafer-scale homogeneity, no observable overlap or gap, and a low average contact resistance of 30 kΩ·µm. The resulting graphene edge contacts show linear current-voltage (I-V) characteristics at room temperature, with ohmic behavior maintained down to liquid helium temperatures.