Wafer-scale δ waveguides for integrated two-dimensional photonics.

The efficient, large-scale generation and control of photonic modes guided by van der Waals materials remains as a challenge despite their potential for on-chip photonic circuitry. We report three-atom-thick waveguides-δ waveguides-based on wafer-scale molybdenum disulfide (MoS2) monolayers that can guide visible and near-infrared light over millimeter-scale distances with low loss and an efficient in-coupling. The extreme thinness provides a light-trapping mechanism analogous to a δ-potential well in quantum mechanics and enables the guided waves that are essentially a plane wave freely propagating along the in-plane, but confined along the out-of-plane, direction of the waveguide. We further demonstrate key functionalities essential for two-dimensional photonics, including refraction, focusing, grating, interconnection, and intensity modulation, by integrating thin-film optical components with δ waveguides using microfabricated dielectric, metal, or patterned MoS2.

Two-Dimensional Mechanics of Atomically Thin Solids on Water.

Movement of a three-dimensional solid at an air-water interface is strongly influenced by the extrinsic interactions between the solid and the water. The finite thickness and volume of a moving solid causes capillary interactions and water-induced drag. In this Letter, we report the fabrication and dynamical imaging of freely floating MoS2 solids on water, which minimizes such extrinsic effects. For this, we delaminate a synthesized wafer-scale monolayer MoS2 onto a water surface, which shows negligible height difference across water and MoS2. Subsequently patterning by a laser generates arbitrarily shaped MoS2 with negligible in-plane strain. We introduce photoswitchable surfactants to exert a lateral force to floating MoS2 with a spatiotemporal control. Using this platform, we demonstrate a variety of two-dimensional mechanical systems that show reversible shape changes. Our experiment provides a versatile approach for designing and controlling a large array of atomically thin solids on water for intrinsically two-dimensional dynamics and mechanics.

Robotic four-dimensional pixel assembly of van der Waals solids.

Van der Waals (vdW) solids can be engineered with atomically precise vertical composition through the assembly of layered two-dimensional materials1,2. However, the artisanal assembly of structures from micromechanically exfoliated flakes3,4 is not compatible with scalable and rapid manufacturing. Further engineering of vdW solids requires precisely designed and controlled composition over all three spatial dimensions and interlayer rotation. Here, we report a robotic four-dimensional pixel assembly method for manufacturing vdW solids with unprecedented speed, deliberate design, large area and angle control. We used the robotic assembly of prepatterned 'pixels' made from atomically thin two-dimensional components. Wafer-scale two-dimensional material films were grown, patterned through a clean, contact-free process and assembled using engineered adhesive stamps actuated by a high-vacuum robot. We fabricated vdW solids with up to 80 individual layers, consisting of 100 × 100 µm2 areas with predesigned patterned shapes, laterally/vertically programmed composition and controlled interlayer angle. This enabled efficient optical spectroscopic assays of the vdW solids, revealing new excitonic and absorbance layer dependencies in MoS2. Furthermore, we fabricated twisted N-layer assemblies, where we observed atomic reconstruction of twisted four-layer WS2 at high interlayer twist angles of ≥4°. Our method enables the rapid manufacturing of atomically resolved quantum materials, which could help realize the full potential of vdW heterostructures as a platform for novel physics2,5,6 and advanced electronic technologies7,8.

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.

Extremely anisotropic van der Waals thermal conductors.

The densification of integrated circuits requires thermal management strategies and high thermal conductivity materials1-3. Recent innovations include the development of materials with thermal conduction anisotropy, which can remove hotspots along the fast-axis direction and provide thermal insulation along the slow axis4,5. However, most artificially engineered thermal conductors have anisotropy ratios much smaller than those seen in naturally anisotropic materials. Here we report extremely anisotropic thermal conductors based on large-area van der Waals thin films with random interlayer rotations, which produce a room-temperature thermal anisotropy ratio close to 900 in MoS2, one of the highest ever reported. This is enabled by the interlayer rotations that impede the through-plane thermal transport, while the long-range intralayer crystallinity maintains high in-plane thermal conductivity. We measure ultralow thermal conductivities in the through-plane direction for MoS2 (57 ± 3 mW m-1 K-1) and WS2 (41 ± 3 mW m-1 K-1) films, and we quantitatively explain these values using molecular dynamics simulations that reveal one-dimensional glass-like thermal transport. Conversely, the in-plane thermal conductivity in these MoS2 films is close to the single-crystal value. Covering nanofabricated gold electrodes with our anisotropic films prevents overheating of the electrodes and blocks heat from reaching the device surface. Our work establishes interlayer rotation in crystalline layered materials as a new degree of freedom for engineering-directed heat transport in solid-state systems.

Atomically Thin, Optically Isotropic Films with 3D Nanotopography.

Flat optics aims for the on-chip miniaturization of optical systems for high-speed and low-power operation, with integration of thin and lightweight components. Here, we present atomically thin yet optically isotropic films realized by using three-dimensional (3D) topographic reconstruction of anisotropic two-dimensional (2D) films to balance the out-of-plane and in-plane optical responses on the subwavelength scale. We achieve this by conformal growth of monolayer transition metal dichalcogenide (TMD) films on nanodome-structured substrates. The resulting films show an order-of-magnitude increase in the out-of-plane susceptibility for enhanced angular performance, displaying polarization isotropy in the off-axis absorption, as well as improved photoluminescence emission profiles, compared to their flat-film counterparts. We further show that such 3D geometric programming of optical properties is applicable to different TMD materials, offering spectral generalization over for the entire visible range. Our approach presents a powerful platform for advancing the development of atomically thin flat optics with custom-designed light-matter interactions.

Sub-10 fs Intervalley Exciton Coupling in Monolayer MoS2 Revealed by Helicity-Resolved Two-Dimensional Electronic Spectroscopy.

The valley pseudospin at the K and K' high-symmetry points in monolayer transition metal dichalcogenides (TMDs) has potential as an optically addressable degree of freedom in next-generation optoelectronics. However, intervalley scattering and relaxation of charge carriers leads to valley depolarization and limits practical applications. In addition, enhanced Coulomb interactions lead to pronounced excitonic effects that dominate the optical response and initial valley depolarization dynamics but complicate the interpretation of ultrafast spectroscopic experiments at short time delays. Employing broadband helicity-resolved two-dimensional electronic spectroscopy (2DES), we observe ultrafast (∼10 fs) intervalley coupling between all A and B valley exciton states that results in a complete breakdown of the valley index in large-area monolayer MoS2 films. These couplings and subsequent dynamics exhibit minimal excitation fluence or temperature dependence and are robust toward changes in sample grain size and inherent strain. Our observations strongly suggest that this direct intervalley coupling on the time scale of optical excitation is an inherent property of large-area MoS2 distinct from dynamic carrier or exciton scattering, phonon-driven processes, and multiexciton effects. This ultrafast intervalley coupling poses a fundamental challenge for exciton-based valleytronics in monolayer TMDs and must be overcome to fully realize large-area valleytronic devices.

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.

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.

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.

Wafer-scale synthesis of monolayer two-dimensional porphyrin polymers for hybrid superlattices.

The large-scale synthesis of high-quality thin films with extensive tunability derived from molecular building blocks will advance the development of artificial solids with designed functionalities. We report the synthesis of two-dimensional (2D) porphyrin polymer films with wafer-scale homogeneity in the ultimate limit of monolayer thickness by growing films at a sharp pentane/water interface, which allows the fabrication of their hybrid superlattices. Laminar assembly polymerization of porphyrin monomers could form monolayers of metal-organic frameworks with Cu2+ linkers or covalent organic frameworks with terephthalaldehyde linkers. Both the lattice structures and optical properties of these 2D films were directly controlled by the molecular monomers and polymerization chemistries. The 2D polymers were used to fabricate arrays of hybrid superlattices with molybdenum disulfide that could be used in electrical capacitors.

Two-Dimensional Material Tunnel Barrier for Josephson Junctions and Superconducting Qubits.

Quantum computing based on superconducting qubits requires the understanding and control of the materials, device architecture, and operation. However, the materials for the central circuit element, the Josephson junction, have mostly been focused on using the AlOx tunnel barrier. Here, we demonstrate Josephson junctions and superconducting qubits employing two-dimensional materials as the tunnel barrier. We batch-fabricate and design the critical Josephson current of these devices via layer-by-layer stacking N layers of MoS2 on the large scale. Based on such junctions, MoS2 transmon qubits are engineered and characterized in a bulk superconducting microwave resonator for the first time. Our work allows Josephson junctions to access the diverse material properties of two-dimensional materials that include a wide range of electrical and magnetic properties, which can be used to study the effects of different material properties in superconducting qubits and to engineer novel quantum circuit elements in the future.

Capillary Origami with Atomically Thin Membranes.

Small-scale optical and mechanical components and machines require control over three-dimensional structure at the microscale. Inspired by the analogy between paper and two-dimensional materials, origami-style folding of atomically thin materials offers a promising approach for making microscale structures from the thinnest possible sheets. In this Letter, we show that a monolayer of molybdenum disulfide (MoS2) can be folded into three-dimensional shapes by a technique called capillary origami, in which the surface tension of a droplet drives the folding of a thin sheet. We define shape nets by patterning rigid metal panels connected by MoS2 hinges, allowing us to fold micron-scale polyhedrons. Finally, we demonstrate that these shapes can be folded in parallel without the use of micropipettes or microfluidics by means of a microemulsion of droplets that dissolves into the bulk solution to drive folding. These results demonstrate controllable folding of the thinnest possible materials using capillary origami and indicate a route forward for design and parallel fabrication of more complex three-dimensional micron-scale structures and machines.