Saien Xie

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 cm2 V−1 s−1 at room temperature and 114 cm2 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.

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.

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.

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.

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

Coherent strained superlattices Two-dimensional superlattices represent the atomic-thickness limit of heterostructures that enable technologies such as strain-engineered multiferroics and quantum-cascade lasers. Xie et al. were able to produce monolayer superlattices of transition metal dichalcogenides (WS2 and WSe2) with full lattice coherence, despite a 4% lattice mismatch. They used a modulated metal-organic chemical vapor deposition process that precisely controlled each precursor. Furthermore, the authors could strain-engineer the optical properties of the superlattices to observe out-of-plane rippling. Science, this issue p. 1131 Omnidirectional epitaxy produced superlattices with strain-engineered optical properties and mechanical deformations. 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.

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.Combining an electron microscope pixel-array detector that collects the entire distribution of scattered electrons with full-field ptychography greatly improves image resolution and contrast compared to traditional techniques, even at low beam energies.

Strain Accommodation and Coherency in Laterally-Stitched WSe 2 /WS 2 Junctions

Monolayer transition metal dichalcogenides (TMDs), which are flexible and stretchable semiconductor films with direct band gaps, have attracted much interest for their applications in electronics and optoelectronics. We have used MOCVD [1] process for the epitaxial growth of defect-free lateral stitched heterojunctions between TMDs. These include WSe2/WS2 junctions, also previously reported by others [2,3], which should have a ~4.4% lattice mismatch based on their isolated lattice constants, while the reported absence of defects would imply large lattice strains at the interface, and these have been predicted to influence electronic and optical properties [3]. Here we examined this interface using dark field TEM (DF-TEM) and atomic-resolution annular dark field scanning transmission electron microscopy (ADF-STEM), where the contrast is proportional to ~Z. We mapped the lattice mismatch and strain using geometric phase analysis (GPA) and bond-length calculations. We observed that WSe2 and WS2 exert uniaxial lattice strain parallel to the junction, resulting in largely coherent, latticematched structures, while the lattice perpendicular to the junction is distorted consistent with a Poisson dilation/contraction.

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.