Immunity to Contact Scaling in MoS2 Transistors Using in Situ Edge Contacts.

Atomically thin two-dimensional (2D) materials are promising candidates for sub-10 nm transistor channels due to their ultrathin body thickness, which results in strong electrostatic gate control. Properly scaling a transistor technology requires reducing both the channel length (distance from source to drain) and the contact length (distance that source and drain interface with semiconducting channel). Contact length scaling remains an unresolved epidemic for transistor scaling, affecting devices from all semiconductors-silicon to 2D materials. Here, we show that clean edge contacts to 2D MoS2 can provide immunity to the contact-scaling problem, with performance that is independent of contact length down to the 20 nm regime. Using a directional ion beam, in situ edge contacts of various metal-MoS2 interfaces are studied. Characterization of the intricate edge interface using cross-sectional electron microscopy reveals distinct morphological effects on the MoS2 depending on its thickness-from monolayer to few-layer films. The in situ edge contacts also exhibit an order of magnitude higher performance compared to the best-reported ex situ metal edge contacts. Our work provides experimental evidence for a solution to contact scaling in transistors, using 2D materials with clean edge contact interfaces, opening a new way of designing devices with 2D materials.

Dense Electron-Hole Plasma Formation and Ultralong Charge Lifetime in Monolayer MoS2 via Material Tuning.

Many-body interactions in photoexcited semiconductors can bring about strongly interacting electronic states, culminating in the fully ionized matter of electron-hole plasma (EHP) and electron-hole liquid (EHL). These exotic phases exhibit unique electronic properties, such as metallic conductivity and metastable high photoexcitation density, which can be the basis for future transformative applications. However, the cryogenic condition required for its formation has limited the study of dense plasma phases to a purely academic pursuit in a restricted parameter space. This paradigm can potentially change with the recent experimental observation of these phases in atomically thin MoS2 and MoTe2 at room temperature. A fundamental understanding of EHP and EHL dynamics is critical for developing novel applications on this versatile layered platform. In this work, we studied the formation and dissipation of EHP in monolayer MoS2. Unlike previous results in bulk semiconductors, our results reveal that electromechanical material changes in monolayer MoS2 during photoexcitation play a significant role in dense EHP formation. Within the free-standing geometry, photoexcitation is accompanied by an unconstrained thermal expansion, resulting in a direct-to-indirect gap electronic transition at a critical lattice spacing and fluence. This dramatic altering of the material's energetic landscape extends carrier lifetimes by 2 orders of magnitude and allows the density required for EHP formation. The result is a stable dense plasma state that is sustained with modest optical photoexcitation. Our findings pave the way for novel applications based on dense plasma states in two-dimensional semiconductors.

Surface-enhanced Raman scattering of monolayer transition metal dichalcogenides on Ag nanorod arrays.

In this work, we studied surface-enhanced Raman scattering (SERS) of MS2 (M=Mo, W) monolayers that were transferred onto Ag nanorod arrays. Compared to the suspended monolayers, the Raman intensity of monolayers on an Ag nanorod substrate was strongly enhanced for both in-plane and out-of-plane vibration modes: up to 8 (5) for E2g and 20 (23) for A1g in MoS2 (WS2). This finding reveals a promising SERS substrate for achieving uniform and strong enhancement for two-dimensional materials in the applications of optical detecting and sensing.

Giant Gating Tunability of Optical Refractive Index in Transition Metal Dichalcogenide Monolayers.

We report that the refractive index of transition metal dichacolgenide (TMDC) monolayers, such as MoS2, WS2, and WSe2, can be substantially tuned by >60% in the imaginary part and >20% in the real part around exciton resonances using complementary metal-oxide-semiconductor (CMOS) compatible electrical gating. This giant tunablility is rooted in the dominance of excitonic effects in the refractive index of the monolayers and the strong susceptibility of the excitons to the influence of injected charge carriers. The tunability mainly results from the effects of injected charge carriers to broaden the spectral width of excitonic interband transitions and to facilitate the interconversion of neutral and charged excitons. The other effects of the injected charge carriers, such as renormalizing bandgap and changing exciton binding energy, only play negligible roles. We also demonstrate that the atomically thin monolayers, when combined with photonic structures, can enable the efficiencies of optical absorption (reflection) tuned from 40% (60%) to 80% (20%) due to the giant tunability of the refractive index. This work may pave the way toward the development of field-effect photonics in which the optical functionality can be controlled with CMOS circuits.

Dynamic Optical Tuning of Interlayer Interactions in the Transition Metal Dichalcogenides.

Modulation of weak interlayer interactions between quasi-two-dimensional atomic planes in the transition metal dichalcogenides (TMDCs) provides avenues for tuning their functional properties. Here we show that above-gap optical excitation in the TMDCs leads to an unexpected large-amplitude, ultrafast compressive force between the two-dimensional layers, as probed by in situ measurements of the atomic layer spacing at femtosecond time resolution. We show that this compressive response arises from a dynamic modulation of the interlayer van der Waals interaction and that this represents the dominant light-induced stress at low excitation densities. A simple analytic model predicts the magnitude and carrier density dependence of the measured strains. This work establishes a new method for dynamic, nonequilibrium tuning of correlation-driven dispersive interactions and of the optomechanical functionality of TMDC quasi-two-dimensional materials.

Activating MoS2 for pH-Universal Hydrogen Evolution Catalysis.

MoS2 presents a promising catalyst for the hydrogen evolution reaction (HER) in water splitting, but its worse catalytic performance in neutral and alkaline media than in acidic environment may be problematic for practical application. This is because the other half reaction of water splitting, i.e., oxygen evolution reaction, often needs to be implemented in alkaline environment. Here we demonstrate a universal strategy that may be used to significantly improve the HER catalysis of MoS2 in all kinds of environments from acidic to alkaline, proton intercalation. Protons may be enabled to intercalate between monolayer MoS2 and underlying substrates or in the interlayer space of thicker MoS2 by two processes: electrochemically polarizing MoS2 at negative potentials (vs RHE) in acidic media or immersing MoS2 into certain acid solutions like TFSI. The improvement in catalytic performance is due to the activity enhancement of the active sites in MoS2 by the intercalated protons, which might be related with the effect of the intercalated protons on electrical conductance and the adsorption energy of hydrogen atoms. The enhancement in catalytic activity by the intercalated proton is very stable even in neutral and alkaline electrolytes.

All The Catalytic Active Sites of MoS2 for Hydrogen Evolution.

MoS2 presents a promising low-cost catalyst for the hydrogen evolution reaction (HER), but the understanding about its active sites has remained limited. Here we present an unambiguous study of the catalytic activities of all possible reaction sites of MoS2, including edge sites, sulfur vacancies, and grain boundaries. We demonstrate that, in addition to the well-known catalytically active edge sites, sulfur vacancies provide another major active site for the HER, while the catalytic activity of grain boundaries is much weaker. The intrinsic turnover frequencies (Tafel slopes) of the edge sites, sulfur vacancies, and grain boundaries are estimated to be 7.5 s-1 (65-75 mV/dec), 3.2 s-1 (65-85 mV/dec), and 0.1 s-1 (120-160 mV/dec), respectively. We also demonstrate that the catalytic activity of sulfur vacancies strongly depends on the density of the vacancies and the local crystalline structure in proximity to the vacancies. Unlike edge sites, whose catalytic activity linearly depends on the length, sulfur vacancies show optimal catalytic activities when the vacancy density is in the range of 7-10%, and the number of sulfur vacancies in high crystalline quality MoS2 is higher than that in low crystalline quality MoS2, which may be related with the proximity of different local crystalline structures to the vacancies.

Equally efficient interlayer exciton relaxation and improved absorption in epitaxial and nonepitaxial MoS2/WS2 heterostructures.

Semiconductor heterostructures provide a powerful platform to engineer the dynamics of excitons for fundamental and applied interests. However, the functionality of conventional semiconductor heterostructures is often limited by inefficient charge transfer across interfaces due to the interfacial imperfection caused by lattice mismatch. Here we demonstrate that MoS(2)/WS(2) heterostructures consisting of monolayer MoS(2) and WS(2) stacked in the vertical direction can enable equally efficient interlayer exciton relaxation regardless the epitaxy and orientation of the stacking. This is manifested by a similar 2 orders of magnitude decrease of photoluminescence intensity in both epitaxial and nonepitaxial MoS(2)/WS(2) heterostructures. Both heterostructures also show similarly improved absorption beyond the simple superimposition of the absorptions of monolayer MoS(2) and WS(2). Our result indicates that 2D heterostructures bear significant implications for the development of photonic devices, in particular those requesting efficient exciton separation and strong light absorption, such as solar cells, photodetectors, modulators, and photocatalysts. It also suggests that the simple stacking of dissimilar 2D materials with random orientations is a viable strategy to fabricate complex functional 2D heterostructures, which would show similar optical functionality as the counterpart with perfect epitaxy.

Dynamic Structural Response and Deformations of Monolayer MoS2 Visualized by Femtosecond Electron Diffraction.

Two-dimensional materials are subject to intrinsic and dynamic rippling that modulates their optoelectronic and electromechanical properties. Here, we directly visualize the dynamics of these processes within monolayer transition metal dichalcogenide MoS2 using femtosecond electron scattering techniques as a real-time probe with atomic-scale resolution. We show that optical excitation induces large-amplitude in-plane displacements and ultrafast wrinkling of the monolayer on nanometer length-scales, developing on picosecond time-scales. These deformations are associated with several percent peak strains that are fully reversible over tens of millions of cycles. Direct measurements of electron-phonon coupling times and the subsequent interfacial thermal heat flow between the monolayer and substrate are also obtained. These measurements, coupled with first-principles modeling, provide a new understanding of the dynamic structural processes that underlie the functionality of two-dimensional materials and open up new opportunities for ultrafast strain engineering using all-optical methods.

Deterministic phase engineering for optical Fano resonances with arbitrary lineshape and frequencies.

We present an approach of deterministic phase engineering that can enable the rational design of optical Fano resonances with arbitrarily pre-specified lineshapes. Unlike all the approaches previously used to design optical Fano resonances, which fall short of designing the resonances with arbitrary lineshapes because of the lack of information for the optical phases involved, we develop our approach by capitalizing on unambiguous knowledge for the phase of optical modes. Optical Fano resonances arise from the interference of photons interacting with two optical modes with substantially different quality factors. We find that the phase difference of the two modes involved in optical Fano resonances is determined by the eigenfrequency difference of the modes. This allows us to deterministically engineer the phase by tuning the eigenfrequency, which may be very straightforward. We use dielectric grating structures as an example to illustrate the notion of deterministic engineering for the design of optical Fano resonances with arbitrarily pre-specified symmetry, linewidth, and wavelengths.

Many-body effects in valleytronics: direct measurement of valley lifetimes in single-layer MoS2.

Single layer MoS2 is an ideal material for the emerging field of "valleytronics" in which charge carrier momentum can be finely controlled by optical excitation. This system is also known to exhibit strong many-body interactions as observed by tightly bound excitons and trions. Here we report direct measurements of valley relaxation dynamics in single layer MoS2, by using ultrafast transient absorption spectroscopy. Our results show that strong Coulomb interactions significantly impact valley population dynamics. Initial excitation by circularly polarized light creates electron-hole pairs within the K-valley. These excitons coherently couple to dark intervalley excitonic states, which facilitate fast electron valley depolarization. Hole valley relaxation is delayed up to about 10 ps due to nondegeneracy of the valence band spin states. Intervalley biexciton formation reveals the hole valley relaxation dynamics. We observe that biexcitons form with more than an order of magnitude larger binding energy compared to conventional semiconductors. These measurements provide significant insight into valley specific processes in 2D semiconductors. Hence they could be used to suggest routes to design semiconducting materials that enable control of valley polarization.

Layer-dependent electrocatalysis of MoS2 for hydrogen evolution.

The quantitative correlation of the catalytic activity with the microscopic structure of heterogeneous catalysts is a major challenge for the field of catalysis science. It requests synergistic capabilities to tailor the structure with atomic scale precision and to control the catalytic reaction to proceed through well-defined pathways. Here we leverage on the controlled growth of MoS2 atomically thin films to demonstrate that the catalytic activity of MoS2 for the hydrogen evolution reaction decreases by a factor of ∼ 4.47 for the addition of every one more layer. Similar layer dependence is also found in edge-riched MoS2 pyramid platelets. This layer-dependent electrocatalysis can be correlated to the hopping of electrons in the vertical direction of MoS2 layers over an interlayer potential barrier. Our experimental results suggest the potential barrier to be 0.119 V, consistent with theoretical calculations. Different from the conventional wisdom, which states that the number of edge sites is important, our results suggest that increasing the hopping efficiency of electrons in the vertical direction is a key for the development of high-efficiency two-dimensional material catalysts.

General modal properties of optical resonances in subwavelength nonspherical dielectric structures.

Subwavelength dielectric structures offer an attractive low-loss alternative to plasmonic materials for the development of resonant optics functionalities such as metamaterials and optical antennas. Nonspherical-like rectangular dielectric structures are of the most interest from the standpoint of device development due to fabrication convenience. However, no intuitive fundamental understanding of the optical resonance in nonspherical dielectric structures is available, which has substantially delayed the development of dielectric resonant optics devices. Here, we elucidate the general fundamentals of the optical resonance in nonspherical subwavelength dielectric structures with different shapes (rectangular or triangular) and dimensionalities (1D nanowires or 0D nanoparticles). We demonstrate that the optical properties of nonspherical dielectric structures are dictated by the eigenvalue of the structure's leaky modes. Leaky modes are defined as optical modes with propagating waves outside the structure. We also elucidate the dependence of the modal eigenvalue on physical features of the structure. The eigenvalue shows scale invariance with respect to the size of the structure, weak dependence on the refractive index, but linear dependence on the size ratio of different sides of the structure. We propose a modified Fabry-Perot model to account for the linear dependence. The knowledge of leaky modes, including the role in optical responses and the dependence on physical features, can serve as a powerful guide for the rational design of devices with desired optical resonances. It may open up a pathway to design devices with functionality that has not been explored due to the lack of intuitive understanding, for instance, imaging devices able to sense incident angle or superabsorbing photodetectors.

Epitaxial nanosheet-nanowire heterostructures.

We demonstrate synthesis of a new type of heterostructures that comprise two-dimensional (2D) nanosheets (NSs) epitaxially grown at one-dimensional (1D) nanowires (NWs). The synthesis involves materials with a graphite-like layered structure in which covalently bonded layers are held by weak van der Waals forces. GeS was used as a prototype material in this work. The synthesis also involves a seeded-growth process, where GeS NWs are grown first as seeds followed by a seeded growth of NSs at the pre-grown NWs. We observe that exposing the pre-grown NWs to air prior to the seeded growth is critical for the formation of NSs to yield NS-NW heterostructures. Our experimental results suggest that this might be due to a mild oxidation at the NW surface caused by the air exposure, which could subsequently facilitate the nucleation of NSs at the NWs. It also suggests that the surface oxidation needs to be controlled in a proper range in order to achieve optimized NS growths. We believe that this synthetic strategy may generally apply to the growth of NS-NW heterostructures of other layered chalcogenide materials. NS-NW heterostructures provide capabilities to monolithically integrate the functionality of 1D NWs and 2D NSs into a 3D space. It holds great potential in applications that request complex nanomaterials with multiple functionality, high surface area, and efficient charge transport, such as energy storage, chemical sensing, solar energy conversion, and 3D electric and photonic devices.

Redesigning photodetector electrodes as an optical antenna.

At the nanoscale, semiconductor and metallic structures naturally exhibit strong, tunable optical resonances that can be utilized to enhance light-matter interaction and to dramatically increase the performance of chipscale photonic elements. Here, we demonstrate that the metallic leads used to extract current from a Ge nanowire (NW) photodetector can be redesigned to serve as optical antennas capable of concentrating light in the NW. The NW itself can also be made optically resonant and an overall performance optimization involves a careful tuning of both resonances. We show that such a procedure can result in broadband absorption enhancements of up to a factor 1.7 at a target wavelength of 660 nm and an ability to control the detector's polarization-dependent response. The results of this study demonstrate the critical importance of performing a joint optimization of the electrical and optical properties of the metallic and semiconductor building blocks in optoelectronic devices with nanoscale components.

The phase shift of light scattering at sub-wavelength dielectric structures.

We present a new theoretical analysis for the light scattering at sub-wavelength dielectric structures. This analysis can provide new intuitive insights into the phase shift of the scattered light that cannot be obtained from the existing approaches. Unlike the traditional analytical (e.g. Mie formalism) and numerical (e.g. FDTD) approaches, which simulate light scattering by rigorously matching electromagnetic fields at boundaries, we consider sub-wavelength dielectric structures as leaky resonators and evaluate the light scattering as a coupling process between incident light and leaky modes of the structure. Our analysis indicates that the light scattering is fundamentally dictated by the eigenvalue of the leaky modes. It indicates that the upper limit for the scattering efficiency of a cylindrical cylinder in free space is 4n, where n is the refractive index. It also indicates that the phase shift of the forward scattered light at dielectric structures can only cover half of the phase space [0, 2π], but backward scattering can provide a full phase coverage.

Dielectric core-shell optical antennas for strong solar absorption enhancement.

We demonstrate a new light trapping technique that exploits dielectric core-shell optical antennas to strongly enhance solar absorption. This approach can allow the thickness of active materials in solar cells lowered by almost 1 order of magnitude without scarifying solar absorption capability. For example, it can enable a 70 nm thick hydrogenated amorphous silicon (a-Si:H) thin film to absorb 90% of incident solar radiation above the bandgap, which would otherwise require a thickness of 400 nm in typical antireflective coated thin films. This strong enhancement arises from a controlled optical antenna effect in patterned core-shell nanostructures that consist of absorbing semiconductors and nonabsorbing dielectric materials. This core-shell optical antenna benefits from a multiplication of enhancements contributed by leaky mode resonances (LMRs) in the semiconductor part and antireflection effects in the dielectric part. We investigate the fundamental mechanism for this enhancement multiplication and demonstrate that the size ratio of the semiconductor and the dielectric parts in the core-shell structure is key for optimizing the enhancement. By enabling strong solar absorption enhancement, this approach holds promise for cost reduction and efficiency improvement of solar conversion devices, including solar cells and solar-to-fuel systems. It can generally apply to a wide range of inorganic and organic active materials. This dielectric core-shell antenna can also find applications in other photonic devices such as photodetectors, sensors, and solid-state lighting diodes.

Phase Diagram of High-Temperature Electron-Hole Quantum Droplet in Two-Dimensional Semiconductors.

Quantum liquids, systems exhibiting effects of quantum mechanics and quantum statistics at macroscopic levels, represent one of the most exciting research frontiers of modern physical science and engineering. Notable examples include Bose-Einstein condensation (BEC), superconductivity, quantum entanglement, and a quantum liquid. However, quantum liquids are usually only stable at cryogenic temperatures, significantly limiting fundamental studies and device development. Here we demonstrate the formation of stable electron-hole liquid (EHL) with the quantum statistic nature at temperatures as high as 700 K in monolayer MoS2 and elucidate that the high-temperature EHL exists as droplets in sizes of around 100-160 nm. We also develop a thermodynamic model of high-temperature EHL and, based on the model, compile an exciton phase diagram, revealing that the ionized photocarrier drives the gas-liquid transition, which is subsequently validated with experimental results. The high-temperature EHL provides a model system to enable opportunities for studies in the pursuit of other high-temperature quantum liquids. The results can also allow for the development of quantum liquid devices with practical applications in quantum information processing, optoelectronics, and optical interconnections.