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.

Distinct Contact Scaling Effects in MoS2 Transistors Revealed with Asymmetrical Contact Measurements.

2D semiconducting materials have immense potential for future electronics due to their atomically thin nature, which enables better scalability. While the channel scalability of 2D materials has been extensively studied, the current understanding of contact scaling in 2D devices is inconsistent and oversimplified. Here physically scaled contacts and asymmetrical contact measurements (ACMs) are combined to investigate the contact scaling behavior in 2D field-effect transistors. The ACMs directly compare electron injection at different contact lengths while using the exact same MoS2  channel, eliminating channel-to-channel variations. The results show that scaled source contacts can limit the drain current, whereas scaled drain contacts do not. Compared to devices with long contact lengths, devices with short contact lengths (scaled contacts) exhibit larger variations, 15% lower drain currents at high drain-source voltages, and a higher chance of early saturation and negative differential resistance. Quantum transport simulations reveal that the transfer length of Ni-MoS2  contacts can be as short as 5 nm. Furthermore, it is clearly identified that the actual transfer length depends on the quality of the metal-2D interface. The ACMs demonstrated here will enable further understanding of contact scaling behavior at various interfaces.

Are 2D Interfaces Really Flat?

Two-dimensional (2D) van der Waals materials are subject to mechanical deformation and thus forming bubbles and wrinkles during exfoliation and transfer. A lack of interfacial "flatness" has implications for interface properties, such as those formed by metal contacts or insulating layers. Therefore, an understanding of the detailed properties of 2D interfaces, especially their flatness under different conditions, is of high importance. Here we use cross-sectional scanning transmission electron microscopy (STEM) to investigate various 2D interfaces (2D-2D and 3D-2D) under the effects of stacking, atomic layer deposition (ALD), and metallization. We characterize and compare the flatness of the hBN-2D and metal-2D interfaces down to angstrom resolution. It is observed that the dry transfer of hexagonal boron nitride (hBN) can dramatically alter the interface structure. When characterizing 3D metal-2D interfaces, we find that Ni-MoS2 interfaces are more uneven and have larger nanocavities compared to other metal-2D interfaces. The electrical characteristics of a MoS2-based field-effect transistor are correlated to the interfacial transformation in the contact and channel regions. The device transconductance is improved by 40% after the hBN encapsulation, likely due to the interface interactions at both the channel and contacts. Overall, these observations reveal the intricacy of 2D interfaces and their dependence on the fabrication processes.

Giant enhancement of exciton diffusivity in two-dimensional semiconductors.

Two-dimensional (2D) semiconductors bear great promise for application in optoelectronic devices, but the low diffusivity of excitons stands as a notable challenge for device development. Here, we demonstrate that the diffusivity of excitons in monolayer MoS2 can be improved from 1.5 ± 0.5 to 22.5 ± 2.5 square centimeters per second with the presence of trapped charges. This is manifested by a spatial expansion of photoluminescence when the incident power reaches a threshold value to enable the onset of exciton Mott transition. The trapped charges are estimated to be in a scale of 1010 per square centimeter and do not affect the emission features and recombination dynamics of the excitons. The result indicates that trapped charges provide an attractive strategy to screen exciton scattering with phonons and impurities/defects. Pointing towards a new pathway to control exciton transport and many-body interactions in 2D semiconductors.

Engineering Substrate Interaction To Improve Hydrogen Evolution Catalysis of Monolayer MoS2 Films beyond Pt.

MoS2 holds great promise as a cost-effective alternative to Pt for catalyzing the hydrogen evolution reaction (HER) of water, but its reported catalytic efficiency is still worse than that of Pt, the best HER catalyst but too rare and expensive for mass production of hydrogen. We report a strategy to enable the catalytic activity of monolayer MoS2 films that are even better than that of Pt via engineering the interaction of the monolayer with supporting substrates. The monolayer films were grown with chemical vapor deposition processes and controlled to have an optimal density (7-10%) of sulfur vacancies. We find that the catalytic activity of MoS2 can be affected by substrates in two ways: forming an interfacial tunneling barrier with MoS2 and modifying the chemical nature of MoS2 via charge transfer (proximity doping). Following this understanding, we enable excellent catalytic activities at the monolayer MoS2 films by using substrates that can provide n-doping to MoS2 and form low interfacial tunneling barriers with MoS2, such as Ti. The catalytic performance may be further boosted to be even better than Pt by crumpling the films on Ti coated flexible polymer substrates, as the Tafel slope of the film is substantially decreased with the presence of crumpling-induced compressive strain. The monolayer MoS2 films show no degradation in catalytic performance after being continuously tested for over 2 months.

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.

Room-Temperature Electron-Hole Liquid in Monolayer MoS2.

Excitons in semiconductors are usually noninteracting and behave like an ideal gas, but may condense to a strongly correlated liquid-like state, i.e., electron-hole liquid (EHL), at high density and appropriate temperature. An EHL is a macroscopic quantum state with exotic properties and represents the ultimate attainable charge excitation density in steady states. It bears great promise for a variety of fields such as ultra-high-power photonics and quantum science and technology. However, the condensation of gas-like excitons to an EHL has often been restricted to cryogenic temperatures, which significantly limits the prospect of EHLs for use in practical applications. Herein we demonstrate the formation of an EHL at room temperature in monolayer MoS2 by taking advantage of the monolayer's extraordinarily strong exciton binding energy. This work demonstrates the potential for the liquid-like state of charge excitations to be a useful platform for the studies of macroscopic quantum phenomena and the development of optoelectronic devices.

Reversible Photoluminescence Tuning by Defect Passivation via Laser Irradiation on Aged Monolayer MoS2.

Atomically thin (1L)-MoS2 emerged as a direct band gap semiconductor with potential optical applications. The photoluminescence (PL) of 1L-MoS2 degrades due to aging-related defect formation. The passivation of these defects leads to substantial improvement in optical properties. Here, we report the enhancement of PL on aged 1L-MoS2 by laser treatment. Using photoluminescence and Raman spectroscopy in a gas-controlled environment, we show that the enhancement is associated with efficient adsorption of oxygen on existing sulfur vacancies preceded by removal of adsorbates from the sample's surface. Oxygen adsorption depletes negative charges, resulting in suppression of trions and improved neutral exciton recombination. The result is a 6- to 8-fold increase in PL emission. The laser treatment in this work does not cause any measurable damage to the sample as verified by Raman spectroscopy, which is important for practical applications. Surprisingly, the observed PL enhancement is reversible by both vacuum and ultrafast femtosecond excitation. While the former approach allows switching a designed micropattern on the sample ON and OFF, the latter provides a controllable mean for accurate PL tuning, which is highly desirable for optoelectronic and gas sensing applications.

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.

Recording interfacial currents on the subnanometer length and femtosecond time scale by terahertz emission.

Electron dynamics at interfaces is a subject of great scientific interest and technological importance. Detailed understanding of such dynamics requires access to the angstrom length scale defining interfaces and the femtosecond time scale characterizing interfacial motion of electrons. In this context, the most precise and general way to remotely measure charge dynamics is through the transient current flow and the associated electromagnetic radiation. Here, we present quantitative measurements of interfacial currents on the subnanometer length and femtosecond time scale by recording the emitted terahertz radiation following ultrafast laser excitation. We apply this method to interlayer charge transfer in heterostructures of two transition metal dichalcogenide monolayers less than 0.7 nm apart. We find that charge relaxation and separation occur in less than 100 fs. This approach allows us to unambiguously determine the direction of current flow, to demonstrate a charge transfer efficiency of order unity, and to characterize saturation effects.

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.

Friction and work function oscillatory behavior for an even and odd number of layers in polycrystalline MoS2.

A large effort is underway to investigate the properties of two-dimensional (2D) materials for their potential to become building blocks in a variety of integrated nanodevices. In particular, the ability to understand the relationship between friction, adhesion, electric charges and defects in 2D materials is of key importance for their assembly and use in nano-electro-mechanical and energy harvesting systems. Here, we report on a new oscillatory behavior of nanoscopic friction in continuous polycrystalline MoS2 films for an odd and even number of atomic layers, where odd layers show higher friction and lower work function. Friction force microscopy combined with Kelvin probe force microscopy and X-ray photoelectron spectroscopy demonstrates that an enhanced adsorption of charges and OH molecules is at the origin of the observed increase in friction for 1 and 3 polycrystalline MoS2 layers. In polycrystalline films with an odd number of layers, each crystalline nano-grain carries a dipole due to the MoS2 piezoelectricity, therefore charged molecules adsorb at the grain boundaries all over the surface of the continuous MoS2 film. Their displacement during the sliding of a nano-size tip gives rise to the observed enhanced dissipation and larger nanoscale friction for odd layer-numbers. Similarly, charged adsorbed molecules are responsible for the work function decrease in odd layer-number.

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.

Enhancing Multifunctionalities of Transition-Metal Dichalcogenide Monolayers via Cation Intercalation.

We have demonstrated that multiple functionalities of transition-metal dichalcogenide (TMDC) monolayers may be substantially improved by the intercalation of small cations (H+ or Li+) between the monolayers and underlying substrates. The functionalities include photoluminescence (PL) efficiency and catalytic activity. The improvement in PL efficiency may be up to orders of magnitude and can be mainly ascribed to two effects of the intercalated cations: p-doping to the monolayers and reducing the influence of substrates, but more studies are necessary to better understand the mechanism for the improvement in the catalytic functionality. The cation intercalation may be achieved by simply immersing substrate-supported monolayers into the solution of certain acids or salts. It is more difficult to intercalate under the monolayers interacting with substrates stronger, such as as-grown monolayers or the monolayers on 2D material substrates. This result presents a versatile strategy to simultaneously optimize multiple functionalities of TMDC monolayers.

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.

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.

Van der Waals Force Isolation of Monolayer MoS2.

Monolayer MoS2 can effectively screen the vdW interaction of underlying substrates with external systems by >90% because of the substantial increase in the separation between the substrate and external systems due to the presence of the monolayer. This substantial screening of vdW interactions by MoS2 monolayer is different from what reported at graphene.