Exciton Polarization and Renormalization Effect for Optical Modulation in Monolayer Semiconductors.

The ideal quantum confinement structure of monolayer semiconductors offers prominent optical modulation capabilities that are mediated by enhanced many-body interactions. Herein, we establish an electrolyte-gating method for tuning the luminescence properties that are in transition metal dichalcogenide (TMDC) monolayers. We fabricate electric double-layer capacitors on TMDC/graphite heterostructures to investigate electric-field- and carrier-density-dependent photoluminescence. The exciton peak energy initially shows a slight quadratic red shift of ∼1 meV without carrier accumulations, which is caused by the quantum-confined Stark effect. In contrast, the exciton resonance exhibits a larger red shift up to 10 meV with the accumulated carrier density above 1013 cm-2. These results indicate that the optical transitions can be largely modulated by the carrier density control in S- and Se-based TMDCs, as triggered by the doping-induced band gap renormalization effect. To further inspire this modulation capability, we also apply our method to electrolyte-based TMDC light-emitting devices. Biasing solely in electrolyte-induced p-i-n junctions yields pronounced red shifts up to 40 meV for exciton and trion electroluminescence. Consequently, our approach reveals that the doping effects in the high-carrier-density regimes are potentially significant for efficient optical modulation in monolayer semiconductors.

Modulating Charge Density Wave Order in a 1T-TaS2/Black Phosphorus Heterostructure.

Controllability of collective electron states has been a long-sought scientific and technological goal and promises development of new devices. Herein, we investigate the tuning of charge density wave (CDW) in 1T-TaS2 via a two-dimensional (2D) van der Waals heterostructure of 1T-TaS2/BP. Unusual gate-dependent conductance oscillations were observed in 1T-TaS2 nanoflake supported on BP in transport measurements. Scanning tunneling microscopy study shows that the nearly commensurate (NC) CDW phase survived to 4.5 K in this system, which is substantially lower than the NC to commensurate CDW phase transition temperature of 180 K. A Coulomb blockade model was invoked to explain the conductance oscillations, where the domain walls and domains in NC phase serve as series of quantum dot arrays and tunnelling barriers, respectively. Density functional theory calculations show that a range of interfacial interactions, including strain and charge transfer, influences the CDW stabilities. Our work sheds light on tuning CDW orders via 2D heterostructure stacking and provides new insights on the CDW phase transition and sliding mechanism.

Crested two-dimensional transistors.

Two-dimensional transition metal dichalcogenide (TMD) materials, albeit promising candidates for applications in electronics and optoelectronics1-3, are still limited by their low electrical mobility under ambient conditions. Efforts to improve device performance through a variety of routes, such as modification of contact metals4 and gate dielectrics5-9 or encapsulation in hexagonal boron nitride10, have yielded limited success at room temperature. Here, we report a large increase in the performance of TMD field-effect transistors operating under ambient conditions, achieved by engineering the substrate's surface morphology. For MoS2 transistors fabricated on crested substrates, we observed an almost two orders of magnitude increase in carrier mobility compared to standard devices, as well as very high saturation currents. The mechanical strain in TMDs has been predicted to boost carrier mobility11, and has been shown to influence the local bandgap12,13 and quantum emission properties14 of TMDs. With comprehensive investigation of different dielectric environments and morphologies, we demonstrate that the substrate's increased corrugation, with its resulting strain field, is the dominant factor driving performance enhancement. This strategy is universally valid for other semiconducting TMD materials, either p-doped or n-doped, opening them up for applications in heterogeneous integrated electronics.

Surface-Limited Superconducting Phase Transition on 1 T-TaS2.

Controlling superconducting phase transition on a two-dimensional (2D) material is of great fundamental and technological interest from the viewpoint of making 2D resistance-free electronic circuits. Here, we demonstrate that a 1 T-to-2 H phase transition can be induced on the topmost monolayer of bulk (<100 nm thick) 1 T-TaS2 by thermal annealing. The monolayer 2 H-TaS2 on bulk 1 T-TaS2 exhibits a superconducting transition temperature ( Tc) of 2.1 K, which is significantly enhanced compared to that of bulk 2 H-TaS2. Scanning tunneling microscopy measurements reveal a 3 × 3 charge density wave (CDW) in the phase-switched monolayer at 4.5 K. The enhanced Tc is explained by the suppressed 3 × 3 CDW and a charge-transfer doping from the 1 T substrate. We further show that the monolayer 2 H-TaS2 could be switched back to 1 T phase by applying a voltage pulse. The observed surface-limited superconducting phase transition offers a convenient way to prepare robust 2D superconductivity on bulk 1 T-TaS2 crystal, thereby bypassing the need to exfoliate monolayer samples.

Molecularly thin two-dimensional hybrid perovskites with tunable optoelectronic properties due to reversible surface relaxation.

Due to their layered structure, two-dimensional Ruddlesden-Popper perovskites (RPPs), composed of multiple organic/inorganic quantum wells, can in principle be exfoliated down to few and single layers. These molecularly thin layers are expected to present unique properties with respect to the bulk counterpart, due to increased lattice deformations caused by interface strain. Here, we have synthesized centimetre-sized, pure-phase single-crystal RPP perovskites (CH3(CH2)3NH3)2(CH3NH3)n-1PbnI3n+1 (n = 1-4) from which single quantum well layers have been exfoliated. We observed a reversible shift in excitonic energies induced by laser annealing on exfoliated layers encapsulated by hexagonal boron nitride. Moreover, a highly efficient photodetector was fabricated using a molecularly thin n = 4 RPP crystal, showing a photogain of 105 and an internal quantum efficiency of ~34%. Our results suggest that, thanks to their dynamic structure, atomically thin perovskites enable an additional degree of control for the bandgap engineering of these materials.

Molecular Beam Epitaxy of Highly Crystalline MoSe2 on Hexagonal Boron Nitride.

Molybdenum diselenide (MoSe2) is a promising two-dimensional material for next-generation electronics and optoelectronics. However, its application has been hindered by a lack of large-scale synthesis. Although chemical vapor deposition (CVD) using laboratory furnaces has been applied to grow two-dimensional (2D) MoSe2 cystals, no continuous film over macroscopically large area has been produced due to the lack of uniform control in these systems. Here, we investigate the molecular beam epitaxy (MBE) of 2D MoSe2 on hexagonal boron nitride (hBN) substrate, where highly crystalline MoSe2 film can be grown with electron mobility ∼15 cm2/(V s). Scanning transmission electron microscopy (STEM) shows that MoSe2 grains grown at an optimum temperature of 500 °C are highly oriented and coalesced to form continuous film with predominantly mirror twin boundaries. Our work suggests that van der Waals epitaxy of 2D materials is tolerant of lattice mismatch but is facilitated by substrates with similar symmetry.

Vapour-liquid-solid growth of monolayer MoS2 nanoribbons.

Chemical vapour deposition of two-dimensional materials typically involves the conversion of vapour precursors to solid products in a vapour-solid-solid mode. Here, we report the vapour-liquid-solid growth of monolayer MoS2, yielding highly crystalline ribbons with a width of few tens to thousands of nanometres. This vapour-liquid-solid growth is triggered by the reaction between MoO3 and NaCl, which results in the formation of molten Na-Mo-O droplets. These droplets mediate the growth of MoS2 ribbons in the 'crawling mode' when saturated with sulfur. The locally well-defined orientations of the ribbons reveal the regular horizontal motion of the droplets during growth. Using atomic-resolution scanning transmission electron microscopy and second harmonic generation microscopy, we show that the ribbons are grown homoepitaxially on monolayer MoS2 with predominantly 2H- or 3R-type stacking. Our findings highlight the prospects for the controlled growth of atomically thin nanostructure arrays for nanoelectronic devices and the development of unique mixed-dimensional structures.

Excitonic Properties of Chemically Synthesized 2D Organic-Inorganic Hybrid Perovskite Nanosheets.

2D organic-inorganic hybrid perovskites (OIHPs) represent a unique class of materials with a natural quantum-well structure and quasi-2D electronic properties. Here, a versatile direct solution-based synthesis of mono- and few-layer OIHP nanosheets and a systematic study of their electronic structure as a function of the number of monolayers by photoluminescence and absorption spectroscopy are reported. The monolayers of various OIHPs are found to exhibit high electronic quality as evidenced by high quantum yield and negligible Stokes shift. It is shown that the ground exciton peak blueshifts by ≈40 meV when the layer thickness reduces from bulk to monolayer. It is also shown that the exciton binding energy remains effectively unchanged for (C6 H5 (CH2 )2 NH3 )2 PbI4 with the number of layers. Similar trends are observed for (C4 H9 NH3 )2 PbI4 in contrast to the previous report. Further, the photoluminescence lifetime is found to decrease with the number of monolayers, indicating the dominant role of surface trap states in nonradiative recombination of the electron-hole pairs.

A non-dispersion strategy for large-scale production of ultra-high concentration graphene slurries in water.

It is difficult to achieve high efficiency production of hydrophobic graphene by liquid phase exfoliation due to its poor dispersibility and the tendency of graphene sheets to undergo π-π stacking. Here, we report a water-phase, non-dispersion exfoliation method to produce highly crystalline graphene flakes, which can be stored in the form of a concentrated slurry (50 mg mL-1) or filter cake for months without the risk of re-stacking. The as-exfoliated graphene slurry can be directly used for 3D printing, as well as fabricating conductive graphene aerogels and graphene-polymer composites, thus avoiding the use of copious quantities of organic solvents and lowering the manufacturing cost. This non-dispersion strategy paves the way for the cost-effective and environmentally friendly production of graphene-based materials.

Quasi-Monolayer Black Phosphorus with High Mobility and Air Stability.

Black phosphorus (BP) exhibits thickness-dependent band gap and high electronic mobility. The chemical intercalation of BP with alkali metal has attracted attention recently due to the generation of universal superconductivity regardless of the type of alkali metals. However, both ultrathin BP, as well as alkali metal-intercalated BP, are highly unstable and corrode rapidly under ambient conditions. This study demonstrates that alkali metal hydride intercalation decouples monolayer to few layers BP from the bulk BP, allowing an optical gap of ≈1.7 eV and an electronic gap of 1.98 eV to be measured by photoluminescence and electron energy loss spectroscopy at the intercalated regions. Raman and transport measurements confirm that chemically intercalated BP exhibits enhanced stability, while maintaining a high hole mobility of up to ≈800 cm2 V-1 s-1 and on/off ratio exceeding 103 . The use of alkali metal hydrides as intercalants should be applicable to a wide range of layered 2D materials and pave the way for generating highly stable, quasi-monolayer 2D materials.

Efficient Carrier-to-Exciton Conversion in Field Emission Tunnel Diodes Based on MIS-Type van der Waals Heterostack.

We report on efficient carrier-to-exciton conversion and planar electroluminescence from tunnel diodes based on a metal-insulator-semiconductor (MIS) van der Waals heterostack consisting of few-layer graphene (FLG), hexagonal boron nitride (hBN), and monolayer tungsten disulfide (WS2). These devices exhibit excitonic electroluminescence with extremely low threshold current density of a few pA·µm-2, which is several orders of magnitude lower compared to the previously reported values for the best planar EL devices. Using a reference dye, we estimate the EL quantum efficiency to be ∼1% at low current density limit, which is of the same order of magnitude as photoluminescence quantum yield at the equivalent excitation rate. Our observations reveal that the efficiency of our devices is not limited by carrier-to-exciton conversion efficiency but by the inherent exciton-to-photon yield of the material. The device characteristics indicate that the light emission is triggered by injection of hot minority carriers (holes) to n-doped WS2 by Fowler-Nordheim tunneling and that hBN serves as an efficient hole-transport and electron-blocking layer. Our findings offer insight into the intelligent design of van der Waals heterostructures and avenues for realizing efficient excitonic devices.

Charge transport in ion-gated mono-, bi-, and trilayer MoS2 field effect transistors.

Charge transport in MoS2 in the low carrier density regime is dominated by trap states and band edge disorder. The intrinsic transport properties of MoS2 emerge in the high density regime where conduction occurs via extended states. Here, we investigate the transport properties of mechanically exfoliated mono-, bi-, and trilayer MoS2 sheets over a wide range of carrier densities realized by a combination of ion gel top gate and SiO2 back gate, which allows us to achieve high charge carrier (>10(13) cm(-2)) densities. We discuss the gating properties of the devices as a function of layer thickness and demonstrate resistivities as low as 1 kΩ for monolayer and 420 Ω for bilayer devices at 10 K. We show that from the capacitive coupling of the two gates, quantum capacitance can be roughly estimated to be on the order of 1 µF/cm(2) for all devices studied. The temperature dependence of the carrier mobility in the high density regime indicates that short-range scatterers limit charge transport at low temperatures.

Transport properties of monolayer MoS2 grown by chemical vapor deposition.

Recent success in the growth of monolayer MoS2 via chemical vapor deposition (CVD) has opened up prospects for the implementation of these materials into thin film electronic and optoelectronic devices. Here, we investigate the electronic transport properties of individual crystallites of high quality CVD-grown monolayer MoS2. The devices show low temperature mobilities up to 500 cm(2) V(-1) s(-1) and a clear signature of metallic conduction at high doping densities. These characteristics are comparable to the electronic properties of the best mechanically exfoliated monolayers in literature, verifying the high electronic quality of the CVD-grown materials. We analyze the different scattering mechanisms and show that the short-range scattering plays a dominant role in the highly conducting regime at low temperatures. Additionally, the influence of optical phonons as a limiting factor is discussed.

Evolution of electronic structure in atomically thin sheets of WS2 and WSe2.

Geometrical confinement effect in exfoliated sheets of layered materials leads to significant evolution of energy dispersion in mono- to few-layer thickness regime. Molybdenum disulfide (MoS(2)) was recently found to exhibit indirect-to-direct gap transition when the thickness is reduced to a single monolayer. Emerging photoluminescence (PL) from monolayer MoS(2) opens up opportunities for a range of novel optoelectronic applications of the material. Here we report differential reflectance and PL spectra of mono- to few-layer WS(2) and WSe(2) that indicate that the band structure of these materials undergoes similar indirect-to-direct gap transition when thinned to a single monolayer. The transition is evidenced by distinctly enhanced PL peak centered at 630 and 750 nm in monolayer WS(2) and WSe(2), respectively. Few-layer flakes are found to exhibit comparatively strong indirect gap emission along with direct gap hot electron emission, suggesting high quality of synthetic crystals prepared by a chemical vapor transport method. Fine absorption and emission features and their thickness dependence suggest a strong effect of Se p-orbitals on the d electron band structure as well as interlayer coupling in WSe(2).