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In this study, we use differential phase contrast images obtained by scanning transmission electron microscopy combined with computer simulations to map the atomic electrostatic fields of MoS2 monolayers and investigate the effect of sulfur monovacancies and divancancies on the atomic electric field and total charge distribution. A significant redistribution of the electric field in the regions containing defects is observed, with a progressive decrease in the strength of the projected electric field for each sulfur atom removed from its position. The electric field strength at the sulfur monovacancy sites is reduced by approximately 50% and nearly vanishes at the divacancy sites, where it drops to around 15% of the original value, demonstrating the tendency of these defects to attract positively charged ions or particles. In addition, the absence of the sulfur atoms leads to an inversion in the polarity of the total charge distribution in these regions. more...

Nonvanishing Berry curvature dipole (BCD) and persistent spin texture (PST) are intriguing physical manifestations of electronic states in noncentrosymmetric 2D materials. The former induces a nonlinear Hall conductivity while the latter offers a coherent spin current. Based on density-functional-theory (DFT) calculations, we demonstrate the coexistence of both phenomena in a Bi(110) monolayer with a distorted phosphorene structure. Both effects are concurrently enhanced due to the strong spin-orbit coupling of Bi while the structural distortion creates internal in-plane ferroelectricity with inversion asymmetry. We further succeed in fabricating a Bi(110) monolayer in the desired phosphorene structure on the NbSe2 substrate. Detailed atomic and electronic structures of the Bi(110)/NbSe2 heterostructure are characterized by scanning tunneling microscopy/spectroscopy and angle-resolved-photoemission spectroscopy. These results are consistent with DFT calculations which indicate the large BCD and PST are retained. Our results suggest the Bi(110)/NbSe2 heterostructure as a promising platform to exploit nonlinear Hall and coherent spin transport properties together. more...

The van der Waals (vdW) heterostructures have rich functions and intriguing physical properties, which has attracted wide attention. Effective control of excitons in vdW heterostructures is still urgent for fundamental research and realistic applications. Here, we successfully achieved quantitative tuning of the intralayer exciton of monolayers and observed the transition from intralayer excitons to interlayer excitons in WS2/MoSe2 heterostructures, via hydrostatic pressure. The energy of interlayer excitons is in a "locked" or "superstable" state, which is not sensitive to pressure. The first-principles calculation reveals the stronger interlayer interaction which leads to enhanced interlayer exciton behavior in WS2/MoSe2 heterostructures under external pressure and reveals the robust peak of interlayer excitons. This work provides an effective strategy to study the interlayer interaction in vdW heterostructures and reveals the enhanced interlayer excitons in WS2/MoSe2, which could be of great importance for the material and device design in various similar quantum systems. more...

A unique feature of two-dimensional (2D) materials is the ultralow friction at their van der Waals interfaces. A key question in a new generation of 2D heterostructure-based nanoelectromechanical systems (NEMS) is how the low friction interfaces will affect the dynamic performance. Here, we apply the exquisite sensitivity of graphene nanoelectromechanical drumhead resonators to compare the dissipation from monolayer, Bernal-stacked bilayer, and twisted bilayer graphene membranes. We find a significant difference in the average quality factors of three resonator types: 53 for monolayer, 40 for twisted and 31 for Bernal-stacked membranes. We model this difference as a combination of change in stiffness and additional dissipation from interlayer friction during motion. We find even the lowest frictions measured on sliding 2D interfaces are sufficient to alter dissipation in 2D NEMS. This model provides a generalized approach to quantify dissipation in NEMS based on 2D heterostructures which incorporate interlayer slip and friction. more...

Vertically stacked transition metal dichalcogenide-graphene heterostructures provide a platform for novel optoelectronic applications with high photoresponse speeds. Photoinduced nonequilibrium carrier and lattice dynamics in such heterostructures underlie these applications but have not been understood. In particular, the dependence of these photoresponses on the twist angle, a key tuning parameter, remains elusive. Here, using ultrafast electron diffraction, we report the simultaneous visualization of charge transfer and electron-phonon coupling in MoS2-graphene heterostructures with different stacking configurations. We find that the charge transfer timescale from MoS2 to graphene varies strongly with twist angle, becoming faster for smaller twist angles, and show that the relaxation timescale is significantly shorter in a heterostructure as compared to a monolayer. These findings illustrate that twist angle constitutes an additional tuning knob for interlayer charge transfer in heterobilayers and deepen our understanding of fundamental photophysical processes in heterostructures, of importance for future applications in optoelectronics and light harvesting. more...

Tuning intermediate adsorption energy by shifting the d-band center offers a powerful strategy to tailor the reactivity of metal catalysts. Here we report a potential sweep method to grow Pd layer-by-layer on Au with the capability to in situ measure the surface structure through an ethanol oxidation reaction. Spectroscopic characterizations reveal charge-transfer induced valence band restructuring in the Pd overlayer, which shifts the d-band center away from the Fermi level compared to bulk Pd. Precise overlayer control gives the optimal bimetallic surface of two monolayers (ML) Pd on Au, which exhibits more than 370-fold mass activity enhancement in oxygen reduction reaction (at 0.9 V vs. reversible hydrogen electrode) and 40 mV increase in half-wave potential compared to the Pt/C. Tested in a homemade Zn-air battery, the 2-ML-Pd/Au/C exhibits a maximum power density of 296 mW/cm2 and specific activity of 804 mAh/gZn, much higher than Pt/C with the same catalyst loading amount. Agency for Science, Technology and Research (A*STAR) Ministry of Education (MOE) This work was supported by the fund from the Singapore Ministry of Education Academic Research Fund (AcRF) Tier 1: RG4/20 and Tier 2: MOET2EP10120-0002, and Agency for Science, Technology, and Research (A*Star IRG: A20E5c0080). more...

Two-dimensional monolayer structures of transition metal dichalogenides (TMDs) have been shown to allow many higher-order excitonic bound states, including trions (charged excitons), biexcitons (excitonic molecules), and charged biexcitons. We report here experimental evidence and the theoretical basis for a new bound excitonic complex, consisting two free carriers bound to an exciton in a bilayer structure. Our experimental measurements on structures made using two different materials show a new spectral line at the predicted energy with two different TMD materials (MoSe2 and WSe2) with both n- and p-doping if and only if all the required theoretical conditions for this complex are fulfilled, in particular, only in the presence of a parallel metal layer that significantly screens the repulsive interaction between the like-charge carriers. Because these four-carrier bound states are charged bosons, they could eventually be the basis for a new path to superconductivity without Cooper pairing. more...

In healthy eyes, the tear film lipid layer (TFLL) is considered to act as an evaporation resistant barrier, which prevents eyes from drying. Seeking to understand the mechanisms behind the evaporation resistance of the TFLL, we studied mixtures of lipid layer wax esters and O-acyl-omega-hydroxy fatty acids. Analyzing their self-assembly and biophysical properties led to new discoveries concerning the structure and function of the TFLL. We discovered how these lipids self-assemble at the air-water interface and form an efficient antievaporative barrier, demonstrating for the first time how the interaction of different tear film lipid species can improve the evaporation resistance compared with individual lipid classes on their own. These results provide a potential mechanism for the evaporation resistance of the lipid layer. In addition, the results serve as a base for the future development of improved dry eye treatments and other applications where the evaporation of water represents a significant challenge. more...

Monolayer transition metal dichalcogenides have intrinsic spin-valley degrees of freedom, drawing broad interests due to their potential applications in information storage and processing. Here, we demonstrate the possibility of using cylindrical vector pumped beams, which are nonseparable in their polarization and spatial modes, to manipulate nonlinear valley-locked twisted-vortex emissions in monolayer tungsten disulfide (WS2). The second-harmonic (SH) photons from K and K' valleys are encoded with opposite optical vortices, thus allowing the SH beams to emerge as cylindrical vector beams with doubled topological orders compared to the fundamental beams. The conically refracted pumped beams allow us to generate the first-order SH cylindrical vector and full Poincare beams via tuning the valley-locked emitted light field profiles. With fanshaped WS2 films breaking the axial symmetry of SH beams, the SH valley photons are routed to opposite directions. Our results pave the way to develop atomically thin nonlinear photonic devices and valleytronic nanodevices. more...

Ionic liquid gating has proved to be effective in inducing emergent quantum phenomena such as superconductivity, ferromagnetism, and topological states. The electrostatic doping at two-dimensional interfaces relies on ionic motion, which thus is operated at sufficiently high temperature. Here, we report the in situ tuning of quantum phases by shining light on an ionic liquid-gated interface at cryogenic temperatures. The light illumination enables flexible switching of the quantum transition in monolayer WS2 from an insulator to a superconductor. In contrast to the prevailing picture of photoinduced carriers, we find that in the presence of a strong interfacial electric field conducting electrons could escape from the surface confinement by absorbing photons, mimicking the field emission. Such an optical tuning tool in conjunction with ionic liquid gating greatly facilitates continuous modulation of carrier densities and hence electronic phases, which would help to unveil novel quantum phenomena and device functionality in various materials. more...

As an intrinsically layered material, FeSe has been extensively explored for potentially revealing the underlying mechanisms of high transition temperature (high-Tc) superconductivity and realizing topological superconductivity and Majorana zero modes. Here we use first-principles approaches to identify that the cobalt pnictides of CoX (X = As, Sb, Bi), none of which is a layered material in bulk form. Nevertheless, all can be stabilized as monolayered systems either in freestanding form or supported on the SrTiO3(001) substrate. We further show that each of the cobalt pnictides may potentially harbor high-Tc superconductivity beyond the Cu- and Fe-based superconducting families, and the underlying mechanism is inherently tied to their isovalency nature with the FeSe monolayer. Most strikingly, each of the monolayered CoX's on SrTiO3 is shown to be topologically nontrivial, and our findings provide promising new platforms for realizing topological superconductors in the two-dimensional limit. more...

The electronic structure and dynamics of 2D transition metal dichalcogenide (TMD) monolayers provide important underpinnings both for understanding the many-body physics of electronic quasi-particles and for applications in advanced optoelectronic devices. However, extensive experimental investigations of semiconducting monolayer TMDs have yielded inconsistent results for a key parameter, the quasi-particle band gap (QBG), even for measurements carried out on the same layer and substrate combination. Here, we employ sensitive time- and angle-resolved photoelectron spectroscopy (trARPES) for a high-quality large-area MoS2 monolayer to capture its momentum-resolved equilibrium and excited-state electronic structure in the weak-excitation limit. For monolayer MoS2 on graphite, we obtain QBG values of ≈2.10 eV at 80 K and of ≈2.03 eV at 300 K, results well-corroborated by the scanning tunneling spectroscopy (STS) measurements on the same material. more...

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. more...

Polarity often refers to the charge carrier type of a semiconductor or the charging state of a functional group, generally dominating their functionality and performance. Herein we uncover a spontaneous and stochastic polarity-flipping phenomenon in monolayer WSe2, which randomly switches between the n-type and p-type states and is essentially triggered by fluctuating carrier flows from or to the adjacent WS2 monolayer. We have traced such fluctuating carrier flows by interfacial photocurrent measurements in a zero-bias two-terminal device. Such polarity flipping results in switching between the negative and positive correlations between the emission intensities of WS2 and WSe2 in the heterobilayer, which is further well-controlled by the electrostatic gate-tuning experiments in a capacitor-structure device. Our work not only demonstrates giant and intermittent carrier flows through long-range coupling in 2D heterostructures and a consequent spontaneous polarity flipping phenomenon but also provides a two-emitter system with a switchable correlation sign that could project future applications in optical logic devices. more...

The Mott state in 1T-TaS2 is predicted to host quantum spin liquids (QSLs). However, its insulating mechanism is controversial due to complications from interlayer coupling. Here, we study the charge transfer state in monolayer 1T-NbSe2, an electronic analogue to TaS2 exempt from interlayer coupling, using spectroscopic imaging scanning tunneling microscopy and first-principles calculations. Monolayer NbSe2 surprisingly displays two types of star of David (SD) motifs with different charge transfer gap sizes, which are interconvertible via temperature variation. In addition, bilayer 1T-NbSe2 shows a Mott collapse by interlayer coupling. Our calculation unveils that the two types of SDs possess distinct structural distortions, altering the effective Coulomb energies of the central Nb orbital. Our calculation suggests that the charge transfer gap, the same parameter for determining the QSL regime, is tunable with strain. This finding offers a general strategy for manipulating the charge transfer state in related systems, which may be tuned into the potential QSL regime. more...

Monolayer transition metal dichalcogenides (ML-TMDCs) are a versatile platform to explore the transport dynamics of the tightly bound excitonic states. The diffusion of neutral excitons in various ML-TMDCs has been observed. However, the transport of charged excitons (trions), which can be driven by an in-plane electric field and facilitate the formation of an excitonic current, has yet been well investigated. Here, we report the direct observation of diffusion and drift of the trions in ML-WS2 through spatially and time-resolved photoluminescence. An effective diffusion coefficient of 0.47 cm2/s was extracted from the broadening of spatial profiles of the trion emission. When an in-plane electric field is applied, the spatial shift of the trion emission profiles indicated a drift velocity of 7400 cm/s. Both the diffusion caused broadening and the drift caused shift of the emission profiles saturate because of the Coulomb interactions between trions and the background charges. more...

Grain boundaries (GBs) are vital to crystal materials and their applications. Although GBs in bulk and two-dimensional materials have been extensively studied, the segmented GBs observed in transition metal dichalcogenide monolayers by a sequence of folded segments remain a mystery. We visualize the large-area distribution of the segmented GBs in MoSe2 monolayers and unravel their structural origin using ab initio calculations combined with high-resolution atomic characterizations. Unlike normal GBs in two-dimensional materials with commonly one type of dislocation cores, the segmented GBs consist of two basic elements-4|8 and 4|4|8 cores, whose alloying results in structural diversity and distinctly high stability due to relieved stress fields nearby. The defective polygons can uniquely migrate along the segmented GBs via the movement of single molybdenum atoms, unobtrusively endowing a given GB with variable appearances. Furthermore, the segmented GBs can achieve useful functionalities such as intrinsic magnetism and highly active electrocatalysis. Agency for Science, Technology and Research (A*STAR) Ministry of Education (MOE) National Research Foundation (NRF) This work was supported by the National Key Research and Development Program of China (2019YFA0705400), the National Natural Science Foundation of China (11772153, 22073048, 51802153), the Natural Science Foundation of Jiangsu Province (BK20190018), the Research Fund of State Key Laboratory of Mechanics and Control of Mechanical Structures (MCMS-I-0419K01, MCMS-E-0420K01), the Fundamental Research Funds for the Central Universities (NJ2020003, NZ2020001), and a Project by the Priority Academic Program Development of Jiangsu Higher Education Institutions. It was also supported by the National Research Foundation Singapore program (NRF-CRP21-2018-0007, NRF-CRP22-2019-0007), the Singapore Ministry of Education via AcRF Tier 3 Program 'Geometrical Quantum Materials' (MOE2018-T3-1-002), AcRF Tier 2 (MOE2016-T2-1-131), and AcRF Tier 1 RG4/17 and RG7/18. This research was also supported by A*STAR under its AME IRG Grant (19283074). more...

Impurity doping is a viable route toward achieving desired subgap optical response in semiconductors. In strongly excitonic two-dimensional (2D) semiconductors such as transition metal dichalcogenides (TMDs), impurities are expected to result in bound-exciton emission. However, doped TMDs often exhibit a broad Stokes-shifted emission without characteristic features, hampering strategic materials engineering. Here we report observation of a well-defined impurity-induced emission in monolayer WS2 substitutionally doped with rhenium (Re), which is an electron donor. The emission exhibits characteristics of localized states and dominates the spectrum up to 200 K. Gate dependence reveals that neutral impurity centers are responsible for the observed emission. Using GW-Bethe-Salpeter equation (GW-BSE) calculations, we attribute the emission to transitions between spin-split upper Re band and valence band edge. more...

Room-temperature photoluminescence enhancement of molybdenum disulfide (MoS2) monolayers on epitaxial titanium nitride (TiN) thin films grown by molecular-beam-epitaxy as well as magnetron-sputtered TiN films is observed by a confocal laser scanning microscope with excitation wavelengths covering the transition of TiN's macroscopic optical properties from dielectric to plasmonic. The photoluminescence enhancement increases as TiN becomes more metallic, and strong enhancement is obtained at the excitation wavelengths equal to or longer than the epsilon-near-zero (ENZ) wavelength of TiN films. A good agreement is observed between measured and calculated enhancements. The enhancement is attributed to the increased excitation field in MoS2 at TiN's ENZ wavelength and interference effects for thick spacers that separate the MoS2 flakes from TiN films in the metallic regime. This study enriches the fundamental understanding of emission properties on ENZ substrates that could be important for the development of advanced nanoscale lasers/light sources, optical/biosensors, and nano-optoelectronic devices. more...

Realizing a state of matter in two dimensions has repeatedly proven a novel route of discovering new physical phenomena. Van der Waals (vdW) materials have been at the center of these now extensive research activities. They offer a natural way of producing a monolayer of matter simply by mechanical exfoliation. This work demonstrates that the possible multiferroic state with coexisting antiferromagnetic and ferroelectric orders possibly persists down to the bilayer flake of NiI$_{2}$. By exploiting the optical second-harmonic generation technique, both magnitude and direction of the ferroelectric order, arising from the cycloidal spin order, are successfully traced. The possible multiferroic state's transition temperature decreases from 58 K for the bulk to about 20 K for the bilayer. Our observation will spur extensive efforts to demonstrate multi-functionality in vdW materials, which have been tried mostly by using heterostructures of singly ferroic ones until now. more...

Moire superlattices (MSLs) formed in van der Waals materials have become a promising platform to realize novel two-dimensional electronic states. Angle-aligned trilayer structures can form two sets of MSLs which could potentially interfere. In this work, we directly image the moire patterns in both monolayer and twisted bilayer graphene aligned on hexagonal boron nitride (hBN), using combined scanning microwave impedance microscopy and conductive atomic force microscopy. Correlation of the two techniques reveals the contrast mechanism for the achieved ultrahigh spatial resolution ( more...

Interlayer excitons in heterobilayers of transition-metal dichalcogenides (TMDCs) have generated enormous interest due to their permanent vertical dipole moments and long lifetimes. However, the effects of mechanical strain on the optoelectronic properties of interlayer excitons in heterobilayers remain relatively uncharacterized. Here, we experimentally demonstrate strain tuning of Γ-K interlayer excitons in molybdenum disulfide and tungsten diselenide (MoS2/WSe2) wrinkled heterobilayers and obtain a deformation potential constant of ∼107 meV/% uniaxial strain, which is approximately twice that of the intralayer excitons in the constituent monolayers. We further observe a nonmonotonic dependence of the interlayer exciton photoluminescence intensity with strain, which we interpret as being due to the sensitivity of the Γ point to band hybridization arising from the competition between in-plane strain and out-of-plane interlayer coupling. Strain engineering with interlayer excitons in TMDC heterobilayers offers higher strain tunability and new degrees of freedom compared to their monolayer counterparts. more...

Few-layer transition metal dichalcogenides (TMDs) exhibit out-of-plane wave function confinement with subband quantization. This phenomenon is totally absent in monolayer crystals and is regarded a... more...

Protected and spin-polarized transport channels are the hallmark of topological insulators, coming along with an intrinsic strong spin-orbit coupling. Here we identified such corresponding chiral states in epitaxially grown zigzag graphene nanoribbons (zz-GNRs), albeit with an extremely weak spin-orbit interaction. While the bulk of the monolayer zz-GNR is fully suspended across a SiC facet, the lower edge merges into the SiC(0001) substrate and reveals a surface state at the Fermi energy, which is extended along the edge and splits in energy toward the bulk. All of the spectroscopic details are precisely described within a tight binding model incorporating a Haldane term and strain effects. The concomitant breaking of time-reversal symmetry without the application of external magnetic fields is supported by ballistic transport revealing a conduction of G = e2/h. more...

Electrical breakdown is a critical problem in electronics. In molecular electronics, it becomes more problematic because ultrathin molecular monolayers have delicate and defective structures and exhibit intrinsically low breakdown voltages, which limit device performances. Here, we show that interstitially mixed self-assembled monolayers (imSAMs) remarkably enhance electrical stability of molecular-scale electronic devices without deteriorating function and reliability. The SAM of the sterically bulky matrix (SC more...

Monolayer transition metal dichalcogenides (TMDs), direct bandgap materials with an atomically thin nature, are promising materials for electronics and photonics, especially at highly scaled lateral dimensions. However, the characteristically low total absorption of photons in the monolayer TMD has become a challenge in the access to and realization of monolayer TMD-based high-performance optoelectronic functionalities and devices. Here, we demonstrate gate-tunable plasmonic phototransistors (photoFETs) that consist of monolayer molybdenum disulfide (MoS2) photoFETs integrated with the two-dimensional plasmonic crystals. The plasmonic photoFET has an ultrahigh photoresponsivity of 2.7 × 104 AW-1, achieving a 7.2-fold enhancement in the photocurrent compared to pristine photoFETs. This benefits predominately from the combination of the enhancement of the photon-absorption-rate via the strongly localized-electromagnetic-field and the gate-tunable plasmon-induced photocarrier-generation-rate in the monolayer MoS2. These results demonstrate a systematic methodology for designing ultrathin plasmon-enhanced photodetectors based on monolayer TMDs for next-generation ultracompact optoelectronic devices in the trans-Moore era. more...

Interfacial segregation is ubiquitous in mulit-component polycrystalline materials and plays a decisive role in material properties. So far, the discovered solute segregation patterns at special high-symmetry interfaces are usually located at the boundary lines or are distributed symmetrically at the boundaries. Here, in a model Mg-Nd-Mn alloy, we confirm that elastic strain minimization facilitated nonsymmetrical segregation of solutes in four types of linear tilt grain boundaries (TGBs) to generate ordered interfacial superstructures. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy observations indicate that the solutes selectively segregate at substitutional sites at the linear TGBs separated by periodic misfit dislocations to form such two-dimensional planar structures. These findings are totally different from the classical McLean-type segregation which has assumed the monolayer or submonolayer coverage of a grain boundary and refresh understanding on strain-driven interface segregation behaviors. more...

Atomically thin semiconductors provide a highly attractive platform for quantum emitters (QEs): They can be combined with arbitrary substrates, can be spatially aligned with photonic structures, and can be electrically driven. All QEs reported to date in these materials have, however, relied on nominally spin-forbidden transitions, with radiative rates falling substantially below those of other solid-state QE systems. Here we employ strain confinement in monolayer MoSe2 to produce engineered QEs, as confirmed in photon antibunching measurements. We discuss spin-allowed versus spin-forbidden transitions based on magneto- and time-resolved photoluminescence measurements. We calculate a radiative rate for spin-allowed quantum emission greater than 1 ns-1, which exceeds reported radiative rates of WSe2 QEs by 2 orders of magnitude. more...

Crystalline two-dimensional (2D) superconductors (SCs) with low carrier density are an exciting new class of materials in which electrostatic gating can tune superconductivity, electronic interactions play a prominent role, and electrical transport properties may directly reflect the topology of the Fermi surface. Here, we report the dramatic enhancement of superconductivity with decreasing thickness in semimetallic Td-MoTe2, with critical temperature (Tc) increasing up to 7.6 K for monolayers, a 60-fold increase with respect to the bulk Tc. We show that monolayers possess a similar electronic structure and density of states (DOS) as the bulk, implying that electronic interactions play a strong role in the enhanced superconductivity. Reflecting the low carrier density, the critical temperature, magnetic field, and current density are all tunable by an applied gate voltage. The response to high in-plane magnetic fields is distinct from that of other 2D SCs and reflects the canted spin texture of the electron pockets. more...

We investigate the origin of emission lines apparent in the low-temperature photoluminescence spectra of $n$-doped WS$_2$ monolayer embedded in hexagonal BN layers using external magnetic fields and first-principles calculations. Apart from the neutral A exciton line, all observed emission lines are related to the negatively charged excitons. Consequently, we identify emissions due to both the bright (singlet and triplet) and dark (spin- and momentum-forbidden) negative trions as well as the phonon replicas of the latter optically-inactive complexes. The semi-dark trions and negative biexcitons are distinguished. Based on their experimentally extracted and theoretically calculated $g$-factors, we identify three distinct families of emissions due to exciton complexes in WS$_2$: bright, intravalley and intervalley dark. The $g$-factors of the spin-split subbands in both the conduction and valence bands are also determined., Manuscript: 7 pages, 5 figures; SI: 5 pages, 3 figures more...

Single-photon emitters, the basic building blocks of quantum communication and information, have been developed using atomically thin transition metal dichalcogenides (TMDCs). Although the bandgap of TMDCs was spatially engineered in artificially created defects for single-photon emitters, it remains a challenge to precisely align the emitter's dipole moment to optical cavities for the Purcell enhancement. Here, we demonstrate position- and polarization-controlled single-photon emitters in monolayer WSe2. A tensile strain of ∼0.2% was applied to monolayer WSe2 by placing it onto a dielectric rod structure with a nanosized gap. Excitons were localized in the nanogap sites, resulting in the generation of linearly polarized single-photon emission with a g(2) of ∼0.1 at 4 K. Additionally, we measured the abrupt change in polarization of single photons with respect to the nanogap size. Our robust spatial and polarization control of emission provides an efficient way to demonstrate deterministic and scalable single-photon sources by integrating with nanocavities. more...

The efficient nondestructive assessment of quality and homogeneity for two-dimensional (2D) MoS2 is critically important to advance their practical applications. Here, we presented a rapid and large-area assessment method for visually evaluating the quality and uniformity of chemical vapor deposition (CVD)-grown MoS2 monolayers simply with conventional optical microscopes. This was achieved through one-pot adsorbing abundant sulfur particles selectively onto as-grown poorer-quality MoS2 monolayers in a CVD system without any additional treatment. We further revealed that this favorable adsorption of sulfur particles on MoS2 originated from their intrinsic higher-density sulfur vacancies. Based on unadsorbed MoS2 monolayers, superior performance field effect transistors with a mobility of ∼49 cm2 V-1 s-1 were constructed. Importantly, the assessment approach was noninvasive due to the all-vapor-phase and moderate adsorption-desorption process. Our work offers a new route for the performance and yield optimization of devices by quality assessment of 2D semiconductors prior to device fabrication. more...

Monolayers of semiconducting transition metal dichalcogenides are a strongly emergent platform for exploring quantum phenomena in condensed matter, building novel opto-electronic devices with enhanced functionalities. Due to their atomic thickness, their excitonic optical response is highly sensitive to their dielectric environment. In this work, we explore the optical properties of monolayer thick MoSe$_2$ straddling domain wall boundaries in periodically poled LiNbO$_3$. Spatially-resolved photoluminescence experiments reveal spatial sorting of charge and photo-generated neutral and charged excitons across the boundary. Our results reveal evidence for extremely large in-plane electric fields of 3000\,kV/cm at the domain wall whose effect is manifested in exciton dissociation and routing of free charges and trions toward oppositely poled domains and a non-intuitive spatial intensity dependence. By modeling our result using drift-diffusion and continuity equations, we obtain excellent qualitative agreement with our observations and have explained the observed spatial luminescence modulation using realistic material parameters., 29 pages, 6 figures, submetted material more...

Monolayer transition metal dichalcogenides, coupled to metal plasmonic nanocavities, have recently emerged as new platforms for strong light-matter interactions. These systems are expected to have nonlinear-optical properties that will enable them to be used as entangled photon sources, compact wave-mixing devices, and other elements for classical and quantum photonic technologies. Here, we report the first experimental investigation of the nonlinear properties of these strongly coupled systems, by observing second harmonic generation from a WSe2 monolayer strongly coupled to a single gold nanorod. The pump-frequency dependence of the second-harmonic signal displays a pronounced splitting that can be explained by a coupled-oscillator model with second-order nonlinearities. Rigorous numerical simulations utilizing a nonperturbative nonlinear hydrodynamic model of conduction electrons support this interpretation and reproduce experimental results. Our study thus lays the groundwork for understanding the nonlinear properties of strongly coupled nanoscale systems. more...

We first observed the spin-to-charge conversion due to both the inverse Rashba-Edelstein effect (IREE) and inverse spin-Hall effect in a holey multilayer molybdenum disulfide (MoS2) intermediate layer in a Pt/YIG structure via LSSE measurements under nonequilibrium magnetization. We found an enhancement of approximately 238%, 307%, and 290% in the longitudinal spin Seebeck effect (LSSE) voltage, spin-to-charge current, and thermoelectric (TE) power factor, respectively, compared with the monolayer MoS2 interlayer in a Pt/YIG structure. Such an enhancement in the LSSE performance of Pt/holey MoS2/YIG can be explained by the improvement of spin accumulation in the Pt layer by induced spin fluctuation as well as increased additional spin-to-charge conversion due to in-plane IREE. Our findings represent a significant achievement in the understanding of spin transport in atomically thin MoS2 interlayers and pave the way toward large-area TE energy-harvesting devices in two-dimensional transition metal dichalcogenide materials. more...

To develop thermoelectric devices, it is of the utmost importance to design organic building blocks to have efficient thermopower. Whereas conjugated and aromatic molecules with intrinsic narrow band gaps are attractive candidates to achieve efficient thermoelectric properties, saturated molecules are usually avoided owing to intrinsically poor thermopower. Here we demonstrate that thermopower of saturated molecules can be enhanced by superexchange coupling. Specifically, thermoelectric properties of large-area junctions that contain self-assembled monolayers of oligo(ethylene glycol) thiolates and alkanethiolates are compared. Through large-area thermopower measurements using a liquid metal top electrode, we show that the superexchange coupling enhances the Seebeck coefficient and counterintuitively leads to an increase in the Seebeck coefficient with increasing the length in a certain conformation. The improved thermoelectric performance is attributed to the superexchange-induced enhanced ability to mediate metal wave function in junctions. Our work offers new insights for improving the thermoelectric performance of nonconjugated, saturated molecules. more...

Here we reported a hierarchical self-assembly approach toward well-defined superlattices in supramolecular liquid crystals by fullerene-based sphere-cone block molecules. The fullerenes crystallize to form monolayer nanosheets intercalated by the attached soft hydrocarbon cones. The frustration caused by cross-sectional area mismatch between the spheres and the somewhat oversize cones leads to a unique lamellar superlattice whereby each stack of six pairs of alternating sphere-cone sublayers is followed by a cone double layer. While such areal mismatch problems in soft matter are usually solved by interface curvature, the lamellar superlattice solution is best suited to systems with rigid layers. Meanwhile, formation of the superlattice significantly improves the material's transient electron conductivity, with the maximum value being among the highest for π-conjugated organic materials. The design principle of solving steric frustration by forming a superlattice opens a new avenue toward self-assembled optoelectronic materials. more...

Ultrathin two-dimensional (2D) monolayer atomic crystal materials offer great potential for extending the field of novel separation technology due to their infinitesimal thickness and mechanical strength. One difficult and ongoing challenge is to perforate the 2D monolayer material with subnanometer pores with atomic precision for sieving similarly sized molecules. Here, we demonstrate the exceptional separation performance of ionic liquid (IL)/graphene hybrid membranes for challenging separation of CO2 and N2. Notably, the ultrathin ILs afford dynamic tuning of the size and chemical affinity of nanopores while preserving the high permeance of the monolayer nanoporous graphene membranes. The hybrid membrane yields a high CO2 permeance of 4000 GPU and an outstanding CO2/N2 selectivity up to 32. This rational hybrid design provides a universal direction for broadening gas separation capability of atomically thin nanoporous membranes. more...

The extreme elastic strain of monolayer transition metal dichalcogenides provides an ideal platform to achieve efficient exciton funneling via local strain modulation; however, studies conducted thus far have focused on the use of substrates with fixed strain profiles. We prepared 1L-WS2 on a flexible substrate such that the formation of topographic wrinkles could be switched on or off, and the depth or the direction of the wrinkle could be modified by external strain, thereby providing full control of the periodic undulation of the band gap profile of 1L-WS2 in the range 0-57 meV. Nanoscale photoluminescence (PL) imaging unambiguously evinced that the photoexcited excitons of 1L-WS2 were accumulated at the top regions of the wrinkles with less band gap than the valley region. Our results of broad tunability of the two-dimensional (2D) exciton funneling suggest a promising route to control exciton drift for enhanced optoelectronic performances and future 2D exciton devices. more...