Ultrathin quantum light source with van der Waals NbOCl2 crystal.

Interlayer electronic coupling in two-dimensional materials enables tunable and emergent properties by stacking engineering. However, it also results in significant evolution of electronic structures and attenuation of excitonic effects in two-dimensional semiconductors as exemplified by quickly degrading excitonic photoluminescence and optical nonlinearities in transition metal dichalcogenides when monolayers are stacked into van der Waals structures. Here we report a van der Waals crystal, niobium oxide dichloride (NbOCl2), featuring vanishing interlayer electronic coupling and monolayer-like excitonic behaviour in the bulk form, along with a scalable second-harmonic generation intensity of up to three orders higher than that in monolayer WS2. Notably, the strong second-order nonlinearity enables correlated parametric photon pair generation, through a spontaneous parametric down-conversion (SPDC) process, in flakes as thin as about 46 nm. To our knowledge, this is the first SPDC source unambiguously demonstrated in two-dimensional layered materials, and the thinnest SPDC source ever reported. Our work opens an avenue towards developing van der Waals material-based ultracompact on-chip SPDC sources as well as high-performance photon modulators in both classical and quantum optical technologies1-4.

Optical Gain Spectrum and Confinement Factor of a Monolayer Semiconductor in an Ultrahigh-Quality Cavity.

Two-dimensional (2D) semiconductors have attracted great attention as a novel class of gain materials for low-threshold, on-chip coherent light sources. Despite several experimental reports on lasing, the underlying gain mechanism of 2D materials remains elusive due to a lack of key information, including modal gain and the confinement factor. Here, we demonstrate a novel approach to directly determine the absorption coefficient of monolayer WS2 by characterizing the whispering gallery modes in a van der Waals microdisk cavity. By exploiting the cavity's high intrinsic quality factor of 2.5 × 104, the absorption coefficient spectrum and confinement factor are experimentally resolved with unprecedented accuracy. The excitonic gain reduces the WS2 absorption coefficient by 2 × 104 cm-1 at room temperature, and the experimental confinement factor is found to agree with the theoretical prediction. These results are essential for unveiling the gain mechanism in emergent, low-threshold 2D-semiconductor-based laser devices.

Gate-Tunable Bound Exciton Manifolds in Monolayer MoSe2.

Two-dimensional (2D) semiconductors with point defects are predicted to host a variety of bound exciton complexes analogous to trions and biexcitons due to strong many-body effects. However, despite the common observation of defect-mediated subgap emission, the existence of such complexes remains elusive. Here, we report the observation of bound exciton (BX) complex manifolds in monolayer MoSe2 with intentionally created monoselenium vacancies (VSe) using proton beam irradiation. The emission intensity of different BX peaks is found to exhibit contrasting dependence on electrostatic doping near the onset of free electron injection. The observed trend is consistent with the model in which free excitons exist in equilibrium with excitons bound to neutral and charged VSe defects, which act as deep acceptors. These complexes are more strongly bound than trions and biexcitons, surviving up to around 180 K, and exhibit moderate valley polarization memory, indicating partial free exciton character.

Impurity-Induced Emission in Re-Doped WS2 Monolayers.

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.

Harnessing Exciton-Exciton Annihilation in Two-Dimensional Semiconductors.

Strong many-body interactions in two-dimensional (2D) semiconductors give rise to efficient exciton-exciton annihilation (EEA). This process is expected to result in the generation of unbound high energy carriers. Here, we report an unconventional photoresponse of van der Waals heterostructure devices resulting from efficient EEA. Our heterostructures, which consist of monolayer transition metal dichalcogenide (TMD), hexagonal boron nitride (hBN), and few-layer graphene, exhibit photocurrent when photoexcited carriers possess sufficient energy to overcome the high energy barrier of hBN. Interestingly, we find that the device exhibits moderate photocurrent quantum efficiency even when the semiconducting TMD layer is excited at its ground exciton resonance despite the high exciton binding energy and large transport barrier. Using ab initio calculations, we show that EEA yields highly energetic electrons and holes with unevenly distributed energies depending on the scattering condition. Our findings highlight the dominant role of EEA in determining the photoresponse of 2D semiconductor optoelectronic devices.

Synergistic additive-mediated CVD growth and chemical modification of 2D materials.

Research on 2D materials has recently become one of the hottest topics that has attracted broad interdisciplinary attention. 2D materials offer fascinating platforms for fundamental science and technological explorations at the nanometer scale and molecular level, and exhibit diverse potential applications for future advanced nano-photonics and electronics. The chemical vapor deposition (CVD) technique has shown great promise for producing high-quality 2D materials with superior electro-optical performance. However, it is difficult to synthesize continuous single-crystal 2D materials with large domain sizes and good uniformity due to the low vapor pressure of their precursors. It has been observed that the addition of selected synergistic additives to the CVD process under mild conditions can result in uniformly large-area and highly crystalline monolayer 2D materials with exceptional optical/electrical properties. Moreover, the 2D material-based devices chemically modified by synergistic additives can achieve superior performances compared to those previously reported. In this review, we compare several typical synergistic additive-mediated CVD growth processes of 2D materials, as well as their superior properties, and provide some perspectives and challenges for the future of this emerging research field.

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.

Polarity Tunable Trionic Electroluminescence in Monolayer WSe2.

Monolayer WSe2 exhibits luminescence arising from various types of exciton complexes due to strong many-body effects. Here, we demonstrate selective electrical excitation of positive and negative trions in van der Waals metal-insulator-semiconductor (MIS) heterostructure consisting of few-layer graphene (FLG), hexagonal boron nitride (hBN), and monolayer WSe2. Intentional unbalanced injection of electrons and holes is achieved via field-emission tunneling and electrostatic accumulation. The device exhibits planar electroluminescence from either positive trion X+ or negative trion X- depending on the bias conditions. We show that hBN serves as a tunneling barrier material allowing selective injection of electron or holes into WSe2 from FLG layer. Our observation offers prospects for hot carrier injection, trion manipulation, and on-chip excitonic devices based on two-dimensional semiconductors.

High-Energy Gain Upconversion in Monolayer Tungsten Disulfide Photodetectors.

Photodetectors usually operate in the wavelength range with photon energy above the bandgap of channel semiconductors so that incident photons can excite electrons from valence band to conduction band to generate photocurrent. Here, however, we show that monolayer WS2 photodetectors can detect photons with energy even lying 219 meV below the bandgap of WS2 at room temperature. With the increase of excitation wavelength from 620 to 680 nm, photoresponsivity varies from 551 to 59 mA/W. This anomalous phenomenon is ascribed to energy upconversion, which is a combination effect of one-photon excitation and multiphonon absorption through an intermediate state created most likely by sulfur divacancy with oxygen adsorption. These findings will arouse research interests on other upconversion optoelectronic devices, photovoltaic devices, for example, of monolayer transition metal dichalcogenides (TMDCs).

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.

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.

Photoluminescence Upconversion by Defects in Hexagonal Boron Nitride.

Hexagonal boron nitride (h-BN) was recently reported to display single photon emission from ultraviolet to near-infrared range due to the existence of defects. Single photon emission has potential applications in quantum information processing and optoelectronics. These findings trigger increasing research interests in h-BN defects, such as revealing the nature of the defects. Here, we report another intriguing defect property in h-BN, namely photoluminescence (PL) upconversion (anti-Stokes process). The energy gain by the PL upconversion is about 162 meV. The anomalous PL upconversion is attributed to optical phonon absorption in the one-photon excitation process, based on excitation power, excitation wavelength, and temperature-dependence investigations. Possible constitutions of the defects are discussed from the results of scanning transmission electron microscopy (STEM) studies and theoretical calculations. These findings show that defects in h-BN exhibit strong defect-phonon coupling. The results from STEM and theoretical calculations are beneficial for understanding the constitution of the h-BN defects.

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.

Chemical Stabilization of 1T' Phase Transition Metal Dichalcogenides with Giant Optical Kerr Nonlinearity.

The 2H-to-1T' phase transition in transition metal dichalcogenides (TMDs) has been exploited to phase-engineer TMDs for applications in which the metallicity of the 1T' phase is beneficial. However, phase-engineered 1T'-TMDs are metastable; thus, stabilization of the 1T' phase remains an important challenge to overcome before its properties can be exploited. Herein, we performed a systematic study of the 2H-to-1T' phase evolution by lithiation in ultrahigh vacuum. We discovered that by hydrogenating the intercalated Li to form lithium hydride (LiH), unprecedented long-term (>3 months) air stability of the 1T' phase can be achieved. Most importantly, this passivation method has wide applicability for other alkali metals and TMDs. Density functional theory calculations reveal that LiH is a good electron donor and stabilizes the 1T' phase against 2H conversion, aided by the formation of a greatly enhanced interlayer dipole-dipole interaction. Nonlinear optical studies reveal that air-stable 1T'-TMDs exhibit much stronger optical Kerr nonlinearity and higher optical transparency than the 2H phase, which is promising for nonlinear photonic applications.

Ultrafast charge transfer dynamics pathways in two-dimensional MoS2-graphene heterostructures: a core-hole clock approach.

Two-dimensional van der Waals heterostructures are attractive candidates for optoelectronic nanodevice applications. The charge transport process in these systems has been extensively investigated, however the effect of coupling between specific electronic states on the charge transfer process is not completely established yet. Here, interfacial charge transfer (CT) in the MoS2/graphene/SiO2 heterostructure is investigated from static and dynamic points of view. Static CT in the MoS2-graphene interface was elucidated by an intensity quenching, broadening and a blueshift of the photoluminescence peaks. Atomic and electronic state-specific CT dynamics on a femtosecond timescale are characterized using a core-hole clock approach and using the S1s core-hole lifetime as an internal clock. We demonstrate that the femtosecond electron transfer pathway in the MoS2/SiO2 heterostructure is mainly due to the electronic coupling between S3p-Mo4d states forming the Mo-S covalent bond in the MoS2 layer. For the MoS2/graphene/SiO2 heterostructure, we identify, with the support of density functional calculations, new pathways that arise due to the high density of empty electronic states of the graphene conduction band. The latter makes the transfer process time in the MoS2/graphene/SiO2/Si twice as fast as in the MoS2/SiO2/Si sample. Our results show that ultrafast electron delocalization pathways in van der Waals heterostructures are dependent on the electronic properties of each involved 2D material, creating opportunities to modulate their transport properties.

Evidence for Fast Interlayer Energy Transfer in MoSe2/WS2 Heterostructures.

Strongly bound excitons confined in two-dimensional (2D) semiconductors are dipoles with a perfect in-plane orientation. In a vertical stack of semiconducting 2D crystals, such in-plane excitonic dipoles are expected to efficiently couple across van der Waals gap due to strong interlayer Coulomb interaction and exchange their energy. However, previous studies on heterobilayers of group 6 transition metal dichalcogenides (TMDs) found that the exciton decay dynamics is dominated by interlayer charge transfer (CT) processes. Here, we report an experimental observation of fast interlayer energy transfer (ET) in MoSe2/WS2 heterostructures using photoluminescence excitation (PLE) spectroscopy. The temperature dependence of the transfer rates suggests that the ET is Förster-type involving excitons in the WS2 layer resonantly exciting higher-order excitons in the MoSe2 layer. The estimated ET time of the order of 1 ps is among the fastest compared to those reported for other nanostructure hybrid systems such as carbon nanotube bundles. Efficient ET in these systems offers prospects for optical amplification and energy harvesting through intelligent layer engineering.

Electronic structure and optical signatures of semiconducting transition metal dichalcogenide nanosheets.

CONSPECTUS: Two-dimensional (2D) crystals derived from transition metal dichalcogenides (TMDs) are intriguing materials that offer a unique platform to study fundamental physical phenomena as well as to explore development of novel devices. Semiconducting group 6 TMDs such as MoS2 and WSe2 are known for their large optical absorption coefficient and their potential for high efficiency photovoltaics and photodetectors. Monolayer sheets of these compounds are flexible, stretchable, and soft semiconductors with a direct band gap in contrast to their well-known bulk crystals that are rigid and hard indirect gap semiconductors. Recent intense research has been motivated by the distinct electrical, optical, and mechanical properties of these TMD crystals in the ultimate thickness regime. As a semiconductor with a band gap in the visible to near-IR frequencies, these 2D MX2 materials (M = Mo, W; X = S, Se) exhibit distinct excitonic absorption and emission features. In this Account, we discuss how optical spectroscopy of these materials allows investigation of their electronic properties and the relaxation dynamics of excitons. We first discuss the basic electronic structure of 2D TMDs highlighting the key features of the dispersion relation. With the help of theoretical calculations, we further discuss how photoluminescence energy of direct and indirect excitons provide a guide to understanding the evolution of the electronic structure as a function of the number of layers. We also highlight the behavior of the two competing conduction valleys and their role in the optical processes. Intercalation of group 6 TMDs by alkali metals results in the structural phase transformation with corresponding semiconductor-to-metal transition. Monolayer TMDs obtained by intercalation-assisted exfoliation retains the metastable metallic phase. Mild annealing, however, destabilizes the metastable phase and gradually restores the original semiconducting phase. Interestingly, the semiconducting 2H phase, metallic 1T phase, and a charge-density-wave-like 1T' phase can coexist within a single crystalline monolayer sheet. We further discuss the electronic properties of the restacked films of chemically exfoliated MoS2. Finally, we focus on the strong optical absorption and related exciton relaxation in monolayer and bilayer MX2. Monolayer MX2 absorbs as much as 30% of incident photons in the blue region of the visible light despite being atomically thin. This giant absorption is attributed to nesting of the conduction and valence bands, which leads to diversion of optical conductivity. We describe how the relaxation pathway of excitons depends strongly on the excitation energy. Excitation at the band nesting region is of unique significance because it leads to relaxation of electrons and holes with opposite momentum and spontaneous formation of indirect excitons.

Effect of oxygen and ozone on p-type doping of ultra-thin WSe2 and MoSe2 field effect transistors.

We report on the p-type doping effect of oxygen and ozone molecules on mono- and few-layer WSe2 and MoSe2 field effect transistors. We show that adsorption of oxygen and ozone under ambient conditions results in subtantial doping and corresponding enhancement in the hole conductivity of the devices. Ozone-induced doping is found to be rapid and efficient, saturating within minutes of exposure whereas oxygen-induced doping occurs over a period of days to reach the equivalent level of doping. Our observations reveal that the water adlayer on the material surface plays a crucial role in solubilizing oxygen and ozone and in forming a redox couple with a large chemical potential.

Electronic transport properties of transition metal dichalcogenide field-effect devices: surface and interface effects.

Recent explosion of interest in two-dimensional (2D) materials research has led to extensive exploration of physical and chemical phenomena unique to this new class of materials and their technological potential. Atomically thin layers of group 6 transition metal dichalcogenides (TMDs) such as MoS2 and WSe2 are remarkably stable semiconductors that allow highly efficient electrostatic control due to their 2D nature. Field effect transistors (FETs) based on 2D TMDs are basic building blocks for novel electronic and chemical sensing applications. Here, we review the state-of-the-art of TMD-based FETs and summarize the current understanding of interface and surface effects that play a major role in these systems. We discuss how controlled doping is key to tailoring the electrical response of these materials and realizing high performance devices. The first part of this review focuses on some fundamental features of gate-modulated charge transport in 2D TMDs. We critically evaluate the role of surfaces and interfaces based on the data reported in the literature and explain the observed discrepancies between the experimental and theoretical values of carrier mobility. The second part introduces various non-covalent strategies for achieving desired doping in these systems. Gas sensors based on charge transfer doping and electrostatic stabilization are introduced to highlight progress in this direction. We conclude the review with an outlook on the realization of tailored TMD-based field-effect devices through surface and interface chemistry.

Van der Waals force: a dominant factor for reactivity of graphene.

Reactivity control of graphene is an important issue because chemical functionalization can modulate graphene's unique mechanical, optical, and electronic properties. Using systematic optical studies, we demonstrate that van der Waals interaction is the dominant factor for the chemical reactivity of graphene on two-dimensional (2D) heterostructures. A significant enhancement in the chemical stability of graphene is achieved by replacing the common SiO2 substrate with 2D crystals such as an additional graphene layer, WS2, MoS2, or h-BN. Our theoretical and experimental results show that its origin is a strong van der Waals interaction between the graphene layer and the 2D substrate. This results in a high resistive force on graphene toward geometric lattice deformation. We also demonstrate that the chemical reactivity of graphene can be controlled by the relative lattice orientation with respect to the substrates and thus can be used for a wide range of applications including hydrogen storage.