Monolayer Transition Metal Dichalcogenides Research Articles

Advances in Two-Dimensional Magnetic Semiconductors via Substitutional Doping of Transition Metal Dichalcogenides.

Transition metal dichalcogenides (TMDs) are two-dimensional (2D) materials with remarkable electrical, optical, and chemical properties. One promising strategy to tailor the properties of TMDs is to create alloys through a dopant-induced modification. Dopants can introduce additional states within the bandgap of TMDs, leading to changes in their optical, electronic, and magnetic properties. This paper overviews chemical vapor deposition (CVD) methods to introduce dopants into TMD monolayers, and discusses the advantages, limitations, and their impacts on the structural, electrical, optical, and magnetic properties of substitutionally doped TMDs. The dopants in TMDs modify the density and type of carriers in the material, thereby influencing the optical properties of the materials. The magnetic moment and circular dichroism in magnetic TMDs are also strongly affected by doping, which enhances the magnetic signal in the material. Finally, we highlight the different doping-induced magnetic properties of TMDs, including superexchange-induced ferromagnetism and valley Zeeman shift. Overall, this review paper provides a comprehensive summary of magnetic TMDs synthesized via CVD, which can guide future research on doped TMDs for various applications, such as spintronics, optoelectronics, and magnetic memory devices.

Liquid Phase Edge Epitaxy of Transition-Metal Dichalcogenide Monolayers.

Precise monolayer epitaxy is important for two-dimensional (2D) semiconductors toward future electronics. Here, we report a new self-limited epitaxy approach, liquid phase edge epitaxy (LPEE), for precise-monolayer epitaxy of transition-metal dichalcogenides. In this method, the liquid solution contacts 2D grains only at the edges, which confines the epitaxy only at the grain edges and then precise monolayer epitaxy can be achieved. High-temperature in situ imaging of the epitaxy progress directly supports this edge-contact epitaxy mechanism. Typical transition-metal dichalcogenide monolayers (MX2, M = Mo, W, and Re; X = S or Se) have been obtained by LPEE with a proper choice of molten alkali halide solvents (AL, A = Li, Na, K, and Cs; L = Cl, Br, or I). Furthermore, alloying and magnetic-element doping have also been realized by taking advantage of the liquid phase epitaxy approach. This LPEE method provides a precise and highly versatile approach for 2D monolayer epitaxy and can revolutionize the growth of 2D materials toward electronic applications.

Probing the optical near-field interaction of Mie nanoresonators with atomically thin semiconductors

Optical Mie resonators based on silicon nanostructures allow tuning of light-matter-interaction with advanced design concepts based on complementary metal–oxide–semiconductor (CMOS) compatible nanofabrication. Optically active materials such as transition-metal dichalcogenide (TMD) monolayers can be placed in the near-field region of such Mie resonators. Here, we experimentally demonstrate and verify by numerical simulations coupling between a MoSe2 monolayer and the near-field of dielectric nanoresonators. Through a comparison of dark-field (DF) scattering spectroscopy and photoluminescence excitation experiments (PLE), we show that the MoSe2 absorption can be enhanced via the near-field of a nanoresonator. We demonstrate spectral tuning of the absorption via the geometry of individual Mie resonators. We show that we indeed access the optical near-field of the nanoresonators, by measuring a spectral shift between the typical near-field resonances in PLE compared to the far-field resonances in DF scattering. Our results prove that using MoSe2 as an active probe allows accessing the optical near-field above photonic nanostructures, providing complementary information to sophisticated near-field microscopy equipment.

Ultrafast pulse pumping of topological nanospaser

We theoretically examine a topological nanospaser that is optically pumped using an ultra-fast circularly-polarized pulse. The spasing system consists of a silver nanospheroid, which supports surface plasmon (SP) excitations, and a transition metal dichalcogenide (TMDC) monolayer nanoflake. The silver nanospheroid screens the incoming pulse and creates a non-uniform spatial distribution of electron excitations in the TMDC nanoflake. These excitations decay into the localized SPs, which can be of two types with the corresponding magnetic quantum number ±1. The amount and the type of the generated SPs depend on the intensity of the optical pulse. For small pulse amplitude, only one plasmonic mode is predominantly generated, resulting in far-field elliptically polarized radiation. For large amplitude of the optical pulse, both plasmonic modes are generated in almost the same amount, resulting in linearly polarized far-field radiation.

Plasmonic-hot-electron mediated room-temperature generation of charged biexciton in monolayer WS2

Transition-metal dichalcogenide (TMDC) monolayers exhibit strong many-body Coulomb interaction, which induces rich excitonic states, including neutral exciton, trion (charged exciton), biexciton, and even charged biexciton. Despite the fact that the biexcitons in pristine two-dimensional (2D) TMDCs have great potential in forming correlated exciton pairs at distinct valleys, they lack efficient emission and optical tunability at room temperature, hindering their applications in photonic and optoelectronic devices. Here, we report room-temperature strong emission of the charged biexcitons from a gold nanosphere capped ${\mathrm{WS}}_{2}$ monolayer through localized surface plasmon (LSP) induced hot-electron injection, and demonstrate all-optical control of the emission intensity through on- or off-resonant LSP excitation. Under on-resonant LSP excitation at 2.08 eV, the photoluminescence (PL) intensity shows a superlinear scaling with the laser power density, signifying the existence of charged biexcitons; On the contrary, the off-resonant LSP excitation at 2.33 eV results in no detectable PL signal of the charged biexcitons. By calculating the energy difference between the charged biexciton and trion, we further determine the binding energy of the former to be 25 meV. Our findings offer an opportunity for understanding the many-body effect associated with the charged biexcitons of 2D TMDCs, and could facilitate their potential quantum and optoelectronic applications under ambient environment.

Quasiparticle and Optical Properties of Carrier-Doped Monolayer MoTe2 from First Principles.

The intrinsic weak and highly nonlocal dielectric screening of two-dimensional materials is well-known to lead to high sensitivity of their optoelectronic properties to environment. Less studied theoretically is the role of free carriers in those properties. Here, we use ab initio GW and Bethe-Salpeter equation calculations, with a rigorous treatment of dynamical screening and local-field effects, to study the doping dependence of the quasiparticle and optical properties of a monolayer transition-metal dichalcogenide, 2H MoTe2. We predict a quasiparticle band gap renormalization of several hundreds of meV for experimentally attainable carrier densities and a similarly sizable decrease in the exciton binding energy. This results in an almost constant excitation energy for the lowest-energy exciton resonance with an increasing doping density. Using a newly developed and generally applicable plasmon-pole model and a self-consistent solution of the Bethe-Salpeter equation, we reveal the importance of accurately capturing both dynamical and local-field effects to understand detailed photoluminescence measurements.

Intermediate State between MoSe2 and Janus MoSeS during Atomic Substitution Process

Janus transition metal dichalcogenides (TMDCs), with dissimilar chalcogen atoms on each side of TMDCs, have garnered considerable research attention because of the out-of-plane intrinsic polarization in monolayer TMDCs. Although a plasma process has been proposed for synthesizing Janus TMDCs based on the atomic substitution of surface atoms at room temperature, the formation dynamics and intermediate electronic states have not been completely examined. In this study, we investigated the intermediate state between MoSe2 and Janus MoSeS during plasma processing. Atomic composition analysis and atomic-scale structural observations revealed the intermediate partially substituted Janus (PSJ) structure. Combined with theoretical calculations, we successfully clarified the characteristic Raman modes in the intermediate PSJ structure. The PL exhibited discontinuous transitions that could not be explained by the theoretical calculations. These findings will contribute toward understanding the formation process and electronic-state modulation of Janus TMDCs.

Tunable Couplings of Photons with Bright and Dark Excitons in Monolayer Semiconductors on Plasmonic-Nanosphere-on-Mirror Cavities

Tunable exciton–photon couplings are of great importance for cavity quantum electrodynamics (QED), polariton chemistry, optical computing, and bosonic lasing. In this regard, two-dimensional (2D) excitons in transition metal dichalcogenides (TMDs) have attracted tremendous interest─the huge oscillator strengths endow sensitive responses to optical modes, and their excitonic properties can be actively tuned by external stimuli. However, tunable coupling with spin-forbidden dark excitons in monolayer TMDs has rarely been demonstrated, and how the bright/dark-exciton–photon couplings coexist in one system is still a mystery. Herein, we utilize waveguide and antenna modes in a gold nanosphere-on-mirror cavity to match the in-plane and out-of-plane dipole moments of bright and dark excitons in monolayer WS2, respectively, and simultaneously. Strong bright-exciton–photon couplings with a coupling strength of up to 60 meV are observed at room temperature. We show that the waveguide mode can be tuned in wavelengths by controlling the spacer thickness and demonstrate the anti-crossing feature of polaritons. Next, by increasing the excitation angle, we dynamically enlarge the relative contribution from the antenna mode coupled with dark excitons and suppress the waveguide mode coupled with bright states. Moreover, a tunable bright exciton linewidth is achieved as a result of suppressed homogeneous broadening caused by the dominant dark exciton decays under strong dark-exciton–photon couplings. This is not only proof of tunable couplings with dark excitons but also an insightful finding that reveals the novel interactions between bright- and dark-exciton–photon hybrids in a single optical cavity, opening new possibilities in tunable QED.

Energy transfer and charge transfer between semiconducting nanocrystals and transition metal dichalcogenide monolayers

Energy transfer and charge transfer between semiconducting nanocrystals and transition metal dichalcogenide monolayers

Temperature Dependence of Excitonic Auger Recombination in Excitonic-Complex-Free Monolayer WS2 by Considering Auger Broadening and Generation Efficiency.

Monolayer transition metal dichalcogenides (TMDs) have been extensively studied for their optoelectronic properties and applications. However, even at moderate exciton densities, their light-emitting capability is severely limited by Auger-type exciton-exciton annihilation (EEA). Previous work on EEA used oversimplified models in the presence of excitonic complexes, resulting in seriously underestimated values for the Auger coefficient. In this work, we transferred monolayer WS2 on a gold substrate with hBN encapsulation, where excitons persist as the main species at 3-300 K via metal proximity. We numerically solved the rate equation for excitons to accurately determine the Auger coefficient as a function of temperature by considering laser pulse width and spatially inhomogeneous exciton distribution. We found that the Auger coefficient consists of temperature-dependent and independent terms, consistent with a theoretical model for direct and exchange processes, respectively. We believe that our results provide a guide for enhancing the luminescence quantum yield of TMDs.

Single Photon Emitters with Polarization and Orbital Angular Momentum Locking in Monolayer Semiconductors.

Excitons in monolayer transition metal dichalcogenide are endowed with intrinsic valley-orbit coupling between their center-of-mass motion and valley pseudospin. When trapped in a confinement potential, e.g., generated by strain field, we find that intralayer excitons are valley and orbital angular momentum (OAM) entangled. By tuning the trap profile and external magnetic field, one can engineer the exciton states at the ground state and realize a series of valley-OAM entangled states. We further show that the OAM of excitons can be transferred to emitted photons, and these novel exciton states can naturally serve as polarization-OAM locked single photon emitters, which under certain circumstance become polarization-OAM entangled, highly tunable by strain trap and magnetic field. Our proposal demonstrates a novel scheme to generate polarization-OAM locked/entangled photons at the nanoscale with a high degree of integrability and tunability, pointing to exciting opportunities for quantum information applications.

Strain-tunable valley polarization and localized excitons in monolayer WSe2.

Monolayer transition metal dichalcogenides (TMDs) have a crystalline structure with broken spatial inversion symmetry, making them promising candidates for valleytronic applications. However, the degree of valley polarization is usually not high due to the presence of intervalley scattering. Here, we use the nanoindentation technique to fabricate strained structures of WSe2 on Au arrays, thus demonstrating the generation and detection of strained localized excitons in monolayer WSe2. Enhanced emission of strain-localized excitons was observed as two sharp photoluminescence (PL) peaks measured using low-temperature PL spectroscopy. We attribute these emerging sharp peaks to excitons trapped in potential wells formed by local strains. Furthermore, the valley polarization of monolayer WSe2 is modulated by a magnetic field, and the valley polarization of strained localized excitons is increased, with a high value of up to approximately 79.6%. Our results show that tunable valley polarization and localized excitons can be realized in WSe2 monolayers, which may be useful for valleytronic applications.

Silver nanowire electrodes for transparent light emitting devices based on WS2 monolayers

Transition metal dichalcogenide (TMDC) monolayers with their direct band gap in the visible to near-infrared spectral range have emerged over the past years as highly promising semiconducting materials for optoelectronic applications. Progress in scalable fabrication methods for TMDCs like metal-organic chemical vapor deposition (MOCVD) and the ambition to exploit specific material properties, such as mechanical flexibility or high transparency, highlight the importance of suitable device concepts and processing techniques. In this work, we make use of the high transparency of TMDC monolayers to fabricate transparent light-emitting devices (LEDs). MOCVD-grown WS2 is embedded as the active material in a scalable vertical device architecture and combined with a silver nanowire (AgNW) network as a transparent top electrode. The AgNW network was deposited onto the device by a spin-coating process, providing contacts with a sheet resistance below 10 Ω sq−1 and a transmittance of nearly 80%. As an electron transport layer we employed a continuous 40 nm thick zinc oxide (ZnO) layer, which was grown by atmospheric pressure spatial atomic layer deposition (AP-SALD), a precise tool for scalable deposition of oxides with defined thickness. With this, LEDs with an average transmittance over 60% in the visible spectral range, emissive areas of several mm2 and a turn-on voltage of around 3 V are obtained.

Multiple Electronic Phases Coexisting under Inhomogeneous Strains in the Correlated Insulator.

Monolayer transition metal dichalcogenides (TMDs) can host exotic phenomena such as correlated insulating and charge-density-wave (CDW) phases. Such properties are strongly dependent on the precise atomic arrangements. Strain, as an effective tuning parameter in atomic arrangements, has been widely used for tailoring material's structures and related properties, yet to date, a convincing demonstration of strain-induced dedicate phase transition at nanometer scale in monolayer TMDs has been lacking. Here, a strain engineering technique is developed to controllably introduce out-of-plane atomic deformations in monolayer CDW material 1T-NbSe2 . The scanning tunneling microscopy and spectroscopy (STM and STS) measurements, accompanied by first-principles calculations, demonstrate that the CDW phase of 1T-NbSe2 can survive under both tensile and compressive strains even up to 5%. Moreover, significant strain-induced phase transitions are observed, i.e., tensile (compressive) strains can drive 1T-NbSe2 from an intrinsic-correlated insulator into a band insulator (metal). Furthermore, experimental evidence of the multiple electronic phase coexistence at the nanoscale is provided. The results shed new lights on the strain engineering of correlated insulator and useful for design and development of strain-related nanodevices.

Water-Assisted Growth of Twisted 3R-Stacked MoSe2 Spirals and Its Dramatically Enhanced Second Harmonic Generations.

Enhanced second-harmonic generation (SHG) responses are reported in monolayer transition metal dichalcogenides (e.g., MX2 , M: Mo, W; X: S, Se) due to the broken symmetries. The 3R-like stacked MX2 spiral structures possessing the similar broken inversion symmetry should present dramatically enhanced SHG responses, thus providing great flexibility in designing miniaturized on-chip nonlinear optical devices. To achieve this, the first direct synthesis of twisted 3R-stacked chiral molybdenum diselenide (MoSe2 ) spiral structures with specific screw dislocations (SD) arms is reported, via designing a water-assisted chemical vapor transport (CVT) approach. The study also clarifies the formation mechanism of the MoSe2 spiral structures, by precisely regulating the precursor supply accompanying with multiscale characterizations. Significantly, an up to three orders of magnitude enhancement of the SHG responses in twisted 3R stacked MoSe2 spirals is demonstrated, which is proposed to arise from the synergistic effects of broken inversion symmetry, strong light-matter interaction, and band nesting effects. Briefly, the work provides an efficient synthetic route for achieving the 3R-stacked TMDCs spirals, which can serve as perfect platforms for promoting their applications in on-chip nonlinear optical devices.

Electronic and Optoelectronic Monolayer WSe2 Devices via Transfer-Free Fabrication Method.

Monolayer transition metal dichalcogenides (TMDs) have drawn significant attention for their potential applications in electronics and optoelectronics. To achieve consistent electronic properties and high device yield, uniform large monolayer crystals are crucial. In this report, we describe the growth of high-quality and uniform monolayer WSe2 film using chemical vapor deposition on polycrystalline Au substrates. This method allows for the fabrication of continuous large-area WSe2 film with large-size domains. Additionally, a novel transfer-free method is used to fabricate field-effect transistors (FETs) based on the as-grown WSe2. The exceptional metal/semiconductor interfaces achieved through this fabrication method result in monolayer WSe2 FETs with extraordinary electrical performance comparable to those with thermal deposition electrodes, with a high mobility of up to ≈62.95 cm2 V-1 s-1 at room temperature. In addition, the as-fabricated transfer-free devices can maintain their original performance after weeks without obvious device decay. The transfer-free WSe2-based photodetectors exhibit prominent photoresponse with a high photoresponsivity of ~1.7 × 104 A W-1 at Vds = 1 V and Vg = -60 V and a maximum detectivity value of ~1.2 × 1013 Jones. Our study presents a robust pathway for the growth of high-quality monolayer TMDs thin films and large-scale device fabrication.

Concentration Phase Separation of Substitution-Doped Atoms in TMDCs Monolayer.

The density and spatial distribution of substituted dopants affect the transition metal dichalcogenides (TMDCs) materials properties. Previous studies have demonstrated that the density of dopants in TMDCs increases with the amount of doping, and the phenomenon of doping concentration difference between the nucleation center and the edge is observed, but the spatial distribution law of doping atoms has not been carefully studied. Here, it is demonstrated that the spatial distribution of dopants changes at high doping concentrations. The spontaneous formation of an interface with a steep doping concentration change is named concentration phase separation (CPS). The difference in the spatial distribution of dopants on both sides of the interface can be identified by an optical microscope. This is consistent with the results of spectral analysis and microstructure characterization of scanning transmission electron microscope. According to the calculation results of density functional theory, the chemical potential has two relatively stable energies as the doping concentration increases, which leads to the spontaneous formation of CPS. Understanding the abnormal phenomena is important for the design of TMDCs devices. This work has great significance in the establishment and improvement of the doping theory and the design of the doping process for 2D materials.

Identification of Exciton Complexes in Charge-Tunable Janus WSeS Monolayers.

Janus transition-metal dichalcogenide monolayers are artificial materials, where one plane of chalcogen atoms is replaced by chalcogen atoms of a different type. Theory predicts an in-built out-of-plane electric field, giving rise to long-lived, dipolar excitons, while preserving direct-bandgap optical transitions in a uniform potential landscape. Previous Janus studies had broad photoluminescence (>18 meV) spectra obfuscating their specific excitonic origin. Here, we identify the neutral and the negatively charged inter- and intravalley exciton transitions in Janus WSeS monolayers with ∼6 meV optical line widths. We integrate Janus monolayers into vertical heterostructures, allowing doping control. Magneto-optic measurements indicate that monolayer WSeS has a direct bandgap at the K points. Our results pave the way for applications such as nanoscale sensing, which relies on resolving excitonic energy shifts, and the development of Janus-based optoelectronic devices, which requires charge-state control and integration into vertical heterostructures.

Rydberg Excitons and Trions in Monolayer MoTe2.

Monolayer transition metal dichalcogenide (TMDC) semiconductors exhibit strong excitonic optical resonances, which serve as a microscopic, noninvasive probe into their fundamental properties. Like the hydrogen atom, such excitons can exhibit an entire Rydberg series of resonances. Excitons have been extensively studied in most TMDCs (MoS2, MoSe2, WS2, and WSe2), but detailed exploration of excitonic phenomena has been lacking in the important TMDC material molybdenum ditelluride (MoTe2). Here, we report an experimental investigation of excitonic luminescence properties of monolayer MoTe2 to understand the excitonic Rydberg series, up to 3s. We report a significant modification of emission energies with temperature (4 to 300 K), thereby quantifying the exciton-phonon coupling. Furthermore, we observe a strongly gate-tunable exciton-trion interplay for all the Rydberg states governed mainly by free-carrier screening, Pauli blocking, and band gap renormalization in agreement with the results of first-principles GW plus Bethe-Salpeter equation approach calculations. Our results help bring monolayer MoTe2 closer to its potential applications in near-infrared optoelectronics and photonic devices.

Highly Reproducible Epitaxial Growth of Wafer-Scale Single-Crystal Monolayer MoS2 on Sapphire.

2D semiconducting transition-metal dichalcogenides (TMDs) have attracted considerable attention as channel materials for next-generation transistors. To meet the industry needs, large-scale production of single-crystal monolayer TMDs in highly reproducible and energy-efficient manner is critically significant. Herein, it is reported that the high-reproducible, high-efficient epitaxial growth of wafer-scale monolayer MoS2 single crystals on the industry-compatible sapphire substrates, by virtue of a deliberately designed "face-to-face" metal-foil-based precursor supply route, carbon-cloth-filter based precursor concentration decay strategy, and the precise optimization of the chalcogenides and metal precursor ratio (i.e., S/Mo ratio). This unique growth design can concurrently guarantee the uniform release, short-distance transport, and moderate deposition of metal precursor on a wafer-scale substrate, affording high-efficient and high-reproducible growth of wafer-scale single crystals (over twoinches, six times faster than usual). Moreover, the S/Mo precursor ratio is found as a key factor for the epitaxial growth of MoS2 single crystals with rather high crystal quality, as convinced by the relatively high electronic performances of related devices. This work demonstrates a reliable route for the batch production of wafer-scale single-crystal 2D materials, thus propelling their practical applications in highly integrated high-performance nanoelectronics and optoelectronics.