The role of collective motion in the ultrafast charge transfer in van der Waals heterostructures.
ABSTRACT: The success of van der Waals heterostructures made of graphene, metal dichalcogenides and other layered materials, hinges on the understanding of charge transfer across the interface as the foundation for new device concepts and applications. In contrast to conventional heterostructures, where a strong interfacial coupling is essential to charge transfer, recent experimental findings indicate that van der Waals heterostructues can exhibit ultrafast charge transfer despite the weak binding of these heterostructures. Here we find, using time-dependent density functional theory molecular dynamics, that the collective motion of excitons at the interface leads to plasma oscillations associated with optical excitation. By constructing a simple model of the van der Waals heterostructure, we show that there exists an unexpected criticality of the oscillations, yielding rapid charge transfer across the interface. Application to the MoS2/WS2 heterostructure yields good agreement with experiments, indicating near complete charge transfer within a timescale of 100 fs.
Project description:Van der Waals heterostructures composed of two-dimensional transition-metal dichalcogenides layers have recently emerged as a new family of materials, with great potential for atomically thin opto-electronic and photovoltaic applications. It is puzzling, however, that the photocurrent is yielded so efficiently in these structures, despite the apparent momentum mismatch between the intralayer/interlayer excitons during the charge transfer, as well as the tightly bound nature of the excitons in 2D geometry. Using the energy-state-resolved ultrafast visible/infrared microspectroscopy, we herein obtain unambiguous experimental evidence of the charge transfer intermediate state with excess energy, during the transition from an intralayer exciton to an interlayer exciton at the interface of a WS2/MoS2 heterostructure, and free carriers moving across the interface much faster than recombining into the intralayer excitons. The observations therefore explain how the remarkable charge transfer rate and photocurrent generation are achieved even with the aforementioned momentum mismatch and excitonic localization in 2D heterostructures and devices.
Project description:The heterostructure of monolayer transition metal dichalcogenides (TMDCs) provides a unique platform to manipulate exciton dynamics. The ultrafast carrier transfer across the van der Waals interface of the TMDC hetero-bilayer can efficiently separate electrons and holes in the intralayer excitons with a type II alignment, but it will funnel excitons into one layer with a type I alignment. In this work, we demonstrate the reversible switch from exciton dissociation to exciton funneling in a MoSe2/WS2 heterostructure, which manifests itself as the photoluminescence (PL) quenching to PL enhancement transition. This transition was realized through effectively controlling the quantum capacitance of both MoSe2 and WS2 layers with gating. PL excitation spectroscopy study unveils that PL enhancement arises from the blockage of the optically excited electron transfer from MoSe2 to WS2. Our work demonstrates electrical control of photoexcited carrier transfer across the van der Waals interface, the understanding of which promises applications in quantum optoelectronics.
Project description:Efficient interfacial carrier generation in van der Waals heterostructures is critical for their electronic and optoelectronic applications. We demonstrate broadband photocarrier generation in WS2-graphene heterostructures by imaging interlayer coupling-dependent charge generation using ultrafast transient absorption microscopy. Interlayer charge-transfer (CT) transitions and hot carrier injection from graphene allow carrier generation by excitation as low as 0.8 eV below the WS2 bandgap. The experimentally determined interlayer CT transition energies are consistent with those predicted from the first-principles band structure calculation. CT interactions also lead to additional carrier generation in the visible spectral range in the heterostructures compared to that in the single-layer WS2 alone. The lifetime of the charge-separated states is measured to be ~1 ps. These results suggest that interlayer interactions make graphene-two-dimensional semiconductor heterostructures very attractive for photovoltaic and photodetector applications because of the combined benefits of high carrier mobility and enhanced broadband photocarrier generation.
Project description:Two-dimensional van der Waals heterostructures are of considerable interest for the next generation nanoelectronics because of their unique interlayer coupling and optoelectronic properties. Here, we report a modified Langmuir-Blodgett method to organize two-dimensional molecular charge transfer crystals into arbitrarily and vertically stacked heterostructures, consisting of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF)/C60 and poly(3-dodecylthiophene-2,5-diyl) (P3DDT)/C60 nanosheets. A strong and anisotropic interfacial coupling between the charge transfer pairs is demonstrated. The van der Waals heterostructures exhibit pressure dependent sensitivity with a high piezoresistance coefficient of -4.4?×?10-6?Pa-1, and conductance and capacitance tunable by external stimuli (ferroelectric field and magnetic field). Density functional theory calculations confirm charge transfer between the n-orbitals of the S atoms in BEDT-TTF of the BEDT-TTF/C60 layer and the ?* orbitals of C atoms in C60 of the P3DDT/C60 layer contribute to the inter-complex CT. The two-dimensional molecular van der Waals heterostructures with tunable optical-electronic-magnetic coupling properties are promising for flexible electronic applications.Two-dimensional van der Waals heterostructures are of interest due to their unique interlayer coupling and optoelectronic properties. Here authors develop a Langmuir-Blodgett method to organize charge transfer molecular heterostructures with externally tunable conductance and capacitance and broadband photoresponse.
Project description:2D vertical van der Waals (vdW) heterostructures with atomically sharp interfaces have attracted tremendous interest in 2D photonic and optoelectronic applications. Band alignment engineering in 2D heterostructures provides a perfect platform for tailoring interfacial charge transfer behaviors, from which desired optical and optoelectronic features can be realized. Here, by developing a two-step chemical vapor deposition strategy, direct vapor growth of monolayer PbI2 on monolayer transition metal dichalcogenides (TMDCs) (WS2, WSe2, or alloying WS2(1- x )Se2 x ), forming bilayer vertical heterostructures, is demonstrated. Based on the calculated electron band structures, the interfacial band alignments of the obtained heterostructures can be gradually tuned from type-I (PbI2/WS2) to type-II (PbI2/WSe2). Steady-state photoluminescence (PL) and time-resolved PL measurements reveal that the PL emissions from the bottom TMDC layers can be modulated from apparently enhanced (for WS2) to greatly quenched (for WSe2) compared to their monolayer counterparts, which can be attributed to the band alignment-induced distinct interfacial charge transfer behaviors. The band alignment nature of the heterostructures is further demonstrated by the PL excitation spectroscopy and interlayer exciton investigation. The realization of 2D vertical heterostructures with tunable band alignments will provide a new material platform for designing and constructing multifunctional optoelectronic devices.
Project description:The structural, electronic, and optical properties of heterostructures formed by transition metal dichalcogenides MX2 (M?=?Mo, W; X?=?S, Se) and graphene-like zinc oxide (ZnO) were investigated using first-principles calculations. The interlayer interaction in all heterostructures was characterized by van der Waals forces. Type-II band alignment occurs at the MoS2/ZnO and WS2/ZnO interfaces, together with the large built-in electric field across the interface, suggesting effective photogenerated-charge separation. Meanwhile, type-I band alignment occurs at the MoSe2/ZnO and WSe2/ZnO interfaces. Moreover, all heterostructures exhibit excellent optical absorption in the visible and infrared regions, which is vital for optical applications.
Project description:Two-dimensional layered transition metal dichalcogenides (TMDCs) show great potential for optoelectronic devices due to their electronic and optical properties. A metal-semiconductor interface, as epitaxial graphene - molybdenum disulfide (MoS2), is of great interest from the standpoint of fundamental science, as it constitutes an outstanding platform to investigate the interlayer interaction in van der Waals heterostructures. Here, we study large area MoS2-graphene-heterostructures formed by direct transfer of chemical-vapor deposited MoS2 layer onto epitaxial graphene/SiC. We show that via a direct transfer, which minimizes interface contamination, we can obtain high quality and homogeneous van der Waals heterostructures. Angle-resolved photoemission spectroscopy (ARPES) measurements combined with Density Functional Theory (DFT) calculations show that the transition from indirect to direct bandgap in monolayer MoS2 is maintained in these heterostructures due to the weak van der Waals interaction with epitaxial graphene. A downshift of the Raman 2D band of the graphene, an up shift of the A1g peak of MoS2 and a significant photoluminescence quenching are observed for both monolayer and bilayer MoS2 as a result of charge transfer from MoS2 to epitaxial graphene under illumination. Our work provides a possible route to modify the thin film TDMCs photoluminescence properties via substrate engineering for future device design.
Project description:Strong Coulomb interactions in monolayer transition metal dichalcogenides (TMDs) produce strongly bound excitons, trions, and biexcitons. The existence of multiexcitonic states has drawn tremendous attention because of its promising applications in quantum information. Combining different monolayer TMDs into van der Waals (vdW) heterostructures opens up opportunities to engineer exciton devices and bring new phenomena. Spatially separated electrons and holes in different layers produce interlayer excitons. Although much progress has been made on excitons in single layers, how interlayer excitons contribute the photoluminescence emission and how to tailor the interlayer exciton emission have not been well understood. Here, room temperature strong coupling between interlayer excitons in the WS2/MoS2 vdW heterostructure and cavity-enhanced Mie resonances in individual silicon nanoparticles (Si NPs) are demonstrated. The heterostructures are inserted into a Si film-Si NP all-dielectric platform to realize effective energy exchanges and Rabi oscillations. Besides mode splitting in scattering, tunable interlayer excitonic emission is also observed. The results make it possible to design TMDs heterostructures with various excitonic states for future photonics devices.
Project description:Van der Waals heterostructures formed by two different monolayer semiconductors have emerged as a promising platform for new optoelectronic and spin/valleytronic applications. In addition to its atomically thin nature, a two-dimensional semiconductor heterostructure is distinct from its three-dimensional counterparts due to the unique coupled spin-valley physics of its constituent monolayers. Here, we report the direct observation that an optically generated spin-valley polarization in one monolayer can be transferred between layers of a two-dimensional MoSe2-WSe2 heterostructure. Using non-degenerate optical circular dichroism spectroscopy, we show that charge transfer between two monolayers conserves spin-valley polarization and is only weakly dependent on the twist angle between layers. Our work points to a new spin-valley pumping scheme in nanoscale devices, provides a fundamental understanding of spin-valley transfer across the two-dimensional interface, and shows the potential use of two-dimensional semiconductors as a spin-valley generator in two-dimensional spin/valleytronic devices for storing and processing information.
Project description:Semiconductor heterostructures form the cornerstone of many electronic and optoelectronic devices and are traditionally fabricated using epitaxial growth techniques. More recently, heterostructures have also been obtained by vertical stacking of two-dimensional crystals, such as graphene and related two-dimensional materials. These layered designer materials are held together by van der Waals forces and contain atomically sharp interfaces. Here, we report on a type-II van der Waals heterojunction made of molybdenum disulfide and tungsten diselenide monolayers. The junction is electrically tunable, and under appropriate gate bias an atomically thin diode is realized. Upon optical illumination, charge transfer occurs across the planar interface and the device exhibits a photovoltaic effect. Advances in large-scale production of two-dimensional crystals could thus lead to a new photovoltaic solar technology.