Direct evidence for efficient ultrafast charge separation in epitaxial WS2/graphene heterostructures.
ABSTRACT: We use time- and angle-resolved photoemission spectroscopy (tr-ARPES) to investigate ultrafast charge transfer in an epitaxial heterostructure made of monolayer WS2 and graphene. This heterostructure combines the benefits of a direct-gap semiconductor with strong spin-orbit coupling and strong light-matter interaction with those of a semimetal hosting massless carriers with extremely high mobility and long spin lifetimes. We find that, after photoexcitation at resonance to the A-exciton in WS2, the photoexcited holes rapidly transfer into the graphene layer while the photoexcited electrons remain in the WS2 layer. The resulting charge-separated transient state is found to have a lifetime of ?1 ps. We attribute our findings to differences in scattering phase space caused by the relative alignment of WS2 and graphene bands as revealed by high-resolution ARPES. In combination with spin-selective optical excitation, the investigated WS2/graphene heterostructure might provide a platform for efficient optical spin injection into graphene.
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:The proximity of a transition-metal dichalcogenide (TMD) to graphene imprints a rich spin texture in graphene and complements its high-quality charge/spin transport by inducing spin-orbit coupling (SOC). Rashba and valley-Zeeman SOCs are the origin of charge-to-spin conversion mechanisms such as the Rashba-Edelstein effect (REE) and spin Hall effect (SHE). In this work, we experimentally demonstrate for the first time charge-to-spin conversion due to the REE in a monolayer WS2-graphene van der Waals heterostructure. We measure the current-induced spin polarization up to room temperature and control it by a gate electric field. Our observation of the REE and the inverse of the effect (IREE) is accompanied by the SHE, which we discriminate by symmetry-resolved spin precession under oblique magnetic fields. These measurements also allow for the quantification of the efficiencies of charge-to-spin conversion by each of the two effects. These findings are a clear indication of induced Rashba and valley-Zeeman SOC in graphene that lead to the generation of spin accumulation and spin current without using ferromagnetic electrodes. These realizations have considerable significance for spintronic applications, providing accessible routes toward all-electrical spin generation and manipulation in two-dimensional materials.
Project description:Interfacial interactions allow the electronic properties of graphene to be modified, as recently demonstrated by the appearance of satellite Dirac cones in graphene on hexagonal boron nitride substrates. Ongoing research strives to explore interfacial interactions with other materials to engineer targeted electronic properties. Here we show that with a tungsten disulfide (WS2) substrate, the strength of the spin-orbit interaction (SOI) in graphene is very strongly enhanced. The induced SOI leads to a pronounced low-temperature weak anti-localization effect and to a spin-relaxation time two to three orders of magnitude smaller than in graphene on conventional substrates. To interpret our findings we have performed first-principle electronic structure calculations, which confirm that carriers in graphene on WS2 experience a strong SOI and allow us to extract a spin-dependent low-energy effective Hamiltonian. Our analysis shows that the use of WS2 substrates opens a possible new route to access topological states of matter in graphene-based systems.
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: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:Graphene has gigantic potential in the development of advanced spintronic devices. The interfacial interactions of graphene with semiconducting transition metal dichalcogenides improve the electronic properties drastically, making it an intriguing candidate for spintronic applications. Here, we fabricated bilayer graphene encapsulated by WS2 layers to exploit the interface-induced spin-orbit interaction (SOI). We designed a dual gated device, where the SOI is tuned by gate voltages. The strength of induced SOI in the bilayer graphene is dramatically elevated, which leads to a strong weak antilocalization (WAL) effect at low temperature. The quantitative analysis of WAL demonstrates that the spin relaxation time is 10 times smaller than in bilayer graphene on conventional substrates. To support these results, we also examined Shubnikov-de Haas (SdH) oscillations, which give unambiguous evidence of the zero-field spin-splitting in our bilayer graphene. The spin-orbit coupling constants estimated by two different measurements (i.e., the WAL effect and SdH oscillations) show close values as a function of gate voltage, supporting the self-consistency of this study's experimental results. The gate modulation of the SOI in bilayer graphene encapsulated by WS2 films establishes a novel way to explore the manipulation of spin-dependent transport through an electric field.
Project description:Graphene-like two dimensional materials, such as WS2 and MoS2, are highly anisotropic layered compounds that have attracted growing interest from basic research to practical applications. Similar with MoS2, few-layer WS2 has remarkable physical properties. Here, we demonstrate for the first time that WS2 nanosheets exhibit ultrafast nonlinear saturable absorption property and high optical damage threshold. Soliton mode-locking operations are achieved separately in an erbium-doped fiber laser using two types of WS2-based saturable absorbers, one of which is fabricated by depositing WS2 nanosheets on a D-shaped fiber, while the other is synthesized by mixing WS2 solution with polyvinyl alcohol, and then evaporating them on a substrate. At the maximum pump power of 600 mW, two saturable absorbers can work stably at mode-locking state without damage, indicating that few-layer WS2 is a promising high-power flexible saturable absorber for ultrafast optics. Numerous applications may benefit from the ultrafast nonlinear features of WS2 nanosheets, such as high-power pulsed laser, materials processing, and frequency comb spectroscopy.
Project description:Van der Waals heterostructures of transition metal dichalcogenides with interlayer coupling offer an exotic platform to realize fascinating phenomena. Due to the type II band alignment of these heterostructures, electrons and holes are separated into different layers. The localized electrons induced doping in one layer, in principle, would lift the Fermi level to cross the spin-polarized upper conduction band and lead to strong manipulation of valley magnetic response. Here, we report the significantly enhanced valley Zeeman splitting and magnetic tuning of polarization for the direct optical transition of MoS2 in MoS2/WS2 heterostructures. Such strong enhancement of valley magnetic response in MoS2 stems from the change of the spin-valley degeneracy from 2 to 4 and strong many-body Coulomb interactions induced by ultrafast charge transfer. Moreover, the magnetic splitting can be tuned monotonically by laser power, providing an effective all-optical route towards engineering and manipulating of valleytronic devices and quantum-computation.
Project description:High-responsivity phototransistors with a structure of perovskite-WS2 nanosheet composite optical absorber and a reduced graphene oxide (rGO) channel layer is demonstrated via a facile and low-cost solution-processing method. The WS2 nanosheets are dispersed within the perovskite matrix, forming the perovskite-WS2 bulk heterojunction (BHJ). The hybrid phototransistor exhibits excellent figures of merit including high photoresponsivity of 678.8 A/W, high specific detectivity of 4.99 × 1011 Jones, high EQE value of 2.04 × 105% and rapid response to photoswitching. The high photoresponsivity could be attributed to the WS2 nanosheets induced photo-generated electron-hole separation promotion effects due to the selective electron trapping effects in the WS2 nanosheets, together with the high carrier mobility of the rGO channel. This work provides a promising platform for constructing high-responsivity photodetectors.
Project description:Nowadays, rationally preparing heterostructure materials can not only make up for the shortage of individual components, but also exert unexpected performance through synergistic interactions between the components. Herein, a core-shell of WS2@NiCo2O4 screw-like heterostructure arrays grown on carbon cloth (CC) was prepared by a two-step solvothermal method for supercapacitors. As a binder-free flexible electrode, a high areal capacitance of 2449.9 mF cm-2 can be achieved for WS2@NiCo2O4/CC at a current density of 1 mA cm-2. Benefiting from the core-shell of the WS2@NiCo2O4 heterostructure, the capacitive property of the flexible WS2@NiCo2O4/CC electrode is better than those of WS2/CC and NiCo2O4/CC electrodes. Based on WS2@NiCo2O4/CC electrodes, the assembled flexible solid-state symmetric supercapacitor (FSS) device shows a high energy density of ?45.67 W h kg-1 at a power density of 992.83 W kg-1. Meantime, the WS2@NiCo2O4/CC-assembled FSS device also exhibits high cycling stability with an excellent capacity retention of ?85.59% after 5000 cycles.