Photocarrier generation from interlayer charge-transfer transitions in WS2-graphene heterostructures.
ABSTRACT: 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: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: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:Charge-transfer (CT) excitons at heterointerfaces play a critical role in light to electricity conversion using organic and nanostructured materials. However, how CT excitons migrate at these interfaces is poorly understood. We investigate the formation and transport of CT excitons in two-dimensional WS2/tetracene van der Waals heterostructures. Electron and hole transfer occurs on the time scale of a few picoseconds, and emission of interlayer CT excitons with a binding energy of ~0.3 eV has been observed. Transport of the CT excitons is directly measured by transient absorption microscopy, revealing coexistence of delocalized and localized states. Trapping-detrapping dynamics between the delocalized and localized states leads to stretched-exponential photoluminescence decay with an average lifetime of ~2 ns. The delocalized CT excitons are remarkably mobile with a diffusion constant of ~1 cm2 s-1. These highly mobile CT excitons could have important implications in achieving efficient charge separation.
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:Interlayer coupling in graphene-based van der Waals (vdW) heterostructures plays a key role in determining and modulating their physical properties. Hence, its influence on the optical and electronic properties cannot be overlooked in order to promote various next-generation applications in electronic and opto-electronic devices based on the low-dimensional materials. Herein, the optical and electrical properties of the vertically stacked large area heterostructure of the monolayer graphene transferred onto a monolayer graphene oxide film are investigated. An effective and stable p-doping property of this structure is shown by comparison to that of the graphene device fabricated on a silicon oxide substrate. Through Raman spectroscopy and density functional theory calculations of the charge transport characteristics, it is found that graphene is affected by sustainable p-doping effects induced from underneath graphene oxide even though they have weak interlayer interactions. This finding can facilitate the development of various fascinating graphene-based heterostructures and extend their practical applications in integrated devices with advanced functionalities.
Project description:Recent technological advances in the isolation and transfer of different 2-dimensional (2D) materials have led to renewed interest in stacked Van der Waals (vdW) heterostructures. Interlayer interactions and lattice mismatch between two different monolayers cause elastic strains, which significantly affects their electronic properties. Using a multiscale computational method, we demonstrate that significant in-plane strains and the out-of-plane displacements are introduced in three different bilayer structures, namely graphene-hBN, MoS2-WS2 and MoSe2-WSe2, due to interlayer interactions which can cause bandgap change of up to ~300 meV. Furthermore, the magnitude of the elastic deformations can be controlled by changing the relative rotation angle between two layers. Magnitude of the out-of-plane displacements in graphene agrees well with those observed in experiments and can explain the experimentally observed bandgap opening in graphene. Upon increasing the relative rotation angle between the two lattices from 0° to 10°, the magnitude of the out-of-plane displacements decrease while in-plane strains peaks when the angle is ~6°. For large misorientation angles (>10°), the out-of-plane displacements become negligible. We further predict the deformation fields for MoS2-WS2 and MoSe2-WSe2 heterostructures that have been recently synthesized experimentally and estimate the effect of these deformation fields on near-gap states.
Project description:Electron-phonon scattering is the key process limiting the efficiency of modern nanoelectronic and optoelectronic devices, in which most of the incident energy is converted to lattice heat and finally dissipates into the environment. Here, we report an acoustic phonon recycling process in graphene-WS<sub>2</sub> heterostructures, which couples the heat generated in graphene back into the carrier distribution in WS<sub>2</sub>. This recycling process is experimentally recorded by spectrally resolved transient absorption microscopy under a wide range of pumping energies from 1.77 to 0.48?eV and is also theoretically described using an interfacial thermal transport model. The acoustic phonon recycling process has a relatively slow characteristic time (>100?ps), which is beneficial for carrier extraction and distinct from the commonly found ultrafast hot carrier transfer (~1?ps) in graphene-WS<sub>2</sub> heterostructures. The combination of phonon recycling and carrier transfer makes graphene-based heterostructures highly attractive for broadband high-efficiency electronic and optoelectronic applications.
Project description:Layered materials of graphene and MoS?, for example, have recently emerged as an exciting material system for future electronics and optoelectronics. Vertical integration of layered materials can enable the design of novel electronic and photonic devices. Here, we report highly efficient photocurrent generation from vertical heterostructures of layered materials. We show that vertically stacked graphene-MoS?-graphene and graphene-MoS?-metal junctions can be created with a broad junction area for efficient photon harvesting. The weak electrostatic screening effect of graphene allows the integration of single or dual gates under and/or above the vertical heterostructure to tune the band slope and photocurrent generation. We demonstrate that the amplitude and polarity of the photocurrent in the gated vertical heterostructures can be readily modulated by the electric field of an external gate to achieve a maximum external quantum efficiency of 55% and internal quantum efficiency up to 85%. Our study establishes a method to control photocarrier generation, separation and transport processes using an external electric field.
Project description:Graphene is a very attractive material for broadband photodetection in hyperspectral imaging and sensing systems. However, its potential use has been hindered by tradeoffs between the responsivity, bandwidth, and operation speed of existing graphene photodetectors. Here, we present engineered photoconductive nanostructures based on gold-patched graphene nano-stripes, which enable simultaneous broadband and ultrafast photodetection with high responsivity. These nanostructures merge the advantages of broadband optical absorption, ultrafast photocarrier transport, and carrier multiplication within graphene nano-stripes with the ultrafast transport of photocarriers to gold patches before recombination. Through this approach, high-responsivity operation is realized without the use of bandwidth-limiting and speed-limiting quantum dots, defect states, or tunneling barriers. We demonstrate high-responsivity photodetection from the visible to infrared regime (0.6?A/W at 0.8??m and 11.5?A/W at 20??m), with operation speeds exceeding 50?GHz. Our results demonstrate improvement of the response times by more than seven orders of magnitude and an increase in bandwidths of one order of magnitude compared to those of higher-responsivity graphene photodetectors based on quantum dots and tunneling barriers.