Large-area Heterostructures Research Articles

Solution-Processable Large-Area Black Phosphorus/Reduced Graphene Oxide Schottky Junction for High-Temperature Broadband Photodetectors.

2D materials-based broadband photodetectors have extensive applications in security monitoring and remote sensing fields, especially in supersonic aircraft that require reliable performance under extreme high-temperature conditions. However, the integration of large-area heterostructures with 2D materials often involves high-temperature deposition methods, and also limited options and size of substrates. Herein, a liquid-phase spin-coating method is presented based on the interface engineering to prepare larger-area Van der Waals heterojunctions of black phosphorus (BP)/reduced graphene oxide (RGO) films at room temperature on arbitrary substrates of any required size. Importantly, this method avoids the common requirement of high-temperature, and prevents the curling or stacking in 2D materials during the liquid-phase film formation. The BP/RGO films-based devices exhibit a wide spectral photo-response, ranging from the visible of 532 nm to infrared range of 2200 nm. Additionally, due to Van der Waals interface of Schottky junction, the array devices provide infrared detection at temperatures up to 400 K, with an outstanding photoresponsivity (R) of 12 AW-1 and a specific detectivity (D*) of ≈2.4×109 Jones. This work offers an efficient approach to fabricate large-area 2D Schottky junction films by solution-coating for high-temperature infrared photodetectors.

Secondary-deposited elevated self-assembling nanosphere lithography: A powerful tool to achieve heterostructure metasurface

The heterostructure integration of nanostructures, which can involve higher freedom of degree by applying two or more materials into one integrated photonic or electromagnetic devices, attracted extensively increasing attention among the communities of electrons, photonics, materials science, and engineering. However, it is still a challenging topic to realize heterostructure integration with accurate micro–nano-scale geometry in a large area. Here, we propose the secondary-deposited elevated self-assembling nanosphere lithography for large-area heterostructure integration of plasmonic metasurface. As the proof of concept, an infrared metasurface composed of Au–Ag crescent pairs is realized in the practice. By adjusting the evaporation angle, crescent pairs with different morphologies can be freely machined without changing masks. Optical characterization and numerical results show that the heterostructure crescent-pair metasurface owns uniform and stable geometrical properties and flexible capability on infrared optical field modulation. Our work enriches the degree of freedom of nano-structure-based optical devices and paves the heterostructure integrated metasurface to potential industrial applications with large dimension, low cost, and fast production.

Ultrafast hot carrier transfer in WS2/graphene large area heterostructures

Charge transfer processes in two-dimensional van der Waals heterostructures enable upconversion of low energy photons and efficient charge carriers extraction. Here we use broadband ultrafast optical spectroscopy to track charge transfer dynamics in large-area 2D heterostructures made of epitaxial single-layer tungsten disulfide (WS2) grown by chemical vapour deposition on graphene. Selective carrier photoexcitation in graphene, with tunable near-infrared photon energies as low as 0.8 eV (i.e. lower than half of the optical bandgap of WS2), results in an almost instantaneous bleaching of the WS2 excitonic peaks in the visible range, due to the interlayer charge transfer process. We find that the charge transfer signal is strongly non-linear with the pump fluence and it becomes progressively more linear at increasing pump photon energies, while the interlayer photoinjection rate is constant in energy, reflecting the spectrally flat absorbance of graphene. We ascribe the interlayer charge transfer to a fast transfer of hot carriers, photogenerated in graphene, to the semiconducting layer. The measured sub-20-fs hot-carrier transfer sets the ultimate timescale for this process. Besides their fundamental interest, our results are technologically relevant because, given the capability of large-area deterministic growth of the heterostructure, they open up promising paths for novel 2D photodetectors, also potentially scalable to industrial platforms.

Controllable Epitaxial Growth of Large-Area MoS2 /WS2 Vertical Heterostructures by Confined-Space Chemical Vapor Deposition.

The controllable large-area growth of single-crystal vertical heterostructures based on 2D transition metal dichalcogenides (TMDs) remains a challenge. Here, large-area vertical MoS2 /WS2 heterostructures are synthesized using single-step confined-space chemical vapor epitaxy. The heterostructures can evolve into two different kinds by switching the H2 flow on and off: MoS2 /WS2 heterostructures with multiple WS2 domains can be achieved without introducing the H2 flow due to the numerous nucleation centers on the bottom MoS2 monolayer during the transition stage between the MoS2 and WS2 monolayer growth. In contrast, isolated MoS2 /WS2 heterostructures with single WS2 domain can be obtained with introducing the H2 flow due to the reduced nucleation centers on the bottom MoS2 monolayer arising from the hydrogen etching effect. Both the two kinds of the vertical MoS2 /WS2 heterostructures feature high quality. The photodetectors based on the isolated MoS2 /WS2 heterostructures exhibit a high responsivity of 68 mA W-1 and a short response time of 35ms. This single-step chemical vapor epitaxy can be used to synthesize vertical MoS2 /WS2 heterostructures with high production efficiency. The new epitaxial growth approach may open new pathways to fabricate large-area heterostructures made of different 2D TMDs monolayers of interest to electronics, optoelectronics, and other applications.

Plasma-Induced Phase Transformation of SnS2 to SnS

Layered van der Waals materials have recently attracted attention owing to their exceptional electrical and optical properties in thin layer form. One way to extend their utility is to form a heterostructure which combines various properties of layered materials to reveal intriguing behavior. Conventional heterostructure synthesis methods are difficult to develop and the heterostructure formed can be limited to a small area. Here, we investigate the phase transformation of SnS2 to SnS by removing sulfur atoms at the top surface using Ar plasma. By varying the plasma power and exposure time, we observed that SnS is subsequently formed on top of the mogul-like structure of SnS2. Since SnS is a p-type semiconductor and SnS2 is an n-type semiconductor, we naturally formed a vertical p-n junction. By using graphene at the top and bottom as transparent electrodes, a vertical p-n diode device is constructed. The device demonstrates good rectifying behavior and large photocurrent generation under white light. This method can be applied to large-area heterostructure synthesis using plasma via phase transformation of various metal dichalcogenides to metal monochalcogenides.

Large-Area Heterostructures from Graphene and Encapsulated Colloidal Quantum Dots via the Langmuir-Blodgett Method.

This work explores the assembly of large-area heterostructures comprised of a film of silica-encapsulated, semiconducting colloidal quantum dots, deposited via the Langmuir-Blodgett method, sandwiched between two graphene sheets. The luminescent, electrically insulating film served as a dielectric, with the top graphene sheet patterned into an electrode and successfully used as a top gate for an underlying graphene field-effect transistor. This heterostructure paves the way for developing novel hybrid optoelectronic devices through the integration of 2D and 0D materials.

Vertical Heterostructures of Layered Metal Chalcogenides by Van Der Waals Epitaxy for Solar Energy Conversion and Catalysis

We report a facile chemical vapor deposition (CVD) growth of vertical heterostructures of layered metal dichalcogenides (MX2) enabled by van der Waals epitaxy for the first time. Few layers of MoS2, WS2, and WSe2 were grown uniformly onto microplates of SnS2 under mild CVD reaction conditions and the heteroepitaxy between them was confirmed using cross sectional transmission electron microscopy (TEM) and unequivocally characterized by resolving the large-area Moiré patterns appeared on the basal planes of microplates. Additional photoluminescence peaks were observed in heterostructures of MoS2-SnS2, which can be understood with electronic structure calculations to likely result from electronic coupling and charge separation between MoS2 and SnS2 layers. This work opens up the exploration of novel large-area heterostructures of diverse MX2 nanomaterials as the material platform for electronic structure engineering of atomically thin two-dimensional (2D) semiconducting heterostructures and novel device applications, such as in solar energy conversion. Furthermore, by controlling the nanostructures and polymorphs of group 6 MX2 (M = Mo, W; X = S, Se) materials, we have significant enhanced their catalytic activity in hydrogen evolution reaction for photoelectrochemical water splitting.

Tuning interlayer coupling in large-area heterostructures with CVD-grown MoS2 and WS2 monolayers.

Band offsets between different monolayer transition metal dichalcogenides are expected to efficiently separate charge carriers or rectify charge flow, offering a mechanism for designing atomically thin devices and probing exotic two-dimensional physics. However, developing such large-area heterostructures has been hampered by challenges in synthesis of monolayers and effectively coupling neighboring layers. Here, we demonstrate large-area (>tens of micrometers) heterostructures of CVD-grown WS2 and MoS2 monolayers, where the interlayer interaction is externally tuned from noncoupling to strong coupling. Following this trend, the luminescence spectrum of the heterostructures evolves from an additive line profile where each layer contributes independently to a new profile that is dictated by charge transfer and band normalization between the WS2 and MoS2 layers. These results and findings open up venues to creating new material systems with rich functionalities and novel physical effects.

Vertical heterostructures of layered metal chalcogenides by van der Waals epitaxy.

We report a facile chemical vapor deposition (CVD) growth of vertical heterostructures of layered metal dichalcogenides (MX2) enabled by van der Waals epitaxy. Few layers of MoS2, WS2, and WSe2 were grown uniformly onto microplates of SnS2 under mild CVD reaction conditions (<500 °C) and the heteroepitaxy between them was confirmed using cross-sectional transmission electron microscopy (TEM) and unequivocally characterized by resolving the large-area Moiré patterns that appeared on the basal planes of microplates in conventional TEM (nonsectioned). Additional photoluminescence peaks were observed in heterostructures of MoS2-SnS2, which can be understood with electronic structure calculations to likely result from electronic coupling and charge separation between MoS2 and SnS2 layers. This work opens up the exploration of large-area heterostructures of diverse MX2 nanomaterials as the material platform for electronic structure engineering of atomically thin two-dimensional (2D) semiconducting heterostructures and device applications.