Wen-Hao Chang

Large-Area Synthesis of Highly Crystalline WSe2 Monolayers and Device Applications

The monolayer transition metal dichalcogenides have recently attracted much attention owing to their potential in valleytronics, flexible and low-power electronics and optoelectronic devices. Recent reports have demonstrated the growth of large-size 2-dimensional MoS2 layers by the sulfurization of molybdenum oxides. However, the growth of transition metal selenide monolayer has still been a challenge. Here we report that the introduction of hydrogen in the reaction chamber helps to activate the selenization of WO3, where large-size WSe2 monolayer flakes or thin films can be successfully grown.The monolayer transition metal dichalcogenides have recently attracted much attention owing to their potential in valleytronics, flexible and low-power electronics, and optoelectronic devices. Recent reports have demonstrated the growth of large-size two-dimensional MoS2 layers by the sulfurization of molybdenum oxides. However, the growth of a transition metal selenide monolayer has still been a challenge. Here we report that the introduction of hydrogen in the reaction chamber helps to activate the selenization of WO3, where large-size WSe2 monolayer flakes or thin films can be successfully grown. The top-gated field-effect transistors based on WSe2 monolayers using ionic gels as the dielectrics exhibit ambipolar characteristics, where the hole and electron mobility values are up to 90 and 7 cm(2)/Vs, respectively. These films can be transferred onto arbitrary substrates, which may inspire research efforts to explore their properties and applications. The resistor-loaded inverter based on a WSe2 film, with a gain of ∼13, further demonstrates its applicability for logic-circuit integrations.

Plasmonic Nanolaser Using Epitaxially Grown Silver Film

Going Green with Nanophotonics Plasmons are optically induced collective electronic excitations tightly confined to the surface of a metal, with silver being the metal of choice. The subwavelength confinement offers the opportunity to shrink optoelectronic circuits to the nanometer scale. However, scattering processes within the metal lead to losses. Lu et al. (p. 450) developed a process to produce atomically smooth layers of silver, epitaxially grown on silicon substrates. A cavity in the silver layer is capped with a SiO insulating layer and an AlGaN nanorod was used to produce a low-threshold emission at green wavelengths. An atomically smooth layer of silver enhances the performance of nanophotonic devices. A nanolaser is a key component for on-chip optical communications and computing systems. Here, we report on the low-threshold, continuous-wave operation of a subdiffraction nanolaser based on surface plasmon amplification by stimulated emission of radiation. The plasmonic nanocavity is formed between an atomically smooth epitaxial silver film and a single optically pumped nanorod consisting of an epitaxial gallium nitride shell and an indium gallium nitride core acting as gain medium. The atomic smoothness of the metallic film is crucial for reducing the modal volume and plasmonic losses. Bimodal lasing with similar pumping thresholds was experimentally observed, and polarization properties of the two modes were used to unambiguously identify them with theoretically predicted modes. The all-epitaxial approach opens a scalable platform for low-loss, active nanoplasmonics.

Epitaxial growth of a monolayer WSe2-MoS2 lateral p-n junction with an atomically sharp interface

Electronic junctions on edge Two-dimensional materials such as graphene are attractive materials for making smaller transistors because they are inherently nanoscale and can carry high currents. However, graphene has no band gap and the transistors are “leaky”; that is, they are hard to turn off. Related transition metal dichalcogenides (TMDCs) such as molybdenum sulfide have band gaps. Transistors based on these materials can have high ratios of “on” to “off” currents. However, it is often difficult to make a good voltage-biased (p-n) junction between different TMDC materials. Li et al. succeeded in making p-n heterojunctions between two of these materials, molybdenum sulfide and tungsten selenide. They did this not by stacking the layers, which make a weak junction, but by growing molybdenum sulfide on the edge of a triangle of tungsten selenide with an atomically sharp boundary Science, this issue p. 524 The regrowth of the second transition metal dichalcogenide monolayer by edge epitaxy creates a lateral p-n heterojunction. Two-dimensional transition metal dichalcogenides (TMDCs) such as molybdenum sulfide MoS2 and tungsten sulfide WSe2 have potential applications in electronics because they exhibit high on-off current ratios and distinctive electro-optical properties. Spatially connected TMDC lateral heterojunctions are key components for constructing monolayer p-n rectifying diodes, light-emitting diodes, photovoltaic devices, and bipolar junction transistors. However, such structures are not readily prepared via the layer-stacking techniques, and direct growth favors the thermodynamically preferred TMDC alloys. We report the two-step epitaxial growth of lateral WSe2-MoS2 heterojunction, where the edge of WSe2 induces the epitaxial MoS2 growth despite a large lattice mismatch. The epitaxial growth process offers a controllable method to obtain lateral heterojunction with an atomically sharp interface.

Monolayer MoSe2 Grown by Chemical Vapor Deposition for Fast Photodetection

Monolayer molybdenum disulfide (MoS2) has become a promising building block in optoelectronics for its high photosensitivity. However, sulfur vacancies and other defects significantly affect the electrical and optoelectronic properties of monolayer MoS2 devices. Here, highly crystalline molybdenum diselenide (MoSe2) monolayers have been successfully synthesized by the chemical vapor deposition (CVD) method. Low-temperature photoluminescence comparison for MoS2 and MoSe2 monolayers reveals that the MoSe2 monolayer shows a much weaker bound exciton peak; hence, the phototransistor based on MoSe2 presents a much faster response time (<25 ms) than the corresponding 30 s for the CVD MoS2 monolayer at room temperature in ambient conditions. The images obtained from transmission electron microscopy indicate that the MoSe exhibits fewer defects than MoS2. This work provides the fundamental understanding for the differences in optoelectronic behaviors between MoSe2 and MoS2 and is useful for guiding future designs in 2D material-based optoelectronic devices.

Bandgap tunability at single-layer molybdenum disulphide grain boundaries

Two-dimensional transition metal dichalcogenides have emerged as a new class of semiconductor materials with novel electronic and optical properties of interest to future nanoelectronics technology. Single-layer molybdenum disulphide, which represents a prototype two-dimensional transition metal dichalcogenide, has an electronic bandgap that increases with decreasing layer thickness. Using high-resolution scanning tunnelling microscopy and spectroscopy, we measure the apparent quasiparticle energy gap to be 2.40 ± 0.05 eV for single-layer, 2.10 ± 0.05 eV for bilayer and 1.75 ± 0.05 eV for trilayer molybdenum disulphide, which were directly grown on a graphite substrate by chemical vapour deposition method. More interestingly, we report an unexpected bandgap tunability (as large as 0.85 ± 0.05 eV) with distance from the grain boundary in single-layer molybdenum disulphide, which also depends on the grain misorientation angle. This work opens up new possibilities for flexible electronic and optoelectronic devices with tunable bandgaps that utilize both the control of two-dimensional layer thickness and the grain boundary engineering.

Spectroscopic Signatures for Interlayer Coupling in MoS2–WSe2 van der Waals Stacking

Stacking of MoS2 and WSe2 monolayers is conducted by transferring triangular MoS2 monolayers on top of WSe2 monolayers, all grown by chemical vapor deposition (CVD). Raman spectroscopy and photoluminescence (PL) studies reveal that these mechanically stacked monolayers are not closely coupled, but after a thermal treatment at 300 °C, it is possible to produce van der Waals solids consisting of two interacting transition metal dichalcogenide (TMD) monolayers. The layer-number sensitive Raman out-of-plane mode A(2)1g for WSe2 (309 cm(-1)) is found sensitive to the coupling between two TMD monolayers. The presence of interlayer excitonic emissions and the changes in other intrinsic Raman modes such as E″ for MoS2 at 286 cm(-1) and A(2)1g for MoS2 at around 463 cm(-1) confirm the enhancement of the interlayer coupling.

Second Harmonic Generation from Artificially Stacked Transition Metal Dichalcogenide Twisted Bilayers

Optical second harmonic generation (SHG) is known as a sensitive probe to the crystalline symmetry of few-layer transition metal dichalcogenides (TMDs). Layer-number dependent and polarization resolved SHG have been observed for the special case of Bernal stacked few-layer TMDs, but it remains largely unexplored for structures deviated from this ideal stacking order. Here we report on the SHG from homo- and heterostructural TMD bilayers formed by artificial stacking with an arbitrary stacking angle. The SHG from the twisted bilayers is a coherent superposition of the SH fields from the individual layers, with a phase difference depending on the stacking angle. Such an interference effect is insensitive to the constituent layered materials and thus applicable to hetero-stacked bilayers. A proof-of-concept demonstration of using the SHG to probe the domain boundary and crystal polarity of mirror twins formed in chemically grown TMDs is also presented. We show here that the SHG is an efficient, sensitive, and nondestructive characterization for the stacking orientation, crystal polarity, and domain boundary of van der Waals heterostructures made of noncentrosymmetric layered materials.

Band Gap-Tunable Molybdenum Sulfide Selenide Monolayer Alloy

band gap engineering of TMD has become an important topic. In early studies the TMD solid solutions both in the metal (e.g., Mo x W 1−x S 2 ) and chalcogen (e.g., MoS 2x Se 2(1−x) ) sublattice forms have been realized by the direct vapor transport growth, where the stoichiometric amounts of desired powder elements were introduced into a quartz ampoule for crystal growth. [ 17,18 ] Meanwhile, the growth of MoS 2 , WSe 2 and WS 2 monolayers has been reported recently by using sulfurization or selenization of transition metal oxides with chemical vapor deposition (CVD) techniques. [ 19–21 ] The density-functinoal theory (DFT) calculations show that the single layers of mixed TMDs, such as MoS 2x Se 2(1−x) are thermodynamically stable at room temperature, [ 22 ] so that such materials can be manufactured using chemical-vapor deposition technique. It is therefore useful to know whether it is possible to realize the synthesis of MoS 2x Se 2(1−x) monlayers which exhibit intriguing electronic properties and tunable optical band gaps. Very recently, the transition-metal dichalcogenide monolayer alloys (Mo 1–x W x S 2 ) have been obtained by mechanical cleaving from their bulk crystals, [ 23 ] where the band gap emission ranges from 1.82 eV to 1.99 eV. Note that the mechanical cleavage is valuable for fundamental research; however, a simple and scalable method to obtain TMD monolayers with controllable optical energy gaps is still urgently needed. In this contribution, we report that the MoS 2 monolayer fl akes prepared by CVD can be selenized in the presence of selenium vapors to form MoS x Se y monolayers. The optical band gap of the obtained MoS x Se y , ranging from 1.86 eV to 1.57 eV, is easily controllable by the selenization temperature. It is key demonstration for controlling electronic and optoelectronic structures of TMD monolayers using a simple method, where pproach is straightforward and applicable to the band gap engineering for other TMD monolayers. The CVD-grown MoS 2 monolayers were synthesized based on our previous reports. [ 19 ] In brief, the triangular MoS 2 fl akes are formed by the vapor phase reaction of MoO 3 with S powders, where the MoS 2 monolayers with a lateral size up to tens micron can be obtained and which growth method has been adopted by many other groups . [ 24,25 ] To modulate the electronic structures and optical band gaps of the MoS 2 monolayer, we perform the selenization in a hot-wall furnace at various temperatures. The scheme in Figure 1 a illustrates the experimental set-up for the selenization process, where the inlet gas (a mixture of Ar and H 2 ) carries the vaporized DOI: 10.1002/smll.201302893 2D Materials

Photoluminescence Enhancement and Structure Repairing of Monolayer MoSe2 by Hydrohalic Acid Treatment

Atomically thin two-dimensional transition-metal dichalcogenides (TMDCs) have attracted much attention recently due to their unique electronic and optical properties for future optoelectronic devices. The chemical vapor deposition (CVD) method is able to generate TMDCs layers with a scalable size and a controllable thickness. However, the TMDC monolayers grown by CVD may incorporate structural defects, and it is fundamentally important to understand the relation between photoluminescence and structural defects. In this report, point defects (Se vacancies) and oxidized Se defects in CVD-grown MoSe2 monolayers are identified by transmission electron microscopy and X-ray photoelectron spectroscopy. These defects can significantly trap free charge carriers and localize excitons, leading to the smearing of free band-to-band exciton emission. Here, we report that the simple hydrohalic acid treatment (such as HBr) is able to efficiently suppress the trap-state emission and promote the neutral exciton and trion emission in defective MoSe2 monolayers through the p-doping process, where the overall photoluminescence intensity at room temperature can be enhanced by a factor of 30. We show that HBr treatment is able to activate distinctive trion and free exciton emissions even from highly defective MoSe2 layers. Our results suggest that the HBr treatment not only reduces the n-doping in MoSe2 but also reduces the structural defects. The results provide further insights of the control and tailoring the exciton emission from CVD-grown monolayer TMDCs.

Optically initialized robust valley-polarized holes in monolayer WSe2.

A robust valley polarization is a key prerequisite for exploiting valley pseudospin to carry information in next-generation electronics and optoelectronics. Although monolayer transition metal dichalcogenides with inherent spin–valley coupling offer a unique platform to develop such valleytronic devices, the anticipated long-lived valley pseudospin has not been observed yet. Here we demonstrate that robust valley-polarized holes in monolayer WSe2 can be initialized by optical pumping. Using time-resolved Kerr rotation spectroscopy, we observe a long-lived valley polarization for positive trion with a lifetime approaching 1 ns at low temperatures, which is much longer than the trion recombination lifetime (∼10–20 ps). The long-lived valley polarization arises from the transfer of valley pseudospin from photocarriers to resident holes in a specific valley. The optically initialized valley pseudospin of holes remains robust even at room temperature, which opens up the possibility to realize room-temperature valleytronics based on transition metal dichalcogenides.