Jinhua Hong

Exploring atomic defects in molybdenum disulphide monolayers

Defects usually play an important role in tailoring various properties of two-dimensional materials. Defects in two-dimensional monolayer molybdenum disulphide may be responsible for large variation of electric and optical properties. Here we present a comprehensive joint experiment–theory investigation of point defects in monolayer molybdenum disulphide prepared by mechanical exfoliation, physical and chemical vapour deposition. Defect species are systematically identified and their concentrations determined by aberration-corrected scanning transmission electron microscopy, and also studied by ab-initio calculation. Defect density up to 3.5 × 1013u2009cm−2 is found and the dominant category of defects changes from sulphur vacancy in mechanical exfoliation and chemical vapour deposition samples to molybdenum antisite in physical vapour deposition samples. Influence of defects on electronic structure and charge-carrier mobility are predicted by calculation and observed by electric transport measurement. In light of these results, the growth of ultra-high-quality monolayer molybdenum disulphide appears a primary task for the community pursuing high-performance electronic devices.

Plasma-assisted fabrication of monolayer phosphorene and its Raman characterization

AbstractThere have been continuous efforts to seek novel functional two-dimensional semiconductors with high performance for future applications in nanoelectronics and optoelectronics. In this work, we introduce a successful experimental approach to fabricate monolayer phosphorene by mechanical cleavage and a subsequent Ar+ plasma thinning process. The thickness of phosphorene is unambiguously determined by optical contrast spectra combined with atomic force microscopy (AFM). Raman spectroscopy is used to characterize the pristine and plasma-treated samples. The Raman frequency of the A2g mode stiffens, and the intensity ratio of A2g to A1g modes shows a monotonic discrete increase with the decrease of phosphorene thickness down to a monolayer. All those phenomena can be used to identify the thickness of this novel two-dimensional semiconductor. This work on monolayer phosphorene fabrication and thickness determination will facilitate future research on phosphorene.n

Growth of Large-Area 2D MoS2(l_,)Se2, Semiconductor

Semiconducting MoS₂(₁-x) Se₂x mono-layers where x = 0-0.40 are successfully grown over large areas. A random arrangement of the S and Se atoms and a tunable bandgap photoluminescence are observed. Atomically thin, 2D semiconductor alloys with tunable bandgaps have potential applications in nano- and opto-electronics. Field-effect transistors fabricated with the monolayers exhibit high on/off ratios of >10(5).

Epitaxy and Photoresponse of Two-Dimensional GaSe Crystals on Flexible Transparent Mica Sheets

We present the controlled synthesis of high-quality two-dimensional (2D) GaSe crystals on flexible transparent mica substrates via a facile van der Waals epitaxy method. Single- and few-layer GaSe nanoplates with the lateral size of up to tens of micrometers were produced. The orientation and nucleation sites of GaSe nanoplates were well-controlled. The 2D GaSe crystal-based photodetectors were demonstrated on both mechanically rigid SiO2/Si and flexible mica substrates. Efficient photoresponse was observed in 2D GaSe crystal devices on transparent flexible mica substrates, regardless of repeated bending with different radii. The controlled growth of 2D GaSe crystals with efficient photoresponsivity opens up opportunities for both fundamental aspects and new applications in photodetectors.

Two-Dimensional Molybdenum Tungsten Diselenide Alloys: Photoluminescence, Raman Scattering, and Electrical Transport

Two-dimensional transition-metal dichalcogenide alloys have attracted intense attention due to their tunable band gaps. In the present work, photoluminescence, Raman scattering, and electrical transport properties of monolayer and few-layer molybdenum tungsten diselenide alloys (Mo1-xWxSe2, 0 ≤ x ≤ 1) are systematically investigated. The strong photoluminescence emissions from Mo1-xWxSe2 monolayers indicate composition-tunable direct band gaps (from 1.56 to 1.65 eV), while weak and broad emissions from the bilayers indicate indirect band gaps. The first-order Raman modes are assigned by polarized Raman spectroscopy. Second-order Raman modes are assigned according to its frequencies. As composition changes in Mo1-xWxSe2 monolayers and few layers, the out-of-plane A1g mode showed one-mode behavior, while B2g(1) (only observed in few layers), in-plane E2g(1), and all observed second-order Raman modes showed two-mode behaviors. Electrical transport measurement revealed n-type semiconducting transport behavior with a high on/off ratio (>10(5)) for Mo1-xWxSe2 monolayers.

Atomic Defects in Two-Dimensional Materials: From Single-Atom Spectroscopy to Functionalities in Opto-/Electronics, Nanomagnetism, and Catalysis

Two-dimensional layered graphene-like crystals including transition-metal dichalcogenides (TMDs) have received extensive research interest due to their diverse electronic, valleytronic, and chemical properties, with the corresponding optoelectronics and catalysis application being actively explored. However, the recent surge in two-dimensional materials science is accompanied by equally great challenges, such as defect engineering in large-scale sample synthesis. It is necessary to elucidate the effect of structural defects on the electronic properties in order to develop an application-specific strategy for defect engineering. Here, two aspects of the existing knowledge of native defects in two-dimensional crystals are reviewed. One is the point defects emerging in graphene and hexagonal boron nitride, as probed by atomically resolved electron microscopy, and their local electronic properties, as measured by single-atom electron energy-loss spectroscopy. The other will focus on the point defects in TMDs and their influence on the electronic structure, photoluminescence, and electric transport properties. This review of atomic defects in two-dimensional materials will offer a clear picture of the defect physics involved to demonstrate the local modulation of the electronic properties and possible benefits in potential applications in magnetism and catalysis.

High Mobility 2D Palladium Diselenide Field‐Effect Transistors with Tunable Ambipolar Characteristics

Due to the intriguing optical and electronic properties, 2D materials have attracted a lot of interest for the electronic and optoelectronic applications. Identifying new promising 2D materials will be rewarding toward the development of next generation 2D electronics. Here, palladium diselenide (PdSe2 ), a noble-transition metal dichalcogenide (TMDC), is introduced as a promising high mobility 2D material into the fast growing 2D community. Field-effect transistors (FETs) based on ultrathin PdSe2 show intrinsic ambipolar characteristic. The polarity of the FET can be tuned. After vacuum annealing, the authors find PdSe2 to exhibit electron-dominated transport with high mobility (µe (max) = 216 cm2 V-1 s-1 ) and on/off ratio up to 103 . Hole-dominated-transport PdSe2 can be obtained by molecular doping using F4 -TCNQ. This pioneer work on PdSe2 will spark interests in the less explored regime of noble-TMDCs.

Synthesis of Large-Size 1T′ ReS2xSe2(1−x) Alloy Monolayer with Tunable Bandgap and Carrier Type

Chemical vapor deposition growth of 1T ReS2x Se2(1-x) alloy monolayers is reported for the first time. The composition and the corresponding bandgap of the alloy can be continuously tuned from ReSe2 (1.32 eV) to ReS2 (1.62 eV) by precisely controlling the growth conditions. Atomic-resolution scanning transmission electron microscopy reveals an interesting local atomic distribution in ReS2x Se2(1-x) alloy, where S and Se atoms are selectively occupied at different X sites in each Re-X6 octahedral unit cell with perfect matching between their atomic radius and space size of each X site. This structure is much attractive as it can induce the generation of highly desired localized electronic states in the 2D surface. The carrier type, threshold voltage, and carrier mobility of the alloy-based field effect transistors can be systematically modulated by tuning the alloy composition. Especially, for the first time the fully tunable conductivity of ReS2x Se2(1-x) alloys from n-type to bipolar and p-type is realized. Owing to the 1T structure of ReS2x Se2(1-x) alloys, they exhibit strong anisotropic optical, electrical, and photoelectric properties. The controllable growth of monolayer ReS2x Se2(1-x) alloy with tunable bandgaps and electrical properties as well as superior anisotropic feature provides the feasibility for designing multifunctional 2D optoelectronic devices.

Direct Imaging of Kinetic Pathways of Atomic Diffusion in Monolayer Molybdenum Disulfide

Direct observation of atomic migration both on and below surfaces is a long-standing but important challenge in materials science as diffusion is one of the most elementary processes essential to many vital material behaviors. Probing the kinetic pathways, including metastable or even transition states involved down to atomic scale, holds the key to the underlying physical mechanisms. Here, we applied aberration-corrected transmission electron microscopy (TEM) to demonstrate direct atomic-scale imaging and quasi-real-time tracking of diffusion of Mo adatoms and vacancies in monolayer MoS2, an important two-dimensional transition metal dichalcogenide (TMD) system. Preferred kinetic pathways and the migration potential-energy landscape are determined experimentally and confirmed theoretically. The resulting three-dimensional knowledge of the atomic configuration evolution reveals the different microscopic mechanisms responsible for the contrasting intrinsic diffusion rates for Mo adatoms and vacancies. The new insight will benefit our understanding of material processes such as phase transformation and heterogeneous catalysis.

Layer-dependent anisotropic electronic structure of freestanding quasi-two-dimensional Mo S 2

The anisotropy of the electronic transition is an important physical property not only determining the materials optical property, but also revealing the underlying character of the electronic states involved. Here we used momentum-resolved electron energy-loss spectroscopy to study the evolution of the anisotropy of the electronic transition involving the low energy valence electrons in the free-standing MoS2 systems as the layer thickness was reduced to monolayer. We used the orientation and the spectral-density analysis to show that indirect to direct band-gap transition is accompanied by a three- to two-dimensional anisotropy cross-over. The result provides a logical explanation for the large sensitivity of indirect transition to the change of thickness compared with that for direct transition. By tracking the energy of indirect transition, we also revealed the asymmetric response of the valence band and conduction band to the quantum confinement effect. Our results have implication for future optoelectronic applications of atomic thin MoS2.This work is financially supported by the National Basic nResearch Program of China (Grants No. 2014CB932500 and nNo. 2015CB921004) and National Science Foundation of nChina (GrantsNo. 51222202 and No. 51472215). The research nreported in this paper was partially supported by King Abdullah nUniversity of Science and Technology (KAUST). J.Y. acknowledges nPao Yu-Kong International Foundation for a visiting nChair Professorship in ZJU and EPSRC and Royal Society nfor partial support. Dr. Ray Egerton and Dr. He Tian are kindly nacknowledged for critical reading, comments, and revisions. nJ.H. and K.L. contributed equally to this work.