Ying-Sheng Huang

Atomic mechanism of the semiconducting-to-metallic phase transition in single-layered MoS2

Phase transitions can be used to alter the properties of a material without adding any additional atoms and are therefore of significant technological value. In a solid, phase transitions involve collective atomic displacements, but such atomic processes have so far only been investigated using macroscopic approaches. Here, we show that in situ scanning transmission electron microscopy can be used to follow the structural transformation between semiconducting (2H) and metallic (1T) phases in single-layered MoS2, with atomic resolution. The 2H/1T phase transition involves gliding atomic planes of sulphur and/or molybdenum and requires an intermediate phase (α-phase) as a precursor. The migration of two kinds of boundaries (β- and γ-boundaries) is also found to be responsible for the growth of the second phase. Furthermore, we show that areas of the 1T phase can be controllably grown in a layer of the 2H phase using an electron beam.

Monolayer behaviour in bulk ReS 2 due to electronic and vibrational decoupling

Semiconducting transition metal dichalcogenides consist of monolayers held together by weak forces where the layers are electronically and vibrationally coupled. Isolated monolayers show changes in electronic structure and lattice vibration energies, including a transition from indirect to direct bandgap. Here we present a new member of the family, rhenium disulphide (ReS2), where such variation is absent and bulk behaves as electronically and vibrationally decoupled monolayers stacked together. From bulk to monolayers, ReS2 remains direct bandgap and its Raman spectrum shows no dependence on the number of layers. Interlayer decoupling is further demonstrated by the insensitivity of the optical absorption and Raman spectrum to interlayer distance modulated by hydrostatic pressure. Theoretical calculations attribute the decoupling to Peierls distortion of the 1T structure of ReS2, which prevents ordered stacking and minimizes the interlayer overlap of wavefunctions. Such vanishing interlayer coupling enables probing of two-dimensional-like systems without the need for monolayers.

Tunable Band Gap Photoluminescence from Atomically Thin Transition-Metal Dichalcogenide Alloys

Band gap engineering of atomically thin two-dimensional (2D) materials is the key to their applications in nanoelectronics, optoelectronics, and photonics. Here, for the first time, we demonstrate that in the 2D system, by alloying two materials with different band gaps (MoS2 and WS2), tunable band gap can be obtained in the 2D alloys (Mo(1-x)W(x)S(2) monolayers, x = 0-1). Atomic-resolution scanning transmission electron microscopy has revealed random arrangement of Mo and W atoms in the Mo(1-x)W(x)S(2) monolayer alloys. Photoluminescence characterization has shown tunable band gap emission continuously tuned from 1.82 eV (reached at x = 0.20) to 1.99 eV (reached at x = 1). Further, density functional theory calculations have been carried out to understand the composition-dependent electronic structures of Mo(1-x)W(x)S(2) monolayer alloys.

Electrical Transport Properties of Single-Layer WS2

We report on the fabrication of field-effect transistors based on single layers and bilayers of the semiconductor WS2 and the investigation of their electronic transport properties. We find that the doping level strongly depends on the device environment and that long in situ annealing drastically improves the contact transparency, allowing four-terminal measurements to be performed and the pristine properties of the material to be recovered. Our devices show n-type behavior with a high room-temperature on/off current ratio of ∼10(6). They show clear metallic behavior at high charge carrier densities and mobilities as high as ∼140 cm(2)/(V s) at low temperatures (above 300 cm(2)/(V s) in the case of bilayers). In the insulating regime, the devices exhibit variable-range hopping, with a localization length of about 2 nm that starts to increase as the Fermi level enters the conduction band. The promising electronic properties of WS2, comparable to those of single-layer MoS2 and WSe2, together with its strong spin-orbit coupling, make it interesting for future applications in electronic, optical, and valleytronic devices.

Visualization and quantification of transition metal atomic mixing in Mo1-xWxS2 single layers.

The alloying behaviour of materials is a well-known problem in all kinds of compounds. Revealing the heteroatomic distributions in two-dimensional crystals is particularly critical for their practical use as nano-devices. Here we obtain statistics of the homo- and heteroatomic coordinates in single-layered Mo1−xWxS2 from the atomically resolved scanning transmission electron microscope images and successfully quantify the degree of alloying for the transition metal elements (Mo or W). The results reveal the random alloying of this mixed dichalcogenide system throughout the chemical compositions (x=0 to 1). Such a direct route to gain an insight into the alloying degree on individual atom basis will find broad applications in characterizing low-dimensional heterocompounds and become an important complement to the existing theoretical methods.

Single-Layer ReS2: Two-Dimensional Semiconductor with Tunable In-Plane Anisotropy

Rhenium disulfide (ReS2) and diselenide (ReSe2), the group 7 transition metal dichalcogenides (TMDs), are known to have a layered atomic structure showing an in-plane motif of diamond-shaped-chains (DS-chains) arranged in parallel. Using a combination of transmission electron microscopy and transport measurements, we demonstrate here the direct correlation of electron transport anisotropy in single-layered ReS2 with the atomic orientation of the DS-chains, as also supported by our density functional theory calculations. We further show that the direction of conducting channels in ReS2 and ReSe2 can be controlled by electron beam irradiation at elevated temperatures and follows the strain induced to the sample. Furthermore, high chalcogen deficiency can induce a structural transformation to a nonstoichiometric phase, which is again strongly direction-dependent. This tunable in-plane transport behavior opens up great avenues for creating nanoelectronic circuits in 2D materials.

Properties of Individual Dopant Atoms in Single‐Layer MoS2: Atomic Structure, Migration, and Enhanced Reactivity

Single-layered MoS2 doped with Re (n-type) and Au (p-type) are investigated by in situ scanning transmission electron microscopy. Re atoms substituting Mo sites enhance the local chemical affinity, evidenced by agglomeration of other dopant/impurity atoms. Au atoms exist as adatoms and show larger mobility under the electron beam. These behaviors are consistent with density functional theory calculations.

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.

Growth and characterization of well-aligned densely-packed rutile TiO2 nanocrystals on sapphire substrates via metal?organic chemical vapor deposition

Well-aligned densely-packed rutile TiO(2) nanocrystals (NCs) have been grown on sapphire (SA) (100) and (012) substrates via metal-organic chemical vapor deposition (MOCVD), using titanium-tetraisopropoxide (TTIP, Ti(OC(3)H(7))(4)) as a source reagent. The surface morphology as well as structural and spectroscopic properties of the as-deposited NCs were characterized using field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), selected-area electron diffractometry (SAED), x-ray diffraction (XRD) and micro-Raman spectroscopy. FESEM micrographs reveal that vertically aligned NCs were grown on SA(100), whereas the NCs on the SA(012) were grown with a tilt angle of ∼33° from the normal to substrates. TEM and SAED measurements showed that the TiO(2) NCs on SA(100) with square cross section have their long axis directed along the [001] direction. The XRD results reveal TiO(2) NCs with either (002) orientation on SA(100) substrate or (101) orientation on SA(012) substrate. A strong substrate effect on the alignment of the growth of TiO(2) NCs has been demonstrated and the probable mechanism for the formation of these NCs has been discussed.

Field emission from vertically aligned conductive IrO2 nanorods

We report on the preparation and field-emission properties of vertically aligned conductive IrO2 nanorods. The unique geometrical features of IrO2 nanorods, including nanosized structure and self-assembled sharp tip, exhibit a strong effect on field enhancement (β∼40 000), which result in a low threshold field (Eth∼0.7 V/μm) defined at the beginning of emission. A low turn-on field for driving a current of 10 μA/cm2 is about 5.6 V/μm, which is comparable with the carbon nanotube, diamond, and amorphous carbon. The potential of using IrO2 nanorods as an emitter material has been demonstrated.