Minglin Toh

Evolution of Electronic Structure in Atomically Thin Sheets of WS2 and WSe2

Geometrical confinement effect in exfoliated sheets of layered materials leads to significant evolution of energy dispersion in mono- to few-layer thickness regime. Molybdenum disulfide (MoS(2)) was recently found to exhibit indirect-to-direct gap transition when the thickness is reduced to a single monolayer. Emerging photoluminescence (PL) from monolayer MoS(2) opens up opportunities for a range of novel optoelectronic applications of the material. Here we report differential reflectance and PL spectra of mono- to few-layer WS(2) and WSe(2) that indicate that the band structure of these materials undergoes similar indirect-to-direct gap transition when thinned to a single monolayer. The transition is evidenced by distinctly enhanced PL peak centered at 630 and 750 nm in monolayer WS(2) and WSe(2), respectively. Few-layer flakes are found to exhibit comparatively strong indirect gap emission along with direct gap hot electron emission, suggesting high quality of synthetic crystals prepared by a chemical vapor transport method. Fine absorption and emission features and their thickness dependence suggest a strong effect of Se p-orbitals on the d electron band structure as well as interlayer coupling in WSe(2).

Transport Properties of Monolayer MoS2 Grown by Chemical Vapor Deposition

Recent success in the growth of monolayer MoS2 via chemical vapor deposition (CVD) has opened up prospects for the implementation of these materials into thin film electronic and optoelectronic devices. Here, we investigate the electronic transport properties of individual crystallites of high quality CVD-grown monolayer MoS2. The devices show low temperature mobilities up to 500 cm(2) V(-1) s(-1) and a clear signature of metallic conduction at high doping densities. These characteristics are comparable to the electronic properties of the best mechanically exfoliated monolayers in literature, verifying the high electronic quality of the CVD-grown materials. We analyze the different scattering mechanisms and show that the short-range scattering plays a dominant role in the highly conducting regime at low temperatures. Additionally, the influence of optical phonons as a limiting factor is discussed.

Origin of indirect optical transitions in few-layer MoS2, WS2, and WSe2.

It has been well-established that single layer MX2 (M = Mo, W and X = S, Se) are direct gap semiconductors with band edges coinciding at the K point in contrast to their indirect gap multilayer counterparts. In few-layer MX2, there are two valleys along the Γ-K line with similar energy. There is little understanding on which of the two valleys forms the conduction band minimum (CBM) in this thickness regime. We investigate the conduction band valley structure in few-layer MX2 by examining the temperature-dependent shift of indirect exciton photoluminescence peak. Highly anisotropic thermal expansion of the lattice and the corresponding evolution of the band structure result in a distinct peak shift for indirect transitions involving the K and Λ (midpoint along Γ-K) valleys. We identify the origin of the indirect emission and concurrently determine the relative energy of these valleys.

Nonlinear photoluminescence in atomically thin layered WSe2 arising from diffusion-assisted exciton-exciton annihilation

We studied multiexciton dynamics in monolayer WSe2 using nonlinear photoluminescence (PL) spectroscopy and Monte Carlo simulations. We observed strong nonlinear saturation behavior of exciton PL with increasing excitation power density and long-distance exciton diffusion, reaching several micrometers. We demonstrated that the diffusion-assisted exciton-exciton annihilation (EEA) model accounts for the observed nonlinear PL behavior. The long-distance exciton diffusion and subsequent efficient EEA process determined the unusual multiexciton dynamics in atomically thin layered transition metal dichalcogenides.

Liquid-gated electric-double-layer transistor on layered metal dichalcogenide, SnS2

With ionic liquid (IL) gating in electric-double-layer transistors (EDLTs), we report field effect operation and electronic state modulation in a layered material of SnS2, demonstrating that the EDLT is applicable to modifying the electronic properties of metal dichalcogenides. The IL-gated SnS2 EDLTs allow us to realize high performance transistor operation and to achieve interfacial carrier accumulation to a level as high as 5.4×1014 cm−2, as quantitatively estimated from the Hall effect. A considerable decrease of the activation energy in temperature-dependent sheet resistance implies that liquid gating is an effective way to tune the electronic states of metal dichalcogenides at EDL interfaces.

Wet chemical thinning of molybdenum disulfide down to its monolayer

We report on the preparation of mono- and bi-layer molybdenum disulfide (MoS2) from a bulk crystal by facile wet chemical etching. We show that concentrated nitric acid (HNO3) effectively etches thin MoS2 crystals from their edges via formation of MoO3. Interestingly, etching of thin crystals on a substrate leaves behind unreacted mono- and bilayer sheets. The flakes obtained by chemical etching exhibit electronic quality comparable to that of mechanically exfoliated counterparts. Our findings indicate that the self-limiting chemical etching is a promising top-down route to preparing atomically thin crystals from bulk layer compounds.

Evidence for line width and carrier screening effects on excitonic valley relaxation in 2D semiconductors

Monolayers of transition metal dichalcogenides (TMDC) have recently emerged as excellent platforms for exploiting new physics and applications relying on electronic valley degrees of freedom in two-dimensional (2D) systems. Here, we demonstrate that Coulomb screening by 2D carriers plays a critical role in excitonic valley pseudospin relaxation processes in naturally carrier-doped WSe2 monolayers (1L-WSe2). The exciton valley relaxation times were examined using polarization- and time-resolved photoluminescence spectroscopy at temperatures ranging from 10 to 160 K. We show that the temperature-dependent exciton valley relaxation times in 1L-WSe2 under various exciton and carrier densities can be understood using a unified framework of intervalley exciton scattering via momentum-dependent long-range electron–hole exchange interactions screened by 2D carriers that depend on the carrier density and the exciton linewidth. Moreover, the developed framework was successfully applied to engineer the valley polarization of excitons in 1L-WSe2. These findings may facilitate the development of TMDC-based opto-valleytronic devices.Atomically thin transition metal dichalcogenides offer a platform to explore the valley degree of freedom originating from their electronic band structure. Here, the authors use polarization- and time-resolved spectroscopy to investigate the temperature-dependent valley pseudospin relaxation processes in WSe2 monolayers.