The electronic and optical properties and the recent progress in applications of 2D semiconductor transition metal dichalcogenides with emphasis on strong excitonic effects, and spin- and valley-dependent properties are reviewed. Recent advances in the development of atomically thin layers of van der Waals bonded solids have opened up new possibilities for the exploration of 2D physics as well as for materials for applications. Among them, semiconductor transition metal dichalcogenides, MX2 (M = Mo, W; X = S, Se), have bandgaps in the near-infrared to the visible region, in contrast to the zero bandgap of graphene. In the monolayer limit, these materials have been shown to possess direct bandgaps, a property well suited for photonics and optoelectronics applications. Here, we review the electronic and optical properties and the recent progress in applications of 2D semiconductor transition metal dichalcogenides with emphasis on strong excitonic effects, and spin- and valley-dependent properties.

Photonics and optoelectronics of 2D semiconductor transition metal dichalcogenides

Semiconductor technology is currently based on the manipulation of electronic charge; however, electrons have additional degrees of freedom, such as spin and valley, that can be used to encode and process information. Over the past several decades, there has been significant progress in manipulating electron spin for semiconductor spintronic devices, motivated by potential spin-based information processing and storage applications. However, experimental progress towards manipulating the valley degree of freedom for potential valleytronic devices has been limited until very recently. We review the latest advances in valleytronics, which have largely been enabled by the isolation of 2D materials (such as graphene and semiconducting transition metal dichalcogenides) that host an easily accessible electronic valley degree of freedom, allowing for dynamic control. The energy extrema of an electronic band are referred to as valleys. In 2D materials, two distinguishable valleys can be used to encode information and explore other valleytronic applications.

Valleytronics in 2D materials

To enhance and optimize nanocatalyst performance and durability for the oxygen reduction reaction in fuel-cell applications, we look beyond Pt-metal disordered alloys and describe a new class of Pt-Co nanocatalysts composed of ordered Pt(3)Co intermetallic cores with a 2-3 atomic-layer-thick platinum shell. These nanocatalysts exhibited over 200% increase in mass activity and over 300% increase in specific activity when compared with the disordered Pt(3)Co alloy nanoparticles as well as Pt/C. So far, this mass activity for the oxygen reduction reaction is the highest among the Pt-Co systems reported in the literature under similar testing conditions. Stability tests showed a minimal loss of activity after 5,000 potential cycles and the ordered core-shell structure was maintained virtually intact, as established by atomic-scale elemental mapping. The high activity and stability are attributed to the Pt-rich shell and the stable intermetallic Pt(3)Co core arrangement. These ordered nanoparticles provide a new direction for catalyst performance optimization for next-generation fuel cells.

Structurally ordered intermetallic platinum–cobalt core–shell nanoparticles with enhanced activity and stability as oxygen reduction electrocatalysts

The two-dimensional semiconducting material molybdenum disulphide shows strong piezoelectricity in its single-layered form, suggesting possible applications in nanoscale electromechanical devices for sensing and energy harvesting. Two-dimensional semiconducting materials are the focus of much research effort thanks to their unusual and potentially useful physical properties. Wenzhou Wu and colleagues now confirm theoretical expectations that one such material — molybdenum disulphide — exhibits strong piezoelectricity in its single-layered form. Such a coupling of mechanical and electrical properties suggests possible applications in nanoscale electromechanical devices for sensing and energy harvesting. The piezoelectric characteristics of nanowires, thin films and bulk crystals have been closely studied for potential applications in sensors, transducers, energy conversion and electronics1,2,3. With their high crystallinity and ability to withstand enormous strain4,5,6, two-dimensional materials are of great interest as high-performance piezoelectric materials. Monolayer MoS2 is predicted to be strongly piezoelectric, an effect that disappears in the bulk owing to the opposite orientations of adjacent atomic layers7,8. Here we report the first experimental study of the piezoelectric properties of two-dimensional MoS2 and show that cyclic stretching and releasing of thin MoS2 flakes with an odd number of atomic layers produces oscillating piezoelectric voltage and current outputs, whereas no output is observed for flakes with an even number of layers. A single monolayer flake strained by 0.53% generates a peak output of 15 mV and 20 pA, corresponding to a power density of 2 mW m−2 and a 5.08% mechanical-to-electrical energy conversion efficiency. In agreement with theoretical predictions, the output increases with decreasing thickness and reverses sign when the strain direction is rotated by 90°. Transport measurements show a strong piezotronic effect in single-layer MoS2, but not in bilayer and bulk MoS2. The coupling between piezoelectricity and semiconducting properties in two-dimensional nanomaterials may enable the development of applications in powering nanodevices, adaptive bioprobes and tunable/stretchable electronics/optoelectronics.

Piezoelectricity of single-atomic-layer MoS2 for energy conversion and piezotronics.

Supramolecular Chirality in Self-Assembled Systems

We have measured optical second-harmonic generation (SHG) from atomically thin samples of MoS2 and h-BN with one to five layers. We observe strong SHG from materials with odd layer thickness, for which a noncentrosymmetric structure is expected, while the centrosymmetric materials with even layer thickness do not yield appreciable SHG. SHG for materials with odd layer thickness was measured as a function of crystal orientation. This dependence reveals the rotational symmetry of the lattice and is shown to provide a purely optical method of determining the orientation of crystallographic axes. We report values for the nonlinearity of monolayers and odd-layers of MoS2 and h-BN and compare the variation as a function of layer thickness with a model that accounts for wave propagation effects.

Probing symmetry properties of few-layer MoS2 and h-BN by optical second-harmonic generation.

Sum frequency generation vibrational spectroscopy (SFG-VS) has been proven to be a uniquely effective spectroscopic technique in the investigation of molecular structure and conformations, as well as the dynamics of molecular interfaces. However, the ability to apply SFG-VS to complex molecular interfaces has been limited by the ability to abstract quantitative information from SFG-VS experiments. In this review, we try to make assessments of the limitations, issues and techniques as well as methodologies in quantitative orientational and spectral analysis with SFG-VS. Based on these assessments, we also try to summarize recent developments in methodologies on quantitative orientational and spectral analysis in SFG-VS, and their applications to detailed analysis of SFG-VS data of various vapour/neat liquid interfaces. A rigorous formulation of the polarization null angle (PNA) method is given for accurate determination of the orientational parameter D = ⟨cos θ ⟩/⟨cos3 θ⟩, and comparison between the PNA me...

Quantitative spectral and orientational analysis in surface sum frequency generation vibrational spectroscopy (SFG-VS)

Monolayer MoS2 is a direct-gap two-dimensional semiconductor that exhibits strong electron–hole interactions, leading to the formation of stable excitons and trions. Here we report the existence of efficient exciton–exciton annihilation, a four-body interaction, in this material. Exciton–exciton annihilation was identified experimentally in ultrafast transient absorption measurements through the emergence of a decay channel varying quadratically with exciton density. The rate of exciton–exciton annihilation was determined to be (4.3 ± 1.1) × 10–2 cm2/s at room temperature.

Observation of Rapid Exciton–Exciton Annihilation in Monolayer Molybdenum Disulfide

Quantitative spectral and orientational analysis in surface sum frequency generation vibrational spectroscopy (SFG-VS). Int Rev Phys Chem

Monolayer MoS2 is a direct-gap two-dimensional semiconductor that exhibits strong electron-hole interactions, leading to the formation of stable excitons and trions. Here we report the existence of efficient exciton-exciton annihilation, a four-body interaction, in this material. Exciton-exciton annihilation was identified experimentally in ultrafast transient absorption measurements through the emergence of a decay channel varying quadratically with exciton density. The rate of exciton-exciton annihilation was determined to be (4.3 ± 1.1) × 10(-2) cm(2)/s at room temperature.

http://absimage.aps.org/image/MAR15/MWS_MAR15-2014-006549.pdf

Yi Rao

Papers

Probing symmetry properties of few-layer MoS2 and h-BN by optical second-harmonic generation.

Quantitative spectral and orientational analysis in surface sum frequency generation vibrational spectroscopy (SFG-VS)

Observation of Rapid Exciton–Exciton Annihilation in Monolayer Molybdenum Disulfide

Quantitative spectral and orientational analysis in surface sum frequency generation vibrational spectroscopy (SFG-VS). Int Rev Phys Chem

Observation of Rapid Exciton-Exciton Annihilation in Monolayer Molybdenum Disulfide