Optical Properties Of Transition Metal Dichalcogenides Research Articles

Ultralocalized Optoelectronic Properties of Nanobubbles in 2D Semiconductors.

The optical properties of transition-metal dichalcogenides have previously been modified at the nanoscale by using mechanical and electrical nanostructuring. However, a clear experimental picture relating the local electronic structure with emission properties in such structures has so far been lacking. Here, we use a combination of scanning tunneling microscopy (STM) and near-field photoluminescence (nano-PL) to probe the electronic and optical properties of single nanobubbles in bilayer heterostructures of WSe2 on MoSe2. We show from tunneling spectroscopy that there are electronic states deeply localized in the gap at the edge of such bubbles, which are independent of the presence of chemical defects in the layers. We also show a significant change in the local band gap on the bubble, with a continuous evolution to the edge of the bubble over a length scale of ∼20 nm. Nano-PL measurements observe a continuous redshift of the interlayer exciton on entering the bubble, in agreement with the band-to-band transitions measured by STM. We use self-consistent Schrödinger-Poisson simulations to capture the essence of the experimental results and find that strong doping in the bubble region is a key ingredient to achieving the observed localized states, together with mechanical strain.

Low-loss composite photonic platform based on 2D semiconductor monolayers

Two dimensional materials such as graphene and transition metal dichalcogenides (TMDs) are promising for optical modulation, detection, and light emission since their material properties can be tuned on-demand via electrostatic doping. The optical properties of TMDs have been shown to change drastically with doping in the wavelength range near the excitonic resonances. However, little is known about the effect of doping on the optical properties of TMDs away from these resonances, where the material is transparent and therefore could be leveraged in photonic circuits. Here, we probe the electro-optic response of monolayer TMDs at near infrared (NIR) wavelengths (i.e. deep in the transparency regime), by integrating them on silicon nitride (SiN) photonic structures to induce strong light$-$matter interaction with the monolayer. We dope the monolayer to carrier densities of ($7.2 \pm 0.8$) $\times$ $10^{13} \textrm{cm}^{-2}$, by electrically gating the TMD using an ionic liquid. We show strong electro-refractive response in monolayer tungsten disulphide (WS$_2$) at NIR wavelengths by measuring a large change in the real part of refractive index $\Delta$n = $0.53$, with only a minimal change in the imaginary part $\Delta$k = $0.004$. The doping induced phase change ($\Delta$n), compared to the induced absorption ($\Delta$k) measured for WS$_2$ ($\Delta$n/$\Delta$k $\sim 125$), a key metric for photonics, is an order of magnitude higher than the $\Delta$n/$\Delta$k for bulk materials like silicon ($\Delta$n/$\Delta$k $\sim 10$), making it ideal for various photonic applications. We further utilize this strong tunable effect to demonstrate an electrostatically gated SiN-WS$_2$ phase modulator using a WS$_2$-HfO$_2$ (Hafnia)-ITO (Indium Tin Oxide) capacitive configuration, that achieves a phase modulation efficiency (V$_\pi$L) of 0.8 V $\cdot$ cm with a RC limited bandwidth of 0.3 GHz.

Chiral Coupling of Valley Excitons and Light through Photonic Spin–Orbit Interactions

AbstractSpintronics employs the spin of electrons to encode information. Akin to spintronics, valleytronics exploits the valley as pseudospin‐carrying controllable binary information. 2D transition metal dichalcogenides (TMDCs) have asymmetric +K and −K valleys. The valley pseudospins of these materials can be manipulated by selective pumping, giving rise to valley‐dependent circularly polarized photoluminescence. The photonic spin–orbit interactions (SOIs) in nanophotonic systems allow the transformation or coupling of optical spin angular momentum to orbital angular momentum of light. Hybridizing 2D TMDC electronic systems with nanophotonic systems can open up an avenue for merging TMDC valley polarization and photonic SOIs to uncover new mechanisms of on‐chip optical information processing and transport. This review focuses on the fundamentals and implications of TMDC valley polarization, photonic SOI effects, and their chiral coupling in hybrid TMDCs–nanophotonic systems. First, the deterministic valley‐dependent optical properties of TMDCs and recent efforts in achieving large valley polarization contrast are reviewed. Then, various SOI effects in nanophotonic systems and their physical mechanisms are summarized. At the end, recent demonstrations of chiral coupling between TMDC valley excitons and light through spin‐direction locking at hybrid interfaces are highlighted.

Ultrafast time-resolved investigations of excitons and biexcitons at room temperature in layered WS2

Strong light-matter interactions in layered transition metal dichalcogenides (TMDs) open up vivid possibilities for novel excitonic quasiparticle-based devices. The optical properties of TMDs are dominated mostly by the tightly bound excitons and more complex quasiparticles, the biexcitons. Instead of physically exfoliated monolayers, the solvent-mediated chemical exfoliation of these 2D crystals is a cost-effective, large-scale production method suitable for substantial practical implications. Here, we explore the ultrafast excitonic phenomena in layered WS2 (mono-to-quad) dispersion using broadband (350–750 nm) femtosecond pump-probe spectroscopy at room temperature (300 K) which are inaccessible to the steady-state absorption or emission spectroscopy. The transient absorption spectra (TAS) suggest that the mono-to-quad layered dispersion of WS2 has similar spectral features as monolayer WS2 in terms of saturation absorptions (SA) and excited state absorptions (ESA). Similar to monolayer TMDs, we are able to identify excitons and biexcitons in multi-layered 2D stratum of WS2 as well as calculate the biexciton binding energies ( 69 meV and 66 meV), which are in excellent agreement with earlier theoretical predictions. Furthermore, using many-body physics, we demonstrate that the excitons in layered WS2 behave like Wannier–Mott excitons and explain their origins via first-principles calculations. Our detailed time-resolved investigation provides ultrafast radiative and non-radiative lifetimes of the excitons and biexcitons in layered WS2. Indeed, our results unravel the complex optical response of layered TMDs, which should lead to numerous technological applications for developing excitonic quasiparticle-based valleytronic devices and ultrafast biexciton lasers at room temperature.

Controllable, Wide-Ranging n-Doping and p-Doping of Monolayer Group 6 Transition-Metal Disulfides and Diselenides.

Developing processes to controllably dope transition-metal dichalcogenides (TMDs) is critical for optical and electrical applications. Here, molecular reductants and oxidants are introduced onto monolayer TMDs, specifically MoS2 , WS2 , MoSe2 , and WSe2 . Doping is achieved by exposing the TMD surface to solutions of pentamethylrhodocene dimer as the reductant (n-dopant) and "Magic Blue," [N(C6 H4 -p-Br)3 ]SbCl6 , as the oxidant (p-dopant). Current-voltage characteristics of field-effect transistors show that, regardless of their initial transport behavior, all four TMDs can be used in either p- or n-channel devices when appropriately doped. The extent of doping can be controlled by varying the concentration of dopant solutions and treatment time, and, in some cases, both nondegenerate and degenerate regimes are accessible. For all four TMD materials, the photoluminescence intensity; for all four materials the PL intensity is enhanced with p-doping but reduced with n-doping. Raman and X-ray photoelectron spectroscopy (XPS) also provide insight into the underlying physical mechanism by which the molecular dopants react with the monolayer. Estimates of changes of carrier density from electrical, PL, and XPS results are compared. Overall a simple and effective route to tailor the electrical and optical properties of TMDs is demonstrated.

Correlatively Dependent Lattice and Electronic Structural Evolutions in Compressed Monolayer Tungsten Disulfide.

Transition-metal dichalcogenides (TMDs) are promising materials for optoelectronic devices. Their lattice and electronic structural evolutions under high strain conditions and their relations remain open questions. We exert pressure on WS2 monolayers on different substrates, namely, Si/SiO2 substrate and diamond anvil surface up to ∼25 GPa. Structural distortions in various degree are disclosed based on the emergence of Raman-inactive B mode. Splits of out-of-plane B and A1' modes are only observed on Si/SiO2 substrate due to extra strain imported from volume decrease in Si and corrugation of SiO2 surface, and its photoluminescence (PL) quenches quickly because of decreased K-K transition by conspicuous distortion of Brillouin zone. While diamond anvil surface provides better hydrostatic environment, combined analysis of PL and absorption proves that pressure effectively tunes PL emission energy and enhances Coulomb interactions. Knowledge of these distinct pressure tunable characteristics of monolayer WS2 improves further understanding of structural and optical properties of TMDs.

Optical Spectroscopies of Lithium-Intercalated Compounds

AbstractLayered compounds are known to form lithium intercalation complexes as electron donor systems. A charge transfer which can strongly affect the electronic properties of the host lattice, and a change of preferential crystallographic parameters without destruction of the original structure are the main effects occuring during intercalation. Optical spectroscopies such as Raman scattering, far-infrared reflectivity, absorption measurements and photoluminescence have been carried out for the study of electronic and structural modifications. Upon lithium intercalation, lattice dynamics and electronic band structure change in numerous layered compounds. The optical properties of transition-metal dichalcogenides, non-transition metal chalcogenides and transition-metal oxides are presented and discussed with the aim of a better understanding of the intercalation process and establish some guide lines for improving the performances of these materials in their most important applications.