Composition-Tunable Synthesis of Large-Scale Mo_1–<i>x</i>W_<i>x</i>S₂ Alloys with Enhanced Photoluminescence

Alloying two-dimensional transition metal dichalcogenides (2D TMDs) is a promising avenue for band gap engineering. In addition, developing a scalable synthesis process is essential for the practical application of these alloys with tunable band gaps in optoelectronic devices. Here, we report the synthesis of optically uniform and scalable single-layer Mo_1–<i>x</i>W_<i>x</i>S₂ alloys by a two-step chemical vapor deposition (CVD) method followed by a laser thinning process. The amount of W content (<i>x</i>) in the Mo_1–<i>x</i>W_<i>x</i>S₂ alloy is systemically controlled by the co-sputtering technique. The post-laser process allows layer-by-layer thinning of the Mo_1–<i>x</i>W_<i>x</i>S₂ alloys down to a single-layer; such a layer exhibits tunable properties with the optical band gap ranging from 1.871 to 1.971 eV with variation in the W content, <i>x</i> = 0 to 1. Moreover, the predominant exciton complexes, trions, are transitioned to neutral excitons with increasing W concentration; this is attributed to the decrease in excessive charge carriers with an increase in the W content of the alloy. Photoluminescence (PL) and Raman mapping analyses suggest that the laser-thinning of the Mo_1–<i>x</i>W_<i>x</i>S₂ alloys is a self-limiting process caused by heat dissipation to the substrate, resulting in spatially uniform single-layer Mo_1–<i>x</i>W_<i>x</i>S₂ alloy films. Our findings present a promising path for the fabrication of large-scale single-layer 2D TMD alloys and the design of versatile optoelectronic devices

Observation of Charge Transfer in Heterostructures Composed of MoSe₂ Quantum Dots and a Monolayer of MoS₂ or WSe₂

Monolayer transition metal dichalcogenides (TMDs) are atomically thin semiconductor films that are ideal platforms for the study and engineering of quantum heterostructures for optoelectronic applications. We present a simple method for the fabrication of TMD heterostructures containing MoSe₂ quantum dots (QDs) and a MoS₂ or WSe₂ monolayer. The strong modification of photoluminescence and Raman spectra that includes the quenching of MoSe₂ QDs and the varied spectral weights of trions for the MoS₂ and WSe₂ monolayers were observed, suggesting the charge transfer occurring in these TMD heterostructures. Such optically active heterostructures, which can be conveniently fabricated by dispersing TMD QDs onto TMD monolayers, are likely to have various nanophotonic applications because of their versatile and controllable properties

Impeding Exciton–Exciton Annihilation in Monolayer WS₂ by Laser Irradiation

Monolayer (1L) transition metal dichalcogenides (TMDs) are two-dimensional direct-bandgap semiconductors with promising applications of quantum light emitters. Recent studies have shown that intrinsically low quantum yields (QYs) of 1L-TMDs can be greatly improved by chemical treatments. However, nonradiative exciton–exciton annihilation (EEA) appears to significantly limit light emission of 1L-TMDs at a nominal density of photoexcited excitons due to strong Coulomb interaction. Here we show that the EEA rate constant (γ) can be reduced by laser irradiation treatment in mechanically exfoliated monolayer tungsten disulfide (1L-WS₂), causing significantly improved light emission at the saturating optical pumping level. Time-resolved photoluminescence (PL) measurements showed that γ reduced from 0.66 ± 0.15 cm²/s to 0.20 ± 0.05 cm²/s simply using our laser irradiation. The laser-irradiated region exhibited lower PL response at low excitation levels, however at the high excitation level displayed 3× higher PL intensity and QY than the region without laser treatment. The shorter PL lifetime and lower PL response at low excitation levels suggested that laser irradiation increased the density of sulfur vacancies of 1L-WS₂, but we attribute these induced defects, adsorbed by oxygen in air, to the origin for reduced EEA by hindering exciton diffusion. Our laser irradiation was likewise effective for reducing EEA and increasing PL of chemically treated 1L-WS₂ with a high QY, exhibiting the general applicability of our method. Our results suggest that exciton–exciton interaction in 1L-TMDs may be conveniently controlled by the laser treatment, which may lead to unsaturated exciton emission at high excitation levels

Local Strain Induced Band Gap Modulation and Photoluminescence Enhancement of Multilayer Transition Metal Dichalcogenides

The photocarrier relaxation between direct and indirect band gaps along the high symmetry K−Γ line in the Brillion zone reveals interesting electronic properties of the transition metal dichalcogenides (TMDs) multilayer films. In this study, we reported on the local strain engineering and tuning of an electronic band structure of TMDs multilayer films along the K−Γ line by artificially creating one-dimensional wrinkle structures. Significant photoluminescence (PL) intensity enhancement in conjunction with continuously tuned optical energy gaps was recorded at the high strain regions. A direct optical band gap along K–K points and an indirect optical gap along Γ–K points measured from the PL spectra of multilayer samples monotonically decreased as the strain increased, while the indirect band gap along Λ–Γ was unaffected owing to the same level of local strain in the range of 0%–2%. The experimental results of band gap tuning were in agreement with the density functional theory calculation results. Local strain modified the band structure in which K-conduction band valley (CBV) was aligned below the Λ-CBV, and this explained the observed local PL enhancement that made the material indirect via the K−Γ transition. The study also reported experimental evidence for the funneling of photogenerated excitons toward regions of a higher strain at the top of the wrinkle geometry

Atomic Observation of Filling Vacancies in Monolayer Transition Metal Sulfides by Chemically Sourced Sulfur Atoms

Chemical treatment using bis­(trifluoromethane) sulfonimide (TFSI) was shown to be particularly effective for increasing the photoluminescence (PL) of monolayer (1L) MoS₂, suggesting a convenient method for overcoming the intrinsically low quantum yield of this material. However, the underlying atomic mechanism of the PL enhancement has remained elusive. Here, we report the microscopic origin of the defect healing observed in TFSI-treated 1L-MoS₂ through a correlative combination of optical characterization and atomic-scale scanning transmission electron microscopy, which showed that most of the sulfur vacancies were directly repaired by the extrinsic sulfur atoms produced from the dissociation of TFSI, concurrently resulting in a significant PL enhancement. Density functional theory calculations confirmed that the reactive sulfur dioxide molecules that dissociated from TFSI can be reduced to sulfur and oxygen gas at the vacancy site to form strongly bound SMo. Our results reveal how defect-mediated nonradiative recombination can be effectively eliminated by a simple chemical treatment method, thereby advancing the practical applications of monolayer semiconductors

Enhanced Light Emission from Monolayer Semiconductors by Forming Heterostructures with ZnO Thin Films

Monolayer transition-metal dichalcogenides (1L-TMDs) are atomically thin direct band gap semiconductors, from which the emission of light is determined by optical transitions of exciton complexes such as neutral excitons and trions. While the quantum yields of 1L-TMDs are quite low, the ability to control the populations of exciton complexes in 1L-TMDs through various doping processes is an interesting advantage, and provides ample possibilities for engineering the optical properties of these semiconductor monolayers. Here we demonstrate a simple method of controlling the populations of excitons and trions to enhance the light emission of 1L-TMDs by having them form heterostructures with ZnO thin films (TFs). 1Ls of MoS₂ or MoSe₂ showed up to 17-fold increases in photoluminescence (PL) when they were placed on ∼50 nm thick ZnO TFs. This enhancement of the PL was due to charge exchanges occurring through the 1L-TMD/ZnO interface. The PL enhancements and changes in the PL spectra of the 1L-TMDs were greater when the 1L-TMD/ZnO heterostructures were subjected to 355 nm wavelength laser excitation than when they were excited with a 514 nm wavelength laser, which we attributed to the onset of energy transfer by photoexcited excitons and/or the additional p-doping by photoexcited holes in ZnO. The p-doping phenomenon and the enhanced light emission of 1L-TMD/ZnO heterostructures were unambiguously visualized in spatially resolved PL and Raman spectral maps. Our approach using the 1L-TMD/ZnO TF heterostructure suggests that a rich variety of options for engineering the optical properties of 1L-TMDs may be made available by carrying out simple and intuitive manipulations of exciton complexes, and these endeavors may yield practical applications for 1L-TMDs in nanophotonic devices