Two-dimensional (2D) transition metal dichalcogenides have emerged as a promising material system for optoelectronic applications, but their primary figure of merit, the room-temperature photoluminescence quantum yield (QY), is extremely low. The prototypical 2D material molybdenum disulfide (MoS2) is reported to have a maximum QY of 0.6%, which indicates a considerable defect density. Here we report on an air-stable, solution-based chemical treatment by an organic superacid, which uniformly enhances the photoluminescence and minority carrier lifetime of MoS2 monolayers by more than two orders of magnitude. The treatment eliminates defect-mediated nonradiative recombination, thus resulting in a final QY of more than 95%, with a longest-observed lifetime of 10.8 ± 0.6 nanoseconds. Our ability to obtain optoelectronic monolayers with near-perfect properties opens the door for the development of highly efficient light-emitting diodes, lasers, and solar cells based on 2D materials.

Covalent functionalization of transition metal dichalcogenides (TMDCs) is investigated for air-stable chemical doping. Specifically, p-doping of WSe(2) via NOx chemisorption at 150 °C is explored, with the hole concentration tuned by reaction time. Synchrotron based soft X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) depict the formation of various WSe(2-x-y)O(x)N(y) species both on the surface and interface between layers upon chemisorption reaction. Ab initio simulations corroborate our spectroscopy results in identifying the energetically favorable complexes, and predicting WSe(2):NO at the Se vacancy sites as the predominant dopant species. A maximum hole concentration of ∼ 10(19) cm(-3) is obtained from XPS and electrical measurements, which is found to be independent of WSe(2) thickness. This degenerate doping level facilitates 5 orders of magnitude reduction in contact resistance between Pd, a common p-type contact metal, and WSe(2). More generally, the work presents a platform for manipulating the electrical properties and band structure of TMDCs using covalent functionalization.

CrCl3 is a layered insulator that undergoes a crystallographic phase transition below room temperature and orders antiferromagnetically at low temperature. Weak van der Waals bonding between the layers and ferromagnetic in-plane magnetic order make it a promising material for obtaining atomically thin magnets and creating van der Waals heterostructures. In this work we have grown crystals of CrCl3, revisited the structural and thermodynamic properties of the bulk material, and explored mechanical exfoliation of the crystals. We find two distinct anomalies in the heat capacity at 14 and 17 K confirming that the magnetic order develops in two stages on cooling, with ferromagnetic correlations forming before long range antiferromagnetic order develops between them. This scenario is supported by magnetization data. A magnetic phase diagram is constructed from the heat capacity and magnetization results. We also find an anomaly in the magnetic susceptibility at the crystallographic phase transition, indicating some coupling between the magnetism and the lattice. First principles calculations accounting for van der Waals interactions also indicate spin-lattice coupling, and find multiple nearly degenerate crystallographic and magnetic structures consistent with the experimental observations. Finally, we demonstrate that monolayer and few-layer CrCl3 specimens can be produced from the bulk crystals by exfoliation, providing a path for the study of heterostructures and magnetism in ultrathin crystals down to the monolayer limit.

In this work, surface oxidation of monolayer MoS 2 (one of the representative semiconductors in transition-metal dichalcogenides) has been investigated using density functional theory method. Oxygen interaction with MoS 2 shows that, thermodynamically, the surface tends to be oxidized. However, the dissociative absorption of molecular oxygen on the MoS 2 surface is kinetically limited due to the large energy barrier at low temperature. This finding elucidates the air stability of MoS 2 surface in the atmosphere. Furthermore, the presence of defects significantly alters the surface stability and adsorption mechanisms. The electronic properties of the oxidized surface have been examined as a function of oxygen adsorption and coverage as well as substitutional impurities. Our results on energetics and kinetics of oxygen interaction with the MoS 2 monolayer are useful for the understanding of surface oxidation, air stability, and electronic properties of transition-metal dichalcogenides at the atomic scale. V

Semiconductors with a moderate bandgap have enabled modern electronic device technology, and the current scaling trends down to nanometer scale have introduced two-dimensional (2D) semiconductors. The bandgap of a semiconductor has been an intrinsic property independent of the environments and determined fundamental semiconductor device characteristics. In contrast to bulk semiconductors, we demonstrate that an atomically thin two-dimensional semiconductor has a bandgap with strong dependence on dielectric environments. Specifically, monolayer MoS2 bandgap is shown to change from 2.8 eV to 1.9 eV by dielectric environment. Utilizing the bandgap modulation property, a tunable bandgap transistor, which can be in general made of a two-dimensional semiconductor, is proposed.

Monolayer MoS2 is a direct band gap semiconductor which has been recently investigated for low-power field effect transistors. The initial studies have shown promising performance, including a high on/off current ratio and carrier mobility with a high-κ gate dielectric. However, the performance of these devices strongly depends on the crystalline quality and defect morphology of the monolayers. In order to obtain a detailed understanding of the MoS2 electronic device properties, we examine possible defect structures and their impact on the MoS2 monolayer electronic properties, using density functional theory in combination with scanning tunneling microscopy to identify the nature of the most likely defects. Quantitative understanding based on a detailed knowledge of the atomic and electronic structures will facilitate the search of suitable defect passivation techniques. Our results show that S adatoms are the most energetically favorable type of defect and that S vacancies are energetically more favorable than Mo vacancies. This approach may be extended to other transition-metal dichalcogenides (TMDs), thus providing useful insights to optimize TMD-based electronic devices.

Metal-insulator transitions in low-dimensional materials under ambient conditions are rare and worth pursuing due to their intriguing physics and rich device applications. Monolayer MoTe2 and WTe2 are distinguished from other TMDs by the existence of an exceptional semimetallic distorted octahedral structure (T') with a quite small energy difference from the semiconducting H phase. In the process of transition metal alloying, an equal stability point of the H and the T' phase is observed in the formation energy diagram of monolayer WxMo1-xTe2. This thermodynamically driven phase transition enables a controlled synthesis of the desired phase (H or T') of monolayer WxMo1-xTe2 using a growth method such as chemical vapor deposition (CVD) and molecular beam epitaxy (MBE). Furthermore, charge mediation, as a more feasible method, is found to make the T' phase more stable than the H phase and induce a phase transition from the H phase (semiconducting) to the T' phase (semimetallic) in monolayer WxMo1-xTe2 alloy. This suggests that a dynamic metal-insulator phase transition can be induced, which can be exploited for rich phase transition applications in two-dimensional nanoelectronics.

Defects formed during chemical vapor deposition (CVD) of two‐dimensional (2D) transition metal dichalcogenides (TMDs) currently limit their quality and optoelectronic properties. Effective synthesis and processing strategies to suppress defects and enhance the quality of 2D TMDs are urgently needed to enable next generation optoelectronic devices. In this work, isoelectronic doping is presented as a new strategy to form stable alloys and suppress defects and enhance photoluminescence (PL) in CVD‐grown TMD monolayers. The isoelectronic substitution of W atoms for Mo atoms in CVD‐grown monolayers of Mo1– x W x Se2 (0 < x < 0.18) is shown to effectively suppress Se vacancy concentration by 50% compared to those found in pristine MoSe2 monolayers, resulting in a decrease in defect‐mediated nonradiative recombination, ≈10 times more intense PL, and an increase in the carrier lifetime by a factor of 3. Theoretical predictions reveal that isoelectronic W alloying to form Mo1– x W x Se2 monolayers raises the energy of deep level defects in MoSe2 to enable faster quenching, which is confirmed by low temperature (4–125 K) PL from defect‐related localized states. Isoelectronic substitution therefore appears to be a promising synthetic method to control the heterogeneity of 2D TMDs to realize the scalable production of high performance optoelectronic and electronic devices.