We investigate the hydrogen evolution activity in the dark and under illumination above the band gap of individual mono-, bi- and few-layer (bulk) MoS2 flakes. We demonstrate that the electrocatalytic activity of 2H-MoS2 immersed in 1 M H2SO4 increases with decreasing number of layers. For monolayers, we observe the highest exchange current density, which is one magnitude larger than in the bulk case. The onset potential scales with the number of layers, which is consistent with a previous report, suggesting that hopping transport across inter-layer barriers within the MoS2 flakes is responsible for this scaling. A specially designed micro-sized catalytic cell enables us to investigate individual MoS2 flakes with well-known geometry and edge-to-surface ratio. Taking these geometric parameters into account, we tentatively attribute the catalytic activity mainly to sulfur vacancies in the basal planes acting as active sites. The associated turn over frequencies (TOF) for mono- and bi-layer MoS2 yield values higher than 103 s−1 at an overpotential of −0.2 V vs. RHE. In view of light driven hydrogen evolution as a means of solar energy conversion, we investigate the photocatalytic activity of few-layer MoS2 under white light illumination.

Structuring materials with atomic precision is the ultimate goal of nanotechnology and is becoming increasingly relevant as an enabling technology for quantum electronics/spintronics and quantum photonics. Here, we create atomic defects in monolayer MoS₂ by helium ion (He-ion) beam lithography with a spatial fidelity approaching the single-atom limit in all three dimensions. Using low-temperature scanning tunneling microscopy (STM), we confirm the formation of individual point defects in MoS₂ upon He-ion bombardment and show that defects are generated within 9 nm of the incident helium ions. Atom-specific sputtering yields are determined by analyzing the type and occurrence of defects observed in high-resolution STM images and compared with Monte Carlo simulations. Both theory and experiment indicate that the He-ion bombardment predominantly generates sulfur vacancies.

For two-dimensional (2D) layered semiconductors, control over atomic defects and understanding of their electronic and optical functionality represent major challenges towards developing a mature semiconductor technology using such materials. Here, we correlate generation, optical spectroscopy, atomic resolution imaging, and ab initio theory of chalcogen vacancies in monolayer MoS₂. Chalcogen vacancies are selectively generated by in-vacuo annealing, but also focused ion beam exposure. The defect generation rate, atomic imaging and the optical signatures support this claim. We discriminate the narrow linewidth photoluminescence signatures of vacancies, resulting predominantly from localized defect orbitals, from broad luminescence features in the same spectral range, resulting from adsorbates. Vacancies can be patterned with a precision below 10 nm by ion beams, show single photon emission, and open the possibility for advanced defect engineering of 2D semiconductors at the ultimate scale.

Integration of semiconducting transition metal dichalcogenides (TMDs) into functional optoelectronic circuitries requires an understanding of the charge transfer across the interface between the TMD and the contacting material. Here, we use spatially resolved photocurrent microscopy to demonstrate electronic uniformity at the epitaxial graphene/molybdenum disulfide (EG/MoS₂) interface. A 10× larger photocurrent is extracted at the EG/MoS₂ interface when compared to the metal (Ti/Au)/MoS₂ interface. This is supported by semi-local density functional theory (DFT), which predicts the Schottky barrier at the EG/MoS₂ interface to be ∼2× lower than that at Ti/MoS₂. We provide a direct visualization of a 2D material Schottky barrier through combination of angle-resolved photoemission spectroscopy with spatial resolution selected to be ∼300 nm (nano-ARPES) and DFT calculations. A bending of ∼500 meV over a length scale of ∼2-3 μm in the valence band maximum of MoS₂ is observed via nano-ARPES. We explicate a correlation between experimental demonstration and theoretical predictions of barriers at graphene/TMD interfaces. Spatially resolved photocurrent mapping allows for directly visualizing the uniformity of built-in electric fields at heterostructure interfaces, providing a guide for microscopic engineering of charge transport across heterointerfaces. This simple probe-based technique also speaks directly to the 2D synthesis community to elucidate electronic uniformity at domain boundaries alongside morphological uniformity over large areas.