Two-dimensional (2D) transition metal dichalcogenides (TMDs), like MoS2, have unique electronic and optical properties, which can further be tuned using ion bombardment and post-synthesis ion-beam mediated methods combined with exposure of the irradiated sample to precursor gases. The optimization of these techniques requires a complete understanding of the response of 2D TMDs to ion irradiation, which is affected by the reduced dimensionality of the system. By combining analytical potential molecular dynamics with first-principles calculations, we study the production of defects in free-standing MoS2 sheets under noble gas ion irradiation for a wide range of ion energies when nuclear stopping dominates, and assess the probabilities for different defects to appear. We show that depending on the incident angle, ion type and energy, sulfur atoms can be sputtered away predominantly from the top or bottom layers, creating unique opportunities for engineering mixed MoSX compounds where X are chemical elements from group V or VII. We study the electronic structure of such systems, demonstrate that they can be metals, and finally discuss how metal/semiconductor/metal junctions, which exhibit negative differential resistance, can be designed using focused ion beams combined with the exposure of the system to fluorine.

The development of an active, earth-abundant, and inexpensive catalyst for the oxygen evolution reaction (OER) is highly desirable but remains a great challenge. Here, by combining experiments and first-principles calculations, we demonstrate that MoS2 quantum dots (MSQDs) are efficient materials for the OER. We use a simple route for the synthesis of MSQDs from a single precursor in aqueous medium, avoiding the formation of unwanted carbon quantum dots (CQDs). The as-synthesized MSQDs exhibit higher OER activity with a lower Tafel slope in comparison to that for the state of the art catalyst IrO2/C. The potential cycling of the MSQDs activates the surface and improves the OER catalytic properties. Density functional theory calculations reveal that MSQD vertices are reactive and the vacancies at the edges also promote the reaction, which indicates that the small flakes with defects at the edges are efficient for the OER. The presence of CQDs affects the adsorption of reaction intermediates and dramatically suppresses the OER performance of the MSQDs. Our theoretical and experimental findings provide important insights into the synthesis process of MSQDs and their catalytic properties and suggest promising routes to tailoring the performance of the catalysts for OER applications.

Production of defects under electron irradiation in a transmission electron microscope (TEM) due to inelastic effects has been reported for various materials, but the microscopic mechanism of damage development in periodic solids through this channel is not fully understood. We employ non-adiabatic Ehrenfest, along with constrained density functional theory molecular dynamics, and simulate defect production in two-dimensional MoS2 under electron beam. We show that when excitations are present in the electronic system, formation of vacancies through ballistic energy transfer is possible at electron energies which are much lower than the knock-on threshold for the ground state. We further carry out TEM experiments on single layers of MoS2 at electron voltages in the range of 20–80 kV and demonstrate that indeed there is an additional channel for defect production. The mechanism involving a combination of the knock-on damage and electronic excitations we propose is relevant to other bulk and nanostructured semiconducting materials.

Focused ion beams perfectly suit for patterning two-dimensional (2D) materials, but the optimization of irradiation parameters requires full microscopic understanding of defect production mechanisms. In contrast to freestanding 2D systems, the details of damage creation in supported 2D materials are not fully understood, whereas the majority of experiments have been carried out for 2D targets deposited on substrates. Here, we suggest a universal and computationally efficient scheme to model the irradiation of supported 2D materials, which combines analytical potential molecular dynamics with Monte Carlo simulations and makes it possible to independently assess the contributions to the damage from backscattered ions and atoms sputtered from the substrate. Using the scheme, we study the defect production in graphene and MoS sheets, which are the two most important and wide-spread 2D materials, deposited on a SiO substrate. For helium and neon ions with a wide range of initial ion energies including those used in a commercial helium ion microscope (HIM), we demonstrate that depending on the ion energy and mass, the defect production in 2D systems can be dominated by backscattered ions and sputtered substrate atoms rather than by the direct ion impacts and that the amount of damage in 2D materials heavily depends on whether a substrate is present or not. We also study the factors which limit the spatial resolution of the patterning process. Our results, which agree well with the available experimental data, provide not only insights into defect production but also quantitative information, which can be used for the minimization of damage during imaging in HIM or optimization of the patterning process.

We study the applicability of collisional models for non-Markovian dynamics of open quantum systems. By allowing interactions between the separate environmental degrees of freedom in between collisions we are able to construct a collision model that allows to study quantum memory effects in open system dynamics. We also discuss the possibility to embed non-Markovian collision model dynamics into Markovian collision model dynamics in an extended state space. As a concrete example we show how using the proposed class of collision models we can discretely model nonMarkovian amplitude damping of a qubit. In the time-continuous limit, we obtain the well-known results for spontaneous decay of a two level system in to a structured zero-temperature reservoir.