Thermal transport in MoS2 from molecular dynamics using different empirical potentials

Thermal properties of molybdenum disulfide (MoS2) have recently attracted attention related to fundamentals of heat propagation in strongly anisotropic materials, and in the context of potential applications to optoelectronics and thermoelectrics. Multiple empirical potentials have been developed for classical molecular dynamics (MD) simulations of this material, but it has been unclear which provides the most realistic results. Here, we calculate lattice thermal conductivity of single- and multilayer pristine MoS2 by employing three different thermal transport MD methods: equilibrium, nonequilibrium, and homogeneous nonequilibrium ones. We mainly use the Graphics Processing Units Molecular Dynamics code for numerical calculations, and the Large-scale Atomic/Molecular Massively Parallel Simulator code for crosschecks. Using different methods and computer codes allows us to verify the consistency of our results and facilitate comparisons with previous studies, where different schemes have been adopted. Our results using variants of the Stillinger-Weber potential are at odds with some previous ones and we analyze the possible origins of the discrepancies in detail. We show that, among the potentials considered here, the reactive empirical bond order (REBO) potential gives the most reasonable predictions of thermal transport properties as compared to experimental data. With the REBO potential, we further find that isotope scattering has only a small effect on thermal conduction in MoS2 and the in-plane thermal conductivity decreases with increasing layer number and saturates beyond about three layers. We identify the REBO potential as a transferable empirical potential for MD simulations of MoS2 which can be used to study thermal transport properties in more complicated situations such as in systems containing defects or engineered nanoscale features. This work establishes a firm foundation for understanding heat transport properties of MoS2 using MD simulations

Single- and Multilayers of Alkali Metal Atoms inside Graphene/MoS₂ Heterostructures: A Systematic First-Principles Study

Stacking various 2D materials in van der Waals heterostructures is a novel approach to design new systems, which can host alkali metal (AM) atoms to tune their electronic properties or store energy. Using state-of-the-art first-principles calculations, we systematically study the intercalation of the most widespread AMs (Li, Na, and K) into a graphene/MoS2 heterostructure. Contrary to the previous work on the intercalation of AMs into various heterostructures based on 2D materials, we consider not only single-, but also multi-layer configurations of AM atoms. We assess the intercalation energetics for various concentrations of AM atoms, calculate charge transfer from AM atoms to the host system, and show that although intercalation of AMs as a single layer is energetically preferable, multi-layer configurations can exist at high concentrations of AM atoms. We further demonstrate that the transition of the MoS2 layer from the H to T′ phase is possible upon Li intercalation, but not for Na or K. Our findings should help to better understand the behavior of heterostructures upon AM atom intercalation and may stimulate further experiments aimed at the tailoring of heterostructure properties and increasing the capacity of anode materials in AM ion batteries

Semiconductor to Metal to Half-Metal Transition in Pt-Embedded Zigzag Graphene Nanoribbons

The electronic and magnetic properties of Pt-embedded zigzag graphene nanoribbons (Pt–ZGNRs) are investigated using density-functional theory calculations. It is found that Pt–ZGNRs exhibit a semiconductor–metal–half-metal transition as the position of Pt substitutional impurities in the ribbon changes from the center to edge sites. This behavior can be attributed to the interaction between Pt impurities and edge states of ZGNRs, which governs the electron occupation of the edge states. The transition always occurs independent of ribbon width. However, Pt impurity concentration is important for obtaining this transition. Our results demonstrate that Pt–ZGNRs can be used as versatile electronic devices

Solid-State Growth of One- and Two-Dimensional Silica Structures on Metal Surfaces

Crystalline or vitreous silica layers are new two-dimensional (2D) nanomaterials, which have shown surprising structural similarities with graphene and promise interesting properties. In this study, one-dimensional (1D) silica structures are formed on metal surfaces. In an in situ electron microscopy experiment it is demonstrated that lines of silica grow along step edges on metal surfaces. The growth of 1D silica occurs in competition with the formation of 2D networks and adopts the crystalline symmetry of the metal surface. Transformations between 1D and 2D structures are observed. Density functional theory calculations show that 1D silica is energetically favorable over 2D structures if surface steps prevail on the substrate. Our results indicate that lateral heterostructures with interesting properties may be developed on metal substrates

Magnetic State Control of Non-van der Waals 2D Materials by Hydrogenation

Controlling the magnetic state of two-dimensional (2D) materials is crucial for spintronics. By employing data-mining and autonomous density functional theory calculations, we demonstrate the switching of magnetic properties of 2D non-van der Waals materials upon hydrogen passivation. The magnetic configurations are tuned to states with flipped and enhanced moments. For 2D CdTiO3a diamagnetic compound in the pristine casewe observe an onset of ferromagnetism upon hydrogenation. Further investigation of the magnetization density of the pristine and passivated systems provides a detailed analysis of modified local spin symmetries and the emergence of ferromagnetism. Our results indicate that selective surface passivation is a powerful tool for tailoring magnetic properties of nanomaterials, such as non-vdW 2D compounds

Solubility of Boron, Carbon, and Nitrogen in Transition Metals: Getting Insight into Trends from First-Principles Calculations

Efficient chemical vapor deposition synthesis of two-dimensional (2D) materials such as graphene, boron nitride, and mixed BCN systems with tunable band gaps requires precise knowledge of the solubility and mobility of B/C/N atoms in the transition metals (TMs) used as substrates for the growth. Yet, surprisingly little is known about these quantities either from experiments or simulations. Using first-principles calculations, we systematically study the behavior of B/C/N impurity atoms in a wide range of TMs. We compute formation energies of B/C/N interstitials and demonstrate that they exhibit a peculiar but common behavior for TMs in different rows of the periodic table, as experimentally observed for C. Our simulations indicate that this behavior originates from an interplay between the unit cell volume and filling of the d-shell electronic states of the metals. We further assess the vibrational and electronic entropic contributions to the solubility, as well as the role of anharmonic effects. Finally, we calculate the migration barriers, an important parameter in the growth kinetics. Our results not only unravel the fundamental behavior of interstitials in TMs but also provide a large body of reference data, which can be used for optimizing the growth of 2D BCN materials

Experimental Observation of Boron Nitride Chains

We report the formation and characterization of boron nitride atomic chains. The chains were made from hexagonal boron nitride sheets using the electron beam inside a transmission electron microscope. We find that the stability and lifetime of the chains are significantly improved when they are supported by another boron nitride layer. With the help of first-principles calculations, we prove the heteroatomic structure of the chains and determine their mechanical and electronic properties. Our study completes the analogy between various boron nitride and carbon polymorphs, in accordance with earlier theoretical predictions

<i>In Situ</i> Growth of Cellular Two-Dimensional Silicon Oxide on Metal Substrates

Crystalline hexagonally ordered silicon oxide layers with a thickness of less than a nanometer are grown on transition metal surfaces in an <i>in situ</i> electron microscopy experiment. The nucleation and growth of silica bilayers and monolayers, which represent the thinnest possible ordered structures of silicon oxide, are monitored in real time. The emerging layers show structural defects reminiscent of those in graphene and can also be vitreous. First-principles calculations provide atomistic insight into the energetics of the growth process. The interplay between the gain in silica–metal interaction energy due to their epitaxial match and energy loss associated with the mechanical strain of the silica network is addressed. The results of calculations indicate that both ordered and vitreous mono/bilayer structures are possible, so that the actual morphology of the layer is defined by the kinetics of the growth process

<i>In Situ</i> Growth of Cellular Two-Dimensional Silicon Oxide on Metal Substrates

Crystalline hexagonally ordered silicon oxide layers with a thickness of less than a nanometer are grown on transition metal surfaces in an <i>in situ</i> electron microscopy experiment. The nucleation and growth of silica bilayers and monolayers, which represent the thinnest possible ordered structures of silicon oxide, are monitored in real time. The emerging layers show structural defects reminiscent of those in graphene and can also be vitreous. First-principles calculations provide atomistic insight into the energetics of the growth process. The interplay between the gain in silica–metal interaction energy due to their epitaxial match and energy loss associated with the mechanical strain of the silica network is addressed. The results of calculations indicate that both ordered and vitreous mono/bilayer structures are possible, so that the actual morphology of the layer is defined by the kinetics of the growth process

Formation of In-Plane Semiconductor–Metal Contacts in 2D Platinum Telluride by Converting PtTe₂ to Pt₂Te₂

Monolayer PtTe2 is a narrow gap semiconductor while Pt2Te2 is a metal. Here we show that the former can be transformed into the latter by reaction with vapor-deposited Pt atoms. The transformation occurs by nucleating the Pt2Te2 phase within PtTe2 islands, so that a metal–semiconductor junction is formed. A flat band structure is found with the Fermi level of the metal aligning with that of the intrinsically p-doped PtTe2. This is achieved by an interface dipole that accommodates the ∼0.2 eV shift in the work functions of the two materials. First-principles calculations indicate that the origin of the interface dipole is the atomic scale charge redistributions at the heterojunction. The demonstrated compositional phase transformation of a 2D semiconductor into a 2D metal is a promising approach for making in-plane metal contacts that are required for efficient charge injection and is of particular interest for semiconductors with large spin–orbit coupling, like PtTe2