Direct Observation of Magnon-Phonon Strong Coupling in Two-Dimensional Antiferromagnet at High Magnetic Fields.

We report the direct observation of strong coupling between magnons and phonons in a two-dimensional antiferromagnetic semiconductor FePS_{3}, via magneto-Raman spectroscopy at magnetic fields up to 30 Tesla. A Raman-active magnon at 121 cm^{-1} is identified through Zeeman splitting in an applied magnetic field. At a field-driven resonance with a nearby phonon mode, a hybridized magnon-phonon quasiparticle is formed due to strong coupling between the two modes. We develop a microscopic model of the strong coupling in the two-dimensional magnetic lattice, which enables us to elucidate the nature of the emergent quasiparticle. Our polarized Raman results directly show that the magnons transfer their spin angular momentum to the phonons and generate phonon spin through the strong coupling.

First-principles study of the lattice dynamics of Sb2S3.

We present a lattice dynamics study of orthorhombic antimony sulphide (Sb2S3) obtained using density-functional calculations in conjunction with the supercell force-constant method. The effect of Born effective charges is taken into account using a mixed-space approach, resulting in the splitting of longitudinal and transverse optical (LO-TO) phonon branches near the zone center. Zone-center frequencies agree well with Raman scattering experiments. Due to the slow decay of the interatomic force constants (IFC), a minimal 2 × 4 × 2 supercell (Pnma setting) with 320 atoms is crucial for an accurate determination of the dispersion relations. Smaller supercells result in artificial acoustic phonon softening and unphysical lifting of degeneracies along high symmetry directions. We propose a scheme to investigate the convergence of the IFC with respect to the supercell sizes. The phonon softening can be attributed to the periodic images that affect the accuracy of the force constants, and the truncation of long-ranged forces. The commensuration of the q-vectors with the supercell size is crucial to preserve degeneracies in Sb2S3 crystals.

Theoretical study of thermoelectric properties of few-layer MoS2 and WSe2.

Molybdenum disulfide (MoS2) and tungsten diselenide (WSe2) are prototypical layered two-dimensional transition metal dichalcogenide materials, with each layer consisting of three atomic planes. We refer to each layer as a trilayer (TL). We study the thermoelectric properties of 1-4TL MoS2 and WSe2 using a ballistic transport approach based on the electronic band structures and phonon dispersions obtained from first-principles calculations. Our results show that the thickness dependence of the thermoelectric properties is different under n-type and p-type doping conditions. Defining ZT1st peak as the first peak in the thermoelectric figure of merit ZT as doping levels increase from zero at 300 K, we found that ZT1st peak decreases as the number of layers increases for MoS2, with the exception of 2TL in n-type doping, which has a slightly higher value than 1TL. However, for WSe2, 2TL has the largest ZT1st peak in both n-type and p-type doping, with a ZT1st peak value larger than 1 for n-type WSe2. At high temperatures (T > 300 K), ZT1st peak dramatically increases when the temperature increases, especially for n-type doping. The ZT1st peak of n-type 1TL-MoS2 and 2TL-WSe2 can reach 1.6 and 2.1, respectively.

Interlayer breathing and shear modes in few-trilayer MoS2 and WSe2.

Two-dimensional (2D) layered transition metal dichalcogenides (TMDs) have recently attracted tremendous interest as potential valleytronic and nanoelectronic materials, in addition to being well-known as excellent lubricants in the bulk. The interlayer van der Waals (vdW) coupling and low-frequency phonon modes and how they evolve with the number of layers are important for both the mechanical and the electrical properties of 2D TMDs. Here we uncover the ultralow frequency interlayer breathing and shear modes in few-layer MoS2 and WSe2, prototypical layered TMDs, using both Raman spectroscopy and first principles calculations. Remarkably, the frequencies of these modes can be perfectly described using a simple linear chain model with only nearest-neighbor interactions. We show that the derived in-plane (shear) and out-of-plane (breathing) force constants from experiment remain the same from two-layer 2D crystals to the bulk materials, suggesting that the nanoscale interlayer frictional characteristics of these excellent lubricants should be independent of the number of layers.

Step flow versus mosaic film growth in hexagonal boron nitride.

Many emerging applications of hexagonal boron nitride (h-BN) in graphene-based nanoelectronics require high-quality monolayers as the ultrathin dielectric. Here, the nucleation and growth of h-BN monolayer on Ru(0001) surface are investigated using scanning tunneling microscopy with a view toward understanding the process of defect formation on a strongly interacted interface. In contrast to homoelemental bonding in graphene, the heteroelemental nature of h-BN gives rise to growth fronts with elemental polarity. This can have consequences in the different stages of film growth, from the nucleation of h-BN magic clusters and their sintering to form compact triangular islands to the growth of patchwork mosaic monolayer with a high density of misfit boundaries. The parallel alignment of triangular islands on the same terrace produces translational fault lines when growth fronts merge, while antiparallel alignment of islands on adjacent terraces produces non-bonded fault lines between domains terminated by like atoms. With these insights into the generation of void defects and fault lines at grain boundaries, we demonstrate a strategy to obtain high-quality h-BN monolayer film based on step flow growth.

Strain dependence of the heat transport properties of graphene nanoribbons.

Using a combination of accurate density-functional theory and a nonequilibrium Green's function method, we calculate the ballistic thermal conductance characteristics of tensile-strained armchair (AGNR) and zigzag (ZGNR) edge graphene nanoribbons, with widths between 3 and 50 Å. The optimized lateral lattice constants for AGNRs of different widths display a three-family behavior when the ribbons are grouped according to N modulo 3, where N represents the number of carbon atoms across the width of the ribbon. Two lowest-frequency out-of-plane acoustic modes play a decisive role in increasing the thermal conductance of AGNR-N at low temperatures. At high temperatures the effect of tensile strain is to reduce the thermal conductance of AGNR-N and ZGNR-N. These results could be explained by the changes in force constants in the in-plane and out-of-plane directions with the application of strain. This fundamental atomistic understanding of the heat transport in graphene nanoribbons paves a way to effect changes in their thermal properties via strain at various temperatures.

First-principles study of heat transport properties of graphene nanoribbons.

We use density-functional theory and the nonequilibrium Green's function method as well as phonon dispersion calculations to study the thermal conductance of graphene nanoribbons with armchair and zigzag edges, with and without hydrogen passivation. We find that low-frequency phonon bands of the zigzag ribbons are more dispersive than those of the armchair ribbons and that this difference accounts for the anisotropy in the thermal conductance of graphene nanoribbons. Comparing our results with data on large-area graphene, edge effects are shown to contribute to thermal conductance, enhance the anisotropy in thermal conductance of graphene nanoribbons, and increase thermal conductance per unit width. The edges with and without hydrogen passivation modify the atomic structure and ultimately influence the phonon thermal transport differently for the two ribbon types.

A first-principles investigation of the linear thermal expansion coefficients of BeF2: giant thermal expansion.

We present the results of a theoretical investigation of the linear thermal expansion coefficients (TECs) of BeF2, within a direct Grüneisen formalism where symmetry-preserving deformations are employed. The required physical quantities such as the optimized crystal structures, elastic constants, mode Grüneisen parameters, and phonon density of states are calculated from first-principles. BeF2 shows an extensive polymorphism at low pressures, and the lowest energy phases [α-cristobalite with space group (SG) P41212 and its similar phase with SG P43212] are considered in addition to the experimentally observed α-quartz phase. For benchmarking purposes, similar calculations are performed for the rutile phase of ZnF2, where the volumetric TEC (α v), derived from the calculated linear TECs along the a (α a ) and c (α c ) directions, is in very good agreement with experimental data and previous theoretical results. For the considered phases of BeF2, we do not find any negative thermal expansion (NTE). However we observe diverse thermal properties for the distinct phases. The linear TECs are very large, especially α c of the α-cristobalite phase and its similar phase, leading to giant α v (∼175 × 10-6 K-1 at 300 K). The giant α v arises from large Grüneisen parameters of low-frequency phonon modes, and the C 13 elastic constant that is negatively signed and large in magnitude for the α-cristobalite phase. The elastic constants, high-frequency dielectric constants, Born effective charge tensors, and thermal properties of the above phases of BeF2 are reported for the first time and hence serve as predictions.

Interaction potential for indium phosphide: a molecular dynamics and first-principles study of the elastic constants, generalized stacking fault and surface energies.

Indium phosphide is investigated using molecular dynamics (MD) simulations and density-functional theory calculations. MD simulations use a proposed effective interaction potential for InP fitted to a selected experimental dataset of properties. The potential consists of two- and three-body terms that represent atomic-size effects, charge-charge, charge-dipole and dipole-dipole interactions as well as covalent bond bending and stretching. Predictions are made for the elastic constants as a function of density and temperature, the generalized stacking fault energy and the low-index surface energies.

Large thermal anisotropy in monoclinic niobium trisulfide: a thermal expansion tensor study.

We present a method based on the Grüneisen formalism to calculate the thermal expansion coefficient (TEC) tensor that is applicable to any crystal system, where the number of phonon calculations associated with different deformations scales linearly with the number of lattice parameters. Compared to simple high-symmetry systems such as cubic or hexagonal systems, a proper consideration of low-symmetry systems such as monoclinic or triclinic crystals demands a clear distinction between the TEC tensor and the lattice-parameter TECs along the crystallographic direction. The latter is more complicated and it involves integrating the equations of motion for the primitive lattice vectors, with input from the TEC tensor. A first-principles study of the TEC is carried out for the first time on a monoclinic crystal, where we unveil high TEC anisotropies in a recently reported monoclinic phase of niobium trisulfide (NbS3-IV) crystal with a relatively large primitive cell (32 atoms per cell) using density-functional theory. We find the occurrence of a negative TEC tensor component is largely due to the mechanical property rather than the anharmonic effect, contrary to common belief. Our theoretical treatment of the monoclinic system with a single off-diagonal tensor element could be routinely generalized to any crystal system, including the lowest-symmetry triclinic system with three off-diagonal tensor elements.

Manipulating efficient light emission in two-dimensional perovskite crystals by pressure-induced anisotropic deformation.

The hybrid nature and soft lattice of organolead halide perovskites render their structural changes and optical properties susceptible to external driving forces such as temperature and pressure, remarkably different from conventional semiconductors. Here, we investigate the pressure-induced optical response of a typical two-dimensional perovskite crystal, phenylethylamine lead iodide. At a moderate pressure within 3.5 GPa, its photoluminescence red-shifts continuously, exhibiting an ultrabroad energy tunability range up to 320 meV in the visible spectrum, with quantum yield remaining nearly constant. First-principles calculations suggest that an out-of-plane quasi-uniaxial compression occurs under a hydrostatic pressure, while the energy is absorbed by the reversible and elastic tilting of the benzene rings within the long-chain ligands. This anisotropic structural deformation effectively modulates the quantum confinement effect by 250 meV via barrier height lowering. The broad tunability within a relatively low pressure range will expand optoelectronic applications to a new paradigm with pressure as a tuning knob.

Coherent Spin and Quasiparticle Dynamics in Solution-Processed Layered 2D Lead Halide Perovskites.

Layered 2D halide perovskites with their alternating organic and inorganic atomic layers that form a self-assembled quantum well system are analogues of the purely inorganic 2D transition metal dichalcogenides. Within their periodic structures lie a hotbed of photophysical phenomena such as dielectric confinement effect, optical Stark effect, strong exciton-photon coupling, etc. Detailed understanding into the strong light-matter interactions in these hybrid organic-inorganic semiconductor systems remains modest. Herein, the intricate coherent interplay of exciton, spin, and phonon dynamics in (C6H5C2H4NH3)2PbI4 thin films using transient optical spectroscopy is explicated. New insights into the hotly debated origins of transient spectral features, relaxation pathways, ultrafast spin relaxation via exchange interaction, and strong coherent exciton-phonon coupling are revealed from the detailed phenomenological modeling. Importantly, this work unravels the complex interplay of spin-quasiparticle interactions in these layered 2D halide perovskites with large spin-orbit coupling.

Nonequilibrium Green's function method for thermal transport in junctions.

We present a detailed treatment of the nonequilibrium Green's function method for thermal transport due to atomic vibrations in nanostructures. Some of the key equations, such as self-energy and conductance with nonlinear effect, are derived. A self-consistent mean-field theory is proposed. Computational procedures are discussed. The method is applied to a number of systems including one-dimensional chains, a benzene ring junction, and carbon nanotubes. Mean-field calculations of the Fermi-Pasta-Ulam model are compared with classical molecular dynamics simulations using a generalized Langevin heat bath. We find that nonlinearity suppresses thermal transport even at moderately high temperatures.

Weak Van der Waals Stacking, Wide-Range Band Gap, and Raman Study on Ultrathin Layers of Metal Phosphorus Trichalcogenides.

2D semiconducting metal phosphorus trichalcogenides, particularly the bulk crystals of MPS3 (M = Fe, Mn, Ni, Cd and Zn) sulfides and MPSe3 (M = Fe and Mn) selenides, have been synthesized, crystallized and exfoliated into monolayers. The Raman spectra of monolayer FePS3 and 3-layer FePSe3 show the strong intralayer vibrations and structural stability of the atomically thin layers under ambient condition. The band gaps can be adjusted by element choices in the range of 1.3-3.5 eV. The wide-range band gaps suggest their optoelectronic applications in a broad wavelength range. The calculated cleavage energies of MPS3 are smaller than that of graphite. Therefore, the monolayers used for building of heterostructures by van der Waals stacking could be considered as the candidates for artificial 2D materials with unusual ferroelectric and magnetic properties.

Using the graphene Moiré pattern for the trapping of C60 and homoepitaxy of graphene.

The graphene Moiré superstructure offers a complex landscape of humps and valleys to molecules adsorbing and diffusing on it. Using C(60) molecules as the classic hard sphere analogue, we examine its assembly and layered growth on this corrugated landscape. At the monolayer level, the cohesive interactions of C(60) molecules adsorbing on the Moiré lattice freeze the molecular rotation of C(60) trapped in the valley sites, resulting in molecular alignment of all similarly trapped C(60) molecules at room temperature. The hierarchy of adsorption potential well on the Moiré lattice causes diffusion-limited dendritic growth of C(60) films, as opposed to isotropic growth observed on a smooth surface like graphite. Due to the strong binding energy of the C(60) film, part of the dentritic C(60) films polymerize at 850 K and act as solid carbon sources for graphene homoepitaxy. Our findings point to the possibility of using periodically corrugated graphene in molecular spintronics due to its ability to trap and align organic molecules at room temperature.

Transforming C60 molecules into graphene quantum dots.

The fragmentation of fullerenes using ions, surface collisions or thermal effects is a complex process that typically leads to the formation of small carbon clusters of variable size. Here, we show that geometrically well-defined graphene quantum dots can be synthesized on a ruthenium surface using C(60) molecules as a precursor. Scanning tunnelling microscopy imaging, supported by density functional theory calculations, suggests that the structures are formed through the ruthenium-catalysed cage-opening of C(60). In this process, the strong C(60)-Ru interaction induces the formation of surface vacancies in the Ru single crystal and a subsequent embedding of C(60) molecules in the surface. The fragmentation of the embedded molecules at elevated temperatures then produces carbon clusters that undergo diffusion and aggregation to form graphene quantum dots. The equilibrium shape of the graphene can be tailored by optimizing the annealing temperature and the density of the carbon clusters.

Linear scaling computation of the Fock matrix. VII. Parallel computation of the Coulomb matrix.

We present parallelization of a quantum-chemical tree-code for linear scaling computation of the Coulomb matrix. Equal time partition is used to load balance computation of the Coulomb matrix. Equal time partition is a measurement based algorithm for domain decomposition that exploits small variation of the density between self-consistent-field cycles to achieve load balance. Efficiency of the equal time partition is illustrated by several tests involving both finite and periodic systems. It is found that equal time partition is able to deliver 91%-98% efficiency with 128 processors in the most time consuming part of the Coulomb matrix calculation. The current parallel quantum chemical tree code is able to deliver 63%-81% overall efficiency on 128 processors with fine grained parallelism (less than two heavy atoms per processor).