Although atomic diffusion on metal surfaces under high electric fields has been studied theoretically and experimentally since the 1970s, its accurate and quantitative theoretical description remains a significant challenge. In our previous work, we developed a theoretical framework that describes the atomic dynamics on metal surfaces in the presence of an electric field in terms of the local polarization characteristics of the surface at the vicinity of a moving atom. Here, we give a deeper analysis of the physics underlying this framework, introducing and rigorously defining the concept of the effective polarization characteristics (permanent dipole moment $μ$ and polarizability $α$) of a moving atom on a metal surface, which are shown to be the relevant atomic quantities determining the dynamics of a moving atom via a compact equation. We use density functional theory (DFT) to calculate $μ$ and $α$ of a W adatom moving on a W {110} surface, where additional adatoms are present in its vicinity. We analyze the dependence of $μ$ and $α$ and hence the migration barriers under electric fields on the local atomic environments (LAE) of an adatom. We find that the LAE significantly affects $μ$ and $α$ of a moving atom in the limited cases we studied, which implies that further systematic DFT calculations are needed to fully parameterize surface diffusion in terms of energy barriers for long-term large scale simulations, such as our recently developed Kinetic Monte Carlo model for surface diffusion under electric field.
We study the rate of activated motion over multiple barriers, in particular the correlated double-jump of an adatom diffusing on a missing-row reconstructed Platinum (110) surface. We develop a Transition Path Theory, showing that the activation energy is given by the minimum-energy trajectory which succeeds in the double-jump. We explicitly calculate this trajectory within an effective-medium molecular dynamics simulation. A cusp in the acceptance region leads to a sqrt{T} prefactor for the activated rate of double-jumps. Theory and numerical results agree.
Employing first principles total energy calculations we have studied the behavior of Ga and Al adatoms on the GaAs(001)-beta2 surface. The adsorption site and two relevant diffusion channels are identified. The channels are characterized by different adatom-surface dimer interaction. Both affect in a novel way the adatom migration: in one channel the diffusing adatom jumps across the surface dimers and leaves the dimer bonds intact, in the other one the surface dimer bonds are broken. The two channels are taken into account to derive effective adatom diffusion barriers. From the diffusion barr…
Strong electric fields are known to create biased adatom migration on metallic surfaces. We present a Kinetic Monte Carlo model that can simulate adatom migration on a tungsten (W) surface in electric fields. We validate our model by using it to calculate the drift velocity of the adatom at different fields and temperature and comparing the results with experimental data from the literature. We obtain excellent agreement.
The combination of the unique properties of graphene with spin polarization and magnetism for the design of new spintronic concepts and devices has been hampered by the small Coulomb interaction and the tiny spin-orbit coupling of carbon in pristine graphene. Such device concepts would take advantage of the control of the spin degree of freedom utilizing the widely available electric fields in electronics or of topological transport mechanisms such as the conjectured quantum anomalous Hall effect. Here we show, using first-principles methods, that 5d transition-metal (TM) adatoms deposited on …
A method has been developed to permit the diffusion of Sb into Ge at high temperatures (~850 C) without contamination by fast diffusing electrically active impurities in particular by Cu. A liquid metal alloy is used as a getter of Cu and other fast diffusing impurities. This alloy, Ga- In eutectic, completely encloses the Ge sample although in physical contact on only one face. The behaviour of Cu as a contaminant in Ge and the methods known to prevent and extract (or gather) Cu contamination are reviewed briefly. Preliminary experiments are described which demonstrate the difficulty of remov…
Although surface diffusion is critical for many physical and chemical processes, including the epitaxial growth of crystals and heterogeneous catalysis, it is particularly challenging to directly study. Here, we estimate the carbon adatom migration barrier on freestanding monolayer graphene by quantifying its temperature-dependent electron knock-on damage. Due to the fast healing of vacancies by diffusing adatoms, the damage rate decreases with increasing temperature. By analyzing the observed damage rates at 300-1073 K using a model describing our finite scanning probe, we find a barrier of (…
The nature of the magnetism brought about by Fe adatoms on the surface of the topological insulator Bi2Se3 was examined in terms of density functional calculations. The Fe adatoms exhibit strong easy-axis magnetic anisotropy in the dilute adsorption limit due to the topological surface states (TSS). The spin exchange J between the Fe adatoms follows a Ruderman-Kittel-Kasuya-Yosida (RKKY) behavior with substantial anisotropy, and the Dzyaloshinskii-Moriya (DM) interaction between them is quite strong with |D/J|~0.3 under the mediation by the TSS, and can be further raised to ~0.6 by an external…
We present first-principles total-energy electronic-structure calculations that provide the microscopic mechanism of the Ag atom diffusion between the half unit cells (HUCs) on the Si(111)-(7x7) surface with and without the tip of the atomic force microscope (AFM). We find that, without the presence of the AFM tip, the diffusions between the two HUCs are almost symmetric with the energy barrier of about 1 eV in the both directions. The diffusion is a two-step process with an intermediate metastable configuration in which the Ag atom is at the boundary of the HUCs. With the presence of the tip,…
The interaction of the strong electron-acceptor tetracyanoethylene (TCNE) with the Cu(100) surface has been studied with scanning tunneling microscopy experiments and first-principles density functional theory calculations. We compare two different adsorption models with the experimental results and show that the molecular self-assembly is caused by a strong structural modification of the Cu(100) surface rather than the formation of a coordination network by diffusing Cu adatoms. Surface atoms become highly buckled and the chemisorption of TCNE is accompanied by a partial charge-transfer.
We describe scanning tunneling spectroscopy (STS) measurements performed on individual cobalt (Co) atoms deposited onto backgated graphene devices. We find that Co adatoms on graphene can be ionized by either the application of a global backgate voltage or by the application of a local electric field from a scanning tunneling microscope (STM) tip. Large screening clouds are observed to form around Co adatoms ionized in this way, and we observe that some intrinsic graphene defects display a similar behavior. Our results provide new insight into charged impurity scattering in graphene, as well a…
The epitaxial growth process of a high symmetry surface occurs because adatoms meet and nucleate new islands, that eventually coalesce and complete atomic layers. During multilayer growth, nucleation usually takes place on top of terraces where the geometry of the diffusion process is well defined: We have studied in detail the spatiotemporal distribution of nucleation events and the resulting nucleation rate, a quantity of primary importance to model experimental results and evaluate diffusion barriers at step-edges. We provide rigorous results for irreversible nucleation and we assess the li…
The paper presents results from kinetic Monte Carlo simulations of kinetic surface roughening using an important and experimentally relevant model of epitaxial growth -- the solid-on-solid model with Arrhenius dynamics. A restriction on diffusing adatoms is included allowing hopping down only at steps of height one monolayer in order to avoid possibly unrealistic events of jumping from arbitrarily high steps. Simulation results and precise analytic expressions representing the time evolution of surface roughness do not depend on the substrate size and clearly put forward the conclusion that fo…
Graphene, a hexagonal sheet of $sp^2$-bonded carbon atoms, has extraordinary properties which hold immense promise for future nanoelectronic applications. Unfortunately, the popular preparation methods of micromechanical cleavage and chemical exfoliation of graphite do not easily scale up for application purposes. Epitaxial graphene provides an attractive alternative, though there are many challenges, not least of which is the absence of an understanding of the complex atomistic assembly kinetics of graphene. Here, we present a simple rate theory of epitaxial graphene growth on close-packed me…
Combining classical electrodynamics and density functional theory (DFT) calculations, we develop a general and rigorous theoretical framework that describes the energetics of metal surfaces under high electric fields. We show that the behavior of a surface atom in the presence of an electric field can be described by the polarization characteristics of the permanent and field-induced charges in its vicinity. We use DFT calculations for the case of a W adatom on a W{110} surface to confirm the predictions of our theory and quantify its system-specific parameters. Our quantitative predictions fo…
Atoms transferred to W(111) and W(110) tip apices from the Au(111) surface during tunneling and approach to mechanical contact experiments in STM are characterized in FIM at room temperature and at 158 K. The different activation energies for diffusion on the (111) and (110) tip planes and the experiment temperature are shown to be important factors controlling the extent of changes to the atomic structure of the tip. W(111) tips are much better suited to scanning probe studies which require the characterization of an atomically defined tip and subsequent verification of its integrity in FIM. …
The motion of molecules on solid surfaces is of interest for technological applications such as catalysis and lubrication, but it is also a theoretical challenge at a more fundamental level. The concept of activation barriers is very convenient for the interpretation of experiments and as input for Monte Carlo simulations but may become inadequate when mismatch with the substrate and molecular vibrations are considered. We study the simplest objects diffusing on a substrate at finite temperature $T$, namely an adatom and a diatomic molecule (dimer), using the Langevin approach. In the driven c…
We study local moment formation for adatoms on bilayer graphene (BLG) within a mean-field theory of the Anderson impurity model. The wavefunctions of the BLG electrons induce strong particle-hole asymmetry and band dependence of the hybridization, which is shown to result in unusual features in the impurity model phase diagram. We also study the effect of varying the chemical potential, as well as varying an electric field perpendicular to the bilayer; the latter modifies the density of states of electrons in BLG and, more significantly, shifts the impurity energy. We show that this leads to r…
Normal incidence 1 keV Ar$^+$ ion bombardment leads to amorphization and ultrasmoothing of Ge at room temperature, but at elevated temperatures the Ge surface remains crystalline and is unstable to the formation of self-organized nanoscale patterns of ordered pyramid-shaped pits. The physical phenomenon distinguishing the high temperature patterning from room temperature ultrasmoothing is believed to be a surface instability due to the Ehrlich-Schwoebel barrier for diffusing vacancies and adatoms, which is not present on the amorphous material. This real-time GISAXS study compares smoothing of…
A PDE-based model combining surface electromigration and wetting is developed for the analysis of morphological stability of ultrathin solid films. Adatom mobility is assumed anisotropic, and two directions of the electric field (parallel and perpendicular to the surface) are discussed and contrasted. Linear stability analyses of small-slope evolution equations are performed, followed by computations of fully nonlinear parametric evolution equations that permit surface overhangs. The results reveal parameter domains of instability for wetting and non-wetting films and variable electric field s…
Using first-principles Density Functional Theory calculations, we showed that electronic and magnetic properties of bare and Ti adatom adsorbed single-layer silicene and germanene, which are charged or exerted by a perpendicular electric field are modified to attain new functionalities. In particular, when exerted by a perpendicular electric field, the symmetry between the planes of buckled atoms is broken to open a gap at the Dirac points. The occupation of 3d-orbitals of adsorbed Ti atom changes with charging or applied electric field to induce significant changes of magnetic moment. We pred…
Controlling magnetism of transition metal atoms by pairing with $π$ electronic states of graphene is intriguing. Herein, through first - principle computation we explore the possibility of switching magnetization by forming the tetrahedral $sp^3$ - metallic $d$ hybrid bonds. Graphene multilayers capped by single - layer cobalt atoms can transform into the $sp^3$ - bonded diamond films upon the hydrogenation of the bottom surface. While the conversion is favored by hybridization between the $sp^3$ dangling bonds and metallic $d_{z^2}$ states, such a strong hybridization can lead to the reorient…
We investigate the effect of atomic ordering on the magnetic anisotropy of Ni80Fe20 at.% (Py). To this end, Py films were grown epitaxially on MgO (001) using dc magnetron sputtering (dcMS) and high power impulse magnetron sputtering (HiPIMS). Aside from twin boundaries observed in the latter case, both methods present high quality single crystals with cube-on-cube epitaxial relationship as verified by the polar mapping of important crystal planes. However, X-ray diffraction results indicate higher order for the dcMS deposited film towards L12 Ni3Fe superlattice. This difference can be underst…
The planar front of a growing a crystal is often destroyed by instabilities. In the case of growth from a condensed phase, the most frequent ones are diffusion instabilities, which will be but briefly discussed in simple terms in chapter II. The present review is mainly devoted to instabilities which arise in ballistic growth, especially Molecular Beam Epitaxy (MBE). The reasons of the instabilities can be geometric (shadowing effect), but they are mostly kinetic or thermodynamic. The kinetic instabilities which will be studied in detail in chapters IV and V result from the fact that adatoms d…
The electronic properties of the novel two dimensional (2D) material silicene are strongly influenced by the application of a perpendicular electric field $E_z$ and of an exchange field $M$ due to adatoms positioned on the surface or a ferromagnetic substrate. Within the random phase approximation, we investigate how electron-electron interactions are affected by these fields and present analytical and numerical results for the dispersion of plasmons, their lifetime, and their oscillator strength. We find that the combination of the fields $E_z$ and $M$ brings a spin and valley texture to the …
Coarse-grained modeling of dynamics on vicinal surfaces concentrates on the diffusion of adatoms on terraces with boundary conditions at sharp steps, as first studied by Burton, Cabrera and Frank (BCF). Recent electromigration experiments on vicinal Si surfaces suggest the need for more general boundary conditions in a BCF approach. We study a discrete 1D hopping model that takes into account asymmetry in the hopping rates in the region around a step and the finite probability of incorporation into the solid at the step site. By expanding the continuous concentration field in a Taylor series e…
