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Nonequilibrium processes during solidification can lead to kinetic stabilization of metastable crystal phases. A general framework for predicting the solidification conditions that lead to metastable-phase growth is developed and applied to a model face-centered cubic (fcc) metal that undergoes phase transitions to the body-centered cubic (bcc) as well as the hexagonal close-packed phases at high temperatures and pressures. Large-scale molecular dynamics simulations of ultrarapid freezing show that bcc nucleates and grows well outside of the region of its thermodynamic stability. An extensive study of crystal-liquid equilibria confirms that at any given pressure, there is a multitude of metastable solid phases that can coexist with the liquid phase. We define for every crystal phase, a solid cluster in liquid (SCL) basin, which contains all solid clusters of that phase coexisting with the liquid. A rigorous methodology is developed that allows for practical calculations of nucleation rates into arbitrary SCL basins from the undercooled melt. It is demonstrated that at large undercoolings, phase selections made during the nucleation stage can be undone by kinetic instabilities amid the growth stage. On these bases, a solidification-kinetic phase diagram is drawn for the model fcc system that delimits the conditions for macroscopic grains of metastable bcc phase to grow from the melt. We conclude with a study of unconventional interfacial kinetics at special interfaces, which can bring about heterogeneous multiphase crystal growth. A first-order interfacial phase transformation accompanied by a growth-mode transition is examined. [ABSTRACT FROM AUTHOR]

We study sputtering by 100 eV deuterium irradiation on deuterated amorphous carbon layers at 300 K using molecular dynamics (MD) simulations. Two main results are reported here. First, a special mechanism for carbon release—additional to and distinct from the standard definitions for physical and chemical sputtering of carbon by hydrogen isotopes—has been identified and quantified. This process, here termed ion induced release of unsaturated hydrocarbons (IRUH’s), is primarily due to a recently identified atomic collision process where momentum from an impacting particle is transferred approximately perpendicular to the C–C bond, severing it. For the prescribed conditions, the IRUH yield has been found to be comparable to that of standard physical and chemical sputtering, the former being also consistently and simultaneously calculated here. IRUH release of single C atoms does not involve any hydrogenic chemistry and is therefore properly considered to be a distinct and additive type of physical sputtering to that of standard physical sputtering. For 100 eV D+ the single C yields of the two physical sputtering mechanisms have been found to be approximately equal. IRUH release of carbon is directly from the surface region of the solid and is separate from, and additional to, standard chemical sputtering (not included in these MD calculations), which typically produces saturated hydrocarbons such as CD4, from regions extending over the stopping depth of the deuteron in the solid. IRUH is evidently included in experimental measurements of total sputtering yield, e.g., by weight loss. The average energy of IRUH carbon products is about 1 eV and the angular distribution is consistent with a cosine distribution. Second, it is found that for the standard physically sputtered single C atoms the energy distribution is roughly consistent with the widely used Thompson distribution—this despite the fact that the assumptions on which the Thompson distribution is based are not satisfied for 100 eV D on C. The angular distribution of the standard physically sputtered single C atoms is also found to be consistent with the usually assumed cosine distribution. [ABSTRACT FROM AUTHOR]

The ability to predict the behavior of point defects in metals, particularly interstitial defects, is central to accurate modeling of the microstructural evolution in environments with high radiation fluxes. Existing interatomic potentials of embedded atom method type predict disparate stable interstitial defect configurations in vanadium. This is not surprising since accurate first-principles interstitial data were not available when these potentials were fitted. In order to provide the input information required to fit a vanadium potential appropriate for radiation damage studies, we perform a series of first-principles calculations on six different interstitial geometries and vacancies. These calculations identify the 〈111〉 dumbbell as the most stable interstitial with a formation energy of approximately 3.1 eV, at variance with predictions based upon existing potentials. Our potential is of Finnis-Sinclair type and is fitted exactly to the experimental equilibrium lattice parameter, cohesive energy, elastic constants and a calculated unrelaxed vacancy formation energy. Two additional potential parameters were used to obtain the best fit to the set of interstitial formation energies determined from the first-principles calculations. The resulting potential was found to accurately predict both the magnitude and ordering of the formation energies of six interstitial configurations and the unrelaxed vacancy ground state, in addition to accurately describing the migration characteristics of the stable interstitial and vacancy. This vanadium potential is capable of describing the point defect properties appropriate for radiation damage simulations as well as for simulations of more common crystal and simple defect properties. [ABSTRACT FROM AUTHOR]

Molecular dynamics simulations are performed to examine the effects of ion beams in selecting MgO island orientations during ion beam assisted deposition. Sputter yields are determined as a function of ion beam orientation for MgO islands of different sizes. While channeling does occur in small islands, the difference in sputter yields between channeling and nonchanneling orientations is much smaller in small islands than in larger islands or a continuous film. The ion beam is capable of disrupting the entire island structure at small island sizes, while channeling dependent sputtering occurs at larger island size. Since less sputtering occurs for channeling orientations, the ion beam produces an orientation-dependent island growth rate. This leads to island orientation-dependent nucleation rates. A new analytical model parameterized using the molecular dynamics sputter yield data is developed which predicts how growth conditions affect these island-orientation nucleation rates. Based upon these simulations and model results, we suggest a strategy to efficiently grow thin, highly textured MgO films. [ABSTRACT FROM AUTHOR]

Analyzes the energetics, interfacial stability, strain fields and film surface morphology in semiconductor heteroepitaxy. Application of continuum elasticity theory and atomistic simulations in the analysis; Computation of critical film thicknesses; Description of the atomistic simulation results; Results and discussion.

Molecular dynamics simulations in the isobaric–isenthalpic ensemble are used to derive various important parameters related to nucleation from the melt. In particular, by using results from liquid–solid phase equilibria, we present a simple, yet reliable, approach to extract melting temperature, critical nucleus size, and liquid–solid interfacial free energy for six different embedded atom FCC systems. Our approach is based on the fundamental thermodynamic relation given by the Gibbs–Thomson equation that uses the heat released during solidification to drive growth of the solid phase until thermodynamic equilibrium is achieved. Equilibrium between the liquid and solid phases is identified by a steady-state evolution in the temperature of the two-phase system. • MD simulations of melting temperature, critical size, and interfacial free energy. • Gibbs–Thomson equation sets equilibrium of solid surrounded by its own liquid. • Robust & general methodology for calculation of thermodynamic liquid–solid properties. [ABSTRACT FROM AUTHOR]

We present and evaluate a semiempirical particle-based model of electrophoretic deposition using extensive mesoscale simulations. We analyze particle configurations in order to observe how colloids accumulate at the electrode and arrange into deposits. In agreement with existing continuum models, the thickness of the deposit increases linearly in time during deposition. Resulting colloidal deposits exhibit a transition between highly ordered and bulk disordered regions that can give rise to an appreciable density gradient under certain simulated conditions. The overall volume fraction increases and falls within a narrow range as the driving force due to the electric field increases and repulsive intercolloidal interactions decrease. We postulate ordering and stacking within the initial layer(s) dramatically impacts the microstructure of the deposits. We find a combination of parameters, i.e., electric field and suspension properties, whose interplay enhances colloidal ordering beyond the commonly known approach of only reducing the driving force. [ABSTRACT FROM AUTHOR]

Molecular dynamics simulations were used to study Ge island nucleation and growth on amorphous SiO 2 substrates. This process is relevant in selective epitaxial growth of Ge on Si, for which SiO 2 is often used as a template mask. The islanding process was studied over a wide range of temperatures and fluxes, using a recently proposed empirical potential model for the Si–SiO 2 –Ge system. The simulations provide an excellent quantitative picture of the Ge islanding and compare well with detailed experimental measurements. These quantitative comparisons were enabled by an analytical rate model as a bridge between simulations and experiments despite the fact that deposition fluxes accessible in simulations and experiments are necessarily different by many orders of magnitude. In particular, the simulations led to accurate predictions of the critical island size and the scaling of island density as a function of temperature. The overall approach used here should be useful not just for future studies in this particular system, but also for molecular simulations of deposition in other materials. [ABSTRACT FROM AUTHOR]

Abstract: The growth of uniform thin films on foreign substrates is impeded by several morphological instabilities. Hill-and-valley structures are formed and enhanced during sputter deposition where surface height perturbations have an opportunity to grow to large amplitudes. We show via kinetic Monte Carlo (kMC) simulations that while surface roughness can be partially controlled by changing growth conditions, such as substrate temperature, the diffusion of particles over step edges plays a very important role in determining both surface roughness and the density of the films. Our kMC simulations provide a way to evaluate the strength of surface instabilities during sputter deposition of thin films. [Copyright &y& Elsevier]

Abstract: In order to provide insight into coarsening mechanisms of pentaerythritol tetranitrate (PETN), we performed kinetic Monte Carlo (KMC) simulations of evaporation from the predominantly exposed (110) surface. Our KMC simulations show that different surface structures, such as islands and straight step segments, move in very different ways during evaporation. We show that closed surface structures (e.g. islands or convex step edges) evaporate faster than open features (e.g. straight or concave step edges) due to inexhaustible sources of kink sites in their edges. From Arrhenius plots of step velocities we obtained activation energies for evaporation that are in excellent agreement with predictions from a model and recent experimental data. The effects of surface diffusion on evaporation rates are discussed within a rate theory model. [Copyright &y& Elsevier]

Abstract: Starting from an accurate inter-atomic potential we develop a simple scheme of generating an “on-lattice”molecular potential of short range, which is then incorporated into a lattice Monte Carlo code for simulating size and shape evolution of nanocrystallites. As a specific example, we test such a procedure on the morphological evolution of a molecular crystal of interest to us, e.g., Pentaerythritol Tetranitrate, or PETN, and obtain realistic facetted structures in excellent agreement with experimental morphologies. We investigate several interesting effects including, the evolution of the initial shape of a “seed” to equilibrium configuration, and the variation of growth morphology as a function of the rate of particle addition relative to diffusion. [Copyright &y& Elsevier]

Abstract: We study the diffusion of self-interstitial atoms (SIAs) and SIA clusters in vanadium via molecular dynamics simulations with an improved Finnis–Sinclair potential (fit to first-principles results for SIA structure and energetics). The present results demonstrate that single SIAs exist in a 〈111〉-dumbbell configuration and migrate easily along 〈111〉 directions. Changes of direction through rotations into other 〈111〉 directions are infrequent at low temperatures, but become prominent at higher temperatures, thereby changing the migration path from predominantly one-dimensional to almost isotropically three-dimensional. SIA clusters (i.e., clusters of 〈111〉-dumbbells) can be described as perfect prismatic dislocation loops with Burgers vector and habit planes of 1/2〈111〉{220} that migrate only along their glide cylinder. SIA clusters also migrate along 〈111〉-directions, but do not rotate. Both single SIAs and their clusters exhibit a highly non-Arrhenius diffusivity, which originates from a combination of a temperature dependent correlation factor and the presence of very low migration barriers. At low temperature, the diffusion is approximately Arrhenius, while above room temperature, the diffusivity is a linear function of temperature. A simple model is proposed to describe these diffusion regimes and the transition between them. [Copyright &y& Elsevier]

A systematic theoretical analysis is presented of the combined effects of substrate compliance and film compositional grading on the relaxation of strain due to lattice mismatch in layer-by-layer semiconductor heteroepitaxy. The analysis is based on a combination of continuum elasticity theory and a novel atomistic simulation approach for modeling structural and compositional relaxation in layer-by-layer heteroepitaxial systems. Results are presented for InAs epitaxy on GaAs(1 1 1)A compliant substrates with some marginal film compositional grading that consists of one monolayer of In0.50Ga0.50As grown on the substrate surface prior to InAs growth. A parametric study is carried out over a wide range of substrate thicknesses. Interfacial stability with respect to misfit dislocation formation, the dependence on substrate thickness of a thermodynamic critical film thickness, and the completion of the coherent-to-semicoherent interfacial transition are examined in detail. In addition, the structural characteristics and compositional distribution of the corresponding semicoherent interfaces, the associated strain fields, as well as the film surface morphological characteristics are analyzed. Most importantly, the role of segregation at defects of a semicoherent interface in the thermodynamics of layer-by-layer heteroepitaxial growth is demonstrated. Our study shows that systematic combination of the mechanical behavior of thin compliant substrates with grading of the epitaxial film composition provides a very promising engineering strategy for strain relaxation in heteroepitaxy. [Copyright &y& Elsevier]

A systematic study is presented of interfacial stability and strain relaxation through misfit dislocation formation in III–V semiconductor layer-by-layer heteroepitaxy. A multiscale modeling strategy is developed that links continuum elasticity theory with atomistic structural relaxation and Monte Carlo simulations using a valence force field description of interatomic interactions. Results are presented for the energetics of the transition from a coherent to a semicoherent film/substrate interface consisting of a misfit dislocation network, the semicoherent interface structures, the associated strain fields, and the film surface morphological characteristics for InAs epitaxy on GaAs(1 1 1)A. The capability of continuum elasticity theory to provide a satisfactory description of the atomistic simulation results is discussed. In addition, using thin compliant substrates and grading the composition of the deposited film are demonstrated to have beneficial effects on film strain relaxation. Furthermore, the dynamics of strain relaxation is analyzed based on a phenomenological mean-field theoretical framework. Our theoretical results are in very good agreement with our experimental measurements on InAs/GaAs(1 1 1)A samples for films grown by molecular beam epitaxy on thick and thin GaAs buffer layers. [Copyright &y& Elsevier]

The relation between stress evolution and surface morphology during deposition of sputtered films is examined by combining kinetic Monte Carlo simulations and stress measurements. We find that the surface morphology is susceptible to an instability, which transforms from layer-by-layer growth to the formation of pillarlike columns. The gaps between these columns prevent complete densification and can lead to a network of pores in the layer. We propose that the formation of this structure changes the stress in the growing layers from compressive to tensile. [ABSTRACT FROM AUTHOR]

We employ molecular dynamics simulations of defect-free nanopillars with realistic cylindrical geometries to obtain an atomic-level picture of their deformation behavior under compression. We find that dislocations are nucleated in the two outermost surface layers. Furthermore, plastic yield depends crucially on the particular arrangement of steps and facets at the surface of the nanopillars. We show that different facet orientations can differ dramatically in their response to external stresses. Freestanding nanopillars exhibit a highly nonuniform distribution of stresses along their height. This causes an elastic deformation that leads to a barrel-like shape attained by the nanopillars under compression. The stress concentration at the center of the pillars due to barreling causes dislocations to preferentially nucleate in this region. [ABSTRACT FROM AUTHOR]

We report the results of a theoretical analysis for the kinetics of strain relaxation in Si1-xGex thin films grown epitaxially on Si(100) substrates. The analysis is based on a properly parametrized dislocation mean-field theoretical model describing plastic deformation dynamics due to threading dislocation propagation and addresses strain relaxation kinetics during both epitaxial growth and thermal annealing, including post-implantation annealing. Theoretical predictions for strain relaxation as a function of film thickness in Si0.80Ge0.20/Si(100) samples annealed after epitaxial growth either unimplanted or after He ion implantation are in excellent agreement with experimental measurements [J. Cai et al., J. Appl. Phys. 95, 5347 (2004)]. [ABSTRACT FROM AUTHOR]

We apply a hybrid Monte Carlo-molecular dynamics code to the study of grain boundary motion upon annealing of pure Cu and Cu with low concentrations of Fe. The hybrid simulations account for segregation and precipitation of the low solubility Fe, together with curvature-driven grain boundary motion. Grain boundaries in two different systems, a Σ7+U-shaped half-loop grain and a nanocrystalline sample, were found to be pinned in the presence of Fe concentrations exceeding 3%. [ABSTRACT FROM AUTHOR]

A comprehensive, quantitative analysis is presented of the deformation behavior of coherently strained InAs/GaAs(111)A heteroepitaxial systems. The analysis combines a hierarchical theoretical approach with experimental measurements. Continuum linear elasticity theory is linked with atomic-scale calculations of structural relaxation for detailed theoretical studies of deformation in systems consisting of InAs thin films on thin GaAs(111)A substrates that are mechanically unconstrained at their bases. Molecular-beam epitaxy is used to grow very thin InAs films on both thick and thin GaAs buffer layers on epi-ready GaAs(111)A substrates. The deformation state of these samples is characterized by x-ray diffraction (XRD). The interplanar distances of thin GaAs buffer layers along the [220] and [111] crystallographic directions obtained from the corresponding XRD spectra indicate clearly that thin buffer layers deform parallel to the InAs/GaAs(111)A interfacial plane, thus aiding in the accommodation of the strain induced by lattice mismatch. The experimental measurements are in excellent agreement with the calculated lattice interplanar distances and the corresponding strain fields in the thin mechanically unconstrained substrates considered in the theoretical analysis. Therefore, this work contributes direct evidence in support of our earlier proposal that thin buffer layers in layer-by-layer semiconductor heteroepitaxy exhibit mechanical behavior similar to that of compliant substrates [see, e.g., B. Z. Nosho, L. A. Zepeda-Ruiz, R. I. Pelzel, W. H. Weinberg, and D. Maroudas, Appl. Phys. Lett. 75, 829 (1999)]. © 2001 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Molecular dynamics simulations are performed to study the fundamental role of the ion beam in determining the in-plane texture of <100> oriented (out-of-plane) MgO films during ion beam assisted deposition (IBAD). Sputter yields are determined as a function of in-plane orientation for Ar ion beams. The minimum sputter yield exists at an ion beam orientation corresponding to the MgO <110> direction. The finite width of the sputter yield minimum is attributable to two main factors: (i) only a fraction of the incident ions are oriented to travel directly down the center of the channel and (ii) ions that are not exactly parallel to the channeling direction may channel. While the simulations imply that it is possible to in-plane orient {001} MgO films using IBAD, there are fundamental limitations on the degree of ordering that can be achieved. © 2001 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Direct molecular dynamics simulation of atomic deposition under realistic conditions is notoriously challenging because of the wide range of time scales that must be captured. Numerous simulation approaches have been proposed to address the problem, often requiring a compromise between model fidelity, algorithmic complexity, and computational efficiency. Coarse projective integration, an example application of the "equation-free" framework, offers an attractive balance between these constraints. Here, periodically applied, short atomistic simulations are employed to compute time derivatives of slowly evolving coarse variables that are then used to numerically integrate differential equations over relatively large time intervals. A key obstacle to the application of this technique in realistic settings is the "lifting" operation in which a valid atomistic configuration is recreated from knowledge of the coarse variables. Using Ge deposition on amorphous SiO2 substrates as an example application, we present a scheme for lifting realistic atomistic configurations comprised of collections of Ge islands on amorphous SiO2 using only a few measures of the island size distribution. The approach is shown to provide accurate initial configurations to restart molecular dynamics simulations at arbitrary points in time, enabling the application of coarse projective integration for this morphologically complex system. [ABSTRACT FROM AUTHOR]

Direct molecular dynamics simulation of atomic deposition under realistic conditions is notoriously challenging because of the wide range of time scales that must be captured. Numerous simulation approaches have been proposed to address the problem, often requiring a compromise between model fidelity, algorithmic complexity, and computational efficiency. Coarse projective integration, an example application of the "equation-free" framework, offers an attractive balance between these constraints. Here, periodically applied, short atomistic simulations are employed to compute time derivatives of slowly evolving coarse variables that are then used to numerically integrate differential equations over relatively large time intervals. A key obstacle to the application of this technique in realistic settings is the "lifting" operation in which a valid atomistic configuration is recreated from knowledge of the coarse variables. Using Ge deposition on amorphous SiO2 substrates as an example application, we present a scheme for lifting realistic atomistic configurations comprised of collections of Ge islands on amorphous SiO2 using only a few measures of the island size distribution. The approach is shown to provide accurate initial configurations to restart molecular dynamics simulations at arbitrary points in time, enabling the application of coarse projective integration for this morphologically complex system. [ABSTRACT FROM AUTHOR]

Examines the surface morphology of indium films by scanning tunneling microscopy. Vertical surface displacement on the films; Atomistic simulations within a valence force field model; Misfit dislocation network at the semicoherent interface.

A phenomenological mean-field theory is presented for the kinetics of strain relaxation due to misfit dislocation generation in the strained-layer growth of epitaxial semiconductor films on thin compliant substrates. The theory provides a generalized dislocation kinetic framework by coupling the mechanics of an epitaxial film on a compliant substrate with a well-known description of plastic deformation dynamics in semiconductor crystals. The theoretical results reproduce successfully recent experimental data for strain relaxation in the InAs/GaAs(110) heteroepitaxial system. © 1998 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Interfacial stability and the morphology of the epitaxial film surface have been studied in InAs/GaAs(111)A heteroepitaxy based on atomistic simulations and scanning tunneling microscopy. Effects of buffer layer thickness were examined by analyzing two heteroepitaxial systems consisting of thin and thick GaAs buffer layers. In both cases, one monolayer of In[sub 0.50]Ga[sub 0.50]As is grown initially on the buffer layer prior to InAs growth. Our results indicate that film compositional grading and the resulting segregation of In atoms at defects in the semicoherent interface can be used effectively in conjunction with the mechanical compliance of thin buffer layers to delay the completion of the coherent-to-semicoherent interfacial transition. © 2000 American Institute of Physics. [ABSTRACT FROM AUTHOR]

The mechanical behavior of thin buffer layers for InAs/GaAs(111)A heteroepitaxy has been investigated by x-ray diffraction (XRD). XRD θ-2θ spectra are presented for the (220) reflection for two monolayers (MLs) of InAs deposited on GaAs buffer layers of both 20 ML and 150 nm (≅ 460 ML) in thickness. For the thicker buffer layer, the XRD spectrum exhibits a single, symmetric peak at a reflected angle corresponding to the bulk GaAs lattice parameter, while for the thinner one it exhibits asymmetry around the GaAs substrate reflection with the spectrum tailing to lower angle. This indicates that the thin buffer layer possesses a distribution of interlayer distances in the [220] direction that are larger than that of the GaAs substrate. The XRD data agree very well with theoretical calculations in which the thin GaAs buffer layer is modeled as unconstrained at its base. Our results provide direct evidence that thin GaAs buffer layers behave mechanically similarly to compliant substrates. © 2000 American Institute of Physics. [ABSTRACT FROM AUTHOR]

The article presents information on the requirement of the Monte Carlo algorithm for the purpose of studying the atomistic simulations of the precipitation in the alloys. The transmutation of the simulations of the multicomponent systems is allowed by the semi-grand-canonical ensemble. Information on the study of the precipitation of copper in the nanocrystalline iron through the algorithm is also presented.