We have recently developed a method to perform Density Functional Theory calculations in systems with a very large number of atoms, which is based on the use of numerical atomic orbitals as basis sets. The method incorporates Order-N techniques both in the calculation of the Kohn-Sham hamiltonian matrix elements and in the solution of the wave functions, which make the CPU time and memory to scale linearly with the number of atoms, allowing calculations in very large system. In this work, we present results on several test systems to show that the approach and the basis sets used with our method are able to provide an accuracy similar to that of other standard DFT techniques.

γ-hydride precipitation and growth in a zirconium bi-crystal were simulated using a phase field kinetic model. The temporal evolution of the spatially dependent field variables is determined by numerically solving the time-dependent Ginzburg-Landau equations for the structural variables and the Cahn-Hilliard diffusion equation for the concentration variable. The morphology evolution of γ-hydride with and without external load was simulated. It is demonstrated that nucleation density of the hydride at the grain boundary increases as compared to the bulk and favorable hydride precipitation at the grain boundary become weaker when an external load is applied.

A highly efficient algorithm for the reconstruction of microstructures of heterogeneous media from spatial correlation functions is presented. Similar to previously proposed algorithms, the new method relies on Monte Carlo optimization, representing the microstructure on a discrete grid. An efficient way to update the correlation functions after local changes to the structure is introduced. In addition, the rate of convergence is substantially enhanced by selective Monte Carlo moves at interfaces. Speedups over prior methods of more than two orders of magnitude are thus achieved. The algorithm is ideally suited for parallel computers. The increase in efficiency brings new classes of problems within the realm of the tractable, notably those involving several different structural length scales and/or components.

A molecular statistical mechanical method is employed to compute the field dependant permittivity of water contained in the hydrophilic pores of hydrated proton exchange membranes. The anionic (-SO-3) groups in proximity to the pore walls generate spatially varying fields resulting in dielectric saturation, the effects of which are investigated.

We present calculated values of effective masses, bandgap reduction, and Fermi energy of p-doped Si and strained p-doped SiGe layers. The calculations have been made for Ge concentrations in the range 0 to 30% and boron concentration in the range 1018 cm−3 to 3×1020 cm−3. Empirical expressions for the effective masses are given. These expressions and calculated values of the other parameters are convenient for use in computer codes for modeling device processing and performance. To validate the calculated values, we have compared them with the available experimental results. Good agreement between the calculated and the experimental values is found.

The full charge density exact muffin-tin orbitals method has been used to study the stability of lithium-manganese oxides exhibiting different crystallographic allotropes. Calculations have been performed for ferromagnetic and antiferromagnetic phases of LiMnO2 as well as for the phase with local moment disorder. For the ordered LiMnO2 compound we reproduced the correct ground state, the antiferromagnetic orthorhombic structure. The effect of doping LiMnO2 by Co was considered with the aim to predict the stabilization of the layered structure.

Using classical molecular-dynamics simulations, we worked out a simple model of Ion Beam Assisted Deposition (IBAD) of silicon dioxide on an amorphous silica substrate, in view to in- vestigate the modifications of the structural and vibrational properties induced by medium-energy bombardment. Atoms are assumed to interact via the two- and three-body potential developed by Nakano et al.[1]. Analysis of the films grown with increasing ratio, R, of medium-(30 eV) to low- (1 eV) kinetic energy SiO2 particles shows that the density rises rapidly, from 1.3 g/cm3 for R =0 to about 2.3 g/cm3 for R = 0.7. This effect can be associated primarily with structural changes occurring at an intermediate length scale (4-10 Å), as it manifests itself by changes in the so-called first sharp diffraction peak (FSDP), the finger-print of medium range order (MRO) in a-SiO2 glass [2, 3]. We found also that the densification results in a significant decrease of the number of “soft” vibrational modes, occurring in the 0.5-3.5 THz frequency range.

Cu is currently being used as the new generation of advanced interconnects. Beneficial additives or dopants to Cu have been sought to improve the electromigration performance of the Cu interconnects primarily through experimental approaches [1]. As a vital alternative, we have established a virtual simulation procedure to screen the potential dopants to Cu by modeling. There are many factors such as film density, stress, stress- voiding, grain boundary defect / diffusion, interface adhesion / defect / diffusion, grain structures (texture, grain size and size distribution) and so on that can affect the electromigration. Here we assume that Cu diffusion along the grain boundaries (GBs) is the dominant mechanism that is responsible for the electromigration performance of the Cu interconnects. As schematically shown in Fig.1, if a dopant is added to Cu, most of the dopant will reside in bulk initially. In order for the dopant to play a beneficial role, it has to be able to segregate to the grain boundary. Then, the dopant is supposed to slow down Cu diffusion along the grain boundary and this can be achieved if the dopant can increase the overall activation energy of Cu grain boundary diffusion.

Fluorescent dyes including Nile Red (NR), fluorescein, rhodamine and 4- (dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM) derivatives were investigated to find an application for the organic light emitting device (OLED). Relationship between the molecular structure and optical property was calculated by ab initio (HF and DFT/6-31G*) and semiempirical (AM1/PM3 and INDO/S) calculation methods for the geometry optimization and for the information of electronic transition, respectively. The absorption maximum and the oscillator strength of molecules strongly depended on the molecular dipole moment, especially for the molecules having both strong electron donor and acceptor group. Since the calculated results were comparable with several experimental results, these semiempirical molecular orbital calculation methods could be used as a powerful prediction tool for optical properties of the luminescent molecules.

A new solid-state embedding approach has been developed which focuses on modelling the surfaces of polar materials. The method is applied to investigate the chemisorption of pre- methanol species on the polar (000-1) surface of zincite (a major phase of zinc oxide having the wurtzite structure). Initial results include the geometries of active sites and adsorbates in different charge states.

The concept of macroscopic polarization is the basic one in the electrostatics of dielectric materials: but for many years this concept has evaded even a precise microscopic definition, and has severely challenged quantum-mechanical calculations. This concept has undergone a genuine revolution in recent years (1992 onwards). It is now pretty clear that—contrary to a widespread incorrect belief—macroscopic polarization has nothing to do with the periodic charge distribution of the polarized crystal: the former is essentially a property of the phase of the electronic wavefunction, while the latter is a property of its modulus. An outline of the modern viewpoint is presented. Experiments invariably address polarization derivatives (permittivity, piezoelectricity, pyroelectricity,…) or polarization differences (ferroelectricity), and these differences are measured as an integrated electrical current. The modern theory addresses this same current, which is dominated by the phase of the electronic wavefunctions. First-principle calculations based on this theory are in spectacular agreement with experiments, and provide thorough understanding of the behavior of dielectric materials.

Following recent works that report a non linear dependence of the lattice parameter versus composition in some semiconductor alloys the InGaAs/InP system has been investigated. The lattice parameter and the composition of InGaAs/InP lattice matched heterostructures have been independently determined by measuring the high resolution X-ray diffraction profile and the absorption of the X-ray beam diffracted from the InP substrate. In contrast with previous results that stated a linear dependence of the lattice parameter with composition, a 6% larger In content in the InGaAs/InP lattice matched alloy is found. Such result has been confirmed by the analysis of the X-ray fluorescence induced by an electron beam on the layer and on standards made of InAs and GaAs fine ground crystals. The result is in good agreement with the predictions of models based on the elasticity theory applied on a microscopic scale.

The continued safe operation of nuclear reactors and their potential for lifetime extension depends on ensuring reactor pressure vessel integrity. Reactor pressure vessels and structural materials used in nuclear energy applications are exposed to intense neutron fields that create atomic displacements and ultimately change material properties. The physical processes involved in radiation damage are inherently multiscale, spanning more than 15 orders of magnitude in length and 24 orders of magnitude in time. This paper reports our progress in developing an integrated, multiscale-multiphysics (MSMP) model of radiation damage for the prediction of reactor pressure vessel embrittlement. Key features of the fully integrated MSMP model include: i) combined molecular dynamics (MD) and kinetic lattice Monte Carlo (KMC) simulations of cascade defect production and cascade aging to produce cross-sections for vacancy, self- interstitial and vacancy-solute cluster size classes for times on the order of seconds; ii) an integrated reaction rate theory and thermodynamic code to predict the evolution of nanostructural and nanochemical features for times on the order of decades; iii) a micromechanics model to calculate the resulting mechanical property changes. This paper will focus on the combined use of MD and KMC to simulate the long-term rearrangement (aging) of defects in displacement cascades and thus, produce late-time production cross-sections for vacancy and vacancy cluster features.

A model for calculating the lattice thermal conductivity in semiconductor thin films and nanowires is developed. It is based on the solution of phonon Boltzmann equation and takes into account phonon dispersion modification due to confinement effects and non-equilibrium phonon redistribution. Phonon spatial confinement at the structure boundaries leads to modification of the acoustic phonon dispersion and corresponding drop in the mode-averaged group velocity. Scattering from rough boundaries and interfaces introduces a change in the non-equilibrium phonon distribution as compared to bulk. These effects lead to a reduction in the in-plane lattice thermal conductivity in both thin films and nanowires. The predicted values for the lattice thermal conductivity and their temperature and interface roughness dependence are in good agreement with available experimental data.

The observation of intense luminescence in Si/SiO2 superlattices (SLs) has lead to new theoretical research on silicon-based materials. We have performed first-principles calculations using three Si/SiO2 SL models in order to examine the role of interfaces on the electronic structure and optical properties. The first two models are derived directly from crystalline structures and have simple interfaces. These models have been studied using the full-potential, linearized-augmented-plane-wave method, in the local-density-approximation (LDA). The optical absorption within the interband transition theory (excluding excitonic effects) have been deduced. The Si(001)-SiO2 interface structure is shown to affect the optical behaviour. Following these observations, we have considered a more realistic, fully-relaxed model. The projector-augmented-wave method under the LDA is used to perform the structural relaxation as well as band structure and optical calculations. The role of confinement on the energy gap is studied by inserting additional silicon slabs into the supercell. Direct energy gaps are observed and the energy gap is found to decrease with increasing silicon slab thickness, as observed experimentally. The role of the interface has been considered in more details by studying the contribution to the energy gap of Si atoms having different oxidation patterns; partially oxidized Si atoms at the interface, as well as Si atoms inside the Si layer, are shown to contribute to the transitions at the energy gap.

We analyze the electron energy spectrum in three-dimensional regimented arrays of semiconductor quantum dots. The coupling among quantum dots results in formation of three- dimensional electron mini-bands. Changing the size of quantum dots, inter-dot distance, barrier height and regimentation, one can control the electronic band structure of this quantum dot superlattice, which can also be referred to as quantum dot crystal due to its structure and energy spectrum that resemble those of a real crystal. Results of computer simulations carried out for a tetragonal InAs/GaAs quantum dot superlattice show that the electron density of states, effective mass tensor and other properties are different from those of bulk and conventional quantum well superlattices.