Band Offsets at Semiconductor-Oxide Interfaces from Hybrid Density Functional Calculations

Band offsets at semiconductor-oxide interfaces are determined through a scheme based on hybrid density functionals, which incorporate a fraction $\alpha$ of Hartree-Fock exchange. For each bulk component, the fraction $\alpha$ is tuned to reproduce the experimental band gap, and the conduction and valence band edges are then located with respect to a reference level. The lineup of the bulk reference levels is determined through an interface calculation, and shown to be almost independent of the fraction $\alpha$. Application of this scheme to the Si-SiO$_2$, SiC-SiO$_2$, and Si-HfO$_2$ interfaces yields excellent agreement with experiment.Comment: 4 pages, 4 figure

Structure and energetics of the Si-SiO_2 interface

Silicon has long been synonymous with semiconductor technology. This unique role is due largely to the remarkable properties of the Si-SiO_2 interface, especially the (001)-oriented interface used in most devices. Although Si is crystalline and the oxide is amorphous, the interface is essentially perfect, with an extremely low density of dangling bonds or other electrically active defects. With the continual decrease of device size, the nanoscale structure of the silicon/oxide interface becomes more and more important. Yet despite its essential role, the atomic structure of this interface is still unclear. Using a novel Monte Carlo approach, we identify low-energy structures for the interface. The optimal structure found consists of Si-O-Si "bridges" ordered in a stripe pattern, with very low energy. This structure explains several puzzling experimental observations.Comment: LaTex file with 4 figures in GIF forma

Pathways of bond topology transitions at the interface of silicon nanocrystals and amorphous silica matrix

The interface chemistry of silicon nanocrystals (NCs) embedded in amorphous oxide matrix is studied through molecular dynamics simulations with the chemical environment described by the reactive force field model. Our results indicate that the Si NC-oxide interface is more involved than the previously proposed schemes which were based on solely simple bridge or double bonds. We identify different types of three-coordinated oxygen complexes, previously not noted. The abundance and the charge distribution of each oxygen complex is determined as a function of the NC size as well as the transitions among them. The oxidation at the surface of NC induces tensile strain to Si-Si bonds which become significant only around the interface, while the inner core remains unstrained. Unlike many earlier reports on the interface structure, we do not observe any double bonds. Furthermore, our simulations and analysis reveal that the interface bond topology evolves among different oxygen bridges through these three-coordinated oxygen complexes.Comment: 5 pages 6 figures 1 tabl

Structure and oxidation kinetics of the Si(100)-SiO2 interface

We present first-principles calculations of the structural and electronic properties of Si(001)-SiO2 interfaces. We first arrive at reasonable structures for the c-Si/a-SiO2 interface via a Monte-Carlo simulated annealing applied to an empirical interatomic potential, and then relax these structures using first-principles calculations within the framework of density-functional theory. We find a transition region at the interface, having a thickness on the order of 20\AA, in which there is some oxygen deficiency and a corresponding presence of sub-oxide Si species (mostly Si^+2 and Si^+3). Distributions of bond lengths and bond angles, and the nature of the electronic states at the interface, are investigated and discussed. The behavior of atomic oxygen in a-SiO2 is also investigated. The peroxyl linkage configuration is found to be lower in energy than interstitial or threefold configurations. Based on these results, we suggest a possible mechanism for oxygen diffusion in a-SiO2 that may be relevant to the oxidation process.Comment: 7 pages, two-column style with 6 postscript figures embedded. Uses REVTEX and epsf macros. Also available at http://www.physics.rutgers.edu/~dhv/preprints/index.html#ng_sio

Hole subbands in strained GaAs-Ga1-xAlxAs quantum wells: Exact solution of the effective-mass equation

Valence subbands of uniaxially stressed GaAs-Ga1-xAlxAs quantum wells are found by solving exactly the multiband effective-mass equation for the envelope function; as in the particle in a box problem, we first solve the effective-mass equation in each bulk material, and then we impose boundary conditions on the linear combinations of bulk solutions. Discrete symmetries of the effective-mass Hamiltonian are used to decouple the spin-degenerate subbands; the energy levels are obtained as the zeros of an 8×8 determinant. The functional form of the wave functions is given analytically, and is used in order to discuss the heavy-hole light-hole mixing at finite values of the in-plane vector k?; the mixing greatly increases when the applied stress reduces the energy separation at k?=0. Resonances are shown to arise and are due to the degeneracy of discrete levels with states of the continuum at different values of k?. © 1987 The American Physical Society

Design of a low band gap oxide ferroelectric: Bi6_6Ti4_4O17_{17}

A strategy for obtaining low band gap oxide ferroelectrics based on charge imbalance is described and illustrated by first principles studies of the hypothetical compound Bi$_6$Ti$_4$O$_{17}$, which is an alternate stacking of the ferroelectric Bi$_4$Ti$_3$O$_{12}$. We find that this compound is ferroelectric, similar to Bi$_4$Ti$_3$O$_{12}$ although with a reduced polarization. Importantly, calculations of the electronic structure with the recently developed functional of Tran and Blaha yield a much reduced band gap of 1.83 eV for this material compared to Bi$_4$Ti$_3$O$_{12}$. Therefore, Bi$_6$Ti$_4$O$_{17}$ is predicted to be a low band gap ferroelectric material

Charging Induced Emission of Neutral Atoms from NaCl Nanocube Corners

Detachment of neutral cations/anions from solid alkali halides can in principle be provoked by donating/subtracting electrons to the surface of alkali halide crystals, but generally constitutes a very endothermic process. However, the amount of energy required for emission is smaller for atoms located in less favorable positions, such as surface steps and kinks. For a corner ion in an alkali halide cube the binding is the weakest, so it should be easier to remove that atom, once it is neutralized. We carried out first principles density functional calculations and simulations of neutral and charged NaCl nanocubes, to establish the energetics of extraction of neutralized corner ions. Following hole donation (electron removal) we find that detachment of neutral Cl corner atoms will require a limited energy of about 0.8 eV. Conversely, following the donation of an excess electron to the cube, a neutral Na atom is extractable from the corner at the lower cost of about 0.6 eV. Since the cube electron affinity level (close to that a NaCl(100) surface state, which we also determine) is estimated to lie about 1.8 eV below vacuum, the overall energy balance upon donation to the nanocube of a zero energy electron from vacuum will be exothermic. The atomic and electronic structure of the NaCl(100) surface, and of the nanocube Na and Cl corner vacancies are obtained and analyzed as a byproduct.Comment: 16 pages, 2 table, 7 figure

Acceleration Schemes for Ab-Initio Molecular Dynamics and Electronic Structure Calculations

We study the convergence and the stability of fictitious dynamical methods for electrons. First, we show that a particular damped second-order dynamics has a much faster rate of convergence to the ground-state than first-order steepest descent algorithms while retaining their numerical cost per time step. Our damped dynamics has efficiency comparable to that of conjugate gradient methods in typical electronic minimization problems. Then, we analyse the factors that limit the size of the integration time step in approaches based on plane-wave expansions. The maximum allowed time step is dictated by the highest frequency components of the fictitious electronic dynamics. These can result either from the large wavevector components of the kinetic energy or from the small wavevector components of the Coulomb potential giving rise to the so called {\it charge sloshing} problem. We show how to eliminate large wavevector instabilities by adopting a preconditioning scheme that is implemented here for the first-time in the context of Car-Parrinello ab-initio molecular dynamics simulations of the ionic motion. We also show how to solve the charge-sloshing problem when this is present. We substantiate our theoretical analysis with numerical tests on a number of different silicon and carbon systems having both insulating and metallic character.Comment: RevTex, 9 figures available upon request, to appear in Phys. Rev.

Identifying the Azobenzene/Aniline reaction intermediate on TiO2-(110) : a DFT Study

Density functional theory (DFT) calculations, both with and without dispersion corrections, have been performed to investigate the nature of the common surface reaction intermediate that has been shown to exist on TiO2(110) as a result of exposure to either azobenzene (C6H5N═NC6H5) or aniline (C6H5NH2). Our results confirm the results of a previous DFT study that dissociation of azobenzene into two adsorbed phenyl imide (C6H5N) fragments, as was originally proposed, is not energetically favorable. We also find that deprotonation of aniline to produce this surface species is even more strongly energetically disfavored. A range of alternative surface species has been considered, and while dissociation of azobenzene to form surface C6H4NH species is energetically favored, the same surface species cannot form from adsorbed aniline. On the contrary, adsorbed aniline is much the most stable surface species. Comparisons with experimental determinations of the local adsorption site, the Ti–N bond length, the molecular orientation, and the associated C 1s and N 1s photoelectron core level shifts are all consistent with the DFT results for adsorbed aniline and are inconsistent with other adsorbed species considered. Possible mechanisms for the hydrogenation of azobenzene required to produce this surface species are discussed

Optical properties of structurally-relaxed Si/SiO2_2 superlattices: the role of bonding at interfaces

We have constructed microscopic, structurally-relaxed atomistic models of Si/SiO$_2$ superlattices. The structural distortion and oxidation-state characteristics of the interface Si atoms are examined in detail. The role played by the interface Si suboxides in raising the band gap and producing dispersionless energy bands is established. The suboxide atoms are shown to generate an abrupt interface layer about 1.60 \AA thick. Bandstructure and optical-absorption calculations at the Fermi Golden rule level are used to demonstrate that increasing confinement leads to (a) direct bandgaps (b) a blue shift in the spectrum, and (c) an enhancement of the absorption intensity in the threshold-energy region. Some aspects of this behaviour appear not only in the symmetry direction associated with the superlattice axis, but also in the orthogonal plane directions. We conclude that, in contrast to Si/Ge, Si/SiO$_2$ superlattices show clear optical enhancement and a shift of the optical spectrum into the region useful for many opto-electronic applications.Comment: 11 pages, 10 figures (submitted to Phys. Rev. B