Band-edge problem in the theoretical determination of defect energy levels: the O vacancy in ZnO as a benchmark case

Calculations of formation energies and charge transition levels of defects routinely rely on density functional theory (DFT) for describing the electronic structure. Since bulk band gaps of semiconductors and insulators are not well described in semilocal approximations to DFT, band-gap correction schemes or advanced theoretical models which properly describe band gaps need to be employed. However, it has become apparent that different methods that reproduce the experimental band gap can yield substantially different results regarding charge transition levels of point defects. We investigate this problem in the case of the (+2/0) charge transition level of the O vacancy in ZnO, which has attracted considerable attention as a benchmark case. For this purpose, we first perform calculations based on non-screened hybrid density functionals, and then compare our results with those of other methods. While our results agree very well with those obtained with screened hybrid functionals, they are strikingly different compared to those obtained with other band-gap corrected schemes. Nevertheless, we show that all the different methods agree well with each other and with our calculations when a suitable alignment procedure is adopted. The proposed procedure consists in aligning the electron band structure through an external potential, such as the vacuum level. When the electron densities are well reproduced, this procedure is equivalent to an alignment through the average electrostatic potential in a calculation subject to periodic boundary conditions. We stress that, in order to give accurate defect levels, a theoretical scheme is required to yield not only band gaps in agreement with experiment, but also band edges correctly positioned with respect to such a reference potential

O2 oxidation reaction at the Si(100)-SiO2 interface: A first-principles investigation

We investigated the oxidation reaction of the O2 molecule at the Si(100)-SiO2 interface by using a constrained ab initio molecular dynamics approach. To represent the Si(100)-SiO2 interface, we adopted several model interfaces whose structural properties are consistent with atomic-scale information obtained from a variety of experimental probes. We addressed the oxidation reaction by sampling different reaction pathways of the O2 molecule at the interface. The reaction proceeds sequentially through the incorporation of the O2 molecule in a Si-Si bond and the dissociation of the resulting network O2-species. The oxidation reaction occurs nearly spontaneously and is exothermic, regardless of the spin state of the O2 molecule. Our study suggests a picture of the silicon oxidation process entirely based on diffusive processe

IS 501 Christian Formation: Kingdom, Church, and World

Clapp, Rodney. Border Crossings. Hauerwas, Stanley and Will Willimon. Resident Aliens Donovan, Vincent. Christianity Rediscovered Wright, Tom. The Challenge of Jesus Yoder, John Howard. The Politics of Jesus Brueggemann, Walter. The Prophetic Imaginationhttps://place.asburyseminary.edu/syllabi/2923/thumbnail.jp

Band Offsets at the Si/SiO2_2 Interface from Many-Body Perturbation Theory

We use many-body perturbation theory, the state-of-the-art method for band gap calculations, to compute the band offsets at the Si/SiO$_2$ interface. We examine the adequacy of the usual approximations in this context. We show that (i) the separate treatment of band-structure and potential lineup contributions, the latter being evaluated within density-functional theory, is justified, (ii) most plasmon-pole models lead to inaccuracies in the absolute quasiparticle corrections, (iii) vertex corrections can be neglected, (iv) eigenenergy self-consistency is adequate. Our theoretical offsets agree with the experimental ones within 0.3 eV

The vibrational dynamics of vitreous silica: Classical force fields vs. first-principles

We compare the vibrational properties of model SiO_2 glasses generated by molecular-dynamics simulations using the effective force field of van Beest et al. (BKS) with those obtained when the BKS structure is relaxed using an ab initio calculation in the framework of the density functional theory. We find that this relaxation significantly improves the agreement of the density of states with the experimental result. For frequencies between 14 and 26 THz the nature of the vibrational modes as determined from the BKS model is very different from the one from the ab initio calculation, showing that the interpretation of the vibrational spectra in terms of calculations using effective potentials can be very misleading.Comment: 7 pages of Latex, 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

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

Isobaric first-principles molecular dynamics of liquid water with nonlocal van der Waals interactions

We investigate the structural properties of liquid water at near ambient conditions using first-principles molecular dynamics simulations based on a semilocal density functional augmented with nonlocal van der Waals interactions. The adopted scheme offers the advantage of simulating liquid water at essentially the same computational cost of standard semilocal functionals. Applied to the water dimer and to ice I-h, we find that the hydrogen-bond energy is only slightly enhanced compared to a standard semilocal functional. We simulate liquid water through molecular dynamics in the N pH statistical ensemble allowing for fluctuations of the system density. The structure of the liquid departs from that found with a semilocal functional leading to more compact structural arrangements. This indicates that the directionality of the hydrogen-bond interaction has a diminished role as compared to the overall attractions, as expected when dispersion interactions are accounted for. This is substantiated through a detailed analysis comprising the study of the partial radial distribution functions, various local order indices, the hydrogen-bond network, and the selfdiffusion coefficient. The explicit treatment of the van der Waals interactions leads to an overall improved description of liquid water

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