We study the charge state of the diffusing O$_2$ molecule during silicon oxidation through hybrid functional calculations. We calculate charge transition levels of O$_2$ in bulk SiO$_2$ and use theoretical band offsets to align these levels with respect to the Si band edges. To overcome the band-gap problem of semilocal density fuctionals, we employ hybrid functionals with both predefined and empirically adjusted mixing coefficients. We find that the charge transition level $ε^{0/-}$ in bulk SiO$_2$ occurs at $\sim$1.1 eV above the silicon conduction band edge, implying that the O$_2$ molecule diffuses through the oxide in the neutral charge state. While interfacial effects concur to lower the charge transition level, our estimates suggest that the neutral charge state persists until silicon oxidation.
We investigate nanoscale local anodic oxidation (LAO) on hydrogen-intercalated graphene grown by controlled sublimation of silicon carbide (SiC). Scanning probe microscopy (SPM) was used as a lithographic and characterization tool in order to investigate the local properties of the nanofabricated structures. The anomalous thickness observed after the graphene oxidation process is linked to the impact of LAO on the substrate. Micro-Raman spectroscopy was employed to demonstrate the presence of two oxidation regimes depending on the applied bias. We show that partial and total etching of monolay…
Raman spectroscopy has been used to identify defective bonding in neon and silicon ion irradiated single crystals of 6H-SiC. Observable differences exist in the C-C bonding region corresponding to different defect structures for neon and silicon ion implantations. Raman spectra of ion irradiated SiC show less tensile strain than neutron irradiations, explained by a residual compressive stress caused by the swelling constrained by the undamaged substrate. Evidence of oxidation during high temperature ion implantation is observed as C-O and Si-O Raman signals. Annealing irradiated SiC while acqu…
Self-limiting oxidation of nanowires has been previously described as a reaction- or diffusion-controlled process. In this letter, the concept of finite reactive region is introduced into a diffusion-controlled model, based upon which a two-dimensional cylindrical kinetics model is developed for the oxidation of silicon nanowires and is extended for tungsten. In the model, diffusivity is affected by the expansive oxidation reaction induced stress. The dependency of the oxidation upon curvature and temperature is modeled. Good agreement between the model predictions and available experimental d…
Antimonene, a new group-VA 2D semiconducting material beyond phosphorene, was recently synthesized through various approaches and was shown to exhibit a good structural integrity in ambient conditions and various interesting properties. In this work, we perform systematical first-principles investigations on the interactions of antimonene with the small molecules CO, NO, NO2, H2O, O2, NH3 and H2. It is found that NO, NO2, H2O, O2, and NH3 serve as charge acceptors, while CO shows a negligible charge transfer. H2 acts as a charge donor to antimonene with the amount of charge transfer being ten …
A study of wetting was carried out on porous silicon films with pore diameters spanning three orders of magnitude. Water contact angle measurements on adjoining porous and nonporous regions yielded Wenzel roughness ratios that were either unphysical (less than unity) or unrealistically low when compared to those expected from specific surface area considerations. Moreover, results obtained from a sample consisting of a microporous film on a macroporous layer gave contact angles that were very similar to those found on films consisting of only a single microporous layer, contrary to what would …
We have performed electronic state calculations to clarify the initial stage of the oxidation of the Si- and C-faces in 4H-SiC based on the density-functional theory. We investigate how each Si and C atomic site is oxidized on C- and Si-face, and explore most probable reaction pathways, corresponding energy barriers, and possible defects generated during the oxidation. We have found that carbon annihilation process is different between on Si- and on C-face, and this difference causes different defects in interface; In C-face case, (1), carbon atoms are dissociated directly from the substrate a…
We report first-principles static and dynamic calculations that clarify the microscopic mechanism of carbon annihilation due to phosphorous treatment upon oxidation of silicon carbide (SiC). We identify the most stable form of the phosphorus (P) in the oxide as the four-fold coordinated with the dangling PO unit and find that the unit attracts carbon ejected from the interface, thus operating as a carbon absorber. This finding provides a microscopic reasoning for the first time for the promotion of the oxidation reaction on one hand and the annihilation of the C-related defects at the interfac…
Arsenene, a new group V two-dimensional (2D) semiconducting material beyond phosphorene and antimonene, has recently gained an increasing attention owning to its various interesting properties which can be altered or intentionally functionalized by chemical reactions with various molecules. This work provides a systematic study on the interactions of arsenene with the small molecules, including H2, NH3, O2, H2O, NO, and NO2. It is predicted that O2, H2O, NO, and NO2 are strong acceptors, while NH3 serves as a donor. Importantly, it is shown a negligible charge transfer between H2 and arsenene …
Many biological materials exhibit a multiscale porosity with small, mostly nanoscale pores as well as large, macroscopic capillaries to simultaneously achieve optimized mass transport capabilities and lightweight structures with large inner surfaces. Realizing such a hierarchical porosity in artificial materials necessitates often sophisticated and expensive top-down processing that limits scalability. Here we present an approach that combines self-organized porosity based on metal-assisted chemical etching (MACE) with photolithographically induced macroporosity for the synthesis of single-cry…
A digital etching method was proposed to achieve excellent control of etching depth. The digital etching characteristics of p+ Si and Si0.7Ge0.3 using the combinations of HNO3 oxidation and BOE oxide removal processes were studied. Experiments showed that oxidation saturates with time due to low activation energy. A physical model was presented to describe the wet oxidation process with nitric acid. The model was calibrated with experimental data and the oxidation saturation time, final oxide thickness, and selectivity between Si0.7Ge0.3 and p+ Si were obtained. The digital etch of laminated S…
The service lives of nickel superalloys are often limited by environmental degradation. The present study compares oxidation, sulfidation and hot corrosion at 750C of three variants of a polycrystalline superalloy: a baseline alloy, a variant containing 1wt% Mn and one containing 0.5wt% Si. Mn reduced the oxidation rate without changing the scale morphology. The MnCr2O4 scale formed proved more protective against sulfidation and hot corrosion, but internal sulfides extended the damage depth. Si modified the oxide morphology to a continuous Cr2O3-Al2O3 dual layer. This provided improved protect…
The first principles density functional theory (DFT) calculations have been used to investigate the atomic and electronic properties of thiadiazole adsorption on the Si(001) surface. A (2x2) reconstructed clean substrate surface has been chosen to give the molecule sufficient space to relax into its most favorable position. A total of eighteen bonding model including bridge-type bonding, and [2+2]/[4+2] cycloaddition mechanisms for four structural isomers of thiadiazole molecule have been discussed in these calculations. The most stable bonding configuration for each of the four isomers on the…
Hydration properties of graphene oxide (GO) are essential for most of its potential applications. In this work, we employ atomistic molecular dynamics simulations to investigate seven GO compositions with different levels of oxygenation. Two atomic charge models for GO are compared: (1) sp2 carbons are purely Lennard-Jones sites; (2) sp2 carbon charges are consistent with the CHELPG scheme. Structural properties were found to depend insignificantly on the charge model, whereas thermodynamics appeared very sensitive. In particular, the simplified model provides systematically stronger GO/water …
Comparison of Process of Diffusion of Interstitial Oxygen Atoms and Interstitial Hydrogen Molecules in Silicon and Germanium Crystals: Quantumchemical Simulation
We determined the interface state density ($D_{\rm it}$) distributions in the vicinity of the conduction band edge in silicon carbide (SiC) metal-oxide-semiconductor (MOS) structures by reproducing the experimental current-voltage characteristics of MOS field effect transistors (MOSFETs) with numerical calculations. In the calculation, potential distributions and energy sub-bands in the inversion layer were calculated by solving Poisson and Schrödinger equations, respectively. We demonstrate that gate characteristics of the MOSFETs are well described by considering that the interface states ar…
Isolated oxygen impurities and fully oxidized structures of four stable two-dimensional (2D) SiS structures are investigated by {\em ab initio} density functional calculations. Binding energies of oxygen impurities for all the four 2D SiS structures are found larger than those for phosphorene, due to the lower electronegativity of Si atoms. The most stable configurations of isolated oxygen impurities for different 2D SiS structures are decided and the corresponding 2D structures with saturated oxidation (SiSO) are predicted. Among all the four fully oxidized structures, $α$-SiSO is demonstrate…
We report static and dynamic first-principles calculations that provide atomistic pictures of the initial stage of the oxidation processes occurring at the ($11\bar20$) surface of 4H-SiC. Our results unveil reaction pathways and their associated free-energy barriers for the adsorption of oxygen and the desorption of carbon atoms. We find that oxygen adsorption shows structural multi-stability and that the surface-bridge sites are the most stable and crucial sites for subsequent oxidation. We find that an approaching O$_2$ molecule is adsorbed, then dissociated and finally migrates toward these…
The measurement of the lattice-parameter of silicon by x-ray interferometry assumes the use of strain-free crystals. This might not be the case because surface relaxation, reconstruction, and oxidation cause strains without the application of any external force. In a previous work, this intrinsic strain was estimated by a finite element analysis, where the surface stress was modeled by an elastic membrane having a 1 N/m tensile strength. The present paper quantities the surface stress by a density functional theory calculation. We found a value exceeding the nominal value used, which potential…
Hydrogen Diffusion in Silicon - An ab initio Study of Hydrogen Kinetic Properties in Silicon
本文采用密度泛函理论计算了硅中氢缺陷的迁移和分解势垒等动力学性质。我们研究了以下缺陷：H原子（H）和离子（H+，H-），氢分子（H2）和氢络合物（H2*）。结果表明，主要的迁移物种是H离子，其电荷无关的迁移势垒为0.46 eV，与实验值[1]非常吻合。在较高的温度下，H2和H2* 分别以1.2和1.5 eV的势垒分解，而H2的迁移势垒为2.2 eV。因此，我们表明，与先前实验暗示的相反[2，3]，在硅中，氢分子不参与通过扩散的氢传输。1. A. Van Wieringen和N. Warmoltz，Physica 22，849（1956）. 2. S.拉奥，S。K. Dianjin，G. Lupke，N. H. Tolk和L. C. Feldman，Physical Review B 75，6（2007）. 3. N. Escherichiata，A. Kasuya和M. Suezawa，Physica B 308，1125（2001）.
Hydrogen point defects in silicon still hold unsolved problems, whose disclosure is fundamental for future advances in Si technologies. Among the open issues is the mechanism for the condensation of atomic hydrogen into molecules in Si quenched from above $T\sim700\,^{\circ}$C to room temperature. Based on first-principles calculations, we investigated the thermodynamics of hydrogen monomers and dimers at finite temperatures within the harmonic approximation. The free energies of formation indicate that the population of H$^{-}$ cannot be neglected when compared that of H$^{+}$ at high tempera…
Inorganic-organic interfaces are important for enhancing the power conversion efficiency of silicon-based solar cells through singlet exciton fission (SF). We elucidated the structure of the first monolayers of tetracene (Tc), a SF molecule, on hydrogen-passivated Si(111) [H-Si(111)] and hydrogenated amorphous Si (a-Si:H) by combining near-edge X-ray absorption fine structure (NEXAFS) and X-ray photoelectron spectroscopy (XPS) experiments with density functional theory (DFT) calculations. For samples grown at or below substrate temperatures of 265 K, the resulting ultrathin Tc films are domina…
