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In the same way that gases interact with oxide semiconductor surfaces from above, point defects interact from below. Previous experiments have described defect–surface reactions for TiO2(110), but an atomistic picture of the mechanism remains unknown. The present work employs computations by density functional theory of the thermodynamic stabilities of metastable states to elucidate possible reaction pathways for oxygen interstitial atoms at TiO2(110). The simulations uncover unexpected metastable states including dumbbell and split configurations in the surface plane that resemble analogous interstitial species in the deep bulk. Comparison of the energy landscapes involving neutral (unionized) and charged intermediates shows that the Fermi energy EF exerts a strong influence on the identity of the most likely pathway. The largest elementary-step thermodynamic barrier for interstitial injection trends mostly downward by 2.1 eV as EF increases between the valence and conduction band edges, while that for annihilation trends upward by 2.1 eV. Several charged intermediates become stabilized for most values of EF upon receiving conduction band electrons from TiO2, and the behavior of these species governs much of the overall energy landscape. [ABSTRACT FROM AUTHOR]

Low bond coordination of surface atoms facilitates the injection of oxygen interstitial atoms into the bulk near room temperature from the clean surfaces of semiconducting metal oxides when exposed to liquid water, opening new prospects for postsynthesis defect engineering and isotopic fractionation. The injection rate and penetration depth vary considerably under identical experimental conditions, however, with the adsorption of adventitious carbon suggested as the cause. For water-submerged rutile TiO2(110) and wurtzite ZnO(0001), this work bolsters and refines that hypothesis by combining the isotopic self-diffusion measurements of oxygen with characterization by x-ray photoelectron spectroscopy and atomic force microscopy. Adventitious carbon likely diminishes injection rates by poisoning small concentrations of exceptionally active surface sites that either inject O or dissociate adsorbed OH to injectable O. These effects propagate into the penetration depth via the progressive saturation of Oi traps near the surface, which occurs less extensively as the injected flux decreases. [ABSTRACT FROM AUTHOR]

Polar surfaces of semiconducting metal oxides can exhibit structures and chemical reactivities that are distinct from their non-polar surfaces. Using first-principles calculations, we examine O adatom and O2 molecule adsorption on 8 different known ZnO reconstructions including Zn-terminated (Zn-ZnO) and O-terminated (O-ZnO) polar surfaces, and non-polar surfaces. We find that adsorption tendencies are largely governed by the thermodynamic environment, but exhibit variations due to the different surface chemistries of various reconstructions. The Zn-ZnO surface reconstructions which appear under O-rich and H-poor environments are found to be most amenable to O and O2 adsorption. We attribute this to the fact that on Zn-ZnO, the O-rich environments that promote O adsorption also simultaneously favor reconstructions that involve adsorbed O species. On these Zn-ZnO surfaces, O2 dissociatively adsorbs to form O adatoms. By contrast, on O-ZnO surfaces, the O-rich conditions required for O or O2 adsorption tend to promote reconstructions involving adsorbed H species, making further O species adsorption more difficult. These insights about O2 adsorption on ZnO surfaces suggest possible design rules to understand the adsorption properties of semiconductor polar surfaces. [ABSTRACT FROM AUTHOR]

Photostimulated diffusion within solid semiconductors has been examined for many years, but its existence above room temperature has not been unambiguously confirmed. Here, diffusion rates for silicon self-diffusion are shown to change by factors of up to 25 in response to optical fluxes on the order of 1 W/cm2. Results depend on doping type; the rates of both interstitial formation and migration are affected in the case of n-type material. A model based on photostimulated changes in defect charge state explains the primary results, and the basic outlines should apply to a wide variety of semiconductors. [ABSTRACT FROM AUTHOR]

Millisecond annealing techniques with flash lamps or lasers have become increasingly common for activating dopants and eliminating implantation-induced damage after ion implantation for transistor junction formation in silicon. Empirical data show that such techniques confer significant benefits, but key physical mechanisms underlying these benefits are not well understood. The present work employs numerical simulation and analytical modeling to show that for boron, millisecond annealing reduces unwanted dopant spreading by greatly reducing the time for diffusion, which more than compensates for an increased concentration of Si interstitials that promote dopant spreading. Millisecond annealing also favorably alters the relative balance of boron interstitial sequestration by the crystal lattice vs interstitial clusters, which leads to improved electrical activation at depths just short of the junction. [ABSTRACT FROM AUTHOR]

An exact expression for the effective diffusivity of foreign atoms migrating via a fast intermediate, which is valid in all time regimes, is derived for a delta function initial profile. This expression is helpful in the interpretation of dopant diffusion measurements in the case of semiconductor solids.