Calculation of point defects in rutile TiO 2 by the screened-exchange hybrid functional

The formation energies of the oxygen vacancy and titanium interstitial in rutile TiO 2 were calculated by the screened-exchange (sX) hybrid density functional method, which gives a band gap of 3.1 eV, close to the experimental value. The oxygen vacancy gives rise to a gap state lying 0.7 eV below the conduction band edge, whose charge density is localized around the two of three Ti atoms next to the vacancy. The Ti interstitial (Ti int) generates four defect states in the gap, whose unpaired electrons lie on the interstitial and the adjacent Ti 3d orbitals. The formation energy for the neutral oxygen vacancy is 1.9 eV for the O-poor chemical potential. The neutral Ti interstitial has a lower formation energy than the O vacancy under O-poor conditions. This indicates that both the O vacancy and Ti int are relevant for oxygen deficiency in rutile TiO 2 but the O vacancy will dominate under O-rich conditions. This resolves questions about defect localization and defect predominance in the literature. © 2012 American Physical Society.

Creation and suppression of point defects through a kick-out substitution process of Fe in InP

Indium antisite defect In-P-related photoluminescence has been observed in Fe-diffused semi-insulating (SI) InP. Compared to annealed undoped or Fe-predoped SI InP, there are fewer defects in SI InP obtained by long-duration, high-temperature Fe diffusion. The suppression of the formation of point defects in Fe-diffused SI InP can be explained in terms of the complete occupation by Fe at indium vacancy. The In-P defect is enhanced by the indium interstitial that is caused by the kick out of In and the substitution at the indium site of Fe in the diffusion process. Through these Fe-diffusion results, the nature of the defects in annealed undoped SI InP is better understood. (C) 2002 American Institute of Physics.

Point defects in III-V compound semiconductors

Point defects in III-V compound semiconductors were analyzed systematically in this paper. The effects of substitutes, antisites, interstitials, and vacancies on lattice parameters in III-V compound semiconductors were calculated with a simple model. The formation energies of vacancies in compound semiconductors can be obtained by this calculation. A practical technique established on this model has been utilized for measuring the stoichiometry in GaAs. The relationship between stoichiometry and deep level centers in GaAs was also investigated.

Evolution from point defects to arsenic clusters in low-temperature grown GaAs/AlGaAs multiple quantum wells

Optical transient current spectroscopy (OTCS), photoluminescence (PL) spectroscopy and excitonic electroabsorption spectroscopy have been used to investigate the evolution of defects in the low-temperature grown GaAs/AlGaAs multiple quantum well structures during the postgrowth rapid thermal annealing. The sample was grown at 350 degrees C by molecular beam epitaxy on miscut (3.4 degrees off (001) towards (111)A) (001) GaAs substrate. After growth, the sample was subjected to 30s rapid thermal annealing in the range of 500-800 degrees C. It is found that the integrated PL intensity first decreases with the annealing temperature, then gets a minimum at 600 degrees C and finally recovers at higher temperatures. OTCS measurement shows that besides As,, antisites and arsenic clusters, there are several relatively shallower deep levels with excitation energies less than 0.3 eV in the as-grown and 500 degrees C-annealed samples. Above 600 degrees C, OTCS signals from As,, antisites and shallower deep levels become weaker, indicating the decrease of these defects. It is argued that the excess arsenic atoms group together to form arsenic clusters during annealing. (C) 2000 Elsevier Science B.V. All rights reserved.

Ultrafast low-temperature grown AlGaAs/GaAs photorefractive quantum wells using point defects as capture centers

At a medium substrate temperature of 400 degrees C and a lower As flux, we have grown an ultrafast AlGaAs/GaAs photorefractive multiple quantum well (MQW) structure by molecular beam epitaxy. The as-grown sample exhibits strong photorefractive effect under the transverse Frantz-Keldysh geometry. A peak electroabsorption of 2100 cm(-1) is measured in the as-grown sample in an 11 kV/cm dc electric field, and the peak photorefractive diffraction efficiency can be 1.2%. After postgrowth annealing, the photorefractive effect becomes weak and disappears in samples annealed above 700 degrees C. Using optical transient current spectroscopy, deep levels are measured in these samples. It is found that deep levels are stable against annealing until 700 degrees C. Using a pump-probe technique, carrier lifetimes are measured at room temperature. We find that the as-grown sample has a lifetime of 20 ps, while the 700 degrees C annealed sample has a lifetime of more than 200 ps. The ultrafast lifetime in the as-grown sample is caused by point defects, not by As clusters. Our result show that AlGaAs/GaAs MQW structure grown around 400 degrees C has better performance of the photorefractive effect. (C) 1999 American Institute of Physics. [S0003-6951(99)04036-X].

Effects of point defects on lattice parameters of semiconductors

A model for analyzing the correlation between lattice parameters and point defects in semiconductors has been established. The results of this model for analyzing the substitutes in semiconductors are in accordance with those from Vegard's law and experiments. Based on this model, the lattice strains caused by the antisites, the tetrahedral and octahedral single interstitials, and the interstitial couples are analyzed. The superdilation in lattice parameters of GaAs grown at low temperatures by molecular-beam epitaxy can be interpreted by this model, which is in accordance with the experimental results. This model provides a way of analyzing the stoichiometry in bulk and epitaxial compound semiconductors nondestructively.

The Influence of Point Defects and Inhomogeneous Strain on the Functional Behaviour of Thin film Ferroelectrics

An attempt has been made to unequivocally identify the influence that inhomogeneous strain fields, surrounding point defects, have on the functional properties of thin film ferroelectrics. Single crystal thin film lamellae of BaTiO3 have been integrated into capacitor structures, and the functional differences between those annealed in oxygen and those annealed in nitrogen have been mapped. Key features, such as the change in the paraelectric-ferroelectric phase transition from first to second order were noted and found to be consistent with mean field modeling predictions for the effects of inhomogeneous strain. Switching characteristics appeared to be unaffected, suggesting that point defects have a low efficacy in domain wall pinning.

Measurement of the full stress tensor in a crystal using photoluminescence from point defects: The example of nitrogen vacancy centers in diamond

We introduce a method for measuring the full stress tensor in a crystal utilising the properties of individual point defects. By measuring the perturbation to the electronic states of three point defects with C 3 v symmetry in a cubic crystal, sufficient information is obtained to construct all six independent components of the symmetric stress tensor. We demonstrate the method using photoluminescence from nitrogen-vacancy colour centers in diamond. The method breaks the inverse relationship between spatial resolution and sensitivity that is inherent to existing bulk strain measurement techniques, and thus, offers a route to nanoscale strain mapping in diamond and other materials in which individual point defects can be interrogated.

Electronic structure of point defects in controlled self-doping of the TiO2 (110) surface: Combined photoemission spectroscopy and density functional theory study

Point defects in metal oxides such as TiO2 are key to their applications in numerous technologies. The investigation of thermally induced nonstoichiometry in TiO2 is complicated by the difficulties in preparing and determining a desired degree of nonstoichiometry. We study controlled self-doping of TiO2 by adsorption of 1/8 and 1/16 monolayer Ti at the (110) surface using a combination of experimental and computational approaches to unravel the details of the adsorption process and the oxidation state of Ti. Upon adsorption of Ti, x-ray and ultraviolet photoemission spectroscopy (XPS and UPS) show formation of reduced Ti. Comparison of pure density functional theory (DFT) with experiment shows that pure DFT provides an inconsistent description of the electronic structure. To surmount this difficulty, we apply DFT corrected for on-site Coulomb interaction (DFT+U) to describe reduced Ti ions. The optimal value of U is 3 eV, determined from comparison of the computed Ti 3d electronic density of states with the UPS data. DFT+U and UPS show the appearance of a Ti 3d adsorbate-induced state at 1.3 eV above the valence band and 1.0 eV below the conduction band. The computations show that the adsorbed Ti atom is oxidized to Ti2+ and a fivefold coordinated surface Ti atom is reduced to Ti3+, while the remaining electron is distributed among other surface Ti atoms. The UPS data are best fitted with reduced Ti2+ and Ti3+ ions. These results demonstrate that the complexity of doped metal oxides is best understood with a combination of experiment and appropriate computations.

Point defects in carbon nanostructures studied by in-situ electron microscopy

In the present work, the formation and migration of point defects induced by electron irradiation in carbon nanostructures, including carbon onions, nanotubes and graphene layers, were investigated by in-situ TEM. The mobility of carbon atoms normal to the layers in graphitic nanoparticles, the mobility of carbon interstitials inside SWCNTs, and the migration of foreign atoms in graphene layers or in layers of carbon nanotubes were studied. The diffusion of carbon atoms in carbon onions was investigated by annealing carbon onions and observing the relaxation of the compressed clusters in the temperature range of 1200 – 2000oC. An activation energy of 5.0±0.3 eV was obtained. This rather high activation energy for atom exchange between the layers not only prevents the exchange of carbon atoms between the layers at lower temperature but also explains the high morphological and mechanical stability of graphite nanostructures. The migration of carbon atoms in SWCNTs was investigated quantitatively by cutting SWCNT bundles repeatedly with a focused electron beam at different temperatures. A migration barrier of about 0.25 eV was obtained for the diffusion of carbon atoms inside SWCNTs. This is an experimental confirmation of the high mobility of interstitial atoms inside carbon nanotubes, which corroborates previously developed theoretical models of interstitial diffusivity. Individual Au and Pt atoms in one- or two-layered graphene planes and MWCNTs were monitored in real time at high temperatures by high-resolution TEM. The direct observation of the behavior of Au and Pt atoms in graphenic structures in a temperature range of 600 – 700°C allows us to determine the sites occupied by the metal atoms in the graphene layer and the diffusivities of the metal atoms. It was found that metal atoms were located in single or multiple carbon vacancies, not in off-plane positions, and diffused by site exchange with carbon atoms. Metal atoms showed a tendency to form clusters those were stable for a few seconds. An activation energy of around 2.5 eV was obtained for the in-plane migration of both Au and Pt atoms in graphene (two-dimensional diffusion). The rather high activation energy indicates covalent bonding between metal and carbon atoms. Metal atoms were also observed to diffuse along the open edge of graphene layers (one-dimensional diffusion) with a slightly lower activation energy of about 2.3 eV. It is also found that the diffusion of metal atoms in curved graphenic layers of MWCNTs is slightly faster than in planar graphene.

From point defects to plate tectonic faults

Understanding and explaining emergent constitutive laws in the multi-scale evolution from point defects, dislocations and two-dimensional defects to plate tectonic scales is an arduous challenge in condensed matter physics. The Earth appears to be the only planet known to have developed stable plate tectonics as a means to get rid of its heat. The emergence of plate tectonics out of mantle convection appears to rely intrinsically on the capacity to form extremely weak faults in the top 100 km of the planet. These faults have a memory of at least several hundred millions of years, yet they appear to rely on the effects of water on line defects. This important phenomenon was first discovered in laboratory and dubbed ``hydrolytic weakening''. At the large scale it explains cycles of co-located resurgence of plate generation and consumption (the Wilson cycle), but the exact physics underlying the process itself and the enormous spanning of scales still remains unclear. We present an attempt to use the multi-scale non-equilibrium thermodynamic energy evolution inside the deforming lithosphere to move phenomenological laws to laws derived from basic scaling quantities, develop self-consistent weakening laws at lithospheric scale and give a fully coupled deformation-weakening constitutive framework. At meso- to plate scale we encounter in a stepwise manner three basic domains governed by the diffusion/reaction time scales of grain growth, thermal diffusion and finally water mobility through point defects in the crystalline lattice. The latter process governs the planetary scale and controls the stability of its heat transfer mode.