We have performed a comprehensive first-principles investigation of native point defects in ZnO based on density functional theory within the local density approximation (LDA) as well as the $\mathrm{LDA}+U$ approach for overcoming the band-gap problem. Oxygen deficiency, manifested in the form of oxygen vacancies and zinc interstitials, has long been invoked as the source of the commonly observed unintentional $n$-type conductivity in ZnO. However, contrary to the conventional wisdom, we find that native point defects are very unlikely to be the cause of unintentional $n$-type conductivity. Oxygen vacancies, which have most often been cited as the cause of unintentional doping, are deep rather than shallow donors and have high formation energies in $n$-type ZnO (and are therefore unlikely to form). Zinc interstitials are shallow donors, but they also have high formation energies in $n$-type ZnO and are fast diffusers with migration barriers as low as $0.57\phantom{\rule{0.3em}{0ex}}\mathrm{eV}$; they are therefore unlikely to be stable. Zinc antisites are also shallow donors but their high formation energies (even in Zn-rich conditions) render them unlikely to be stable under equilibrium conditions. We have, however, identified a different low-energy atomic configuration for zinc antisites that may play a role under nonequilibrium conditions such as irradiation. Zinc vacancies are deep acceptors and probably related to the frequently observed green luminescence; they act as compensating centers in $n$-type ZnO. Oxygen interstitials have high formation energies; they can occur as electrically neutral split interstitials in semi-insulating and $p$-type materials or as deep acceptors at octahedral interstitial sites in $n$-type ZnO. Oxygen antisites have very high formation energies and are unlikely to exist in measurable concentrations under equilibrium conditions. Based on our results for migration energy barriers, we calculate activation energies for self-diffusion and estimate defect-annealing temperatures. Our results provide a guide to more refined experimental studies of point defects in ZnO and their influence on the control of $p$-type doping.

Native point defects in ZnO

Silicon carbide (SiC), a material long known with potential for high-temperature, high-power, high-frequency, and radiation hardened applications, has emerged as the most mature of the wide-bandgap (2.0 eV ≲ Eg ≲ 7.0 eV) semiconductors since the release of commercial 6HSiC bulk substrates in 1991 and 4HSiC substrates in 1994. Following a brief introduction to SiC material properties, the status of SiC in terms of bulk crystal growth, unit device fabrication processes, device performance, circuits and sensors is discussed. Emphasis is placed upon demonstrated high-temperature applications, such as power transistors and rectifiers, turbine engine combustion monitoring, temperature sensors, analog and digital circuitry, flame detectors, and accelerometers. While individual device performances have been impressive (e.g. 4HSiC MESFETs with fmax of 42 GHz and over 2.8 W mm−1 power density; 4HSiC static induction transistors with 225 W power output at 600 MHz, 47% power added efficiency (PAE), and 200 V forward blocking voltage), material defects in SiC, in particular micropipe defects, remain the primary impediment to wide-spread application in commercial markets. Micropipe defect densities have been reduced from near the 1000 cm−2 order of magnitude in 1992 to 3.5 cm−2 at the research level in 1995.

Status of silicon carbide (SiC) as a wide-bandgap semiconductor for high-temperature applications: A review

A common misconception is that the irradiation of solids with energetic electrons and ions has exclusively detrimental effects on the properties of target materials. In addition to the well-known cases of doping of bulk semiconductors and ion beam nitriding of steels, recent experiments show that irradiation can also have beneficial effects on nanostructured systems. Electron or ion beams may serve as tools to synthesize nanoclusters and nanowires, change their morphology in a controllable manner, and tailor their mechanical, electronic, and even magnetic properties. Harnessing irradiation as a tool for modifying material properties at the nanoscale requires having the full microscopic picture of defect production and annealing in nanotargets. In this article, we review recent progress in the understanding of effects of irradiation on various zero-dimensional and one-dimensional nanoscale systems, such as semiconductor and metal nanoclusters and nanowires, nanotubes, and fullerenes. We also consider the t...

Ion and electron irradiation-induced effects in nanostructured materials

A fractal model for predicting the effective thermal conductivity of liquid with suspension of nanoparticles

Silicon in its liquid and amorphous forms occupies a unique position among amorphous materials. Obviously important in its own right, the amorphous form is structurally close to the group of 4–4, 3–5 and 2–6 amorphous semiconductors that have been found to have interesting pressure-induced semiconductor-to-metal phase transitions1,2. On the other hand, its liquid form has much in common, thermodynamically, with water and other ‘tetrahedral network’ liquids that show density maxima3,4,5,6,7. Proper study of the ‘liquid–amorphous transition’, documented for non-crystalline silicon by both experimental and computer simulation studies8,9,10,11,12,13,14,15,16,17, may therefore also shed light on phase behaviour in these related materials. Here, we provide detailed and unambiguous simulation evidence that the transition in supercooled liquid silicon, in the Stillinger–Weber potential18, is thermodynamically of first order and indeed occurs between two liquid states, as originally predicted by Aptekar10. In addition we present evidence to support the relevance of spinodal divergences near such a transition, and the prediction3 that the transition marks a change in the liquid dynamic character from that of a fragile liquid to that of a strong liquid.

Liquid-liquid phase transition in supercooled silicon.

Ferromagnetism persisting above 375 K and anisotropic ferromagnetic resonance (FMR) spectra have been detected for the first time in Si co-implanted with Mn and As and annealed under appropriate conditions. For comparison, semi-insulating GaAs samples have been implanted with the same ions and subsequently annealed. They also exhibit ferromagnetism with a Curie temperature well in excess of 375 K. High-resolution transmission electron microscopy (TEM) performed on the samples with the best magnetic characteristics has shown the presence of nanoclusters due to the segregation of the implanted species in both Si and GaAs. The angular dependence of the FMR spectra also reveals the existence of magnetic clusters with the hard magnetization axis aligned along the four equivalent crystal axes. The spectra are very similar in Si and GaAs, indicating that the clusters in both materials probably consist of hexagonal MnAs.

Ferromagnetism and Ferromagnetic Resonance in Mn Implanted Si and GaAs

RBS and Ellipsometric Investigation of Amorphous GaAs Layers

This work presents data on topographical structure, chemical surface composition, physicochemical properties and corrosion resistance of medical grade titanium after ion implantation. Pure commercial titanium has been implanted with 30 keV Na-, Ca- and P-ions at fluences of 2.0 × 1017 cm-2 and 1.5 × 1017 cm-2, respectively. Some of the samples were heat treated at 600 °C for 40 min. Atomic force microscopy (AFM) was used for surface analysis. The chemical composition was investigated using Rutherford backscattering spectrometry (RBS). Physicochemical investigations were carried out using contact angle measurements to determine the polarity of the modified titanium surfaces. Moreover, the electrokinetic zeta potentials on a physiological pH value have been determined. Finally, the corrosion resistance was examined in simulated body fluid (SBF) containing 4 g/l bovine serum albumin (BSA) using cyclic voltametry. Considering the P-implantations, the measured depth distribution of phosphorus agrees well with calculations. For the implantation of Na and Ca, the concentration of implanted atoms in the maximum of the depth distribution is noticeably lower and the distribution extends to larger depths compared to the predictions. This finding is associated with a strong incorporation of oxygen over the whole penetration depth of the implanted ions. According to topographical and chemical changes different contact angles as well as zeta potentials have been detected for the ion implanted surfaces compared to pure titanium. The electrochemical examinations indicate that the implantation has no negative influence on the corrosion resistance in comparison to unmodified medical grade titanium. The results show that ion implantation using certain ions can be used to design tailor-made titanium surfaces from a physicochemical point of view.

Chemical Behavior and Corrosion Resistance of Medical Grade Titanium after Surface Modification by Means of Ion Implantation Techniques

The amorphisation kinetics of In x Ga 1− x As alloys were investigated using Rutherford backscattering spectrometry in channelling configuration. Using metal organic chemical vapour deposition, epitaxial In x Ga 1− x As layers were grown on either GaAs, InP or InAs over a wide range of stoichiometries. Ion implantation was then performed using 60 keV Ge ions at room temperature. In contrast with Al x Ga 1− x As alloys, In x Ga 1− x As does not exhibit amorphisation kinetics intermediate between the two binary extremes. The amorphisation behaviour was fit using the Hecking model yielding a determination of the relative probabilities of direct impact amorphisation ( P a ) and stimulated amorphisation ( A s ). For In x Ga 1− x As, P a is effectively independent of the stoichiometry whilst A s exhibits a quadratic dependence on x with a maximum at x  ≈ 0.31 (where the critical ion fluence for amorphisation is at a minimum). We attribute the rapid In x Ga 1− x As amorphisation to the local strain induced by a bimodal bond length distribution, the latter demonstrated by previous EXAFS studies.

Amorphous phase formation in ion implanted InxGa1−xAs

Ru Schottky barrier diodes (SBD’s) were fabricated on the Zn face of n-type ZnO. These diodes were irradiated with 1.8 MeV at fluences ranging from 1 ´ 1013 cm-2 to 2.4 ´ 1014 cm-2. Capacitance and current (I) deep level transient spectroscopy (DLTS) was used to characterise the irradiation induced defects. Capacitance DLTS showed that proton irradiation introduced a level, Ep1, at 0.52 eV below the conduction band at an introduction rate of 13±1 cm-1. A defect with a very similar DLTS signature was also present in low concentrations in unirradiated ZnO. I-DLTS revealed that this proton irradiation introduced a defect with an energy level at (0.036± 0.004) eV below the conduction band. This defect is clearly distinguishable from a defect with a level at (0.033± 0.004) eV below the conduction band that was present in the unirradiated sample. It is speculated that these shallow level defects are related to zinc interstitials or complexes involving them.

Werner Wesch

Papers

Ferromagnetism and Ferromagnetic Resonance in Mn Implanted Si and GaAs

RBS and Ellipsometric Investigation of Amorphous GaAs Layers

Chemical Behavior and Corrosion Resistance of Medical Grade Titanium after Surface Modification by Means of Ion Implantation Techniques

Amorphous phase formation in ion implanted InxGa1−xAs

Electrical Characterization of Proton Irradiated n-Type ZnO