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 (HR 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 reveals the existence of magnetic entities with the hard magnetization axes aligned along the four equivalent 〈1 1 1〉 crystal axes. The spectra are very similar in Si and GaAs, indicating that hexagonal MnAs clusters might be formed in Si.

Ferromagnetism and ferromagnetic resonance in Mn and As co-implanted Si and GaAs

http://elib.bsu.by/bitstream/123456789/170239/1/107-110.pdf

Threshold and criterion for ion track etching in SiO2 layers grown on Si

Two methods for maskless patterning of SiC using a focused Ga+ beam are demonstrated: the enhancement of the chemical etching rate by amorphization of c-SiC to a-SiC and physical sputtering if deep structures are required. Both methods are followed by wet chemical etching in HF:HNO3=1:1 at 80 °C to remove the remaining a-SiC. Assuming the critical displacement density for amorphization to be about the same as for the onset of etching, the measured depths of the structures were compared with the depths of amorphization estimated with TRIM 87 calculations. To find optimum sputtering parameters the energy dependence of the sputter yield was investigated and compared with TRIM 87 simulations, too. Damage after implantation and after wet chemical etching was investigated by means of Raman spectroscopy. No damaged material remaining after wet chemical etching could be detected.

Maskless sub-μm patterning of silicon carbide using a focused ion beam in combination with wet chemical etching

We present a study of the effect of ion implantation induced damage on the optical absorption spectra of Si films, extending from energies above the band gap down to energies far into the subgap region of Si. The changes induced in the optical band gap, band edge slopes and in the subgap features of the spectra are described. The various stages of formation and quenching of divacancies were monitored as a function of implantation conditions and annealing cycles through their 1.8 μm absorption band. The study of the structural relaxation process in implanted and sputtered a-Si gave indications that the process is associated with annihilation of defects as well as average strain reduction in the material, in agreement with earlier indications.

Optical absorption in ion implanted Si films

The lifetime of the minority charge carriers in polycrystalline Cadmium Telluride (pc-CdTe) for solar cell applications is a crucial material parameter and has been determined by analysis of the decay curves of the luminescence signal. Both the lateral and the transversal distributions of the carrier lifetime on the surface and in the bulk of pc-CdTe material as well as the respective solar cell characteristics were measured as a function of the deposition technique, the activation treatment, and the incorporation of additional group-V elements. The results are compared to prior studies. It was found that an activation process passivates grain boundaries and increases the carrier lifetime, which is then higher at the pn-junction than at the surface. Furthermore, nitrogen and phosphorus doping of the CdTe absorber material influences the charge carrier lifetime. The results show that the spatial resolved measurement of the carrier lifetime in pc-CdTe gives an important insight to the charge carrier dynamics of the material.

Werner Wesch

Papers

Ferromagnetism and ferromagnetic resonance in Mn and As co-implanted Si and GaAs

Threshold and criterion for ion track etching in SiO2 layers grown on Si

Maskless sub-μm patterning of silicon carbide using a focused ion beam in combination with wet chemical etching

Optical absorption in ion implanted Si films

Spatially resolved measurements of charge carrier lifetimes in CdTe solar cells