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.

Extended x-ray absorption fine structure (EXAFS) measurements have been used to characterize the ion-irradiation-induced crystalline-to-amorphous phase transformation in Ge nanocrystals. The atomic-scale structure of Ge nanocrystals in a silica matrix is first shown to deviate from that of bulk crystalline material with an increase in both Gaussian and non-Gaussian forms of structural disorder. The magnitude of the disorder in the bond-length distribution is comparable to that of relaxed amorphous Ge. The amorphization of such nanocrystals is then demonstrated at an ion dose {approx}100 times less than that required for bulk crystalline material irradiated simultaneously. Specifically, Ge nanocrystals irradiated at -196 deg. C are rendered amorphous at {approx}0.01 displacements per atom. Finally, we show the atomic-scale structure of amorphized nanocrystals and bulk amorphous material is comparable. The rapid amorphization of Ge nanocrystals is potentially the result of several factors including (i) the preferential nucleation of the amorphous phase at the nanocrystal/matrix interface (ii) the preirradiation, higher-energy structural state of the nanocrystals themselves (iii) an enhanced vacancy concentration within the nanocrystals due to inhibited Frenkel pair recombination when Ge interstitials are recoiled into the matrix, and (iv) ion-beam mixing and the subsequent increase in nanocrystal impurity concentrations.

Ion-Irradiation-Induced Preferential Amorphization of Ge Nanocrystals in Silica

https://repository.up.ac.za/bitstream/handle/2263/17808/Friedland_Investigation%282011%29.pdf?sequence=1

Investigation of silver and iodine transport through silicon carbide layers prepared for nuclear fuel element cladding

Heavy-ion irradiation of crystalline germanium (c-Ge) results in the formation of a homogeneous amorphous germanium (a-Ge) layer at the surface. This a-Ge layer undergoes structural modification such as a strong volume expansion accompanied by drastic surface blackening with further ion irradiation. In the present paper we investigate the mechanism of this ion-induced structural modification in a-Ge basically for the irradiation with I ions (3 and 9 MeV) at room and low temperature as a function of ion fluence for the ion incidence angles of $\ensuremath{\Theta}={7}^{\ensuremath{\circ}}$ and $\ensuremath{\Theta}={45}^{\ensuremath{\circ}}$. For comparison, Ag- and Au-ion irradiations were performed at room temperature as a function of the ion fluence. At fluences two orders of magnitude above the amorphization threshold, morphological changes were observed for all irradiation conditions used. Over a wide range of ion fluences we demonstrate that the volume expansion is caused by the formation of voids at the surface and in the depth of the projected ion range. At high ion fluences the amorphous layer transforms into a porous structure as established by cross section and plan view electron microscopy investigations. However, the formation depth of the surface and buried voids as well as the shape and the dimension of the final porous structure depend on the ion fluence, ion species, and irradiation temperature and will be discussed in detail. The rate of the volume expansion (i.e., porous layer formation) depends linearly on the value of ${\ensuremath{\epsilon}}_{n}$. This clearly demonstrates that the structural changes are determined solely by the nuclear energy deposited within the amorphous phase. In addition, at high ion fluences all perpendicular ion irradiations lead to a formation of a microstructure at the surface, whereas for nonperpendicular ion irradiations a nonsaturating irreversible plastic deformation (ion hammering) without a microstructure formation is observed. For the irradiation with ion energies of several MeV, the effect of plastic deformation shows a linear dependence on the ion fluence. Based on these results, we provide an explanation for the differences in surface morphology observed for different angles of incidence of the ion beam will be discussed in detail.

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Structural modifications of low-energy heavy-ion irradiated germanium

Defects in single-crystalline InP induced by relaxation of electronic excitations from 250 MeV Xe ions are investigated by transmission electron microscopy (TEM) in both conventional and high-resolution modes. The formation of latent tracks is investigated as a function of the ion fluence and irradiation temperature. The morphology and atomic structure of the tracks are analyzed. The results are discussed in the frame of a thermal spike approach which assumes both track melting and imperfect crystallization. A shock wave generation around the trajectory of ions is also supposed to take place at the early stage of track formation.

Damage evolution in crystalline InP during irradiation with swift Xe ions

The damage evolution in ion implanted InP, GaAs, GaP and InAs is studied as a function of the ion fluence in the temperature range 20–420 K using various ion masses. It is shown that the macroscopic behaviour can be described in terms of critical temperatures T c which depend on the ion mass and on the dose rate for a given material. At temperatures T I T c amorphization is obtained by direct impact amorphization and the growing of the amorphous zones. However, athermal in-cascade annealing is observed even at 20 K, which is the more pronounced the lighter the ion is. This indicates the influence of the density of the primary cascades on defect recombination. Around T c intrinsic defects are mobile leading to an equilibrium between defect production and annealing over a broad dose region. Amorphization at very large ion fluences is the consequence of complex processes which are influenced by the high ion concentration and the formation of dislocation bands near the end of range. Using an empirical formula which describes the ion mass and dose rate dependence of the critical temperature, the damage evolution for certain implantation conditions becomes predictable.

Werner Wesch

Papers

Ion-Irradiation-Induced Preferential Amorphization of Ge Nanocrystals in Silica

Investigation of silver and iodine transport through silicon carbide layers prepared for nuclear fuel element cladding

Structural modifications of low-energy heavy-ion irradiated germanium

Damage evolution in crystalline InP during irradiation with swift Xe ions

Comparative study of damage production in ion implanted III–V-compounds at temperatures from 20 to 420 K