Structural dynamics of Schottky and Frenkel defects in ThO2: a density-functional theory study

Thorium dioxide (ThO2) is a promising alternative to mixed-oxide nuclear fuels due to its longer fuel cycle and resistance to proliferation. Understanding the thermal properties, in particular the thermal conductivity,...

Evidence for the formation of two types of oxygen interstitials in neutron-irradiated α-Al2O3 single crystals

Due to unique optical/mechanical properties and significant resistance to harsh radiation environments, corundum (α-Al2O3) is considered as a promising candidate material for windows and diagnostics in forthcoming fusion reactors. However, its properties are affected by radiation-induced (predominantly, by fast neutrons) structural defects. In this paper, we analyze thermal stability and recombination kinetics of primary Frenkel defects in anion sublattice − the F-type electronic centers and complementary oxygen interstitials in fast-neutron-irradiated corundum single crystals. Combining precisely measured thermal annealing kinetics for four types of primary radiation defects (neutral and charged Frenkel pairs) and the advanced model of chemical reactions, we have demonstrated for the first time a co-existence of the two types of interstitial defects – neutral O atoms and negatively charged O- ions (with attributed optical absorption bands peaked at energies of 6.5 eV and 5.6 eV, respectively). From detailed analysis of interrelated kinetics of four oxygen-related defects, we extracted their diffusion parameters (interstitials serve as mobile recombination partners) required for the future prediction of secondary defect-induced reactions and, eventually, material radiation tolerance.

Cooperative excitations in superionic PbF 2

Links between dynamical Frenkel defects and collective diffusion of fluorides in β -PbF 2 are explored using Born–Oppenheimer molecular dynamics. The calculated self-diffusion coefficient and ionic conductivity are 3.2 × 10 −5 cm 2 s −1 and 2.4 Ω −1 cm −1 at 1000 K in excellent agreement with pulsed field gradient and conductivity measurements. The calculated ratio of the tracer-diffusion coefficient and the conductivity-diffusion coefficient (the Haven ratio) is slightly less than unity (about 0.85), which in previous work has been interpreted as providing evidence against collective ‘multi-ion’ diffusion. By contrast, our molecular dynamics simulations show that fluoride diffusion is highly collective. Analysis of different mechanisms shows a preference for direct collinear ‘kick-out’ chains where a fluoride enters an occupied tetrahedral hole/cavity and pushes the resident fluoride out of its cavity. Jumps into an occupied cavity leave behind a vacancy, thereby forming dynamic Frenkel defects which trigger a chain of migrating fluorides assisted by local relaxations of the lead ions to accommodate these chains. The calculated lifetime of the Frenkel defects and the collective chains is approximately 1 ps in good agreement with that found from neutron diffraction. This article is part of the Theo Murphy meeting issue ‘Understanding fast-ion conduction in solid electrolytes’.

Frenkel defects promote polaronic exciton dissociation in methylammonium lead iodide perovskites

Interactive Frenkel defects promote spatial separation of electron–hole pairs in CH3NH3PbI3 owing to light-triggered charge transfer by Frenkel defects.