Oxygen vacancy $\left(V_{\mathrm{O}}\right)$ is a common native point defect that plays crucial roles in determining the physical and chemical properties of metal oxides such as ZnO. However, fundamental understanding of $V_{\mathrm{O}}$ is still very sparse. Specifically, whether $V_{\mathrm{O}}$ is mainly responsible for the $n$-type conductivity in ZnO has been still unsettled in the past 50 years. Here, we report on a study of oxygen self-diffusion by conceiving and growing oxygen-isotope ZnO heterostructures with delicately controlled chemical potential and Fermi level. The diffusion process is found to be predominantly mediated by $V_{\mathrm{O}}$. We further demonstrate that, in contrast to the general belief of their neutral attribute, the oxygen vacancies in ZnO are actually $+2$ charged and thus responsible for the unintentional $n$-type conductivity as well as the nonstoichiometry of ZnO. The methodology can be extended to study oxygen-related point defects and their energetics in other technologically important oxide materials.

Nitrogen doping is a promising method of engineering the electronic structure of a metal oxide to modify its optical and electrical properties; however, the doping effect strongly depends on the types of defects introduced. Herein, we report a comparative study of nitrogen-doping-induced defects in Cu2O. Even in the lightly doped samples, a considerable number of nitrogen interstitials (Ni) formed, accompanied by nitrogen substitutions (NO) and oxygen vacancies (VO). In the course of high-temperature annealing, these Ni atoms interacted with VO, resulting in an increase in NO and decreases in Ni and VO. The properties of the annealed sample were significantly modified as a result. Our results suggest that Ni is a significant defect type in nitrogen-doped Cu2O.

Radiation tolerance is determined as the ability of crystalline materials to withstand the accumulation of the radiation induced disorder. Nevertheless, for sufficiently high fluences, in all by far known semiconductors it ends up with either very high disorder levels or amorphization. Here we show that gamma/beta (γ/β) double polymorph Ga₂O₃ structures exhibit remarkably high radiation tolerance. Specifically, for room temperature experiments, they tolerate a disorder equivalent to hundreds of displacements per atom, without severe degradations of crystallinity; in comparison with, e.g., Si amorphizable already with the lattice atoms displaced just once. We explain this behavior by an interesting combination of the Ga- and O- sublattice properties in γ-Ga₂O₃. In particular, O-sublattice exhibits a strong recrystallization trend to recover the face-centered-cubic stacking despite the stronger displacement of O atoms compared to Ga during the active periods of cascades. Notably, we also explained the origin of the β-to-γ Ga₂O₃ transformation, as a function of the increased disorder in β-Ga₂O₃ and studied the phenomena as a function of the chemical nature of the implanted atoms. As a result, we conclude that γ/β double polymorph Ga₂O₃ structures, in terms of their radiation tolerance properties, benchmark a class of universal radiation tolerant semiconductors.

Polymorphs are common in nature and can be stabilized by applying external pressure in materials. The pressure and strain can also be induced by the gradually accumulated radiation disorder. However, in semiconductors, the radiation disorder accumulation typically results in the amorphization instead of engaging polymorphism. By studying these phenomena in gallium oxide we found that the amorphization may be prominently suppressed by the monoclinic to orthorhombic phase transition. Utilizing this discovery, a highly oriented single-phase orthorhombic film on the top of the monoclinic gallium oxide substrate was fabricated. Exploring this system, a novel mode of the lateral polymorphic regrowth, not previously observed in solids, was detected. In combination, these data envisage a new direction of research on polymorphs in ${\mathrm{Ga}}_2{\mathrm{O}}_3$ and, potentially, for similar polymorphic families in other materials.

In this work we present a significant advancement in cubic silicon carbide (3C-SiC) growth in terms of crystal quality and domain size, and indicate its potential use in photovoltaics. To date, the use of 3C-SiC for photovoltaics has not been considered due to the band gap of 2.3 eV being too large for conventional solar cells. Doping of 3C-SiC with boron introduces an energy level of 0.7 eV above the valence band. Such energy level may form an intermediate band (IB) in the band gap. This IB concept has been presented in the literature to act as an energy ladder that allows absorption of sub-bandgap photons to generate extra electron-hole pairs and increase the efficiency of a solar cell. The main challenge with this concept is to find a materials system that could realize such efficient photovoltaic behavior. The 3C-SiC bandgap and boron energy level fits nicely into the concept, but has not been explored for an IB behavior. For a long time crystalline 3C-SiC has been challenging to grow due to its metastable nature. The material mainly consists of a large number of small domains if the 3C polytype is maintained. In our work a crystal growth process was realized by a new approach that is a combination of initial nucleation and step-flow growth. In the process, the domains that form initially extend laterally to make larger 3C-SiC domains, thus leading to a pronounced improvement in crystalline quality of 3C-SiC. In order to explore the feasibility of IB in 3C-SiC using boron, we have explored two routes of introducing boron impurities; ion implantation on un-doped samples and epitaxial growth on un-doped samples using pre-doped source material. The results show that 3C-SiC doped with boron is an optically active material, and thus is interesting to be further studied for IB behavior. For the ion implanted samples the crystal quality was maintained even after high implantation doses and subsequent annealing. The same was true for the samples grown with pre-doped source material, even with a high concentration of boron impurities. We present optical emission and absorption properties of as-grown and boron implanted 3C-SiC. The low-temperature photoluminescence spectra indicate the formation of optically active deep boron centers, which may be utilized for achieving an IB behavior at sufficiently high dopant concentrations. We also discuss the potential of boron doped 3C-SiC base material in a broader range of applications, such as in photovoltaics, biomarkers and hydrogen generation by splitting water. (C) 2015 Elsevier B.V. All rights reserved.Funding Agencies|Angpanneforeningen Research Foundation (AForsk); NFR SunSic project; Swedish Energy Agency; Swedish Governmental Agency for Innovation Systems (Vinnova); STAEDTLER Foundation