Oxygen diffusion coefficients in pure and doped ZnO polycrystals were determined by means of the gas-solid isotope exchange method using the isotope 18O as oxygen tracer. The diffusion experiments were performed from 900 to 1000 °C, under an oxygen pressure of 10(5) Pa. After the diffusion annealings, the 18O diffusion profiles were determined by secondary ion mass spectrometry. The results of the experiments show that oxygen diffusion in Li-doped ZnO is similar to the oxygen diffusion in pure ZnO, while in Al-doped ZnO the oxygen diffusion is enhanced in relation to that observed in pure ZnO, in the same experimental conditions. Based on these results is proposed an interstitial mechanism for oxygen diffusion in ZnO. Moreover, it was found that oxygen grain-boundary diffusion is ca. 3 to 4 orders of magnitude greater than oxygen volume diffusion in pure and doped ZnO, which means that the grain-boundary is a fast path for oxygen diffusion in ZnO
Bulk Zn1−xCoxO samples were synthesized via standard solid-state reaction route with different Co molar concentrations up to 21%. A detailed microstructural analysis was carried out to investigate alternative sources of ferromagnetism, such as secondary phases and nanocrystals embedded in the bulk material. Conjugating different techniques we confirmed the Zn replacement by Co ions in the wurtzite ZnO structure, which retains, however, a high crystalline quality. No segregated secondary phases neither Co-rich nanocrystals were detected. Superconducting quantum interference device magnetometry demonstrates a paramagnetic Curie–Weiss behavior with antiferromagnetic interactions. We discuss the observed room temperature paramagnetism of our samples considering the current models for the magnetic properties of diluted magnetic semiconductors.
Zinc self-diffusion coefficients were measured in polycrystalline ZnO of high density (>99% of the theoretical density) and of high purity (> 99.999%). The diffusion experiments were performed from 1006 to 1377 °C, in oxygen atmosphere, for times between 16 and 574 h. The diffusion profiles were established by means of Residual Activity Method using the 65Zn radioactive isotope as zinc tracer. In our experimental conditions, the zinc volume diffusion coefficients can be described by the following Arrhenius relationship: D(cm²/s) = 1.57×10-3 exp[(-2.66 ± 0.26) eV/kT]. In the same experimental conditions, the grain-boundary diffusion coefficients are approximately 4 orders of magnitude greater than the volume diffusion coefficients, and can be described by the Arrhenius relation: D'delta (cm³/s) = 1.59×10-6 exp[(-2.44 ± 0.45) eV/kT], where D' is the grain-boundary diffusion coefficient and delta is the grain boundary width
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