| dc.description.abstract | In this work we have investigated the possibility for solid state precipitation of spinel crystals in zinc oxide by separate addition of three different dopant elements. These dopant elements were iron, antimony and vanadium, and were generally introduced as oxide powders. The dopant compounds were mixed with zinc oxide using a powder synthesis route, where the annealing temperature was mostly kept below the solidus temperature in the given system. Some experiments were also performed using a single crystal of zinc oxide embedded in iron oxide and zinc oxide powders. These samples are referred to as diffusion couples.
The characterization of samples was carried out by adopting several observation methods. That is light microscopy, x-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, transmission electron microscopy and scanning transmission electron microscopy. This variety of methods enabled complementary information to be obtained.
It was found that the zinc oxide – iron system displays the most promising features in regard to precipitating spinels crystals in the zinc oxide matrix. This property is attributed to a highly temperature dependent solid solubility of iron in zinc oxide. Observations made in this system indicate that two different spinel forming mechanisms are possible. One includes a high solute iron concentration in zinc oxide and consequently precipitation during cooling of the sample. In the other route a second annealing step is added to promote the precipitation from a somewhat low iron concentration in the zinc oxide matrix. The physical appearance of the precipitates was different depending on precipitation route, however the same orientation relationship with adjacent zinc oxide grains/matrix was found for both spinel precipitates. In addition, iron rich inversion domain boundaries were seen in the single crystal. These were explored, and it was found that the spacing between the domains matched the iron concentration profile in the same region. The transition from inversion domain boundaries to spinel grains was probed to understand nucleation mechanisms for both features.
In the two other systems, antimony and vanadium doped zinc oxide, no precipitations were found. However, it was found that zinc oxide had low and more or less constant solid solubility when temperature was varied in these systems, which is assumed to be a determining factor in limiting the possibility for precipitations. Therefore, attempts were done in the zinc oxide – vanadium system to increase the solubility. However, despite interesting synthesis development, we were not able to increase the solid solubility.
In the zinc oxide – antimony system we show that etching of surfaces could be a way to render inversion domain boundaries visible in scanning electron microscopes. We also confirm the volatility of antimony by the use of x-ray diffraction and energy dispersible spectroscopy. | en_US |