Redox-based memristive switching has been observed in many binary transition metal oxides and related compounds. Since, on the one hand, many recent reports utilize TiO(2) for their studies of the memristive phenomenon and, on the other hand, there is a long history of the electronic structure and the crystallographic structure of TiO(2) under the impact of reduction and oxidation processes, we selected this material as a prototypical material to provide deeper insight into the mechanisms behind memristive switching. In part I, we briefly outline the results of the historical and recent studies of electroforming and resistive switching of TiO(2)-based cells. We describe the (tiny) stoichiometrical range for TiO(2 - x) as a homogeneous compound, the aggregation of point defects (oxygen vacancies) into extended defects, and the formation of the various Magnéli phases. Furthermore, we discuss the driving forces for these solid-state reactions from the thermodynamical point of view. In part II, we provide new experimental details about the hierarchical transformation of TiO(2) single crystals into Magnéli phases, and vice versa, under the influence of chemical, electrical and thermal gradients, on the basis of the macroscopic and nanoscopic measurements. Those include thermogravimetry, high-temperature x-ray diffraction (XRD), high-temperature conductivity measurements, as well as low-energy electron diffraction (LEED), x-ray photoelectron spectroscopy (XPS), and LC-AFM (atomic force microscope equipped with a conducting tip) studies. Conclusions are drawn concerning the relevant parameters that need to be controlled in order to tailor the memristive properties.
Eight silicate glasses were prepared by directly fusing and stirring 50‐100 g each of basalt, andesite, komatiite, peridotite, rhyolite, and quartz‐diorite. These are referred to as MPI‐DING glasses and were made for the purpose of providing reference materials for geochemical, in‐situ microanalytical work. Results from various analytical techniques indicate that individual glass fragments are well homogenised with respect to major and trace elements at the μm to mm scale. Heterogeneities due to quench crystallisation of olivine have been observed in small and limited areas of the two komatiitic glasses. In order to obtain concentration values for as many elements as possible, the glasses were analysed by a variety of bulk and microanalytical methods in a number of laboratories. The analytical uncertainties of most elements are estimated to be between 1% and 10%. From the analytical data, preliminary reference values for more than sixty elements were calculated. The analytical uncertainties of most elements are estimated to be between 1% and 10%.
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