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.

We use a tight binding approach and density functional theory calculations to study the band structure of graphene/hexagonal boron nitride bilayer system in the most stable configuration. We show that an electric field applied in the direction perpendicular to the layers significantly modifies the electronic structure of the whole system, including shifts, anticrossing and other deformations of bands, which can allow to control the value of the energy gap. It is shown that band structure of biased system may be tailored for specific requirements of nanoelectronics applications. The carriers' mobilities are expected to be higher than in the bilayer graphene devices.

Various experimental data revealing large-area high-quality graphene films grown by the CVD method on Ge(001)/Si(001) substrates are presented. SEM images have shown that the structure of nano-facets is formed on the entire surface of Ge(001), which is covered by a graphene layer over the whole macroscopic sample surface of 1 cm(2). The hill-and-valley structures are positioned 90° to each other and run along the <100> direction. The hill height in relation to the valley measured by STM is about 10 nm. Raman measurements have shown that a uniform graphene monolayer covers the nano-facet structures on the Ge(001) surface. Raman spectroscopy has also proved that the grown graphene monolayer is characterized by small strain variations and minimal charge fluctuations. Atomically resolved STM images on the hills of the nanostructures on the Ge(001) surface have confirmed the presence of a graphene monolayer. In addition, the STS/CITS maps show that high-quality graphene has been obtained on such terraces. The subsequent coalescence of graphene domains has led to a relatively well-oriented large-area layer. This is confirmed by LEED measurements, which have indicated that two orientations are preferable in the grown large-area graphene monolayer. The presence of large-area coverage by graphene has been also confirmed by low temperature Hall measurements of a macroscopic sample, showing an n-type concentration of 9.3 × 10(12) cm(-2) and a mobility of 2500 cm(2) V(-1) s(-1). These important characteristic features of graphene indicate a high homogeneity of the layer grown on the large area Ge(001)/Si(001) substrates.

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Protection of Cu(111) surface by chemical vapor deposition graphene coating is investigated. The X-ray photoemission spectroscopy results do not reveal any signs of corrosion on graphene-coated Cu(111), and suggest perfect protection of copper surface against interaction with atmospheric gases. However, the scanning tunneling spectroscopy results show that cracks in the graphene sheet open up windows for nanoscale corrosion. We have shown also that such local corrosions are not only limited to the discontinuities but may also progresses underneath the graphene cover.