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.
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.
The electronic structure of showing a metal-insulator transition and a sequence of different charge density wave (CDW) transformations was discussed in the frame of variable temperature angle-resolved photoelectron spectroscopy (ARPES), scanning tunneling spectroscopy (STS), and density functional theory (DFT) calculations. For the commensurate charge density wave phase (CCDW) the Mott gap was estimated to be 0.4 eV and energy gaps were observed. For the nearly commensurate charge density wave phase (NCCDW), the reminiscent of higher and lower Hubbard bands and a very pronounced electronic state associated with the parabolic band at the point in the Brillouin zone were identified. The incommensurate charge density wave phase (ICCDW) showed a high value of local density of states at the Fermi level and a very pronounced edge of the metallic surface state located in the range of 0.15–0.20 eV above the Fermi level. The obtained STS and ARPES results were consistent with our theoretical calculations performed within DFT formalism including spin-orbit coupling.
The overprints produced in inkjet technology with graphene oxide dispersion are presented. The graphene oxide ink is developed to be fully compatible with standard industrial printers and polyester substrates. Post-printing chemical reduction procedure is proposed, which leads to the restoration of electrical conductivity without destroying the substrate. The presented results show the outstanding potential of graphene oxide for rapid and cost efficient commercial implementation to production of flexible electronics. Properties of graphene-based electrodes are characterized on the macro- and nano-scale. The observed nano-scale inhomogeneity of overprints' conductivity is found to be essential in the field of future industrial applications.
We investigate the thermal reduction of TiO2 in ultra-high vacuum. Contrary to what is usually assumed, we observe that the maximal surface reduction occurs not during the heating, but during the cooling of the sample back to room temperature. We describe the self-reduction, which occurs as a result of differences in the energies of defect formation in the bulk and surface regions. The findings presented are based on X-ray photoelectron spectroscopy carried out in-operando during the heating and cooling steps. The presented conclusions, concerning the course of redox processes, are especially important when considering oxides for resistive switching and neuromorphic applications and also when describing the mechanisms related to the basics of operation of solid oxide fuel cells.