Self-reduction of the native TiO2 (110) surface during cooling after thermal annealing - in-operando investigations.

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.

Large-area high-quality graphene on Ge(001)/Si(001) substrates.

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.

TiO2--a prototypical memristive material.

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.

The new high-temperature surface structure on reduced TiO2(001).

Scanning tunnelling microscopy, ultraviolet photoelectron spectroscopy and current imaging tunnelling spectroscopy (STM/UPS/CITS) were used to study the topographic and electronic structure of a high-temperature structure formed on the TiO(2)(001) surface after heating at 1173 K. The STM images revealed different domain-like ordering and periodicity on the surface in comparison to those observed previously. The UPS studies showed the presence of a surface state at energy about 1.1 eV below the Fermi level. This result was confirmed by the CITS data showing pronounced periodic maxima of the electron local density of states at energy around 1.1-1.2 eV below the Fermi level and located on top of every row of the new high-temperature structure. The CITS results recorded for small grains, which coexist with the observed structure, showed that their chemical composition is closer to the Ti(2)O(3) material than to TiO(2-x) for x << 1.