Studies on dislocations in prototypic binary and ternary oxides (here TiO 2 and SrTiO 3 ) using modern TEM and scanning probe microscopy (SPM) techniques, combined with classical etch pits methods, are reviewed. Our review focuses on the important role of dislocations in the insulator-to-metal transition and for redox processes, which can be preferentially induced along dislocations using chemical and electrical gradients. It is surprising that, independently of the growth techniques, the density of dislocations in the surface layers of both prototypical oxides is high (10 9 /cm 2 for epipolished surfaces and up to 10 12 /cm 2 for the rough surface). The TEM and locally-conducting atomic force microscopy (LCAFM) measurements show that the dislocations create a network with the character of a hierarchical tree. The distribution of the dislocations in the plane of the surface is, in principle, inhomogeneous, namely a strong tendency for the bundling and creation of arrays or bands in the crystallographic <100> and <110> directions can be observed. The analysis of the core of dislocations using scanning transmission electron microscopy (STEM) techniques (such as EDX with atomic resolution, electron-energy loss spectroscopy (EELS)) shows unequivocally that the core of dislocations possesses a different crystallographic structure, electronic structure and chemical composition relative to the matrix. Because the Burgers vector of dislocations is per se invariant, the network of dislocations (with additional d 1 electrons) causes an electrical short-circuit of the matrix. This behavior is confirmed by LCAFM measurements for the stoichiometric crystals, moreover a similar dominant role of dislocations in channeling of the current after thermal reduction of the crystals or during resistive switching can be observed. In our opinion, the easy transformation of the chemical composition of the surface layers of both model oxides should be associated with the high concentration of extended defects in this region. Another important insight for the analysis of the physical properties in real oxide crystals (matrix + dislocations) comes from the studies of the nucleation of dislocations via in situ STEM indentation, namely that the dislocations can be simply nucleated under mechanical stimulus and can be easily moved at room temperature.

The understanding of the resistive switching mechanisms in perovskites is of particular importance for the development of novel non-volatile memories. Nanoscale investigations recently revealed that in the model material SrTiO 3 a filamentary type of switching is present. In this paper, we show that upon donor doping with Nb the switching type changes fundamentally. We report on the observation of conducting clusters that can be switched independently between a high resistance and a low resistance state when applying a voltage. Furthermore, we show that the resistive switching takes place in a semiconducting surface layer on top of the metallic bulk of SrTiO 3 :Nb single crystals, which can change its properties easily under external gradients.

In this work, the results of the electrocoloration of strontium titanate single crystals with different iron concentrations are presented. The samples of SrTiO3(100) doped with 0.06 at. % and 0.13 at. % of iron were electroreduced at low pressure (10−8 mbar) and elevated temperature (250 °C) using a DC voltage of 200 V. This led to the migration of oxygen vacancies and subsequent electrocoloration of the samples, which was confirmed by optical analysis and electrical measurements. Evolution of the color front was compared with finite element calculations of electric potential indicating good agreement. Both macroscopic and nanoscopic measurements showed insulator-metal transition at several hundreds of seconds (0.06%Fe) and resistive switching behavior. We found that the resistive switching is clearly modified by the oxygen partial pressure of the ambient atmosphere. Moreover, after electroreduction, in the region between the electrodes, stripes can be found following simple crystallographic directions connected with the extended defects and easy diffusion paths also observed in the single crystals of undoped strontium titanate. Furthermore, migration of negatively charged oxygen ions towards the anode led to the formation of oxygen bubbles trapped between the surface of the crystal and the electrode. Using atomic force microscopy, we were able to measure the geometry of a bubble and calculate the oxygen pressure necessary for the formation of such bubbles and the total amount of oxygen ions trapped within.

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The homogeneity of Verneuil-grown SrTiO3:Nb crystals was investigated. Due to the fast crystal growth process, inhomogeneities in the donor dopant distribution and variation in the dislocation density are expected to occur. In fact, for some crystals optical studies show variations in the density of Ti3+ states on the microscale and a cluster-like surface conductivity was reported in tip-induced resistive switching studies. However, our investigations by TEM, EDX mapping, and 3D atom probe reveal that the Nb donors are distributed in a statistically random manner, indicating that there is clearly no inhomogeneity on the macro-, micro-, and nanoscale in high quality Verneuil-grown crystals. In consequence, the electronic transport in the bulk of donor-doped crystals is homogeneous and it is not significantly channelled by extended defects such as dislocations which justifies using this material, for example, as electronically conducting substrate for epitaxial oxide film growth.