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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. [ABSTRACT FROM AUTHOR]

Mixed ionic-electronic-conducting perovskites such as SrTiO 3 are promising materials to be employed in efficient energy conversion or information processing. These materials exhibit a self-doping effect related to the formation of oxygen vacancies and electronic charge carriers upon reduction. It has been found that dislocations play a prominent role in this self-doping process, serving as easy reduction sites, which result in the formation of conducting filaments along the dislocations. While this effect has been investigated in detail with theoretical calculations and direct observations using local-conductivity atomic force microscopy, the present work highlights the optical properties of dislocations in SrTiO 3 single crystals. Using the change in optical absorption upon reduction as an indicator, two well-defined arrangements of dislocations, namely a bicrystal boundary and a slip band induced by mechanical deformation, are investigated by means of scanning near-field optical microscopy. In both cases, the regions with enhanced dislocation density can be clearly identified as regions with higher optical absorption. Assisted by ab initio calculations, confirming that the agglomeration of oxygen vacancies significantly change the local dielectric constants of the material, the results provide direct evidence that reduced dislocations can be classified as alien matter embedded in the SrTiO 3 matrix.

Electroreduction experiments on metal oxides are well established for investigating the nature of the material change in memresistive devices, whose basic working principle is an electrically-induced reduction. While numerous research studies on this topic have been conducted, the influence of extended defects such as dislocations has not been addressed in detail hitherto. Here, we show by employing thermal microscopy to detect local Joule heating effects in the first stage of electroreduction of SrTiO 3 that the current is channelled along extended defects such as dislocations which were introduced mechanically by scratching or sawing. After prolonged degradation, the matrix of the crystal is also electroreduced and the influence of the initially present dislocations diminished. At this stage, a hotspot at the anode develops due to stoichiometry polarisation leading not only to the gliding of existing dislocations, but also to the evolution of new dislocations. Such a formation is caused by electrical and thermal stress showing dislocations may play a significant role in resistive switching effects.

The electrical properties of SrTiO 3 (100) single crystals were investigated in-situ at different stages of thermal reduction by means of a 4-tip STM. Using the tips of the STM as electrical probes, distance-dependent four-point measurements were performed at the surface of the crystal at room temperature after reduction by thermal treatment. For annealing temperatures T ≤ 700 °C, charge transport is confined to a surface region <3 μm below the surface. For reduction at T ≥ 900 °C a transition from a conducting 2D sheet with insulating bulk to a system with dominant 3D bulk conductivity is found. At an intermediate reduction temperature of T = 800 °C, a regime with mixed 2D/3D contributions is observed in the distance-dependent resistance measurements. Describing the depth-dependent conductivity with an analytical N-layer model, this regime of mixed 2D/3D conductivity is evaluated quantitatively under the assumption of an exponentially decaying conductivity profile, correlated with the previously observed depth-dependent dislocation density in the sample. A non-monotonous temperature dependence of the 3D conductivity in the respective conducting layer is found and possible underlying mechanisms are discussed, particularly with regard to non-intrinsic material properties depending on details of the sample preparation.