Thorsten J.M. Bayer

Observation of structural inhomogeneity at degraded Fe-doped SrTiO3 interfaces

We report on the detection of structural inhomogeneity across anode and cathode interfaces in electrically degraded reduced and oxidized Fe-doped SrTiO3 (Fe:STO) single crystals by optical second harmonic generation (SHG) spectroscopy. SHG spectra were collected from several regions across the anode and cathode interfaces in both degraded reduced and oxidized Fe:STO crystals. We identify the formation of defect concentration gradients along both degraded reduced and oxidized anode interfaces. While the broken symmetries decrease from the outer region towards the central region of the reduced anode, the opposite trend is seen in the degraded oxidized anode. These results are attributed to the formation of centrosymmetric Fe4+:Ti4+-O6 octahedral structures in the central region of the reduced samples degraded anode and non-centrosymmetric Jahn-Teller distortions in the central region of the oxidized samples degraded anode. The observed changes in SHG intensity from the outer region towards the central reg...

Degradation and recovery of iron doped barium titanate single crystals via modulus spectroscopy and thermally stimulated depolarization current

Understanding resistance degradation during the application of DC bias and recovery after removing the DC bias provides insight into failure mechanisms and defects in dielectric materials. In this experiment, modulus spectroscopy and thermally stimulated depolarization current (TSDC) techniques were used to characterize the degradation and recovery of iron-doped barium titanate single crystals. Modulus spectroscopy is a very powerful analytical tool applied during degradation and recovery to observe changes in the local conductivity distribution. During degradation, oxygen vacancies migrate to the cathode region, and a counter flow of oxygen anions migrates towards the anode. With increasing time during degradation, the distribution of conductivity broadens only slightly exhibiting crucial differences to iron doped strontium titanate. After removing the DC bias, the recovery shows that a second previously unobserved and distinct conductivity maximum arises in the modulus data. This characteristic with two...

Unexpected significant increase in bulk conductivity of a dielectric arising from charge injection

Charge injection is a common phenomenon in heterostructures or devices containing metal-insulator interfaces under a voltage bias ranging from dielectric capacitors to electroluminescent and lasing devices. It is generally believed that charge injection only significantly increases the conductivity near the interfacial region or in capacitors with very thin dielectric layers. In this work, the impact of charge injection on bulk conductivity of a 0.5 mm thick Fe-doped SrTiO3 single crystal is investigated with a combination of experimental impedance measurements and computational modelling. It is found that the interfacial charge injection may increase the predicted bulk conductivity of a dielectric by more than one order of magnitude as a consequence of Schottky barrier height lowering.

Impedance spectroscopy utilized to study the spatial distribution of conductivity within capacitors during operation

Impedance spectroscopy is a very powerful tool to characterize and separate physical processes that can occur simultaneously in any material. For parallel plate capacitors, consideration of the modulus has proven to be very effective to study materials that exhibit a spatial variation in conductivity in the direction of the electric field. This was demonstrated with in-situ impedance measurements by monitoring the real-time changes of Fe-doped SrTiO3 during degradation. It is the purpose of this article to adapt these findings and to highlight the possibility to extract information such as local conductivity from complex modulus data of degraded SrTiO3.

Investigation of Electric Field–Induced Structural Changes at Fe-Doped SrTiO3 Anode Interfaces by Second Harmonic Generation

We report on the detection of electric field–induced second harmonic generation (EFISHG) from the anode interfaces of reduced and oxidized Fe-doped SrTiO3 (Fe:STO) single crystals. For the reduced crystal, we observe steady enhancements of the susceptibility components as the imposed dc-voltage increases. The enhancements are attributed to a field-stabilized electrostriction, leading to Fe:Ti-O bond stretching and bending in Fe:Ti-O6 octahedra. For the oxidized crystal, no obvious structural changes are observed below 16 kV/cm. Above 16 kV/cm, a sharp enhancement of the susceptibilities occurs due to local electrostrictive deformations in response to oxygen vacancy migrations away from the anode. Differences between the reduced and oxidized crystals are explained by their relative oxygen vacancy and free carrier concentrations which alter internal electric fields present at the Pt/Fe:STO interfaces. Our results show that the optical SHG technique is a powerful tool for detecting structural changes near perovskite-based oxide interfaces due to field-driven oxygen vacancy migration.

Determination of electrical properties of degraded mixed ionic conductors: Impedance studies with applied dc voltage

Under electrical bias, mixed ionic conductors such as SrTiO3 are characterized by oxygen vacancy migration which leads to resistance degradation. The defect chemistry to describe the relationship between conductivity and oxygen vacancies is usually obtained by high temperature conductivity data or quenching experiments. These techniques can investigate the equilibrated state only. Here, we introduce a new approach using in-situ impedance studies with applied dc voltage to analyze the temperature dependent electrical properties of degraded SrTiO3 single crystals. This procedure is most beneficial since it includes electric field driven effects. The benefits of the approach are highlighted by comparing acceptor doped and undoped SrTiO3. This approach allows the determination of the temperature activation of both anodic and cathodic conductivity of Fe-doped SrTiO3 in the degraded state. The anodic activation energy matches well with the published results, while the activation energy of the degraded cathode r...