Evidence for power-law frequency dependence of intrinsic dielectric response in the CaCu3_{3}Ti4_{4}O12_{12}

We investigated the dielectric response of CaCu$_3$Ti$_4$O$_{12}$ (CCTO) thin films grown epitaxially on LaAlO$_3$ (001) substrates by Pulsed Laser Deposition (PLD). The dielectric response of the films was found to be strongly dominated by a power-law in frequency, typical of materials with localized hopping charge carriers, in contrast to the Debye-like response of the bulk material. The film conductivity decreases with annealing in oxygen, and it suggests that oxygen deficit is a cause of the relatively high film conductivity. With increase of the oxygen content, the room temperature frequency response of the CCTO thin films changes from the response indicating the presence of some relatively low conducting capacitive layers to purely power law, and then towards frequency independent response with a relative dielectric constant $\epsilon'\sim10^2$. The film conductance and dielectric response decrease upon decrease of the temperature with dielectric response being dominated by the power law frequency dependence. Below $\sim$80 K, the dielectric response of the films is frequency independent with $\epsilon'$ close to $10^2$. The results provide another piece of evidence for an extrinsic, Maxwell-Wagner type, origin of the colossal dielectric response of the bulk CCTO material, connected with electrical inhomogeneity of the bulk material.Comment: v4: RevTeX, two-column, 9 pages, 7 figures; title modified, minor content change in p.7, reference adde

Correlative confocal Raman and scanning probe microscopy in the ionically active particles of LiMn 2 O 4 cathodes

In this contribution, a correlative confocal Raman and scanning probe microscopy approach was implemented to find a relation between the composition, lithiation state, and functional electrochemical response in individual micro-scale particles of a LiMn 2 O 4 spinel in a commercial Li battery cathode. Electrochemical strain microscopy (ESM) was implemented both at a low-frequency (3.5 kHz) and in a high-frequency range of excitation (above 400 kHz). It was shown that the high-frequency ESM has a significant cross-talk with topography due to a tip-sample electrostatic interaction, while the low-frequency ESM yields a response correlated with distributions of Li ions and electrochemically inactive phases revealed by the confocal Raman microscopy. Parasitic contributions into the electromechanical response from the local Joule heating and flexoelectric effect were considered as well and found to be negligible. It was concluded that the low-frequency ESM response directly corresponds to the confocal Raman microscopy data. The analysis implemented in this work is an important step towards the quantitative measurement of diffusion coefficients and ion concentration via strain-based scanning probe microscopy methods in a wide range of ionically active materials. © 2019 by the authors

Mn-Doped BaTiO3Ceramics: Thermal and electrical properties for multicaloric applications

Multiferroic materialsare widely used in microelectronics because they are sensitive to elastic, magnetic, and electric fields and there is an intrinsic coupling between them. In particular, transition metal-doped BaTiO3 is consideredas a viable multiferroic because of the simultaneous presence of ferroelectricity and magnetism.In this work, we study the electrical and thermal properties of Mn-doped BaTiO3 ceramics that can be used for multicaloric applications. We found that Mn doping leads to the broadening and shifting of the phase transition accompanied with simultaneous decrease of latent heat and entropy. Mn doping causes a decrease in the bulk resistivity while contact resistance remains intact. Doped ceramics can withstand high electric fields(up to 40 kV/cm) and exhibit linear I-V characteristics followed by the Schottkylimited current in contrast to earlier observations. As such, these ceramics are promising for multicaloric applications. © 2019 by the authors.Russian Science Foundation, RSF: № 18-19-00512Funding: This work was supported by the Russian Science Foundation (grant № 18-19-00512)

Nanometer-scale mapping of irreversible electrochemical nucleation processes on solid Li-ion electrolytes

Electrochemical processes associated with changes in structure, connectivity or composition typically proceed via new phase nucleation with subsequent growth of nuclei. Understanding and controlling reactions requires the elucidation and control of nucleation mechanisms. However, factors controlling nucleation kinetics, including the interplay between local mechanical conditions, microstructure and local ionic profile remain inaccessible. Furthermore, the tendency of current probing techniques to interfere with the original microstructure prevents a systematic evaluation of the correlation between the microstructure and local electrochemical reactivity. In this work, the spatial variability of irreversible nucleation processes of Li on a Li-ion conductive glass-ceramics surface is studied with ~30 nm resolution. An increased nucleation rate at the boundaries between the crystalline AlPO4 phase and amorphous matrix is observed and attributed to Li segregation. This study opens a pathway for probing mechanisms at the level of single structural defects and elucidation of electrochemical activities in nanoscale volumes

Full-wave modeling of broadband near field scanning microwave microscopy

The authors would like to thank professor Dr. Gabriel Gomila from Institut de Bioenginyeria de Catalunya (IBEC) and Universitat de Barcelona for the fruitful discussion and support, as well as to Dr. Georg Gramse from Johannes Kepler University Linz for the experimental data. B.W. thanks the funding from the China Scholarship Council (CSC) for the support of his research at Queen Mary University of London, UK. Y.H. would like to thank EU-FP7 Nanomicrowave project for the financial support