Electromechanical Probing of Ionic Currents in Energy Storage Materials

The electrochemical processes in energy storage materials are generally linked with changes of molar volume of the host compound. Here, the frequency dependent strain response of 1D electrochemically active systems to periodic electric bias is analyzed. The sensitivity and resolution of these electrochemical strain measurements are compared to the current-based electrochemical impedance spectroscopy. The resolution and detection limits of interferometric and atomic force microscopy based systems for probing electrochemical reactions on the nanoscale are analyzed.Comment: 12 pages, 4 figures, 2 tables, 2 appendices, submitted to Appl. Phys. Let

Modelling of Pyroelectric Response in Inhomogeneous Ferroelectric-Semiconductor Films

We have modified Landau-Khalatnikov approach and shown that the pyroelectric response of inhomogeneous ferroelectric-semiconductor films can be described by using six coupled equations for six order parameters: average displacement, its mean-square fluctuation and correlation with charge defects density fluctuations, average pyroelectric coefficient, its fluctuation and correlation with charge defects density fluctuations. Coupled equations demonstrate the inhomogeneous reversal of pyroelectric response in contrast to the equations of Landau-Khalatnikov type, which describe the homogeneous reversal with the sharp pyroelectric coefficient peak near the thermodynamic coercive field value. Within the framework of our model pyroelectric hysteresis loop becomes much smoother, thinner and lower as well as pyroelectric coefficient peaks near the coercive field completely disappear under the increase of disordering caused by defects. This effect is similar to the well-known "square to slim transition" of the ferroelectric hysteresis loops in relaxor ferroelectrics. Also the increase of defect concentration leads to the drastic decrease of the coercive field typical for disordered ferroelectrics. Usually pyroelectric hysteresis loops of doped and inhomogeneous ferroelectrics have typical smooth shape without any pyroelectric coefficient peaks and coercive field values much lower than the thermodynamic one. Therefore our approach qualitatively explains available experimental results. Rather well quantitative agreement between our modelling and typical Pb(Zr,Ti)O3-film pyroelectric and ferroelectric loops has been obtained.Comment: 14 pages, 5 figure