Local electronic transport across probe/ionic conductor interface in scanning probe microscopy.

Charge carrier transport through the probe-sample junction can have substantial consequences for outcomes of electrical and electromechanical atomic-force-microscopy (AFM) measurements. For understanding physical processes under the probe, we carried out conductive-AFM (C-AFM) measurements of local current-voltage (I-V) curves as well as their derivatives on samples of a mixed ionic-electronic conductor Li1-xMn2O4 and developed an analytical framework for the data analysis. The implemented approach discriminates between contributions the highly resistive sample surface layer and the bulk with the account of ion redistribution in the field of the probe. It was found that, with increasing probe voltage, the conductance mechanism in the surface layer transforms from Pool-Frenkel to space-charge-limited current. The surface layer significantly alters the ion dynamics in the sample bulk under the probe, which leads, in particular, to a decrease of the effective electromechanical AFM signal associated with the ionic motion in the sample. The framework can be applied for the analysis of electronic transport mechanisms across the probe/sample interface as well as to uncover the role of the charge transport in the electric field distribution, mechanical, and other responses in AFM measurements of a broad spectrum of conducting materials.

Quantitative characterization of the ionic mobility and concentration in Li-battery cathodes via low frequency electrochemical strain microscopy.

Electrochemical strain microscopy (ESM) can provide useful information on the ionic processes in materials at the local scale. This is especially important for ever growing applications of Li-batteries whose performance is limited by the intrinsic and extrinsic degradation. However, the ESM method used so far has been only qualitative due to multiple contributions to the apparent ESM signal. In this work, we provide a viable approach for the local probing of ionic concentration and diffusion coefficients based on the frequency dependence of the ESM signal. A theoretical basis considering the dynamic behavior of ion migration and relaxation and change of ion concentration profiles under the action of the electric field of the ESM tip is developed. We argue that several parasitic contributions to the ESM signal discussed in the literature can be thus eliminated. The analysis of ESM images using the proposed approach allows a quantitative mapping of the ionic diffusion coefficients and concentration in ionic conductors. The results are validated on Li-battery cathodes (LiMn2O4) extracted from commercial Li-batteries and can provide novel possibilities for their development and further insight into the mechanisms of their degradation.