Invited Presentation: Probing Local Ionic Dynamics in Functional Oxides: From Nanometer to Atomic Scales

Vacancy-mediated electrochemical reactions in oxides underpin multiple applications ranging from electroresistive non-volatile memory and neuromorphic logic devices memories, to chemical sensors and electrochemical gas pumps, to energy conversion systems such as fuel cells. Understanding the functionality in these systems requires probing reversible (oxygen reduction/evolution reaction) and irreversible (cathode degradation and activation, formation of conductive filaments) electrochemical processes. In this talk, I summarize recent advances in probing and controlling these transformations locally on nanometer level using scanning probe microscopy. The localized tip concentrates the electric field in the nanometer scale volume of material, inducing local transition. Measured simultaneously electromechanical response (piezoresponse) or current (conductive AFM) provides the information on the bias-induced changes in material. Here, I illustrate how these methods can be extended to study local electrochemical transformations, including vacancy dynamics in oxides such as titanates, La_xSr_1-xCoO₃, and Y_xZr_1-xO₂. The formation of electromechanical hysteresis loops and their bias-, temperature- and environment dependences provide insight into local electrochemical mechanisms and can be directly linked to the defect chemistry. In materials such as lanthanum-strontium cobaltite, mapping both reversible vacancy motion and vacancy ordering and static deformation is possible, and can be corroborated by post mortemSTEM/EELS studies. In ceria, a broad gamut of electrochemical behaviors is observed as a function of temperature and humidity. The possible strategies for elucidation of origins of ionic motion at the electroactive interfaces in oxides using high-resolution electron microscopy and combined ex-situ and in-situ STEM-SPM studies are discussed. In the second part of the talk, probing electrochemical phenomena on in-situ grown surfaces with atomic resolution is illustrated.

Research supported (SVK) by the U.S. Department of Energy, Basic Energy Sciences, Materials Sciences and Engineering Division and partially performed at the Center for Nanophase Materials Sciences, a DOE-BES user facility.