Isotope Exchange Raman Spectroscopy (IERS): A Novel Technique to Probe Physicochemical Processes In Situ

A novel in situ methodology for the direct study of mass-transport properties in oxides with spatial and unprecedented time resolution, based on Raman spectroscopy coupled to isothermal isotope exchanges, is developed. Changes in the isotope concentration, resulting in a Raman frequency shift, can be followed in real time, which is not accessible by conventional methods, enabling complementary insights for the study of ion-transport properties of electrode and electrolyte materials for advanced solid-state electrochemical devices. The proof of concept and strengths of isotope exchange Raman spectroscopy (IERS) is demonstrated by studying the oxygen isotope back-exchange in gadolinium-doped ceria (CGO) thin films. Resulting oxygen self-diffusion and surface exchange coefficients are compared to conventional time-of-flight secondary-ion mass spectrometry (ToF-SIMS) characterization and literature values, showing good agreement, while at the same time providing additional insight, challenging established assumptions. IERS captivates through its rapidity, simple setup, non-destructive nature, cost effectiveness, and versatile fields of application and thus can readily be integrated as new standard tool for in situ and operando characterization in many laboratories worldwide. The applicability of this method is expected to consolidate the understanding of elementary physicochemical processes and impact various emerging fields including solid oxide cells, battery research, and beyond.