In Situ Method Correlating Raman Vibrational Characteristics to Chemical Expansion via Oxygen Nonstoichiometry of Perovskite Thin Films

Eva Sediva, Thomas Defferriere, Nicola H. Perry, Harry L. Tuller, Jennifer L.M. Rupp

Research output: Contribution to journalArticlepeer-review

37 Scopus citations

Abstract

Effective integration of perovskite films into devices requires knowledge of their electro-chemomechanical properties. Raman spectroscopy is an excellent tool for probing such properties as the films' vibrational characteristics couple to the lattice volumetric changes during chemical expansion. While lattice volumetric changes are typically accessed by analyzing Raman shifts as a function of pressure, stress, or temperature, such methods can be impractical for thin films and do not capture information on chemical expansion. An in situ Raman spectroscopy technique using an electrochemical titration cell to change the oxygen nonstoichiometry of a model perovskite film, Sr(Ti,Fe)O3− y, is reported and the lattice vibrational properties are correlated to the material's chemical expansion. How to select an appropriate Raman vibrational mode to track the evolution in oxygen nonstoichiometry is discussed. Subsequently, the frequency of the oxygen stretching mode around Fe4+ is tracked, as it decreases during reduction as the material expands and increases during reoxidation as the material shrinks. This methodology of oxygen pumping and in situ Raman spectroscopy of oxide films enables future in operando measurements even for small material volumes, as is typical for applications of films as electrodes or electrolytes utilized in electrochemical energy conversion or memory devices.

Original languageEnglish
Article number1902493
JournalAdvanced Materials
Volume31
Issue number33
DOIs
StatePublished - Aug 2019
Externally publishedYes

Keywords

  • Raman spectroscopy
  • chemomechanical coupling
  • electrochemical titration
  • oxide perovskites

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