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

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

doi:10.1002/adma.201902493

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

Journal Article · 25 June 2019 · Advanced Materials

DOI: https://doi.org/10.1002/adma.201902493 · OSTI ID:1529431

Sediva, Eva ^[1]; Defferriere, Thomas ^[2]; Perry, Nicola H. ^[3]; Tuller, Harry L. ^[2];

^[4]

Department of Materials Science and Engineering Massachusetts Institute of Technology 77 Massachusetts Av. Cambridge MA 02139 USA, ETHZ Department of Materials Hönggerbergring 64 8093 Zürich Switzerland
Department of Materials Science and Engineering Massachusetts Institute of Technology 77 Massachusetts Av. Cambridge MA 02139 USA
Department of Materials Science and Engineering and Materials Research Laboratory University of Illinois at Urbana‐Champaign 1304 W. Green St. Urbana IL 61801 USA, International Institute for Carbon‐Neutral Energy Research (WPI‐I2CNER) Kyushu University 744 Motooka Nishi‐ku Fukuoka 819‐0395 Japan
Department of Materials Science and Engineering Massachusetts Institute of Technology 77 Massachusetts Av. Cambridge MA 02139 USA, ETHZ Department of Materials Hönggerbergring 64 8093 Zürich Switzerland, Department of Electrical Engineering and Computer Science Massachusetts Institute of Technology 77 Massachusetts Av. Cambridge MA 02139 USA

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)O ₃₋ _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 Fe ⁴⁺ 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.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: DE‐SC0002633

OSTI ID:: 1529431

Journal Information:: Advanced Materials, Journal Name: Advanced Materials Vol. 31 Journal Issue: 33; ISSN 0935-9648

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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