Multi-scale chemo-mechanical evolution during crystallization of mixed conducting SrTi0.65Fe0.35O3–δ films and correlation to electrical conductivity

Buckner, Haley B.; Ma, Qing; Simpson-Gomez, Joshua; Skiba, Emily J.; Perry, Nicola H.

doi:10.1039/d1ta06455j

Title: Multi-scale chemo-mechanical evolution during crystallization of mixed conducting SrTi_0.65Fe_0.35O_3–δ films and correlation to electrical conductivity

Journal Article · Wed Oct 20 00:00:00 EDT 2021 · Journal of Materials Chemistry. A

DOI:https://doi.org/10.1039/d1ta06455j· OSTI ID:1959966

Buckner, Haley B. ^[1];

^[2]; Simpson-Gomez, Joshua ^[1]; Skiba, Emily J. ^[1];

^[1]

Univ. of Illinois at Urbana-Champaign, IL (United States)
Northwestern Synchrotron Research Center at the Advanced Photon Source Argonne, IL (United States)

Recent work has demonstrated a low-temperature route to fabricating mixed ionic/electronic conducting (MIEC) thin films with enhanced oxygen exchange kinetics by crystallizing amorphous-grown thin films under mild temperatures, eluding conditions for deleterious A-site cation surface segregation. Yet, the complex, multiscale chemical and structural changes during MIEC crystallization and their implications for the electrical properties remain relatively unexplored. In this work, micro-structural and atomic-scale structural and chemical changes in crystallizing SrTi_0.65Fe_0.35O_3–δ thin films on insulating (0001)-oriented Al₂O₃ substrates are observed and correlated to changes in the in-plane electrical conductivity, measured in situ by ac impedance spectroscopy. Synchrotron X-ray absorption spectroscopy at the Fe and Ti K-edges gives direct evidence of oxidation occurring with the onset of crystallization and insight into the atomic-scale structural changes driven by the chemical changes. The observed oxidation, increase in B-site polyhedra symmetry, and alignment of neighboring B-site cation coordination units demonstrate increases in both hole concentration and mobility, thus underpinning the measured increase of in-plane conductivity by over two orders of magnitude during crystallization. High resolution transmission electron microscopy and spectroscopy of films at various degrees of crystallinity reveal compositional uniformity with extensive nano-porosity in the crystallized films, consistent with solid phase contraction expected from both oxidation and crystallization. We suggest that this chemo-mechanically driven dynamic nano-structuring is an additional contributor to the observed electrical behavior. By the point that the films become ~60% crystalline (according to X-ray diffraction), the conductivity reaches the value of dense, fully crystalline films. Furthermore, given the resulting high electronic conductivity, this low-temperature processing route leading to semi-crystalline hierarchical films exhibits promise for developing high performance MIECs for low-to-intermediate temperature applications.

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Research Organization:: Univ. of Illinois at Urbana-Champaign, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0018963; AC02-06CH11357

OSTI ID:: 1959966

Alternate ID(s):: OSTI ID: 1828430

Journal Information:: Journal of Materials Chemistry. A, Vol. 10, Issue 5; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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