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Title: Cation and anion topotactic transformations in cobaltite thin films leading to Ruddlesden-Popper phases

Abstract

Topotactic transformations involve structural changes between related crystal structures due to a loss or gain of material while retaining a crystallographic relationship. The perovskite oxide La0.7Sr0.3CoO3 (LSCO) is an ideal system for investigating phase transformations due to its high oxygen vacancy conductivity, relatively low oxygen vacancy formation energy, and strong coupling of the magnetic and electronic properties to the oxygen stoichiometry. While the transition between cobaltite perovskite and brownmillerite (BM) phases has been widely reported, further reduction beyond the BM phase lacks systematic studies. In this paper, we study the evolution of the physical properties of LSCO thin films upon exposure to highly reducing environments. We observe the rarely reported crystalline Ruddlesden-Popper phase, which involves the loss of both oxygen anions and cobalt cations upon annealing where the cobalt is found as isolated Co ions or Co nanoparticles. First-principles calculations confirm that the concurrent loss of oxygen and cobalt ions is thermodynamically possible through an intermediary BM phase. Furthermore, the strong correlation of the magnetic and electronic properties to the crystal structure highlights the potential of utilizing ion migration as a basis for emerging applications such as neuromorphic computing.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4];  [5];  [6];  [5];  [2]; ORCiD logo [1];  [7];  [7]; ORCiD logo [8];  [5]; ORCiD logo [9];  [6]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of California, Davis, CA (United States)
  2. Univ. of California, San Diego, CA (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. Univ. of Chicago, IL (United States)
  5. Univ. of California, Santa Barbara, CA (United States)
  6. Purdue Univ., West Lafayette, IN (United States)
  7. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  8. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  9. Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Univ. of California, Davis, CA (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1814034
Alternate Identifier(s):
OSTI ID: 1798563; OSTI ID: 1807947
Report Number(s):
BNL-221809-2021-JAAM
Journal ID: ISSN 2475-9953; TRN: US2213395
Grant/Contract Number:  
AC02-05CH11231; SC0019273; AC02-76SF00515; FA9550-18-1-0250; FA9550-20-1-0242; SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 5; Journal Issue: 6; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; Topotactic transformations; Ruddlesden-Popper; Cobaltite thin films; Magnetic oxides; Crystal defects; Electrical conductivity; Electronic structure of atoms & molecules; Epitaxial strain; First-principles calculations; Magnetism; Phase transitions

Citation Formats

Chiu, I-Ting, Lee, Min-Han, Cheng, Shaobo, Zhang, Shenli, Heki, Larry, Zhang, Zhen, Mohtashami, Yahya, Lapa, Pavel N., Feng, Mingzhen, Shafer, Padraic, N'Diaye, Alpha T., Mehta, Apurva, Schuller, Jon A., Galli, Giulia, Ramanathan, Shriram, Zhu, Yimei, Schuller, Ivan K., and Takamura, Yayoi. Cation and anion topotactic transformations in cobaltite thin films leading to Ruddlesden-Popper phases. United States: N. p., 2021. Web. doi:10.1103/physrevmaterials.5.064416.
Chiu, I-Ting, Lee, Min-Han, Cheng, Shaobo, Zhang, Shenli, Heki, Larry, Zhang, Zhen, Mohtashami, Yahya, Lapa, Pavel N., Feng, Mingzhen, Shafer, Padraic, N'Diaye, Alpha T., Mehta, Apurva, Schuller, Jon A., Galli, Giulia, Ramanathan, Shriram, Zhu, Yimei, Schuller, Ivan K., & Takamura, Yayoi. Cation and anion topotactic transformations in cobaltite thin films leading to Ruddlesden-Popper phases. United States. https://doi.org/10.1103/physrevmaterials.5.064416
Chiu, I-Ting, Lee, Min-Han, Cheng, Shaobo, Zhang, Shenli, Heki, Larry, Zhang, Zhen, Mohtashami, Yahya, Lapa, Pavel N., Feng, Mingzhen, Shafer, Padraic, N'Diaye, Alpha T., Mehta, Apurva, Schuller, Jon A., Galli, Giulia, Ramanathan, Shriram, Zhu, Yimei, Schuller, Ivan K., and Takamura, Yayoi. Thu . "Cation and anion topotactic transformations in cobaltite thin films leading to Ruddlesden-Popper phases". United States. https://doi.org/10.1103/physrevmaterials.5.064416. https://www.osti.gov/servlets/purl/1814034.
@article{osti_1814034,
title = {Cation and anion topotactic transformations in cobaltite thin films leading to Ruddlesden-Popper phases},
author = {Chiu, I-Ting and Lee, Min-Han and Cheng, Shaobo and Zhang, Shenli and Heki, Larry and Zhang, Zhen and Mohtashami, Yahya and Lapa, Pavel N. and Feng, Mingzhen and Shafer, Padraic and N'Diaye, Alpha T. and Mehta, Apurva and Schuller, Jon A. and Galli, Giulia and Ramanathan, Shriram and Zhu, Yimei and Schuller, Ivan K. and Takamura, Yayoi},
abstractNote = {Topotactic transformations involve structural changes between related crystal structures due to a loss or gain of material while retaining a crystallographic relationship. The perovskite oxide La0.7Sr0.3CoO3 (LSCO) is an ideal system for investigating phase transformations due to its high oxygen vacancy conductivity, relatively low oxygen vacancy formation energy, and strong coupling of the magnetic and electronic properties to the oxygen stoichiometry. While the transition between cobaltite perovskite and brownmillerite (BM) phases has been widely reported, further reduction beyond the BM phase lacks systematic studies. In this paper, we study the evolution of the physical properties of LSCO thin films upon exposure to highly reducing environments. We observe the rarely reported crystalline Ruddlesden-Popper phase, which involves the loss of both oxygen anions and cobalt cations upon annealing where the cobalt is found as isolated Co ions or Co nanoparticles. First-principles calculations confirm that the concurrent loss of oxygen and cobalt ions is thermodynamically possible through an intermediary BM phase. Furthermore, the strong correlation of the magnetic and electronic properties to the crystal structure highlights the potential of utilizing ion migration as a basis for emerging applications such as neuromorphic computing.},
doi = {10.1103/physrevmaterials.5.064416},
journal = {Physical Review Materials},
number = 6,
volume = 5,
place = {United States},
year = {Thu Jun 24 00:00:00 EDT 2021},
month = {Thu Jun 24 00:00:00 EDT 2021}
}

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