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Journal of Materials Science

, Volume 50, Issue 8, pp 3051–3056 | Cite as

Cationic surface segregation in doped LaMnO3

  • V. SharmaEmail author
  • M. K. Mahapatra
  • P. Singh
  • R. Ramprasad
Original Paper

Abstract

The surface cation chemistry in (La, A)MnO3 (A = Ca, Sr and Ba) is investigated using first-principles thermodynamics. We find that, all three dopants tend to segregate to the surface over a wide range of T– \( p_{{{\text{O}}_{2} }} \) conditions and the tendency for segregation increases with the increase in the dopant cationic size. Moving toward the low oxygen pressure, dopants prefer to remain in the surface regions accompanied by the appropriate number of charge compensating oxygen vacancies. The situation when dopants remain in the bulk regions tends to occur close to the thermodynamic conditions that also favor the decomposition of LaMnO3. The present work serves as an important step toward understanding of factors governing the cationic surface segregation in doped LaMnO3 and opens a pathway to study other important chemical environments (such as water- and CO2-containing air) which are crucially given the fact that the ‘real-world’ air enhances cationic segregation.

Keywords

Density Functional Theory Oxygen Reduction Reaction Surface Segregation LaCoO3 Bulk Region 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Notes

Acknowledgements

This work is supported through a grant from the Office of Fossil Energy, US Department of Energy (DE-FE-0009682). Authors acknowledge the partial computational support through a NSF Teragrid Resource Allocation. Discussions with Hom Sharma, Yenny Cardona-Quintero, and Venkatesh Botu at University of Connecticut are gratefully acknowledged.

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Copyright information

© Springer Science+Business Media New York 2015

Authors and Affiliations

  • V. Sharma
    • 1
    • 2
    Email author
  • M. K. Mahapatra
    • 1
    • 3
  • P. Singh
    • 1
    • 3
  • R. Ramprasad
    • 1
    • 2
  1. 1.Materials Science and EngineeringUniversity of ConnecticutStorrsUSA
  2. 2.Institute of Materials ScienceUniversity of ConnecticutStorrsUSA
  3. 3.Center for Clean Energy EngineeringUniversity of ConnecticutStorrsUSA

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