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First-Principles Investigation of the Epitaxial Stabilization of Oxide Polymorphs: TiO2 on (Sr,Ba)TiO3

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    Research Article

    First-Principles Investigation of the Epitaxial Stabilization of Oxide Polymorphs: TiO2 on (Sr,Ba)TiO3
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    † Department of Chemical Engineering, Carnegie Mellon University, 5000 Forbes Ave., Pittsburgh, Pennsylvania 15213, United States
    ‡ Department of Materials Science and Engineering, Carnegie Mellon University, 5000 Forbes Ave., Pittsburgh, Pennsylvania 15213, United States
    *E-mail: [email protected]
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    ACS Applied Materials & Interfaces

    Cite this: ACS Appl. Mater. Interfaces 2017, 9, 4, 4106–4118
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    https://doi.org/10.1021/acsami.6b11791
    Published December 22, 2016
    Copyright © 2016 American Chemical Society
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    Abstract

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    Metastable polymorphs, many of which have never been fabricated, have been predicted to exhibit interesting and technologically relevant properties. Epitaxial synthesis is a powerful structure-directing method that can produce metastable polymorphs but is typically done in a trial and error fashion. Unfortunately, the relevant thermodynamic terms governing epitaxial synthesis of new materials are unknown. Accurate calculation of the relevant thermodynamic terms and their incorporation into predictive models would accelerate the synthesis of metastable polymorphs by identifying thermodynamically favorable paths. Using density functional theory with three different functionals, we computed several relevant terms for TiO2 anatase (A) and rutile (R) film growth on low-index surfaces of SrTiO3 (STO) and BaTiO3 (BTO) cubic perovskites. After identifying potential coherent epitaxial interfaces based on experimental observations, the volumetric formation, volumetric strain, and areal substrate–film interface energies were calculated for (001)A∥(001)(S/B)TO, (102)A∥(011)(S/B)TO, (100)R∥(111)(S/B)TO, and (112)A∥(111)(S/B)TO coherent interfaces. These terms were integrated into a standard model of epitaxial nucleation, and the results yielded reasonable agreement between experimental observations and DFT predictions of the preferred epitaxial polymorph. Predicted trends in epitaxial stability were essentially independent of the three functionals used in the calculations. These results are discussed in light of their promise that DFT-informed epitaxial film growth can accelerate fabrication of new polymorphs. These results also validate the recently proposed 20 kJ/mol stability window for predicting which polymorphs could be epitaxially stabilized.

    Copyright © 2016 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.6b11791.

    • Construction of unit cells required for interface calculations; calculation of strained bulk structures for TiO2 anatase and rutile; calculation of interface energies; storage of all PBE data; analysis of bulk strain energies with PBE functional; conversion of bulk energies from eV/mol to J/m2; construction of publication images; required modules (PDF)

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    This article is cited by 19 publications.

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    ACS Applied Materials & Interfaces

    Cite this: ACS Appl. Mater. Interfaces 2017, 9, 4, 4106–4118
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsami.6b11791
    Published December 22, 2016
    Copyright © 2016 American Chemical Society
    Request reuse permissions

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