Computational Approach for Epitaxial Polymorph Stabilization through Substrate Selection

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• 作者：Hong Ding ; Shyam S. Dwaraknath ; Lauren Garten ; Paul Ndione ; David Ginley ; Kristin A. Persson
• 刊名：ACS Applied Materials & Interfaces
• 出版年：2016
• 出版时间：May 25, 2016
• 年：2016
• 卷：8
• 期：20
• 页码：13086-13093
• 全文大小：423K
• 年卷期：0
• ISSN：1944-8252

文摘

With the ultimate goal of finding new polymorphs through targeted synthesis conditions and techniques, we outline a computational framework to select optimal substrates for epitaxial growth using first principle calculations of formation energies, elastic strain energy, and topological information. To demonstrate the approach, we study the stabilization of metastable VO₂ compounds which provides a rich chemical and structural polymorph space. We find that common polymorph statistics, lattice matching, and energy above hull considerations recommends homostructural growth on TiO₂ substrates, where the VO₂ brookite phase would be preferentially grown on the a–c TiO₂ brookite plane while the columbite and anatase structures favor the a–b plane on the respective TiO₂ phases. Overall, we find that a model which incorporates a geometric unit cell area matching between the substrate and the target film as well as the resulting strain energy density of the film provide qualitative agreement with experimental observations for the heterostructural growth of known VO₂ polymorphs: rutile, A and B phases. The minimal interfacial geometry matching and estimated strain energy criteria provide several suggestions for substrates and substrate–film orientations for the heterostructural growth of the hitherto hypothetical anatase, brookite, and columbite polymorphs. These criteria serve as a preliminary guidance for the experimental efforts stabilizing new materials and/or polymorphs through epitaxy. The current screening algorithm is being integrated within the Materials Project online framework and data and hence publicly available.