Competing Pathways for Nucleation of the Double Perovskite Structure in the Epitaxial Synthesis of La2MnNiO6

Spurgeon, Steven R.; Du, Yingge; Droubay, Timothy; Devaraj, Arun; Sang, Xiahan; Longo, Paolo; Yan, Pengfei; Kotula, Paul G.; Shutthanandan, Vaithiyalingam; Bowden, Mark E.; LeBeau, James M.; Wang, Chongmin; Sushko, Peter V.; Chambers, Scott A.

doi:10.1021/acs.chemmater.6b00829

Title: Competing Pathways for Nucleation of the Double Perovskite Structure in the Epitaxial Synthesis of La₂MnNiO₆

Journal Article · Tue May 10 00:00:00 EDT 2016 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.6b00829· OSTI ID:1257486

Spurgeon, Steven R. ^[1]; Du, Yingge ^[1]; Droubay, Timothy ^[1]; Devaraj, Arun ^[1]; Sang, Xiahan ^[2]; Longo, Paolo ^[3]; Yan, Pengfei ^[1]; Kotula, Paul G. ^[4]; Shutthanandan, Vaithiyalingam ^[1]; Bowden, Mark E. ^[1]; LeBeau, James M. ^[2]; Wang, Chongmin ^[1]; Sushko, Peter V. ^[1]; Chambers, Scott A. ^[1]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
North Carolina State Univ., Raleigh, NC (United States)
Gatan Inc., Pleasanton, CA (United States)
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Double perovskites of the form R₂BB'O₆ (where R is a rare earth cation and B and B' are chemically distinct transition metal cations with half-filled and empty eg orbitals, respectively) are of significant interest for their magnetoelectric properties. La₂MnNiO₆ is particularly attractive because of its large expected ferromagnetic moment per formula unit (5 μB f.u.^–1) and its semiconducting character. If the ideal structure nucleates, superexchange coupling can take place via the B—O—B' bonds that form, and the moment per formula unit can attain its maximum theoretical value. However, we show that even in the case of layer-by-layer deposition via molecular beam epitaxy, the system can follow multiple reaction pathways that lead to deviations from the double perovskite structure. In particular, we observe a spatially extended phase in which B-site cation disorder occurs, resulting in Mn—O—Mn and Ni—O—Ni antiferromagnetic domains, as well as the formation of quasi-epitaxial, antiferromagnetic NiO nanoscale inclusions, surrounded by a Mn-rich double perovskite. The coexistence of the double perovskite and secondary phases in oxygen deficient conditions is supported by first-principles modeling. However, extended annealing in air restores long-range B-site order and begins to dissolve the NiO inclusions, yielding an ideal structure and an enhanced ferromagnetic moment. Furthermore, this study reveals fundamental structure–property relationships that may not be apparent during the design phase of a multielement crystalline solid and illustrates how to engineer a synthetic path to a desired product.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: AC04-94AL85000; DMR-1350273; AC02-06CH11357

OSTI ID:: 1257486

Journal Information:: Chemistry of Materials, Vol. 28, Issue 11; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: ENGLISH

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Cited by: 22 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
oxides
defects
transition metals
cations
materials

Title: Competing Pathways for Nucleation of the Double Perovskite Structure in the Epitaxial Synthesis of La2MnNiO6

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Title: Competing Pathways for Nucleation of the Double Perovskite Structure in the Epitaxial Synthesis of La₂MnNiO₆