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

Abstract

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,more » 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.« less

Authors:
 [1];  [1];  [1];  [1];  [2];  [3];  [1];  [4];  [1];  [1];  [2];  [1];  [1];  [1]
+ Show Author Affiliations
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. North Carolina State Univ., Raleigh, NC (United States)
  3. Gatan Inc., Pleasanton, CA (United States)
  4. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1257486
Grant/Contract Number:  
AC04-94AL85000; DMR-1350273; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 28; Journal Issue: 11; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; oxides; defects; transition metals; cations; materials

Citation Formats

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., and Chambers, Scott A. Competing Pathways for Nucleation of the Double Perovskite Structure in the Epitaxial Synthesis of La2MnNiO6. United States: N. p., 2016. Web. doi:10.1021/acs.chemmater.6b00829.
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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. Competing Pathways for Nucleation of the Double Perovskite Structure in the Epitaxial Synthesis of La2MnNiO6. United States. https://doi.org/10.1021/acs.chemmater.6b00829
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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., and Chambers, Scott A. Tue . "Competing Pathways for Nucleation of the Double Perovskite Structure in the Epitaxial Synthesis of La2MnNiO6". United States. https://doi.org/10.1021/acs.chemmater.6b00829. https://www.osti.gov/servlets/purl/1257486.
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@article{osti_1257486,
title = {Competing Pathways for Nucleation of the Double Perovskite Structure in the Epitaxial Synthesis of La2MnNiO6},
author = {Spurgeon, Steven R. and Du, Yingge and Droubay, Timothy and Devaraj, Arun and Sang, Xiahan and Longo, Paolo and Yan, Pengfei and Kotula, Paul G. and Shutthanandan, Vaithiyalingam and Bowden, Mark E. and LeBeau, James M. and Wang, Chongmin and Sushko, Peter V. and Chambers, Scott A.},
abstractNote = {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.},
doi = {10.1021/acs.chemmater.6b00829},
journal = {Chemistry of Materials},
number = 11,
volume = 28,
place = {United States},
year = {Tue May 10 00:00:00 EDT 2016},
month = {Tue May 10 00:00:00 EDT 2016}
}
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https://doi.org/10.1021/acs.chemmater.6b00829
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Works referenced in this record:

Prediction and accelerated laboratory discovery of previously unknown 18-electron ABX compounds
journal, March 2015

  • Gautier, Romain; Zhang, Xiuwen; Hu, Linhua
  • Nature Chemistry, Vol. 7, Issue 4
  • DOI: 10.1038/nchem.2207

Advances in the growth and characterization of magnetic, ferroelectric, and multiferroic oxide thin films
journal, May 2010

  • Martin, L. W.; Chu, Y. -H.; Ramesh, R.
  • Materials Science and Engineering: R: Reports, Vol. 68, Issue 4-6
  • DOI: 10.1016/j.mser.2010.03.001

Big–deep–smart data in imaging for guiding materials design
journal, September 2015

  • Kalinin, Sergei V.; Sumpter, Bobby G.; Archibald, Richard K.
  • Nature Materials, Vol. 14, Issue 10
  • DOI: 10.1038/nmat4395

The high-throughput highway to computational materials design
journal, February 2013

  • Curtarolo, Stefano; Hart, Gus L. W.; Nardelli, Marco Buongiorno
  • Nature Materials, Vol. 12, Issue 3
  • DOI: 10.1038/nmat3568

Predicting crystal structure by merging data mining with quantum mechanics
journal, July 2006

  • Fischer, Christopher C.; Tibbetts, Kevin J.; Morgan, Dane
  • Nature Materials, Vol. 5, Issue 8
  • DOI: 10.1038/nmat1691

Computational Design of Hierarchically Structured Materials
journal, August 1997

Nanostructured materials: basic concepts and microstructure
journal, January 2000

Atomic disorder effects on half-metallicity of the full-Heusler alloys Co 2 ( Cr 1 − x Fe x ) Al : A first-principles study
journal, April 2004

Review of 3D topological insulator thin-film growth by molecular beam epitaxy and potential applications
journal, January 2013

  • He, Liang; Kou, Xufeng; Wang, Kang L.
  • physica status solidi (RRL) - Rapid Research Letters, Vol. 7, Issue 1-2, p. 50-63
  • DOI: 10.1002/pssr.201307003

Metal-Oxide Heterostructures
journal, August 1995

Instrumental insights
journal, September 2012

  • Rondinelli, James M.; May, Steven J.
  • Nature Materials, Vol. 11, Issue 10
  • DOI: 10.1038/nmat3425

Epitaxial Growth and Properties of Doped Transition Metal and Complex Oxide Films
journal, January 2010

Magnetocapacitance and Magnetoresistance Near Room Temperature in a Ferromagnetic Semiconductor: La2NiMnO6
journal, September 2005

Cation ordering in perovskites
journal, January 2010

  • King, Graham; Woodward, Patrick M.
  • Journal of Materials Chemistry, Vol. 20, Issue 28
  • DOI: 10.1039/b926757c

Local valence and magnetic characteristics of La 2 NiMnO 6
journal, May 2009

Multiple magnetic phases of La 2 CoMnO 6 − δ ( 0 <~ δ <~ 0 . 0 5 )
journal, January 2003

Charge Transfer and Disorder in Double Perovskites
journal, September 2004

  • Menéndez, Nieves; García-Hernández, Mar; Sánchez, Diana
  • Chemistry of Materials, Vol. 16, Issue 18
  • DOI: 10.1021/cm049305t

Phase problem in the B-site ordering of La 2 CoMnO 6 : impact on structure and magnetism
journal, January 2015

  • Egoavil, R.; Hühn, S.; Jungbauer, M.
  • Nanoscale, Vol. 7, Issue 21
  • DOI: 10.1039/C5NR01642H

Influence of defects on structural and magnetic properties of multifunctional La 2 Ni Mn O 6 thin films
journal, May 2008

Size-dependent magnetic properties and Raman spectra of La2NiMnO6 nanoparticles
journal, December 2009

  • Zhao, Shuangyi; Shi, Lei; Zhou, Shiming
  • Journal of Applied Physics, Vol. 106, Issue 12
  • DOI: 10.1063/1.3269707

Absence of long-range Ni∕Mn ordering in ferromagnetic La2NiMnO6 thin films
journal, July 2007

  • Singh, M. P.; Grygiel, C.; Sheets, W. C.
  • Applied Physics Letters, Vol. 91, Issue 1
  • DOI: 10.1063/1.2753715

Long-range order of Ni2+ and Mn4+ and ferromagnetism in multiferroic (Bi0.9La0.1)2NiMnO6 thin films
journal, December 2010

  • Langenberg, E.; Rebled, J.; Estradé, S.
  • Journal of Applied Physics, Vol. 108, Issue 12
  • DOI: 10.1063/1.3524278

Chemical mapping at atomic resolution using energy-dispersive x-ray spectroscopy
journal, January 2012

  • Allen, Leslie J.; D’Alfonso, Adrian J.; Freitag, Bert
  • MRS Bulletin, Vol. 37, Issue 1
  • DOI: 10.1557/mrs.2011.331

Challenges in Ceramic Science: A Report from the Workshop on Emerging Research Areas in Ceramic Science
journal, November 2012

  • Rohrer, Gregory S.; Affatigato, Mario; Backhaus, Monika
  • Journal of the American Ceramic Society, Vol. 95, Issue 12
  • DOI: 10.1111/jace.12033

Atom Probe Tomography of Electronic Materials
journal, August 2007

Laser-Assisted Atom Probe Tomography of Oxide Materials
journal, April 2007

  • Oberdorfer, Christian; Stender, Patrick; Reinke, Christoph
  • Microscopy and Microanalysis, Vol. 13, Issue 5
  • DOI: 10.1017/S1431927607070274

Laser assisted field evaporation of oxides in atom probe analysis
journal, May 2011

Visualizing nanoscale 3D compositional fluctuation of lithium in advanced lithium-ion battery cathodes
journal, August 2015

  • Devaraj, A.; Gu, M.; Colby, R.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9014

Long-range Ni/Mn structural order in epitaxial double perovskite La 2 NiMnO 6 thin films
journal, June 2009

Ferromagnetic properties of epitaxial La2NiMnO6 thin films grown by pulsed laser deposition
journal, March 2009

  • Kitamura, M.; Ohkubo, I.; Kubota, M.
  • Applied Physics Letters, Vol. 94, Issue 13
  • DOI: 10.1063/1.3111436

Growth of epitaxial thin films of the ordered double perovskite La2NiMnO6 on different substrates
journal, July 2006

  • Guo, H.; Burgess, J.; Street, S.
  • Applied Physics Letters, Vol. 89, Issue 2
  • DOI: 10.1063/1.2221894

Magnetic exchange interactions in perovskite LaMnO3/LaMO3 (M=Ni, Co, Cr, Fe) superlattices
journal, March 1999

Magnetism in Double Perovskites
journal, December 2012

Electronic Structure, Phonons, and Dielectric Anomaly in Ferromagnetic Insulating Double Pervoskite La 2 NiMnO 6
journal, May 2008

Local electronic and geometrical structure of LaNi 1 − x Mn x O 3 + δ perovskites determined by x-ray-absorption spectroscopy
journal, March 2002

Challenges to Quantitative Multivariate Statistical Analysis of Atomic-Resolution X-Ray Spectral
journal, July 2012

  • Kotula, Paul G.; Klenov, Dmitri O.; von Harrach, H. Sebastian
  • Microscopy and Microanalysis, Vol. 18, Issue 4
  • DOI: 10.1017/S1431927612001201

Automated Analysis of SEM X-Ray Spectral Images: A Powerful New Microanalysis Tool
journal, January 2003

  • Kotula, Paul G.; Keenan, Michael R.; Michael, Joseph R.
  • Microscopy and Microanalysis, Vol. 9, Issue 1
  • DOI: 10.1017/S1431927603030058

Non-stoichiometry, structural defects and properties of LaMnO3+δ with high δ values (0.11≤δ≤0.29)
journal, January 1997

  • Alonso, J. A.; Martínez-lope, M. J.; Casais, M. T.
  • Journal of Materials Chemistry, Vol. 7, Issue 10
  • DOI: 10.1039/a704088a

Polarity-driven nickel oxide precipitation in LaNiO 3 -LaAlO 3 superlattices
journal, November 2011

  • Detemple, E.; Ramasse, Q. M.; Sigle, W.
  • Applied Physics Letters, Vol. 99, Issue 21
  • DOI: 10.1063/1.3663568

Atom probe tomography
journal, June 2009

Atom Probe Tomography of Yttrium-Doped Barium-Cerium-Zirconium Oxide with NiO Addition
journal, July 2014

  • Diercks, David R.; Gorman, Brian P.; Manerbino, Anthony
  • Journal of the American Ceramic Society, Vol. 97, Issue 10
  • DOI: 10.1111/jace.13093

Analysis of Three-dimensional Atom-probe Data by the Proximity Histogram
journal, September 2000

  • Hellman, Olof C.; Vandenbroucke, Justin A.; Rüsing, Järg
  • Microscopy and Microanalysis, Vol. 6, Issue 05
  • DOI: 10.1007/S100050010051

Role of Photoexcitation and Field Ionization in the Measurement of Accurate Oxide Stoichiometry by Laser-Assisted Atom Probe Tomography
journal, March 2013

  • Devaraj, A.; Colby, R.; Hess, W. P.
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 6
  • DOI: 10.1021/jz400015h

Multiferroic double perovskites: Opportunities, issues, and challenges
journal, May 2010

  • Singh, M. P.; Truong, K. D.; Jandl, S.
  • Journal of Applied Physics, Vol. 107, Issue 9
  • DOI: 10.1063/1.3362922

Epitaxial thin films of (Bi0.9La0.1)2NiMnO6 obtained by pulsed laser deposition
journal, June 2009

  • Langenberg, E.; Varela, M.; García-Cuenca, M. V.
  • Journal of Magnetism and Magnetic Materials, Vol. 321, Issue 11
  • DOI: 10.1016/j.jmmm.2009.02.005

Epitaxial growth, structure, and intermixing at the LaAlO 3 / SrTiO 3 interface as the film stoichiometry is varied
journal, February 2011

Reversible nano-structuring of SrCrO3-δ through oxidation and reduction at low temperature
journal, August 2014

  • Zhang, K. H. L.; Sushko, P. V.; Colby, R.
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5669

In situ site-specific specimen preparation for atom probe tomography
journal, February 2007

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

Projector augmented-wave method
journal, December 1994

Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
journal, April 2008

Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998

  • Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
  • Physical Review B, Vol. 57, Issue 3, p. 1505-1509
  • DOI: 10.1103/PhysRevB.57.1505

Vibrational properties of MnO and NiO from DFT + U -based density functional perturbation theory
journal, October 2011

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    Works referencing / citing this record:

    Interface Engineered Room‐Temperature Ferromagnetic Insulating State in Ultrathin Manganite Films
    journal, November 2019

    Role of spontaneous strains on the biphasic nature of partial B-site disorder double perovskite La 2 NiMnO 6
    journal, June 2018

    • Yang, Dexin; Wang, Wei; Yang, Tao
    • APL Materials, Vol. 6, Issue 6
    • DOI: 10.1063/1.5031486

    Interface Engineered Room-Temperature Ferromagnetic Insulating State in Ultrathin Manganite Films.
    text, January 2020

    • Li, Weiwei; Zhu, Bonan; He, Qian
    • Apollo - University of Cambridge Repository
    • DOI: 10.17863/cam.45761

    Interface Engineered Room-Temperature Ferromagnetic Insulating State in Ultrathin Manganite Films.
    text, January 2019

    • Li, Weiwei; Zhu, Bonan; He, Qian
    • Apollo - University of Cambridge Repository
    • DOI: 10.17863/cam.49048
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