DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Layer-by-layer epitaxial growth of defect-engineered strontium cobaltites

Abstract

Control over structure and composition of (ABO(3)) perovskite oxides offers exciting opportunities since these materials possess unique, tunable properties. Perovskite oxides with cobalt B-site cations are particularly promising, as the range of the cations stable oxidation states leads to many possible structural frameworks. Here, we report growth of strontium cobalt oxide thin films by molecular beam epitaxy, and conditions necessary to stabilize different defect concentration phases. In situ X-ray scattering is used to monitor structural evolution during growth, while in situ X-ray absorption near-edge spectroscopy is used to probe oxidation state and measure changes to oxygen vacancy concentration as a function of film thickness. Experimental results are compared to kinetically limited thermodynamic predictions, in particular, solute trapping, with semiquantitative agreement. Agreement between observations of dependence of cobaltite phase on oxidation activity and deposition rate, and predictions indicates that a combined experimental/theoretical approach is key to understanding phase behavior in the strontium cobalt oxide system.

Authors:
ORCiD logo [1];  [1];  [2];  [2];  [3];  [2]
  1. Argonne National Lab. (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Northwestern Univ., Evanston, IL (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)
OSTI Identifier:
1417645
Alternate Identifier(s):
OSTI ID: 1425224
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 10; Journal Issue: 6; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; perovskite; thin film; oxide; cobaltite; epitaxy; metal oxides; strontium cobalt oxide; molecular beam epitaxy; defects in oxides; perovskite oxides; thin films

Citation Formats

Andersen, Tassie K., Cook, Seyoung, Wan, Gang, Hong, Hawoong, Marks, Laurence D., and Fong, Dillon D. Layer-by-layer epitaxial growth of defect-engineered strontium cobaltites. United States: N. p., 2018. Web. doi:10.1021/acsami.7b16970.
Andersen, Tassie K., Cook, Seyoung, Wan, Gang, Hong, Hawoong, Marks, Laurence D., & Fong, Dillon D. Layer-by-layer epitaxial growth of defect-engineered strontium cobaltites. United States. https://doi.org/10.1021/acsami.7b16970
Andersen, Tassie K., Cook, Seyoung, Wan, Gang, Hong, Hawoong, Marks, Laurence D., and Fong, Dillon D. Thu . "Layer-by-layer epitaxial growth of defect-engineered strontium cobaltites". United States. https://doi.org/10.1021/acsami.7b16970. https://www.osti.gov/servlets/purl/1417645.
@article{osti_1417645,
title = {Layer-by-layer epitaxial growth of defect-engineered strontium cobaltites},
author = {Andersen, Tassie K. and Cook, Seyoung and Wan, Gang and Hong, Hawoong and Marks, Laurence D. and Fong, Dillon D.},
abstractNote = {Control over structure and composition of (ABO(3)) perovskite oxides offers exciting opportunities since these materials possess unique, tunable properties. Perovskite oxides with cobalt B-site cations are particularly promising, as the range of the cations stable oxidation states leads to many possible structural frameworks. Here, we report growth of strontium cobalt oxide thin films by molecular beam epitaxy, and conditions necessary to stabilize different defect concentration phases. In situ X-ray scattering is used to monitor structural evolution during growth, while in situ X-ray absorption near-edge spectroscopy is used to probe oxidation state and measure changes to oxygen vacancy concentration as a function of film thickness. Experimental results are compared to kinetically limited thermodynamic predictions, in particular, solute trapping, with semiquantitative agreement. Agreement between observations of dependence of cobaltite phase on oxidation activity and deposition rate, and predictions indicates that a combined experimental/theoretical approach is key to understanding phase behavior in the strontium cobalt oxide system.},
doi = {10.1021/acsami.7b16970},
journal = {ACS Applied Materials and Interfaces},
number = 6,
volume = 10,
place = {United States},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 3 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: Structures of the stable members of the SrCoO(3n-1)/n homologous series for $n$ = 2 (a), 4 (b), 8 (c), and ∞ (d) on SrTiO3 (0 0 1) and (e-h) their corresponding (calculated) X-ray scattered intensities along the (0 0 $L$) specular rod assuming films are coherently strained, respectively.more » The $n$ = 4, and 8 members (b) and (c) have two possible orientations, shown separated by the dotted line, the (0 0 $L$) in (f) and (g) are an average of these two. The polyhedra corresponding to CoO4, CoO5, and CoO6 are shown in cyan, blue, and violet, respectively. Strontium atoms and oxygen atoms are green and red respectively. The defect structures are expected to evolve from left to right when moving from reducing to more oxidizing conditions.« less

Save / Share:

Works referenced in this record:

Lowering the Temperature of Solid Oxide Fuel Cells
journal, November 2011


Catalytic Activity and Stability of Oxides: The Role of Near-Surface Atomic Structures and Compositions
journal, April 2016


Reversible redox reactions in an epitaxially stabilized SrCoOx oxygen sponge
journal, August 2013

  • Jeen, Hyoungjeen; Choi, Woo Seok; Biegalski, Michael D.
  • Nature Materials, Vol. 12, Issue 11
  • DOI: 10.1038/nmat3736

Water electrolysis on La1−xSrxCoO3−δ perovskite electrocatalysts
journal, March 2016

  • Mefford, J. Tyler; Rong, Xi; Abakumov, Artem M.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms11053

Science and Engineering Beyond Moore's Law
journal, May 2012

  • Cavin, R. K.; Lugli, P.; Zhirnov, V. V.
  • Proceedings of the IEEE, Vol. 100, Issue Special Centennial Issue
  • DOI: 10.1109/JPROC.2012.2190155

Mott Memory and Neuromorphic Devices
journal, August 2015


Interface Physics in Complex Oxide Heterostructures
journal, March 2011


MATERIALS SCIENCE: The Renaissance of Magnetoelectric Multiferroics
journal, July 2005


Beyond Condensed Matter Physics on the Nanoscale: The Role of Ionic and Electrochemical Phenomena in the Physical Functionalities of Oxide Materials
journal, November 2012

  • Kalinin, Sergei V.; Borisevich, Albina; Fong, Dillon
  • ACS Nano, Vol. 6, Issue 12
  • DOI: 10.1021/nn304930x

Orienting Oxygen Vacancies for Fast Catalytic Reaction
journal, October 2013

  • Jeen, Hyoungjeen; Bi, Zhonghe; Choi, Woo Seok
  • Advanced Materials, Vol. 25, Issue 44
  • DOI: 10.1002/adma.201302919

Prediction of solid oxide fuel cell cathode activity with first-principles descriptors
journal, January 2011

  • Lee, Yueh-Lin; Kleis, Jesper; Rossmeisl, Jan
  • Energy & Environmental Science, Vol. 4, Issue 10
  • DOI: 10.1039/c1ee02032c

Design Principles of Perovskites for Thermochemical Oxygen Separation
journal, April 2015


Magnetic phase separation in SrCoOx (2.5 ≤ x ≤ 3)
journal, August 2011

  • Xie, C.; Nie, Y.; Wells, B.
  • Applied Physics Letters, Vol. 99, Issue 5, Article No. 052503
  • DOI: 10.1063/1.3622644

Kinetics of Oxygen Surface Exchange on Epitaxial Ruddlesden–Popper Phases and Correlations to First-Principles Descriptors
journal, January 2016

  • Lee, Yueh-Lin; Lee, Dongkyu; Wang, Xiao Renshaw
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 2
  • DOI: 10.1021/acs.jpclett.5b02423

Cathode materials for solid oxide fuel cells: a review
journal, October 2009

  • Sun, Chunwen; Hui, Rob; Roller, Justin
  • Journal of Solid State Electrochemistry, Vol. 14, Issue 7
  • DOI: 10.1007/s10008-009-0932-0

Advances in layered oxide cathodes for intermediate temperature solid oxide fuel cells
journal, January 2010

  • Tarancón, Albert; Burriel, Mónica; Santiso, José
  • Journal of Materials Chemistry, Vol. 20, Issue 19
  • DOI: 10.1039/b922430k

Synthesis of cubic SrCoO 3 single crystal and its anisotropic magnetic and transport properties
journal, June 2011


Reduction and oxidation of SrCoO2.5 thin films at low temperatures
journal, January 2012

  • Ichikawa, Noriya; Iwanowska, Monika; Kawai, Masanori
  • Dalton Transactions, Vol. 41, Issue 35, p. 10507-10510
  • DOI: 10.1039/c2dt30317e

Time-Resolved in Situ Studies of Oxygen Intercalation into SrCoO2.5, Performed by Neutron Diffraction and X-ray Absorption Spectroscopy
journal, October 2006

  • Le Toquin, Ronan; Paulus, Werner; Cousson, Alain
  • Journal of the American Chemical Society, Vol. 128, Issue 40, p. 13161-13174
  • DOI: 10.1021/ja063207m

Electric-field control of tri-state phase transformation with a selective dual-ion switch
journal, May 2017

  • Lu, Nianpeng; Zhang, Pengfei; Zhang, Qinghua
  • Nature, Vol. 546, Issue 7656
  • DOI: 10.1038/nature22389

Resistance switching in epitaxial SrCoO x thin films
journal, August 2014

  • Tambunan, Octolia T.; Parwanta, Kadek J.; Acharya, Susant K.
  • Applied Physics Letters, Vol. 105, Issue 6
  • DOI: 10.1063/1.4893323

Homologous Series of SrCoO (3 n −1)/ n Perovskites Obtained Through Br 2 Oxygenation of SrCoO 2.5
journal, October 2008

  • Karvonen, Lassi; Yamauchi, Hisao; Karppinen, Maarit
  • Chemistry of Materials, Vol. 20, Issue 22
  • DOI: 10.1021/cm801761p

Recent advances in pulsed-laser deposition of complex oxides
journal, June 2008


Pulsed laser vaporization and deposition
journal, January 2000


Cationic Redistribution at Epitaxial Interfaces in Superconducting Two-Dimensionally Doped Lanthanum Cuprate Films
journal, September 2016

  • Baiutti, Federico; Gregori, Giuliano; Wang, Yi
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 40
  • DOI: 10.1021/acsami.6b09739

Perspective: Oxide molecular-beam epitaxy rocks!
journal, June 2015


Dynamic layer rearrangement during growth of layered oxide films by molecular beam epitaxy
journal, August 2014

  • Lee, J. H.; Luo, G.; Tung, I. C.
  • Nature Materials, Vol. 13, Issue 9
  • DOI: 10.1038/nmat4039

Interface attachment kinetics in alloy solidification
journal, March 1996

  • Aziz, Michael J.
  • Metallurgical and Materials Transactions A, Vol. 27, Issue 3
  • DOI: 10.1007/BF02648954

Solute trapping by rapid solidification
journal, May 1969


A nonlinear model for surface segregation and solute trapping during planar film growth
journal, April 2007

  • Han, Xiaoying; Spencer, Brian J.
  • Journal of Applied Physics, Vol. 101, Issue 8
  • DOI: 10.1063/1.2709554

Quasi-ideal strontium titanate crystal surfaces through formation of strontium hydroxide
journal, November 1998

  • Koster, Gertjan; Kropman, Boike L.; Rijnders, Guus J. H. M.
  • Applied Physics Letters, Vol. 73, Issue 20
  • DOI: 10.1063/1.122630

Atomically layered heteroepitaxial growth of single‐crystal films of superconducting Bi 2 Sr 2 Ca 2 Cu 3 O x
journal, August 1990

  • Eckstein, J. N.; Bozovic, I.; von Dessonneck, K. E.
  • Applied Physics Letters, Vol. 57, Issue 9
  • DOI: 10.1063/1.104270

Epitaxial growth of high-temperature superconducting thin films
journal, March 1989

  • Eckstein, J. N.
  • Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 7, Issue 2
  • DOI: 10.1116/1.584741

Molecular beam epitaxial growth of layered Bi-Sr-Ca-Cu-O compounds
journal, May 1990


In situ surface/interface x-ray diffractometer for oxide molecular beam epitaxy
journal, January 2016

  • Lee, J. H.; Tung, I. C.; Chang, S. -H.
  • Review of Scientific Instruments, Vol. 87, Issue 1
  • DOI: 10.1063/1.4939100

Improved data acquisition in grazing-incidence X-ray scattering experiments using a pixel detector
journal, June 2005

  • Schlepütz, C. M.; Herger, R.; Willmott, P. R.
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 61, Issue 4
  • DOI: 10.1107/S0108767305014790

Correlation between reconstructive phase transitions and transport properties from SrCoO2.5 brownmillerite: A neutron diffraction study
journal, December 2008


Crystallographic and magnetic structure of SrCoO 2.5 brownmillerite: Neutron study coupled with band-structure calculations
journal, August 2008


Time Resolved in Situ XAFS Study of the Electrochemical Oxygen Intercalation in SrFeO 2.5 Brownmillerite Structure: Comparison with the Homologous SrCoO 2.5 System
journal, September 2010

  • Piovano, Andrea; Agostini, Giovanni; Frenkel, Anatoly I.
  • The Journal of Physical Chemistry C, Vol. 115, Issue 4
  • DOI: 10.1021/jp107173b

Local atomic and electronic structures of epitaxial strained LaCoO 3 thin films
journal, January 2012


Phase diagram of the Sr–Co–O system
journal, March 2015


Synthesis, structures, and magnetic properties of novel Roddlesden–Popper homologous series Srn+1ConO3n+1 (n=1,2,3,4, and ∞)
journal, May 2005

  • Wang, X. L.; Sakurai, H.; Takayama-Muromachi, E.
  • Journal of Applied Physics, Vol. 97, Issue 10
  • DOI: 10.1063/1.1855534

Epitaxial growth of the first five members of the Srn+1TinO3n+1 Ruddlesden–Popper homologous series
journal, May 2001

  • Haeni, J. H.; Theis, C. D.; Schlom, D. G.
  • Applied Physics Letters, Vol. 78, Issue 21
  • DOI: 10.1063/1.1371788

Epitaxial growth and magnetic properties of the first five members of the layered Srn+1RunO3n+1 oxide series
journal, January 2007

  • Tian, W.; Haeni, J. H.; Schlom, D. G.
  • Applied Physics Letters, Vol. 90, Issue 2
  • DOI: 10.1063/1.2430941

Transmission electron microscopy study of n = 1–5 Sr n +1 Ti n O 3 n +1 epitaxial thin films
journal, July 2001

  • Tian, W.; Pan, X. Q.; Haeni, J. H.
  • Journal of Materials Research, Vol. 16, Issue 7
  • DOI: 10.1557/JMR.2001.0276

Structure and Oxygen Stoichiometry in Sr3Co2O7-y (0.94 ≤ y ≤ 1.22)
journal, March 1995


Structure and magnetic properties of the orthorhombic n=2 Ruddlesden–Popper phases Sr3Co2O5+δ (δ=0.91, 0.64 and 0.38)
journal, February 2006


Thermodynamic guiding principles in selective synthesis of strontium iridate Ruddlesden-Popper epitaxial films
journal, March 2016

  • Nishio, Kazunori; Hwang, Harold Y.; Hikita, Yasuyuki
  • APL Materials, Vol. 4, Issue 3
  • DOI: 10.1063/1.4943519

Thermodynamic modeling of the Sr–Co–Fe–O system
journal, September 2016


Symmetry-Driven Atomic Rearrangement at a Brownmillerite-Perovskite Interface
journal, December 2015

  • Meyer, Tricia L.; Jeen, Hyoungjeen; Gao, Xiang
  • Advanced Electronic Materials, Vol. 2, Issue 1
  • DOI: 10.1002/aelm.201500201

Use of Ozone to Prepare Silver Oxides
journal, August 1999


Alloy decomposition and surface instabilities in thin films
journal, February 1998


Spontaneous decomposition and ordering during epitaxial growth
journal, December 1999


Phase stability and interfacial structures in the SrO–SrTiO 3 system
journal, March 1997

  • Mccoy, Michael A.; Grimes, Robin W.; Lee, William E.
  • Philosophical Magazine A, Vol. 75, Issue 3
  • DOI: 10.1080/01418619708207205

Isotope effect and self-diffusion in face-centred cubic cobalt
journal, November 1979


Works referencing / citing this record:

Nonequilibrium Solute Capture in Passivating Oxide Films
journal, October 2018


Solute Capture and Doping of Al in Cu 2 O: Corrosion, Tarnish Resistance, and Cation Release of High-Purity Cu-Al Alloys in Artificial Perspiration
journal, January 2018

  • Hutchison, M. J.; Scully, J. R.
  • Journal of The Electrochemical Society, Vol. 165, Issue 10
  • DOI: 10.1149/2.1301810jes

Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.