Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Surface reconstructions and modified surface states in L a 1 – x C a x Mn O 3

Abstract

Here, the unique functionalities present at surfaces and interfaces of complex oxides have attracted intense research in the past decade. Yet, the fundamental mechanisms underpinning functionality are often elusive, especially in doped manganites, limiting their implementation in functional electronic devices such as memristors and spin valves. Here, we present a local probe-based study on mixed-terminated La5/8Ca3/8MnO3 (LCMO) films, and reveal surface metallicity in a thin film grown by pulsed-laser deposition. Using first-principles density-functional theory calculations with Hubbard correction that are more accurate to capture effects of correlation in these systems, we show that for Ca-segregated (001) LCMO surfaces the (La,Ca)O-site terminated surfaces are half metallic due to delocalized Mn-d states populating the Fermi level, whereas the MnO2-site terminated surfaces exhibit a half-metallic or insulating character depending on the type of surface reconstruction. Computations not only explain the current measurements, but also explain other recent surface measurements on LCMO thin films, leading to a coherent picture of how the crucial link between surface segregation and Jahn-Teller couplings in the manganese oxides tune the surface electronic/magnetic structure, thereby pointing to the fine control of transport and magnetism at the conductive oxide surface independent of the bulk.

Authors:
ORCiD logo [1];  [2];  [3];  [4];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); GLOBALFOUNDRIES, Malta, NY (United States)
  3. Univ. of Aveiro, Aveiro (Portugal)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); The Univ. of Manchester, Manchester (United Kingdom)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1489604
Alternate Identifier(s):
OSTI ID: 1480158
Grant/Contract Number:  
AC05-00OR22725; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 2; Journal Issue: 10; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Vasudevan, Rama K., Dixit, Hemant M., Tselev, Alexander, Qiao, Liang, Meyer, Tricia L., Cooper, Valentino R., Baddorf, Arthur P., Lee, Ho Nyung, Ganesh, Panchapakesan, and Kalinin, Sergei V. Surface reconstructions and modified surface states in La1–xCaxMnO3. United States: N. p., 2018. Web. doi:10.1103/PhysRevMaterials.2.104418.
Copy to clipboard
Vasudevan, Rama K., Dixit, Hemant M., Tselev, Alexander, Qiao, Liang, Meyer, Tricia L., Cooper, Valentino R., Baddorf, Arthur P., Lee, Ho Nyung, Ganesh, Panchapakesan, & Kalinin, Sergei V. Surface reconstructions and modified surface states in La1–xCaxMnO3. United States. https://doi.org/10.1103/PhysRevMaterials.2.104418
Copy to clipboard
Vasudevan, Rama K., Dixit, Hemant M., Tselev, Alexander, Qiao, Liang, Meyer, Tricia L., Cooper, Valentino R., Baddorf, Arthur P., Lee, Ho Nyung, Ganesh, Panchapakesan, and Kalinin, Sergei V. Wed . "Surface reconstructions and modified surface states in La1–xCaxMnO3". United States. https://doi.org/10.1103/PhysRevMaterials.2.104418. https://www.osti.gov/servlets/purl/1489604.
Copy to clipboard
@article{osti_1489604,
title = {Surface reconstructions and modified surface states in La1–xCaxMnO3},
author = {Vasudevan, Rama K. and Dixit, Hemant M. and Tselev, Alexander and Qiao, Liang and Meyer, Tricia L. and Cooper, Valentino R. and Baddorf, Arthur P. and Lee, Ho Nyung and Ganesh, Panchapakesan and Kalinin, Sergei V.},
abstractNote = {Here, the unique functionalities present at surfaces and interfaces of complex oxides have attracted intense research in the past decade. Yet, the fundamental mechanisms underpinning functionality are often elusive, especially in doped manganites, limiting their implementation in functional electronic devices such as memristors and spin valves. Here, we present a local probe-based study on mixed-terminated La5/8Ca3/8MnO3 (LCMO) films, and reveal surface metallicity in a thin film grown by pulsed-laser deposition. Using first-principles density-functional theory calculations with Hubbard correction that are more accurate to capture effects of correlation in these systems, we show that for Ca-segregated (001) LCMO surfaces the (La,Ca)O-site terminated surfaces are half metallic due to delocalized Mn-d states populating the Fermi level, whereas the MnO2-site terminated surfaces exhibit a half-metallic or insulating character depending on the type of surface reconstruction. Computations not only explain the current measurements, but also explain other recent surface measurements on LCMO thin films, leading to a coherent picture of how the crucial link between surface segregation and Jahn-Teller couplings in the manganese oxides tune the surface electronic/magnetic structure, thereby pointing to the fine control of transport and magnetism at the conductive oxide surface independent of the bulk.},
doi = {10.1103/PhysRevMaterials.2.104418},
journal = {Physical Review Materials},
number = 10,
volume = 2,
place = {United States},
year = {Wed Oct 31 00:00:00 EDT 2018},
month = {Wed Oct 31 00:00:00 EDT 2018}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1103/PhysRevMaterials.2.104418
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 7 works
Citation information provided by
Web of Science

Figures / Tables:

FIG. 1 FIG. 1: (a) Large-scale STM topography of the surface of the LCMO film. (b) Atomically resolved image of the surface, showing two distinct terminations and two different reconstructions. FFT of the white boxed regions in [(b), inset] highlights the two different lattice structures. Scale bar in inset, 4 nm−1. (c)more » Height distribution showing half-unit-cell intervals. (d) Line profile of segment “1” in (a), confirming half-unit-cell steps. Schematic view of (1 × 1) and (√2 × √2)R45° surfaces for (e) (La, Ca)O and (f) MnO2 termination. Black lines highlight the unit cell for each type of surface. Green atoms are La/Ca, red atoms are oxygen, and purple atoms are Mn.« less
All figures and tables (5 total)
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Orbital ordering and exchange interaction in the manganites
journal, August 2001

Projector augmented-wave method
journal, December 1994

In situ characterization of strontium surface segregation in epitaxial La0.7Sr0.3MnO3 thin films as a function of oxygen partial pressure
journal, October 2008

  • Fister, Tim T.; Fong, Dillon D.; Eastman, Jeffrey A.
  • Applied Physics Letters, Vol. 93, Issue 15
  • DOI: 10.1063/1.2987731

Oxygen Control of Atomic Structure and Physical Properties of SrRuO 3 Surfaces
journal, April 2013

  • Tselev, Alexander; Ganesh, P.; Qiao, Liang
  • ACS Nano, Vol. 7, Issue 5
  • DOI: 10.1021/nn400923n

Atomic-scale electrochemistry on the surface of a manganite by scanning tunneling microscopy
journal, April 2015

  • Vasudevan, Rama K.; Tselev, Alexander; Gianfrancesco, Anthony G.
  • Applied Physics Letters, Vol. 106, Issue 14
  • DOI: 10.1063/1.4917299

Structure and Properties of Functional Oxide Thin Films: Insights From Electronic-Structure Calculations
journal, July 2011

Interplay of Octahedral Tilts and Polar Order in BiFeO 3 Films
journal, March 2013

Growth Mode Transition in Complex Oxide Heteroepitaxy: Atomically Resolved Studies
journal, April 2016

  • Tselev, Alexander; Vasudevan, Rama K.; Gianfrancesco, Anthony G.
  • Crystal Growth & Design, Vol. 16, Issue 5
  • DOI: 10.1021/acs.cgd.5b01826

LaAlO3 stoichiometry is key to electron liquid formation at LaAlO3/SrTiO3 interfaces
journal, August 2013

  • Warusawithana, M. P.; Richter, C.; Mundy, J. A.
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3351

Tunable Metallicity of the La 5 / 8 Ca 3 / 8 MnO 3 ( 001 ) Surface by an Oxygen Overlayer
journal, February 2009

Electronic Structure of the Perovskite Oxides: La 1 − x Ca x MnO 3
journal, February 1996

  • Satpathy, S.; Popović, Zoran S.; Vukajlović, Filip R.
  • Physical Review Letters, Vol. 76, Issue 6
  • DOI: 10.1103/PhysRevLett.76.960

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

Magnetism and metal-insulator transition in oxygen-deficient SrTiO 3
journal, September 2015

  • Lopez-Bezanilla, Alejandro; Ganesh, P.; Littlewood, Peter B.
  • Physical Review B, Vol. 92, Issue 11
  • DOI: 10.1103/PhysRevB.92.115112

Visualization of Localized Holes in Manganite Thin Films with Atomic Resolution
journal, December 2005

Survey of fractured SrTiO3 surfaces: From the micrometer to nanometer scale
journal, July 2010

  • Chien, TeYu; Guisinger, Nathan P.; Freeland, John W.
  • Journal of Vacuum Science & Technology B, Nanotechnology and Microelectronics: Materials, Processing, Measurement, and Phenomena, Vol. 28, Issue 4
  • DOI: 10.1116/1.3420395

Effects of lattice distortion and Jahn - Teller coupling on the magnetoresistance of and epitaxial films
journal, May 1997

Controlled mechnical modification of manganite surface with nanoscale resolution
journal, November 2014

CMR manganites: physics, thin films and devices
journal, April 2003

Direct observation of ferroelectric field effect and vacancy-controlled screening at the BiFeO3/LaxSr1−xMnO3 interface
journal, August 2014

  • Kim, Young-Min; Morozovska, Anna; Eliseev, Eugene
  • Nature Materials, Vol. 13, Issue 11
  • DOI: 10.1038/nmat4058

Strain-induced crossover of the metal-insulator transition in perovskite manganites
journal, February 2005

Effect of silver doping on the surface of La 5/8 Ca 3/8 MnO 3 epitaxial films
journal, September 2014

  • Tselev, A.; Vasudevan, R. K.; Kalinin, S. V.
  • Applied Physics Letters, Vol. 105, Issue 10
  • DOI: 10.1063/1.4895026

Erratum: Orbital ordering and exchange interaction in the manganites [Phys. Rev. B 64 , 094433 (2001)]
journal, July 2003

Direct Probe of Interplay between Local Structure and Superconductivity in FeTe 0.55 Se 0.45
journal, March 2013

  • Lin, Wenzhi; Li, Qing; Sales, Brian C.
  • ACS Nano, Vol. 7, Issue 3
  • DOI: 10.1021/nn400012q

Ferroelectric tunnel junctions for information storage and processing
journal, July 2014

  • Garcia, Vincent; Bibes, Manuel
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5289

Effect of strains on electrical and optical properties of thin La 0.67Ca0.33MnO3 films
journal, March 2000

Reversible electrical switching of spin polarization in multiferroic tunnel junctions
journal, February 2012

  • Pantel, D.; Goetze, S.; Hesse, D.
  • Nature Materials, Vol. 11, Issue 4
  • DOI: 10.1038/nmat3254

Low Temperature Magnetoresistance and the Magnetic Phase Diagram of La 1 − x Ca x MnO 3
journal, October 1995

Surface Control of Epitaxial Manganite Films via Oxygen Pressure
journal, February 2015

  • Tselev, Alexander; Vasudevan, Rama K.; Gianfrancesco, Anthony G.
  • ACS Nano, Vol. 9, Issue 4
  • DOI: 10.1021/acsnano.5b00743

Strong Reciprocal Interaction between Polarization and Surface Stoichiometry in Oxide Ferroelectrics
journal, October 2014

  • Saidi, Wissam A.; Martirez, John Mark P.; Rappe, Andrew M.
  • Nano Letters, Vol. 14, Issue 11
  • DOI: 10.1021/nl5035013

Large Room-Temperature Electroresistance in Dual-Modulated Ferroelectric Tunnel Barriers
journal, March 2015

  • Radaelli, Greta; Gutiérrez, Diego; Sánchez, Florencio
  • Advanced Materials, Vol. 27, Issue 16
  • DOI: 10.1002/adma.201405117

Cross-Sectional Scanning Tunneling Microscopy Applied to Complex Oxide Interfaces
journal, March 2013

  • Chien, Te Yu; Chakhalian, Jak; Freeland, John W.
  • Advanced Functional Materials, Vol. 23, Issue 20
  • DOI: 10.1002/adfm.201203430

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

Effect of Interfacial Octahedral Behavior in Ultrathin Manganite Films
journal, April 2014

  • Moon, E. J.; Balachandran, P. V.; Kirby, B. J.
  • Nano Letters, Vol. 14, Issue 5
  • DOI: 10.1021/nl500235f

Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

Understanding the interactions between oxygen vacancies at SrTiO 3 (001) surfaces
journal, August 2014

Correlation between magnetic homogeneity, oxygen content, and electrical and magnetic properties of perovskite manganite thin films
journal, November 1998

  • Rajeswari, M.; Shreekala, R.; Goyal, A.
  • Applied Physics Letters, Vol. 73, Issue 18
  • DOI: 10.1063/1.122549

Are strain-induced effects truly strain induced? A comprehensive study of strained LCMO thin films
journal, May 2005

  • Dvorak, Joseph; Idzerda, Y. U.; Ogale, S. B.
  • Journal of Applied Physics, Vol. 97, Issue 10
  • DOI: 10.1063/1.1845974

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

Artificial chemical and magnetic structure at the domain walls of an epitaxial oxide
journal, November 2014

  • Farokhipoor, S.; Magén, C.; Venkatesan, S.
  • Nature, Vol. 515, Issue 7527
  • DOI: 10.1038/nature13918

The physics of manganites: Structure and transport
journal, August 2001

Formation enthalpies by mixing GGA and GGA + U calculations
journal, July 2011

Tunneling Evidence of Half-Metallic Ferromagnetism in La 0.7 Ca 0.3 MnO 3
journal, December 1997

Role of Jahn-Teller disorder in Raman scattering of mixed-valence manganites
journal, June 2003

Adaptive oxide electronics: A review
journal, October 2011

  • Ha, Sieu D.; Ramanathan, Shriram
  • Journal of Applied Physics, Vol. 110, Issue 7
  • DOI: 10.1063/1.3640806

Diffusion and segregation effects in doped manganite/titanate heterostructures
journal, May 2004

  • Simon, J.; Walther, T.; Mader, W.
  • Applied Physics Letters, Vol. 84, Issue 19
  • DOI: 10.1063/1.1738930

Cation Size Mismatch and Charge Interactions Drive Dopant Segregation at the Surfaces of Manganite Perovskites
journal, May 2013

  • Lee, Wonyoung; Han, Jeong Woo; Chen, Yan
  • Journal of the American Chemical Society, Vol. 135, Issue 21
  • DOI: 10.1021/ja3125349

Strong Surface-Termination Effect on Electroresistance in Ferroelectric Tunnel Junctions
journal, March 2015

  • Yamada, Hiroyuki; Tsurumaki-Fukuchi, Atsushi; Kobayashi, Masaki
  • Advanced Functional Materials, Vol. 25, Issue 18
  • DOI: 10.1002/adfm.201500371

Visualizing Atomistic Formation Process of SrO x Thin Films on SrTiO 3
journal, March 2014

  • Ohsawa, Takeo; Shimizu, Ryota; Iwaya, Katsuya
  • ACS Nano, Vol. 8, Issue 3
  • DOI: 10.1021/nn405359u

Conducting Jahn-Teller domain walls in undoped manganites
journal, June 2010

Surfaces of the perovskite manganites La 1 − x Ca x MnO 3
journal, May 1999

Direct imaging of the coexistence of ferromagnetism and superconductivity at the LaAlO3/SrTiO3 interface
journal, September 2011

  • Bert, Julie A.; Kalisky, Beena; Bell, Christopher
  • Nature Physics, Vol. 7, Issue 10, p. 767-771
  • DOI: 10.1038/nphys2079

Theory of the Role of Covalence in the Perovskite-Type Manganites [ La ,   M ( II ) ] Mn O 3
journal, October 1955

    Sort by:
    [ × clear filter / sort ]

    Figures / Tables found in this record:

    FIG. 1 (p. 3)figure
    FIG. 2 (p. 4)figure
    FIG. 3 (p. 4)figure
    FIG. 4 (p. 5)figure
    FIG. 5 (p. 6)figure
      [ × clear filter / sort ]
      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

      Similar Records in DOE PAGES and OSTI.GOV collections: