skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Surface and interface properties of L a 2 / 3 S r 1 / 3 Mn O 3 thin films on SrTiO 3 (001)

Abstract

Understanding and manipulating properties emerging at a surface or an interface require a thorough knowledge of structure-property relationships. We report a study of a prototype oxide system, La 2/3Sr 1/3MnO 3 grown on SrTiO 3(001), by combining in situ angle-resolved x-ray photoelectron spectroscopy, ex situ x-ray diffraction, and scanning transmission electron microscopy/spectroscopy with electric transport measurements. We find that La 2/3Sr 1/3MnO 3 films thicker than 20 unit cells (u.c.) exhibit a universal behavior with no more than one u.c. intermixing at the interface but at least 3 u.c. of Sr segregation near the surface, which is (La/Sr)O terminated. The conductivity vs film thickness shows the existence of nonmetallic layers with thickness ~6.5±0.9u.c., which is independent of film thickness but mainly relates to the deviation of Sr concentration near the surface region. Below 20 u.c., the surface of the films appears mixed, (La/Sr)O with MnO 2 termination. Decreasing film thickness to less than 10 u.c. leads to the enhanced deviation of chemical composition in the films and eventually drives the film insulating. Finally, our observation offers a natural explanation for the thickness-driven metal-nonmetal transition in thin films based on the variation of film stoichiometry.

Authors:
 [1];  [2];  [3];  [4];  [3];  [5]; ORCiD logo [6];  [3];  [3]
  1. Louisiana State Univ., Baton Rouge, LA (United States); Nanjing Univ., Nanjing (People's Republic of China)
  2. Louisiana State Univ., Baton Rouge, LA (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Louisiana State Univ., Baton Rouge, LA (United States)
  4. Louisiana State Univ., Baton Rouge, LA (United States); Fudan Univ., Shanghai (People's Republic of China)
  5. Louisiana State Univ., Baton Rouge, LA (United States); Univ. of Science and Technology of China Hefei, Anhui (People's Republic of China)
  6. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1529072
Alternate Identifier(s):
OSTI ID: 1508190
Report Number(s):
BNL-211778-2019-JAAM
Journal ID: ISSN 2475-9953; PRMHAR
Grant/Contract Number:  
SC0012704; SC0002136; AC02-98CH10886
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 3; Journal Issue: 4; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Chen, Lina, Wang, Zhen, Wang, Gaomin, Guo, Hangwen, Saghayezhian, Mohammad, Liao, Zhaoliang, Zhu, Yimei, Plummer, E. W., and Zhang, Jiandi. Surface and interface properties of La2/3Sr1/3MnO3 thin films on SrTiO3 (001). United States: N. p., 2019. Web. doi:10.1103/PhysRevMaterials.3.044407.
Chen, Lina, Wang, Zhen, Wang, Gaomin, Guo, Hangwen, Saghayezhian, Mohammad, Liao, Zhaoliang, Zhu, Yimei, Plummer, E. W., & Zhang, Jiandi. Surface and interface properties of La2/3Sr1/3MnO3 thin films on SrTiO3 (001). United States. doi:10.1103/PhysRevMaterials.3.044407.
Chen, Lina, Wang, Zhen, Wang, Gaomin, Guo, Hangwen, Saghayezhian, Mohammad, Liao, Zhaoliang, Zhu, Yimei, Plummer, E. W., and Zhang, Jiandi. Mon . "Surface and interface properties of La2/3Sr1/3MnO3 thin films on SrTiO3 (001)". United States. doi:10.1103/PhysRevMaterials.3.044407. https://www.osti.gov/servlets/purl/1529072.
@article{osti_1529072,
title = {Surface and interface properties of La2/3Sr1/3MnO3 thin films on SrTiO3 (001)},
author = {Chen, Lina and Wang, Zhen and Wang, Gaomin and Guo, Hangwen and Saghayezhian, Mohammad and Liao, Zhaoliang and Zhu, Yimei and Plummer, E. W. and Zhang, Jiandi},
abstractNote = {Understanding and manipulating properties emerging at a surface or an interface require a thorough knowledge of structure-property relationships. We report a study of a prototype oxide system, La2/3Sr1/3MnO3 grown on SrTiO3(001), by combining in situ angle-resolved x-ray photoelectron spectroscopy, ex situ x-ray diffraction, and scanning transmission electron microscopy/spectroscopy with electric transport measurements. We find that La2/3Sr1/3MnO3 films thicker than 20 unit cells (u.c.) exhibit a universal behavior with no more than one u.c. intermixing at the interface but at least 3 u.c. of Sr segregation near the surface, which is (La/Sr)O terminated. The conductivity vs film thickness shows the existence of nonmetallic layers with thickness ~6.5±0.9u.c., which is independent of film thickness but mainly relates to the deviation of Sr concentration near the surface region. Below 20 u.c., the surface of the films appears mixed, (La/Sr)O with MnO2 termination. Decreasing film thickness to less than 10 u.c. leads to the enhanced deviation of chemical composition in the films and eventually drives the film insulating. Finally, our observation offers a natural explanation for the thickness-driven metal-nonmetal transition in thin films based on the variation of film stoichiometry.},
doi = {10.1103/PhysRevMaterials.3.044407},
journal = {Physical Review Materials},
issn = {2475-9953},
number = 4,
volume = 3,
place = {United States},
year = {2019},
month = {4}
}

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

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Temperature-Dependent Surface States and Transitions of Si(111)-7×7
journal, December 1983


Creation and control of a two-dimensional electron liquid at the bare SrTiO3 surface
journal, January 2011

  • Meevasana, W.; King, P. D. C.; He, R. H.
  • Nature Materials, Vol. 10, Issue 2
  • DOI: 10.1038/nmat2943

A Surface-Tailored, Purely Electronic, Mott Metal-to-Insulator Transition
journal, October 2007


Manifestations of Broken Symmetry: The Surface Phases of Ca 2 x Sr x RuO 4
journal, February 2008


Hidden phases revealed at the surface of double-layered S r 3 ( R u 1 x M n x ) 2 O 7
journal, August 2016


A high-mobility electron gas at the LaAlO3/SrTiO3 heterointerface
journal, January 2004


Magnetic effects at the interface between non-magnetic oxides
journal, June 2007

  • Brinkman, A.; Huijben, M.; van Zalk, M.
  • Nature Materials, Vol. 6, Issue 7, p. 493-496
  • DOI: 10.1038/nmat1931

Superconducting Interfaces Between Insulating Oxides
journal, August 2007


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

Why some interfaces cannot be sharp
journal, January 2006

  • Nakagawa, Naoyuki; Hwang, Harold Y.; Muller, David A.
  • Nature Materials, Vol. 5, Issue 3, p. 204-209
  • DOI: 10.1038/nmat1569

Structural Basis for the Conducting Interface between LaAlO3 and SrTiO3
journal, October 2007


Cationic Disorder and Phase Segregation in LaAlO 3 / SrTiO 3 Heterointerfaces Evidenced by Medium-Energy Ion Spectroscopy
journal, September 2009


Origin of Charge Density at LaAlO3 on SrTiO3 Heterointerfaces: Possibility of Intrinsic Doping
journal, May 2007

  • Siemons, Wolter; Koster, Gertjan; Yamamoto, Hideki
  • Physical Review Letters, Vol. 98, Issue 19, Article No. 196802
  • DOI: 10.1103/PhysRevLett.98.196802

High Mobility in LaAlO3/SrTiO3 Heterostructures: Origin, Dimensionality, and Perspectives
journal, May 2007


Avoiding the Polarization Catastrophe in LaAlO 3 Overlayers on SrTiO 3 ( 001 ) through Polar Distortion
journal, March 2009


Dimensional-Crossover-Driven Metal-Insulator Transition in SrVO 3 Ultrathin Films
journal, April 2010


Critical thickness for itinerant ferromagnetism in ultrathin films of SrRuO 3
journal, April 2009


Dimensionality Control of Electronic Phase Transitions in Nickel-Oxide Superlattices
journal, May 2011


Metal-Insulator Transition in Ultrathin LaNiO 3 Films
journal, June 2011


Atomically defined epitaxy and physical properties of strained La0.6Sr0.4MnO3 films
journal, October 1998

  • Izumi, M.; Konishi, Y.; Nishihara, T.
  • Applied Physics Letters, Vol. 73, Issue 17
  • DOI: 10.1063/1.122494

Critical thickness and orbital ordering in ultrathin La 0.7 Sr 0.3 MnO 3 films
journal, September 2008


Electronics with Correlated Oxides: SrVO 3 / SrTiO 3 as a Mott Transistor
journal, June 2015


Evidence of Orbital Reconstruction at Interfaces in Ultrathin La 0.67 Sr 0.33 MnO 3 Films
journal, April 2008


Ground-state oxygen holes and the metal–insulator transition in the negative charge-transfer rare-earth nickelates
journal, October 2016

  • Bisogni, Valentina; Catalano, Sara; Green, Robert J.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms13017

Interface Effects in Perovskite Thin Films
journal, February 2012


Surface segregation and restructuring of colossal-magnetoresistant manganese perovskites La 0.65 Sr 0.35 MnO 3
journal, December 2000


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

New Insights into the Strain Coupling to Surface Chemistry, Electronic Structure, and Reactivity of La 0.7 Sr 0.3 MnO 3
journal, March 2011

  • Jalili, Helia; Han, Jeong Woo; Kuru, Yener
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 7
  • DOI: 10.1021/jz200160b

Electron tunneling characteristics on La0.7Sr0.3MnO3 thin-film surfaces at high temperature
journal, August 2009

  • Katsiev, Khabiboulakh; Yildiz, Bilge; Balasubramaniam, Kavaipatti
  • Applied Physics Letters, Vol. 95, Issue 9
  • DOI: 10.1063/1.3204022

Surface stoichiometry of La0.7Sr0.3MnO3 during in vacuo preparation; A synchrotron photoemission study
journal, September 2012


A Combined Ion Scattering, Photoemission, and DFT Investigation on the Termination Layer of a La 0.7 Sr 0.3 MnO 3 Spin Injecting Electrode
journal, June 2014

  • Poggini, L.; Ninova, S.; Graziosi, P.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 25
  • DOI: 10.1021/jp5026619

Chemical and structural characterization of La0.5Sr0.5MnO3 thin films prepared by pulsed-laser deposition
journal, May 2001

  • Decorse, P.; Quenneville, E.; Poulin, S.
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 19, Issue 3
  • DOI: 10.1116/1.1368200

Interface and Surface Cation Stoichiometry Modified by Oxygen Vacancies in Epitaxial Manganite Films
journal, June 2012

  • Li, Zhipeng; Bosman, Michel; Yang, Zhen
  • Advanced Functional Materials, Vol. 22, Issue 20
  • DOI: 10.1002/adfm.201200143

Grain boundary mobility – a brief review
journal, April 2004

  • Rollett, A. D.; Gottstein, G.; Shvindlerman, L. S.
  • Zeitschrift für Metallkunde, Vol. 95, Issue 4
  • DOI: 10.3139/146.017938

Unraveling how electronic and spin structures control macroscopic properties of manganite ultra-thin films
journal, July 2015

  • Yin, Xinmao; Majidi, Muhammad Aziz; Chi, Xiao
  • NPG Asia Materials, Vol. 7, Issue 7
  • DOI: 10.1038/am.2015.65

Interface-controlled magnetism and transport of ultrathin manganite films
journal, May 2013

  • Shapoval, O.; Hühn, S.; Verbeeck, J.
  • Journal of Applied Physics, Vol. 113, Issue 17
  • DOI: 10.1063/1.4795422

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

Preventing the Reconstruction of the Polar Discontinuity at Oxide Heterointerfaces
journal, March 2012

  • Boschker, H.; Verbeeck, J.; Egoavil, R.
  • Advanced Functional Materials, Vol. 22, Issue 11
  • DOI: 10.1002/adfm.201102763

Ga segregation in DyBa2Cu3O7−δ/PrBa2Cu3−xGaxO7−δ/DyBa2Cu3O7−δ ramp-type Josephson junctions
journal, March 1997

  • Verbist, K.; Lebedev, O. I.; Van Tendeloo, G.
  • Applied Physics Letters, Vol. 70, Issue 9
  • DOI: 10.1063/1.118515

Influence of dopant segregation on the work function and electrical properties of Ge-doped in comparison to Sn-doped In 2 O 3 thin films : Dopant segregation of Ge-doped In
journal, October 2016

  • Hoyer, Karoline L.; Hubmann, Andreas H.; Klein, Andreas
  • physica status solidi (a), Vol. 214, Issue 2
  • DOI: 10.1002/pssa.201600486

Electrical and structural properties of low resistivity tin‐doped indium oxide films
journal, April 1992

  • Shigesato, Yuzo; Takaki, Satoru; Haranoh, Takeshi
  • Journal of Applied Physics, Vol. 71, Issue 7
  • DOI: 10.1063/1.350931

Effect of In segregation on the structural and optical properties of ultrathin InAs films in GaAs
journal, December 1992

  • Brandt, O.; Tapfer, L.; Ploog, K.
  • Applied Physics Letters, Vol. 61, Issue 23
  • DOI: 10.1063/1.108046

Effects of interfacial atomic segregation on optical properties of InAs/GaSb superlattices
journal, August 2001


A Novel Multiple Interface Structure with the Segregation of Dopants in Lead-Free Ferroelectric (K 0.5 Na 0.5 )NbO 3 Thin Films
journal, December 2017

  • Li, Chao; Wang, Lingyan; Chen, Wen
  • Advanced Materials Interfaces, Vol. 5, Issue 2
  • DOI: 10.1002/admi.201700972

Magnetism at high-index transition-metal surfaces and the effect of metalloid impurities: Ni(210)
journal, January 2001


Magnetically dead layers at s p -impurity-decorated grain boundaries and surfaces in nickel
journal, July 2011


Structure determination of monolayer-by-monolayer grown La 1 x Sr x MnO 3 thin films and the onset of magnetoresistance
journal, February 2008


Direct Demonstration of a Magnetic Dead Layer Resulting from A-Site Cation Inhomogeneity in a (La,Sr)MnO 3 Epitaxial Film System
journal, July 2016

  • Jin, Lei; Jia, Chun-Lin; Lindfors-Vrejoiu, Ionela
  • Advanced Materials Interfaces, Vol. 3, Issue 18
  • DOI: 10.1002/admi.201600414

Artificial charge-modulationin atomic-scale perovskite titanate superlattices
journal, September 2002

  • Ohtomo, A.; Muller, D. A.; Grazul, J. L.
  • Nature, Vol. 419, Issue 6905
  • DOI: 10.1038/nature00977

Interface-induced multiferroism by design in complex oxide superlattices
journal, June 2017

  • Guo, Hangwen; Wang, Zhen; Dong, Shuai
  • Proceedings of the National Academy of Sciences
  • DOI: 10.1073/pnas.1706814114

Origin of the metal-insulator transition in ultrathin films of L a 2 / 3 S r 2 / 3 Mn O 3
journal, September 2015


Relative intensities in ESCA and quantitative depth profiling
journal, January 1988


Insulator-metal transition and giant magnetoresistance in La 1 x Sr x MnO 3
journal, May 1995


Magnetism and structural distortion in the La 0.7 Sr 0.3 Mn O 3 metallic ferromagnet
journal, June 1996


Calculations of electron inelastic mean free paths. V. Data for 14 organic compounds over the 50-2000 eV range
journal, March 1994

  • Tanuma, S.; Powell, C. J.; Penn, D. R.
  • Surface and Interface Analysis, Vol. 21, Issue 3
  • DOI: 10.1002/sia.740210302

Chemical Heterogeneities on La 0.6 Sr 0.4 CoO 3−δ Thin Films—Correlations to Cathode Surface Activity and Stability
journal, March 2012

  • Cai, Zhuhua; Kubicek, Markus; Fleig, Jürgen
  • Chemistry of Materials, Vol. 24, Issue 6
  • DOI: 10.1021/cm203501u

Activation, microstructure, and polarization of solid oxide fuel cell cathodes
journal, November 2005


Investigation of surface Sr segregation in model thin film solid oxidefuel cell perovskite electrodes
journal, January 2012

  • Jung, WooChul; Tuller, Harry L.
  • Energy Environ. Sci., Vol. 5, Issue 1
  • DOI: 10.1039/C1EE02762J

Doped CeO 2 –LaFeO 3 Composite Oxide as an Active Anode for Direct Hydrocarbon-Type Solid Oxide Fuel Cells
journal, December 2011

  • Shin, Tae Ho; Ida, Shintaro; Ishihara, Tatsumi
  • Journal of the American Chemical Society, Vol. 133, Issue 48
  • DOI: 10.1021/ja206278f

Dense Perovskite, La1-xA′xFe1-yCoyO3-δ (A′= Ba, Sr, Ca), Membrane Synthesis, Applications, and Characterization
journal, June 1998


A New Series of Sr(Co,Fe,Zr)O 3 - δ Perovskite-Type Membrane Materials for Oxygen Permeation
journal, May 2003

  • Yang, Li; Tan, Liang; Gu, Xuehong
  • Industrial & Engineering Chemistry Research, Vol. 42, Issue 11
  • DOI: 10.1021/ie020931e

Structural Mechanism of the Phase Transitions in the Mg−Cu−Mo 6 S 8 System Probed by ex Situ Synchrotron X-ray Diffraction
journal, October 2007

  • Levi, E.; Mitelman, A.; Aurbach, D.
  • Chemistry of Materials, Vol. 19, Issue 21
  • DOI: 10.1021/cm0715489

Large low-field magnetoresistance and TC in polycrystalline (Ba0.8Sr0.2)2−xLaxFeMoO6 double perovskites
journal, June 2002

  • Serrate, D.; De Teresa, J. M.; Blasco, J.
  • Applied Physics Letters, Vol. 80, Issue 24
  • DOI: 10.1063/1.1485119

Donor Characteristics of Transition-Metal-Doped Oxides: Cr-Doped MgO versus Mo-Doped CaO
journal, July 2012

  • Stavale, Fernando; Shao, Xiang; Nilius, Niklas
  • Journal of the American Chemical Society, Vol. 134, Issue 28
  • DOI: 10.1021/ja304497n

Combined theoretical and experimental analysis of processes determining cathode performance in solid oxide fuel cells
journal, January 2013

  • Kuklja, M. M.; Kotomin, E. A.; Merkle, R.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 15
  • DOI: 10.1039/C3CP44363A