Surface and interface properties of thin films on (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, 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.
- Authors:
-
- Louisiana State Univ., Baton Rouge, LA (United States); Nanjing Univ., Nanjing (People's Republic of China)
- Louisiana State Univ., Baton Rouge, LA (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
- Louisiana State Univ., Baton Rouge, LA (United States)
- Louisiana State Univ., Baton Rouge, LA (United States); Fudan Univ., Shanghai (People's Republic of China)
- Louisiana State Univ., Baton Rouge, LA (United States); Univ. of Science and Technology of China Hefei, Anhui (People's Republic of China)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (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:
- 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. https://doi.org/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. https://doi.org/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},
number = 4,
volume = 3,
place = {United States},
year = {Mon Apr 22 00:00:00 EDT 2019},
month = {Mon Apr 22 00:00:00 EDT 2019}
}
Web of Science
Works referenced in this record:
Temperature-Dependent Surface States and Transitions of Si(111)-7×7
journal, December 1983
- Demuth, J. E.; Persson, B. N. J.; Schell-Sorokin, A. J.
- Physical Review Letters, Vol. 51, Issue 24
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
A Surface-Tailored, Purely Electronic, Mott Metal-to-Insulator Transition
journal, October 2007
- Moore, R. G.; Zhang, Jiandi; Nascimento, V. B.
- Science, Vol. 318, Issue 5850
Manifestations of Broken Symmetry: The Surface Phases of
journal, February 2008
- Moore, R. G.; Nascimento, V. B.; Zhang, Jiandi
- Physical Review Letters, Vol. 100, Issue 6
Hidden phases revealed at the surface of double-layered
journal, August 2016
- Chen, Chen; Kim, Jisun; Nascimento, V. B.
- Physical Review B, Vol. 94, Issue 8
A high-mobility electron gas at the LaAlO3/SrTiO3 heterointerface
journal, January 2004
- Ohtomo, A.; Hwang, H. Y.
- Nature, Vol. 427, Issue 6973
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
Superconducting Interfaces Between Insulating Oxides
journal, August 2007
- Reyren, N.; Thiel, S.; Caviglia, A. D.
- Science, Vol. 317, Issue 5842
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
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
Structural Basis for the Conducting Interface between and
journal, October 2007
- Willmott, P. R.; Pauli, S. A.; Herger, R.
- Physical Review Letters, Vol. 99, Issue 15, Article No. 155502
Cationic Disorder and Phase Segregation in Heterointerfaces Evidenced by Medium-Energy Ion Spectroscopy
journal, September 2009
- Kalabukhov, A. S.; Boikov, Yu. A.; Serenkov, I. T.
- Physical Review Letters, Vol. 103, Issue 14
Origin of Charge Density at on Heterointerfaces: Possibility of Intrinsic Doping
journal, May 2007
- Siemons, Wolter; Koster, Gertjan; Yamamoto, Hideki
- Physical Review Letters, Vol. 98, Issue 19, Article No. 196802
High Mobility in Heterostructures: Origin, Dimensionality, and Perspectives
journal, May 2007
- Herranz, G.; Basletić, M.; Bibes, M.
- Physical Review Letters, Vol. 98, Issue 21, Article No. 216803
Avoiding the Polarization Catastrophe in Overlayers on through Polar Distortion
journal, March 2009
- Pentcheva, Rossitza; Pickett, Warren E.
- Physical Review Letters, Vol. 102, Issue 10
Dimensional-Crossover-Driven Metal-Insulator Transition in Ultrathin Films
journal, April 2010
- Yoshimatsu, K.; Okabe, T.; Kumigashira, H.
- Physical Review Letters, Vol. 104, Issue 14
Critical thickness for itinerant ferromagnetism in ultrathin films of
journal, April 2009
- Xia, Jing; Siemons, W.; Koster, G.
- Physical Review B, Vol. 79, Issue 14
Dimensionality Control of Electronic Phase Transitions in Nickel-Oxide Superlattices
journal, May 2011
- Boris, A. V.; Matiks, Y.; Benckiser, E.
- Science, Vol. 332, Issue 6032
Metal-Insulator Transition in Ultrathin Films
journal, June 2011
- Scherwitzl, R.; Gariglio, S.; Gabay, M.
- Physical Review Letters, Vol. 106, Issue 24
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
Critical thickness and orbital ordering in ultrathin films
journal, September 2008
- Huijben, M.; Martin, L. W.; Chu, Y. -H.
- Physical Review B, Vol. 78, Issue 9
Electronics with Correlated Oxides: as a Mott Transistor
journal, June 2015
- Zhong, Zhicheng; Wallerberger, Markus; Tomczak, Jan M.
- Physical Review Letters, Vol. 114, Issue 24
Evidence of Orbital Reconstruction at Interfaces in Ultrathin Films
journal, April 2008
- Tebano, A.; Aruta, C.; Sanna, S.
- Physical Review Letters, Vol. 100, Issue 13
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
Interface Effects in Perovskite Thin Films
journal, February 2012
- Lepetit, Marie-Bernadette; Mercey, Bernard; Simon, Charles
- Physical Review Letters, Vol. 108, Issue 8
Surface segregation and restructuring of colossal-magnetoresistant manganese perovskites
journal, December 2000
- Dulli, Hani; Dowben, P. A.; Liou, S. -H.
- Physical Review B, Vol. 62, Issue 22
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
Evidence for strontium segregation in La 0.7 Sr 0.3 MnO 3 thin films grown by pulsed laser deposition: consequences for tunnelling junctions
journal, June 2002
- Bertacco, R.; Contour, J. P.; Barthélemy, A.
- Surface Science, Vol. 511, Issue 1-3
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
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
Surface stoichiometry of La0.7Sr0.3MnO3 during in vacuo preparation; A synchrotron photoemission study
journal, September 2012
- Monsen, Å. F.; Song, F.; Li, Z. S.
- Surface Science, Vol. 606, Issue 17-18
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
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
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
Grain boundary mobility – a brief review
journal, April 2004
- Rollett, A. D.; Gottstein, G.; Shvindlerman, L. S.
- Zeitschrift für Metallkunde, Vol. 95, Issue 4
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
Electronic and Magnetic Reconstructions in Heterostructures: A Case of Enhanced Interlayer Coupling Controlled by the Interface
journal, April 2011
- Bruno, F. Y.; Garcia-Barriocanal, J.; Varela, M.
- Physical Review Letters, Vol. 106, Issue 14
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
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
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
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
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
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
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
Effects of interfacial atomic segregation on optical properties of InAs/GaSb superlattices
journal, August 2001
- Magri, Rita; Zunger, Alex
- Physical Review B, Vol. 64, Issue 8
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
Magnetism at high-index transition-metal surfaces and the effect of metalloid impurities: Ni(210)
journal, January 2001
- Geng, W. T.; Freeman, A. J.; Wu, R. Q.
- Physical Review B, Vol. 63, Issue 6
Magnetically dead layers at -impurity-decorated grain boundaries and surfaces in nickel
journal, July 2011
- Všianská, M.; Šob, M.
- Physical Review B, Vol. 84, Issue 1
Structure determination of monolayer-by-monolayer grown thin films and the onset of magnetoresistance
journal, February 2008
- Herger, R.; Willmott, P. R.; Schlepütz, C. M.
- Physical Review B, Vol. 77, Issue 8
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
The layer-by-layer stoichiometry of La 0.7 Sr 0.3 MnO 3 /SrTiO 3 thin films and interfaces : The layer-by-layer stoichiometry of LSMO/STO thin films and interfaces
journal, March 2013
- Song, F.; Monsen, Å. F.; Li, Z. S.
- Surface and Interface Analysis, Vol. 45, Issue 7
Artificial charge-modulationin atomic-scale perovskite titanate superlattices
journal, September 2002
- Ohtomo, A.; Muller, D. A.; Grazul, J. L.
- Nature, Vol. 419, Issue 6905
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
Origin of the metal-insulator transition in ultrathin films of
journal, September 2015
- Liao, Zhaoliang; Li, Fengmiao; Gao, Peng
- Physical Review B, Vol. 92, Issue 12
Relative intensities in ESCA and quantitative depth profiling
journal, January 1988
- Nefedov, V. I.; Baschenko, O. A.
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 47
Insulator-metal transition and giant magnetoresistance in
journal, May 1995
- Urushibara, A.; Moritomo, Y.; Arima, T.
- Physical Review B, Vol. 51, Issue 20
Magnetism and structural distortion in the Mn metallic ferromagnet
journal, June 1996
- Martin, Michael C.; Shirane, G.; Endoh, Y.
- Physical Review B, Vol. 53, Issue 21
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
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
Activation, microstructure, and polarization of solid oxide fuel cell cathodes
journal, November 2005
- Jiang, San Ping
- Journal of Solid State Electrochemistry, Vol. 11, Issue 1
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
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
Dense Perovskite, La1-xA′xFe1-yCoyO3-δ (A′= Ba, Sr, Ca), Membrane Synthesis, Applications, and Characterization
journal, June 1998
- Tsai, Chung-Yi; Dixon, Anthony G.; Ma, Yi Hua
- Journal of the American Ceramic Society, Vol. 81, Issue 6
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
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
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
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