Hostname: page-component-78c5997874-94fs2 Total loading time: 0 Render date: 2024-11-19T12:37:00.043Z Has data issue: false hasContentIssue false
  • English
  • Français

Atomic-Scale Measurement of Structure and Chemistry of a Single-Unit-Cell Layer of LaAlO3 Embedded in SrTiO3

Published online by Cambridge University Press:  04 March 2013

Chun-Lin Jia ,
Juri Barthel ,
Felix Gunkel ,
Regina Dittmann ,
Susanne Hoffmann-Eifert ,
Lothar Houben ,
Markus Lentzen  and
Andreas Thust
Chun-Lin Jia*
Affiliation:
Peter Grünberg Institute (PGI), Forschungszentrum Jülich GmbH, 52425 Jülich, Germany Ernst Ruska-Centre (ER-C) for Microscopy and Spectroscopy with Electrons, Forschungszentrum Jülich GmbH, 52425 Jülich, Germany International Centre for Dielectric Research, Xi'an Jiaotong University, 710049 Xi'an, China
Juri Barthel
Affiliation:
Ernst Ruska-Centre (ER-C) for Microscopy and Spectroscopy with Electrons, Forschungszentrum Jülich GmbH, 52425 Jülich, Germany Central Facility for Electron Microscopy (GFE), Aachen University (RWTH), 52074 Aachen, Germany
Felix Gunkel
Affiliation:
Peter Grünberg Institute (PGI), Forschungszentrum Jülich GmbH, 52425 Jülich, Germany
Regina Dittmann
Affiliation:
Peter Grünberg Institute (PGI), Forschungszentrum Jülich GmbH, 52425 Jülich, Germany
Susanne Hoffmann-Eifert
Affiliation:
Peter Grünberg Institute (PGI), Forschungszentrum Jülich GmbH, 52425 Jülich, Germany
Lothar Houben
Affiliation:
Peter Grünberg Institute (PGI), Forschungszentrum Jülich GmbH, 52425 Jülich, Germany Ernst Ruska-Centre (ER-C) for Microscopy and Spectroscopy with Electrons, Forschungszentrum Jülich GmbH, 52425 Jülich, Germany
Markus Lentzen
Affiliation:
Peter Grünberg Institute (PGI), Forschungszentrum Jülich GmbH, 52425 Jülich, Germany Ernst Ruska-Centre (ER-C) for Microscopy and Spectroscopy with Electrons, Forschungszentrum Jülich GmbH, 52425 Jülich, Germany
Andreas Thust
Affiliation:
Peter Grünberg Institute (PGI), Forschungszentrum Jülich GmbH, 52425 Jülich, Germany Ernst Ruska-Centre (ER-C) for Microscopy and Spectroscopy with Electrons, Forschungszentrum Jülich GmbH, 52425 Jülich, Germany
*
*Corresponding author. E-mail: [email protected], [email protected]
Get access

Abstract

A single layer of LaAlO3 with a nominal thickness of one unit cell, which is sandwiched between a SrTiO3 substrate and a SrTiO3 capping layer, is quantitatively investigated by high-resolution transmission electron microscopy. By the use of an aberration-corrected electron microscope and by employing sophisticated numerical image simulation procedures, significant progress is made in two aspects. First, the structural as well as the chemical features of the interface are determined simultaneously on an atomic scale from the same specimen area. Second, the evaluation of the structural and chemical data is carried out in a fully quantitative way on the basis of the absolute image contrast, which has not been achieved so far in materials science investigations using high-resolution electron microscopy. Considering the strong influence of even subtle structural details on the electronic properties of interfaces in oxide materials, a fully quantitative interface analysis, which makes positional data available with picometer precision together with the related chemical information, can contribute to a better understanding of the functionality of such interfaces.

Keywords

aberration-corrected transmission electron microscopyatomic structureinterfacemultilayer thin filmsoxides
Type
Materials Applications
Information
Microscopy and Microanalysis , Volume 19 , Issue 2 , April 2013 , pp. 310 - 318
Copyright
Copyright © Microscopy Society of America 2013

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Bals, S., Van Aert, S., Van Tendeloo, G. & Avila-Brande, D. (2006). Statistical estimation of atomic positions from exit wave reconstruction with a precision in the picometer range. Phys Rev Lett 96, 096106. Google Scholar
Barthel, J. & Thust, A. (2008). Quantification of the information limit of transmission electron microscopes. Phys Rev Lett 101, 200801. CrossRefGoogle ScholarPubMed
Barthel, J. & Thust, A. (2010). Aberration measurement in HRTEM: Implementation and diagnostic use of numerical procedures for the highly precise recognition of diffractogram patterns. Ultramicroscopy 111, 27–46.CrossRefGoogle ScholarPubMed
Brinkman, A., Huijben, M., van Zalk, M., Huijben, J., Zeitler, U., Maan, J.C., van der Wiel, W.G., Rijnders, G., Blank, D.H.A. & Hilgenkamp, H. (2007). Magnetic effects at the interface between non-magnetic oxides. Nat Mater 6, 493–496.CrossRefGoogle ScholarPubMed
Chambers, S.A., Engelhard, M.H., Shutthanandan, V., Zhu, Z., Droubay, T.C., Qiao, L., Sushko, P.V., Feng, T., Lee, H.D., Gustafsson, T., Garfunkel, E., Shah, A.B., Zuo, J.-M. & Ramasse, Q.M. (2011). Instability, intermixing and electronic structure at the epitaxial LaAlO3/SrTiO3 heterojunction. Surf Sci Rep 65, 317–352.CrossRefGoogle Scholar
Chang, H.J., Kalinin, S.V., Morozovska, A.N., Huijben, M., Chu, Y.-H., Yu, P., Ramesh, R., Eliseev, E.A., Svechnikov, G.S., Pennycook, S.J. & Borisevich, A.Y. (2011). Atomically resolved mapping of polarization and electric fields across ferroelectric/oxide interfaces by Z-contrast imaging. Adv Mater 23, 2474–2479.Google Scholar
Gunkel, F., Hoffmann-Eifert, S., Dittmann, R., Mi, S.B., Jia, C.L., Meuffels, P. & Waser, R. (2010). High temperature conductance characteristics of LaAlO3/SrTiO3-heterostructures under equilibrium oxygen atmospheres. Appl Phys Lett 97, 012103. Google Scholar
Houben, L. (2012). iMtools electron microscope image processing software. Research Center Jülich. Available at http://www.er-c.org/methods/software.htm.Google Scholar
Houben, L., Heidelmann, M. & Gunkel, F. (2012). Spatial resolution and radiation damage in quantitative high-resolution STEM-EEL spectroscopy in oxides. Micron 43, 532–537.CrossRefGoogle Scholar
Houben, L., Thust, A. & Urban, K. (2006). Atomic-precision determination of the reconstruction of a 90° tilt boundary in YBa2Cu3O7-δ by aberration corrected HRTEM. Ultramicroscopy 106, 200–214.Google Scholar
Hÿtch, M.J. & Stobbs, W.M. (1994). Quantitative comparison of high resolution TEM images with image simulations. Ultramicroscopy 53, 191–203.Google Scholar
Jang, H.W., Felker, D.A., Bark, C.W., Wang, Y., Niranjan, M.K., Nelson, C.T., Zhang, Y., Su, D., Folkman, C.M., Baek, S.H., Lee, S., Janicka, K., Zhu, Y., Pan, X.Q., Fong, D.D., Tsymbal, E.Y., Rzchowski, M.S. & Eom, C.B. (2011). Metallic and insulating oxide interfaces controlled by electronic correlations. Science 331, 886–889.Google Scholar
Jia, C.L., Houben, L., Thust, A. & Barthel, J. (2010). On the benefit of the negative-spherical-aberration imaging technique for quantitative HRTEM. Ultramicroscopy 110, 500–505.Google Scholar
Jia, C.L., Lentzen, M. & Urban, K. (2003). Atomic-resolution imaging of oxygen in perovskite ceramics. Science 299, 870–873.Google Scholar
Jia, C.L., Lentzen, M. & Urban, K. (2004). High-resolution transmission electron microscopy using negative spherical aberration. Microsc Microanal 10, 174–184.Google Scholar
Jia, C.L., Mi, S.B., Faley, M., Poppe, U., Schubert, J. & Urban, K. (2009). Oxygen octahedron reconstruction in the SrTiO3/LaAlO3 heterointerfaces investigated using aberration-corrected ultrahigh-resolution transmission electron microscopy. Phys Rev B 79, 081405(R).Google Scholar
Jia, C.L., Mi, S.B., Urban, K., Vrejoiu, I., Alexe, M. & Hesse, D. (2008). Atomic-scale study of electric dipoles near charged and uncharged domain walls in ferroelectric films. Nat Mater 7, 57–61.Google Scholar
Jia, C.L. & Urban, K. (2004). Atomic-resolution measurement of oxygen concentration in oxide materials. Science 303, 2001–2004.CrossRefGoogle ScholarPubMed
Jia, C.L., Urban, K., Vrejoiu, I., Alexe, M. & Hesse, D. (2011). Direct observation of continuous electric dipole rotation in flux-closure domains in ferroelectric Pb(Zr,Ti)O3 . Science 331, 1420–1423.Google Scholar
Kalabukhov, A.S., Boikov, Yu.A., Serenkov, I.T., Sakharov, V.I., Popok, V.N., Gunnarsson, R., Borjesson, J., Ljustina, N., Olsson, E., Winkler, D. & Claeson, T. (2009). Cationic disorder and phase segregation in LaAlO3/SrTiO3 heterointerfaces evidenced by medium-energy ion spectroscopy. Phys Rev Lett 103, 146101. Google Scholar
Keeble, D.J., Wicklein, S., Dittmann, R., Ravelli, L., Mackie, R.A. & Egger, W. (2010). Identification of A- and B-site cation vacancy defects in perovskite oxide thin films. Phys Rev Lett 105, 226102. Google Scholar
Kim, S., Oshima, Y., Sawada, H., Kaneyama, T., Kondo, Y., Takeguchi, M., Nakayama, Y., Tanishiro, Y. & Takayanagi, K. (2011). Quantitative annular dark-field STEM images of a silicon crystal using a large-angle convergent electron probe with a 300-kV cold field-emission gun. J Electron Microsc 60, 109–116.CrossRefGoogle ScholarPubMed
Krivanek, O.L., Chisholm, M.F., Nicolosi, V., Pennycook, T.J., Corbin, G.J., Dellby, N., Murfitt, M.F., Own, C.S., Szilagyi, Z.S., Oxley, M.P., Pantelides, S.T. & Pennycook, S.J. (2010). Atom-by-atom structural and chemical analysis by annular dark-field electron microscopy. Nature 464, 571–574.CrossRefGoogle ScholarPubMed
LeBeau, J.M., Findlay, S.D., Allen, L.J. & Stemmer, S. (2010). Standardless atom counting in scanning transmission electron microscopy. Nano Lett 10, 4405–4408.Google Scholar
Luysberg, M., Heidelmann, M., Houben, L., Boese, M., Heeg, T., Schubert, J. & Roeckerath, M. (2009). Intermixing and charge neutrality at DyScO3/SrTiO3 interfaces. Acta Mater 57, 3192–3198.Google Scholar
MacLaren, I., Villaurrutia, R., Schaffer, B., Houben, L. & Peláiz-Barranco, A. (2011). Atomic-scale imaging and quantification of electrical polarisation in incommensurate antiferroelectric lanthanum-doped lead zirconate titanate. Adv Funct Mater 22, 261–266.Google Scholar
Maurice, J.-L., Herranz, G., Colliex, C., Devos, I., Carretero, C., Barthelemy, A., Bouzehouane, K., Fusil, S., Imhoff, D., Jacquet, E., Jomard, F., Ballutaud, D. & Basletic, M. (2008). Electron energy loss spectroscopy determination of Ti oxidation state at the (001) LaAlO3/SrTiO3 interface as a function of LaAlO3 growth conditions. EPL 82, 17003. Google Scholar
Molina, S.I., Sales, D.L., Galindo, P.L., Fuster, D., González, Y., Alén, B., González, L., Varela, M. & Pennycook, S.J. (2009). Column-by-column compositional mapping by Z-contrast imaging. Ultramicroscopy 109, 172–176.CrossRefGoogle ScholarPubMed
Muller, D.A., Fitting Kourkoutis, L., Murfitt, M., Song, J. H., Hwang, H.Y., Silcox, J., Dellby, N. & Krivanek, O.L. (2008). Atomic-scale chemical imaging of composition and bonding by aberration-corrected microscopy. Science 319, 1073–1076.Google Scholar
Nakagawa, N., Hwang, H.Y. & Muller, D.A. (2006). Why some interfaces cannot be sharp. Nat Mater 5, 204–209.Google Scholar
Ohnishi, T., Shibuya, K., Yamamoto, T. & Lippmaa, M. (2008). Defects and transport in complex oxide thin films. J Appl Phys 103, 103703. Google Scholar
Ohtomo, A. & Hwang, H.Y. (2004). A high-mobility electron gas at the LaAlO3/SrTiO3 heterointerface. Nature 427, 423–426.Google Scholar
O'Keefe, M.A. & Kilaas, R. (1988). Advances in high-resolution image simulation. Scan Microsc Suppl 2, 225–244.Google Scholar
Pauli, S.A., Leake, S.J., Delley, B., Bjorck, M., Schneider, C.W., Schlepütz, C.M., Martoccia, D., Paetel, S., Mannhart, J. & Willmott, P.R. (2011). Evolution of the interfacial structure of LaAlO3 on SrTiO3 . Phys Rev Lett 106, 036101. Google Scholar
Peng, L.-M. (1997). Anisotropic thermal vibrations and dynamical electron diffraction by crystals. Acta Crystallogr A 53, 663–672.Google Scholar
Pentcheva, R., Huijben, M., Otte, K., Pickett, W.E., Kleibeuker, J.E., Huijben, J., Boschker, H., Kockmann, D., Siemons, W., Koster, G., Zandvliet, H.J.W., Rijnders, G., Blank, D.H.A., Hilgenkamp, H. & Brinkman, A. (2010). Parallel electron-hole bilayer conductivity from electronic interface reconstruction. Phys Rev Lett 104, 166804. Google Scholar
Reyren, N., Thiel, S., Caviglia, A.D., Fitting Kourkoutis, L., Hammerl, G., Richter, C., Schneider, C.W., Kopp, T., Rüetschi, A.-S., Jaccard, D., Gabay, M., Muller, D.A., Triscone, J.-M. & Mannhart, J. (2007). Superconducting interfaces between insulating oxides. Science 317, 1196–1199.Google Scholar
Saito, M., Kimoto, K., Nagai, T., Fukushima, S., Akahoshi, D., Kuwahara, H., Matsui, Y. & Ishizuka, K. (2009). Local crystal structure analysis with 10-pm accuracy using scanning transmission electron microscopy. J Electron Microsc 58, 131–136.Google Scholar
Thust, A. (2009). High-resolution transmission electron microscopy on an absolute contrast scale. Phys Rev Lett 102, 220801. CrossRefGoogle Scholar
Van Aert, S., Batenburg, K.J., Rossell, M.D., Erni, R. & Van Tendeloo, G. (2011). Three-dimensional atomic imaging of crystalline nanoparticles. Nature 470, 374–377.CrossRefGoogle ScholarPubMed
Van Aert, S., Verbeeck, J., Erni, R., Bals, S., Luysberg, M., Van Dyck, D. & Van Tendeloo, G. (2009). Quantitative atomic resolution mapping using high-angle annular dark field scanning transmission electron microscopy. Ultramicroscopy 109, 1236–1244.Google Scholar
Weickenmeier, A. & Kohl, H. (1991). Computation of absorptive form factors for high-energy electron diffraction. Acta Crystallogr A 47, 590–597.Google Scholar
Willmott, P.R., Pauli, S.A., Herger, R., Schlepütz, C.M., Martoccia, D., Patterson, B.D., Delley, B., Clarke, R., Kumah, D., Cionca, C. & Yacoby, Y. (2007). Structural basis for the conducting interface between LaAlO3 and SrTiO3 . Phys Rev Lett 99, 155502. CrossRefGoogle ScholarPubMed
Zemlin, F., Weiss, K., Schiske, P., Kunath, W. & Herrmann, K.-H. (1978). Coma-free alignment of high resolution electron microscopes with the aid of optical diffractograms. Ultramicroscopy 3, 49–60.Google Scholar