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A homologous series of structures on the surface of SrTiO3(110)

Nature Materials volume 9, pages 245–248 (2010)Cite this article

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Abstract

Strontium titanate is seeing increasing interest in fields ranging from thin-film growth to water-splitting catalysis and electronic devices. Although the surface structure and chemistry are of vital importance to many of these applications, theories about the driving forces vary widely1,2. We report here a solution to the 3×1 SrTiO3(110) surface structure obtained through transmission electron diffraction and direct methods, and confirmed through density functional theory calculations and scanning tunnelling microscopy images and simulations, consisting of rings of six or eight corner-sharing TiO4 tetrahedra. Further, by changing the number of tetrahedra per ring, a homologous series of n×1 (n≥2) surface reconstructions is formed. Calculations show that the lower members of the series (n≤6) are thermodynamically stable and the structures agree with scanning tunnelling microscopy images. Although the surface energy of a crystal is usually thought to determine the structure and stoichiometry, we demonstrate that the opposite can occur. The n×1 reconstructions are sufficiently close in energy for the stoichiometry in the near-surface region to determine which reconstruction is formed. Our results indicate that the rules of inorganic coordination chemistry apply to oxide surfaces, with concepts such as homologous series and intergrowths as valid at the surface as they are in the bulk.

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Figure 1: The surface structure of the 3×1 reconstruction and the top bulk layer.
Figure 2: The surface structures of calculated members of the homologous series of n×1 surface structures viewed perpendicular to the surface.
Figure 3: A plot of the surface energies for n×1 surfaces and several previously proposed surfaces.
Figure 4: An STM image of a 3×1 surface with an intergrowth of 4×1 with simulations overlaid.

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References

  1. Pashley, M. D. Electron counting model and its application to island structures on molecular-beam epitaxy grown GaAs(001) and ZnSe(001). Phys. Rev. B 40, 10481–10487 (1989).

    Article  CAS  Google Scholar 

  2. Wolf, D. Reconstruction of NaCl surfaces from a dipolar solution to the Madelung problem. Phys. Rev. Lett. 68, 3315–3318 (1992).

    Article  CAS  Google Scholar 

  3. Goniakowski, J., Finocchi, F. & Noguera, C. Polarity of oxide surfaces and nanostructures. Rep. Prog. Phys. 71, 016501 (2008).

    Article  Google Scholar 

  4. Deak, D. S. Strontium titanate surfaces. Mater. Sci. Technol. 23, 127–136 (2007).

    Article  CAS  Google Scholar 

  5. Noguera, C. Polar oxide surfaces. J. Phys. Condens. Matter 12, R367–R410 (2000).

    Article  CAS  Google Scholar 

  6. Erdman, N. et al. The structure and chemistry of the TiO2-rich surface of SrTiO3(001). Nature 419, 55–58 (2002).

    Article  CAS  Google Scholar 

  7. Russell, B. C. & Castell, M. R. Reconstructions on the polar SrTiO3(110) surface: Analysis using STM, LEED, and AES. Phys. Rev. B 77, 245414 (2008).

    Article  Google Scholar 

  8. Brunen, J. & Zegenhagen, J. Investigation of the SrTiO3(110) surface by means of LEED, scanning tunnelling microscopy and Auger spectroscopy. Surf. Sci. 389, 349–365 (1997).

    Article  CAS  Google Scholar 

  9. Bando, H. et al. Structure and electronic states on reduced SrTiO3(110) surface observed by scanning-tunnelling-microscopy and spectroscopy. J. Vac. Sci. Technol. B 13, 1150–1154 (1995).

    Article  CAS  Google Scholar 

  10. Bottin, F., Finocchi, F. & Noguera, C. Facetting and (n×1) reconstructions of SrTiO3(110) surfaces. Surf. Sci. 574, 65–76 (2005).

    Article  CAS  Google Scholar 

  11. Heifets, E. et al. Ab initio calculations of the SrTiO3(110) polar surface. Phys. Rev. B 69, 035408 (2004).

    Article  Google Scholar 

  12. Kotomin, E. A. et al. Comparative study of polar perovskite surfaces. Surf. Sci. 566, 231–235 (2004).

    Article  Google Scholar 

  13. Eglitis, R. I. & Vanderbilt, D. First-principles calculations of atomic and electronic structure of SrTiO3(001) and (011) surfaces. Phys. Rev. B 77, 195408 (2008).

    Article  Google Scholar 

  14. Marks, L. D., Sinkler, W. & Landree, E. A feasible set approach to the crystallographic phase problem. Acta Crystallogr. Sect. A 55, 601–612 (1999).

    Article  CAS  Google Scholar 

  15. Chiaramonti, A. N. & Marks, L. D. Atomic resolution transmission electron microscopy of surfaces. J. Mater. Res. 20, 1619–1627 (2005).

    Article  CAS  Google Scholar 

  16. Blaha, P. et al. WIEN2k, An Augmented Plane Wave Plus Local Orbitals Program for Calculating Crystal Properties (Technical Univ. Vienna, 2001).

    Google Scholar 

  17. Warschkow, O. et al. Structure and local-equilibrium thermodynamics of the c(2×2) reconstruction of rutile TiO2(100). Phys. Rev. Lett. 100, 86102 (2008).

    Article  CAS  Google Scholar 

  18. Jayaram, G., Xu, P. & Marks, L. D. Structure of Si(100)–(2×1) surface using UHV transmission electron-diffraction. Phys. Rev. Lett. 71, 3489–3492 (1993).

    Article  CAS  Google Scholar 

  19. Xu, P., Jayaram, G. & Marks, L. D. Cross-correlation method for intensity measurement of transmission electron-diffraction patterns. Ultramicroscopy 53, 15–18 (1994).

    Article  Google Scholar 

  20. Marks, L. D., Chiaramonti, A., Tran, F. & Blaha, P. The small unit cell reconstructions of SrTiO3(111). Surf. Sci. 603, 2179–2187 (2009).

    Article  CAS  Google Scholar 

  21. Tersoff, J. & Hamann, D. R. Theory of the scanning tunnelling microscope. Phys. Rev. B 31, 805–813 (1985).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the Northwestern University Institute for Catalysis in Energy Processing, funded through the US Department of Energy, Office of Basic Energy Science (award number DE-FG02-03-ER15457, J.A.E., K.R.P. and L.D.M.). We also acknowledge funding on NSF DMR-0455371/001 (A.K.S.), DOE DE-FG02-01ER45945 (L.D.M. and computer hardware) and NSF DMR-0710643 (B.C.R., M.R.C., L.D.M. and computer hardware).

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Author notes

  1. Arun K. Subramanian

    Present address: Present address: 2140 Research Drive, Livermore, California 94550, USA,

Authors and Affiliations

  1. Department of Chemistry, Northwestern University, Evanston, Illinois 60208, USA

    James A. Enterkin & Kenneth R. Poeppelmeier

  2. Institute for Catalysis in Energy Processes, Northwestern University, Evanston, Illinois 60208, USA

    James A. Enterkin, Kenneth R. Poeppelmeier & Laurence D. Marks

  3. Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208, USA

    Arun K. Subramanian & Laurence D. Marks

  4. Department of Materials, University of Oxford, Parks Road, Oxford, OX1 3PH, UK

    Bruce C. Russell & Martin R. Castell

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  1. James A. Enterkin
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Contributions

A.K.S. obtained the transmission electron diffraction patterns. B.C.R. and M.R.C. obtained the STM images. J.A.E. and L.D.M. carried out the DFT calculations. J.A.E., with contributions from L.D.M. and K.R.P., carried out direct methods, structure solution and analysis of the homologous series. J.A.E. wrote the manuscript, which M.R.C., K.R.P. and L.D.M. edited.

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Correspondence to James A. Enterkin or Arun K. Subramanian.

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The authors declare no competing financial interests.

Supplementary information

Supplementary Information

Supplementary Information (PDF 311 kb)

Supplementary Information

Crystallographic information for SrTiO3 (110) 2x1 surface structure CCDC-421515 (CIF 1 kb)

Supplementary Information

Crystallographic information for SrTiO3 (110) 3x1 surface structure CCDC-421516 (CIF 2 kb)

Supplementary Information

Crystallographic information for SrTiO3 (110) 4x1 surface structure CCDC-421517 (CIF 2 kb)

Supplementary Information

Crystallographic information for SrTiO3 (110) 5x1 surface structure CCDC-421518 (CIF 3 kb)

Supplementary Information

Crystallographic information for SrTiO3 (110) 6x1 surface structure CCDC-421519 (CIF 3 kb)

Supplementary Information

Crystallographic information for SrTiO3 (110) ∞x1 surface structure CCDC-421520 (CIF 1 kb)

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Enterkin, J., Subramanian, A., Russell, B. et al. A homologous series of structures on the surface of SrTiO3(110). Nature Mater 9, 245–248 (2010). https://doi.org/10.1038/nmat2636

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