Skip to main content
SpringerLink
Log in

Manipulation and Spectroscopy of Individual Phthalocyanine Molecules on InAs(111)A with a Low-Temperature Scanning Tunneling Microscope

  • Conference paper
  • First Online:
Imaging and Manipulating Molecular Orbitals

Part of the book series: Advances in Atom and Single Molecule Machines ((AASMM))

Abstract

Single free-base phthalocyanine (H2Pc), copper phthalocyanine (CuPc), and naphthalocyanine (NPc) molecules on the III-V semiconductor surface InAs(111)A-(2 × 2) were investigated by cryogenic scanning tunneling microscopy (STM) at 5 K. STM imaging of largely unperturbed frontier orbitals of NPc on InAs(111)A reveals that the molecule is physisorbed. In the adsorbed state, the molecular electronic structure of NPc is preserved to a large extent, indicating a weak electronic coupling to the underlying substrate surface. As a free molecule, H2Pc is bistable because of an internal hydrogen transfer reaction (tautomerization). When adsorbed on the InAs(111)A surface, H2Pc experiences rotational fluctuations about its center because of excitations induced by inelastic electron tunneling (IET). STM-based atom and molecule manipulation techniques were used to sterically hinder the molecular rotation by assembling In adatom-molecule complexes, facilitating to probe the hydrogen transfer reaction in a controlled way. STM imaging of the Inad-H2Pc-Inad complex clearly reveals the presence of a left-handed and a right-handed conformer, indicating that the H2Pc tautomerization is left unperturbed by the substrate and the pinning adatoms, and that it can be triggered by the tunneling electrons.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 129.00
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
Hardcover Book
USD 169.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

Notes

  1. 1.

    An upper bound of the tunnel current detection rate is set by the bandwidth of the preamplifier corresponding to 550 Hz. In the constant-current imaging mode, a further reduction may arise from the actual feedback loop setting.

  2. 2.

    Here, the normalized rate corresponds to the probability per tunneling electron to induce a discrete tautomerization switching event.

References

  1. Aviram, A., Ratner, M.A.: Molecular rectifiers. Chem. Phys. Lett. 29, 277–283 (1974)

    Article  ADS  Google Scholar 

  2. Joachim, C., Gimzewski, J.K., Aviram, A.: Electronics using hybrid-molecular and mono-molecular devices. Nature 408, 541–548 (2000)

    Article  ADS  Google Scholar 

  3. Nitzan, A., Ratner, M.A.: Electron transport in molecular wire junctions. Science 303, 1384–1389 (2003)

    Article  ADS  Google Scholar 

  4. Heath, J.R.: Molecular electronics. Annu. Rev. Mater. Res. 39, 1–23 (2009)

    Article  ADS  Google Scholar 

  5. Wolkow, R.A.: Controlled molecular adsorption on silicon: Layng a foundation for molecular electronics. Annu. Rev. Phys. Chem. 50, 413–441 (1999)

    Article  ADS  Google Scholar 

  6. Hamers, R.J., Coulter, S.K., Ellison, M.D., Hovis, S.J., Padowitz, D.F., Schwartz, M.P., Greenlief, C.M., Russel, J.N.: Cycloaddition chemistry of organic molecules with semiconductor surfaces. Acc. Chem. Res. 33, 617–624 (2000)

    Article  Google Scholar 

  7. Lin, R., Galili, M., Quaade, U.J., Brandbyge, M., Bjørnholm, T., Esposti, A.D., Biscarini, F., Stokbro, K.: Spontaneous dissociation of a conjugated molecule on the Si(100) surface. J. Chem. Phys. 117, 321–330 (2002)

    Article  ADS  Google Scholar 

  8. Liljeroth, P., Repp, J., Meyer, G.: Current-induced hydrogen tautomerization and switching of naphthalocyanine molecules. Science 317, 1203–1206 (2007)

    Article  ADS  Google Scholar 

  9. Wang Y., Kroeger J., Berndt R., Hofer W.A.: Pushing and pulling a Sn Ion through an adsorbed phthalocyanine molecule. J. Am. Chem. Soc. 131, 3639–3643 (2008)

    Google Scholar 

  10. Stróżecka, A., Soriano, M., Pascual, J.I., Palacios, J.J.: Reversible change of the spin state in a manganese phthalocyanine by coordination of CO molecule. Phys. Rev. Lett. 109, 147202–147206 (2012)

    Article  ADS  Google Scholar 

  11. Tsukahara, N., Shiraki, S., Itou, S., Ohta, N., Takagi, N., Kawai, M.: Evolution of Kondo resonance from a single impurity molecule to the two-dimensional lattice. Phys. Rev. Lett. 106, 187201–187205 (2011)

    Article  ADS  Google Scholar 

  12. Brede, J., Atodiresei, N., Kuck, S., Lazić, P., Caciuc, V., Morikawa, Y., Hoffmann, G., Blügel, S., Wiesendanger, R.: Spin- and energy-dependent tunneling through a single molecule with intramolecular spatial resolution. Phys. Rev. Lett. 105, 047204–047207 (2010)

    Article  ADS  Google Scholar 

  13. Stroscio, J.A., Eigler, D.M.: Atomic and molecular manipulation with the scanning tunneling microscope. Science 254, 1319–1326 (1991)

    Article  ADS  Google Scholar 

  14. Nacci, C., Erwin, S.C., Kanisawa, K., Fölsch, S.: Controlled switching within an organic molecule deliberately pinned to a semiconductor surface. ACS Nano 6(5), 4190–4195 (2012)

    Article  Google Scholar 

  15. Taguchi, A., Kanisawa, K.: Stable reconstruction and adsorbates of InAs(111)A surface. Appl. Surf. Sci. 252, 5263–5266 (2006)

    Article  ADS  Google Scholar 

  16. Kanisawa, K., Butcher, M.J., Yamaguchi, H., Hirayama, Y.: Imaging of Friedel oscillation patterns of two-dimensionally accumulated electrons at epitaxially grown InAs(111)A surfaces. Phys. Rev. Lett. 86, 3384–3387 (2001)

    Article  ADS  Google Scholar 

  17. Ishimure, N., Akiyama, T., Nakamura, K., Ito, T.: Ab initio-based approach to the reconstruction on InAs(111)A wetting layer grown on GaAs substrate. Physica E 42, 2731–2734 (2010)

    Article  ADS  Google Scholar 

  18. Kanisawa K., Fujisawa T.: Mechanism of electron accumulation layer formation at the MBE-grown InAs(111)A surface. Hyomen Kagaku 29, 747–757 (2008)

    Google Scholar 

  19. Stroscio, J.A., Feenstra, R.M., Newns, D.M.: Voltage-dependent scanning tunneling microscopy imaging of semiconductor surfaces. J. Vac. Sci. Technol. A 6, 499–507 (1988)

    Article  ADS  Google Scholar 

  20. Fölsch S., Yang J., Nacci C., Kanisawa K.: Atom-by-atom quantum state control in adatom chains on a semiconductor. Phys. Rev. Lett. 103, 096104–096107 (2009)

    Google Scholar 

  21. Niimi Y., Kanisawa K., Kojima H., Kambara H., Hirayama Y., Tarucha S., Fukuyama H.: STM/STS measurements of two-dimensional electronics states in magnetic fields at epitaxially grown InAs(111)A surfaces. J. Phys.: Conf. Ser. 61, 874–878 (2007)

    Google Scholar 

  22. Olsson, L.Ö., Anderrson, C.B.M., Håkansson, M.C., Kanski, J., Ilver, L., Karlsson, U.O.: Charge accumulation at InAs surfaces. Phys. Rev. Lett. 76, 3626–3629 (1996)

    Article  ADS  Google Scholar 

  23. Cortina H., Senent M.L., Smeyers Y.G.: Ab initio comparative study of the structure and properties of H2-porphyn and H2-phthalocyanine. The electronic absorption spectra. J. Phys. Chem. 107, 8968–8974 (2003)

    Google Scholar 

  24. Völker, S., van der Waals, J.H.: Laser-induced photochemical isomerization of free base porphyrin in an n-octane crystal at 4.2 K. Mol. Phys. 32, 1703–1718 (1976)

    Article  ADS  Google Scholar 

  25. Münnich G., Albrecht F., Nacci C., Utz M., Schuh D., Kanisawa K., Fölsch S., Repp J.: Probing individual weakly-coupled π-conjugated molecules on semiconductor surfaces. J. Appl. Phys. 112, 034312–034315 (2012)

    Google Scholar 

  26. Stroscio, J.A., Celotta, R.J.: Controlling the dynamics of a single atom in lateral atom manipulation. Science 306, 242–247 (2004)

    Article  ADS  Google Scholar 

  27. Stipe B.C., Rezaei M.A., Ho W.: Inducing and viewing the rotational motion of a single molecule. Science 279, 1907–1909 (1998)

    Google Scholar 

  28. Matsumoto, C., Kim, Y., Okawa, T., Sainoo, Y., Kawai, M.: Low-temperature STM investigation of acetylene on Pd(111). Surf. Sci. 587, 19–24 (2005)

    Article  ADS  Google Scholar 

  29. Wang W., Shi X., Jin M., Minot C., Van Hove M.A., Collin J.-P., Lin N.: Electron stimulation of internal torsion of a surface-mounted molecular rotor. ACS Nano 4, 4929–4935 (2010)

    Google Scholar 

  30. Tierney, H.L., Murphy, C.J., Jewell, A.D., Baber, A.E., Iski, E.V., Khodaverdian, H.Y., McGuire, A.F., Klebanov, N., Sykes, E.C.H.: Experimental demonstration of a single-molecule electric motor. Nat. Nanotechnol. 6, 625–629 (2011)

    Article  ADS  Google Scholar 

  31. Yang J., Nacci C., Martínez-Blanco J., Kanisawa K., Fölsch S.: Vertical manipulation of native adatoms on the InAs(111)A surface. J. Phys.: Condens. Matter 24, 354008–354013 (2012)

    Google Scholar 

  32. Nacci C., Kanisawa K., Fölsch S.: Reversible switching of single tin phthalocyanine molecules on the InAs(111)A. J. Phys.: Condens. Matter 24, 394004–394008 (2012)

    Google Scholar 

  33. Day, P.N., Wang, Z., Pachter, R.: Calculation of the structure and absorption spectra of phthalocyanine in the gas phase and in solution. THEOCHEM 455, 33–50 (1998)

    Article  Google Scholar 

Download references

Acknowledgments

We gratefully acknowledge financial support of this research by the Japanese Agency of Science and Technology, and the German Research Foundation (FO 362/1-3; SFB 658, TP A2).

Author information

Authors and Affiliations

  1. Paul-Drude-Institut für Festkörperelektronik, Hausvogteiplatz 5-7, 10117, Berlin, Germany

    Christophe Nacci & Stefan Fölsch

  2. NTT Basic Research Laboratories, NTT Corporation, Atsugi, Kanagawa, 243-0198, Japan

    Kiyoshi Kanisawa

  3. Fritz-Haber-Institut der Max-Planck-Gesellschaft, Abteilung für Physikalische Chemie, Faradayweg 4-6, 14195, Berlin, Germany

    Christophe Nacci

Authors
  1. Christophe Nacci
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Kiyoshi Kanisawa
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Stefan Fölsch
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Christophe Nacci .

Editor information

Editors and Affiliations

  1. Fritz-Haber-Institute Department of Physical Chemistry, Berlin, Germany

    Leonhard Grill

  2. GNS, CNRS, Toulousse Cedex, France

    Christian Joachim

Rights and permissions

Reprints and permissions

Copyright information

© 2013 Springer-Verlag Berlin Heidelberg

About this paper

Cite this paper

Nacci, C., Kanisawa, K., Fölsch, S. (2013). Manipulation and Spectroscopy of Individual Phthalocyanine Molecules on InAs(111)A with a Low-Temperature Scanning Tunneling Microscope. In: Grill, L., Joachim, C. (eds) Imaging and Manipulating Molecular Orbitals. Advances in Atom and Single Molecule Machines. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-38809-5_6

Download citation

Publish with us

Policies and ethics

Search

Navigation