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Quantitative imaging of electric surface potentials with single-atom sensitivity

Nature Materials volume 18, pages 853–859 (2019)Cite this article

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Abstract

Because materials consist of positive nuclei and negative electrons, electric potentials are omnipresent at the atomic scale. However, due to the long range of the Coulomb interaction, large-scale structures completely outshine small ones. This makes the isolation and quantification of the electric potentials that originate from nanoscale objects such as atoms or molecules very challenging. Here we report a non-contact scanning probe technique that addresses this challenge. It exploits a quantum dot sensor and the joint electrostatic screening by tip and surface, thus enabling quantitative surface potential imaging across all relevant length scales down to single atoms. We apply the technique to the characterization of a nanostructured surface, thereby extracting workfunction changes and dipole moments for important reference systems. This authenticates the method as a versatile tool to study the building blocks of materials and devices down to the atomic scale.

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Fig. 1: Principle and quantitative nature of SQDM.
Fig. 2: Electrostatic screening and image deconvolution in SQDM.
Fig. 3: SQDM images of nanostructures on Ag(111).
Fig. 4: Surface dipoles of selected nanostructures and dipole density within a layer.

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The custom code that was used for the deconvolution in this study is available from the corresponding author upon reasonable request.

References

  1. He, Z. et al. Enhanced power-conversion efficiency in polymer solar cells using an inverted device structure. Nat. Photon. 6, 593–597 (2012).

    CAS  Google Scholar 

  2. Tung, R. T. The physics and chemistry of the Schottky barrier height. Appl. Phys. Rev. 1, 011304 (2014).

    Article  CAS  Google Scholar 

  3. Chuang, C.-H. M., Brown, P. R., Bulović, V. & Bawendi, M. G. Improved performance and stability in quantum dot solar cells through band alignment engineering. Nat. Mater. 13, 796–801 (2014).

    Article  CAS  Google Scholar 

  4. Fuchs, F., Caffy, F., Demadrille, R., Mélin, T. & Grévin, B. High-resolution kelvin probe force microscopy imaging of interface dipoles and photogenerated charges in organic donor–acceptor photovoltaic blends. ACS Nano 10, 739–746 (2016).

    Article  CAS  Google Scholar 

  5. Courtland, R. Moore’s law’s next step: 10 nanometers. IEEE Spectrum 54, 52–53 (2017).

    Article  Google Scholar 

  6. Fuechsle, M. et al. A single-atom transistor. Nat. Nanotechnol. 7, 242–246 (2012).

    Article  CAS  Google Scholar 

  7. Lin, J. et al. Flexible metallic nanowires with self-adaptive contacts to semiconducting transition-metal dichalcogenide monolayers. Nat. Nanotechnol. 9, 436–442 (2014).

    Article  CAS  Google Scholar 

  8. Xiang, D., Wang, X., Jia, C., Lee, T. & Guo, X. Molecular-scale electronics: from concept to function. Chem. Rev. 116, 4318–4440 (2016).

    Article  CAS  Google Scholar 

  9. de Boer, B., Hadipour, A., Mandoc, M. M., van Woudenbergh, T. & Blom, P. W. M. Tuning of metal work functions with self-assembled monolayers. Adv. Mater. 17, 621–625 (2005).

    Article  CAS  Google Scholar 

  10. Watson, J. D. & Crick, F. H. C. Molecular structure of nucleic acids. Nature 171, 737–738 (1953).

    Article  CAS  Google Scholar 

  11. Moreira, I. S., Fernandes, P. A. & Ramos, M. J. Hot spots—a review of the protein–protein interface determinant amino-acid residues. Proteins 86, 803–812 (2007).

    Article  CAS  Google Scholar 

  12. Warshel, A. et al. Electrostatic basis for enzyme catalysis. Chem. Rev. 106, 3210–3235 (2006).

    Article  CAS  Google Scholar 

  13. Zerweck, U., Loppacher, C., Otto, T., Grafström, S. & Eng, L. M. Accuracy and resolution limits of kelvin probe force microscopy. Phys. Rev. B 71, 125424 (2005).

    Article  CAS  Google Scholar 

  14. Baier, R., Leendertz, C., Lux-Steiner, M. C. & Sadewasser, S. Toward quantitative kelvin probe force microscopy of nanoscale potential distributions. Phys. Rev. B 85, 165436 (2012).

    Article  CAS  Google Scholar 

  15. Musumeci, C., Liscio, A., Palermo, V. & Samorì, P. Electronic characterization of supramolecular materials at the nanoscale by conductive atomic force and kelvin probe force microscopies. Mater. Today 17, 504–517 (2014).

    Article  CAS  Google Scholar 

  16. Söngen, H. et al. The weight function for charges—a rigorous theoretical concept for kelvin probe force microscopy. J. Appl. Phys. 119, 025304 (2016).

    Article  CAS  Google Scholar 

  17. Gross, L. et al. Measuring the charge state of an adatom with noncontact atomic force microscopy. Science 324, 1428–1431 (2009).

    Article  CAS  Google Scholar 

  18. Sadewasser, S. et al. New insights on atomic-resolution frequency-modulation kelvin-probe force-microscopy imaging of semiconductors. Phys. Rev. Lett. 103, 266103 (2009).

    Article  CAS  Google Scholar 

  19. Schuler, B. et al. Contrast formation in kelvin probe force microscopy of single pi-conjugated molecules. Nano Lett. 14, 3342–3346 (2014).

    Article  CAS  Google Scholar 

  20. Albrecht, F. et al. Probing charges on the atomic scale by means of atomic force microscopy. Phys. Rev. Lett. 115, 076101 (2015).

    Article  CAS  Google Scholar 

  21. Hapala, P. et al. Mapping the electrostatic force of single molecules from high-resolution scanning probe images. Nat. Commun. 7, 11560 (2016).

    Article  CAS  Google Scholar 

  22. Lee, J., Tallarida, N., Chen, X., Jensen, L. & Apkarian, V. A. Microscopy with a single-molecule scanning electrometer. Sci. Adv. 4, eaat5472 (2018).

    Article  CAS  Google Scholar 

  23. Fournier, N., Wagner, C., Weiss, C., Temirov, R. & Tautz, F. S. Force-controlled lifting of molecular wires. Phys. Rev. B 84, 035435 (2011).

    Article  CAS  Google Scholar 

  24. Wagner, C., Fournier, N., Tautz, F. S. & Temirov, R. Measurement of the binding energies of the organic-metal perylene-teracarboxylic-dianhydride/Au(111) bonds by molecular manipulation using an atomic force microscope. Phys. Rev. Lett. 109, 076102 (2012).

    Article  CAS  Google Scholar 

  25. Wagner, C. et al. Scanning quantum dot microscopy. Phys. Rev. Lett. 115, 026101 (2015).

    Article  CAS  Google Scholar 

  26. Green, M. F. B. et al. Scanning quantum dot microscopy: a quantitative method to measure local electrostatic potential near surfaces. Jpn J. Appl. Phys. 55, 08NA04 (2016).

    Article  CAS  Google Scholar 

  27. Maiworm, M., Wagner, C., Temirov, R., Tautz, F. S. & Findeisen, R. Two-degree-of-freedom control combining machine learning and extremum seeking for fast scanning quantum dot microscopy. In American Control Conference (ACC) 4360–4366 (IEEE, 2018).

  28. Likharev, K. Single-electron devices and their applications. Proc. IEEE 87, 606–632 (1999).

    Article  CAS  Google Scholar 

  29. Jackson, J. D. Classical Electrodynamics 3 edn (Wiley, 1999).

  30. Wagner, C. & Tautz, F. S. The theory of scanning quantum dot microscopy. Preprint at https://arxiv.org/pdf/1905.06153 (2019)

  31. Stomp, R. et al. Detection of single-electron charging in an individual InAs quantum dot by noncontact atomic-force microscopy. Phys. Rev. Lett. 94, 056802 (2005).

    Article  CAS  Google Scholar 

  32. Miyahara, Y., Roy-Gobeil, A. & Grutter, P. Quantum state readout of individual quantum dots by electrostatic force detection. Nanotechnology 28, 064001 (2017).

    Article  CAS  Google Scholar 

  33. Temirov, R. et al. Molecular model of a quantum dot beyond the constant interaction approximation. Phys. Rev. Lett. 120, 206801 (2018).

    Article  CAS  Google Scholar 

  34. Tautz, F. S. Structure and bonding of large aromatic molecules on noble metal surfaces: the example of PTCDA. Prog. Surf. Sci. 82, 479–520 (2007).

    Article  CAS  Google Scholar 

  35. Zou, Y. et al. Chemical bonding of PTCDA on Ag surfaces and the formation of interface states. Surf. Sci. 600, 1240–1251 (2006).

    Article  CAS  Google Scholar 

  36. Kawabe, E. et al. A role of metal d-band in the interfacial electronic structure at organic/metal interface: PTCDA on Au, Ag and Cu. Org. Electron. 9, 783–789 (2008).

    Article  CAS  Google Scholar 

  37. Duhm, S. et al. PTCDA on Au(111), Ag(111) and Cu(111): correlation of interface charge transfer to bonding distance. Org. Electron. 9, 111–118 (2008).

    Article  CAS  Google Scholar 

  38. Ferri, N., DiStasio, R. A. Jr., Ambrosetti, A., Car, R. & Tkatchenko, A. Electronic properties of molecules and surfaces with a self-consistent interatomic van der Waals density functional. Phys. Rev. Lett. 114, 176802 (2015).

    Article  CAS  Google Scholar 

  39. Ruiz, V. G., Liu, W., Zojer, E., Scheffler, M. & Tkatchenko, A. Density-functional theory with screened van der Waals interactions for the modeling of hybrid inorganic–organic systems. Phys. Rev. Lett. 108, 146103 (2012).

    Article  CAS  Google Scholar 

  40. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

    Article  CAS  Google Scholar 

  41. Kellogg, O. D. Foundations of Potential Theory (Springer, 1929).

  42. Pumplin, J. Application of Sommerfeld–Watson transformation to an electrostatics problem. Am. J. Phys. 37, 737 (1969).

    Article  Google Scholar 

  43. Lan, F., Jiang, M., Tao, Q., Wei, F. & Li, G. Reconstruction of kelvin probe force microscopy image with experimentally calibrated point spread function. Rev. Sci. Instrum. 88, 033704 (2017).

    Article  CAS  Google Scholar 

  44. Esat, T., Friedrich, N., Tautz, F. S. & Temirov, R. A standing molecule as a single-electron field emitter. Nature 558, 573–576 (2018).

    Article  CAS  Google Scholar 

  45. Schulman, J. H. & Hughes, A. H. On the surface potentials of unimolecular films. Part IV. The effect of the underlying solution and transition phenomena in the film. Proc. R. Soc. Lond. 138, 430–450 (1932).

    Article  CAS  Google Scholar 

  46. Gross, L., Mohn, F., Moll, N., Liljeroth, P. & Meyer, G. The chemical structure of a molecule resolved by atomic force microscopy. Science 325, 1110–1114 (2009).

    Article  CAS  Google Scholar 

  47. Wagner, C. & Temirov, R. Tunnelling junctions with additional degrees of freedom: an extended toolbox of scanning probe microscopy. Prog. Surf. Sci. 90, 194–222 (2015).

    Article  CAS  Google Scholar 

  48. Schneiderbauer, M., Emmrich, M., Weymouth, A. J. & Giessibl, F. J. CO tip functionalization inverts atomic force microscopy contrast via short-range electrostatic forces. Phys. Rev. Lett. 112, 166102 (2014).

    Article  CAS  Google Scholar 

  49. Schwarz, A., Köhler, A., Grenz, J. & Wiesendanger, R. Detecting the dipole moment of a single carbon monoxide molecule. Appl. Phys. Lett. 105, 011606 (2014).

    Article  CAS  Google Scholar 

  50. van der Lit, J., Di Cicco, F., Hapala, P., Jelinek, P. & Swart, I. Submolecular resolution imaging of molecules by atomic force microscopy: the influence of the electrostatic force. Phys. Rev. Lett. 116, 096102 (2016).

    Article  CAS  Google Scholar 

  51. Feibelman, P. J. et al. The CO/Pt(111) puzzle. J. Phys. Chem. B 105, 4018–4025 (2001).

    Article  CAS  Google Scholar 

  52. Ren, X., Rinke, P. & Scheffler, M. Exploring the random phase approximation: application to CO adsorbed on Cu(111). Phys. Rev. B 80, 045402 (2009).

    Article  CAS  Google Scholar 

  53. Kraft, A. et al. Lateral adsorption geometry and site-specific electronic structure of a large organic chemisorbate on a metal surface. Phys. Rev. B 74, 041402 (2006).

    Article  CAS  Google Scholar 

  54. Willenbockel, M. et al. The interplay between interface structure, energy level alignment and chemical bonding strength at organic–metal interfaces. Phys. Chem. Chem. Phys. 17, 1530 (2015).

    Article  CAS  Google Scholar 

  55. Repp, J., Meyer, G. & Rieder, K. H. Snell’s law for surface electrons: refraction of an electron gas imaged in real space. Phys. Rev. Lett. 92, 036803 (2004).

    Article  CAS  Google Scholar 

  56. Ariyur, K. B. & Krstić, M. Real-Time Optimization by Extremum-Seeking Control (Wiley, 2003).

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Acknowledgements

C.W. acknowledges funding through the European Research Council (ERC-StG 757634 ‘CM3’). A.T. and N.F. acknowledge funding by DFG-SFB 951 (project A10). F.S.T. acknowledges funding by DFG-SFB 1083 (project A12).

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Authors and Affiliations

  1. Peter Grünberg Institut (PGI-3), Forschungszentrum Jülich, Jülich, Germany

    Christian Wagner, Matthew. F. B. Green, Philipp Leinen, Taner Esat, Niklas Friedrich, Ruslan Temirov & F. Stefan Tautz

  2. Jülich Aachen Research Alliance (JARA)-Fundamentals of Future Information Technology, Jülich, Germany

    Christian Wagner, Matthew. F. B. Green, Philipp Leinen, Taner Esat, Niklas Friedrich, Ruslan Temirov & F. Stefan Tautz

  3. Experimentalphysik IV A, RWTH Aachen University, Aachen, Germany

    Matthew. F. B. Green, Philipp Leinen, Taner Esat, Niklas Friedrich & F. Stefan Tautz

  4. Otto-von-Guericke-Universität Magdeburg, Laboratory for Systems Theory and Automatic Control, Magdeburg, Germany

    Michael Maiworm & Rolf Findeisen

  5. Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin, Germany

    Nicola Ferri & Alexandre Tkatchenko

  6. Physics and Materials Science Research Unit, University of Luxembourg, Luxembourg, Luxembourg

    Alexandre Tkatchenko

  7. II. Physikalisches Institut, Universität zu Köln, Köln, Germany

    Ruslan Temirov

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Contributions

C.W., R.T. and F.S.T. conceived and designed this research. M.F.B.G., P.L., T.E., N.Fr. and M.M. performed the experiments, C.W. and M.F.B.G. analysed the data. M.M. and R.F. designed and provided the feedback controller, N.Fe. and A.T. conducted the DFT simulations. C.W. and F.S.T. interpreted the data, developed the theory of SQDM imaging and wrote the paper.

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Correspondence to Christian Wagner.

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Wagner, C., Green, M.F.B., Maiworm, M. et al. Quantitative imaging of electric surface potentials with single-atom sensitivity. Nat. Mater. 18, 853–859 (2019). https://doi.org/10.1038/s41563-019-0382-8

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