journal article·2014-10Open access

Nanoelectrical analysis of single molecules and atomic-scale materials at the solid/liquid interface

Peter Nirmalraj, Damien Thompson, Agustín Molina-Ontoria, Marilyne Sousa, Nazario Martín, Bernd Gotsmann, Heike Riel

Nature Materials· Volume 13· Issue 10

Abstract

Evaluating the built-in functionality of nanomaterials under practical conditions is central for their proposed integration as active components in next-generation electronics. Low-dimensional materials from single atoms to molecules have been consistently resolved and manipulated under ultrahigh vacuum at low temperatures. At room temperature, atomic-scale imaging has also been performed by probing materials at the solid/liquid interface. We exploit this electrical interface to develop a robust electronic decoupling platform that provides precise information on molecular energy levels recorded using in situ scanning tunnelling microscopy/spectroscopy with high spatial and energy resolution in a high-density liquid environment. Our experimental findings, supported by ab initio electronic structure calculations and atomic-scale molecular dynamics simulations, reveal direct mapping of single-molecule structure and resonance states at the solid/liquid interface. We further extend this approach to resolve the electronic structure of graphene monolayers at atomic length scales under standard room-temperature operating conditions.
Source: europepmc · Quality: candidate unverified · Source record ↗

Research context

OpenAlex topics: Surface Chemistry and Catalysis · Molecular Junctions and Nanostructures · Surface and Thin Film Phenomena

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (55)

Show source-provided references
1. De Oteyza, D. G. et al. Direct imaging of covalent bond structure in single-molecule chemical reactions. Science 340, 1434–1437 (2013).10.1126/science.1238187 ↗
2. 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).10.1126/science.1176210 ↗
3. Repp, J., Meyer, G., Stojkovic, S. M., Gourdon, A. & Joachim, C. Molecules on insulating films: Scanning-tunneling microscopy imaging of individual molecular orbitals. Phys. Rev. Lett. 94, 026803 (2005).10.1103/PhysRevLett.94.026803 ↗
4. Shin, H. J. et al. State-selective dissociation of a single water molecule on an ultrathin MgO film. Nature Mater. 9, 442–447 (2010).10.1038/nmat2740 ↗
5. Rabe, J. P. Molecules at interfaces: STM in materials and life sciences. Ultramicroscopy 42–44, 41–54 (1992).10.1016/0304-3991(92)90244-E ↗
6. Uji, I. H. et al. Scanning tunneling microscopy and spectroscopy of donor–acceptor–donor triads at the liquid/solid interface. ChemPhysChem 6, 2389–2395 (2005).10.1002/cphc.200500241 ↗
7. De Feyter, S. & De Schryver, F. C. Self-assembly at the liquid/solid interface: STM reveals. J. Phys. Chem. 109, 4290–4302 (2005).10.1021/jp045298k ↗
8. Hulsken, B. et al. Real-time single-molecule imaging of oxidation catalysis at a liquid–solid interface. Nature Nanotech. 2, 285–289 (2007).10.1038/nnano.2007.106 ↗
9. Sonnenfeld, R. & Hansma, P. K. Atomic-resolution microscopy in water. Science 232, 211–213 (1986).10.1126/science.232.4747.211 ↗
10. Itaya, K., Sugawara, S. & Higaki, K. In situ scanning tunneling microscopy for platinum surfaces in aqueous solutions. J. Phys. Chem. 92, 6714–6718 (1988).10.1021/j100334a045 ↗
11. Giambattista, B. et al. Atomic resolution images of solid–liquid interfaces. Proc. Natl Acad. Sci. USA 84, 4671–4674 (1987).10.1073/pnas.84.14.4671 ↗
12. De Feyter, S., Xu, H. & Mali, K. Dynamics in self-assembled organic monolayers at the liquid/solid interface revealed by scanning tunneling microscopy. Chimia 66, 38–43 (2012).10.2533/chimia.2012.38 ↗
13. Katsonis, N., Marchenko, A. & Fichou, D. Dynamics and spectroscopy of single C60 molecules adsorbed on Au(111) at the liquid–solid interface. J. Photochem. Photobiol. A 158, 101–104 (2003).10.1016/S1010-6030(03)00022-4 ↗
14. Rabe, J. P. & Buchholz, S. Direct observation of molecular structure and dynamics at the interface between a solid wall and an organic solution by scanning tunneling microscopy. Phys. Rev. Lett. 66, 2096–2099 (1991).10.1103/PhysRevLett.66.2096 ↗
15. Den Boer, D. et al. Detection of different oxidation states of individual manganese porphyrins during their reaction with oxygen at a solid/liquid interface. Nature Chem. 5, 621–627 (2013).10.1038/nchem.1667 ↗
16. Ciesielski, A., Palma, C. A., Bonini, M. & Samori, P. Towards supramolecular engineering of functional nanomaterials: Pre-programming multi-component 2D self-assembly at solid–liquid interfaces. Adv. Mater. 22, 3506–3520 (2010).10.1002/adma.201001582 ↗
17. Elemans, J. A. A. W. & De Feyter, S. Structure and function revealed with submolecular resolution at the liquid-solid interface. Soft Matter 5, 721–735 (2009).10.1039/B811090E ↗
18. Samori, P. et al. Supramolecular staircase via self-assembly of disklike molecules at the solid–liquid interface. J. Am. Chem. Soc. 123, 11462–11467 (2001).10.1021/ja0111380 ↗
19. Jackel, F., Watson, M. D., Mullen, K. & Rabe, J. P. Prototypical single-molecule chemical-field-effect transistor with nanometer-sized gates. Phys. Rev. Lett. 92, 188303 (2004).10.1103/PhysRevLett.92.188303 ↗
20. Albrecht, T. et al. Scanning tunneling spectroscopy in an ionic liquid. J. Am. Chem. Soc. 128, 6574–6575 (2006).10.1021/ja061993p ↗
21. Moth-Poulsen, K. & Bjornholm, T. Molecular electronics with single molecules in solid-state devices. Nature Nanotech. 4, 551–556 (2009).10.1038/nnano.2009.176 ↗
22. Gopakumar, T. G. et al. Coverage-driven electronic decoupling of Fe-phthalocyanine from a Ag(111) substrate. J. Phys. Chem. C 115, 12173–12179 (2011).10.1021/jp2038619 ↗
23. Gross, L. Recent advances in submolecular resolution with scanning probe microscopy. Nature Chem. 3, 273–278 (2011).10.1038/nchem.1008 ↗
24. Nirmalraj, P. N., Schmid, H., Gotsmann, B. & Riel, H. Nanoscale origin of defects at metal/molecule engineered interfaces. Langmuir 29, 1340–1345 (2013).10.1021/la3046109 ↗
25. Zhang, H-M., Xie, Z-X., Mao, B-W. & Xu, X. Self-assembly of normal alkanes on the Au (111) surfaces. Chem. Eur. J. 10, 1415–1422 (2004).10.1002/chem.200305334 ↗
26. Marchenko, O. & Cousty, J. Molecule length-induced reentrant self-organization of alkanes in monolayers adsorbed on Au(111). Phys. Rev. Lett. 84, 5363–5366 (2000).10.1103/PhysRevLett.84.5363 ↗
27. Nerngchamnong, N. et al. The role of van der Waals forces in the performance of molecular diodes. Nature Nanotech. 8, 113–118 (2013).10.1038/nnano.2012.238 ↗
28. Akari, S. et al. Anomalous voltage dependence of tunnelling microscopy in WSe2 . J. Microsc. 152, 521–526 (1988).10.1111/j.1365-2818.1988.tb01416.x ↗
29. Marchenko, A. & Cousty, J. C60 self-organization at the interface between a liquid C60 solution and a Au(111) surface. Surf. Sci. 513, 233–237 (2002).10.1016/S0039-6028(02)01726-0 ↗
30. Weckesser, J., Barth, J. V. & Kern, K. Mobility and bonding transition of C60 on Pd(110). Phys. Rev. B 64, 161403 (2001).10.1103/PhysRevB.64.161403 ↗
31. Heinz, H., Vaia, R. A., Farmer, B. L. & Naik, R. R. Accurate simulation of surfaces and interfaces of face-centered cubic metals using 12-6 and 9-6 Lennard-Jones potentials. J. Phys. Chem. 112, 17281–17290 (2008).
32. Grill, L. Functionalized molecules studied by STM: Motion, switching and reactivity. J. Phys. Condens. Matter 20, 053001 (2008).10.1088/0953-8984/20/05/053001 ↗
33. Neel, N. et al. Controlled contact to a C60 molecule. Phys. Rev. Lett. 98, 065502 (2007).10.1103/PhysRevLett.98.065502 ↗
34. Griessl, S. J. H. et al. Room-temperature scanning tunneling microscopy manipulation of single C60 molecules at the liquid–solid interface: Playing nanosoccer. J. Phys. Chem. B 108, 11556–11560 (2004).10.1021/jp049521p ↗
35. Lu, J. et al. Using the graphene Moiré pattern for the trapping of C60 and homoepitaxy of graphene. ACS Nano 6, 944–950 (2011).10.1021/nn204536e ↗
36. Nikolai Severin, J. B., Alexey, A. K. & Jurgen, P. R. Manipulation and overstretching of genes on solid substrates. Nano Lett. 4, 577–579 (2004).10.1021/nl035147d ↗
37. Wang, Y., Kroger, J., Berndt, R. & Tang, H. Molecular nanocrystals on ultrathin NaCl films on Au(111). J. Am. Chem. Soc. 132, 12546–12547 (2010).10.1021/ja105110d ↗
38. Franke, K. J. et al. Reducing the molecule–substrate coupling in C60-based nanostructures by molecular interactions. Phys. Rev. Lett. 100, 036807 (2008).10.1103/PhysRevLett.100.036807 ↗
39. Bilan, S., Zotti, L. A., Pauly, F. & Cuevas, J. C. Theoretical study of the charge transport through C60-based single-molecule junctions. Phys. Rev. B 85, 205403 (2012).10.1103/PhysRevB.85.205403 ↗
40. Néel, N. et al. Controlled contact to a C60 molecule. Phys. Rev. Lett. 98, 065502 (2007).10.1103/PhysRevLett.98.065502 ↗
41. Franke, K. J. & Pascual, J. I. Effects of electron–vibration coupling in transport through single molecules. J. Phys. Condens. Matter 24, 394002 (2012).10.1088/0953-8984/24/39/394002 ↗
42. Lu, X., Grobis, M., Khoo, K. H., Louie, S. G. & Crommie, M. F. Charge transfer and screening in individual C60 molecules on metal substrates: A scanning tunneling spectroscopy and theoretical study. Phys. Rev. B 70, 115418 (2004).10.1103/PhysRevB.70.115418 ↗
43. Martin, C. A. et al. Fullerene-based anchoring groups for molecular electronics. J. Am. Chem. Soc. 130, 13198–13199 (2008).10.1021/ja804699a ↗
44. Lortscher, E. et al. Bonding and electronic transport properties of fullerene and fullerene derivatives in break-junction geometries. Small 9, 209–214 (2013).10.1002/smll.201201688 ↗
45. Markussen, T., Settnes, M. & Thygesen, K. S. Robust conductance of dumbbell molecular junctions with fullerene anchoring groups. J. Chem. Phys. 135, 144104–144106 (2011).10.1063/1.3646510 ↗
46. Nirmalraj, P. N., Lutz, T., Kumar, S., Duesberg, G. S. & Boland, J. J. Nanoscale mapping of electrical resistivity and connectivity in graphene strips and networks. Nano Lett. 11, 16–22 (2011).10.1021/nl101469d ↗
47. Decker, R. et al. Local electronic properties of graphene on a BN substrate via scanning tunneling microscopy. Nano Lett. 11, 2291–2295 (2011).10.1021/nl2005115 ↗
48. Ugeda, M. M. et al. Point defects on graphene on metals. Phys. Rev. Lett. 107, 116803 (2011).10.1103/PhysRevLett.107.116803 ↗
49. Zheng, J. et al. Interfacial properties of bilayer and trilayer graphene on metal substrates. Sci. Rep. 3, 2081 (2013).10.1038/srep02081 ↗
50. Banhart, F., Kotakoski, J. & Krasheninnikov, A. V. Structural defects in graphene. ACS Nano 5, 26–41 (2010).10.1021/nn102598m ↗
51. Cho, J. et al. Structural and electronic decoupling of C60 from epitaxial graphene on SiC. Nano Lett. 12, 3018–3024 (2012).10.1021/nl3008049 ↗
52. Luican, A., Li, G. & Andrei, E. Y. Quantized Landau level spectrum and its density dependence in graphene. Phys. Rev. B 83, 041405 (2011).10.1103/PhysRevB.83.041405 ↗
53. Miller, D. L. et al. Observing the quantization of zero mass carriers in graphene. Science 324, 924–927 (2009).10.1126/science.1171810 ↗
54. Giovannetti, G. et al. Doping graphene with metal contacts. Phys. Rev. Lett. 101, 026803 (2008).10.1103/PhysRevLett.101.026803 ↗
55. Schull, G., Frederiksen, T., Brandbyge, M. & Berndt, R. Passing current through touching molecules. Phys. Rev. Lett. 103, 206803 (2009).10.1103/PhysRevLett.103.206803 ↗