Abstract
The realization of efficient organic electronic devices requires the controlled preparation of molecular thin films and heterostructures. As top-down structuring methods such as lithography cannot be applied to van der Waals bound materials1, surface diffusion becomes a structure-determining factor that requires microscopic understanding. Scanning probe techniques provide atomic resolution, but are limited to observations of slow movements, and therefore constrained to low temperatures. In contrast, the helium-3 spin-echo (HeSE) technique achieves spatial and time resolution on the nm and ps scale, respectively, thus enabling measurements at elevated temperatures2. Here we use HeSE to unveil the intricate motion of pentacene admolecules diffusing on a chemisorbed monolayer of pentacene on Cu(110) that serves as a stable, well-ordered organic model surface3. We find that pentacene moves along rails parallel and perpendicular to the surface molecules. The experimental data are explained by admolecule rotation that enables a switching between diffusion directions, which extends our molecular level understanding of diffusion in complex organic systems.
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References
Forrest, S. R. The path to ubiquitous and low-cost organic electronic appliances on plastic. Nature 428, 911–918 (2004).
Jardine, A. P., Hedgeland, H., Alexandrowicz, G., Allison, W. & Ellis, J. Helium-3 spin-echo: principles and application to dynamics at surfaces. Prog. Surf. Sci. 84, 323–379 (2009).
Söhnchen, S., Lukas, S. & Witte, G. Epitaxial growth of pentacene films on Cu(110). J. Chem. Phys. 121, 525–534 (2004).
Barth, J. V. Transport of adsorbates at metal surfaces: from thermal migration to hot precursors. Surf. Sci. Rep. 40, 75–149 (2000).
Dimitrakopoulos, C. D. & Malenfant, P. R. L. Organic thin film transistors for large area electronics. Adv. Mater. 14, 99–117 (2002).
O’Neill, M. & Kelly, S. M. Ordered materials for organic electronics and photonics. Adv. Mater. 23, 566–584 (2011).
Sarikaya, M., Tamerler, C., Jen, A. K.-Y., Schulten, K. & Baneyx, F. Molecular biomimetics: nanotechnology through biology. Nature Mater. 2, 577–585 (2003).
Grimsdale, A. C. & Müllen, K. The chemistry of organic nanomaterials. Angew. Chem. Int. Ed. 44, 5592–5629 (2005).
Otero, R. et al. Lock-and-key effect in the surface diffusion of large organic molecules probed by STM. Nature Mater. 3, 779–782 (2004).
Bartels, L., Wang, F., Möller, D., Knoesel, E. & Heinz, T. F. Real-space observation of molecular motion induced by femtosecond laser pulses. Science 305, 648–651 (2004).
Wong, K. L. et al. A molecule carrier. Science 315, 1391–1393 (2007).
Komeda, T., Kim, Y., Kawai, M., Persson, B. N. J. & Ueba, H. Lateral hopping of molecules induced by excitation of internal vibration mode. Science 295, 2055–2058 (2002).
Kim, Y., Motobayashi, K., Frederiksen, T., Ueba, H. & Kawai, M. Action spectroscopy for single-molecule reactions—experiments and theory. Prog. Surf. Sci. 90, 85–143 (2015).
Ruiz, R. et al. Pentacene thin film growth. Chem. Mater. 16, 4497–4508 (2004).
Hlawacek, G. et al. Characterization of step-edge barriers in organic thin-film growth. Science 321, 108–111 (2008).
Fouquet, P. et al. Measurements of molecule diffusion on surfaces using neutron and helium spin echo. Physica B 385–386, 269–271 (2006).
Poelsema, B. & Comsa, G. Scattering of Thermal Energy Atoms (Springer Tracts in Modern Physics 115, Springer, 1989).
Van Hove, L. Correlations in space and time and Born approximation scattering in systems of interacting particles. Phys. Rev. 95, 249–262 (1954).
Chudley, C. T. & Elliott, R. J. Neutron scattering from a liquid on a jump diffusion model. Proc. Phys. Soc. 77, 353–361 (1961).
Ellis, J. & Toennies, J. P. Observation of jump diffusion of isolated sodium atoms on a Cu(001) surface by helium atom scattering. Phys. Rev. Lett. 70, 2118–2121 (1993).
Hedgeland, H. et al. Measurement of single-molecule frictional dissipation in a prototypical nanoscale system. Nature Phys. 5, 561–564 (2009).
de Wijn, A. S. Internal degrees of freedom and transport of benzene on graphite. Phys. Rev. E 84, 011610 (2011).
Lechner, B. A. J. et al. Atomic scale friction of molecular adsorbates during diffusion. J. Chem. Phys. 138, 194710 (2013).
Lechner, B. A. J. et al. Jumping, rotating, and flapping: the atomic-scale motion of thiophene on Cu(111). J. Phys. Chem. Lett. 4, 1953–1958 (2013).
Clancy, P. Application of molecular simulation techniques to the study of factors affecting the thin-film morphology of small-molecule organic semiconductors. Chem. Mater. 23, 522–543 (2011).
Allinger, N. L., Yuh, Y. H. & Lii, J. H. Molecular mechanics. The MM3 force field for hydrocarbons. 1. J. Am. Chem. Soc. 111, 8551–8566 (1989).
Cantrell, R. A., James, C. & Clancy, P. Computationally derived rules for persistence of C60 nanowires on recumbent pentacene bilayers. Langmuir 27, 9944–9954 (2011).
Tuddenham, F. E. et al. Lineshapes in quasi-elastic scattering from species hopping between non-equivalent surface sites. Surf. Sci. 604, 1459–1475 (2010).
Farias, D. & Rieder, K.-H. Atomic beam diffraction from solid surfaces. Rep. Prog. Phys. 61, 1575–1664 (1998).
Ponder, J. W. TINKER—Software Tools for Molecular Design (2015); http://dasher.wustl.edu/tinker
Acknowledgements
The authors acknowledge financial support from the EPSRC (EP/E0049621, B.A.J.L., D.J.W., D.M.C., A.P.J., J.E., W.A.), the Austrian Academy of Sciences (B.A.J.L.), the Royal Society (A.P.J.), the E.U. ERASMUS programme (A.M.) and the Deutsche Forschungsgemeinschaft (GRK 1782, P.R.). Underlying data are available at the University of Cambridge Research data repository (https://www.repository.cam.ac.uk).
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G.W. initiated the project. G.W., W.A. and A.P.J. planned the experiment. A.M., B.A.J.L., D.M.C. and D.J.W. performed the HeSE measurements. A.M., P.R., B.A.J.L. and J.E. analysed the data. P.R. ran the simulations. P.R. and B.E. developed the model. P.R., G.W., B.A.J.L. and B.E. wrote the manuscript.
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Rotter, P., Lechner, B., Morherr, A. et al. Coupling between diffusion and orientation of pentacene molecules on an organic surface. Nature Mater 15, 397–400 (2016). https://doi.org/10.1038/nmat4575
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DOI: https://doi.org/10.1038/nmat4575
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