Abstract
Organic semiconductors on single-crystalline metal surfaces are model systems for injection contacts in organic field-effect transistors (OFET) and light-emitting diodes. They allow us to classify possible metal–organic interaction scenarios and to elucidate general tendencies, which most likely will also be found at metal–organic interfaces in real devices. In this contribution, we report a comprehensive investigation of the interface of perylene, a promising material for OFETs, with the close-packed noble metal surface Ag(111), using high-resolution electron energy loss spectroscopy, low-energy electron diffraction, and scanning tunneling microscopy as surface analytical techniques. The most important findings are: In the monolayer, molecules are oriented flat and form an incommensurate, most probably fluid overlayer. The molecules interact electronically with the substrate and become weakly metallic. Scanning tunneling microscopy reveals a propensity of perylene molecules toward a specific adsorption site on Ag(111), if the influence of intermolecular interactions is inhibited. Film growth at room temperature is similar to Stranski–Krastanov type. Finally, co-planar adsorption of perylene on Ag(111) is metastable, and annealing the monolayer at 420 K leads to a structural transformation of the film. The perylene–Ag(111) interface can therefore be classified as weakly interacting.
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H.E. Katz: Organic molecular solids as thin film transistor semiconductors. J. Mater. Chem. 7, 369 (1997).
G. Horowitz: Organic field-effect transistors. Adv. Mater. 10, 365 (1998).
A. Dodabalapur: Organic light-emitting diodes. Solid State Commun. 102, 259 (1997).
C.D. Dimitrakopoulos and P.R.L. Malenfant: Organic Thin Film Transistors for Large Area Electronics. Adv. Mater. 14, 99 (2002).
N. Karl: Charge Carrier Mobility in Organic Molecular Crystals, in Organic Electronic Materials, edited by R. Farchioni and G. Grosso (Springer, Berlin, 2001) p. 283.
S.H. Kim, Y.S. Yang, J.H. Lee, J.I. Lee, H.Y. Chu, H. Lee, J. Oh, L.M. Do, and T. Zyung: Organic field-effect transistors using perylene. Opt. Mater. 21, 439 (2003).
E. Umbach, K. Glöckler, and M. Sokolowski: Surface “architecture” with large organic molecules: interface order and epitaxy. Surf. Sci. 402, 20 (2000).
K. Glöckler, C. Seidel, A. Soukopp, M. Sokolowski, E. Umbach, M. Böhringer, R. Berndt, and W-D. Schneider: Highly ordered structures and submolecular scanning tunneling microscopy contrast of PTCDA and DM-PBDCI monolayers on Ag(111) on Ag(110). Surf. Sci. 405, 1 (1998).
F.S. Tautz, S. Sloboshanin, J.A. Schaefer, R. Scholz, V. Shklover, M. Sokolowski, and E. Umbach: Vibrational properties of ultrathin PTCDA films on Ag(110). Phys. Rev. B 61, 16933 (2000).
F.S. Tautz, M. Eremtchenko, J.A. Schaefer, M. Sokolowski, V. Shklover, and E. Umbach: Strong electron-phonon-coupling at a metal/organic interface: PTCDA/Ag(111). Phys. Rev. B 65, 125405 (2002).
F.S. Tautz, M. Eremtchenko, J.A. Schaefer, M. Sokolowski, V. Shklover, K. Glöckler, and E. Umbach: A comparison on the chemisorption behavior of PTCDA on different Ag surfaces. Surf. Sci. 502, 176 (2002).
M. Eremtchenko, J.A. Schaefer, and F.S. Tautz: Understanding and tuning the epitaxy of large aromatic adsorbates by molecular design. Nature 425, 602 (2003).
S.R. Langhoff: Theoretical Infrared Spectra for Polycyclinic Aromatic Hydrocarbon Neutrals, Cations, and Anions. J. Phys. Chem. 100, 2819 (1996).
D.M. Hudgins and S.A. Sandford: Infrared Spectroscopy of Matrix Isolated Polycyclic Aromatic Hydrocarbons. 2. PAHs Containing Five or More Rings. J. Phys. Chem. A 102, 344 (1996).
Q. Chen, T. Rada, A. McDowall, and N.V. Richardson: Epitaxial growth of a crystalline organic semiconductor: perylene/Cu(110). Chem. Mater. 14, 743 (2002).
Z.Q. Wei, C. Wang, C.F. Zhu, C.Q. Zhou, B. Xu, and C.L. Bai: Adlayer structures of pyrene and perylene on Cu(111): an in situ STM study. Surf. Sci. 478, L320 (2001).
C. Seidel, R. Ellerbrake, L. Gross, and H. Fuchs: Structural transitions of perylene and coronene on silver and gold surfaces: a molecular-beam epitaxy LEED study. Phys. Rev. B 64, 195418 (2001).
P. Yannoulis, R. Dudde, K.H. Frank, and E.E. Koch: Orientation of aromatic hydrocarbons on metal surfaces as determined by NEXAFS. Surf. Sci. 189–190, 519 (1987).
L. Gross, C. Seidel, and H. Fuchs: Organic monolayers with uniform domain orientation and reduced antiphase boundaries—MBE of perylene on Au(110). Org. Electr. 3, 1 (2002).
X. Lu, S.H. Mohamed, J.M. Ngaruiya, M. Wuttig, and T. Michely: Modifying the growth of organic thin films by a self-assembled monolayer. J. Appl. Phys. 93, 4852 (2003).
P.J. Unwin and T.S. Jones: Growth of ordered perylene thin films on GaAs(100) and InAs(111)A. Proceedings of the 7th International Conference on Nanometre-scale Science and Technology and 21st European Conference on Surface Science. Lund University, Lund, Sweden, 2002.
L. Chkoda, M. Schneider, V. Shklover, L. Kilian, M. Sokolowski, C. Heske, and E. Umbach: Chem. Phys. Lett. 371, 548 (2003).
B. Krause, A.C. Duerr, K. Ritley, F. Schreiber, H. Dosch, and D. Smilgies: Structure and growth morphology of an archetypal system for organic epitaxy: PTCDA on Ag(111). Phys. Rev. B 66, 235404 (2002).
M. Eremtchenko, D. Bauer, J.A. Schaefer, and F.S. Tautz: Polycyclic aromates on close-packed metal surfaces: functionalization, molecular chemisorption, and organic epitaxy. New Journal of Physics 6, 4 (2004).
V. Shklover, F.S. Tautz, R. Scholz, S. Sloboshanin, M. Sokolowski, J.A. Schaefer, and E. Umbach: Differences in vibronic and electronic excitations of PTCDA on Ag(111) and Ag(110). Surf. Sci. 454, 60 (2000).
M.J. Frisch, G.W. Trucks, and H.B. Schlegel et al. Gaussian 98 (Gaussian Inc., Pittsburgh, PA, 1998).
L.C. Sander and S.A. Wise: National Institute of Standards and Technology (USA), Polycyclic Aromatic Hydrocarbon Structure Index, NIST Special Publication SP922, 1997. Available at http://ois.nist.gov/pah/.
M. Böhringer, W-D. Schneider, and R. Berndt: Scanning tunneling microscope-induced molecular motion and its effect on the image formation. Surf. Sci. 408, 72 (1998).
J. Li, R. Berndt, and W-D. Schneider: Tip-Assisted Diffusion on Ag(110) in Scanning Tunneling Microscopy. Phys. Rev. Lett. 76, 1888 (1996).
M. Böhringer, W-D. Schneider, K. Glöckler, E. Umbach, and R. Berndt: Adsorption site determination of PTCDA on Ag(110) by manipulation of adatoms. Surf. Sci. Lett. 419, L95 (1998).
L. Bartels, G. Meyer, and K-H. Rieder: Basic steps of lateral manipulation of single atoms and diatomic clusters with a scanning tunneling microscope tip. Phys. Rev. Lett. 79, 697 (1997).
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Eremtchenko, M., Bauer, D., Schaefer, J.A. et al. Structure, bonding, and growth at a metal–organic interface in the weak chemisorption regime: Perylene–Ag(111). Journal of Materials Research 19, 2028–2039 (2004). https://doi.org/10.1557/JMR.2004.0253
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DOI: https://doi.org/10.1557/JMR.2004.0253