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Charge-transfer-induced structural rearrangements at both sides of organic/metal interfaces

Nature Chemistry volume 2, pages 374–379 (2010)Cite this article

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Abstract

Organic/metal interfaces control the performance of many optoelectronic organic devices, including organic light-emitting diodes or field-effect transistors. Using scanning tunnelling microscopy, low-energy electron diffraction, X-ray photoemission spectroscopy, near-edge X-ray absorption fine structure spectroscopy and density functional theory calculations, we show that electron transfer at the interface between a metal surface and the organic electron acceptor tetracyano-p-quinodimethane leads to substantial structural rearrangements on both the organic and metallic sides of the interface. These structural modifications mediate new intermolecular interactions through the creation of stress fields that could not have been predicted on the basis of gas-phase neutral tetracyano-p-quinodimethane conformation.

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Figure 1: Chemical structure of TCNQ, TCNQ•− and TCNQ2−.
Figure 2: Elongated self-assembled islands of TCNQ on Cu(100).
Figure 3: Highly ordered self-assembled monolayer of TCNQ on Cu(100).
Figure 4: Charge transfer in a self-assembled monolayer of TCNQ on Cu(100).
Figure 5: NEXAFS measurements of TCNQ / Cu(100).
Figure 6: Structural rearrangements at both sides of the TCNQ/Cu(100) interface from DFT calculations.

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Acknowledgements

Studies at MPI Stuttgart were supported by the European Science Foundation (ESF) EUROCORES-SONS2 programme FunSMARTs II. Work in Madrid was financed by the Spanish MICINN (projects FIS2007-61114, FIS2007-60064, NAN2004-08881-C02-01, CTQ2006-08558 and Consolider CSD2007-00010), the Comunidad de Madrid (projects S-0505-MAT-0194 and S2009/MAT-1726) and the European Union (‘MONET’ project, MEST-CT-2005-020908). R.O. thanks the MEC for salary support through the Ramón & Cajal programme. All the computations were performed at Mare Nostrum Barcelona Supercomputer Center and Centro de Computación Científica de la UAM.

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Authors and Affiliations

  1. Max Planck Institute for Solid State Research, Stuttgart, D-70569, Germany

    Tzu-Chun Tseng, Steven L. Tait, Nian Lin, Mitsuharu Konuma, Ulrich Starke, Alexander Langner & Klaus Kern

  2. Departamento de Física de la Materia Condensada, Universidad Autónoma de Madrid, Cantoblanco, 28049, Madrid, Spain

    Christian Urban, Roberto Otero, David Écija, Marta Trelka & Rodolfo Miranda

  3. Departamento de Química, Universidad Autónoma de Madrid, 28049, Madrid, Spain

    Yang Wang, Manuel Alcamí & Fernando Martín

  4. Instituto Madrileño de Estudios Avanzados en Nanociencia (IMDEA-Nanociencia), Cantoblanco, 28049, Madrid, Spain

    Roberto Otero, Nazario Martín & Rodolfo Miranda

  5. Department of Chemistry, Indiana University, Bloomington, 47405, Indiana, USA

    Steven L. Tait

  6. Instituto de Ciencia de Materiales de Madrid - CSIC, Cantoblanco, 28049, Madrid, Spain

    José María Gallego

  7. Department of Physics, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China

    Nian Lin

  8. Lehrstuhl für Physikalische Chemie, Ruhr-Universität Bochum, Bochum, 44780, Germany

    Alexei Nefedov

  9. Institute of Functional Interfaces, Karlsruhe Institute of Technology (KIT), Karlsruhe, 76012, Germany

    Christof Wöll

  10. Departamento de Química Orgánica, Universidad Complutense de Madrid, Madrid, 28040, Spain

    María Ángeles Herranz & Nazario Martín

  11. Institut de Physique de la Matière Condensée, Ecole Polytechnique Fédérale de Lausanne, Lausanne, CH-1015, Switzerland

    Klaus Kern

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  1. Tzu-Chun Tseng
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Contributions

STM experiments were carried out by T.-C.T., C.U. and M.T. T.-C.T. and C.U. contributed equally to this work. T.-C.T., C.U. and D.E. were involved in STM data analysis. Y.W., M.A. and F.M. carried out the DFT calculations shown in this paper. T.-C.T., S. L.T., M.K. and U.S. performed the XPS and LEED measurements and analysis, and T.-C.T., A.L., S.L.T. and A.N. performed the NEXAFS experiments and analysis, supervised by C.W. The molecules were provided by M.A.H. and N.M. and they supervised the chemical discussions. R.O., J.M.G. and S.L.T. wrote the paper and coordinated all the experimental work. Experiments were planned and designed by R.O., J.M.G., S.L.T., U.S. and N.L. under the supervision of K.K. and R.M.

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Correspondence to Roberto Otero or Steven L. Tait.

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Tseng, TC., Urban, C., Wang, Y. et al. Charge-transfer-induced structural rearrangements at both sides of organic/metal interfaces. Nature Chem 2, 374–379 (2010). https://doi.org/10.1038/nchem.591

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