Customized Electronic Coupling in Self‐Assembled Donor–Acceptor Nanostructures |
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Authors: | Dimas G de Oteyza Juan M García‐Lastra Martina Corso Bryan P Doyle Luca Floreano Alberto Morgante Yutaka Wakayama Angel Rubio J Enrique Ortega |
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Affiliation: | 1. Donostia International Physics Center Paseo Manuel Lardizabal 4, 20018 San Sebastián (Spain);2. Advanced Electronic Materials Center National Institute for Materials Science 1‐1 Namiki, Tsukuba 305‐0044 (Japan);3. Nano‐Bio Spectroscopy group and European Theoretical Spectroscopy Facility (ETSF) Departamento Fisica de Materiales UPV/EHU Apdo. 1072, San Sebastián (Spain);4. Laboratorio Nazionale TASC INFM‐CNR National Area Science Park, I‐34012 Basovizza, Trieste (Italy);5. Centro de Fisica de Materiales Materials Physics Center, CSIC‐UPV/EHU Paseo Manuel Lardizabal 3, 20018 San Sebastián (Spain);6. Departamento de Fisica Aplicada, UPV/EHU Plaza de O?ate 2, 20018 San Sebastián (Spain) |
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Abstract: | Charge transfer processes between donor–acceptor complexes and metallic electrodes are at the heart of novel organic optoelectronic devices such as solar cells. Here, a combined approach of surface‐sensitive microscopy, synchrotron radiation spectroscopy, and state‐of‐the‐art ab initio calculations is used to demonstrate the delicate balance that exists between intermolecular and molecule–substrate interactions, hybridization, and charge transfer in model donor–acceptor assemblies at metal‐organic interfaces. It is shown that charge transfer and chemical properties of interfaces based on single component layers cannot be naively extrapolated to binary donor–acceptor assemblies. In particular, studying the self‐assembly of supramolecular nanostructures on Cu(111), composed of fluorinated copper‐phthalocyanines (F16CuPc) and diindenoperylene (DIP), it is found that, in reference to the associated single component layers, the donor (DIP) decouples electronically from the metal surface, while the acceptor (F16CuPc) suffers strong hybridization with the substrate. |
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Keywords: | density functional calculations electronic structure self‐assembly supramolecular chemistry X‐ray spectroscopy |
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