We demonstrate that the insertion of an electron acceptor molecular (sub-) monolayer at organic/metal interfaces enables systematic tuning of the hole injection barrier height (Delta(h)). Ultraviolet photoemission spectroscopy results show that Delta(h) for alpha-sexithiophene thin films deposited on Ag(111) can be reduced from 1.3 to 1.0 eV by introducing a chemisorbed monolayer of 11,11,12,12-tetracyano-9,10-anthraquinodimethane (TCAQ) on the metal surface. Fine-tuning of Delta(h) within the interval of 0.3 eV is achieved by using TCAQ coverages in the submonolayer range. (c) 2005 American Institute of Physics.
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