Gap states at organic–metal interfaces: A combined spectroscopic and theoretical study

A systematic understanding and controlling of gap states formed at the organic–metal interfaces is a key factor for fabricating functional organic–metal systems, as in case of heterojunctions in semiconductor devices. We report here the characterization of gap states near the Fermi level of metal substrate by metastable atom electron spectroscopy and first-principles density functional calculations. The gap states in organic–metal systems are classified into two types, i. e., chemisorption-induced gap states (CIGSs) and complex-based gap states (CBGSs). CIGSs can be further classified whether the metal wave function tails a short distance into the chemisorbed species with the exponential decay (damping type) or is exposed sufficiently to the chemisorbed species by mixing with the organic orbitals (propagating type). CIGSs observed in alkanethiolate and C 60 on Pt(1 1 1) are their typical examples, respectively. As a consequence, alkanethiolate serves as a poor mediator of metal wave function, whereas C 60 acts as a good mediator, which is responsible for tunneling mechanism and eventually electric conductivity in the relevant metal–organic–metal junctions. CBGSs are identified in bathocuproine films deposited on K-covered Au, where the K atoms migrate into the film to form an organic–metal complex. The CBGSs are distributed over the multilayer film, in contrast to the case of CIGS. With increasing film thickness, the CBGSs exhibit incommensurate energy shifts with the valence band top of the film, indicating that the Schottky-Mott model breaks down as evaluating charge transport in organic–metal systems.