Molecular Ion Formation by Photoinduced Electron Transfer at the Tetracyanoquinodimethane/Au(111) Interface.

Optically induced processes in organic materials are essential for light harvesting, switching, and sensor technologies. Here we studied the electronic properties of the tetracyanoquinodimethane(TCNQ)/Au(111) interface by using two-photon photoemission spectroscopy. For this interface we demonstrated the lack of charge-transfer interactions, but we found a significant increase in the sample work function due to UV-light illumination, while the electronic structure of the TCNQ-derived states remain unaffected. Thereby the work function of the interface can be tuned over a wide range via the photon dose. We assigned this to a photoinduced metal-to-molecule electron transfer creating negative ions. The electrons are bound by a small potential barrier. Thus thermal activation reverses the process resulting in the original work function value. The presented photoinduced charge transfer at the TCNQ/Au(111) interface can be used for continuous work function tuning across the substrate's work function, which can be applied in device-adapted hole-injection layers or organic UV-light sensors.