Direct analytical method of contact position effects on the energy-level alignments at organic semiconductor/electrode interfaces using photoemission spectroscopy combined with Ar gas cluster ion beam sputtering

Poly(3, 4-ethylenedioxythiophene) (PEDOT) polymerized with poly(4-styrenesulfonate) (PSS) is one of the most widely used conducting organic electrodes owing to its outstanding optical/electrical properties and high work function. Because its work function depends significantly on the molecular arrangements between PEDOT and PSS molecules on the surface, the contact position of PEDOT:PSS films on organic semiconductors (OSCs) must also be an essential consideration. However, existing analysis methods based on in situ deposition/analysis are limited in their ability to accurately investigate the electronic structures of the buried interface regions under the solution-processed electrode or OSC layer in organic devices. Therefore, to overcome such limitations, we propose a top-down method based on photoemission spectroscopy analysis combined with Ar gas cluster ion beam (GCIB) sputtering. Through this method, both energy-level alignments and molecular distributions at various OSC/electrode interfaces can be successfully characterized without reference to any deposition process.