On the Origin of Gap States in Molecular SemiconductorsA Combined UPS, AFM, and X‑ray Diffraction Study

• Published in: Journal of physical chemistry. C 2021-08, Vol.125 (32), p.17929-17938
• Main Authors: Hagenlocher, Jan, Scheffczyk, Niels, Broch, Katharina, Duva, Giuliano, Rußegger, Nadine, Egenberger, Lisa, Banerjee, Rupak, Kera, Satoshi, Schreiber, Frank, Hinderhofer, Alexander
• Format: Article
• Language: English
• Subjects: C: Physical Properties of Materials and Interfaces
• ISSN: 1932-7447; 1932-7455
• DOI: 10.1021/acs.jpcc.1c03096

Electronic states within the HOMO–LUMO gap of organic semiconductors play a key role in the energy level alignment of substrate–organic and organic–organic interfaces and therefore are a defining parameter for device functionality and efficiency. They are thought to result from structural defects influencing the specific environment of a molecule. Varying the substrate temperature for samples grown by molecular beam deposition, we are able to control their density. Using atomic force microscopy and X-ray scattering techniques, we can differentiate defects depending on their length scale and effective direction. Comparison of the respective defect density with the density of gap states, measured directly via ultra-low-background ultraviolet photoelectron spectroscopy, enables to correlate structural and electronic properties for different prototypical organic semiconductors. We investigate the impact of gap states on the energy level alignment and find a direct link between structural defects and the interface dipole.