Conjugated polymer, regioregular poly(3-hexylthiophene) (rr-P3HT), films were prepared by spin-coating the rr-P3HT chloroform solution onto clean silicon wafer surfaces. The chemical re-action and electronic structure of Ca deposition on rr-P3HT surfaces were in situ investigated by synchrotron radiation photoemission spectroscopy (SRPES) and X-ray photoemission spectros-copy (XPS). Upon Ca deposition, Ca-induced band bending of rr-P3HT is observed. In addition, Ca atoms preferentially react with S atoms of rr-P3HT. No obvious reaction between Ca and C atoms can be found. Through the investigation of the evolution of valence band spectra and secondary electron cut-off of rr-P3HT during the process of Ca deposition, an energy level alignment diagram at the Ca/rr-P3HT interface is derived.
