The change in the valence electronic structure of thin films of the electro
luminescent material p-sexiphenyl (6P) has been investigated as a function
of the deposition of an alkaline earth metal under ultrahigh vacuum conditi
ons. This was done by in situ evaporation of increasing amounts of calcium
onto the 6P film and recording the photoemission spectra. Two different sub
strates for the 6P films were used, namely Au and Ca. New emissions within
the formerly empty energy gap of the pristine organic material were observe
d upon the metal deposition for both substrates. For 6P/Au this was accompa
nied by a significant shift of the Fermi level (E-F) toward lower binding e
nergy for increasing amounts of Ca. For low metal coverage the density of o
ccupied valence states (DOVS) of the intragap emission was observed at E-F,
whereas for higher amounts of Ca coverage no DOVS are observed at E-F Comm
only, this would be interpreted that first polarons (radical anions) are fo
rmed, and later on bipolarons (dianions) for higher Ca concentration. In co
ntrast, on the basis of the different experimental findings when Ca was use
d as substrate and a line shape analysis of the intragap emission, we concl
ude that in 6P bipolarons are formed throughout all doping levels.