In this Letter we report the results of a study of the energy level alignme
nt at interfaces between ultra-thin films of poly(9,9-dioctylfluorene) and
AlxOy SiO2 or gold substrates, prepared under ambient (air) conditions. In
all the cases, vacuum level alignment occurs, and the work function tracks
that of the substrates. There is no evidence of band bending in the pristin
e polymer layers up to 1100 Angstrom in film thickness. Upon increasing the
electrical conductivity of the polymer films by continuous doping with sod
ium under ultra-high-vacuum conditions, the energy levels of the polymer fi
lm gradually shift towards higher binding energies and finally become subst
rate independent. (C) 2000 Elsevier Science B.V. All rights reserved.