Two mutually exclusive mechanisms have been proposed to explain the improved electron injection by the insertion of a LiF layer between the metal cathode and the active organic layer of organic photoelectronic devices: the dipole and the doping mechanism. The possibility of the doping mechanism was studied by investigating the interface of poly[2-methoxy-5-(3',7'dimethyl-octyloxyl)-1,4-phenylenevinylene] (MDMO-PPV) or 1-(3-(methoxycarbonyl)propyl)-1-phenyl[6,6]C-61 (PCBM) with Al, LiF, or Al/LiF. In this mechanism, Li dopes the organic layer, after liberation via the reaction Al+3LiF-->AlF3+3Li. If this reaction takes place, AlF3 should be detectable at the surface. However, SIMS measurements showed that AlF3 is not present at the Al/LiF/MDMO-PPV and Al/LiF/PCBM interfaces. This is evidence that the proposed reaction does not occur. Other evidence that the doping mechanism cannot be the general mechanism to explain the enhanced electron injection comes from the presence of LiF on both organic surfaces. XPS measurements indicate that there is a reaction of Al with the carboxylic oxygen of PCBM, and that a LiF layer between PCBM and Al prevents this reaction.