The exciton binding energy (E-b) and the band gap energy (E-g) of poly(phen
ylene vinylene) are determined by high-resolution measurements of the photo
conductivity excitation profile as a function of light polarization, applie
d electric field, and temperature. At high applied electric fields, a peak
in the photoconductivity is observed when the sample is pumped at a photon
energy just below the onset of the band-to-band pi-pi* absorption. This pea
k is interpreted as resulting from field ionization of a weakly bound excit
on with E-b approximate to 60 meV. The binding energy is obtained from the
energy of the exciton peak relative to the band edge and independently from
analysis of the dependence of the exciton dissociation on field and temper
ature.