Ns. Sariciftci et al., ABSENCE OF PHOTOINDUCED ELECTRON-TRANSFER FROM THE EXCITONIC ELECTRON-HOLE BOUND-STATE IN POLYDIACETYLENE CONJUGATED POLYMERS, Physical review. B, Condensed matter, 50(16), 1994, pp. 12044-12051
We present the results of comparative studies of photoinduced electron
transfer from semiconducting polymers onto C-60, focusing on the effe
ct of strong Coulomb correlations, which lead to excitons (bound elect
ron-hole pairs) as the primary photoexcitations. For this purpose, we
investigated two different soluble polydiacetylene (PDA) derivatives i
n which the lowest-energy photoexcitations are excitons with a binding
energy of approximately 0.5 eV. The experimental studies (absorption
and emission spectroscopy, subpicosecond and millisecond photoinduced
absorption spectroscopy, and picosecond transient and near-steady-stat
e photoconductivity) were carried out in pristine materials and in com
posites of PDA with C-60. The PDA data are compared with the results o
f similar studies on semiconducting conjugated polymers such as poly(p
ara-phenylene-vinylene) and its derivatives, the PPV's, and polythioph
ene and its derivatives, the P3AT's. The results show clearly that in
contrast to the high quantum efficiency photoinduced electron transfer
discovered earlier in the PPV's and the P3AT's, the excitonic bound s
tate of the electron and hole inhibits photoinduced electron transfer
from PDA onto C-60. We conclude that in the PPV's and the P3AT's, the
Coulomb interaction is sufficiently well screened that upon photoexcit
ation free carriers are created, thereby making possible facile electr
on transfer to a near-by acceptor.