Magnetic
resonance, relaxation, and dynamic parameters of polarons
and methanofullerene radical anions photoinduced in photovoltaic composites
formed by narrow-bandgap poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-(bithiophene)] (F8T2), poly[2,7-(9,9-dioctylfluorene)-alt-4,7-bis(thiophen-2-yl)benzo-2,1,3-thiadiazole] (PFO–DBT),
and poly[N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)]
(PCDTBT) copolymers as electron donors with [6,6]-phenyl-C61-butanoic acid methyl ester (PC61BM) as electron acceptor
were comparatively studied by the direct light-induced electron paramagnetic
resonance (LEPR) spectroscopy in combination with spectral simulations
in a wide temperature range. A number of mobile polarons are captured
by deep spin traps formed in bulk heterojunctions due to their disorder.
It was shown that the concentration, transport, and recombination
of photoinitiated charge carriers depend on the structure of the copolymer
matrix and the interaction between the other spin packets, as well
as on the number, spatial distribution, and energy depth of the spin
traps. The recombination of polarons and methanofullerene radical
anions can be described in the framework of a second-order bimolecular
process in the F8T2:PC61BM and PFO–DBT:PC61BM composites and a first-order monomolecular process in the PCDTBT:PC61BM bulk heterojunctions. The dependence of the ambipolarity
of the copolymer matrix on the anisotropy of spin dynamics is shown.
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