Charge Separation in PCPDTBT:PCBM Blends from an EPR Perspective

Using time-resolved electron paramagnetic resonance (EPR) spectroscopy in conjunction with optical excitation we study charge separation in conjugated polymers blended with [6,6]-phenyl C61-butyric acid methyl ester (PCBM). A direct comparison between samples comprising poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (C-PCPDTBT) and their analogues containing poly[(4,4′-bis(2-ethylhexyl)dithieno[3,2-b:2′,3′-d]silole)-2,6-diyl-alt-(4,7-bis(2-thienyl)-2,1,3-benzothiadiazole)-5,5′-diyl] (Si-PCPDTBT) reveals a remarkable influence of the bridging atom (carbon vs silicon) in the polymer on the EPR spectra. While the EPR signatures of photogenerated positive polarons in C- and Si-bridged PCPDTBT are virtually identical, significant differences are observed with respect to the spin-relaxation behavior. The spin–lattice relaxation time of positive polarons in C-PCPDTBT at low temperature (T = 80 K) is found to be more than two orders or magnitude longer t...