Photainduced Carrier Generation and Decay Dynamics in Intercalated and Non-intercalated Polymer: Fullerene Bulk Heterojunctions

The dependence of photoinduced carrier generation and decay on donor acceptor nanomorphology is reported as a function of composition for blends of the polymer poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene) (pBTTT-C-14) with two electron-accepting fullerenes: phenyl-C-71-butyric acid methyl ester (PC71BM) or the bisadduct of phenyl-C-61-butyric add methyl ester (bis-PC61BM). The formation of partially or fully intercalated bimolecular crystals at weight ratios up to 1:1 for pBTTT-C-14:PC71BM blends leads to efficient exciton quenching due to a combination of static and dynamic mechanisms. At higher fullerene loadings, pure PC71BM domains are formed that result in an enhanced free carrier lifetime, as a consequence of spatial separation of the electron and hole into different phases, and the dominant contribution to the photoconductance comes from the high:frequency electron mobility In the fullerene dusters. In the pBM-C-14:bisPC(61)BM system, phase separation results In a non-intercalated structure, Independent of composition, which Is characterized by exciton quenching that is dominated by a dynamic process, an enhanced carrier lifetime and a hole-dominated photoconductance signal. The results indicate that intercalation of fullerene Into crystalline polymer domains is not detrimental to the density of long-lived carriers, suggesting that efficient organic photovoltaic devices could be fabricated that incorporate intercalated structures, provided that an additional pure fullerene phase is present for charge extraction.