Cooperative effects of solvent and polymer acceptor co-additives in P3HT:PDI solar cells: simultaneous optimization in lateral and vertical phase separationElectronic supplementary information (ESI) available. See DOI: 10.1039/c3cp55075c

In this work, solvent chloronaphthalene (CN) and polymer acceptor an alternating copolymer of perylene diimide and carbazole (PCPDI) were utilized as co-additives to optimize the nanoscale phase-separated morphology and photovoltaic properties of bulk-heterojunction (BHJ) polymer solar cells based on the poly(3-hexyl thiophene) (P3HT)/ N , N ′-bis(1-ethylpropyl)-perylene-3,4,9,10-tetracarboxylic diimide (EP-PDI) system. The domain size of EP-PDI molecules together with that of P3HT distinctly decreased by adding a 0.75 vol% CN additive. The optimized lateral phase separation increased the donor-acceptor interfacial area and facilitated the exciton dissociation process, leading to 5-fold enhancement of short-circuit current ( J SC ). Furthermore, when PCPDI was employed as a co-additive, acceptor materials (including PCPDI and EP-PDI) were prone to aggregation towards the top surface of blend films, improving vertical phase separation of active layers. PCPDI incorporation, which improved the percolation pathways for electron carriers, suppressed the crystallinity of P3HT distinctly. Thus, much more balanced charge transport was achieved by PCPDI addition, which resulted in almost 1-fold enhancement of open-circuit voltage ( V OC ) by reducing nongeminate recombination. As a consequence, cooperative effects of CN and PCPDI additives improved the nanoscale phase-separated morphology in lateral and vertical directions simultaneously, achieving the enhancement in both V OC and J SC . Cooperative effects of CN and PCPDI improved the phase-separated morphology of PDI-based solar cells in lateral and vertical directions simultaneously.