Intermediate-Sized Conjugated Donor Molecules for Organic Solar Cells: Comparison of Benzodithiophene and Benzobisthiazole-Based Cores

Two intermediate-sized donor molecules, BBTz-X and BDT-X, have been synthesized by the Stille coupling between 4-(4,4-bis­(2-ethylhexyl)-6-(trimethylstannyl)-4H-silolo­[3,2-b:4,5-b′]­dithiophen-2-yl)-7-(5′-hexyl-[2,2′-bithiophen]-5-yl)-[1,2,5]­thiadiazolo­[3,4-c]­pyridine and either 4,8-bis­(5-(2-ethylhexyl)­thiophen-2-yl)-2,6-diiodobenzo­[1,2-d:4,5-d′]­bis­(thiazole) or 2,6-dibromo-4,8-bis­(5-(2-ethylhexyl)­thiophen-2-yl)­benzo­[1,2-b:4,5-b′]­dithiophene, respectively. Both oxidation and reduction potentials for BBTz-X are anodically shifted relative to those for BDT-X, but the oxidation potential is more sensitive to the identity of the core; this is consistent with what is seen for DFT-calculated HOMO and LUMO energies and with a slightly blue-shifted absorption maximum for BBTz-X. Although DFT calculations, along with crystal structures of related compounds, suggest more planar molecular structures for BBTz-X than for BDT-X, film structures and the effects of various annealing processes on these films, as revealed by GIWAXS, are similar. The performance of BDT-X:PC₆₁BM bulk-heterojunction solar cells is more sensitive to annealing conditions than that of BBTz-X:PC₆₁BM cells, but under appropriate conditions, both yield power conversion efficiencies of >7%.