Spatially Resolving Ordered and Disordered Conformers and Photocurrent Generation in Intercalated Conjugated Polymer/Fullerene Blend Solar Cells

[Image: see text] Resonance Raman spectroscopy was used to identify ordered and disordered conformers of poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT) blended with the electron acceptor [6,6]-phenyl C(61) butyric acid methyl ester (PCBM) in bulk heterojunction (BHJ) solar cells where PCBM intercalates into PBTTT side groups. We show that the PBTTT thiophene ring symmetric C=C stretching mode consists of contributions from ordered (ℏω(C=C) = 1489 cm(–1), fwhm ∼ 15 cm(–1)) and disordered (ℏω(C=C) = 1500 cm(–1), fwhm ∼ 25 cm(–1)) components and their relative amounts are sensitive to PCBM loading, annealing and excitation energy. The 1500 cm(–1) PBTTT component originates from twisted thiophene rings and disordered side groups due to PCBM intercalation in a mixed kinetic phase and thermal annealing promotes ordering of PBTTT chains from the formation of bimolecular PBTTT/PCBM crystals. Density functional theory (DFT) Raman simulations of PBTTT monomers support these assignments. Resonance Raman images of annealed PBTTT/PCBM model solar cells confirm that ordered PBTTT chains are most concentrated in PCBM-rich bimolecular crystals and corresponding intensity modulated photocurrent spectroscopy (IMPS) and imaging measurements show increased nongeminate charge recombination at the boundaries of ordered/disordered regions.