Spatially Resolving Ordered and Disordered Conformers and Photocurrent Generation in Intercalated Conjugated...

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 C₆₁ 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.