Bulk Heterojunction Solar Cells: The Role of Alkyl Side Chain on Nanoscale Morphology of Sulfur Over-rich Regioregular Polythiophene/Fullerene Blends

R e g i o r e g u l a r HH-TT p o l y ( 3 , 3 ′ - thioalkylbithiophene)s-bearing branched or linear alkyl sidechain substituents (PT2SR) have been synthesized and characterized to investigate their behavior, when used as electron-donor components in blend with a fullerene derivative [[6,6]-phenyl-C61-butyric acid methyl ester (PCBM)] as an electron acceptor, in air-processed photovoltaic solar cells with bulk heterojunction architecture. The optoelectronic characteristics, energy gap, nanoscale morphology, and crystallinity of the blends (PT2SR/PCBM) were examined by ultraviolet− visible spectroscopy, cyclic voltammetry, Kelvin probe force microscopy (KPFM), and X-ray diffraction (XRD). We demonstrate that thioalkyl substituents are able to influence the PCBM self-assembly and the morphology of the polymeric film, important parameters to maximize the efficiency of the solar cell. In particular, the presence of chemical branching in the side chain of the sulfur over-rich polythiophene backbone favors the formation of PCBM clusters, of size of about 100 ± 30 nm, as confirmed by XRD and KPFM measurements. This facilitates the intermixing between donor and acceptor materials at the nanoscale level, determining an increase in the device performance.