Relationship between Diode Saturation Current and Open Circuit Voltage in Poly(3-alkylthiophene) Solar Cells as a Function of Device Architecture, Processing Conditions, and Alkyl Side Chain Length

The important role of processing conditions, phase separation, and device geometry on open circuit voltage, V-oc, is examined for regioregular poly(3-alkylthiophene) (P3AT) solar cells with hexyl, octyl, dodecyl, and hexadecyl solubilizing side chains. Both bilayer and bulk heterojunction devices were investigated. In bilayer devices with C-60 as the electron acceptor, thermal annealing produces large increases in V-oc for short side chain P3ATs, concurrent with a suppression of the dark forward current and associated reduction in the saturation current density, J(o). Systematic measurements of J(o) versus temperature revealed clear Arrhenius behavior and a significant decrease in the exponential prefactor for J(o) for the annealed devices, while there was:Very little change in the activation energy barrier (phi) for annealed versus unannealed cells. In bulk heterojunctions based on 23ATS and [6,6]-phenyl-C-61-butyric acid methyl ester (PCBM), correlated changes in Jo and V-oc were dominated by dependence of the occupied molecular orbital (HOMO) position on both the side chain length and the degree of mixing with PCBM, which was Manipulated by employing solvent annealing to drive phase separation. Overall, the device data and analysis presented here demonstrate that, in both the bilayer and bulk heterojunction solar cells, the impact of side chain length on J(o) and V-oc is dependent on phase, separation morphology, which can be manipulated by choice of device architecture and processing conditions.