Spin-dependent recombination affected by post-annealing of organic photovoltaic devices

Abstract

Organic photovoltaic devices (OPVs) are attracting attention because of recent rapid enhancement of their power conversion efficiency. For further improvement, optimization of fabrication processes is one useful path to a solution. During OPV fabrication, particularly of the bulk heterojunction active layer, annealing treatments contribute to the device performance. Many studies have examined annealing-related properties. However, further research must clarify how paramagnetic species in the devices play their roles by annealing. Using well-known OPVs, we investigated the relation between spin-dependent recombination (SDR) current and the paramagnetic species, which vary the numbers by post-annealing with active layers consisting of poly(3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM). A simultaneous detection method of electron spin resonance (ESR) and electrically detected magnetic resonance (EDMR), which we originally developed, was applied to OPVs for the first time ever reported. Results show that PC61BM anion radicals generated by post-annealing of P3HT:PC61BM OPVs with a lithium fluoride (LiF)/aluminum (Al) electrode do not contribute to the SDR current at the interface and that P3HT cation radicals enhance the SDR current. By contrast, devices with an Al electrode without LiF decrease the total SDR current, although the quantities of cation radical molecules do not vary. This finding suggests that changes of the hole blocking layer in the devices caused by the annealing treatment affect the size of capture cross sections of P3HT cation radicals. Our new method of quantitative observation of the EDMR changes through the ESR signals is expected to be useful for investigating the capture cross sections in OPVs.