Mechanism of Light-Soaking Effect in Inverted Polymer Solar Cells with Open-Circuit Voltage Increase

[Image: see text] In this study, we present novel insights into the light-soaking effect of inverted polymer solar cells (PSCs), where the open-circuit voltage (V(oc)) of the cells improves over time under light irradiation. The effect was investigated by electron spin resonance (ESR) studies of bare indium tin oxide (ITO) and piperazine derivative-modified ITO/regioregular poly(3-hexylthiophene) (P3HT):[6,6]-phenyl C(61) butyric acid methyl ester (PCBM) substrates. These results were combined with alternating current impedance spectroscopy (IS) measurements of inverted PSCs based on the above substrates. In ESR experiments with the substrates under white light irradiation, with a UV light component, many P3HT(•+) radical cations were observed in the bare-ITO/P3HT:PCBM substrate. The number of radical cations was considerably suppressed in the ITO/P3HT:PCBM substrates with ITO modified by piperazine derivatives. This is because adsorbed oxygen molecules on the ITO acted as acceptor dopants for photoexcited P3HT, and the amount of adsorbed oxygen was decreased by modifying the ITO with piperazine derivatives. In IS measurements of the inverted PSCs under white light irradiation, a decrease in the electric capacitance (CPE2) of an electric double layer formed at the ITO/P3HT:PCBM interface was observed. A strong correlation was observed between the decrease of CPE2 and the increase of V(oc). From these results, the light-soaking behavior was attributed to the removal of an electron injection barrier formed between ITO and PCBM, under white light irradiation.