Three kinds of charged star‐shaped conjugated macroelectrolytes, named as PhNBr, TPANBr, and TrNBr, are synthesized as electron‐collecting interlayers for inverted polymer solar cells (i‐PSCs). Based on these well‐defined structured interlayer materials, the light soaking (LS) effect observed in i‐PSCs was studied systematically and accurately. The general character of the LS effect is further verified by studying additional i‐PSC devices functionalized with other common interlayers. The key‐role of UV photons was confirmed by electrochemical impedance spectroscopy and electron‐only devices. In addition, the ultraviolet photoelectron spectroscopy measurements indicate that the work function of the indium tin oxide (ITO)/interlayer cathode is significantly reduced after UV treatment. In these i‐PSC devices the LS effect originates from the adsorbed oxygen on the ITO substrates when oxygen plasma is used; however, even a small amount of oxygen from the ambient is also enough for triggering the LS effect, albeit with a weaker intensity. Our results suggest that the effect of adsorbed oxygen on ITO needs to be considered with attention while preparing i‐PSCs. This is an important finding that can aid the large‐scale manufacturing of organic solar cells via printing technologies, which do not always ensure the full protection of the device electrode substrates from oxygen.

A novel fulleropyrrolidine derivative, named as FPNOH, was designed, synthesized and utilized as an efficient electron-collecting (EC) layer for inverted organic solar cells (i-OSCs). The grafted diethanolamino-polar moieties can not only trigger its function as an EC interlayer, but also induce orthogonal solubility that guarantees subsequent multi-layer processing without interfacial mixing. A higher power conversion efficiency (PCE) value of 8.34% was achieved for i-OSC devices with ITO/FPNOH EC electrode, compared to that of the sol-gel ZnO based reference devices with an optimized PCE value of 7.92%. High efficiency exceeding 7.7% was still achieved even for the devices with a relatively thick PFNOH film (16.9 nm). It is worthwhile to mention that this kind of material exhibits less thickness dependent performance, in contrast to widely utilized p-type conjugated polyelectrolytes (CPEs) as well as the non-conjugated polyelectrolytes (NCPEs). Further investigation on illuminating intensity dependent parameters revealed the role of FPNOH in reducing interfacial traps-induced recombination at ITO/active layer interface.