Spontaneous Heterointerface Modulation by a Methylammonium Tetrafluoroborate Additive for a Narrow-Bandgap FAPbI <sub>3</sub> Photoabsorber in Perovskite Solar Cells
Daisuke Kubota, Ryuzi Katoh, Hiroyuki Kanda, Hiroyuki Yaguchi, Takurou N. Murakami, Naoyuki Nishimura
Abstract
Over the past decade, the photovoltaic (PV) performance of perovskite solar cells (PSCs) has been considerably improved with the development of perovskite photoabsorbers. Among these, formamidinium-lead-iodide (FAPbI 3 ) is a promising photoabsorber owing to its narrow bandgap and is mainly used in n–i–p-structured PSCs. The property modulation of FAPbI 3 photoabsorbers while retaining their narrow bandgap is imperative for further development of PSCs. Molecular tetrafluoroborate anion (BF 4 – )-based materials can be used as additives in perovskite layers to prevent bandgap widening, while facilitating perovskite crystal growth; thus, they are suitable for FAPbI 3 photoabsorbers in principle. However, BF 4 – -based additives for narrow-bandgap FAPbI 3 photoabsorbers have not been developed. This is presumably because of the higher temperatures required for FAPbI 3 formation than that for other wide-bandgap perovskites, which likely changes the effects of BF 4 -based additives from those for wide-bandgap perovskites. In this study, we verified the applicability of methylammonium tetrafluoroborate (MABF 4 ) as an additive in narrow-bandgap FAPbI 3 photoabsorbers for improving their PV performance primarily via the spontaneous modulation of the heterointerfaces between FAPbI 3 and carrier-transport materials, rather than the bulk quality improvement of FAPbI 3 perovskite. At the interface of the hole-transport material and FAPbI 3, MABF 4 addition effectively eliminates the surface defects in all FAPbI 3 components, even in the absence of BF 4 – over the heated FAPbI 3 surface, suggesting a defect-suppression mechanism that differs from that observed in conventional ones. Moreover, at the interface of FAPbI 3 and the TiO 2 electron-transport material, the BF 4 -derived species, which likely includes decomposed BF 4 – owing to the high-temperature heating, spontaneously segregates upon deposition, thereby modulating the heterointerface. Furthermore, in addition to the carrier mobility ratio in FAPbI 3 (e –:h + ≈ 7:3), a time-resolved microwave conductivity measurement revealed that MABF 4 addition eliminates carrier traps at the heterointerfaces. Our findings provide insights into promising FAPbI 3 -based PSCs, offering a valuable tool for their further development.