Performance improvement mechanisms of perovskite solar cells by modification of NiO_x hole-selective contacts with self-assembled-monolayers

This study investigates effects of the modification of NiO_x hole-selective contacts (HSCs) with self-assembled monolayers (SAMs), [2-(9H-carbazol-9-yl) ethyl]phosphonic acid (2PACz), on the characteristics of perovskite solar cells, used for perovskite–silicon tandem cells. After the NiO_x layers were fabricated by RF sputtering, the 2PACz modification was performed by the spin-coating of a 2PACz solution and subsequent annealing at 100 °C for 10 min. The 2PACz-modified NiO_x layer improved the solar cells' open-circuit voltage and short-circuit current density. Photoelectron yield spectroscopy measurements imply that the 2PACz monolayers increase the work function of the NiO_x HSCs, thereby enhancing field-effect passivation at the perovskite–HSC interface. Density functional theory calculations and electron spin resonance measurements indicate that an increase in the work function results from a vacuum level shift due to the electric dipole moment of 2PACz molecules and formation of space-charge region at the NiO_x–2PACz interface. The performance improvement is explained as a result of enhanced field-effect passivation caused by the vacuum level shift and thus the increase in the work function. These findings, which clarify SAM modification effects of HSCs on solar-cells’ performance, can contribute to the development of highly efficient and reliable perovskite–silicon tandem solar cells.