Metal phthalocyanines (MPcs) have gained considerable research attention as hole-transport materials (HTMs) in perovskite solar cells (PSCs) because of their superb stability. However, the photovoltaic performance of MPc-based HTMs in PSCs is still lagging behind their small molecule and polymeric counterparts, largely due to their relatively low hole mobility. Here, we report for the first time the application of a copper naphthalocyanine derivative (namely tBu-CuNc) as a hole-transport material (HTM) in perovskite solar cells (PSCs), and systematically study its optoelectronic and photovoltaic property compared with its CuPc analog (tBu-CuPc). Combined experiments disclose that the extension of π-conjugation from Pc to Nc core leads to not only an enhanced hole-carrier mobility associated with a stronger intermolecular interaction, but also an elevated glass transition temperature (T_g) of 252 °C. The resultant PSCs employing tBu-CuNc deliver an excellent power conversion efficiency of 24.03%, which is the record efficiency reported for metal complex-based HTMs in PSCs. More importantly, the encapsulated tBu-CuNc-based devices also show dramatically improved thermal stability than the devices using the well-known Spiro-OMeTAD, with a T₈₀ lifetime for more than 1,000 h under damp-heat stress. This study unfolds a new avenue for developing efficient and stable HTMs in PSCs.

金属酞菁（MPc）作为钙钛矿太阳能电池（PSC）中的空穴传输材料（HTM）因其卓越的稳定性而受到广泛的研究关注。然而，PSC 中基于 MPc 的 HTM 的光伏性能仍然落后于其小分子和聚合物对应物，这主要是由于其空穴迁移率相对较低。在此，我们首次报道了萘酞菁铜衍生物（即tBu-CuNc）作为空穴传输材料（HTM）在钙钛矿太阳能电池（PSC）中的应用，并系统研究了其与CuPc相比的光电和光伏性能类似物（tBu-CuPc）。联合实验表明，π-共轭从 Pc 延伸至 Nc 核不仅导致空穴载流子迁移率增强（与更强的分子间相互作用相关），而且导致玻璃化转变温度 (T _g ) 升高252℃。采用 tBu-CuNc 制成的 PSC 具有 24.03% 的出色功率转换效率，这是 PSC 中基于金属络合物的 HTM 的效率记录。更重要的是，与使用众所周知的 Spiro-OMeTAD 的器件相比，基于 tBu-CuNc 的封装器件还表现出显着提高的热稳定性，在湿热应力下 T ₈₀ 寿命超过 1,000 小时。这项研究为在 PSC 中开发高效稳定的 HTM 开辟了一条新途径。