The adoption of perovskite solar cells (PSCs) requires improved resistance to high temperatures and temperature variations. Hole-selective self-assembled monolayers (SAMs) have enabled progress in the performance of inverted PSCs, yet they may compromise temperature stability owing to desorption and weak interfacial contact. Here we developed a self-assembled bilayer by covalently interconnecting a phosphonic acid SAM with a triphenylamine upper layer. This polymerized network, formed through Friedel–Crafts alkylation, resisted thermal degradation up to 100 °C for 200 h. Meanwhile, the face-on-oriented upper layer exhibited adhesive contact with perovskites, leading to a 1.7-fold improvement in adhesion energy compared with the SAM–perovskite interface. We reported power conversion efficiencies exceeding 26% for inverted PSCs. The champion devices demonstrated less than 4% and 3% efficiency loss after 2,000 h damp heat exposure (85 °C and 85% relative humidity) and over 1,200 thermal cycles between −40 °C and 85 °C, respectively, meeting the temperature stability criteria outlined in the International Electrotechnical Commission 61215:2021 standards.

钙钛矿太阳能电池 （PSC） 的采用需要提高对高温和温度变化的抵抗力。空穴选择性自组装单层 （SAM） 使倒置 PSC 的性能取得了进展，但由于解吸和弱界面接触，它们可能会损害温度稳定性。在这里，我们通过将膦酸 SAM 与三苯胺上层共价互连来开发自组装双层。这种通过 Friedel-Crafts 烷基化形成的聚合网络可在 100 °C 的温度下抵抗 200 小时的热降解。同时，面朝向上的上层表现出与钙钛矿的粘合接触，导致与 SAM-钙钛矿界面相比，粘附能提高了 1.7 倍。我们报告了倒置 PSC 的功率转换效率超过 26%。冠军器件在湿热暴露 2,000 小时（85 °C 和 85% 相对湿度）和 −40 °C 和 85 °C 之间超过 1,200 次热循环后，效率损失分别小于 4% 和 3%，符合国际电工委员会 61215：2021 标准中概述的温度稳定性标准。