Monolithic textured perovskite/silicon tandem solar cells (TSCs) are expected to achieve maximum light capture at the lowest cost, potentially exhibiting the best power conversion efficiency. However, it is challenging to fabricate high-quality perovskite films and preferred crystal orientation on commercially textured silicon substrates with micrometer-size pyramids. Here, we introduced a bulky organic molecule (4-fluorobenzylamine hydroiodide (F-PMAI)) as a perovskite additive. It is found that F-PMAI can retard the crystallization process of perovskite film through hydrogen bond interaction between F⁻ and FA⁺ and reduce (111) facet surface energy due to enhanced adsorption energy of F-PMAI on the (111) facet. Besides, the bulky molecular is extruded to the bottom and top of perovskite film after crystal growth, which can passivate interface defects through strong interaction between F-PMA⁺ and undercoordinated Pb²⁺/I⁻. As a result, the additive facilitates the formation of large perovskite grains and (111) preferred orientation with a reduced trap-state density, thereby promoting charge carrier transportation, and enhancing device performance and stability. The perovskite/silicon TSCs achieved a champion efficiency of 30.05% based on a silicon thin film tunneling junction. In addition, the devices exhibit excellent long-term thermal and light stability without encapsulation. This work provides an effective strategy for achieving efficient and stable TSCs.

单片织构钙钛矿/硅串联太阳能电池（TSC）有望以最低的成本实现最大的光捕获，从而有可能表现出最佳的功率转换效率。然而，在具有微米尺寸金字塔的商业织构硅基板上制造高质量的钙钛矿薄膜和优选的晶体取向具有挑战性。在这里，我们引入了一种大体积有机分子（4-氟苄胺氢碘化物（F-PMAI））作为钙钛矿添加剂。研究发现，F-PMAI可以通过F ^-和FA ⁺之间的氢键相互作用延迟钙钛矿薄膜的结晶过程，并由于F-PMAI在（111）面上的吸附能增强而降低（111）面表面能。此外，晶体生长后，大分子被挤出到钙钛矿薄膜的底部和顶部，通过F-PMA ⁺与欠配位的Pb ²⁺ /I ^-之间的强相互作用可以钝化界面缺陷。因此，该添加剂有利于形成大的钙钛矿晶粒和（111）择优取向，并降低陷阱态密度，从而促进电荷载流子传输，并增强器件性能和稳定性。基于硅薄膜隧道结的钙钛矿/硅 TSC 实现了 30.05% 的冠军效率。此外，该器件无需封装即可表现出优异的长期热稳定性和光稳定性。这项工作为实现高效稳定的 TSC 提供了有效的策略。