Inhibiting the irreversible escape of organic cations and iodide species in perovskite films is crucial for the fabrication of efficient and stable perovskite solar cells (PSCs). Here, we develop a reaction-and-assembly approach using monoamine zinc porphyrin (ZnP) to modify methylammonium (MA⁺) lead iodide perovskite film. The amine group in ZnP reacts with MA⁺ and I⁻ ions to yield monoammonium zinc porphyrin (ZnP-H⁺I⁻). The resultant films show no escape of iodide when immersed in ether solutions. Measurements from space-charge limited currents and transient photoluminescence indicate the modified films have reduced density of defects. These results suggest the formed ZnP-H⁺I⁻ is bound on the surface and grain boundary of perovskite film to retard migrations of ions. DFT calculations also show that the energy alignment between ZnP-H⁺ and perovskite facilitates the electron transfer and reduces charge recombination at the perovskite grains. Furthermore, post-treating the ZnP-doped film with ZnP again results in the formation of a one dimension zig-zag coordination polymer on the surface of the perovskite film. The single crystal structure of ZnP shows the polymer layer is formed through the coordination interaction between the Zn(II) metal center and a neighboring monoamine. The polymer facilitates the interfacial charge transfer, and reduces the escape of organic cations and iodide species in perovskite films, thereby keeping the excellent cell performance (20.0%) and further realizing the ion encapsulation. Finally, the modified PSCs retain over 90% of its original efficiency over 2,000 h at 85 °C or AM 1.5 G continuous illumination, or over 6,000 h in 45% humidity without encapsulation. This work affords a new strategy to achieve the efficient ions immobilization and encapsulation by in situ reaction and coordination assembly of mono-amine zinc porphyrin.

抑制钙钛矿薄膜中有机阳离子和碘化物的不可逆逃逸对于制造高效，稳定的钙钛矿太阳能电池（PSC）至关重要。在这里，我们开发了一种使用单胺卟啉锌（ZnP）修饰甲基铵（MA ⁺）碘化钙钛矿型钙钛矿薄膜的反应和组装方法。与MA ZNP反应的胺基⁺和我^-离子，得到单铵锌卟啉（ZNP-H ⁺我^- ）。当浸入乙醚溶液中时，所得薄膜没有碘化物逸出。从空间电荷限制电流和瞬态光致发光的测量结果表明，改性膜的缺陷密度降低。这些结果表明形成的ZnP-H ⁺ I^-结合在钙钛矿薄膜的表面和晶界上，以阻止离子迁移。DFT计算还表明ZnP-H ⁺之间的能量对准钙钛矿有助于电子转移并减少钙钛矿晶粒上的电荷复合。此外，用ZnP对ZnP掺杂的膜进行后处理再次导致在钙钛矿膜的表面上形成一维之字形配位聚合物。ZnP的单晶结构表明聚合物层是通过Zn（II）金属中心与相邻单胺之间的配位相互作用形成的。该聚合物有助于界面电荷转移，并减少钙钛矿薄膜中有机阳离子和碘化物的逸出，从而保持优异的电池性能（20.0％）并进一步实现离子包封。最终，经过修改的PSC在85°C或AM 1.5 G连续照明或超过6小时的2,000小时内，仍能保持其原始效率的90％以上，在45％的湿度下000 h，无需密封。这项工作提供了一种新的策略，可以通过以下方式实现有效的离子固定和包封单胺锌卟啉的原位反应和配位组装