Gollino Liam, Mercier Nicolas, Pauporté Thierry
Institut de Recherche de Chimie-Paris (IRCP), UMR8247, CNRS, Chimie-ParisTech, PSL Université, 11 rue Pierre et Marie Curie, CEDEX 5, 75231 Paris, France.
MOLTECH-Anjou, UMR 6200, University of Angers, 2 boulevard de Lavoisier, 49045 Angers, France.
Nanomaterials (Basel). 2023 Mar 31;13(7):1245. doi: 10.3390/nano13071245.
Perovskite solar cells have become more and more attractive and competitive. However, their toxicity induced by the presence of lead and their rather low stability hinders their potential and future commercialization. Reducing lead content while improving stability then appears as a major axis of development. In the last years, we have reported a new family of perovskite presenting PbI unit vacancies inside the lattice caused by the insertion of big organic cations that do not respect the Goldschmidt tolerance factor: hydroxyethylammonium HO-(CH)-NH (HEA) and thioethylammonium HS-(CH)-NH (TEA). These perovskites, named d-HPs for lead and halide-deficient perovskites, present a 3D perovskite corner-shared PbI network that can be assimilated to a lead-iodide-deficient MAPbI or FAPbI network. Here, we propose the chemical engineering of both systems for solar cell optimization. For d-MAPbI-HEA, the power conversion efficiency (PCE) reached 11.47% while displaying enhanced stability and reduced lead content of 13% compared to MAPbI. On the other hand, d-FAPbI-TEA delivered a PCE of 8.33% with astounding perovskite film stability compared to classic α-FAPI. The presence of TEA within the lattice impedes α-FAPI degradation into yellow δ-FAPbI by direct degradation into inactive Pb(OH)I, thus dramatically slowing the aging of d-FAPbI-TEA perovskite.
钙钛矿太阳能电池已经变得越来越有吸引力和竞争力。然而，铅的存在所导致的毒性以及其相当低的稳定性阻碍了它们的潜力和未来商业化。在降低铅含量的同时提高稳定性，于是成为了一个主要的发展方向。在过去几年中，我们报道了一类新型的钙钛矿，其晶格内部存在由插入不符合戈尔德施密特容忍因子的大有机阳离子所导致的PbI单元空位：羟乙铵HO-(CH₂)-NH₃⁺（HEA）和硫乙铵HS-(CH₂)-NH₃⁺（TEA）。这些钙钛矿，因铅和卤化物缺陷型钙钛矿而被命名为d-HPs，呈现出一种三维钙钛矿角共享PbI网络，可被视作一种碘化铅缺陷的MAPbI₃或FAPbI₃网络。在此，我们提出对这两种体系进行化学工程改造以优化太阳能电池。对于d-MAPbI₃-HEA，功率转换效率（PCE）达到了11.47%，同时与MAPbI₃相比，稳定性增强且铅含量降低了13%。另一方面，d-FAPbI₃-TEA的PCE为8.33%，与经典的α-FAPbI₃相比，钙钛矿薄膜稳定性惊人。晶格中TEA的存在通过直接降解为无活性的Pb(OH)I来阻止α-FAPbI₃降解为黄色的δ-FAPbI，从而极大地减缓了d-FAPbI₃-TEA钙钛矿的老化。
