Fluoride Chemistry in Tin Halide Perovskites,Angewandte Chemie International Edition

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Fluoride Chemistry in Tin Halide Perovskites
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2021-07-06 , DOI: 10.1002/anie.202107599
Jorge Pascual ₁ , Marion Flatken ₁ , Roberto Félix ₁ , Guixiang Li ₁ , Silver-Hamill Turren-Cruz ₂ , Mahmoud H Aldamasy _{1,

3} , Claudia Hartmann ₁ , Meng Li ₁ , Diego Di Girolamo ₄ , Giuseppe Nasti ₄ , Elif Hüsam ₁ , Regan G Wilks ₁ , André Dallmann ₅ , Marcus Bär _{1,

6,

7} , Armin Hoell ₁ , Antonio Abate _{1,

4}

Affiliation

Tin is the frontrunner for substituting toxic lead in perovskite solar cells. However, tin suffers the detrimental oxidation of Sn^II to Sn^IV. Most of reported strategies employ SnF₂ in the perovskite precursor solution to prevent Sn^IV formation. Nevertheless, the working mechanism of this additive remains debated. To further elucidate it, we investigate the fluoride chemistry in tin halide perovskites by complementary analytical tools. NMR analysis of the precursor solution discloses a strong preferential affinity of fluoride anions for Sn^IV over Sn^II, selectively complexing it as SnF₄. Hard X-ray photoelectron spectroscopy on films shows the lower tendency of SnF₄ than SnI₄ to get included in the perovskite structure, hence preventing the inclusion of Sn^IV in the film. Finally, small-angle X-ray scattering reveals the strong influence of fluoride on the colloidal chemistry of precursor dispersions, directly affecting perovskite crystallization.

中文翻译：

卤化锡钙钛矿中的氟化物化学

锡是替代钙钛矿太阳能电池中有毒铅的领跑者。然而，锡会遭受 Sn ^II到 Sn ^IV的有害氧化。大多数报道的策略在钙钛矿前体溶液中使用 SnF ₂以防止形成Sn ^IV。尽管如此，这种添加剂的工作机制仍有争议。为了进一步阐明它，我们通过补充分析工具研究了卤化锡钙钛矿中的氟化物化学。前体溶液的 NMR 分析表明氟阴离子对 Sn ^{IV 的}亲和性强于 Sn ^II，选择性地将其络合为 SnF _{4 。}. 薄膜上的硬 X 射线光电子能谱显示 SnF ₄比 SnI _{4 更}容易包含在钙钛矿结构中，因此防止了薄膜中包含 Sn ^IV。最后，小角度 X 射线散射揭示了氟化物对前驱体分散体胶体化学的强烈影响，直接影响钙钛矿结晶。

更新日期：2021-09-14

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