Guvenc C Meric, Toso Stefano, Ivanov Yurii P, Saleh Gabriele, Balci Sinan, Divitini Giorgio, Manna Liberato
Department of Materials Science and Engineering, İzmir Institute of Technology, 35433 Urla, İzmir, Turkey.
Nanochemistry, Istituto Italiano di Tecnologia, Via Morego 30, Genova 16163, Italy.
ACS Nano. 2025 Jan 14;19(1):1557-1565. doi: 10.1021/acsnano.4c14536. Epub 2024 Dec 26.
We report the synthesis of ethylammonium lead iodide (EAPbI) colloidal nanocrystals as another member of the lead halide perovskites family. The insertion of an unusually large -cation (274 pm in diameter) in the perovskite structure, hitherto considered unlikely due to the unfavorable Goldschmidt tolerance factor, results in a significantly larger lattice parameter compared to the Cs-, methylammonium- and formamidinium-based lead halide perovskite homologues. As a consequence, EAPbI nanocrystals are highly unstable, evolving to a nonperovskite δ-EAPbI polymorph within 1 day. Also, EAPbI nanocrystals are very sensitive to electron irradiation and quickly degrade to PbI upon exposure to the electron beam, following a mechanism similar to that of other hybrid lead iodide perovskites (although degradation can be reduced by partially replacing the EA ions with Cs ions). Interestingly, in some cases during this degradation the formation of an epitaxial interface between (EACs)PbI and PbI is observed. The photoluminescence emission of the EAPbI perovskite nanocrystals, albeit being characterized by a low quantum yield (∼1%), can be tuned in the 664-690 nm range by regulating their size during the synthesis. The emission efficiency can be improved upon partial alloying at the A site with Cs or formamidinium cations. Furthermore, the morphology of the EAPbI nanocrystals can be chosen to be either nanocube or nanoplatelet, depending on the synthesis conditions.
我们报道了碘化乙铵铅(EAPbI)胶体纳米晶体的合成,它是卤化铅钙钛矿家族的另一个成员。在钙钛矿结构中插入一个异常大的阳离子(直径274 pm),由于不利的戈尔德施密特容忍因子,迄今为止被认为不太可能,这导致与基于铯、甲铵和甲脒的卤化铅钙钛矿同系物相比,晶格参数显著更大。因此,EAPbI纳米晶体非常不稳定,在1天内就会演变成非钙钛矿的δ-EAPbI多晶型物。此外,EAPbI纳米晶体对电子辐照非常敏感,在电子束照射下会迅速降解为PbI,其降解机制与其他混合碘化铅钙钛矿类似(尽管用铯离子部分取代EA离子可以减少降解)。有趣的是,在这种降解过程中的某些情况下,会观察到(EACs)PbI和PbI之间形成外延界面。EAPbI钙钛矿纳米晶体的光致发光发射,尽管量子产率较低(约1%),但在合成过程中通过调节其尺寸可以在664 - 690 nm范围内进行调谐。在A位点与铯或甲脒阳离子进行部分合金化时,发射效率可以提高。此外,根据合成条件,EAPbI纳米晶体的形态可以选择为纳米立方体或纳米片。