Influence of Halides on the Interactions of Ammonium Acids with Metal Halide Perovskites
Influence of Halides on the Interactions of Ammonium Acids with Metal Halide Perovskites
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DOI：
10.1021/acsami.3c01432
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发表时间：
2023-05-10
影响因子：
9.5
通讯作者：
Printz, Adam D.
中科院分区：
文献类型：
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作者：
Li, Yanan;Lohr, Patrick J.;Printz, Adam D.
增材工程是通过调节结晶动力学和钝化表面缺陷来改善金属卤化物钙钛矿的性能和稳定性的常用策略。然而，大部分工作缺乏必要的系统方法来了解添加剂的功能和分子结构如何影响钙钛矿的性能和稳定性。本文描述了将低浓度的5-氨基戊酸（5-AVA）及其铵酸衍生物、5-碘化戊酸铵（5-AVAI）和5-氯代戊酸铵（5-AVACl）包含到用于甲基铵三碘化铅（MAPbI 3）钙钛矿的前体油墨中，并强调了卤化物在影响添加剂与钙钛矿的相互作用和膜性质方面的重要作用。的膜质量，通过X射线衍射（XRD）和光致发光（PL）分光光度法测定，示出与所有添加剂的列入，但增加退火时间从5到30分钟是必要的。我们观察到的晶粒尺寸的增加和膜的粗糙度与5-AVAI和5-AVACl与扫描电子显微镜（SEM）和原子力显微镜（AFM）的结合减少。重要的是，X射线光电子能谱（XPS）测量和密度泛函理论（DFT）计算表明，5-AVAI和5-AVACl优先通过铵官能团与MAPbI 3表面相互作用，而5-AVA将与氨基或羧酸官能团相互作用。电荷定位分析显示了令人惊讶的结果，即HCl在真空中从5-AVACl解离，导致铵酸分解为5-AVA。我们表明，器件的可重复性随着所有添加剂的加入而提高，并且5-AVACl将器件的功率转换效率从17.61 +/-1.07%增加到18.07 +/-0.42%。最后，我们显示了暴露于50%相对湿度的未封装器件的稳定性改善，其中包含5-AVAI和5AVACl的器件表现出最大的改善。
Additive engineering is a common strategy to improve the performance and stability of metal halide perovskite through the modulation of crystallization kinetics and passivation of surface defects. However, much of this work has lacked a systematic approach necessary to understand how the functionality and molecular structure of the additives influence perovskite performance and stability. This paper describes the inclusion of low concentrations of 5-aminovaleric acid (5-AVA) and its ammonium acid derivatives, 5-ammoniumvaleric acid iodide (5-AVAI) and 5ammoniumvaleric acid chloride (5-AVACl), into the precursor inks for methylammonium lead triiodide (MAPbI3) perovskite and highlights the important role of halides in affecting the interactions of additives with perovskite and film properties. The film quality, as determined by X-ray diffraction (XRD) and photoluminescence (PL) spectrophotometry, is shown to improve with the inclusion of all additives, but an increase in annealing time from 5 to 30 min is necessary. We observe an increase in grain size and a decrease in film roughness with the incorporation of 5-AVAI and 5-AVACl with scanning electron microscopy (SEM) and atomic force microscopy (AFM). Critically, X-ray photoelectron spectroscopy (XPS) measurements and density functional theory (DFT) calculations show that 5-AVAI and 5-AVACl preferentially interact with MAPbI3 surfaces via the ammonium functional group, while 5-AVA will interact with either amino or carboxylic acid functional groups. Charge localization analysis shows the surprising result that HCl dissociates from 5-AVACl in vacuum, resulting in the decomposition of the ammonium acid to 5-AVA. We show that device repeatability is improved with the inclusion of all additives and that 5-AVACl increases the power conversion efficiency of devices from 17.61 +/- 1.07 to 18.07 +/- 0.42%. Finally, we show stability improvements for unencapsulated devices exposed to 50% relative humidity, with devices incorporating 5-AVAI and 5AVACl exhibiting the greatest improvements.