The Phosphine Oxide Route toward Lead Halide Perovskite Nanocrystals.
The Phosphine Oxide Route toward Lead Halide Perovskite Nanocrystals.
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DOI：
10.1021/jacs.8b08978
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发表时间：
2018-11-07
影响因子：
15
通讯作者：
Manna L
中科院分区：
文献类型：
--
作者：
Almeida G;Ashton OJ;Goldoni L;Maggioni D;Petralanda U;Mishra N;Akkerman QA;Infante I;Snaith HJ;Manna L
我们报道了卤化铅钙钛矿（LHP）纳米晶体的无胺合成，使用三辛基氧化膦（TOPO）代替脂肪族胺，与质子酸（例如，油酸）。在配体与化学前体的配位方面，整体合成方案与LHP薄膜和单晶制备背后的化学有许多相似之处。环境的酸度以及TOPO分子的质子化程度调节了PbX 2前体的反应性，从而调节了纳米晶体的尺寸。另一方面，TOPO分子实际上不存在于我们的纳米晶体的表面，其简单地被一种类型的配体（例如，Cs-油酸酯）。此外，我们的研究表明，Cs-油酸酯是动态绑定到纳米晶体的表面，最佳的表面覆盖率是实现高的光致发光量子产率的关键。我们的方案提供了具有可控尺寸和形状的NC：无论测试的反应条件如何，都只形成立方体，没有血小板污染。我们将这样的形状均匀性归因于在我们的反应环境中不存在脂肪族伯胺，因为已知这些伯胺在某些反应条件下促进具有片/小片形态或层状相的纳米晶体的形成。TOPO路线对于合成用于大规模制造的LHP纳米晶体特别有吸引力，因为所生产的材料的产率接近理论极限：即，合成中使用的几乎所有前体都转化为纳米晶体。
We report an amine-free synthesis of lead halide perovskite (LHP) nanocrystals, using trioctylphosphine oxide (TOPO) instead of aliphatic amines, in combination with a protic acid (e.g., oleic acid). The overall synthesis scheme bears many similarities to the chemistry behind the preparation of LHP thin films and single crystals, in terms of ligand coordination to the chemical precursors. The acidity of the environment and hence the extent of protonation of the TOPO molecules tune the reactivity of the PbX2 precursor, regulating the size of the nanocrystals. On the other hand, TOPO molecules are virtually absent from the surface of our nanocrystals, which are simply passivated by one type of ligand (e.g., Cs-oleate). Furthermore, our studies reveal that Cs-oleate is dynamically bound to the surface of the nanocrystals and that an optimal surface coverage is critical for achieving high photoluminescence quantum yield. Our scheme delivers NCs with a controlled size and shape: only cubes are formed, with no contamination with platelets, regardless of the reaction conditions that were tested. We attribute such a shape homogeneity to the absence of primary aliphatic amines in our reaction environment, since these are known to promote the formation of nanocrystals with sheet/platelet morphologies or layered phases under certain reaction conditions. The TOPO route is particularly appealing with regard to synthesizing LHP nanocrystals for large-scale manufacturing, as the yield in terms of material produced is close to the theoretical limit: i.e., almost all precursors employed in the synthesis are converted into nanocrystals.
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