具有N杂环阳离子的聚合碘代铋酸盐{[Bi 3 I 10 ]}和{[BiI 4 ]}：电子设备中很有希望的钙钛矿型光敏材料<a href="#fn1" title="可用的电子补充信息（ESI）：XRD实验的详细信息和1–6的选定键长，漫反射光谱和PXRD图，1、3和5薄膜的XRD数据，GIWAXS分析数据，化合物3的电特性。 CCDC 1566485–1566490。有关CIF或其他电子格式的ESI和晶体学数据，请参见DOI：10.1039 / c8ta09204d">†</a>,Journal of Materials Chemistry A

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具有N杂环阳离子的聚合碘代铋酸盐{[Bi ₃ I ₁₀ ]}和{[BiI ₄ ]}：电子设备中很有希望的钙钛矿型光敏材料 †
Journal of Materials Chemistry A ( IF 10.7 ) Pub Date : 2018-12-19 00:00:00 , DOI: 10.1039/c8ta09204d
Andrey N. Usoltsev _{1,

2,

3} , Moneim Elshobaki _{3,

4,

5,

6,

7} , Sergey A. Adonin _{1,

2,

3,

4,

5} , Lyubov A. Frolova _{3,

4,

5,

8,

9} , Tatiyana Derzhavskaya _{3,

8,

9} , Pavel A. Abramov _{1,

2,

2,

3,

10} , Denis V. Anokhin _{3,

8,

9,

11,

12} , Ilya V. Korolkov _{1,

2,

2,

3,

10} , Sergey Yu. Luchkin _{3,

4,

5} , Nadezhda N. Dremova _{3,

8,

9} , Keith J. Stevenson _{3,

4,

5} , Maxim N. Sokolov _{1,

2,

2,

3,

10} , Vladimir P. Fedin _{1,

2,

2,

3,

10} , Pavel A. Troshin _{3,

4,

5,

8,

9}

Affiliation

通过筛选BiI ₃和不同N-烷基化杂环（吡啶，喹啉，异喹啉）的碘化物盐之间的反应，可以制备和表征六个新颖的碘代铋酸盐配合物，其中包括显示出前所未有的{[Bi ₃ I ₁₀ ]的两种化合物}聚合物部分。已经显示碘代铋酸盐的化学组成和结构显着影响其光学和电子性能。特别是，{[Bi ₃ I ₁₀ ]}碘铋酸盐显示出最窄的带隙（E _g），而掺入{[BiI ₄ ]}聚合物骨架的化合物的E宽0.2-0.3 eV。_G。GIXRD分析表明，在薄膜中研究的所有三种碘代铋酸盐都主要显示一维聚合物Bi–I骨架的水平（平行于基底）取向。由于导电的Bi-I链被绝缘的大体积有机阳离子分隔开，因此这种布置会阻止电荷在垂直方向（垂直于基底）的传输。结果，基于新型碘铋酸盐的标准平面结太阳能电池显示出低功率转换效率，仅接近0.12％。但是，碘铋酸盐在平面内具有很强的光电导性，因此可以制造出高效的平面光电探测器，这为这种奇特的材料系列的实际应用铺平了道路。最重要的是，

"点击查看英文标题和摘要"

Polymeric iodobismuthates {[Bi3I10]} and {[BiI4]} with N-heterocyclic cations: promising perovskite-like photoactive materials for electronic devices†

A screening of the reactions between BiI₃ and iodide salts of different N-alkylated heterocycles (pyridine, quinoline, isoquinoline) resulted in the preparation and structural characterization of six novel iodobismuthate complexes, including two compounds exhibiting an unprecedented {[Bi₃I₁₀]} polymeric moiety. It has been shown that the chemical composition and structure of the iodobismuthates significantly affect their optical and electronic properties. In particular, the narrowest band gaps (E_g) were revealed by {[Bi₃I₁₀]} iodobismuthates, while the compounds incorporating {[BiI₄]} polymeric frameworks showed 0.2–0.3 eV wider E_g. GIXRD analysis evidenced that all three iodobismuthates investigated in thin films show mainly the horizontal (parallel to the substrate) orientation of the 1D polymeric Bi–I frameworks. Such arrangement blocks the charge transport in vertical direction (orthogonal to the substrate) since the conductive Bi–I chains are separated with insulating bulky organic cations. As a consequence, standard planar junction solar cells based on new iodobismuthates revealed low power conversion efficiencies approaching 0.12% only. However, strong in-plane photoconductivity observed for iodobismuthates enabled the fabrication of efficient planar photodetectors, which paves a way to the practical use of this exotic family of materials. Most importantly, the presented systematic study revealed the most general guidelines for future rational design of perovskite-like materials for emerging generation of environment-friendly perovskite photovoltaics emphasizing the importance of the isotropic charge transport in the films of 3D materials and achieving proper orientation of 1D and 2D frameworks with respect to the charge collecting electrodes in anisotropic low dimensional systems.

更新日期：2018-12-19

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