Synthesis of semiconducting thin films with nanometer-scale periodicity by solution-phase coassembly of zintl clusters with surfactants.
Synthesis of semiconducting thin films with nanometer-scale periodicity by solution-phase coassembly of zintl clusters with surfactants.
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通过 zintl 簇与表面活性剂的溶液相共组装合成具有纳米级周期性的半导体薄膜。
DOI：
10.1002/anie.200501361
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发表时间：
2005
影响因子：
--
通讯作者：
S. Tolbert
中科院分区：
文献类型：
--
作者：
A. Riley;Scott D. Korlann;E. Richman;S. Tolbert
无机前驱体与有机表面活性剂或聚合物结构导向剂的协同自组装导致了许多氧化物基纳米结构复合材料的合成，这些材料显示出周期性。氧化物粉末，整料，和薄膜具有不同的组成范围（TiO 2，ZrO 2，Nb 2 O 5，SnO 2，MnxOy，Al 2 O 3，和其他）已经制备的工作后，表面模板化的二氧化硅（MCM-41型材料）。[1-17]虽然这些材料的粉末形式有许多建议的用途，包括催化和尺寸选择性分离，但薄膜形式显着扩大了它们的潜力。[18-23]薄膜形态有几个应用，其中大块材料是没有用的，包括低k电介质涂层，光波导和膜。[24-27]尽管这些周期性表面模板化薄膜有许多令人兴奋的潜在应用，但对氧化物基材料仍然存在重大限制。这些限制中最重要的是，大多数氧化物是绝缘体或宽带隙半导体，这限制了它们在基于导电性的应用中的使用，因为它们的高固有电阻和低载流子密度。基于非氧化物前体的自组装无机/有机复合材料的发展导致了各种具有纳米周期性的半导体复合材料的合成。[28-36]这些复合材料使用高度还原的可溶性金属簇或Zintl簇作为无机构建块。Zintl簇可以在过渡金属交联剂的帮助下在溶液中与有机结构导向剂自组装。所得材料是一种高度周期性的无机合金，其有序性类似于液晶系统。这些材料最初被设计为二氧化硅和其他氧化物复合物的类似物，在光电应用中具有优于大多数氧化物系统的优势，因为它们的带隙范围可以在0.6和3.4 eV之间调节，这取决于它们的化学组成。[28-37]尽管如此，
The cooperative self-assembly of inorganic precursors with organic surfactants or polymeric structure-directing agents has led to the synthesis of many oxide-based, nanostructured composite materials that show periodicity. Oxide powders, monoliths, and thin films with a diverse range of compositions (TiO2, ZrO2, Nb2O5, SnO2, MnxOy, Al2O3, and others) have been prepared following the work on surfactant-templated silicas (MCM-41-type materials).[1–17] Although the powdered forms of these materials have many proposed uses, including catalysis and size-selective separation, the thin-film forms have significantly expanded their potential.[18–23] The thin-film morphology has several applications for which bulk materials are not useful, including low-k dielectric coatings, optical waveguides, and membranes.[24–27] Despite the many exciting potential applications of these periodic surfactant-templated thin films, there are still significant limitations to oxide-based materials. The most significant of these limitations is that most oxides are insulators, or wide-band-gap semiconductors, which limits their use in applications based on electrical conductivity because of their high intrinsic resistance and low carrier densities.The development of self-assembled inorganic/organic composites based on non-oxide precursors has led to the synthesis of a variety of semiconducting composites with nanoscale periodicity.[28–36] These composite materials use highly reduced soluble metal clusters, or Zintl clusters, as an inorganic building block. The Zintl clusters can self-assemble with organic structure-directing agents in solution with the help of transition-metal cross-linkers. The resulting material is a highly periodic inorganic alloy with ordering similar to liquid-crystalline systems. These materials, which were initially designed to be analogues of silica and other oxide composites, have an advantage over most oxide systems for optoelectronic applications in that their range of band gaps can be tuned between 0.6 and 3.4 eV depending on their chemical composition.[28–37] Unfortunately, although compo-