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A guest-free germanium clathrate

机译:无客人包合物的锗

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The challenges associated with synthesizing expanded semiconductor frameworks with cage-like crystal structures continue to be of interest(1,2). Filled low-density germanium and silicon framework structures have distinct properties that address important issues in thermoelectric phonon glass - electron crystals(3), superconductivity(4) and the possibility of Kondo insulators(5). Interest in empty framework structures of silicon and germanium is motivated by their predicted wide optical bandgaps of the same magnitude as quantum dots and porous silicon, making them and their alloys promising materials for silicon-based optoelectronic devices(6,7). Although almost-empty Na1-xSi136 has already been reported(8,9), the synthesis of guest-free germanium clathrate has so far been unsuccessful. Here we report the high-yield synthesis and characteristics of germanium with the empty clathrate-II structure through the oxidation of Ge-9(4-) Zintl anions in ionic liquids under ambient conditions. The approach demonstrates the potential of ionic liquids as media for the reactions of polar intermetallic phases.
机译:与具有笼状晶体结构的扩展半导体框架的合成相关的挑战仍然是关注的(1,2)。填充的低密度锗和硅骨架结构具有独特的特性,可解决热电声子玻璃中的重要问题-电子晶体(3),超导性(4)和近藤绝缘子的可能性(5)。人们对空的硅和锗骨架结构的兴趣是由其与量子点和多孔硅具有相同幅度的预测宽光学带隙引起的,这使得它们和它们的合金有望成为硅基光电器件的材料(6,7)。尽管已经报道了几乎为空的Na1-xSi136(8,9),但迄今为止,无客体的笼形锗锗的合成仍未成功。在这里,我们报告了在环境条件下,通过离子液体中的Ge-9(4-)Zintl阴离子的氧化,具有空包合物-II结构的锗的高产率合成和特征。该方法证明了离子液体作为极性金属间相反应介质的潜力。

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