Department Chemie, Technische Universität München, Lichtenbergstraße 4, 85747, Garching, Germany.
University of Munich (LMU) and Center for NanoScience (CeNS), Butenandtstrasse 5-13 (Haus E), 81377, München, Germany.
Angew Chem Int Ed Engl. 2016 Feb 12;55(7):2441-5. doi: 10.1002/anie.201508246. Epub 2015 Dec 3.
Ge9 Zintl clusters are used as soluble germanium source for a bottom-up fabrication of Ge nanomorphologies such as inverse opal structures with tunable composition. The method is based on the assembly and oxidation of Ge9 clusters in a template mold using SiCl4 , GeCl4 , and PCl3 leading to Si and P-containing Ge phases as shown by X-ray diffraction, Raman spectroscopy, and energy-dispersive X-ray analysis. Ge9 clusters are retained using ethylenediamine (en) as a transfer medium to a mold after removal of the solvent if water is thoroughly excluded, but are oxidized to amorphous Ge in presence of water traces. (1)H NMR spectroscopy reveals the oxidative deprotonation of en by Ge9. Subsequent annealing leads to crystalline Ge. As an example for wet-chemical synthesis of complex Ge nanomorphologies, we describe the fabrication of undoped and P-doped inverse opal-structured Ge films with a rather low oxygen contents. The morphology of the films with regular volume porosity is characterized by SEM, TEM, and grazing incidence small-angle X-ray scattering.
Ge9 富勒烯簇被用作可溶性锗源，用于自下而上制造锗纳米形态，如具有可调组成的反蛋白石结构。该方法基于使用 SiCl4、GeCl4 和 PCl3 在模板模具中组装和氧化 Ge9 簇，导致形成 Si 和 P 含量的 Ge 相，如 X 射线衍射、拉曼光谱和能量色散 X 射线分析所示。如果彻底排除水，则可以使用乙二胺 (en) 将 Ge9 簇作为转移介质保留在模具中，而在存在水痕的情况下，它们会被氧化为非晶态 Ge。(1)H NMR 光谱揭示了 Ge9 的氧化去质子化作用。随后的退火导致结晶 Ge 的形成。作为复杂锗纳米形态湿化学合成的一个例子，我们描述了具有低氧含量的未掺杂和 P 掺杂反蛋白石结构 Ge 薄膜的制备。具有规则体积孔隙率的薄膜的形态通过 SEM、TEM 和掠入射小角 X 射线散射进行表征。
