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Mesostructured germanium with cubic pore symmetry


Regular mesoporous oxide materials have been widely studied1,2,3,4,5,6,7,8 and have a range of potential applications, such as catalysis, absorption and separation. They are not generally considered for their optical and electronic properties. Elemental semiconductors with nanopores running through them represent a different form of framework material with physical characteristics contrasting with those of the more conventional bulk, thin film and nanocrystalline forms1. Here we describe cubic mesostructured germanium, MSU-Ge-1, with gyroidal channels containing surfactant molecules, separated by amorphous walls that lie on the gyroid (G) minimal surface as in the mesoporous silica MCM-48 (ref. 2). Although Ge is a high-melting, covalent semiconductor that is difficult to prepare from solution polymerization, we succeeded in assembling a continuous Ge network using a suitable precursor for Ge4- atoms. Our results indicate that elemental semiconductors from group 14 of the periodic table can be made to adopt mesostructured forms such as MSU-Ge-1, which features two three-dimensional labyrinthine tunnels obeying space group symmetry and separated by a continuous germanium minimal surface that is otherwise amorphous. A consequence of this new structure for germanium, which has walls only one nanometre thick, is a wider electronic energy bandgap (1.4 eV versus 0.66 eV) than has crystalline or amorphous Ge. Controlled oxidation of MSU-Ge-1 creates a range of germanium suboxides with continuously varying Ge:O ratio and a smoothly increasing energy gap.

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Figure 1: 1 X-ray scattering of mesostructured MSU-Ge-1, bicontinuous gyroid minimal surface and energy-dispersive X-ray spectrum.
Figure 2: TEM images of mesoporous germanium semiconductor MSU-Ge-1.
Figure 3: PDF analysis, FTIR and optical absorption spectra and TGA data.

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We thank C. Malliakas for his help with the PDF data processing. We thank the National Science Foundation for financial support.

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Correspondence to Mercouri G. Kanatzidis.

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Supplementary information

Supplementary Notes

This file contains Supplementary Figures and Legends 1–2 and Supplementary Discussions about the chemical environment of Ge atoms of MSU-Ge-1 semiconductor by X-ray photoelectron spectroscopy (XPS) experiments; including Supplementary Figure 3. (DOC 1077 kb)

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Armatas, G., Kanatzidis, M. Mesostructured germanium with cubic pore symmetry. Nature 441, 1122–1125 (2006).

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