There has been interest in the past years in the visible luminescence properties of germanium nanocrystals. Most of the previous works refer to Ge nanocrystals embedded in an oxide matrix. In this work nanocrystalline germanium has been prepared by high-energy ball milling of Ge single crystals and Ge powder. The structure of the milled samples has been assessed by x-ray diffraction (XRD) and transmission electron microscopy (TEM) while the luminescence has been investigated by cathodoluminescence (CL) in the scanning electron microscope (SEM). The samples consist of a powder of particles with sizes of hundreds of nanometres, normally aggregated to form larger panicles. TEM reveals that the particles consist of nanocrystals with a wide range of sizes including crystallites of some nanometres. Milled Ge shows two CL bands at about 2.4-2.5 eV and 3.1 eV, respectively. Both emissions appear to be related to the presence of Ge nanocrystals. The CL of untreated and milled GeO2 powder has been also investigated for comparison.

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