A highly efficient purification process has been developed to enhance the purity of germanium (Ge) up to 13 N from an initial 4N purity. Hall effect measurements demonstrated that part of the zone refined Ge (ZRGe) bars exhibited p-type conductivity and high purity with a net charge carrier concentration of around 4–9 × 1010 cm−3. Noteworthy observations include a rise in carrier concentration (1011 to 1012 cm−3) at a very low zone refining (ZR) velocity of 1 mm/min, which is attributed to the diffusion of impurities from the container into the Ge melt. The purification efficiency was enhanced by optimizing the ZR velocity to around 4–5 mm/min. Purification was carried out at different process steps using graphite and quartz containers. Subsequent microstructural examinations, conducted in conjunction with wet-chemical etching of the sample unveiled the presence of various grains, grain boundaries (GBs), and low & high-density of dislocation clusters: These observations were made in samples that had undergone zone refining under various gas atmospheres including argon, nitrogen and hydrogen. Electron back scattered diffraction (EBSD) analysis reveals the characteristics of multiple grains and grain boundaries (GBs) of Ge refined in argon and nitrogen atmosphere, including low-angle GBs, high-angle GBs with coincide site lattice (CSL) Σ3, Σ9, Σ27a, and random angle GBs. In contrast, the EBSD results of Ge refined in hydrogen atmosphere shows larger grains with only a few low-angle grain boundaries. The materials refined in argon and nitrogen show a lower carrier lifetime (10–30 μs) owing to the presence of various high angle grains boundaries as well as low purity. Conversely, zone refining in hydrogen resulted in the carrier lifetime of around 50 μs in polycrystalline Ge wafers with larger grains.
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