Study of superconducting Ba-Ge-Co compounds
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We prepared samples with starting composition Ba8-Ge 46-x-Cox (x=0, 4 and 6) by direct melting. These Ge-based compounds were characterized by X-ray diffraction and WDS, and we found two superconducting transitions at TC=10 and 4 K in the Co-free sample. Co-doping results in the suppression of TC to 7 K. The superconducting volume fraction also decreases with increasing Co-doping. For Co-doped samples, there is no 4 K superconducting transition. X-ray refinement shows that the compounds are mixtures of several phases. The dominant phase is diamond Ge, and we found no Ge-clathrate phases. Besides diamond Ge, there are also several weak diffractions from an unknown Ba-Ge phase, and most of them were indexed on the basis of a monoclinic unit cell. Diffraction peaks for Ba2Ge, BaGe, BaGe2, BaGe2O5, BaGeO3, Ba3GeO5, -BaGeO3, BaGe2O5, Ba2Ge5O12, -BaGeO3, Ba2GeO4 and BaGe 4O9 were carefully searched for but not seen in the samples. For the Co-doped sample, besides the main diamond Ge phase, there is also a semiconducting phase CoGe2. With increasing Co content, the CoGe2 content increases. The WDS results agree with this result. The main phase composition for the Co-free sample is Ba0.01Ge 99.9. We also discuss the origin of two superconducting transitions in Ge-based compounds. 2004 Elsevier B.V. All rights reserved.