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The Cu-III-Se2 (III= Al, Ga, In) ternary chalcopyrite family have been object of a great quantity of work in the last years, because they form an wide group of semiconductor materials with diverse optical and electrical properties1. These materials crystallize with tetragonal symmetry in the space group I4 2d (N°122), and the addition of a Fe-Se binary compound produces alloys of the type (Cu-IIISe2)1-x (FeSe)x 2. Some previous results on the formation, structural characterization, thermal and magnetic properties on these alloys with compositions Cu-Fe-III-Se3 (x = 1⁄2), Cu-Fe2-III-Se4 (x = 2⁄3) and Cu2-Fe-III-Se5 (x = 1⁄3) have been reported3-15. All these phases fulfill the rules of formation of adamantane compounds2 and belong to the normal semiconductor compound families of the third, fourth and fifth-order derivatives of the II-VI binary semiconductors, respectively16. Adamantane compounds are binary, ternary or quaternary normal tetrahedral structure compounds which are closely related to either cubic or hexagonal diamond. The first crystal structure characterization of one I--VI3 semiconductor member, CuFeInSe3, indicated a degradation of symmetry from the chalcopyrite structure I42d to a related structure P42c6. In this work, we report a detailed synthesis and structural analysis of three new members of this family; CuMnAlSe3, CuMnGaSe3 and CuMnInSe3, which was performed using X-ray powder diffraction by means of the Rietveld method.

Synthesis and Crystal Structure of Three New Quaternary Compounds in the system Cu-Mn-III-Se3 (III = Al, Ga, In)