Substitution effects of 3d transition metal (TM) impurities on electronic and magnetic properties for Cu12Sb4S13 tetrahedrite are investigated by the combination of low-temperature experiments and first-principles electronic-structure calculations. The electrical resistivity for the cubic phase of Cu12Sb4S13 exhibits metallic behavior due to an electron-deficient character of the compound. Whereas that for 0.5 ≤ x ≤ 2.0 of Cu12−xNixSb4S13 exhibits semiconducting behavior. The substituted Ni for Cu is in the divalent ionic state with a spin magnetic moment and creates impurity bands just above the Fermi level at the top of the valence band. Therefore, the semiconducting behavior of the electrical resistivity is attributed to the thermal excitation of electrons from the valence band to the impurity band. The substitution effect of TM on the electronic structure and the valency of TM for Cu11.0TM1.0Sb4S13 are systematically studied by the calculation. The substituted Mn, Fe, and Co for Cu are found to be in the ionic states with the spin magnetic moments due to the large exchange splitting of the 3d bands between the minority- and majority-spin states.

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