Suppression of antiferromagnetic interactions through Cu vacancies in Mn-substituted CuInSe2 chalcopyrites

Stoichiometric and Cu-poor Cu(0.95-x)Mn(0.05)InSe(2) (x = 0-0.20) compounds were synthesized by high-temperature, solid-state reactions. The presence of copper vacancies is revealed by Rietveld refinements of combined neutron and x-ray powder diffraction data. The antiferromagnetic interaction is depressed by the copper deficiency, which may be explained as the competition between the antiferromagnetic Mn-Se-Mn superexchange interaction and the hole-mediated ferromagnetic exchange induced by the copper vacancy. The introduction of copper vacancies is proposed to be a viable route to impart carrier-mediated ferromagnetic exchange in the chalcopyrite-based dilute magnetic semiconductors.