The origin of magnetism in wide-gap semiconductors doped with non-ferromagnetic 3d transition metals still remains intriguing. In this article, insights in the magnetic properties of ordered mesoporous Cu-doped SnO₂ powders, prepared by hard-templating, have been unraveled. Whereas, both oxygen vacancies and Fe-based impurity phases could be a plausible explanation for the observed room temperature ferromagnetism, the low temperature magnetism is mainly and unambiguously arising from the nanoscale nature of the formed antiferromagnetic CuO, which results in a net magnetization that is reminiscent of ferromagnetic behavior. This is ascribed to uncompensated spins and shape-mediated spin canting effects. The reduced blocking temperature, which resides between 30 and 5 K, and traces of vertical shifts in the hysteresis loops confirm size effects in CuO. The mesoporous nature of the system with a large surface-to-volume ratio likely promotes the occurrence of uncompensated spins, spin canting, and spin frustration, offering new prospects in the use of magnetic semiconductors for energy-efficient spintronics.
Keywords: diluted magnetic semiconductors; mesoporous SnO2 particles; nanocasting.