Coexistence of antiferromagnetism and ferromagnetism in Mn²⁺/CdS nanocrystals and their photophysical properties

Manganous ion doped CdS nanocrystals with different concentrations of Mn2+ have been synthesized by a chemical synthesis route. The as-synthesized Mn2+/CdS nanocrystals evince interesting optical emission properties; the intensity of cadmium vacancy emissions VCd decreases on the addition of the dopant ion, proving the displacement of cadmium by manganese which is accompanied by the appearance and enhancement of the Mn2+ d-d emission, 4T1 → 6A1. However, the intensity of the latter emission decreases on further increase in [Mn2+] due to strong cluster formation, such as Mn2+-Mn2+. The low temperature electron paramagnetic resonance measurements suggest strong antiferromagnetism due to strong exchange coupling between the spins of nearby Mn2+ centres both in pre- and post-annealed 5% Mn2+/CdS samples. These magnetic properties for pre- and post-annealed 5% Mn2+/CdS samples are explained by a core/shell (antiferromagnetism/ferromagnetism) model. The pre-annealed sample, on one hand, shows antiferromagnetic behavior with weak ferromagnetism below the Néel temperature, the latter due to uncompensated surface spins. On the other hand, annealing leads to the formation of more Mn2+-Mn2+ dimers or clusters due to ionic migration. This will result in increased antiferromagnetic character as compared to the pre-annealed sample. Both are confirmed by magnetization hysteresis curves at various temperatures. The electron microscopy images confirm the morphology prediction by XRD. © 2013 The Royal Society of Chemistry.