Recent advances in the chemistry of colloidal semiconductor nanocrystal doping have led to new materials showing fascinating physical properties of potential technological importance. This article provides an overview of efforts to dope one of the most widely studied colloidal semiconductor nanocrystal systems, CdSe quantum dots, with one of the most widely studied transition‐metal dopant ions, Mn2+, and describes the major new physical properties that have emerged following successful synthesis of this material. These properties include spin‐polarizable excitonic photoluminescence, magnetic circular dichroism, exciton storage, and excitonic magnetic polaron formation. A brief survey of parallel advances in the characterization of analogous self‐assembled Mn2+‐doped quantum dots grown by molecular beam epitaxy is also presented, and the physical properties of the colloidal quantum dots are shown to compare favorably with those of the self‐assembled quantum dots. The rich variety of physical properties displayed by colloidal Mn2+‐doped CdSe quantum dots highlights the attractiveness of this material for future fundamental and applied research.

Electrical control over the magnetic states of doped semiconductor nanostructures could enable new spin-based information processing technologies. To this end, extensive research has recently been devoted to examination of carrier-mediated magnetic ordering effects in substrate-supported quantum dots at cryogenic temperatures, with carriers introduced transiently by photon absorption. The relatively weak interactions found between dopants and charge carriers have suggested that gated magnetism in quantum dots will be limited to cryogenic temperatures. Here, we report the observation of a large, reversible, room-temperature magnetic response to charge state in free-standing colloidal ZnO nanocrystals doped with Mn(2+) ions. Injected electrons activate new ferromagnetic Mn(2+)-Mn(2+) interactions that are strong enough to overcome antiferromagnetic coupling between nearest-neighbour dopants, making the full magnetic moments of all dopants observable. Analysis shows that this large effect occurs in spite of small pairwise electron-Mn(2+) exchange energies, because of competing electron-mediated ferromagnetic interactions involving distant Mn(2+) ions in the same nanocrystal.

The "extra" electrons in colloidal n-type ZnO nanocrystals formed by aliovalent doping and photochemical reduction are compared. Whereas the two are similar spectroscopically, they show very different electron-transfer reactivities, attributable to their different charge-compensating cations (Al(3+)vs. H(+)).

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