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.

An attractive approach to controlling spin effects in semiconductor nanostructures for applications in electronics is the use of light to generate, manipulate, or read out spins. Here, we demonstrate spontaneous photoinduced polarization of manganese(II) spins in doped colloidal cadmium selenide quantum dots. Photoexcitation generates large dopant-carrier exchange fields, enhanced by strong spatial confinement, that lead to giant Zeeman splittings of the semiconductor band structure in the absence of applied magnetic fields. These internal exchange fields allow spontaneous magnetic saturation of the manganese(II) spins to be achieved at zero external magnetic field up to approximately 50 kelvin. Photomagnetic effects are observed all the way up to room temperature.

The defining attribute of a diluted magnetic semiconductor (DMS) is the existence of dopant-carrier magnetic exchange interactions. In this letter, we report the first direct observation of such exchange interactions in colloidal doped CdSe nanocrystals. Doped CdSe quantum dots were synthesized by thermal decomposition of (Me4N)2[Cd4(SePh)10] in the presence of TMCl2 (TM2+ = Mn2+ or Co2+) in hexadecylamine and were characterized by several analytical and spectroscopic techniques. Using magnetic circular dichroism spectroscopy, successful doping and the existence of giant excitonic Zeeman splittings in both Mn2+- and Co2+-doped wurtzite CdSe quantum dots are demonstrated unambiguously.

The photoluminescence of colloidal Mn2+-doped CdSe nanocrystals has been studied as a function of nanocrystal diameter. These nanocrystals are shown to be unique among colloidal doped semiconductor nanocrystals reported to date in that quantum confinement allows tuning of the CdSe bandgap energy across the Mn2+ excited-state energies. At small diameters, the nanocrystal photoluminescence is dominated by Mn 2+ emission. At large diameters, CdSe excitonic photoluminescence dominates. The latter scenario has allowed spin-polarized excitonic photoluminescence to be observed in colloidal doped semiconductor nanocrystals for the first time.

Colloidal Mn2+-doped CdSe quantum dots showing long excitonic photoluminescence decay times of up to τexc = 15 μs at temperatures over 100 K are described. These decay times exceed those of undoped CdSe quantum dots by ∼103 and are shown to arise from the creation of excitons by back energy transfer from excited Mn2+ dopant ions. A kinetic model describing thermal equilibrium between Mn2+ 4T1 and CdSe excitonic excited states reproduces the experimental observations and reveals that, for some quantum dots, excitons can emit with near unity probability despite being ∼100 meV above the Mn2+ 4T1 state. The effect of Mn2+ doping on CdSe quantum dot luminescence at high temperatures is thus completely opposite from that at low temperatures described previously.