Excitonic Zeeman splittings in colloidal CdSe quantum dots doped with single magnetic impurities

Abstract

Doping a semiconductor quantum dot with just a single impurity atom can completely transform its physical properties. Here, we report and analyze the magnetic circular dichroism (MCD) spectra of colloidal CdSe quantum dot samples containing on average fewer than one Mn²⁺ per quantum dot. Even at this sub-single-dopant level, the low-temperature low-field data are dominated by impurity-induced Zeeman splittings caused by dopant–carrier sp–d exchange. Unlike in more heavily doped quantum dots, however, the MCD intensity at the first CdSe exciton shows a field-induced sign flip as the field strength is increased, reflecting competition between sp–d exchange and the intrinsic Zeeman splittings of comparable magnitude. Most unusually, the competition between these two effects leads to a large apparent shift in the first MCD peak maximum, which we show is attributable to a difference in sign of the intrinsic excitonic g factor between the first and second excitons. Finally, the sp–d and intrinsic contributions to the excitonic Zeeman splittings each exhibit unique magnetic-field and temperature dependencies, allowing the MCD spectra of undoped, singly doped, and bi-doped quantum dot sub-ensembles to be analyzed.