Surface Contributions to Mn²⁺ Spin Dynamics in Colloidal Doped Quantum Dots

Colloidal impurity-doped quantum dots (QDs) are attractive model systems for testing the fundamental spin properties of semiconductor nanostructures relevant to future spin-based information processing technologies. Although static spin properties of this class of materials have been studied extensively in recent years, their spin dynamics remain largely unexplored. Here we use pulsed electron paramagnetic resonance (pEPR) spectroscopy to probe the spin relaxation dynamics of colloidal Mn²⁺-doped ZnO, ZnSe, and CdSe quantum dots in the limit of one Mn²⁺ per QD. pEPR spectroscopy is particularly powerful for identifying the specific nuclei that accelerate electron spin relaxation in these QDs. We show that the spin-relaxation dynamics of these colloidal QDs are strongly influenced by dipolar coupling with proton nuclear spins outside the QDs and especially those directly at the QD surfaces. Using this information, we demonstrate that spin-relaxation times can be elongated significantly via ligand (or surface) deuteration or shell growth, providing two tools for chemical adjustment of spin dynamics in these nanomaterials. These findings advance our understanding of the spin properties of solution-grown semiconductor nanostructures relevant to spin-based information technologies