Ligands Slow Down Pure-Dephasing in Semiconductor Quantum Dots.
It is well-known experimentally and theoretically that surface ligands provide additional pathways for energy relaxation in colloidal semiconductor quantum dots (QDs). They increase the rate of inelastic charge-phonon scattering and provide trap sites for the charges. We show that, surprisingly, ligands have the opposite effect on elastic electron-phonon scattering. Our simulations demonstrate that elastic scattering slows down in CdSe QDs passivated with ligands compared to that in bare QDs. As a result, the pure-dephasing time is increased, and the homogeneous luminescence line width is decreased in the presence of ligands. The lifetime of quantum superpositions of single and multiple excitons increases as well, providing favorable conditions for multiple excitons generation (MEG). Ligands reduce the pure-dephasing rates by decreasing phonon-induced fluctuations of the electronic energy levels. Surface atoms are most mobile in QDs, and therefore, they contribute greatly to the electronic energy fluctuations. The mobility is reduced by interaction with ligands. A simple analytical model suggests that the differences between the bare and passivated QDs persist for up to 5 nm diameters. Both low-frequency acoustic and high-frequency optical phonons participate in the dephasing processes in bare QDs, while low-frequency acoustic modes dominate in passivated QDs. The theoretical predictions regarding the pure-dephasing time, luminescence line width, and MEG can be verified experimentally by studying QDs with different surface passivation.
Department of Chemical Engineering, University of Rochester , Rochester, New York 14627, United States.
Jin
J
Liu
Department of Chemistry, North Dakota State University , Fargo, North Dakota 58108, United States.
Svetlana V
SV
Kilina
Los Alamos National Laboratory , Los Alamos, New Mexico 87545, United States.
Sergei
S
Tretiak
Department of Chemistry, University of Southern California , Los Angeles, California 90089, United States.
Oleg V
OV
Prezhdo
colloidal quantum dots; electron−phonon scattering; luminescence; multiple exciton generation; pure dephasing