Intrinsic Exciton Photophysics of PbS Quantum Dots Revealed by Low-Temperature Single Nanocrystal Spectroscopy.

With a tunable size-dependent photoluminescence (PL) over a wide infrared wavelength range, lead chalcogenide quantum dots (QDs) have attracted significant scientific and technological interest. Nevertheless, the investigation of intrinsic exciton photophysics at the single-QD level has remained a challenge. Herein, we present a comprehensive study of PL properties for the individual core/shell PbS/CdS QDs emissive near 1.0 eV. In contrast to the sub-meV spectral line widths observed for II/VI QDs, PbS/CdS QDs are predicted to possess broad homogeneous line widths. Performing spectroscopy at cryogenic (4 K) temperatures, we provide direct evidence confirming theoretical predictions, showing that intrinsic line widths for PbS/CdS QDs are in the range of 8-25 meV, with an average of 16.4 meV. In addition, low-temperature, single-QD spectroscopy reveals a broad low-energy side emission attributable to optical as well as localized acoustic phonon-assisted transitions. By tracking single QDs from 4 to 250 K, we were able to probe temperature-dependent evolutions of emission energy, line width, and line shape. Finally, polarization-resolved PL imaging showed that PbS/CdS QDs are characterized by a 3D emission dipole, in contrast with the 2D dipole observed for CdSe QDs.