Intra-band transitions in colloidal quantum dots (QDs) are promising for opto-electronic applications in the mid-IR spectral region. However, such intra-band transitions are typically very broad and spectrally overlapping, making the study of individual excited states and their ultrafast dynamics very challenging. Here, we present the first full spectrum two-dimensional continuum infrared (2D CIR) spectroscopy study of intrinsically n-doped HgSe QDs, which exhibit mid-infrared intra-band transitions in their ground state. The obtained 2D CIR spectra reveal that underneath the broad absorption line shape of ∼500 cm−1, the transitions exhibit surprisingly narrow intrinsic linewidths with a homogeneous broadening of 175–250 cm−1. Furthermore, the 2D IR spectra are remarkably invariant, with no sign of spectral diffusion dynamics at waiting times up to 50 ps. Accordingly, we attribute the large static inhomogeneous broadening to the distribution of size and doping level of the QDs. In addition, the two higher-lying P-states of the QDs can be clearly identified in the 2D IR spectra along the diagonal with a cross-peak. However, there is no indication of cross-peak dynamics indicating that, despite the strong spin–orbit coupling in HgSe, transitions between the P-states must be longer than our maximum waiting time of 50 ps. This study illustrates a new frontier of 2D IR spectroscopy enabling the study of intra-band carrier dynamics in nanocrystalline materials across the entire mid-infrared spectrum.
Narrow homogeneous linewidths and slow cooling dynamics across infrared intra-band transitions in n-doped HgSe colloidal quantum dots
Note: This paper is part of the JCP Special Topic on Celebrating 25 Years of Two-dimensional Infrared (2D IR) Spectroscopy.
Ashley M. Stingel, Jari Leemans, Zeger Hens, Pieter Geiregat, Poul B. Petersen; Narrow homogeneous linewidths and slow cooling dynamics across infrared intra-band transitions in n-doped HgSe colloidal quantum dots. J. Chem. Phys. 21 March 2023; 158 (11): 114202. https://doi.org/10.1063/5.0139795
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