Theory of Photoluminescence Spectral Line Shapes of Semiconductor Nanocrystals

Lin, Kailai; Jasrasaria, Dipti; Yoo, Jason J.; Bawendi, Moungi; Utzat, Hendrik; Rabani, Eran

doi:10.1021/acs.jpclett.3c01630

Title: Theory of Photoluminescence Spectral Line Shapes of Semiconductor Nanocrystals

Journal Article · Tue Aug 08 00:00:00 EDT 2023 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.3c01630· OSTI ID:2323300

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Univ. of California, Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States); Columbia Univ., New York, NY (United States)
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Tel Aviv Univ., Tel Aviv (Israel)

Single-molecule photoluminescence (PL) spectroscopy of semiconductor nanocrystals (NCs) reveals the nature of exciton–phonon interactions in NCs. Understanding the homogeneous spectral line shapes and their temperature dependence remains an open problem. Here, we develop an atomistic model to describe the PL spectrum of NCs, accounting for excitonic effects, phonon dispersion relations, and exciton–phonon couplings. We validate our model using single-NC measurements on CdSe/CdS NCs from T = 4 to 290 K, and we find that the slightly asymmetric main peak at low temperatures is comprised of a narrow zero-phonon line (ZPL) and acoustic phonon sidebands. Furthermore, we identify the specific phonon modes that give rise to the optical phonon sidebands. At temperatures above 200 K, the spectral line width shows a stronger dependence upon the temperature, which we demonstrate to be correlated with higher order exciton–phonon couplings. We also identify the line width dependence upon reorganization energy, NC core sizes, and shell thicknesses.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231; SC0019323

OSTI ID:: 2323300

Journal Information:: Journal of Physical Chemistry Letters, Vol. 14, Issue 32; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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coupling reactions
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Title: Theory of Photoluminescence Spectral Line Shapes of Semiconductor Nanocrystals

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