Distinguishing Electron and Hole Dynamics in Functionalized CdSe/CdS Core/Shell Quantum Dots Using Complementary Ultrafast Spectroscopies and Kinetic Modeling

Taheri, Mohammad M.; Elbert, Katherine C.; Yang, Shengsong; Diroll, Benjamin T.; Park, Jungmi; Murray, Christopher B.; Baxter, Jason B.

doi:10.1021/acs.jpcc.0c07037

Title: Distinguishing Electron and Hole Dynamics in Functionalized CdSe/CdS Core/Shell Quantum Dots Using Complementary Ultrafast Spectroscopies and Kinetic Modeling

Journal Article · Thu Dec 31 00:00:00 EST 2020 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.0c07037· OSTI ID:1760171

^[1]; Elbert, Katherine C. ^[2]; Yang, Shengsong ^[2];

^[3]; Park, Jungmi ^[2]; Murray, Christopher B. ^[2];

^[1]

Drexel Univ., Philadelphia, PA (United States)
Univ. of Pennsylvania, Philadelphia, PA (United States)
Argonne National Lab. (ANL), Lemont, IL (United States). Center for Nanoscale Materials

The evolution of excitation energy and photogenerated charges in semiconductor quantum dots (QDs) functionalized with molecular acceptors can be probed on ultrafast time scales using techniques such as transient absorption (TA) spectroscopy. However, historical interpretations that the 1S(e)-1S_3/2(h) transition in Cd-chalcogenide QDs is fully attributable to electrons may be misleading, and multiexponential models used to fit TA kinetics do not correspond directly to specific photophysical processes. Here, we present visible-wavelength and mid-IR TA and time-resolved photoluminescence measurements to inform a comprehensive kinetic model of the photoexcited CdSe/CdS core/shell QDs functionalized with passivating oleic acid (OA), hole-accepting ferrocene, or electron-accepting naphthalene bisimide (NBI). We show that ~30% of the 1S signal and 72% of the IR signal can originate from holes in well-passivated core/shell QDs. We also demonstrate evidence of electron trapping in OA-capped core/shell QDs, with additional electron transfer and hole trapping in the QDs functionalized with NBI. Electron (hole) trapping and detrapping occur in 450 ± 100 ps (430 ± 70 ps) and 340 ± 100 ps (1.1 ± 0.4 ns) respectively, while the time constant for electron transfer to NBI is ~1.8 ns. The comprehensive picture of photophysical processes provided by the complementary ultrafast techniques and kinetic modeling can accelerate both the fundamental science and application development of nanostructured and molecular systems.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357; CHE-1708991; CHE-1709827; DGE-1321851

OSTI ID:: 1760171

Journal Information:: Journal of Physical Chemistry. C, Vol. 125, Issue 1; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Quantum dots
Charge transfer
Kinetic modeling
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Title: Distinguishing Electron and Hole Dynamics in Functionalized CdSe/CdS Core/Shell Quantum Dots Using Complementary Ultrafast Spectroscopies and Kinetic Modeling

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