Ligand Desorption and Fragmentation in Oleate-Capped CdSe Nanocrystals under High-Intensity Photoexcitation

Harvey, Samantha M.; Olshansky, Jacob H.; Li, Alice; Panuganti, Shobhana; Kanatzidis, Mercouri G.; Hupp, Joseph T.; Wasielewski, Michael R.; Schaller, Richard D.

doi:10.1021/jacs.3c10232

Title: Ligand Desorption and Fragmentation in Oleate-Capped CdSe Nanocrystals under High-Intensity Photoexcitation

Journal Article · 31 January 2024 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.3c10232 · OSTI ID:2513855

Harvey, Samantha M. ^[1];

^[1];

^[2]

Northwestern Univ., Evanston, IL (United States)
Northwestern Univ., Evanston, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States). Center for Nanoscale Materials (CNM)

Semiconductor nanocrystals (NCs) offer prospective use as active optical elements in photovoltaics, light-emitting diodes, lasers, and photocatalysts due to their tunable optical absorption and emission properties, high stability, and scalable solution processing, as well as compatibility with additive manufacturing routes. Over the course of experiments, during device fabrication, or while in use commercially, these materials are often subjected to intense or prolonged electronic excitation and high carrier densities. The influence of such conditions on ligand integrity and binding remains underexplored. Here, in this study, we expose CdSe NCs to laser excitation and monitor changes in oleate that is covalently attached to the NC surface using nuclear magnetic resonance as a function of time and laser intensity. Higher photon doses cause increased rates of ligand loss from the particles, with upward of 50% total ligand desorption measured for the longest, most intense excitation. Surprisingly, for a range of excitation intensities, fragmentation of the oleate is detected and occurs concomitantly with formation of aldehydes, terminal alkenes, H₂, and water. After illumination, NC size, shape, and bandgap remain constant although low-energy absorption features (Urbach tails) develop in some samples, indicating formation of substantial trap states. The observed reaction chemistry, which here occurs with low photon to chemical conversion efficiency, suggests that ligand reactivity may require examination for improved NC dispersion stability but can also be manipulated to yield desired photocatalytically accessed chemical species.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-06CH11357; FG02-87ER13808; FG02-99ER14999

OSTI ID:: 2513855

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 6 Vol. 146; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ligand desorption
photoexcitation
quantum dots
semiconductor nanocrystals

Title: Ligand Desorption and Fragmentation in Oleate-Capped CdSe Nanocrystals under High-Intensity Photoexcitation

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