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

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

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

1 Scopus citations


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, 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.

Original languageEnglish (US)
Pages (from-to)3732-3741
Number of pages10
JournalJournal of the American Chemical Society
Issue number6
StatePublished - Feb 14 2024

ASJC Scopus subject areas

  • General Chemistry
  • Biochemistry
  • Catalysis
  • Colloid and Surface Chemistry


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