Tuning Colloidal Quantum Dot Band Edge Positions through Solution-Phase Surface Chemistry Modification

Daniel M. Kroupa, Márton Vörös, Nicholas P. Brawand, Brett W. McNichols, Elisa M. Miller, Jing Gu, Arthur J. Nozik, Alan Sellinger, Giulia Galli, Matthew C. Beard

Research output: Contribution to journalArticlepeer-review

228 Scopus Citations


Band edge positions of semiconductors determine their functionality in many optoelectronic applications such as photovoltaics, photoelectrochemical cells and light emitting diodes. Here we show that band edge positions of lead sulfide (PbS) colloidal semiconductor nanocrystals, specifically quantum dots (QDs), can be tuned over 2.0 eV through surface chemistry modification. We achieved this remarkable control through the development of simple, robust and scalable solution-phase ligand exchange methods, which completely replace native ligands with functionalized cinnamate ligands, allowing for well-defined, highly tunable chemical systems. By combining experiments and ab initio simulations, we establish clear relationships between QD surface chemistry and the band edge positions of ligand/QD hybrid systems. We find that in addition to ligand dipole, inter-QD ligand shell inter-digitization contributes to the band edge shifts. We expect that our established relationships and principles can help guide future optimization of functional organic/inorganic hybrid nanostructures for diverse optoelectronic applications.

Original languageAmerican English
Article number15257
Number of pages8
JournalNature Communications
StatePublished - 16 May 2017

Bibliographical note

Publisher Copyright:
© The Author(s) 2017.

NREL Publication Number

  • NREL/JA-5900-66738


  • band edge positions
  • ligand exchange
  • quantum dots
  • solar-photochemistry


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