Controlling Electronic Coupling of Acene Chromophores on Quantum Dot Surfaces through Variable-Concentration Ligand Exchange

Marissa Martinez, Michelle Nolen, Nicholas Pompetti, Lee Richter, Carrie Farberow, Justin Johnson, Matthew Beard

Research output: Contribution to journalArticlepeer-review

1 Scopus Citations

Abstract

Controlling the binding of functional organic molecules on quantum dot (QD) surfaces and the resulting ligand/QD interfacial structure determines the resulting organic-inorganic hybrid behavior. In this study, we vary the binding of tetracenedicarboxylate ligands bound to PbS QDs cast in thin films by performing solid-state ligand exchange of as-produced bound oleate ligands. We employ comprehensive Fourier-transform infrared (FTIR) analysis coupled with ultraviolet-visible (UV-vis) spectrophotometric measurements, transient absorption, and Density Functional Theory (DFT) simulations to study the QD/ligand surface structure and resulting optoelectronic properties. We find that there are three primary QD/diacid structures, each with a distinct binding mode dictated by the QD-ligand and ligand-ligand intermolecular and steric interactions. They can be accessed nearly independently of one another via different input ligand concentrations. Low concentrations produce mixed oleate/tetracene ligand structures where the tetracene carboxylates tilt toward QD surfaces. Intermediate concentrations produce mixed oleate/tetracene ligand structures with ligand-ligand interactions through intramolecular hydrogen bonding with the ligands perpendicular to the QD surface and weaker QD/ligand electronic interactions. High concentrations result in full ligand exchange, and the ligands tilt toward the surface while the QD film compacts. When the tetracene ligands tilt or lie flat on the QD surface, the benzene ring pi-system interacts strongly with the p-orbitals at the PbS surface and produces strong QD-ligand interactions evidenced through QD/ligand state mixing, with a coupling energy of approximately 700 meV.
Original languageAmerican English
Pages (from-to)14916-14929
Number of pages14
JournalACS Nano
Volume17
Issue number15
DOIs
StatePublished - 2023

NREL Publication Number

  • NREL/JA-5900-86006

Keywords

  • electronic hybridization
  • lead sulfide
  • ligand orientation
  • QD films
  • quantum dots
  • solar-photochemistry

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