Plasmonic metal oxide nanocrystals present intriguing material properties that have been shown valuable in many applications from sensing, spectroscopy, and catalysis. The usefulness of these materials is greatly dependent on regulating dopant activation (number of free electrons contributed per dopant atom) and mitigating plasmonic damping. Dopant activation and plasmonic damping are highly dependent on the synthetic pathway for nanocrystal formation, and simultaneously increasing dopant activation while reducing damping has been shown to be synthetically challenging. Here we show that angstrom-level control over radial distribution of dopants within an oxide nanocrystal can allow chemists to simultaneously reduce plasmonic damping and increase dopant activation. Through a multi-stage living growth synthesis, and using Sn-doped In<sub>2</sub>O<sub>3</sub> (ITO) as a model system, well-defined core/shell doped/undoped nanocrystals can readily be synthesized. Through careful core/shell dimensional control we illustrate that: 1) doped/undoped core/shell nanocrystals structures can be tailor synthesized controllably without intermittent purification, 2) oxide nanocrystal surfaces contain inactive dopants that can be readily activated upon undoped shell growth, and 3) radial dopant distribution is a new strategy for sculpting plasmonic spectra that will be applicable in all plasmonic oxide systems. The synthetic approach presented in this work allows for angstrom-level precision for atomic placement within a nanocrystal and highlights new opportunities is designing plasmonic properties. These results are applicable to a wide range of nanomaterials and will aid in the fundamental understating of dopant-induced plasmonic properties.

Radial dopant placement with angstom-level control for tuning plasmonic properties in metal oxide nanocrystals

255th National Meeting (2018)

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