Redox Chemistries and Plasmon Energies of Photodoped In2O3 and Sn-Doped In2O3 (ITO) Nanocrystals

Plasmonic doped semiconductor nanocrystals promise exciting opportunities for new technologies, but basic features of the relationships between their structures, compositions, electronic structures, and optical properties remain poorly understood. Here, we report a quantitative assessment of the impact of composition on the energies of localized surface plasmon resonances (LSPRs) in colloidal tin-doped indium oxide (Sn:In2O3, or ITO) nanocrystals. Using a combination of aliovalent doping and photodoping, the effects of added electrons and impurity ions on the energies of LSPRs in colloidal In2O3 and ITO nanocrystals have been evaluated. Photodoping allows electron densities to be tuned post-synthetically in ITO nanocrystals, independent of their Sn content. Because electrons added photochemically are easily titrated, photodoping also allows independent quantitative determination of the dependence of the LSPR energy on nanocrystal composition and changes in electron density. The data show that ITO LSPR energies are affected by both electron and Sn concentrations, with composition yielding a broader plasmon tuning range than achievable by tuning carrier densities alone. Aspects of the photodoping energetics, as well as magneto-optical properties of these ITO LSPRs, are also discussed.