Nanomaterials exhibiting plasmonic optical responses are impacting sensing, information processing, catalysis, solar, and photonics technologies. Recent advances have expanded the portfolio of plasmonic nanostructures into doped semiconductor nanocrystals, which allow dynamic manipulation of carrier densities. Once interpreted as intraband single-electron transitions, the infrared absorption of doped semiconductor nanocrystals is now commonly attributed to localized surface plasmon resonances and analyzed using the classical Drude model to determine carrier densities. Here, we show that the experimental plasmon resonance energies of photodoped ZnO nanocrystals with controlled sizes and carrier densities diverge from classical Drude model predictions at small sizes, revealing quantum plasmons in these nanocrystals. A Lorentz oscillator model more adequately describes the data and illustrates a closer link between plasmon resonances and single-electron transitions in semiconductors than in metals, highlighting a fundamental contrast between these two classes of plasmonic materials.

No abstract

Electron energy-loss spectroscopy (EELS) offers a window to view nanoscale properties and processes. When performed in a scanning transmission electron microscope, EELS can simultaneously render images of nanoscale objects with sub-nanometer spatial resolution and correlate them with spectroscopic information of ∼ 10 − 100 meV spectral resolution. Consequently, EELS is a nearperfect tool for understanding the optical and electronic properties of individual and few-particle plasmonic metal nanoparticles assemblies, which are significant in a wide range of fields. This review presents an overview of basic plasmonics and EELS theory and highlights several recent noteworthy experiments involving the electron-beam interrogation of plasmonic metal nanoparticle systems.