Ultrathin Plasmonic Tungsten Oxide Quantum Wells with Controllable Free Carrier Densities.

We report the colloidal synthesis of ~3 tungsten-oxygen (W-O) layer thick (~1 nm), two-dimensional (2D) WO3-x nanoplatelets (NPLs) (x ~ 0.55 - 1.03), which display tunable near-infrared localized surface plasmon resonances (LSPR) spectra and high free electron density (Ne) that arises predominantly from their large shape factor. Importantly, the W to O composition ratios inferred from their LSPR measurements show much higher percentage of oxygen vacancies than those determined by X-ray diffraction analysis, suggesting that the aspect ratio of ultrathin WO3-x NPLs is the key to producing an unprecedentedly large Ne, although synthesis temperature is also an independent factor. We find that NPL formation is kinetically controlled, whereas thermodynamic parameter manipulation leads to Ne as high as 4.13 X 1022 cm-3, which is close to that of plasmonic noble metals, and thus our oxide-based nanostructures can be considered as quasi-metallic. The unique structural properties of 2D nanomaterials along with the high Ne of WO3-x NPLs provide an attractive alternative to plasmonic noble metal nanostructures for energy conversions photochromic nanodevices.