Surface Depletion Layers in Plasmonic Metal Oxide Nanocrystals

• Published in: Accounts of chemical research Vol. 52; no. 9; pp. 2516 - 2524
• Main Authors: Gibbs, Stephen L, Staller, Corey M, Milliron, Delia J
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 17-09-2019
• DOI: 10.1021/acs.accounts.9b00287
• EISSN: 1520-4898
• ISSN: 0001-4842

Conspectus Strong infrared (IR) light–matter interaction and spectral tunability combine to make plasmonic metal oxide nanocrystals (NCs) a compelling choice for IR applications. In particular, visible transparency paired with strong, dynamically tunable IR absorption has motivated their implementation in electrochromic smart windows, but these NCs hold promise for a far broader range of plasmonically driven processes such as surface-enhanced infrared sensing, photothermal therapy, and enhanced photocatalysis. These unique properties result from localized surface plasmon resonance (LSPR) sustained by a relatively low free charge carrier concentration, which in turn requires consideration of distinct materials physics relative to traditional plasmonic materials (i.e., metals). Particularly important is the formation of insulating shells devoid of charge carriers (depletion layers) near the NC surface. Surface states as well as applied surface potentials can give rise to a potential difference between the NC surface and its core that depletes free charge carriers from the surface, forming an insulating shell that reduces the conductivity in NC films, lowers the dielectric sensitivity of the LSPR, and diminishes the incident electric field enhancement. In this Account, we report recent investigations of depletion layers in plasmonic metal oxide NCs that have advanced understanding of the semiconductor physics underlying the optoelectronic properties of these NCs and the electrochemical modulation of their LSPR, establishing a conceptual framework with which to broaden their applicability and optimize their performance. As a result of surface depletion, larger, highly doped NCs have improved dielectric sensitivity compared with their smaller, lightly doped counterparts. Concentrating dopants near the NC surface compresses the depletion layer, resulting in improved conductivity of NC films. Moreover, atomic layer deposition of alumina to infill NC films enhances the film conductivity by more than 2 orders of magnitude, ascribed to the elimination of depletion effects by reactive removal of surface water species. At the conclusion, we reflect on how our newfound understanding of surface depletion in plasmonic metal oxide NCs is quickly leading to rational material design. This insight is already resulting in significant performance improvements, and the same principles can be applied to new, exciting opportunities in hot carrier extraction and resonant IR energy transduction.