Heterovalent dopant ions, such as Sn 4+ , in In 2 O 3 nanocrystals (NCs) provide free electrons for localized surface plasmon resonance (LSPR). But the same heterovalent dopants act as electron scattering centers, both independently and by forming complexes with interstitial oxygen, thereby increasing LSPR line width. Also, such complexes decrease free carrier density. These detrimental effects diminish the figureof-merit of LSPR known as the quality factor (Q-factor). Herein, we designed colloidal Cr−Sn codoped In 2 O 3 NCs, where both high carrier density and low carrier scattering can be achieved simultaneously, yielding a high LSPR Q-factor of 7.2, which is a record high number compared to prior reports of doped In 2 O 3 NCs. Q-factors increase systematically from 3.2 for 6.6% Sn doped In 2 O 3 NCs to 7.2 for 23.8% Cr−6.6% Sn codoped In 2 O 3 NCs by increasing the Cr codoping concentration, which is also accompanied by an increase in NC size from 6.7 to 22.1 nm. Detailed characterization and analysis of LSPR spectra using Drude model suggest that the increase in NC size (induced by Cr codoping) is mainly responsible for the enhanced LSPR Q-factor. Sn 4+ dopants on the surface of NCs are more vulnerable to form irreducible complexes with interstitial oxide ions, compared to Sn 4+ ions in the core. Therefore, an increase in the concentration ratio of [Sn core ]/[Sn surface ] (or [Sn]/ [interstitial oxide]) by increasing the size of NCs, increases the carrier density. Furthermore, such increase in both NC size and Cr doping influences multiple factors reducing the scattering of charge carriers, thereby increasing the optical carrier mobility. This unique combination, which increases both the density and mobility of charge carriers, improves the LSPR Q-factor.

Degenerately doped semiconductor nanocrystals (NCs) exhibit strong light−matter interactions due to localized surface plasmon resonance (LSPR) in the near-to mid-infrared region. Besides being readily tuned through dopant concentration introduced during synthesis, this LSPR can also be dynamically modulated by applying an external electrochemical potential. This characteristic makes these materials candidates for electrochromic window applications. Here, using prototypical doped indium oxide NCs as a model system, we find that the extent of electrochemical modulation of LSPR frequency is governed by the depletion width and the extent of inter-NC LSPR coupling, which are indirectly controlled by the dopant density, size, and packing density of the NCs. The depletion layer is a near-surface region with a sharply reduced free carrier population that occurs whenever the surface potential lies below the Fermi level. Changes in the depletion width under applied bias substantially control the spectral modulation of the LSPR of individual NCs and also modify the inter-NC LSPR coupling, which additionally modulates the LSPR absorption on the NC film scale. Here, we show that both of these effects must be considered primary factors in determining the extent of LSPR frequency modulation and that the dominant factor depends on NC size. For a constant doping concentration, depletion effects govern LSPR modulation for smaller NCs, while LSPR coupling is prevalent in larger NCs. Consequently, as the size of the NCs is increased while keeping the doping concentration constant, we observe a reversal in the sign of the LSPR frequency modulation from positive to negative.

We prepared Fe- and Sn-codoped colloidal In2O3 nanocrystals (∼6 nm). Sn doping provides free electrons in the conduction band, originating localized surface plasmon resonance (LSPR) and electrical conductivity. The LSPR band can be tuned between 2000 and >3000 nm, depending on the extent and kind of dopant ions. Fe doping, on the other hand, provides unpaired electrons, resulting in weak ferromagnetism at room temperature. Fe doping shifts the LSPR band of 10% Sn-doped In2O3 nanocrystals to a longer wavelength along with a reduction in intensity, suggesting trapping of charge carriers around the dopant centers, whereas Sn doping increases the magnetization of 10% Fe-doped In2O3 nanocrystals, probably because of the free electron mediated interactions between distant magnetic ions. The combination of plasmonics and magnetism, in addition to electronic conductivity and visible-light transparency, is a unique feature of our colloidal codoped nanocrystals.

When aliovalent dopants are sufficiently segregated to the core or near the surface of semiconductor nanocrystals, charge carriers donated by the dopants are also segregated to the core or near the surface, respectively. In Sn-doped indium oxide nanocrystals, we find that this contrast in free charge carrier concentration creates a core and shell with differing dielectric properties and results in two distinctly observable plasmonic extinction peaks. The trends in this dual-mode optical response with shell growth differ from core/shell nanoparticles composed of traditional plasmonic metals such as Au and Ag. We developed a model employing a core/shell effective medium approximation that can fit the dual-mode spectra and explain the trends in the extinction response. Lastly, we show that dopant segregation can improve sensitivity of plasmon spectra to changes in refractive index of the surrounding environment.