Size Control of the Mechanism of Exciton Polarization in Metal Oxide Nanocrystals through Fermi Level Pinning.

Light-matter interaction in certain aliovalently doped metal oxide nanocrystals (NCs) results in the generation of localized surface plasmon resonance (LSPR) in the near- to mid-infrared, allowing for their implementation in various technologies, including photovoltaics, sensing, and electrochromics. These materials could also facilitate coupling between plasmonic and semiconducting properties, making them highly interesting for electronic and quantum information technologies. In the absence of dopants, free charge carriers can arise from native defects such as oxygen vacancies. Here we show using magnetic circular dichroism spectroscopy that the exciton splitting in In2O3 NCs is induced by both localized and delocalized electrons and that contributions from the two mechanisms are strongly dependent on the NC size, owing to Fermi level pinning and the formation of a surface depletion layer. In large NCs, the angular momentum transfer from delocalized cyclotron electrons to the excitonic states is the dominant mechanism of exciton polarization. This process diminishes with decreasing NC size, owing to the rapidly reduced volume of the plasmonic core. On the other hand, exciton polarization in small NCs is dominated by localized electron-spin-induced splitting of the excitonic states. This mechanism is independent of NC size, suggesting that wave functions of localized spin states on NC surfaces do not overlap with the excitonic states. The results of this work demonstrate that the effects of individual and collective electronic properties on excitonic states can be simultaneously controlled by NC size, making metal oxide NCs a promising class of materials for quantum, spintronic, and photonic technologies.

Photopolymerized silk fibroin gel for advanced burn wound care.

The future of burn wound treatment lies in developing bioactive dressings for faster and more effective healing and regeneration. Silk fibroin (SF) hydrogels have proven regenerative abilities and are being explored as a burn wound dressing. However, unfavorable gelation conditions limit the processability and clinical application. Herein a white light-responsive photopolymerization technique was adapted for gelation via photooxidation of tyrosine. To render the gel suitable for application to irregular and non-planar burn surfaces, SF gel-incorporated dressing (SFD) was fabricated. The mild gelation conditions using white light afforded the loading of drugs for local delivery. The moisture balance ability of the dressing was confirmed by the favorable measures of swelling capacity (106 ± 1 %) and moisture retention (≈10 h). The in vitro cytocompatibility of the gel was confirmed using HaCaT cells. Finally, in vivo performance of the SFD was tested on a second-degree burn in a rodent model. The gross analysis and histological assessment revealed scarless healing in SFD-treated groups. Overall, the SFD developed in this work is shown to be a promising candidate for advanced burn wound care.

Silk composite interfacial layer eliminates rebleeding with chitosan-based hemostats.

Chitosan foams are among the approved hemostats for pre-hospital hemorrhagic control but suffer from drawbacks related to mucoadhesiveness and rebleeding. Herein, we have developed a designer bilayered hemostatic foam consisting of a bioactive layer composed of silica particles (≈300 nm) and silk fibroin to serve as the tissue interfacing component on a chitosan foam. The foam composition was optimized based on the in vitro clotting behavior and cytocompatibility of individual components. In vivo analysis in a rat model demonstrated that the developed hemostat could achieve rapid clotting (31 ± 4 s), similar to a chitosan-based hemostat, but the former had significantly lower blood loss. Notably, removal of the bilayered hemostat prevented rebleeding, unlike the chitosan foam, which was associated with markedly higher incidences of rebleeding (50 %) and left behind material residue. Thus, the designer bilayered foam presented here is a potent inducer of blood clotting whilst affording easy removal with minimal rebleeding.

Highly Responsive Plasmon Modulation in Dopant-Segregated Nanocrystals.

Electron transfer to and from metal oxide nanocrystals (NCs) modulates their infrared localized surface plasmon resonance (LSPR), revealing fundamental aspects of their photophysics and enabling dynamic optical applications. We synthesized and chemically reduced dopant-segregated Sn-doped In2O3 NCs, investigating the influence of radial dopant segregation on LSPR modulation and near-field enhancement (NFE). We found that core-doped NCs show large LSPR shifts and NFE change during chemical titration, enabling broadband modulation in LSPR energy of over 1000 cm-1 and of peak extinction over 300%. Simulations reveal that the evolution of the LSPR spectra during chemical reduction results from raising the surface Fermi level and increasing the donor defect density in the shell region. These results establish dopant segregation as a useful strategy to engineer the dynamic optical modulation in plasmonic semiconductor NC heterostructures going beyond what is possible with conventional plasmonic metals.

Magnetoplasmonics beyond Metals: Ultrahigh Sensing Performance in Transparent Conductive Oxide Nanocrystals.

Active modulation of the plasmonic response is at the forefront of today's research in nano-optics. For a fast and reversible modulation, external magnetic fields are among the most promising approaches. However, fundamental limitations of metals hamper the applicability of magnetoplasmonics in real-life active devices. While improved magnetic modulation is achievable using ferromagnetic or ferromagnetic-noble metal hybrid nanostructures, these suffer from severely broadened plasmonic response, ultimately decreasing their performance. Here we propose a paradigm shift in the choice of materials, demonstrating for the first time the outstanding magnetoplasmonic performance of transparent conductive oxide nanocrystals with plasmon resonance in the near-infrared. We report the highest magneto-optical response for a nonmagnetic plasmonic material employing F- and In-codoped CdO nanocrystals, due to the low carrier effective mass and the reduced plasmon line width. The performance of state-of-the-art ferromagnetic nanostructures in magnetoplasmonic refractometric sensing experiments are exceeded, challenging current best-in-class localized plasmon-based approaches.

Dual-Mode Infrared Absorption by Segregating Dopants within Plasmonic Semiconductor 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.

Competition between Depletion Effects and Coupling in the Plasmon Modulation of Doped Metal Oxide Nanocrystals.

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.

Multifunctional Sn- and Fe-Codoped In2O3 Colloidal Nanocrystals: Plasmonics and Magnetism.

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.