Plasmonic semiconductor nanocrystals (NCs) are a new and exciting class of materials that enable higher control of their localized surface plasmon resonance (LSPR) than metallic counterparts. Additionally, earth-abundant and non-toxic materials such as copper iron sulfides are gaining interest as alternatives to heavy metal-based semiconductor materials. Colloidal bornite (Cu5FeS4) is an interesting but underexplored example of a heavy metal-free plasmonic semiconductor. This report details the hot-injection synthesis of bornite yielding NCs ranging from 2.7 to 6.1 nm in diameter with stoichiometric control of the copper and iron content. The absorbance spectra of bornite NCs with different Cu:Fe ratios change at different rates as the particles oxidize and develop LSPR in the near-infrared region. X-ray photoelectron spectroscopy results indicate that oxidation produces sulfates rather than metal oxides as well as a decrease in the iron content within the NCs. Additionally, increasing iron content leads to decreases in carrier density and effective mass of the carrier, as determined by the Drude model. This controlled synthesis, combined with a further understanding of the relationship between the particle structure and optical properties, will enable the continued development and application of these fascinating heavy metal-free plasmonic semiconductor nanoparticles.

The assembly of monodisperse particles into colloidal arrays that diffract visible light through constructive interference is of considerable interest due to their resilience against color fading. In particular, noniridescent structurally colored materials are promising as a means of coloration for paints, inks, cosmetics, and displays because their color is angle independent. A rapid and tunable assembly method for producing noniridescent structurally colored colloidal-based materials that are pliable after fabrication is described. Structurally colored particle arrays were fabricated by centrifuging highly charged silica particles suspended in deionized water. By tuning the particle diameter, the colors displayed by the arrays spanned the visible spectrum while retaining angle-independent structural color. The color of centrifuged colloids of a single particle diameter was precisely controlled within 50 nm by modulating the particle concentration. The peak wavelength diffracted by the material was further tuned by altering the centrifugal rate and assembly time. Centrifugation assembly of particles in a polymer solution also produces noniridescent colloidal films, and the control of their color is reported. Together, these results offer design considerations for the centrifugation-based assembly of colloidal films with tunable structural color that are transferable after fabrication and are angle independent.

Nanoparticle hydrogels undergo a degradation-directed assembly producing tunable structural color changes for potential sensor applications.