Colloidal Cu₂O nanoparticles can exhibit both photocatalytic activity under visible light illumination and resonant Mie scattering, but, for their practical application, they have to be immobilized on a substrate. Butterfly wings, with complex hierarchical photonic nanoarchitectures, constitute a promising substrate for the immobilization of nanoparticles and for the tuning of their optical properties. The native wax layer covering the wing scales of Polyommatus icarus butterflies was removed by simple ethanol pretreatment prior to the deposition of Cu₂O nanoparticles, which allowed reproducible deposition on the dorsal blue wing scale nanoarchitectures via drop casting. The samples were investigated by optical and electron microscopy, attenuated total reflectance infrared spectroscopy, UV–visible spectrophotometry, microspectrophotometry, and hyperspectral spectrophotometry. It was found that the Cu₂O nanoparticles integrated well into the photonic nanoarchitecture of the P. icarus wing scales, they exhibited Mie resonance on the glass slides, and the spectral signature of this resonance was absent on Si(100). A novel bio-nanohybrid photonic nanoarchitecture was produced in which the spectral properties of the butterfly wings were tuned by the Cu₂O nanoparticles and their backscattering due to the Mie resonance was suppressed despite the low refractive index of the chitinous substrate.

Plasmonic metallic nanoparticles, like Au, can be used to tune the optical properties of photonic nanoarchitectures occurring in butterfly wing scales possessing structural color. The effect of the nanoscale Au depends on the location and the amount deposited in the chitin-based photonic nanoarchitecture. The following three types of Au introduction methods were compared regarding the structural and optical properties of the resulting hybrid bio-nanocomposites: (i) growth of Au nanoparticles inside the nanopores of butterfly wing scales by a light-induced in situ chemical reduction of HAuCl₄ in aqueous solution containing sodium citrate, as a new procedure we have developed, (ii) drop-drying of the aqueous Au sol formed during procedure (i) in the bulk liquid phase, and (iii) physical vapor deposition of Au thin film onto the butterfly wing. We investigated all three methods at two different Au concentrations on the wings of laboratory-bred blue-colored male Polyommatus icarus butterflies and characterized the optical properties of the resulting hybrid bio-nanocomposites. We found that the drop-drying and the in situ growth produced comparable redshift in the spectral position of the reflectance maximum associated with the chitin-based photonic nanoarchitecture in the wing scales, while the 5 nm or 15 nm thick Au layers vacuum deposited onto the butterfly wing behaved like an optical filter, without inducing spectral shift. The in situ growth in the photonic nanoarchitecture under intense illumination produced uniform Au nanoparticles located in the pores of the biological template, which is more advantageous for further applications. An additional benefit of this method is that the Au nanoparticles do not aggregate on drying, like in the case of drop-drying of preformed Au nanoparticles from the citrate-stabilized sol.