Antireflective (AR) silica/polymer composite coatings on glass and poly(methyl methacrylate) (PMMA) substrates were prepared by silica mineralization of layer-by-layer (LbL) assembled films composed of polystyrene-block-poly(l-lysine)/poly(l-glutamic acid) (PS-b-PLL/PGA) complex vesicles without any post-treatments. PS-b-PLL AB and AB block copolymers with appropriate block ratio can self-assemble to form vesicles, which can be deposited onto substrates without dissociation. Silica deposition specifically onto the complex vesicles in the multilayer films through amine-catalyzed polycondensation results in the continuous, intact composite coatings comprising vesicular nanostructures, which provided an additional parameter for tuning their optical properties. The film thickness and porosity are mainly dictated by the bilayer number and the degree of deformation/fission of vesicles upon complexation and mineralization, depending on polymer composition. The coated PMMA substrate with maximum transmission over 98% can be achieved at the optimized wavelength region. The AR composite films were mechanically stable to withstand both the wipe and adhesion tests due to the preparation of continuous, intact films. This study demonstrated that the concept of preparing composite films comprising vesicular nanostructures through the combination of LbL assembly and biomineralization is feasible.

We report a versatile approach to synthesize silica coatings with antireflective (AR) characteristics through the combination of a layer-by-layer (LbL) assembly technique and biomineralization. LbL assembled decanoyl-modified poly(l-lysine)/poly(l-glutamic acid) (PLL-g-Dec/PLGA) multilayer films were used as templates for silica mineralization, followed by calcination. The specific deposition of silica onto the LbL polypeptide assemblies through amine-catalyzed polycondensation resulted in silica coatings that exhibited the transcription of the nano-/microstructured polypeptide films and their film thickness and porosity can be tuned by varying the number of bilayers, degree of substitution, and PLL molecular weight. AR silica coatings exhibiting more than 6% increase in transmittance in the near UV/visible spectral range can be obtained at an optimized refractive index, thickness, and surface roughness. The abrasion test showed that the silica coatings exhibited sufficient structural durability due to continuous silica nanostructures and low surface roughness. This study demonstrated that nanostructured thin films can be synthesized for AR coatings using the synergy between the LbL assembly technique and biomineralization.