The incorporation of porous structures into films and coatings can transform their properties for applications in optics, separation, electronics, and energy generation and storage. Packing nanoparticles (NPs) is a versatile approach for fabricating nanoporous films with a tunable structure and properties. The mechanical fragility of NP packing-based films and coatings, however, significantly impedes their widespread utilization. Although infiltrating a polymer into the interstices of these NP packings has been shown to enhance their mechanical durability, this method completely eliminates the porosity of the structures, compromising their properties and functionality. This study presents a new approach to fabricate highly loaded porous nanocomposite films with a gradient in the refractive index by infiltrating subsaturating amounts of poly(methyl methacrylate) (PMMA) into disordered packings of hollow silica NPs. We demonstrate that dual porosity is a critical feature that enhances their antireflection (AR) and mechanical properties. The hollow cores of NPs prevent a substantial increase in the refractive index of the resulting films. Moreover, the interparticle voids allow for mechanical reinforcement to occur when the NP packings are infiltrated with PMMA, making them even more suitable for AR coatings. The refractive index and gradient across the nanocomposites can be tailored by adjusting the amount of PMMA infiltrated into the NP packing, the shape of hollow NPs, and the annealing time. The nanocomposite coatings with a continuous gradient in refractive index exhibit excellent AR properties and enhanced mechanical durability. Combined with the unique structural tunability afforded by the dual porosity, this approach provides a scalable and effective way to create robust and graded nanoporous structures for various applications.
Keywords: antireflection coatings; capillary rise; gradient; hollow silica nanoparticles; nanocomposites; nanoporous.