<p>Bio-inorganic structures have been found to exhibit impressive optical and mechanical properties, such as control of light and/or high fracture strength. Certain species of diatoms (single-celled algae) form siliceous microshells (frustules) with organized structures that affect the transmission of light or fracture strengths. It has been found that <i>Coscinodiscus wailesii</i> diatoms have frustules with a quasi-regular hexagonal pattern of pores, which act as micro-lenses. In terms of mechanical strength, <i>Fragilariopsis kerguelensis</i> diatom SiO₂ frustules have been observed to exhibit impressive compressive and tensile fracture stress values. In this study, shape-preserving chemical conversion (using gas/solid reactions) is used to transform biogenic structures (diatom frustules) into high IR refractive index or ultrahigh specific strength materials. High-fidelity MgO/Si, Mg₂Si, Ca₂Si, MgO/Ti, and Ti replicas are successfully synthesized and characterized by SEM, EDX, XRD, and TEM. Focal point imaging experiments are used to show that focusing behavior of MgO/Si and Mg₂Si replicas can be enhanced in the IR range upon conversion into higher index replicas. Mechanical properties of SiO₂ frustules, MgO/Ti replicas, and Ti replicas have been measured by using in-situ and ex-situ indentation, which revealed that the mechanical properties can be enhanced by the shape-preserved chemical conversion of Bio-inorganic structures.</p><p><br></p>

<p>Impressive examples of the generation of hierarchically-patterned, three-dimensional (3-D) structures for the control of light can be found throughout nature. <i>Morpho rhetenor</i> butterflies, for example, possess scales with periodic parallel ridges, each of which consists of a stack of thin (nanoscale) layers (lamellae). The bright blue color of <i>Morpho</i> butterflies has been attributed to controlled scattering of the incident light by the lamellae of the wing scales. Another stunning example is the frustule (microshell) of the <i>Coscinodiscus wailesii</i> diatom, which is capable of focusing red light without possessing a traditional lens morphology. The photonic structures and the optical behaviors of <i>Morpho</i> butterflies and <i>Coscinodiscus wailesii</i> diatoms have been extensively studied. However, no work has been conducted to shift such light manipulation from the visible to the infrared (IR) range via shape-preserving conversion of such biogenic structures. Controlling IR radiation (i.e., heat) utilizing biogenic or biomimetic structures can be of significant utility for the development of energy-harvesting devices. In order to enhance the optical interaction in the IR range, inorganic replicas of biogenic structures comprised of high-refractive-index materials have been generated in this work. Such replicas of <i>Morpho</i> <i>rhetenor</i> scales were fabricated via a combination of sol-gel solution coating, organic pyrolysis, and gas/solid reaction methods. Diatomimetic structures have also been generated via sol-gel coating, gas/solid reaction, and then patterning of pore arrays using focused ion beam (FIB) milling.</p> Throughout the sol-gel solution coating and chemical conversion steps of the processes developed in this study, attention was paid to preserve the starting shapes of the nanopatterned, microscale biogenic or biomimetic structures. Factors affecting such shape preservation included the thicknesses and uniformities of coatings applied to the biogenic or biomimetic templates, nano/microstructural evolution during thermal treatment, and reaction-induced volume changes. A conformal surface sol-gel (SSG) coating process was developed in this work to generate oxide replicas of <i>Morpho rhetenor</i> butterfly scales with precisely-controlled coating thicknesses. The adsorption kinetics and relevant adsorption isotherm of the SSG process were investigated utilizing a quartz crystal microbalance. Analyses of thermodynamic driving forces, rate-limiting kinetic steps, and volume changes associated with various chemical reactions were used to tailor processing parameters for optimized shape preservation.