Analysis of the optical response of reptile tissues in the visible and UV applying the KKR method.

Structural colors in nature are frequently produced by the ordered arrangement of nanoparticles. Interesting examples include reptiles and birds utilizing lattice-like formation of nanoparticles to produce a variety of colors. A famous example is the panther chameleon which is even able to change its color by actively varying the distance between guanine nanocrystals in its skin. Here, we demonstrate that the application of rigorous electromagnetic methods is important to determine the actual optical response of such biological systems. By applying the Korringa-Kohn-Rostoker (KKR) method we calculate the efficiencies of the reflected diffraction orders that can be viewed from directions other than the specular. Our results reveal that important characteristics of the reflectance spectra, especially within the ultraviolet (UV) and short visible wavelengths region, cannot be predicted by approximate models like the often-applied Maxwell-Garnett approach. Additionally, we show that the KKR method can be employed for the design of multi-layer structures with a desired optical response in the UV regime.

Porous polymeric microparticles foamed with supercritical CO2as scattering white pigments.

Nowadays, titanium dioxide (TiO2) is the most commercially relevant white pigment. Nonetheless, it is widely criticized due to its energy-intensive extraction and costly disposal of harmful by-products. Furthermore, recent studies discuss its potential harm for the environment and the human health. Environment-friendly strategies for the replacement of TiO2as a white pigment can be inspired from nature. Here whiteness often originates from broadband light scattering air cavities embedded in materials with refractive indices much lower than that of TiO2. Such natural prototypes can be mimicked by introducing air-filled nano-scale cavities into commonly used polymers. Here, we demonstrate the foaming of initially transparent poly(methyl methacrylate) (PMMA) microspheres with non-toxic, inert, supercritical CO2. The properties of the foamed, white polymeric pigments with light scattering nano-pores are evaluated as possible replacement for TiO2pigments. For that, the inner foam structure of the particles was imaged by phase-contrast x-ray nano-computed tomography (nano-CT), the optical properties were evaluated via spectroscopic measurements, and the mechanical stability was examined by micro compression experiments. Adding a diffusion barrier surrounding the PMMA particles during foaming allows to extend the foaming process towards smaller particles. Finally, we present a basic white paint prototype as exemplary application.

Roll-to-roll fabrication of superhydrophobic pads covered with nanofur for the efficient clean-up of oil spills.

Superhydrophobic surfaces, which self-clean through rinsing with water, have gained significant importance during the last decades. A method to fabricate such a surface featuring the lotus effect, solely through structuring, is hot pulling of a polymer surface. This technique provides the so-called nanofur, which consists of a polymer surface densely covered with a polymeric fur of extremely thin hair-like structures. Here, we present a continuous roll-to-roll process for the fabrication of a thin polymeric film covered with nanofur from polypropylene. Our process enables structuring of large areas of the order of square meters using industry standard machinery. This opens up many possible applications for nanofur that could previously not be realized because of the limitations of conventional hot embossing regarding structurable area. The structured film is subsequently processed into an exemplary product, that is, so-called nanopads; polymeric sandwiches of polypropylene film covered with nanofur and filled with an oil-absorbing material. These are well-suited for the cleanup of small oil spills.

Analysis of the optical properties of the silvery spots on the wings of the Gulf Fritillary, Dione vanillae.

The ventral face of the wings of the butterfly Dione vanillae is covered with bright and shiny silvery spots. These areas contain densely packed ground- and coverscales with a bright metallic appearance reflecting more than 50% of light uniformly over the visible range. Our analysis shows that this optically attractive feature is caused by the inner microstructure of the scales located in these areas. Electron microscopy of cross sections through the scales shows that upper and lower lamina, supporting trabeculae, and topping ridges can be approximated by a 'circus tent'-like geometry. By simulating its optical properties, we show that a moderate disorder of this geometry is important for the uniform reflection of light resulting in the silvery appearance.

On the multifunctionality of butterfly scales: a scaling law for the ridges of cover scales.

The bright colors found on the wings of some butterflies have been widely examined during recent decades because they are frequently caused by nano-structures and not by pigments or dyes. Sometimes it is puzzling to discover the physical origin of these structural colors because the color-causing nano-structures are integrated into a complex structure of scales that densely covers the butterfly wings. While the color of the wings serves purposes ranging from mating to camouflage and thermoregulation, the overall structure of the scales is commonly believed to assist with aerodynamics, self-cleaning, and easy release from spider webs. This multi-functionality of butterfly scales causes various constraints for their evolutionary design. Here, we present a structural analysis of the height and distance of the ridges in cover scales of butterfly species from different families. The subsequent analysis reveals a linear scaling law. The height of the ridges is always less than half of the distance between them. Finally, we discuss possible reasons for this geometrical scaling law.

Variation of the frictional anisotropy on ventral scales of snakes caused by nanoscale steps.

The ventral scales of most snakes feature micron-sized fibril structures with nanoscale steps oriented towards the snake's tail. We examined these structures by microtribometry as well as atomic force microscopy (AFM) and observed that the nanoscale steps of the micro-fibrils cause a frictional anisotropy, which varies along the snake's body in dependence of the height of the nanoscale steps. A significant frictional behavior is detected when a sharp AFM tip scans the nanoscale steps up or down. Larger friction peaks appear during upward scans (tail to head direction), while considerably lower peaks are observed for downward scans (head to tail direction). This effect causes a frictional anisotropy on the nanoscale, i.e. friction along the head to tail direction is lower than in the opposite direction. The overall effect increases linearly with the step height of the micro-fibrils. Although the step heights are different for each snake, the general step height distribution along the body of the examined snakes follows a common pattern. The frictional anisotropy, induced by the step height distribution, is largest close to the tail, intermediate in the middle, and lower close to the head. This common distribution of frictional anisotropy suggests that snakes even optimized nanoscale features like the height of micro-fibrils through evolution in order to achieve optimal friction performance for locomotion. Finally, ventral snake scales are replicated by imprinting their micro-fibril structures into a polymer. As the natural prototype, the artificial surface exhibits frictional anisotropy in dependence of the respective step height. This feature is of high interest for the design of tribological surfaces with artificial frictional anisotropy.

3D-Printed Scanning-Probe Microscopes with Integrated Optical Actuation and Read-Out.

Scanning-probe microscopy (SPM) is the method of choice for high-resolution imaging of surfaces in science and industry. However, SPM systems are still considered as rather complex and costly scientific instruments, realized by delicate combinations of microscopic cantilevers, nanoscopic tips, and macroscopic read-out units that require high-precision alignment prior to use. This study introduces a concept of ultra-compact SPM engines that combine cantilevers, tips, and a wide variety of actuator and read-out elements into one single monolithic structure. The devices are fabricated by multiphoton laser lithography as it is a particularly flexible and accurate additive nanofabrication technique. The resulting SPM engines are operated by optical actuation and read-out without manual alignment of individual components. The viability of the concept is demonstrated in a series of experiments that range from atomic-force microscopy engines offering atomic step height resolution, their operation in fluids, and to 3D printed scanning near-field optical microscopy. The presented approach is amenable to wafer-scale mass fabrication of SPM arrays and capable to unlock a wide range of novel applications that are inaccessible by current approaches to build SPMs.

Locally Controlled Growth of Individual Lambda-Shaped Carbon Nanofibers.

The locally defined growth of carbon nanofibers with lambda shape in an open flame process is demonstrated. Via the growth time, the geometry of the structures can be tailored to a Λ- or λ-type shape. Microchannel cantilever spotting and dip-pen nanolithography are utilized for the deposition of catalytic salt NiCl2 · 6H2 O for locally controlled growth of lambda-shaped carbon nanofibers. Rigorous downscaling reveals a critical catalytic salt volume of 0.033 µm³, resulting in exactly one lambda-shaped carbon nanofiber at a highly predefined position. An empirical model explains the observed growth process.

Characterization of the microscopic tribological properties of sandfish (Scincus scincus) scales by atomic force microscopy.

Lizards of the genus Scincus are widely known under the common name sandfish due to their ability to swim in loose, aeolian sand. Some studies report that this fascinating property of sandfish is accompanied by unique tribological properties of their skin such as ultra-low adhesion, friction and wear. The majority of these reports, however, is based on experiments conducted with a non-standard granular tribometer. Here, we characterise microscopic adhesion, friction and wear of single sandfish scales by atomic force microscopy. The analysis of frictional properties with different types of probes (sharp silicon tips, spherical glass tips and sand debris) demonstrates that the tribological properties of sandfish scales on the microscale are not exceptional if compared to snake scales or technical surfaces such as aluminium, Teflon, or highly oriented pyrolytic graphite.

Tuning of Structural Colors Like a Chameleon Enabled by Shape-Memory Polymers.

Nature often uses structuring of materials for coloration rather than incorporating dye molecules, since single-construction materials are capable of producing any vivid visible color in plants and insects. By precisely engineering features that diffract or scatter light, more recently, humans have created similarly intense non-fading colors. Stretchable polymer opals have emerged as a single material which can dynamically shift across the whole visible spectrum using structural colors, by temporary stretching or compression. For energy efficiency and practical considerations, however, it is necessary to fix semi-permanently desired colors without continuous stretching or application of other stimuli or energy. Here, a polymer opal incorporating a shape-memory polymer embedded in its matrix can keep a particular color fixed without the application of external forces, yet can be reprogrammed to a different fixed color on demand. The influence of the material composition on its optical appearance, shape-fixity, and shape recovery abilities in controlled stretch experiments is quantified. High-speed printing-compatible localized compression pattern imprinting is shown to generate stable but easily erasable color patterns. This opens up the potential for durable and energy-efficient yet reusable and reconfigurable displays, wearables, or packaging and security labeling based on such polymeric film materials.

Self-Cleaning Microcavity Array for Photovoltaic Modules.

Development of self-cleaning coatings is of great interest for the photovoltaic (PV) industry, as soiling of the modules can significantly reduce their electrical output and increase operational costs. We fabricated flexible polymeric films with novel disordered microcavity array (MCA) topography from fluorinated ethylene propylene (FEP) by hot embossing. Because of their superhydrophobicity with water contact angles above 150° and roll-off angles below 5°, the films possess self-cleaning properties over a wide range of tilt angles, starting at 10°, and contaminant sizes (30-900 µm). Droplets that impact the FEP MCA surface with velocities of the same order of magnitude as that of rain bounce off the surface without impairing its wetting properties. Additionally, the disordered MCA topography of the films enhances the performance of PV devices by improving light incoupling. Optical coupling of the FEP MCA films to a glass-encapsulated multicrystalline silicon solar cell results in 4.6% enhancement of the electrical output compared to that of an uncoated device.

Topographic cues guide the attachment of diatom cells and algal zoospores.

Surface topography plays a key role in the colonization of substrata by the colonizing stages of marine fouling organisms. For the innovation of marine antifouling coatings, it is essential to understand how topographic cues affect the settlement of these organisms. In this study, tapered, spiked microstructures and discrete honeycombs of varying feature dimensions were designed and fabricated in order to examine the influence of topography on the attachment of zoospores of the green macroalga Ulva linza and cells of the diatom (microalga) Navicula incerta. Contrasting results were obtained with these two species of algae. Indeed, the preferred location of cells of N. incerta was dominated by attachment point theory, which suggested a positive correlation between the density of cells adhering and the amount of available attachment points, while the settlement of spores of U. linza was mainly regulated by both Wenzel roughness and local binding geometry.

Bioinspired phase-separated disordered nanostructures for thin photovoltaic absorbers.

The wings of the black butterfly, Pachliopta aristolochiae, are covered by micro- and nanostructured scales that harvest sunlight over a wide spectral and angular range. Considering that these properties are particularly attractive for photovoltaic applications, we analyze the contribution of these micro- and nanostructures, focusing on the structural disorder observed in the wing scales. In addition to microspectroscopy experiments, we conduct three-dimensional optical simulations of the exact scale structure. On the basis of these results, we design nanostructured thin photovoltaic absorbers of disordered nanoholes, which combine efficient light in-coupling and light-trapping properties together with a high angular robustness. Finally, inspired by the phase separation mechanism of self-assembled biophotonic nanostructures, we fabricate these bioinspired absorbers using a scalable, self-assembly patterning technique based on the phase separation of binary polymer mixture. The nanopatterned absorbers achieve a relative integrated absorption increase of 90% at a normal incident angle of light to as high as 200% at large incident angles, demonstrating the potential of black butterfly structures for light-harvesting purposes in thin-film solar cells.

Bio-inspired micro-to-nanoporous polymers with tunable stiffness.

Background: Inspired by structural hierarchies and the related excellent mechanical properties of biological materials, we created a smoothly graded micro- to nanoporous structure from a thermoplastic polymer. Results: The viscoelastic properties for the different pore sizes were investigated in the glassy regime by dynamic flat-punch indentation. Interestingly, the storage modulus was observed to increase with increasing pore-area fraction. Conclusion: This outcome appears counterintuitive at first sight, but can be rationalized by an increase of the pore wall thickness as determined by our quantitative analysis of the pore structure. Therefore, our approach represents a non-chemical way to tune the elastic properties and their local variation for a broad range of polymers by adjusting the pore size gradient.

Bio-inspired hierarchical micro- and nano-wrinkles obtained via mechanically directed self-assembly on shape-memory polymers.

Inspired by complex multi-functional leaf and petal surfaces, we introduce a mechanically directed self-assembly process to create linearly oriented micro- and nanosized surface wrinkles in an all-polymer bi-layer system based on a shape-memory polymer substrate. By systematically investigating the influence of coating thickness and substrate programming strain on wrinkle period and height, we reveal how to control the structure size from a few hundred nanometers up to several microns. As a parameter unique to shape memory polymers, we demonstrate that the temperature during the recovery process can also be utilized to tailor the structure dimensions. Furthermore, we advance the method with a second structuring step to mimic the hierarchically structured petal surfaces of tulips and daisies. The presented structuring method provides a large-scale, mold-free, and very cost-effective way for the full-polymer fabrication of micro and sub-microstructures with adjustable structure size and intrinsic irregularity.

Bio-inspired, large scale, highly-scattering films for nanoparticle-alternative white surfaces.

Inspired by the white beetle of the genus Cyphochilus, we fabricate ultra-thin, porous PMMA films by foaming with CO2 saturation. Optimising pore diameter and fraction in terms of broad-band reflectance results in very thin films with exceptional whiteness. Already films with 60 µm-thick scattering layer feature a whiteness with a reflectance of 90%. Even 9 µm thin scattering layers appear white with a reflectance above 57%. The transport mean free path in the artificial films is between 3.5 µm and 4 µm being close to the evolutionary optimised natural prototype. The bio-inspired white films do not lose their whiteness during further shaping, allowing for various applications.

Copper atomic-scale transistors.

We investigated copper as a working material for metallic atomic-scale transistors and confirmed that copper atomic-scale transistors can be fabricated and operated electrochemically in a copper electrolyte (CuSO4 + H2SO4) in bi-distilled water under ambient conditions with three microelectrodes (source, drain and gate). The electrochemical switching-on potential of the atomic-scale transistor is below 350 mV, and the switching-off potential is between 0 and -170 mV. The switching-on current is above 1 µA, which is compatible with semiconductor transistor devices. Both sign and amplitude of the voltage applied across the source and drain electrodes (Ubias) influence the switching rate of the transistor and the copper deposition on the electrodes, and correspondingly shift the electrochemical operation potential. The copper atomic-scale transistors can be switched using a function generator without a computer-controlled feedback switching mechanism. The copper atomic-scale transistors, with only one or two atoms at the narrowest constriction, were realized to switch between 0 and 1G0 (G0 = 2e2/h; with e being the electron charge, and h being Planck's constant) or 2G0 by the function generator. The switching rate can reach up to 10 Hz. The copper atomic-scale transistor demonstrates volatile/non-volatile dual functionalities. Such an optimal merging of the logic with memory may open a perspective for processor-in-memory and logic-in-memory architectures, using copper as an alternative working material besides silver for fully metallic atomic-scale transistors.

Adaptable bioinspired special wetting surface for multifunctional oil/water separation.

Inspired by the multifunctionality of biological surfaces necessary for the survival of an organism in its specific environment, we developed an artificial special wetting nanofur surface which can be adapted to perform different functionalities necessary to efficiently separate oil and water for cleaning accidental oil spills or separating industrial oily wastewater. Initial superhydrophobic nanofur surface is fabricated using a hot pulling method, in which nano- and microhairs are drawn out of the polymer surface during separation from a heated sandblasted steel plate. By using a set of simple modification techniques, which include microperforation, plasma treatment and subsequent control of storage environment, we achieved selective separation of either water or oil, variable oil absorption and continuous gravity driven separation of oil/water mixtures by filtration. Furthermore, these functions can be performed using special wetting nanofur made from various thermoplastics, including biodegradable and recyclable polymers. Additionally, nanofur can be reused after washing it with organic solvents, thus, further helping to reduce the environmental impacts of oil/water separation processes.

Dry adhesives from carbon nanofibers grown in an open ethanol flame.

Based on magnetic-field-assisted growth of carbon nanofibers in an open ethanol flame we fabricated arrays of carbon nanofibers with different degrees of orientation. Inspired by the dry adhesive system of geckos we investigated the adhesive properties of such carbon nanofiber arrays with ordered and random orientation. AFM-based force spectroscopy revealed that adhesion force and energy rise linear with preload force. Carbon nanofibers oriented by a magnetic field show a 68% higher adhesion (0.66 N/cm2) than the randomly oriented fibers. Endurance tests revealed that the carbon nanofiber arrays withstand 50.000 attachment/detachment cycles without observable wear.