Hierarchical Colorful Structures by Three-Dimensional Printing of Inverse Opals.

Structural coloration is a recurring solution in biological systems to control visible light. In nature, basic structural coloration results from light interacting with a repetitive nanopattern, but more complex interactions and striking results are achieved by organisms incorporating additional hierarchical structures. Artificial reproduction of single-level structural color has been achieved using repetitive nanostructures, with flat sheets of inverse opals being very popular because of their simple and reliable fabrication process. Here, we control photonic structures at several length scales using a combination of direct laser writing and nanosphere assembly, producing freeform hierarchical constructions of inverse opals with high-intensity structural coloration. We report the first 3D prints of stacked, overhanging and slanted microstructures of inverse opals. Among other characteristics, these hierarchical photonic structures exhibit geometrically tunable colors, focal-plane-dependent patterns, and arbitrary alignment of microstructure facet with self-assembled lattice. Based on those results, novel concepts of multilevel information encoding systems are presented.

Biocompatibility of Biomaterials for Tissue Regeneration or Replacement.

Emerging biomaterials for tissue engineering applications witness a multitude of interaction (both along their interface and internally) with human tissue. Insufficient consideration of the spatial and temporal aspects of these biomaterial-tissue interactions often raise biocompatibility concerns. This review focuses on strategies implemented in some of the recently developed biomaterials-particularly for soft and hard tissue regeneration or replacement-to overcome potential foreign body response and ensure effective functioning of the biomaterial.

Tough and Strong: Cross-Lamella Design Imparts Multifunctionality to Biomimetic Nacre.

The creation of structural composites with combined strength, toughness, low density, and biocompatibility remains a long-standing challenge. On the other hand, bivalve marine shells-Clinocardiumspp.-exhibit strength, stiffness, and toughness that surpass even that of the nacre that is the most widely mimicked model for structural composites. The superior mechanical properties of Clinocardiumspp. shells originate from their cross-lamella design, comprising CaCO3 mineral platelets arranged in an "interlocked" herringbone fashion. Reproduction of such hierarchical designs could offer multifunctionality, potentially combining strength and toughness at low densities, and the capability for seamless integration with biological systems. Here, we demonstrate manufacturing of the cross-lamella design by biomineralizing aragonite films with sawtooth patterns and assembling them in a chitosan/fibroin matrix to generate a composite with interlocked mineral layers. The resultant composite, with a similar constitution to that of the biological counterpart, nearly doubles the strength of previous nacre-mimetic composites while improving the tensile toughness and simultaneously exhibiting stiffness and biocompatibility.

Gecko-Inspired Dry Adhesive Based on Micro-Nanoscale Hierarchical Arrays for Application in Climbing Devices.

The unusual ability of geckos to climb vertical walls underlies a unique combination of a hierarchical structural design and a stiffer material composition. While a dense array of microscopic hierarchical structures enables the gecko toe pads to adhere to various surfaces, a stiffer material (ß-keratin) composition enables them to maintain reliable adhesion over innumerable cycles. This unique strategy has been seldom implemented in engineered dry adhesives because fabrication of high-aspect-ratio hierarchical structures using a stiffer polymer is challenging. Herein, we report the fabrication of high-aspect-ratio hierarchical arrays on flexible polycarbonate sheets (stiffness comparable to that of ß-keratin) by a sacrificial-layer-mediated nanoimprinting technique. Dry-adhesive films comprising the hierarchical arrays showed a formidable shear adhesion of 11.91 ± 0.43 N/cm2. Cyclic adhesion tests also showed that the shear adhesion of the adhesive films reduced by only about 20% after 50 cycles and remained nearly constant until about 200 cycles. Most importantly, the high-aspect-ratio hierarchical arrays were integrated onto the feet of a miniature robot and the locomotion on a 30° inclined surface was demonstrated.

Cellulose Acetate-Poly(N-isopropylacrylamide)-Based Functional Surfaces with Temperature-Triggered Switchable Wettability.

Temperature-triggered switchable nanofibrous membranes are successfully fabricated from a mixture of cellulose acetate (CA) and poly(N-isopropylacrylamide) (PNIPAM) by employing a single-step direct electrospinning process. These hybrid CA-PNIPAM membranes demonstrate the ability to switch between two wetting states viz. superhydrophilic to highly hydrophobic states upon increasing the temperature. At room temperature (23 °C) CA-PNIPAM nanofibrous membranes exhibit superhydrophilicity, while at elevated temperature (40 °C) the membranes demonstrate hydrophobicity with a static water contact angle greater than 130°. Furthermore, the results here demonstrate that the degree of hydrophobicity of the membranes can be controlled by adjusting the ratio of PNIPAM in the CA-PNIPAM mixture.

Multiscale ommatidial arrays with broadband and omnidirectional antireflection and antifogging properties by sacrificial layer mediated nanoimprinting.

Moth's eye inspired multiscale ommatidial arrays offer multifunctional properties of great significance in optoelectronic devices. However, a major challenge remains in fabricating these arrays on large-area substrates using a simple and scalable technique. Here we present the fabrication of these multiscale ommatidial arrays over large areas by a distinct approach called sacrificial layer mediated nanoimprinting, which involves nanoimprinting aided by a sacrificial layer. The fabricated arrays exhibited excellent pattern uniformity over the entire patterned area. Optimum dimensions of the multiscale ommatidial arrays determined by the finite-difference time domain simulations served as the design parameters for replicating the arrays on glass. A broadband suppression of reflectance to a minimum of ∼1.4% and omnidirectional antireflection for highly oblique angles of incidence up to 70° were achieved. In addition, superhydrophobicity and superior antifogging characteristics enabled the retention of optical properties even in wet and humid conditions, suggesting reliable optical performance in practical outdoor conditions. We anticipate that these properties could potentially enhance the performance of optoelectronic devices and minimize the influence of in-service conditions. Additionally, as our technique is solely nanoimprinting-based, it may enable scalable and high-throughput fabrication of multiscale ommatidial arrays.

Fabrication of highly uniform and porous MgF2 anti-reflective coatings by polymer-based sol-gel processing on large-area glass substrates.

Despite recent progress in the fabrication of magnesium fluoride (MgF2) anti-reflective coatings (ARCs), simple, effective and scalable sol-gel fabrication of MgF2 ARCs for large-area glass substrates has prospective application in various optoelectronic devices. In this paper, a polymer-based sol-gel route was devised to fabricate highly uniform and porous MgF2 ARCs on large-area glass substrates. A sol-gel precursor made of polyvinyl acetate and magnesium trifluoroacetate assisted in the formation of uniformly mesoporous MgF2 ARCs on glass substrates, leading to the attainment of a refractive index of ~1.23. Systematic optimization of the thickness of the ARC in the sub-wavelength regime led to achieving ~99.4% transmittance in the case of the porous MgF2 ARC glass. Precise control of the thickness of porous MgF2 ARC glass also resulted in a mere ~0.1% reflection, virtually eliminating reflection off the glass surface at the target wavelength. Further manipulation of the thickness of the ARC on either side of the glass substrate led to the fabrication of relatively broadband, porous MgF2 ARC glass.

Electrospun ZnO nanowire plantations in the electron transport layer for high-efficiency inverted organic solar cells.

Inverted bulk heterojunction organic solar cells having device structure ITO/ZnO/poly(3-hexylthiophene) (P3HT):[6,6]-phenyl C61 butyric acid methyl ester (PCBM) /MoO3/Ag were fabricated with high photoelectric conversion efficiency and stability. Three types of devices were developed with varying electron transporting layer (ETL) ZnO architecture. The ETL in the first type was a sol-gel-derived particulate film of ZnO, which in the second and third type contained additional ZnO nanowires of varying concentrations. The length of the ZnO nanowires, which were developed by the electrospinning technique, extended up to the bulk of the photoactive layer in the device. The devices those employed a higher loading of ZnO nanowires showed 20% higher photoelectric conversion efficiency (PCE), which mainly resulted from an enhancement in its fill factor (FF). Charge transport characteristic of the device were studied by transient photovoltage decay and charge extraction by linearly increasing voltage techniques. Results show that higher PCE and FF in the devices employed ZnO nanowire plantations resulted from improved charge collection efficiency and reduced recombination rate.