Investigating the Effect of Reflectance Tuning on Photocatalytic Dye Degradation with Biotemplated ZnO Photonic Nanoarchitectures Based on Morpho Butterfly Wings.

Photonic nanoarchitectures of butterfly wings can serve as biotemplates to prepare semiconductor thin films of ZnO by atomic layer deposition. The resulting biotemplated ZnO nanoarchitecture preserves the structural and optical properties of the natural system, while it will also have the features of the functional material. The ZnO-coated wings can be used directly in heterogeneous photocatalysis to decompose pollutants dissolved in water upon visible light illumination. We used the photonic nanoarchitectures of different Morpho butterflies with different structural colors as biotemplates and examined the dependence of decomposition rates of methyl orange and rhodamine B dyes on the structural color of the biotemplates and the thickness of the ZnO coating. Using methyl orange, we measured a ten-fold increase in photodegradation rate when the 20 nm ZnO-coated wings were compared to similarly coated glass substrates. Using rhodamine B, a saturating relationship was found between the degradation rate and the thickness of the deposited ZnO on butterfly wings. We concluded that the enhancement of the catalytic efficiency can be attributed to the slow light effect due to a spectral overlap between the ZnO-coated Morpho butterfly wings reflectance with the absorption band of dyes, thus the photocatalytic performance could be changed by the tuning of the structural color of the butterfly biotemplates. The photodegradation mechanism of the dyes was investigated by liquid chromatography-mass spectroscopy.

Mechanical Characterization of Two-Segment Free-Standing ZnO Nanowires Using Lateral Force Microscopy.

Mechanical characterization of quasi one-dimensional nanostructures is essential for the design of novel nanoelectromechanical systems. However, the results obtained on basic mechanical quantities, such as Young's modulus and fracture strength, show significant standard deviation in the literature. This is partly because of diversity in the quality of the nanowire, and partly because of inappropriately performed mechanical tests and simplified mechanical models. Here we present orientation-controlled bending and fracture studies on wet chemically grown vertical ZnO nanowires, using lateral force microscopy. The lateral force signal of the atomic force microscope was calibrated by a diamagnetic levitation spring system. By acquiring the bending curves of 14 nanowires, and applying a two-segment mechanical model, an average bending modulus of 108 ± 17 GPa was obtained, which was 23% lower than the Young's modulus of bulk ZnO in the [0001] direction. It was also found that the average fracture strain and stress inside the nanowire was above 3.1 ± 0.3 % and 3.3 ± 0.3 GPa, respectively. However, the fracture of the nanowires was governed by the quality of the nanowire/substrate interface. The demonstrated technique is a relatively simple and productive way for the accurate mechanical characterization of vertical nanowire arrays.

Spectral Engineering of Hybrid Biotemplated Photonic/Photocatalytic Nanoarchitectures.

Solar radiation is a cheap and abundant energy for water remediation, hydrogen generation by water splitting, and CO2 reduction. Supported photocatalysts have to be tuned to the pollutants to be eliminated. Spectral engineering may be a handy tool to increase the efficiency or the selectivity of these. Photonic nanoarchitectures of biological origin with hierarchical organization from nanometers to centimeters are candidates for such applications. We used the blue wing surface of laboratory-reared male Polyommatus icarus butterflies in combination with atomic layer deposition (ALD) of conformal ZnO coating and octahedral Cu2O nanoparticles (NP) to explore the possibilities of engineering the optical and catalytic properties of hybrid photonic nanoarchitectures. The samples were characterized by UV-Vis spectroscopy and optical and scanning electron microscopy. Their photocatalytic performance was benchmarked by comparing the initial decomposition rates of rhodamine B. Cu2O NPs alone or on the butterfly wings, covered by a 5 nm thick layer of ZnO, showed poor performance. Butterfly wings, or ZnO coated butterfly wings with 15 nm ALD layer showed a 3 to 3.5 times enhancement as compared to bare glass. The best performance of almost 4.3 times increase was obtained for the wings conformally coated with 15 nm ZnO, deposited with Cu2O NPs, followed by conformal coating with an additional 5 nm of ZnO by ALD. This enhanced efficiency is associated with slow light effects on the red edge of the reflectance maximum of the photonic nanoarchitectures and with enhanced carrier separation through the n-type ZnO and the p-type Cu2O heterojunction. Properly chosen biologic photonic nanoarchitectures in combination with carefully selected photocatalyst(s) can significantly increase the photodegradation of pollutants in water under visible light illumination.

Spectral tuning of biotemplated ZnO photonic nanoarchitectures for photocatalytic applications.

The photocatalytic activity of a flat surface can be increased by micro- and nanostructuring the interface to increase the area of the contact surface between the photocatalyst and the solute, and moreover, to optimize charge carrier transfer. Further enhancement can be achieved by using photonic nanostructures, which exhibit photonic band gap (PBG). Structurally coloured butterfly wings offer a rich 'library' of PBGs in the visible spectral range which can be used as naturally tuned sample sets for biotemplating. We used conformal atomic layer deposition of ZnO on the wings of various butterfly species (Arhopala asopia, Hypochrysops polycletus, Morpho sulkowskyi, Polyommatus icarus) possessing structural colour extending from the near UV to the blue wavelength range, to test the effects arising from the nanostructured surfaces and from the presence of different types of PBGs. Aqueous solutions of rhodamine B were used to test the enhancement of photocatalytic activity that was found for all ZnO-coated butterfly wings. The best reaction rate of decomposing rhodamine B when illuminated with visible light was found in 15 nm ZnO coated M. sulkowskyi wing, the reflectance of which had the highest overlap with the absorption band of the dye and had the highest reflectance intensity.

A Rational Fabrication Method for Low Switching-Temperature VO2.

Due to its remarkable switching effect in electrical and optical properties, VO2 is a promising material for several applications. However, the stoichiometry control of multivalent vanadium oxides, especially with a rational deposition technique, is still challenging. Here, we propose and optimize a simple fabrication method for VO2 rich layers by the oxidation of metallic vanadium in atmospheric air. It was shown that a sufficiently broad annealing time window of 3.0-3.5 h can be obtained at an optimal oxidation temperature of 400 °C. The presence of VO2 was detected by selected area diffraction in a transmission electron microscope. According to the temperature dependent electrical measurements, the resistance contrast (R30 °C/R100 °C) varied between 44 and 68, whereas the optical switching was confirmed using in situ spectroscopic ellipsometric measurement by monitoring the complex refractive indices. The obtained phase transition temperature, both for the electrical resistance and for the ellipsometric angles, was found to be 49 ± 7 °C, i.e., significantly lower than that of the bulk VO2 of 68 ± 6 °C.