TiO2 Films with Macroscopic Chiral Nematic-Like Structure Stabilized by Copper Promoting Light-Harvesting Capability for Hydrogen Generation.

Cellulose nanocrystals (CNCs) have inspired the synthesis of various advanced nanomaterials, opening opportunities for different applications. However, a simple and robust approach for transferring the long-range chiral nematic nanostructures into TiO2 photocatalyst is still fancy. Herein, a successful fabrication of freestanding TiO2 films maintaining their macroscopic chiral nematic structures after removing the CNCs biotemplate is reported. It is demonstrated that including copper acetate in the sol avoids the epitaxial growth of the lamellar-like structure of TiO2 and stabilizes the chiral nematic structure instead. The experimental results and optical simulation demonstrate an enhancement at the blue and red edges of the Fabry-Pérot reflectance peak located in the visible range. This enhancement arises from the light scattering effect induced by the formation of the chiral nematic structure. The nanostructured films showed 5.3 times higher performance in the photocatalytic hydrogen generation, compared to lamellar TiO2, and benefited from the presence of copper species for charge carriers' separation. This work is therefore anticipated to provide a simple approach for the design of chiral nematic photocatalysts and also offers insights into the electron transfer mechanisms on TiO2/CuxO with variable oxidation states for photocatalytic hydrogen generation.

Scattering of ultraviolet light by avian eggshells.

Eggshells are essential for the reproduction of birds since the optical properties of shells may have an impact on biological functions such as heating and UV protection, recognition by parents or camouflage. Whereas ultraviolet reflection by some bird eggshells has been recently described, its physical origin remains poorly understood. In this study, we identified a porous structure in eggshells. Using Mie scattering modelling, we found it was most likely responsible for reflectance peaks (intensities of ca. 20-50%) observed in the near-UV range. These peaks were observed by spectrophotometric measurements from eggshells of several breeds of hen, one breed of duck and one breed of quail. This optical response was interpreted in terms of the distinct visual perception of hens and humans: eggshells appearing achromatic for humans proved to be chromatic for hens. Fluorescence emission from these eggs was also characterised and attributed to the presence of protoporphyrin IX and biliverdin IXα in the shells. Electron microscopy observations revealed the presence of pores within the so-called calcified shell part (i.e., at depths between ca. 20 µm and ca. 240 µm from the eggshell's outer surface). Mercury intrusion porosimetry allowed us to quantify the pore size distribution. Simulations of the UV response of this porous structure using Mie scattering theory as well as an effective approach accounting for multiple scattering indicate that these pores are responsible for the backscattering peaks observed in the UV range, in the case of beige hen eggshells. Due to the similarities between the pore size distributions observed for beige hen eggshells and other investigated poultry eggshells, we expect Mie backscattering to be the origin of the UV response of the eggshells of many other bird species.

Optical costs and benefits of disorder in biological photonic crystals.

Photonic structures in ordered, quasi-ordered or disordered forms have evolved across many different animal and plant systems. They can produce complex and often functional optical responses through coherent and incoherent scattering processes, often too, in combination with broadband or narrowband absorbing pigmentation. Interestingly, these systems appear highly tolerant of faults in their photonic structures, with imperfections in their structural order appearing not to impact, discernibly, the systems' optical signatures. The extent to which any such biological system deviates from presenting perfect structural order can dictate the optical properties of that system and, thereby, the optical properties that system delivers. However, the nature and extent of the optical costs and benefits of imperfect order in biological systems demands further elucidation. Here, we identify the extent to which biological photonic systems are tolerant of defects and imperfections. Certainly, it is clear that often significant inherent variations in the photonic structures of these systems, for instance a relatively broad distribution of lattice constants, can consistently produce what appear to be effective visual appearances and optical performances. In this article, we review previously investigated biological photonic systems that present ordered, quasi-ordered or disordered structures. We discuss the form and nature of the optical behaviour of these structures, focusing particularly on the associated optical costs and benefits surrounding the extent to which their structures deviate from what might be considered ideal systems. Then, through detailed analyses of some well-known 1D and 2D structurally coloured systems, we analyse one of the common manifestations of imperfect order, namely, the extent and nature of positional disorder in the systems' spatial distribution of layers and scattering centres. We use these findings to inform optical modelling that presents a quantitative and qualitative description of the optical costs and benefits of such positional disorder among ordered and quasi-ordered 1D and 2D photonic systems. As deviation from perfectly ordered structures invariably limits the performance of technology-oriented synthetic photonic processes, we suggest that the use of bio-inspired fault tolerance principles would add value to applied photonic technologies.

Translucent in air and iridescent in water: structural analysis of a salamander egg sac.

Females of some Asian salamanders of the genus Hynobius deposit in streams their eggs embedded in a translucent envelope called an 'egg sac'. The edges of the envelope exhibit a spectacular blue-to-yellow iridescent glow, which instantaneously disappears when the sac is removed from water. First, our scanning electron microscopy analyses reveal that the inner surface of the 100 µm-thick envelope displays striations (length scale of about 3 µm), which are themselves covered by much smaller (190 ± 30 nm) and quasi-periodic corrugations. The latter could constitute a surface diffraction grating generating iridescence by light interference. Second, our transmission electron microscopy and focused-ion-beam scanning electron microscopy analyses show that the bulk of the egg sac wall is composed of meandering fibres with a quasi-periodic modulation of 190 ± 60 nm along the thickness of the envelope, generating a photonic crystal. Third, Fourier power analyses of 450 electron microscopy images with varying incident angles indicate that changing the surrounding medium from water to air shifts most of the backscattered power spectrum to the ultraviolet range, hence, explaining that the egg sac loses visible iridescence when removed out of the water. Fourth, the results of our photography and optical spectroscopy experiments of submerged and emerged egg sacs rule out the possibility that the iridescence is due to a thin film or a multilayer, whereas the observed non-specular response is compatible with the backscattering expected from surface diffraction gratings and volumetric photonic crystals with spatial 1D modulation. Finally, although we mention several potential biological functions of the egg sac structural colours and iridescence, we emphasise that these optical properties might be the by-products of the envelope material internal structure selected during evolution for its mechanical properties.

Controlled fluorescence in a beetle's photonic structure and its sensitivity to environmentally induced changes.

The scales covering the elytra of the male Hoplia coerulea beetle contain fluorophores embedded within a porous photonic structure. The photonic structure controls both insect colour (reflected light) and fluorescence emission. Herein, the effects of water-induced changes on the fluorescence emission from the beetle were investigated. The fluorescence emission peak wavelength was observed to blue-shift on water immersion of the elytra whereas its reflectance peak wavelength was observed to red-shift. Time-resolved fluorescence measurements, together with optical simulations, confirmed that the radiative emission is controlled by a naturally engineered photonic bandgap while the elytra are in the dry state, whereas non-radiative relaxation pathways dominate the emission response of wet elytra.

Vapor sensing with a natural photonic cell.

Photonic structures encased by a permeable envelope give rise to iridescent blue color in the scales covering the male Hoplia coerulea beetle. This structure comprises a periodic porous multilayer. The color of these scales is known for changing from blue to green upon contact with water despite the presence of the envelope. This optical system has been referred to as a photonic cell due to the role of the envelope that mediates fluid exchanges with the surrounding environment. Following from previously studied liquid-induced changes in the color appearance of H. coerulea, we measured vapor-induced color changes in its appearance. This response to vapor exposure was marked by reflectance redshift and an increase in peak reflectance intensity. Different physico-chemical processes were investigated to explain the increase in reflectance intensity, a property not usually associated with vapor-induced optical signature changes. These simulations indicated the optical response arose from physisorption of a liquid film on the beetle scales followed by liquid penetration through the envelope and the filling of micropores within the body of the photonic structure.

Tuning and transferring slow photons from TiO2 photonic crystals to BiVO4 nanoparticles for unprecedented visible light photocatalysis.

Periodic structures with alternating refractive indices such as inverse opal photonic crystals are capable of reducing the group velocity of light such that this slowed light can be more efficiently harvested for highly enhanced solar energy conversion. However, the generation, the manipulation and, in particular, the practical applications of these slow photons remain highly challenging. Here, we report the first proof of concept on the ability to control, in an inverse opal TiO2-BiVO4 hetero-composite, the transfer of slow photons generated from the inverse opal photonic structure to the photocatalytically active BiVO4 nanoparticles for highly enhanced visible light photoconversion. Tuning the slow photon frequencies, in order to accommodate the electronic band gap of BiVO4 for slow photon transfer and for significantly improved light harvesting, was successfully achieved by varying the structural periodicity (pore size) of inverse opal and the light incidence angle. The photocatalytic activity of BiVO4 in all inverse opal structures, promoted by slow photon effect, reached up to 7 times higher than those in the non-structured compact films. This work opens new avenues for the practical utilization of slow photon effect under visible light in photocatalytic energy-related applications like water splitting and carbon dioxide reduction and in photovoltaics.

Manipulating multi-spectral slow photons in bilayer inverse opal TiO2@BiVO4 composites for highly enhanced visible light photocatalysis.

Manipulation of light has been proved to be a promising strategy to increase light harvesting in solar-to-chemical energy conversion, especially in photocatalysis. Inverse opal (IO) photonic structures are highly promising for light manipulation as their periodic dielectric structures enable them to slow down light and localize it within the structure, thereby improving light harvesting and photocatalytic efficiency. However, slow photons are confined to narrow wavelength ranges and hence limit the amount of energy that can be captured through light manipulation. To address this challenge, we synthesized bilayer IO TiO2@BiVO4 structures that manifested two distinct stop band gap (SBG) peaks, arising from different pore sizes in each layer, with slow photons available at either edge of each SBG. In addition, we achieved precise control over the frequencies of these multi-spectral slow photons through pore size and incidence angle variations, that enabled us to tune their wavelengths to the electronic absorption of the photocatalyst for optimal light utilization in aqueous phase visible light photocatalysis. This first proof of concept involving multi-spectral slow photon utilization enabled us to achieve up to 8.5 times and 2.2 times higher photocatalytic efficiencies than the corresponding non-structured and monolayer IO photocatalysts respectively. Through this work, we have successfully and significantly improved light harvesting efficiency in slow photon-assisted photocatalysis, the principles of which can be extended to other light harvesting applications.

Revealing the Wonder of Natural Photonics by Nonlinear Optics.

Nano-optics explores linear and nonlinear phenomena at the nanoscale to advance fundamental knowledge about materials and their interaction with light in the classical and quantum domains in order to develop new photonics-based technologies. In this perspective article, we review recent progress regarding the application of nonlinear optical methods to reveal the links between photonic structures and functions of natural photonic geometries. Furthermore, nonlinear optics offers a way to unveil and exploit the complexity of the natural world for developing new materials and technologies for the generation, detection, manipulation, and storage of light at the nanoscale, as well as sensing, metrology, and communication.

Linear and nonlinear optical effects in biophotonic structures using classical and nonclassical light.

In this perspective article, we review the optical study of different biophotonic geometries and biological structures using classical light in linear and nonlinear regime, especially highlighting the link between these morphologies and modern biomedical research. Additionally, the importance of nonlinear optical study in biological research, beyond traditional cell imaging is also highlighted and described. Finally, we present a short introduction regarding nonclassical light and describe the new future perspective of quantum optical study in biology, revealing the link between quantum realm and biological research.

Nonlinear optical spectroscopy and two-photon excited fluorescence spectroscopy reveal the excited states of fluorophores embedded in a beetle's elytra.

Upon illumination by ultraviolet light, many animal species emit light through fluorescence processes arising from fluorophores embedded within their biological tissues. Fluorescence studies in living organisms are however relatively scarce and so far limited to the linear regime. Multiphoton excitation fluorescence analyses as well as nonlinear optical techniques offer unique possibilities to investigate the effects of the local environment on the excited states of fluorophores. Herein, these techniques are applied for the first time to study of the naturally controlled fluorescence in insects. The case of the male Hoplia coerulea beetle is investigated because the scales covering the beetle's elytra are known to possess an internal photonic structure with embedded fluorophores, which controls both the beetle's coloration and the fluorescence emission. An intense two-photon excitation fluorescence signal is observed, the intensity of which changes upon contact with water. A third-harmonic generation signal is also detected, the intensity of which depends on the light polarization state. The analysis of these nonlinear optical and fluorescent responses unveils the multi-excited states character of the fluorophore molecules embedded in the beetle's elytra. The role of form anisotropy in the photonic structure, which causes additional tailoring of the beetle's optical responses, is demonstrated by circularly polarized light and nonlinear optical measurements.

Unveiling the nonlinear optical response of Trictenotoma childreni longhorn beetle.

The wings of some insect species are known to fluoresce under illumination by ultraviolet light. Their fluorescence properties are however, not comprehensively documented. In this article, the optical properties of one specific insect, the Trictenotoma childreni yellow longhorn beetle, were investigated using both linear and nonlinear optical (NLO) methods, including one- and two-photon fluorescence and second harmonic generation (SHG). These three distinct optical signals discovered in this beetle are attributed to the presence of fluorophores embedded within the scales covering their elytra. Experimental evidence collected in this study indicates that the fluorophores are non-centrosymmetric, a fundamental requirement for SHG. This study is the first reported optical behavior of this type in insects. We described how NLO techniques can complement other more convenient approaches to achieve a more comprehensive understanding of insect scales and integument properties.

Structural and physical evidence for an endocuticular gold reflector in the tortoise beetle, Charidotella ambita.

Charidotella ambita offers a unique opportunity for unambiguously locating its gold reflector by comparing the structure of reflecting and non-reflecting cuticle of the elytron and pronotum. Using light microscopy and TEM, the reflector was located underneath the macrofiber endocuticle just above the epidermis. The reflector is a multilayer comprising up to 50 bilayers alternating high and low density layers parallel to the surface of the cuticle. It is chirped, i.e., showing a progressive decrease in layer thickness from approximately 150 nm-100 nm across its depth. The high density layers in contact with the endocuticle fuse to the last macrofiber when the reflector is interrupted by a trabecula, demonstrating their cuticular nature. Simulated reflectance spectra from models of the multilayer matched the reflection spectra measured on the major gold patch of the elytron of living specimens. Previous reports in adult insects exhibiting metallic colors located their reflector in the upper strata and structures of the cuticle, i.e., epicuticle, exocuticle, scales and hairs. Thus, the endocuticular location of the reflector in C. ambita (and other tortoise beetles) appears unique for adult insects. Gold reflection appears in C. ambita only when the synthesis of the macrolayer endocuticle is complete, which may take up to 2 weeks. The development of the gold reflector coincides with the start of mating behavior, possibly suggesting a signaling function in conspecific recognition once sexual maturity has been reached.

Vapour sensitivity of an ALD hierarchical photonic structure inspired by Morpho.

The unique architecture of iridescent Morpho butterfly scales is known to exhibit different optical responses to various vapours. However, the mechanism behind this phenomenon is not fully quantitatively understood. This work reports on process developments in the micro-fabrication of a Morpho-inspired photonic structure in atomic layer deposited (ALD) materials in order to investigate the vapour optical sensitivity of such artificial nanostructures. By developing recipes for dry and wet etching of ALD oxides, we micro-fabricated two structures: one combining Al2O3 and TiO2, and the other combining Al2O3 and HfO2. For the first time, we report the optical response of such ALD Morpho-like structures measured under a controlled flow of either ethanol or isopropyl alcohol (IPA) vapour. In spite of the small magnitude of the effect, the results show a selective vapour response (depending on the materials used).

Liquid-induced colour change in a beetle: the concept of a photonic cell.

The structural colour of male Hoplia coerulea beetles is notable for changing from blue to green upon contact with water. In fact, reversible changes in both colour and fluorescence are induced in this beetle by various liquids, although the mechanism has never been fully explained. Changes enacted by water are much faster than those by ethanol, in spite of ethanol's more rapid spread across the elytral surface. Moreover, the beetle's photonic structure is enclosed by a thin scale envelope preventing direct contact with the liquid. Here, we note the presence of sodium, potassium and calcium salts in the scale material that mediate the penetration of liquid through putative micropores. The result leads to the novel concept of a "photonic cell": namely, a biocompatible photonic structure that is encased by a permeable envelope which mediates liquid-induced colour changes in that photonic structure. Engineered photonic cells dispersed in culture media could revolutionize the monitoring of cell-metabolism.