Modeling the Reflectance Changes Induced by Vapor Condensation in Lycaenid Butterfly Wing Scales Colored by Photonic Nanoarchitectures.

Gas/vapor sensors based on photonic band gap-type materials are attractive as they allow a quick optical readout. The photonic nanoarchitectures responsible for the coloration of the wing scales of many butterfly species possessing structural color exhibit chemical selectivity, i.e., give vapor-specific optical response signals. Modeling this complex physical-chemical process is very important to be able to exploit the possibilities of these photonic nanoarchitectures. We performed measurements of the ethanol vapor concentration-dependent reflectance spectra of the Albulina metallica butterfly, which exhibits structural color on both the dorsal (blue) and ventral (gold-green) wing sides. Using a numerical analysis of transmission electron microscopy (TEM) images, we revealed the details of the photonic nanoarchitecture inside the wing scales. On both sides, it is a 1D + 2D structure, a stack of layers, where the layers contain a quasi-ordered arrangement of air voids embedded in chitin. Next, we built a parametric simulation model that matched the measured spectra. The reflectance spectra were calculated by ab-initio methods by assuming variable amounts of vapor condensed to liquid in the air voids, as well as vapor concentration-dependent swelling of the chitin. From fitting the simulated results to the measured spectra, we found a similar swelling on both wing surfaces, but more liquid was found to concentrate in the smaller air voids for each vapor concentration value measured.

Biogeographical patterns in the structural blue of male Polyommatus icarus butterflies.

Color is a widely used communication channel in the living world for a variety of functions ranging from sexual communication to warning colors. A particularly rich spectrum of colors appears on the wings of many butterflies. The males of lycaenid butterflies often exhibit a conspicuous blue coloration generated by photonic nanoarchitectures on their dorsal wing surfaces. Using UV-VIS spectroscopy, we investigated the spatio-temporal variations of this coloration for Polyommatus icarus butterflies, considering an interval of more than 100 years and a geographical range spanning Europe (west) and Asia (east). The blue coloration in Hungary is very stable both within a year (three broods typical in Hungary) and within the period of 100 years (more than 300 generations). East-west geographic variation was investigated among 314 male P. icarus butterflies. In agreement with earlier genetic and morphometric studies, it was found that the western males are not divided in distinct lineages. Clear differences in coloration were found between the eastern and western groups, with a transition in the region of Turkey. These differences are tentatively attributed to bottleneck effects during past glaciations.

Preparing local strain patterns in graphene by atomic force microscope based indentation.

Patterning graphene into various mesoscopic devices such as nanoribbons, quantum dots, etc. by lithographic techniques has enabled the guiding and manipulation of graphene's Dirac-type charge carriers. Graphene, with well-defined strain patterns, holds promise of similarly rich physics while avoiding the problems created by the hard to control edge configuration of lithographically prepared devices. To engineer the properties of graphene via mechanical deformation, versatile new techniques are needed to pattern strain profiles in a controlled manner. Here we present a process by which strain can be created in substrate supported graphene layers. Our atomic force microscope-based technique opens up new possibilities in tailoring the properties of graphene using mechanical strain.

The intrinsic defect structure of exfoliated MoS2 single layers revealed by Scanning Tunneling Microscopy.

MoS2 single layers have recently emerged as strong competitors of graphene in electronic and optoelectronic device applications due to their intrinsic direct bandgap. However, transport measurements reveal the crucial role of defect-induced electronic states, pointing out the fundamental importance of characterizing their intrinsic defect structure. Transmission Electron Microscopy (TEM) is able to image atomic scale defects in MoS2 single layers, but the imaged defect structure is far from the one probed in the electronic devices, as the defect density and distribution are substantially altered during the TEM imaging. Here, we report that under special imaging conditions, STM measurements can fully resolve the native atomic scale defect structure of MoS2 single layers. Our STM investigations clearly resolve a high intrinsic concentration of individual sulfur atom vacancies, and experimentally identify the nature of the defect induced electronic mid-gap states, by combining topographic STM images with ab intio calculations. Experimental data on the intrinsic defect structure and the associated defect-bound electronic states that can be directly used for the interpretation of transport measurements are essential to fully understand the operation, reliability and performance limitations of realistic electronic devices based on MoS2 single layers.

Exfoliation of large-area transition metal chalcogenide single layers.

Isolating large-areas of atomically thin transition metal chalcogenide crystals is an important but challenging task. The mechanical exfoliation technique can provide single layers of the highest structural quality, enabling to study their pristine properties and ultimate device performance. However, a major drawback of the technique is the low yield and small (typically < 10 µm) lateral size of the produced single layers. Here, we report a novel mechanical exfoliation technique, based on chemically enhanced adhesion, yielding MoS2 single layers with typical lateral sizes of several hundreds of microns. The idea is to exploit the chemical affinity of the sulfur atoms that can bind more strongly to a gold surface than the neighboring layers of the bulk MoS2 crystal. Moreover, we found that our exfoliation process is not specific to MoS2, but can be generally applied for various layered chalcogenides including selenites and tellurides, providing an easy access to large-area 2D crystals for the whole class of layered transition metal chalcogenides.

Room-temperature magnetic order on zigzag edges of narrow graphene nanoribbons.

The possibility that non-magnetic materials such as carbon could exhibit a novel type of s-p electron magnetism has attracted much attention over the years, not least because such magnetic order is predicted to be stable at high temperatures. It has been demonstrated that atomic-scale structural defects of graphene can host unpaired spins, but it remains unclear under what conditions long-range magnetic order can emerge from such defect-bound magnetic moments. Here we propose that, in contrast to random defect distributions, atomic-scale engineering of graphene edges with specific crystallographic orientation--comprising edge atoms from only one sub-lattice of the bipartite graphene lattice--can give rise to a robust magnetic order. We use a nanofabrication technique based on scanning tunnelling microscopy to define graphene nanoribbons with nanometre precision and well-defined crystallographic edge orientations. Although so-called 'armchair' ribbons display quantum confinement gaps, ribbons with the 'zigzag' edge structure that are narrower than 7 nanometres exhibit an electronic bandgap of about 0.2-0.3 electronvolts, which can be identified as a signature of interaction-induced spin ordering along their edges. Moreover, upon increasing the ribbon width, a semiconductor-to-metal transition is revealed, indicating the switching of the magnetic coupling between opposite ribbon edges from the antiferromagnetic to the ferromagnetic configuration. We found that the magnetic order on graphene edges of controlled zigzag orientation can be stable even at room temperature, raising hopes of graphene-based spintronic devices operating under ambient conditions.

The well-tuned blues: the role of structural colours as optical signals in the species recognition of a local butterfly fauna (Lepidoptera: Lycaenidae: Polyommatinae).

The photonic nanoarchitectures responsible for the blue colour of the males of nine polyommatine butterfly species living in the same site were investigated structurally by electron microscopy and spectrally by reflectance spectroscopy. Optical characterization was carried out on 110 exemplars. The structural data extracted by dedicated software and the spectral data extracted by standard software were inputted into an artificial neural network software to test the specificity of the structural and optical characteristics. It was found that both the structural and the spectral data allow species identification with an accuracy better than 90 per cent. The reflectance data were further analysed using a colour representation diagram built in a manner analogous to that of the human Commission Internationale de l'Eclairage diagram, but the additional blue visual pigment of lycaenid butterflies was taken into account. It was found that this butterfly-specific colour representation diagram yielded a much clearer distinction of the position of the investigated species compared with previous calculations using the human colour space. The specific colours of the investigated species were correlated with the 285 flight-period data points extracted from museum collections. The species with somewhat similar colours fly in distinct periods of the year such that the blue colours are well tuned for safe mate/competitor recognition. This allows for the creation of an effective pre-zygotic isolation mechanism for closely related synchronic and syntopic species.

Graphene: nanoscale processing and recent applications.

One of the most interesting features of graphene is the rich physics set up by the various nanostructures it may adopt. The planar structure of graphene makes this material ideal for patterning at the nanoscale. The breathtakingly fast evolution of research on graphene growth and preparation methods has made possible the preparation of samples with arbitrary sizes. Available sample production techniques, combined with the right patterning tools, can be used to tailor the graphene sheet into functional nanostructures, even whole electronic circuits. This paper is a review of the existing graphene patterning techniques and potential applications of related lithographic methods.

Raman scattering at pure graphene zigzag edges.

Theory has predicted rich and very distinct physics for graphene devices with boundaries that follow either the armchair or the zigzag crystallographic directions. A prerequisite to disclose this physics in experiment is to be able to produce devices with boundaries of pure chirality. Exfoliated flakes frequently exhibit corners with an odd multiple of 30°, which raised expectations that their boundaries follow pure zigzag and armchair directions. The predicted Raman behavior at such crystallographic edges however failed to confirm pure edge chirality. Here, we perform confocal Raman spectroscopy on hexagonal holes obtained after the anisotropic etching of prepatterned pits using carbothermal decomposition of SiO(2). The boundaries of the hexagonal holes are aligned along the zigzag crystallographic direction and leave hardly any signature in the Raman map indicating unprecedented purity of the edge chirality. This work offers the first opportunity to experimentally confirm the validity of the Raman theory for graphene edges.

Order-disorder effects in structure and color relation of photonic-crystal-type nanostructures in butterfly wing scales.

In order to study local and global order in butterfly wing scales possessing structural colors, we have developed a direct space algorithm, based on averaging the local environment of the repetitive units building up the structure. The method provides the statistical distribution of the local environments, including the histogram of the nearest-neighbor distance and the number of nearest neighbors. We have analyzed how the different kinds of randomness present in the direct space structure influence the reciprocal space structure. It was found that the Fourier method is useful in the case of a structure randomly deviating from an ordered lattice. The direct space averaging method remains applicable even for structures lacking long-range order. Based on the first Born approximation, a link is established between the reciprocal space image and the optical reflectance spectrum. Results calculated within this framework agree well with measured reflectance spectra because of the small width and moderate refractive index contrast of butterfly scales. By the analysis of the wing scales of Cyanophrys remus and Albulina metallica butterflies, we tested the methods for structures having long-range order, medium-range order, and short-range order.

Correlated diffraction and fluorescence in the backscattering iridescence of the male butterfly Troides magellanus (Papilionidae).

The male Troides magellanus--a birdwing butterfly that lives in a restricted area of the Philippines--concentrates on its hindwings at least two distinct optical processes that contribute to its exceptional visual attraction. The first is the very bright uniform yellow coloration caused by a pigment which generates yellow-green fluorescence, and the other is a blue-green iridescence which results from light diffraction at grazing emergence under a specific illumination. Detailed optical measurements reveal that these optical effects are correlated, the fluorescence being enhanced by illuminations conditions that favor the occurrence of the iridescence. These effects are analyzed, with the conclusion that both of them depend on the same optical device: a one-dimensional microribs grating which appear on the sides of the ridges that run along the yellow scales.

Tailoring the atomic structure of graphene nanoribbons by scanning tunnelling microscope lithography.

The practical realization of nanoscale electronics faces two major challenges: the precise engineering of the building blocks and their assembly into functional circuits. In spite of the exceptional electronic properties of carbon nanotubes, only basic demonstration devices have been realized that require time-consuming processes. This is mainly due to a lack of selective growth and reliable assembly processes for nanotubes. However, graphene offers an attractive alternative. Here we report the patterning of graphene nanoribbons and bent junctions with nanometre-precision, well-defined widths and predetermined crystallographic orientations, allowing us to fully engineer their electronic structure using scanning tunnelling microscope lithography. The atomic structure and electronic properties of the ribbons have been investigated by scanning tunnelling microscopy and tunnelling spectroscopy measurements. Opening of confinement gaps up to 0.5 eV, enabling room-temperature operation of graphene nanoribbon-based devices, is reported. This method avoids the difficulties of assembling nanoscale components and may prove useful in the realization of complete integrated circuits, operating as room-temperature ballistic electronic devices.

Switchable reflector in the Panamanian tortoise beetle Charidotella egregia (Chrysomelidae: Cassidinae).

The tortoise beetle Charidotella egregia is able to modify the structural color of its cuticle reversibly, when disturbed by stressful external events. After field observations, measurements of the optical properties in the two main stable color states and scanning electron microscope and transmission electron microscope investigations, a physical mechanism is proposed to explain the color switching of this insect. It is shown that the gold coloration displayed by animals at rest arises from a chirped multilayer reflector maintained in a perfect coherent state by the presence of humidity in the porous patches within each layer, while the red color displayed by disturbed animals results from the destruction of this reflector by the expulsion of the liquid from the porous patches, turning the multilayer into a translucent slab that leaves an unobstructed view of the deeper-lying, pigmented red substrate. This mechanism not only explains the change of hue but also the change of scattering mode from specular to diffuse. Quantitative modeling is developed in support of this analysis.

Gleaming and dull surface textures from photonic-crystal-type nanostructures in the butterfly Cyanophrys remus.

Photonic-crystal-type nanostructures occurring in the scales of the butterfly Cyanophrys remus were investigated by optical and electron microscopy (scanning and transmission electron microscopy), reflectance measurements (specular, integrated, and goniometric), by fast Fourier transform analysis of micrographs, by modeling, and by numerical simulation of the measured reflectance data. By evaluating the collected data in a cross-correlated way, we show that the metallic blue dorsal coloration originates from scales which individually are photonic single crystals of 50 x 120 microm2 , while the matt pea-green coloration of the ventral side arises from the cumulative effect of randomly arranged, bright photonic crystallites (blue, green, and yellow) with typical diameters in the 3-10-mum range. Both structures are based on a very moderate refractive index contrast between air and chitin. Using a bleached specimen in which the pigment has decayed with time, we investigated the role of pigment in photonic-crystal material in the process of color generation. The possible biologic utility of the metallic blue (single-crystal) and dull green (polycrystal) textures both achieved with photonic crystals are briefly discussed. Potential applications in the field of colorants, flat panel displays, smart textiles, and smart papers are surveyed.

Spectral filtering of visible light by the cuticle of metallic woodboring beetles and microfabrication of a matching bioinspired material.

Samples of the cuticle taken from the body of Buprestidae Chrysochroa vittata have been studied by scanning electron microscopy and optical reflectance measurements, related to numerical simulations. The cause of the metallic coloration of the body of these insects is determined to be the structure of the hard carapace constructed as a stack of thin chitin layers separated by very thin irregular air gaps. In particular the change of color as a function of the observation angle is elucidated in terms of an infinite photonic-crystal model, confirmed by finite multilayer calculations. These mechanisms are used to develop an artificial bioinspired multilayer system which reproduces the visual effects provided by the insect surface.

Optical structure and function of the white filamentary hair covering the edelweiss bracts.

The optical properties of the inflorescence of the high-altitude Leontopodium nivale subsp. alpinum (edelweiss) is investigated, in relation with its submicrometer structure, as determined by scanning electron microscopy. The filaments forming the hair layer have been found to exhibit an internal structure which may be one of the few examples of a photonic structure found in a plant. Measurements of light transmission through a self-supported layer of hair pads taken from the bracts supports the idea that the wooly layer covering the plant absorbs near-ultraviolet radiation before it reaches the cellular tissue. Calculations based on a photonic-crystal model provide insight on the way radiation can be absorbed by the filamentary threads.

Interconnecting carbon nanotubes with an inorganic metal complex.

Intermolecular carbon nanotube junctions were formed through amide linkage of amino functionalized multiwall carbon nanotubes and [Ru (dcbpy)(bpy)2](PF6)2, an inorganic metal complex. Nanotube interconnects were visualized using atomic force microscopy. Absorption and emission spectroscopy showed significant changes between starting products and the resulting ruthenium nanotube complex, indicative of successful chemical modification.