Block copolymer self-assembly for nanophotonics

The ability to control and modulate the interaction of light with matter is crucial to achieve desired optical properties including reflection, transmission, and selective polarization. Photonic materials rely upon precise control over the composition and morphology to establish periodic interactions with light on the wavelength and sub-wavelength length scales. Supramolecular assembly provides a natural solution allowing the encoding of a desired 3D architecture into the chemical building blocks and assembly conditions. The compatibility with solution processing and low-overhead manufacturing is a significant advantage over more complex approaches such as lithography or colloidal assembly. Here we review recent advances on photonic architectures derived from block copolymers and highlight the influence and complexity of processing pathways. Notable examples that have emerged from this unique synthesis platform include Bragg reflectors, antireflective coatings, and chiral metamaterials. We further predict expanded photonic capabilities and limits of these approaches in light of future developments of the field

Role of Anisotropy and Refractive Index in Scattering and Whiteness Optimization

This is the final version. Available from Wiley via the DOI in this record.The ability to manipulate light–matter interaction to tailor the scattering properties of materials is crucial to many aspects of everyday life, from paints to lighting, and to many fundamental concepts in disordered photonics. Light transport and scattering in a granular disordered medium are dictated by the spatial distribution (structure factor) and the scattering properties (form factor and refractive index) of its building blocks. As yet, however, the importance of anisotropy in such systems has not been considered. Here, a systematic numerical survey that disentangles and quantifies the role of different kinds and degrees of anisotropy in scattering optimization is reported. It is shown that ensembles of uncorrelated, anisotropic particles with nematic ordering enables to increase by 20% the reflectance of low-refractive index media (n = 1.55), using only three-quarters of material compared to their isotropic counterpart. Additionally, these systems exhibit a whiteness comparable to conventionally used high-refractive index media, e.g., TiO2 (n = 2.60). Therefore, the findings not only provide an understanding of the role of anisotropy in scattering optimization, but they also showcase a novel strategy to replace inorganic white enhancers with sustainable and biocompatible products made of biopolymers.Biotechnology and Biological Sciences Research Council (BBSRC)European Research Council (ERC)Leverhulme Trus

Bio-inspired Highly Scattering Networks via Polymer Phase Separation

A common strategy to optimize whiteness in living organisms consists in using three-dimensional random networks with dense and polydisperse scattering elements constituted by relatively low-refractive index materials. Inspired by these natural architectures, we developed a fast and scalable method to produce highly scattering porous polymer films via phase separation. By varying the molecular weight of the polymer, we modified the morphology of the porous films and therefore tuned their scattering properties. The achieved transport mean free paths are in the micrometer range, improving the scattering strength of analogous low-refractive index systems, e.g. standard white paper, by an order of magnitude. The produced porous films show a broadband reflectivity of approximately 75 % whilst only 4 m thick. In addition, the films are flexible and can be readily index-matched with water (i.e. they become transparent when wet), allowing for various applications such as coatings with tunable transmittance and responsive paints

Hereditary Character of Photonics Structure in Pachyrhynchus sarcitis Weevils: Color Changes via One Generation Hybridization

Pachyrhynchus sarcitis weevils are flightless weevils characterized by colored patches of scales on their dark elytra. The vivid colors of such patches result from the reflection of differently oriented three-dimensional photonic crystals within their scales. Our results show that hybrid P. sarcitis, the first filial generation of two P. sarcitis populations from Lanyu Island (Taiwan) and Babuyan Island (Philippines), mixes the color of its ancestors by tuning the photonic structure in its scales. A careful spectroscopical and anatomical analysis of the weevils in the phylogeny reveals the hereditary characteristics of the photonic crystals within their scales in terms of lattice constant, orientation and domain size. Monitoring how structural coloration is inherited by offspring highlights the versatility of photonic structures to completely redesign the optical response of living organisms. Such finding shed light onto the evolution and development mechanisms of structural coloration in Pachyrhynchus weevils and provides inspiration for the design of visual appearance in artificial photonic materials.NanoBio-ICMG platform (FR 2607) Cambridge Trus

Anisotropic Light Transport in White Beetle Scales

open6sìThe extremely brilliant whiteness shown by the Cyphochilus beetle is generated by multiple scattering of light inside the ultrathin scales that cover its body, whose interior is characterized by an anisotropic nanostructured network of chitin filaments. It is demonstrated that the structural anisotropy of the network is crucial in order to achieve high broadband reflectance from such a thin, low‐refractive‐index system.openCortese, L; Pattelli, L; Utel, F; Vignolini, S; Burresi, M; Wiersma, DSCortese, L; Pattelli, L; Utel, F; Vignolini, S; Burresi, M; Wiersma, D

Biocompatible and Sustainable Optical Strain Sensors for Large-Area Applications

By a simple two-step procedure, large photonic strain sensors using a biocompatible cellulose derivative are fabricated. Transient color shifts of the sensors are explained by a theoretical model that consideres the deformation of cholesteric domains, which is in agreement with the experimental results. The extremely simple fabrication method is suitable for both miniaturization and large-sale manufacture, taking advantage of inexpensive and sustainable materials.Biotechnology and Biological Sciences Research Council (David Phillips fellowship (Grant ID: BB/K014617/1)), The Isaac Newton Trust Cambridge (Grant ID: 76933), European Research Council (Grant ID: ERC-2014-STG H2020 639088

Bright-white beetle scales optimise multiple scattering of light.

Whiteness arises from diffuse and broadband reflection of light typically achieved through optical scattering in randomly structured media. In contrast to structural colour due to coherent scattering, white appearance generally requires a relatively thick system comprising randomly positioned high refractive-index scattering centres. Here, we show that the exceptionally bright white appearance of Cyphochilus and Lepidiota stigma beetles arises from a remarkably optimised anisotropy of intra-scale chitin networks, which act as a dense scattering media. Using time-resolved measurements, we show that light propagating in the scales of the beetles undergoes pronounced multiple scattering that is associated with the lowest transport mean free path reported to date for low-refractive-index systems. Our light transport investigation unveil high level of optimisation that achieves high-brightness white in a thin low-mass-per-unit-area anisotropic disordered nanostructure.The research leading to these results has received funding from the European Research Council under the European Union’s Seventh Framework Programme (FP7/2007–2013)/ERC grant agreement n [291349] and USAF grant FA9550-10-1-0020.This is the final published version, also available from Nature Publishing at http://www.nature.com/srep/2014/140815/srep06075/full/srep06075.html

Ultrafast nonlinear response of gold gyroid three-dimensional metamaterials

We explore the nonlinear optical response of 3D gyroidal metamaterials, which show >10-fold enhancements compared to all other metallic nanomaterials as well as bulk gold. A simple analytical model for this metamaterial response shows how the reflectivity spectrum scales with the metal fill fraction and the refractive index of the material that the metallic nanostructure is embedded in. The ultrafast response arising from the interconnected 3D nanostructure can be separated into electronic and lattice contributions with strong spectral dependences on the dielectric filling of the gyroids, which invert the sign of the nonlinear transient reflectivity changes. These metamaterials thus provide a wide variety of tuneable nonlinear optical properties, which can be utilised for frequency mixing, optical switching, phase modulators, novel emitters, and enhanced sensing.This is the author's accepted manuscript. The final version is available from APS in Physical Review Applied at http://journals.aps.org/prapplied/abstract/10.1103/PhysRevApplied.2.044002#fulltext#fulltext

Hyperspectral Imaging of Photonic Cellulose Nanocrystal Films: Structure of Local Defects and Implications for Self-Assembly Pathways

Cellulose nanocrystals (CNCs) can spontaneously assemble into chiral nematic films capable of reflecting circularly polarized light in the visible range. As many other photonic materials obtained by bottom-up approaches, CNC films often display defects that greatly impact their visual appearance. Here, we study the optical response of defects in photonic CNC films, coupling optical microscopy with hyperspectral imaging, and we compare it to optical simulations of discontinuous cholesteric structures of increasing complexity. Cross-sectional SEM observations of the film structure guided the choice of simulation parameters and showed excellent agreement with experimental optical patterns. More importantly, it strongly suggests that the last fraction of CNCs to self-assemble, upon solvent evaporation, does not undergo the typical nucleation and growth pathway, but a spinodal decomposition, an alternative self-assembly pathway so far overlooked in cast films and that can have far-reaching consequences on choices of CNC sources and assembly conditions