Search

Cellulose nanocrystals (CNCs) are bioderived nanoparticles that can be isolated from various sources of natural cellulose via acid hydrolysis. However, the link between particle morphological characteristics and their ensemble behavior is poorly understood, partly because of the difficulties in controlling the CNC morphology during their extraction process. In this work, the impacts of common post-hydrolysis treatments on the CNC morphology are investigated. The results indicate that the centrifugation step commonly applied during CNC purification favors the formation of composite particles made of aligned crystallites, referred to as 'bundles'. Scanning nanobeam electron diffraction reveals that such bundles are associated preferentially along their hydrophobic faces. This is in stark contrast to the formation of misaligned composite particles that can be achieved with ionic treatments, where an uncontrolled aggregation occurs. The functional relevance of these morphological differences is demonstrated by their effect on the cholesteric self-organization of CNCs, with bundles found to exhibit a greater chiral enhancement, whereas the misaligned composite particles found to promote gelation. This study reveals the importance of the often-disregarded purification steps on the final morphology of CNCs and their resulting ensemble properties, thereby unlocking new routes for tailoring this promising material towards a variety of applications.

When pursuing sustainable approaches to fabricate photonic structures, nature can be used as a source of inspiration for both the nanoarchitecture and the constituent materials. Although several biomaterials have been promised as suitable candidates for photonic materials and pigments, their fabrication processes have been limited to the small to medium-scale production of films. Here, by employing a substrate-free process, structurally coloured microparticles are produced via the confined self-assembly of a cholesteric cellulose nanocrystal (CNC) suspension within emulsified microdroplets. Upon drying, the droplets undergo multiple buckling events, which allow for greater contraction of the nanostructure than predicted for a spherical geometry. This buckling, combined with a solvent or thermal post-treatment, enables the production of dispersions of vibrant red, green, and blue cellulose photonic pigments. The hierarchical structure of these pigments enables the deposition of coatings with angular independent colour, offering a consistent visual appearance across a wide range of viewing angles., Comment: 60 pages, 29 figures and 2 tables

The transfer of chirality across length-scales is an intriguing and universal natural phenomenon. However, connecting the properties of individual building blocks to the emergent features of their resulting large-scale structure remains a challenge. In this work, we investigate the origins of mesophase chirality in cellulose nanocrystal suspensions, whose self-assembly into chiral photonic films has attracted significant interest. By correlating the ensemble behaviour in suspensions and films with a quantitative morphological analysis of the individual nanoparticles, we reveal an inverse relationship between the cholesteric pitch and the abundance of laterally-bound composite particles. These bundles thus act as colloidal chiral dopants, analogous to those used in molecular liquid crystals, providing the missing link in the hierarchical transfer of chirality from the molecular to the colloidal scale.

Increasing the light scattering efficiency of nanostructured materials is becoming an active field of research both in fundamental science and commercial applications. In this context, the challenge is to use inexpensive organic materials that come with a lower refractive index than currently used mineral nanoparticles, which are under increased scrutiny for their toxicity. Although several recent investigations have reported different disordered systems to optimise light scattering by morphological design, no systematic studies comparing and explaining how different topological features contribute to optical properties have been reported yet. Using in silico synthesis and numerical simulations, we demonstrate that the reflectance is primarily determined by second order statistics. While remaining differences are explained by surface area and integrated mean curvature, an equal reflectance can be obtained by further tuning the structural anisotropy. Our results suggest a topological invariance for light scattering, demonstrating that any disordered system can be optimised for whiteness., Comment: submitted to a journal, 12 + 7 pages and 6 + 6 figures (manuscript + supporting information)

The optics of correlated disordered media is a fascinating research topic emerging at the interface between the physics of waves in complex media and nanophotonics. Inspired by photonic structures in nature and enabled by advances in nanofabrication processes, recent investigations have unveiled how the design of structural correlations down to the subwavelength scale could be exploited to control the scattering, transport and localization of light in matter. From optical transparency to superdiffusive light transport to photonic gaps, the optics of correlated disordered media challenges our physical intuition and offers new perspectives for applications. This article reviews the theoretical foundations, state-of-the-art experimental techniques and major achievements in the study of light interaction with correlated disorder, covering a wide range of systems -- from short-range correlated photonic liquids, to L\'evy glasses containing fractal heterogeneities, to hyperuniform disordered photonic materials. The mechanisms underlying light scattering and transport phenomena are elucidated on the basis of rigorous theoretical arguments. We overview the exciting ongoing research on mesoscopic phenomena, such as transport phase transitions and speckle statistics, and the current development of disorder engineering for applications such as light-energy management and visual appearance design. Special efforts are finally made to identify the main theoretical and experimental challenges to address in the near future., Comment: Accepted in Reviews of Modern Physics

PyLlama is a handy Python toolkit to compute the electromagnetic reflection and transmission properties of arbitrary multilayered linear media, including the case of anisotropy. Relying on a $4 \times 4$-matrix formalism, PyLlama implements not only the transfer matrix method, that is the most popular choice in existing codes, but also the scattering matrix method, which is numerically stable in all situations (e.g., thick, highly birefringent cholesteric structures at grazing incident angles). PyLlama is also designed to suit the practical needs by allowing the user to create, edit and assemble layers or multilayered domains with great ease. In this article, we present the electromagnetic theory underlying the transfer matrix and scattering matrix methods and outline the architecture and main features of PyLlama. Finally, we validate the code by comparison with available analytical solutions and demonstrate its versatility and numerical stability by modelling cholesteric media of varying complexity. A detailed documentation and tutorial are provided in a separate user manual. Applications of PyLlama range from the design of optical components to the modelling of polaritonic effects in polar crystals, to the study of structurally coloured materials in the living world.

Living organisms have developed a wide range of appearances from iridescent to matt textures. Interestingly, angular independent structural colors, where isotropy in the scattering structure is present, only produce coloration in the blue wavelength region of the visible spectrum. One might, therefore, wonder if such observation is a limitation of the architecture of the palette of materials available in nature. Here, by exploiting numerical modeling, we discuss the origin of isotropic structural colors without restriction to a specific light scattering regime. We show that high color purity and color saturation cannot be reached in isotropic short-range order structures for red hues. This conclusion holds even in the case of advanced scatterer morphologies, such as core-shell particles or inverse photonic glasses - explaining recent experimental findings reporting very poor performances of visual appearance for such systems.

Photonic materials with angular independent structural colour are highly desirable because they offer the broad viewing angles required for application as colorants in paints, cosmetics, textiles or displays. However, they are challenging to fabricate as they require isotropic nanoscale architectures with only short-range correlation. In this article, porous microparticles with such a structure are produced in a single, scalable step from an amphiphilic bottlebrush block copolymer. This is achieved by exploiting a novel controlled micellization self-assembly mechanism within emulsified toluene-in-water droplets. By restricting water permeation through the droplet interface, the size of the pores can be precisely addressed, resulting in structurally coloured pigments. Furthermore, the reflected colour can be tuned to reflect across the full visible spectrum using only a single polymer (Mn = 290 kDa) by altering the initial emulsification conditions. Such photonic pigments have several key advantages over their crystalline analogues, as they provide isotropic structural coloration that suppresses iridescence and improves colour purity without the need for either refractive index matching or the inclusion of a broadband absorber., Comment: 32 pages, 18 figures, 1 table

The formation of exciton-polaritons allows the transport of energy over hundreds of nanometres at velocities up to 10^6 m s^-1 in organic semiconductors films in the absence of external cavity structures.

Cellulose is the most abundant bio-polymer on earth. Cellulose fibres, such as the one extracted form cotton or woodpulp, have been used by humankind for hundreds of years to make textiles and paper. Here we show how, by engineering light matter-interaction, we can optimise light scattering using exclusively cellulose nanocrystals. The produced material is sustainable, biocompatible and, when compared to ordinary microfibre-based paper, it shows enhanced scattering strength (x4) yielding a transport mean free path as low as 3.5 um in the visible light range. The experimental results are in a good agreement with the theoretical predictions obtained with a diffusive model for light propagation.