Investigation of the Photochromism of WO3, TiO2, and Composite WO3-TiO2 Nanoparticles.

We report the synthesis of WO3, TiO2, and TiO2-WO3 nanoparticles by a polyol route, with the objective of studying the influence of the preparation method on their photochromic properties. By combining transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and diffuse reflectance experiments, we show that low W6+ concentrations and high ripening temperatures allow the preparation of WO3 nanoparticles with high photochromic efficiency. WO3-TiO2 nanocomposites (NCs) prepared by the introduction of a TiO2+ solution in a WO3 nanoparticle suspension exhibit a strong coloring photochromism, which is attributed to the TiO2 coating of the WO3 nanoparticles as it involves the formation of W-O-Ti oxo-bonds in place of W5+-νO defects. Especially, after an oxidative treatment in order to obtain an initial pale-yellow material, such WO3-TiO2 NCs exhibit a fully reversible photochromism with a large contrast between the colored and bleached state. They could therefore be incorporated in hybrid smart films for solar control on building window glasses. On the other hand, while the WO3-TiO2 NCs are functionalized with DPA (n-dodecyl phosphonic acid), the as-prepared nanocomposites exhibit exacerbated coloring contrast but with a nearly nonreversible photochromism (very limited bleaching), which makes them good candidates for the fabrication of smart UV-sensor devices that can indicate the cumulative UV dose which is received.

Solvent-induced assembly of mono- and divalent silica nanoparticles.

Particles with attractive patches are appealing candidates to be used as building units to fabricate novel colloidal architectures by self-assembly. Here, we report the synthesis of one-patch silica nanoparticles, which consist of silica half-spheres whose concave face carries in its center a polymeric patch made of grafted polystyrene chains. The multistage synthesis allows for a fine control of the patch-to-particle size ratio from 0.23 to 0.57. The assembly of the patchy nanoparticles can be triggered by reducing the solvent quality for the polystyrene chains. Dimers or trimers can be obtained by tuning the patch-to-particle size ratio. When mixed with two-patch nanoparticles, one-patch nanoparticles control the length of the resulting chains by behaving as colloidal chain stoppers. The present strategy allows for future elaboration of novel colloidal structures by controlled assembly of nanoparticles.

Transfer of multi-DNA patches by colloidal stamping.

Patchy particles have received great attention due to their ability to develop directional and selective interactions and serve as building units for the self-assembly of innovative colloidal molecules and crystalline structures. Although synthesizing particles with multiple dissimilar patches is still highly challenging and lacks efficient methods, these building blocks would open paths towards a broader range of ordered materials with inherent properties. Herein, we describe a new approach to pattern functional DNA patches at the surface of particles, by the use of colloidal stamps. DNA inks are transferred only at the contact zones between the target particles and the stamps thanks to selective strand-displacement reactions. The produced DNA-patchy particles are ideal candidates to act as advanced precision/designer building blocks to self-assemble the next generation of colloidal materials.

Linear Assembly of Two-Patch Silica Nanoparticles and Control of Chain Length by Coassembly with Colloidal Chain Stoppers.

The self-assembly of patchy nanosized building blocks is an efficient strategy for producing highly organized materials. Herein we report the chaining of divalent silica nanoparticles with polystyrene patches dispersed in tetrahydrofuran triggered by lowering the solvent quality. We study the influence of the patch-to-particle size ratio and show that the nature of the added nonsolvent, for example, ethanol, water, or salty water, and its volume fraction should be carefully adjusted. We demonstrate that colloidal assembly initially obeys the kinetic model of step-growth polymerization and that beyond a certain length, the chains have the possibility to cyclize. We also show that the length of the chains can be controlled by the addition of one-patch silica nanoparticles, which act as colloidal analogues of chain stoppers.

Polyhedral plasmonic nanoclusters through multi-step colloidal chemistry.

We describe a new approach to making plasmonic metamolecules with well-controlled resonances at optical wavelengths. Metamolecules are highly symmetric, subwavelength-scale clusters of metal and dielectric. They are of interest for metafluids, isotropic optical materials with applications in imaging and optical communications. For such applications, the morphology must be precisely controlled: the optical response is sensitive to nanometer-scale variations in the thickness of metal coatings and the distances between metal surfaces. To achieve this precision, we use a multi-step colloidal synthesis approach. Starting from highly monodisperse silica seeds, we grow octahedral clusters of polystyrene spheres using seeded-growth emulsion polymerization. We then overgrow the silica and remove the polystyrene to create a dimpled template. Finally, we attach six silica satellites to the template and coat them with gold. Using single-cluster spectroscopy, we show that the plasmonic resonances are reproducible from cluster to cluster. By comparing the spectra to theory, we show that the multi-step synthesis approach can control the distances between metallic surfaces to nanometer-scale precision. More broadly, our approach shows how metamolecules can be produced in bulk by combining different, high-yield colloidal synthesis steps, analogous to how small molecules are produced by multi-step chemical reactions.

Templated Synthesis and Assembly of Two-, Three- and Six-Patch Silica Nanoparticles with a Controlled Patch-to-Particle Size Ratio.

We report a fabrication route of silica nanoparticles with two, three or six patches with an easily tunable patch-to-particle size ratio. The synthetic pathway includes two main stages: the synthesis of silica/polystyrene multipod-like templates and the selective growth of their silica core through an iterative approach. Electron microscopy of the dimpled nanoparticles obtained after dissolution of the polystyrene nodules of the multipod-like nanoparticles provides evidence of the conformational growth of the silica core. Thanks to the presence of some polymer chains, which remained grafted at the bottom of the dimples after the dissolution of the PS nodules, the solvent-induced assembly of the patchy nanoparticles is performed. Chains, hexagonal suprastructures and cubic lattices are obtained from the assembly of two-, three- and six-patch silica nanoparticles, respectively. Our study can guide future work in both patchy nanoparticle synthesis and self-assembly. It also opens new routes towards the fabrication of specific classes of one-, two- and three-dimensional colloidal lattices, including complex tilings.

From colloidal particles to photonic crystals: advances in self-assembly and their emerging applications.

Over the last three decades, photonic crystals (PhCs) have attracted intense interests thanks to their broad potential applications in optics and photonics. Generally, these structures can be fabricated via either "top-down" lithographic or "bottom-up" self-assembly approaches. The self-assembly approaches have attracted particular attention due to their low cost, simple fabrication processes, relative convenience of scaling up, and the ease of creating complex structures with nanometer precision. The self-assembled colloidal crystals (CCs), which are good candidates for PhCs, have offered unprecedented opportunities for photonics, optics, optoelectronics, sensing, energy harvesting, environmental remediation, pigments, and many other applications. The creation of high-quality CCs and their mass fabrication over large areas are the critical limiting factors for real-world applications. This paper reviews the state-of-the-art techniques in the self-assembly of colloidal particles for the fabrication of large-area high-quality CCs and CCs with unique symmetries. The first part of this review summarizes the types of defects commonly encountered in the fabrication process and their effects on the optical properties of the resultant CCs. Next, the mechanisms of the formation of cracks/defects are discussed, and a range of versatile fabrication methods to create large-area crack/defect-free two-dimensional and three-dimensional CCs are described. Meanwhile, we also shed light on both the advantages and limitations of these advanced approaches developed to fabricate high-quality CCs. The self-assembly routes and achievements in the fabrication of CCs with the ability to open a complete photonic bandgap, such as cubic diamond and pyrochlore structure CCs, are discussed as well. Then emerging applications of large-area high-quality CCs and unique photonic structures enabled by the advanced self-assembly methods are illustrated. At the end of this review, we outlook the future approaches in the fabrication of perfect CCs and highlight their novel real-world applications.

Toward Huygens' Sources with Dodecahedral Plasmonic Clusters.

The design and chemical synthesis of plasmonic nanoresonators exhibiting a strong magnetic response in the visible is a key requirement to the realization of efficient functional and self-assembled metamaterials. However, novel applications like Huygens' metasurfaces or mu-near-zero materials require stronger magnetic responses than those currently reported. Our numerical simulations demonstrate that the specific dodecahedral morphology, whereby 12 silver satellites are located on the faces of a nanosized dielectric dodecahedron, provides sufficiently large electric and magnetic dipolar and quadrupolar responses that interfere to produce so-called generalized Huygens' sources, fulfilling the generalized Kerker condition. Using a multistep colloidal engineering approach, we synthesize highly symmetric plasmonic nanoclusters with a controlled silver satellite size and show that they exhibit a strong forward scattering that may be used in various applications such as metasurfaces or perfect absorbers.

Versatile template-directed synthesis of gold nanocages with a predefined number of windows.

Highly symmetrical gold nanocages can be produced with a controllable number of circular windows of either 2, 3, 4, 6 or 12 via an original fabrication route. The synthetic pathway includes three main stages: the synthesis of silica/polystyrene multipod templates, the regioselective seeded growth of a gold shell on the unmasked part of the silica surface and the development of gold nanocages by dissolving/etching the templates. Electron microscopy and tomography provide evidence of the symmetrical features of the as-obtained nanostructures. The optical properties of nanocages with 4 and 12 windows were measured at the single particle level by spatial modulation spectroscopy and correlated with numerical simulations based on finite-element modeling. The new multi-step synthesis approach reported here also allows the synthesis of rattle-like nanostructures through filling of the nanocages with a guest nano-object. With the potential to adjust the chemical composition, size and geometry of both the guest particle and the host cage, it opens new routes towards the fabrication of hollow nanostructures of high interest for a variety of applications including sensing devices, catalytic reactors and biomedicine.

Solvent-Induced Assembly of One-Patch Silica Nanoparticles into Robust Clusters, Wormlike Chains and Bilayers.

We report the synthesis and solvent-induced assembly of one-patch silica nanoparticles in the size range of 100-150 nm. They consisted, as a first approximation, of silica half-spheres of which the truncated face was itself concave and carried in its center a polymeric patch made of grafted polystyrene chains. The multistage synthesis led to 98% pure batches and allowed a fine control of the patch-to-particle size ratio from 0.69 to 1.54. The self-assembly was performed in equivolume mixtures of tetrahydrofuran and ethanol, making the polymeric patches sticky and ready to coalesce together. The assembly kinetics was monitored by collecting samples over time and analyzing statistically their TEM images. Small clusters, such as dimers, trimers, and tetramers, were formed initially and then evolved in part into micelles. Accordingly to previous simulation studies, more or less branched wormlike chains and planar bilayers were observed in the long term, when the patch-to-particle size ratio was high enough. We focused also on the experimental conditions that could allow preparing small clusters in a good morphology yield.

Colloidal molecules and patchy particles: complementary concepts, synthesis and self-assembly.

This review describes the latest advances in the synthesis and assembly of specific colloids such as the colloidal molecules as defined by van Blaaderen in 2003 and the patchy particles imagined a few years later. The two concepts are closely related because some may serve as precursors of others and vice versa. To best mimic the molecular structures, it is necessary to introduce the notions of directed binding and valence which result in the concept of patches arranged on the particle surface according to the conventional repulsion figures. The assembly of patchy particles has made it possible to reconstitute molecules and macromolecules of simple geometry. But the existence of extended assemblies of larger dimensions has been demonstrated mostly by simulation and it struggles experimentally with the purity of the batches of building blocks.

Clustering of asymmetric dumbbell-shaped silica/polystyrene nanoparticles by solvent-induced self-assembly.

We report a quite simple strategy to assemble silica/polystyrene dumbbell-shaped nanoparticles into clusters with an aggregation number from two to more than 30. The polystyrene lobe serves as a patch that is made sticky and ready to merge with similar ones when the dumbbells are dispersed in an ethanol/DMF mixture. Thanks to transmission electron microscopy experiments, we describe qualitatively and quantitatively the influence of several experimental parameters such as the solvent quality, i.e. DMF fraction, and the patch-to-particle size ratio. We show that the DMF fraction range (30-50 vol%) for the sticky regime can be extended if the incubation process is completed by a centrifugation step. We also demonstrate an unexpected evolution in the average aggregation number with the patch-to-particle size ratio that may be explained by the molar mass distribution within the polystyrene core of the clusters. Lastly, we show that this assembly route may be extended to gold-coated clusters.

Synthesis of Colloidal Molecules: Recent Advances and Perspectives.

The synthesis and study of colloidal molecules, that is to say clusters of a small number of colloidal entities that resemble the configuration of atoms in molecules both in constituent size and angular arrangement to that of valence shell electron pair repulsion model-related space-filling geometries, are of continued and significant interest. The rapid development in this research area has attracted intense interest from researchers with diverse expertise, and numerous methods towards the synthesis of colloidal molecules have been reported. In this Minireview, we attempt to give an overview of these latest developments, classifying them in processes based on controlled phase separation phenomena, on controlled surface nucleation and growth, and on controlled clustering. We also discuss the potential use of colloidal molecules as building blocks to fabricate new hierarchically organized superstructures and functional materials.

Tunable index metamaterials made by bottom-up approaches.

Despite the exciting optical properties metamaterials exhibit, their implementation in technology is being hampered nowadays by the inherent losses of their metal constituents and the expensive and low-throughput procedures used. As an alternative, we present a new design of double fishnet metamaterials that can be easily realized combining two inexpensive and up-scalable techniques: nanosphere lithography and metallic electrodeposition. A monolayer of polystyrene spheres is used as a template for the infiltration of two symmetric gold layers separated by an air gap. The effective refractive index of the metamaterial can be easily tuned by the appropriate choice of the diameter of the spheres and the gap width between the metallic layers, varying its value from positive to negative. The good agreement between optical measurements and finite-difference time-domain simulations confirms the success of our process. Fishnet metamaterials with refractive index going from 1.5 until -1.0 in the near infrared range are demonstrated and the key parameters for these architectures provided.

Energy Transfer and Interference by Collective Electromagnetic Coupling.

The physics of collective optical response of molecular assemblies, pioneered by Dicke in 1954, has long been at the center of theoretical and experimental scrutiny. The influence of the environment on such phenomena is also of great interest due to various important applications in, e.g., energy conversion devices. In this Letter, we demonstrate both experimentally and theoretically the spatial modulations of the collective decay rates of molecules placed in proximity to a metal interface. We show in a very simple framework how the cooperative optical response can be analyzed in terms of intermolecular correlations causing interference between the response of different molecules and the polarization induced on a nearby metallic boundary and predict similar collective interference phenomena in excitation energy transfer between molecular aggregates.

Colloidal chemistry with patchy silica nanoparticles.

We report a new route to synthesize clusters, or so-called colloidal molecules (CMs), which mimic the symmetry of molecular structures made of one central atom. We couple site-specifically functionalized patchy nanoparticles, i.e., valence-endowed colloidal atoms (CAs), with complementary nanospheres through amide bonds. By analogy with the Gillespie formalism, we show that AX4, AX3E1 and AX2E2 CMs can be obtained from tetravalent sp3-like CAs when the relative amount of both building units is varied in a controlled manner. We obtain AX2 CMs from divalent sp-like CAs. We also show that it is possible to covalently attach two different types of satellites to the same central patchy nanoparticle to create more complex CMs, opening the way to the fabrication of new multifunctional nanostructures with well-controlled shape and composition.

Colloidal Molecules from Valence-Endowed Nanoparticles by Covalent Chemistry.

We demonstrate a simple method to create a variety of silica-based colloidal molecules through the covalent assembly of site-specifically functionalized patchy nanoparticles with complementary nanospheres. Colloidal analogues of BeBr2 , BBr3 and CBr4 are obtained from sp-, sp2 - and sp3 -like particles, while Br2 O and NBr3 analogues can be fabricated by varying the relative amounts of both colloidal precursors. We also show that it is possible to attach covalently silica nanospheres of various sizes to one central patchy nanoparticle, which leads to the formation of more complex colloidal molecules, including chiral ones. The possibility to easily extend the strategy to other colloidal precursors which can serve as satellites, for example, ellipsoidal polymer particles or metallic nanoparticles, opens the way to a rich variety of new colloidal analogues of atoms which could serve as building blocks of next generation materials.

Spectral dependence of plasmon-enhanced fluorescence in a hollow nanotriangle assembled by DNA origami: towards plasmon assisted energy transfer.

The precise positioning of plasmonic nanoscale objects and organic molecules can significantly boost our ability to fabricate hybrid nanoarchitectures with specific target functionalities. In this work, we used a DNA origami structure to precisely localize three different fluorescent dyes close to the tips of hollow gold nanotriangles. A spectral dependence of plasmon-enhanced fluorescence is evidenced through co-localized AFM and fluorescence measurements. The experimental results match well with explanatory FDTD simulations. Our findings open the way to the bottom-up fabrication of plasmonic routers operating through plasmon energy transfer. They will allow one to actively control the direction of light propagation.

Nonisotropic Self-Assembly of Nanoparticles: From Compact Packing to Functional Aggregates.

Quantum strongly correlated systems that exhibit interesting features in condensed matter physics often need an unachievable temperature or pressure range in classical materials. One solution is to introduce a scaling factor, namely, the lattice parameter. Synthetic heterostructures named superlattices or supracrystals are synthesized by the assembling of colloidal atoms. These include semiconductors, metals, and insulators for the exploitation of their unique properties. Most of them are currently limited to dense packing. However, some of desired properties need to adjust the colloidal atoms neighboring number. Here, the current state of research in nondense packing is summarized, discussing the benefits, outlining possible scenarios and methodologies, describing examples reported in the literature, briefly discussing the challenges, and offering preliminary conclusions. Penetrating such new and intriguing research fields demands a multidisciplinary approach accounting for the coupling of statistic physics, solid state and quantum physics, chemistry, computational science, and mathematics. Standard interactions between colloidal atoms and emerging fields, such as the use of Casimir forces, are reported. In particular, the focus is on the novelty of patchy colloidal atoms to meet this challenge.

Organization of Microgels at the Air-Water Interface under Compression: Role of Electrostatics and Cross-Linking Density.

Poly(N-isopropylacrylamide) (pNIPAM) microgels are soft and deformable particles, which can adsorb at liquid interfaces. In the present paper, we study the two-dimensional organization of charged and quasi-neutral microgels with different cross-linking densities, under compression at the air-water interface and the transfer of the microgel monolayer onto a solid substrate at different surface pressures. At low cross-linking densities, the microgels form highly ordered hexagonal lattices on the solid substrate over large areas, with a unique lattice parameter that decreases continuously as the surface pressure increases. We thus prove that the microgel conformation evolves at the air-water interface. The microgels undergo a continuous transition from a highly flattened state at low surface coverage, where the maximal polymer segments are adsorbed at the interface, to entangled flattened microgels, and finally the thickening of the layer up to a dense hydrogel layer of compacted microgels. Moreover, two batches of microgels, with and without charges, are compared. The contribution of electrostatic interactions is assessed via changing the charge density of the microgels or modulating the Debye length. In both cases, electrostatics does not change the lattice parameter, meaning that, despite the microgel different swelling ratio, charges do not affect neither interactions between particles at the interface nor microgels adsorption. Conversely, the cross-linking density has a strong impact on microgel packing at the interface: increasing the cross-linking density strongly decreases the extent of microgel flattening and promotes the occurrence of coexisting hexagonally ordered domains with different lattice parameters.