Plasmonic nanoparticles, particularly gold nanoparticles (GNPs) hold a great potential as structural and functional building blocks for three-dimensional (3D) nanoarchitectures with specific optical applications. However, a rational control of their assembly into nanoscale superstructures with defined positioning and overall arrangement still remains challenging. Herein, we propose a solution to this challenge by using as building blocks: (1) nanometric silica helices with tunable handedness and sizes as a matrix and (2) GNPs with diameter varying from 4 to 10 nm to prepare a collection of helical GNPs superstructures (called Goldhelices hereafter). These nanomaterials exhibit well-defined arrangement of GNPs following the helicity of the silica template. Strong chiroptical activity is evidenced by circular dichroism (CD) spectroscopy at the wavelength of the surface plasmon resonance (SPR) of the GNPs with a anisotropy factor (g-factor) of the order of 1 × 10, i.e., 10-fold larger than what is typically reported in the literature. Such CD signals were simulated using a coupled dipole method which fit very well the experimental data. The measured signals are 1-2 orders of magnitude lower than the simulated signals, which is explained by the disordered GNPs grafting, the polydispersity of the GNPs, and the dimension of the nanohelices. These Goldhelices based on inorganic templates are much more robust than previously reported organic-based chiroptical nanostructures, making them good candidates for complex hierarchical organization, providing a promising approach for light management and benefits in applications such as circular polarizers, chiral metamaterials, or chiral sensing in the visible range.

Perovskite nanocrystals (PCNs) exhibited excellent absorption and luminescent optical properties.Inorganic silica nanohelices are used as chiral templates to induce optically active properties to CsPbBr3 PNCs grafted on their surfaces. In suspension, PNCs synthesized and grafted on the right (or left) handed silica helices do not show any detectable chiroptical properties. In contrast, in a dried film state, they show large circular dichroism (CD) and circularly polarized luminescence (CPL) signals with dissymmetric factor up to 6*10 -3 . Grazing incidence X-ray scattering, tomography electron microscopy (EM) and cryo EM have shown closely and helically packed PNCs if the nanohelices@PNCs are dried in contrast to much more loosely organized PNCs solvated in suspension. Simulations based on the coupled dipole method (CDM) demonstrate that the CD comes from the dipolar interaction between PNC assembled into a chiral structure. We show that the CD decreases as the interparticle distance increases. These results indicate that closely packed and helically arranged PNCs on silica nanohelices result in an increase of the optically active properties in the film state.

The optical properties of metallic spherical nanoparticles embedded in host liquid matrix are studied. Extended Maxwell-Garnett-Mie formulation which accounts for size dispersion, the intrinsic confinement, and extrinsic size effect, is proposed for the calculation of the effective dielectric function and absorption coefficient of size dispersion of colloidal solution of Au and Ag nanoparticles in water. We demonstrate that the size distribution induces an inhomogeneous broadening and an increase of the amplitude of the plasmon band. A large redshift of the plasmon band is also observed for silver nanoparticles. Compared to the conventional Maxwell Garnett theory, we demonstrated that this model gives better description of the measured absorption spectra of colloidal gold solutions.

Elaboration of mesoporous titanium oxide film supporting silver nanoparticles is described. Mesoporous titanium oxide films are characterized by TEM analysis. Titania films are infiltrated with a silver salt solution and chemical reduction treatments are performed using either a NaBH(4) or a formaldehyde solution. Infiltrated films are then characterized by TEM, SEM, AFM, UV-visible spectroscopy, X-ray diffraction, and Rutherford Backscattering Spectrometry (RBS). The utilization of a mesoporous titania substrate allows to control the nanoparticle size and the interparticle distance. RBS experiments provide the evidence that NaBH(4) treatment induces a strong accumulation of silver nanoparticles in the subsurface of the layer, while formaldehyde treatment induces the formation of silver nanoparticles embedded into almost the whole depth of the titania film. Large silver nanocrystals are also formed at the film surface whatever the reducer used. A broad visible absorption band related to the surface plasmon resonance (SPR) is obtained in both cases and is strongly red-shifted compared to the SPR obtained for silver nanoparticles inside a silica matrix. Moreover, irradiation with visible light causes the photooxidation of silver nanoparticles by titania and a complete discoloration of the material. The photooxidation is related to a drastic decrease in the silver nanoparticle size and is found to be reversible, particularly in the case of the material obtained by the formaldehyde reduction.

Here, we report for the first time a facile and fast one-step strategy to fabricate monodisperse gold nanocubes (GNCs) by spin-coating a gold precursor-loaded PMMA dispersion on N-doped silicon.

Chirality is found at all length scales in nature, and chiral metasurfaces have recently attracted attention due to their exceptional optical properties and their potential applications. Most of these metasurfaces are fabricated by topdown methods or bottom-up approaches that cannot be tuned in terms of structure and composition. By combining grazing incidence spraying of plasmonic nanowires and nanorods and Layer-by-Layer assembly, we show that nonchiral 1D nanoobjects can be assembled into scalable chiral Bouligand nanostructures whose mesoscale anisotropy is controlled with simple macroscopic tools. Such multilayer helical assemblies of linearly oriented nanowires and nanorods display very high circular dichroism up to 13 000 mdeg and giant dissymmetry factors up to g ≈ 0.30 over the entire visible and near-infrared range. The chiroptical properties of the chiral multilayer stack are successfully modeled using a transfer matrix formalism based on the experimentally determined properties of each individual layer. The proposed approach can be extended to much more elaborate architectures and gives access to templatefree and enantiomerically pure nanocomposites whose structure can be finely tuned through simple design principles.

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