Sulfide Gels and Films: Products of Non-Oxide Gelation

The preparation of concentrated sols and transparent stiff gels of II-VI semiconductors nanocrystals is reported. A two-step process for the production of cadmium sulfide is reported. Sol stabilization and gelation control are achieved through successive passivation and depassivation of the surface of the nanocrystals which are complexed with thiols. The mechanisms driving the aggregation and the gelation are explained on the basis of NMR and SAXS experiments. Thin films as well as monoliths can be produced. The general principles of the method presented are not restricted to chalcogenide systems and thus enlarge the domain of application of the inorganic sol-gel process.     

Inhibition and exaltation of emission in layer-controlled colloidal photonic architectures

We described the engineering and characterization of photonic colloidal crystals based on silica spheres with incorporated YVO₄:Eu luminescent nanoparticles. These structures exhibit strong angle-dependent luminescent properties. The controlled incorporation of a planar defect in the periodic structures gives rise to the creation of a pass band in the pseudo-gap. In the energy range of this pass band, we observed a strong increase in combination with a sharp width of the emission spectrum, which opens new possibilities for the design of low-threshold and/or single mode photonic crystal lasers.     

Synthesis and sol–gel assembly of nanophosphors

Some recent works made in our group on inorganic nanophosphors are briefly reviewed in this paper. We first present the synthesis of highly concentrated semiconductor quantum dot colloids allowing the extension of the well-known oxide sol–gel process to chalcogenide compounds. Secondly, we show the synthesis and the chemical functionalization of lanthanide-doped insulator nanoparticles. In particular, the annealing process of these particles at high temperature leads to highly bright nanocrystals, which can be used as biological luminescent labels or for integration in transparent luminescent coatings. Finally, we consider luminescent transition metal clusters, which combine the inorganic structure of nanoparticles with the monodispersity and the easy functionalization of the organic molecules. Emphasis is put on the original thermochromic luminescence properties of copper iodide clusters trapped in siloxane-based films.     

Transparent coatings made from spray deposited colloidal suspensions

The goal of this study is to elaborate few-micrometer thick optically active coatings based on nanoparticles spray-deposited onto a substrate and to control their scattering properties through a progressive suppression of the coffee-ring effect. The modification of the aggregation state of the nanoparticles to be sprayed induces a change of the surface roughness of the films and consequently of their optical transmission. We draw the counterintuitive conclusion that a nonstable colloidal solution gives a smoother coating than a highly stabilized colloidal solution, leading to a more transparent coating. This phenomenon is demonstrated in the case of commercial TiO(2) nanoparticles, as well as of homemade luminescent YVO(4):Eu nanoparticles, and seems to be generalized to a large range of systems.     

Efficient production of NV colour centres in nanodiamonds using high-energy electron irradiation

Nanodiamond powders with an average size of 50 nm have been irradiated using high-energy electron beam. After annealing and chemical treatment, nanodiamond colloidal solutions were obtained and deposited on silica coverslips by spin-coating. The fluorescence of nanodiamonds was studied by confocal microscopy together with atomic force microscopy. We evaluated the proportion of luminescent nanodiamonds as a function of the irradiation duration and showed that large quantities, exceeding hundreds of mg, of luminescent nanodiamonds can be produced within 1 h of electron irradiation.     

Water-soluble pegylated quantum dots: from a composite hexagonal phase to isolated micelles

We present a simple method based on the dispersion of fluorescent quantum dots (QD) into a liquid crystal phase that provides either nanostructured material or isolated QD micelles depending on water concentration. The liquid-crystal phase was obtained by using a gallate amphiphile with a poly(ethylene glycol) chain as the polar headgroup, named I. The hydration of QD/I mixtures resulted in the formation of a composite hexagonal phase identified by small-angle X-ray scattering and by polarized light and fluorescence optical microscopy, showing a homogeneous distribution of fluorescence within hexagonal phase. This composite mesophase can be converted into isolated QD-I micelles by dilution in water. The fluorescent QD-I micelles, purified by size exclusion chromatography, are well monodisperse with a hydrodynamic diameter of 20-30 nm. Moreover, these QD do not show any nonspecific adsorption on lipid or cell membranes. By simply adjusting the water content, the PEG gallate amphiphile I provides a simple method to prepare a self-organized composite phase or pegylated water soluble QD micelles for biological applications.     

Silver nanoparticle growth in 3D-hexagonal mesoporous silica films

The 3D-hexagonal mesoporous films are used as templates to grow uniform silver nanoparticles. The grafting of hydrophobic groups at the pore surface, significantly slows down the silver ion diffusion, anchoring small silver clusters in micropores and leading to organized domains of silver particles in mesopores with a narrow size distribution.