Develpment of optically active flexible materials based on molecular assembly templated chiral hybrid nanostructures.

In this work, we focused on the creation of optically active chiral nanostructures by fabricating fluorescent silica nanohelices in order to obtain optically active nanoscale soft materials for applications as nanophotonics materials. For this purpose, silica chiral nanohelices were used for grafting and organizing achiral fluorescent inorganic nanocrystals, dyes, molecules, and fluorescent polymers through different approaches. These inorganic helices were formed via sol-gel method using organic helical self–assemblies of surfactant molecules (achiral and cationic gemini surfactant, with chiral counterion, tartrate) as templates. First, the surface of helical silica was functionalized by APTES in order to graft inorganic quantum dots ZnS-AgInS2 with different capping ligands. In the second part, fluorescent anthracene derivative polymer was organized via deposition and absorption on the surface of helical silica. To investigate the chiroptical properties, circular dichroism and circularly polarised luminescence characterization were performed.In the first chapter, the bibliographic study on different chiral organic self-assembling systems and their chiroptical properties are shown. The studies on the formation of chiral self-assembled systems in different conditions, structural morphology, fabrication techniques and their applications are discussed followed by the use of fluorescent nanocrystals, i.e., quantum dots (QDs) and achiral fluorescent polymers on which chiroptical properties can be obtained and their applications in optical nanodevices, sensors, and nano-photonics.In the first part of the second chapter, different characterisation techniques such as transmission electron microscope (TEM) , high resolution transmission electron microscope (HRTEM), and confocal microscopy, UV-Vis spectroscopy and fluorescence spectroscopies, as well as circular dichroism (CD) and circularly polarised luminescence (CPL) spectroscopies are described. In the second part, the synthesis of Gemini 16-2-16 as well as their self-assemblies mechanism, and their transformation to silica replica via sol-gel chemistry are described. These silica nanohelices are functionalized by 3-aminopropyltriethoxysilane (APTES). Their analysis is performed by Thermogravimetric analysis (TGA) and elementary analysis (EA).In the third Chapter, we focused on the synthesis of inorganic ((ZnS)x-1(AgInS2)x) QDs with different compositions molar ratio and its characterizations by TEM, TGA, EA, Fourier-transform infrared spectroscopy (FTIR), zeta potential measurements, absorption, and emission spectroscopy. Four types of ligands were used to cap the QDs via phase ligand exchange as follows: ammonium sulphide (AS), 3-mercaptopropionic acid (MPA), l-cysteine (L-Cys) and the fourth one is oleylamine (OLA). These QDs are grafted on the surface of amine-modified silica helices through ionic interaction. Various techniques were used to show the grafting of QDs on the surface of silica helix, and their optical properties were studied using absorption and emission spectroscopy. After grafting, in each case of ligands, different results were observed as follows: The TEM characterization shows that QDs are grafted on the surface of silica helices. In the case of AS-capped QDs, the helical morphology of silica helices after grafting is destroyed; therefore the further ananlysis was not possible. While, in the cases of QDs with three other ligands MPA, OLA and L-cys, dense and homogeneous grafting of the QDs were observed by TEM and the helical morphology was preserved after their grafting. The HRTEM images were taken on the MPA-QDs@silica helices and energy-dispersive x-ray (EDX) analysis was performed in STEM mode, confirming the QDs elements present on the silica surfaces. [...]