This work deals with the study of the drying-mediated assembly of colloidal gold nanoparticles (Au NPs) in mesoscale aggregation patterns and their manipulation by atomic force microscopy (AFM) on model surfaces. The assembly of NPs in mesoscale and complex aggregation patterns assisted by the wetting and the drying of complex fluids (suspensions of NPs, NPs/biopolymers mixed solutions) on homogeneous and heterogeneous molecular surfaces was studied. This issue is important, both for understanding fundamental processes of self-organization, and for generating new functional mesostructures. The drying of complex fluids often leads to the emergence of highly complex aggregation structures as shown and discussed in this work. The richness and the aesthetics of these complex structures generated by these interfacial phenomena reflect not only the bulk properties of fluids (different sizes and lengths- scales, kinetic changes in state), but more importantly, the coupling between the fluid properties and those of the substrate surface (wetting interactions, confinement, hydrodynamics). In the case of two important heterogeneous fluids which are Au NPs and polysaccharide solutions, these drying-mediated structure formation lead to the genesis of unusually large and highly ramified dendrites aggregation patterns. The growth mechanism and the critical parameters that control the morphogenesis of these complexes structures are addressed in this work. In addition, the aging mechanisms and kinetics of these structures that are metastable and evolve either through direct dislocation via clusters NPs mobility on the surface, or through undulation-induced roughning of the dendrite branches. To better understanding this NPs mobility and thus the dislocation mechanism of the aging, a detailed study based on the manipulation of NPs by atomic force microscopy in tapping mode (AFM) was developed. The threshold dissipated energy to manipulate (move) the NPs can be quantified according to the intrinsic parameters of the particle (size, shape, and chemical nature), the chemical nature and topography of the substrate, and finally the operating and environment conditions. This work enabled us to understand the mechanisms and characterize the critical parameters that may intervene in the dislocation (aging) of NPs-based functional structures, depending on the nature of the environment liquid and the substrate. Finally, this work proposes an approch of evaluation and of monitoring the stability and the aging of these aggregation structures, in particular, those formed from the drying of films and drops of nano-particles solutions (metal nanoparticles, blood: proteins, viruses ...).

Élaborer ou structurer des matériaux à l’échelle nanométrique permet d’aborder une physique nouvelle mais également de réaliser des dispositifs fonctionnant sur des principes originaux utilisées dans divers domaines (médecine, énergie, électronique, optique, catalyse..). Ce travail porte sur l’étude de l’assemblage des nanoparticules d’or colloïdales (NPs) en structures d’agrégation mésoscopiques, assisté par le séchage des fluides complexes et de leur manipulation par Microscope à Force Atomique (AFM) sur des surfaces modèles. Une première partie présente la synthèse des NPs d’or et des surfaces moléculaires auto-assemblées sur des substrats rigides. Ensuite, l’étude de la formation des structures d’agrégation assistée par le mouillage et le séchage des fluides complexes ( NPs et polysaccharide) sur des surfaces moléculaires a permis de mettre en évidence le rôle crucial du couplage entre les propriétés de volume singulières de ces fluides, et celles de surface du substrat dans la formation de structures d’agrégation complexes (fractales, et dendrites en particulier). Dans un troisième temps, les travaux abordent à l’étude et la compréhension du vieillissement (dégénérescence et reconstruction) des structures mésoscopiques élaborées. Entre autres résultats, ces travaux ont mis en évidence la nature ‘diffusionnelle’ de la dislocation des structures, laquelle se traduit par la mobilité d’agrégats nanoparticulaires en surface. Afin de mieux appréhender cette problématique de mobilité individuelle et/ou collective (cluster) des NPs, une étude détaillée basée sur la manipulation des NPs par AFM en mode Tapping a été réalisée. L’ensemble des résultats obtenus au cours de ce travail de thèse a permis d’une part, i) de proposer de nouvelles approches d’assemblage de macromolécules et de particules, assisté par les phénomènes de mouillage, ii) de comprendre les mécanismes à l’origine de la formation de ces structures d’agrégation complexes (fractales compactes et fibrillaires) sur des substrats homogènes et hétérogènes, et d’autre part, iii) de contrôler la stabilité et le vieillissement de ces structures d’agrégation complexes en vue d’une validation de la fiabilité éventuelle de nanomatériaux issus d’assemblages à base de NPs. / This work deals with the study of the drying-mediated assembly of colloidal gold nanoparticles (Au NPs) in mesoscale aggregation patterns and their manipulation by atomic force microscopy (AFM) on model surfaces. The assembly of NPs in mesoscale and complex aggregation patterns assisted by the wetting and the drying of complex fluids (suspensions of NPs, NPs/biopolymers mixed solutions) on homogeneous and heterogeneous molecular surfaces was studied. This issue is important, both for understanding fundamental processes of self-organization, and for generating new functional mesostructures. The drying of complex fluids often leads to the emergence of highly complex aggregation structures as shown and discussed in this work. The richness and the aesthetics of these complex structures generated by these interfacial phenomena reflect not only the bulk properties of fluids (different sizes and lengths- scales, kinetic changes in state), but more importantly, the coupling between the fluid properties and those of the substrate surface (wetting interactions, confinement, hydrodynamics). In the case of two important heterogeneous fluids which are Au NPs and polysaccharide solutions, these drying-mediated structure formation lead to the genesis of unusually large and highly ramified dendrites aggregation patterns. The growth mechanism and the critical parameters that control the morphogenesis of these complexes structures are addressed in this work. In addition, the aging mechanisms and kinetics of these structures that are metastable and evolve either through direct dislocation via clusters NPs mobility on the surface, or through undulation-induced roughning of the dendrite branches. To better understanding this NPs mobility and thus the dislocation mechanism of the aging, a detailed study based on the manipulation of NPs by atomic force microscopy in tapping mode (AFM) was developed. The threshold dissipated energy to manipulate (move) the NPs can be quantified according to the intrinsic parameters of the particle (size, shape, and chemical nature), the chemical nature and topography of the substrate, and finally the operating and environment conditions. This work enabled us to understand the mechanisms and characterize the critical parameters that may intervene in the dislocation (aging) of NPs-based functional structures, depending on the nature of the environment liquid and the substrate. Finally, this work proposes an approch of evaluation and of monitoring the stability and the aging of these aggregation structures, in particular, those formed from the drying of films and drops of nano-particles solutions (metal nanoparticles, blood: proteins, viruses ...).