SearcharxivSearch

arXiv subjects

Damien Alloyeau

Publications and source records attributed to Damien Alloyeau.

3 recordsLinked to original sources

Synthesis, Solvent-dependent Self-Assembly and Partial Oxidation of Ultrathin Cerium Fluoride Nanoplatelets

Two-dimensional colloidal nanoplatelets (NPLs) with atomically defined thickness exhibit unique physical properties, yet understanding their formation mechanism and assembly remains essential for tuning their collective behavior. We report an optimized synthesis of triangular cerium-based NPLs with narrow size and shape distributions via thermal decomposition of cerium trifluoroacetate. Combining X-ray diffraction, XPS, and high-resolution STEM, we show that the expected CeF3 NPL structure undergoes partial oxidation, yielding an oxyfluoride composition CeOxFy. Beyond their composition, we investigate how these oleic acid-capped NPLs organize in solution and at interfaces. The choice of solvent governs both the solution-phase organization and the resulting superstructures formed upon evaporation at the liquid--air interface. In solvents that promote face-to-face stacking in solution, evaporation produces films organized into columnar assemblies tens of micrometers long, with the NPL planes oriented perpendicular to the interface. In contrast, solvents in which NPLs remain individually dispersed yield extended hexagonally ordered superlattices with edge-to-edge stacking spanning several micrometers, where the NPLs lie parallel to the interface in an edge-to-edge arrangement. These results highlight that solvent-mediated interactions and pre-existing organization in solution are decisive factors in determining the outcome of evaporative self-assembly of colloidal nanocrystals.

cond-mat.soft

Metallurgy at the nanoscale: domain walls in nanoalloys

In binary alloys, domain walls play a central role not only on the phase transitions but also on their physical properties and were at the heart of the 70's metallurgy research. Whereas it can be predicted, with simple physics arguments, that such domain walls cannot exist at the nanometer scale due to the typical lengths of the statistical fluctuations of the order parameter, here we show, with both experimental and numerical approaches how orientational domain walls are formed in CuAu nanoparticles binary model systems. We demonstrate that the formation of domains in larger NPs is driven by elastic strain relaxation which is not needed in smaller NPs where surface effects dominate. Finally, we show how the multivariants NPs tend to form an isotropic material through a continuous model of elasticity.

cond-mat.mtrl-sci

Atomic Scale Surface Segregation in Copper-Gold Nanoparticles

In this work, we combine electron microscopy measurements of the surface compositions in Cu-Au nanoparticles and atomistic simulations to investigate the effect of gold segregation. While this mechanism has been extensively investigated within Cu-Au in the bulk state, it was never studied at the atomic level in nanoparticles. By using energy dispersive X-ray analysis across the (100) and (111) facets of nanoparticles, we provide evidence of gold segregation in Cu$_{3}$Au and CuAu$_{3}$ nanoparticles in the 10 nm size range grown by epitaxy on a salt surface with high control of the nanoparticles morphology. To get atomic-scale insights into the segregation properties in Cu-Au nanoparticles on the whole composition range, we perform Monte Carlo calculations employing $N$-body interatomic potentials. These simulations confirm this effect by showing a complete segregation of Au in the (100) and (111) faces of a truncated octahedron for gold nominal composition of the alloy above 70\% and 60\% respectively. Furthermore, we show that there is no size effect on the segregation behaviour since we evidence the same oscillating concentration profile from surface to the nanoparticles core as in the bulk. These results can shed new lights in the interpretation of the enhanced reactivity, selectivity and stability of Cu-Au nanoparticles in various catalytic reactions.

cond-mat.mtrl-sci