The developed three-step synthesis of plasmonic gold nanoparticles allows outstanding control over their growth kinetic, size and habit.

Using coherent X-ray diffraction imaging, the structure of the self-assembled gold mesocrystal was determined with the resolution sufficient to resolve its structural heterogeneity, including defects and local deviations of lattice parameters.

Hybrid metallic nanoparticles (NPs) encapsulated in oxide shells are currently intensely studied for plasmonic applications in sensing, medicine, catalysis, and photovoltaics. Here, a method for the synthesis of Au@Ag@SiO₂ cubes with a uniform silica shell of variable and adjustable thickness in the nanometer range is introduced and their excellent, highly reproducible, and tunable optical response is demonstrated. Varying the silica shell thickness, the excitation energies of the single NP plasmon modes can be tuned in a broad spectral range between 2.55 and 3.25 eV. Most importantly, a strong coherent coupling of the surface plasmons is revealed at the silver–silica interface with Mie resonances at the silica–vacuum interface leading to a significant field enhancement at the encapsulated NP surface in the range of 100% at shell thicknesses t ≃ 20 nm. Consequently, the synthesis method and the field enhancement open pathways to a widespread use of silver NPs in plasmonic applications including photonic crystals and may be transferred to other non‐precious metals.

The self‐assembly of anisotropic nanocrystals (stabilized by organic capping molecules) with pre‐selected composition, size, and shape allows for the creation of nanostructured materials with unique structures and features. For such a material, the shape and packing of the individual nanoparticles play an important role. This work presents a synthesis procedure for ω‐thiol‐terminated polystyrene (PS‐SH) functionalized gold nanooctahedra of variable size (edge length 37, 46, 58, and 72 nm). The impact of polymer chain length (Mw: 11k, 22k, 43k, and 66k g⋅mol⁻¹) on the growth of colloidal crystals (e. g. mesocrystals) and their resulting crystal structure is investigated. Small‐angle X‐ray scattering (SAXS) and scanning transmission electron microscopy (STEM) methods provide a detailed structural examination of the self‐assembled faceted mesocrystals based on octahedral gold nanoparticles of different size and surface functionalization. Three‐dimensional angular X‐ray cross‐correlation analysis (AXCCA) enables high‐precision determination of the superlattice structure and relative orientation of nanoparticles in mesocrystals. This approach allows us to perform non‐destructive characterization of mesocrystalline materials and reveals their structure with resolution down to the nanometer scale.

Mesocrystals are a class of nanostructured material, where a multiple‐length‐scale structure is a prerequisite of many interesting phenomena. Resolving the mesocrystal structure is quite challenging due to their structuration on different length scales. The combination of small‐ and wide‐angle X‐ray scattering (SAXS and WAXS) techniques offers the possibility of non‐destructively probing mesocrystalline structures simultaneously, over multiple length scales to reveal their microscopic structure. This work describes how high dynamical range of modern detectors sheds light on the weak features of scattering, significantly increasing the information content. The detailed analysis of X‐ray diffraction (XRD) from the magnetite mesocrystals with different particle sizes and shapes is described, in tandem with electron microscopy. The revealed features provide valuable input to the models of mesocrystal growth and the choice of structural motif; the impact on magnetic properties is discussed.

Mesocrystals are a class of nanostructured material where individual nanocrystals are arranged in a distinct crystallographic orientation. The multiple-length-scale order in such materials plays an essential role in the emergent physical and chemical phenomena. Our work studies the structure of a faceted mesocrystal composed of polystyrene-functionalized single crystalline gold nanoparticles using complementary ultrasmall- and wide-angle X-ray scattering (USAXS and WAXS) with electron microscopy. The results of the data analysis shed some light on the details of the microscopic structure of mesocrystals and their structuration principle.