Surfactant-assisted seeded growth of metal nanoparticles (NPs) can be engineered to produce anisotropic gold nanocrystals with high chiroptical activity through the templating effect of chiral micelles formed in the presence of dissymmetric cosurfactants. Mixed micelles adsorb on gold nanorods, forming quasihelical patterns that direct seeded growth into NPs with pronounced morphological and optical handedness. Sharp chiral wrinkles lead to chiral plasmon modes with high dissymmetry factors (~0.20). Through variation of the dimensions of chiral wrinkles, the chiroptical properties can be tuned within the visible and near-infrared electromagnetic spectrum. The micelle-directed mechanism allows extension to other systems, such as the seeded growth of chiral platinum shells on gold nanorods. This approach provides a reproducible, simple, and scalable method toward the fabrication of NPs with high chiral optical activity.
Chirality in inorganic nanoparticles and nanostructures has gained increasing scientific interest, because of the possibility to tune their ability to interact differently with left- and right-handed circularly polarized light. In some cases, the optical activity is hypothesized to originate from a chiral morphology of the nanomaterial. However, quantifying the degree of chirality in objects with sizes of tens of nanometers is far from straightforward. Electron tomography offers the possibility to faithfully retrieve the three-dimensional morphology of nanomaterials, but only a qualitative interpretation of the morphology of chiral nanoparticles has been possible so far. We introduce herein a methodology that enables us to quantify the helicity of complex chiral nanomaterials, based on the geometrical properties of a helix. We demonstrate that an analysis at the single particle level can provide significant insights into the origin of chiroptical properties.
Advances in controlling energy migration pathways in core‐shell lanthanide (Ln)‐based hetero‐nanocrystals (HNCs) have relied heavily on assumptions about how optically active centers are distributed within individual HNCs. In this article, it is demonstrated that different types of interface patterns can be formed depending on shell growth conditions. Such interface patterns are not only identified but also characterized with spatial resolution ranging from the nanometer‐ to the atomic‐scale. In the most favorable cases, atomic‐scale resolved maps of individual particles are obtained. It is also demonstrated that, for the same type of core‐shell architecture, the interface pattern can be engineered with thicknesses of just 1 nm up to several tens of nanometers. Total alloying between the core and shell domains is also possible when using ultra‐small particles as seeds. Finally, with different types of interface patterns (same architecture and chemical composition of the core and shell domains) it is possible to modify the output color (yellow, red, and green‐yellow) or change (improvement or degradation) the absolute upconversion quantum yield. The results presented in this article introduce an important paradigm shift and pave the way toward the emergence of a new generation of core‐shell Ln‐based HNCs with better control over their atomic‐scale organization.
Colloidal copper(I) sulfide (Cu2–x S) nanocrystals (NCs) have attracted much attention for a wide range of applications because of their unique optoelectronic properties, driving scientists to explore the potential of using Cu2–x S NCs as seeds in the synthesis of heteronanocrystals to achieve new multifunctional materials. Herein, we developed a multistep synthesis strategy toward Cu2–x S/ZnS heteronanorods. The Janus-type Cu2–x S/ZnS heteronanorods are obtained by the injection of hexagonal high-chalcocite Cu2–x S seed NCs in a hot zinc oleate solution in the presence of suitable surfactants, 20 s after the injection of sulfur precursors. The Cu2–x S seed NCs undergo rapid aggregation and coalescence in the first few seconds after the injection, forming larger NCs that act as the effective seeds for heteronucleation and growth of ZnS. The ZnS heteronucleation occurs on a single (100) facet of the Cu2–x S seed NCs and is followed by fast anisotropic growth along a direction that is perpendicular to the c-axis, thus leading to Cu2–x S/ZnS Janus-type heteronanorods with a sharp heterointerface. Interestingly, the high-chalcocite crystal structure of the injected Cu2–x S seed NCs is preserved in the Cu2–x S segments of the heteronanorods because of the high-thermodynamic stability of this Cu2–x S phase. The Cu2–x S/ZnS heteronanorods are subsequently converted into single-component Cu2–x S and CuInS2 nanorods by postsynthetic topotactic cation exchange. This work expands the possibilities for the rational synthesis of colloidal multicomponent heteronanorods by allowing the design principles of postsynthetic heteroepitaxial seeded growth and nanoscale cation exchange to be combined, yielding access to a plethora of multicomponent heteronanorods with diameters in the quantum confinement regime.
The crystallization of nanomaterials is a primary source of solid-state, photonic structures. Thus, a detailed understanding of this process is of paramount importance for the successful application of photonic nanomaterials in emerging optoelectronic technologies. While colloidal crystallization has been thoroughly studied, for example, with advanced in situ electron microscopy methods, the noncolloidal crystallization (freezing) of nanoparticles (NPs) remains so far unexplored. To fill this gap, in this work, we present proof-of-principle experiments decoding a crystallization of reconfigurable assemblies of NPs at a solid state. The chosen material corresponds to an excellent testing bed, as it enables both in situ and ex situ investigation using X-ray diffraction (XRD), transmission electron microscopy (TEM), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), atomic force microscopy (AFM), and optical spectroscopy in visible and ultraviolet range (UV–vis) techniques. In particular, ensemble measurements with small-angle XRD highlighted the dependence of the correlation length in the NPs assemblies on the number of heating/cooling cycles and the rate of cooling. Ex situ TEM imaging further supported these results by revealing a dependence of domain size and structure on the sample preparation route and by showing we can control the domain size over 2 orders of magnitude. The application of HAADF-STEM tomography, combined with in situ thermal control, provided three-dimensional single-particle level information on the positional order evolution within assemblies. This combination of real and reciprocal space provides insightful information on the anisotropic, reversibly reconfigurable assemblies of NPs. TEM measurements also highlighted the importance of interfaces in the polydomain structure of nanoparticle solids, allowing us to understand experimentally observed differences in UV–vis extinction spectra of the differently prepared crystallites. Overall, the obtained results show that the combination of in situ heating HAADF-STEM tomography with XRD and ex situ TEM techniques is a powerful approach to study nanoparticle freezing processes and to reveal the crucial impact of disorder in the solid-state aggregates of NPs on their plasmonic properties.
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