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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.

Robust synthesis of large-scale self-assembled nanostructures with long-range organization and a prominent response to external stimuli is critical to their application in functional plasmonics. Here, the first example of a material made of liquid crystalline nanoparticles which exhibits UV-light responsive surface plasmon resonance in a condensed state is presented. To obtain the material, metal cores are grafted with two types of organic ligands. A promesogenic derivative softens the system and induces rich liquid crystal phase polymorphism. Second, an azobenzene derivative endows nanoparticles with photoresponsive properties. It is shown that nanoparticles covered with a mixture of these ligands assemble into long-range ordered structures which exhibit a novel dual-responsivity. The structure and plasmonic properties of the assemblies can be controlled by a change in temperature as well as by UV-light irradiation. These results present an efficient way to obtain bulk quantities of self-assembled nanostructured materials with stability that is unattainable by alternative methods such as matrix-assisted or DNA-mediated organization.

Achieving remotely controlled, reversibly reconfigurable assemblies of plasmonic nanoparticles is a prerequisite for the development of future photonic technologies. Here, we obtained a series of gold-nanoparticle-based materials which exhibit long-range order, and which are controlled with light or thermal stimuli. The influence of the metallic core size and organic shell composition on the switchability is considered, with emphasis on achieving light-responsive behavior at room temperature and high yield production of nanoparticles. The latter translates to a wide size distribution of metallic cores but does not prevent their assembly into various, switchable 3D and 2D long-range ordered structures. These results provide clear guidelines as to the impact of size, size distribution, and organic shell composition on self-assembly, thus enhancing the smart design process of multi-responsive nanomaterials in a condensed state, hardly attainable by other self-assembly methods which usually require solvents.

Controlling stability, complexity and optical response of reversibly reconfigurable plasmonic nanocrystal superlattices is of critical importance for emergent optoelectronic technologies and can be achieved by engineering the chemical nature of the ligand shell. In this work, we experimentally explore how the design of surface ligands with semifluorinated alkyl chains impacts dynamic self-assembly of nanoparticles. A series of three promesogenic thiols was synthesized and grafted onto plasmonic nanocrystals via ligand exchange reaction. In all cases, after solvent evaporation, we obtained reversibly reconfigurable, thermally responsive assemblies. We examined these nanomaterials using a variety of techniques such as transmission electron microscopy, UV–vis, and small-angle X-ray scattering. We show that the number of aromatic rings and the length of the fluorinated chain strongly affects symmetry and reconfiguration temperatures of the assemblies. For an optimized material we show that it is possible to a...