The availability of helical assemblies of plasmonic nanoparticles with precisely controlled and tunable structures can play a key role in the future development of chiral plasmonics and metamaterials. Here, a strategy to efficiently yield helical structures based on the cooperative interactions of liquid crystals and gold nanoparticles in thin films is developed. These nanocomposites exhibit exceptional long‐range hierarchical order across length scales, which results from the growth mechanism of nanoparticle‐coated twisted nanoribbons and their ability to form organized bundles. The helical assembly formation is governed by the presence of rationally functionalized nanoparticles. Importantly, the thickness of the achieved nanocomposites can be reversibly reconfigured owing to the polymorphic nature of the liquid crystal. The versatility of the proposed approach is demonstrated by preparing helices assembled from nanoparticles of different geometries and dimensions (spherical and rod‐like). The described strategy may become an enabling technology for structuring nanoparticle assemblies with high precision and fabricating optically active materials.

Thin films sustaining plasmonic circular dichroism (PCD) have acquired high scientific relevance and a great potential for applications. While most efforts in PCD thin film structures focus on lithographically fabricated static metasurfaces, the bottom-up fabrication of active chiral plasmonic films constitutes an alternative approach. Herein, the preparation of PCD thin films by melting and freezing a mixture of liquid crystal (LC), a chiral dopant, and gold nanoparticles (Au NPs), serving as helical matrix, symmetry breaking inducer, and plasmonic component, respectively is reported. UV-vis and circular dichroism spectroscopies, as well as theoretical modeling are used to disclose the interactions among thin film components, toward maximizing the PCD dissymmetry factor (g-factor). Variation of substrate temperature affords reversible off/on switching of the chiroptical response. The soft nature of LC matrix enables patterning of the films via a thermal nanoimprinting method, using a poly dimethylsiloxane mold for transfer-printing onto a flexible substrate, leading to stretchable PCD films. The PCD wavelengths can be readily tuned by varying the geometry of the Au NPs. This work provides an efficient technique to produce PCD thin films with active plasmonic properties and mechanical tunability.

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.

Blue phase liquid crystals (BPLCs) are chiral mesophases with 3D order, which makes them a promising template for doping nanoparticles (NPs), yielding tunable nanomaterials attractive for microlasers and numerous microsensor applications. However, doping NPs to BPLCs causes BP lattice extension, which translates to elongation of operating wavelengths of light reflection. Here, it is demonstrated that small (2.4 nm diameter) achiral gold (Au) NPs decorated with designed LC-like ligands can enhance the chiral twist of BPLCs (i.e., reduce cell size of the single BP unit up to ∼14% and ∼7% for BPI and BPII, respectively), translating to a blue-shift of Bragg reflection. Doping NPs also significantly increases the thermal stability of BPs from 5.5 °C (for undoped BPLC) up to 22.8 °C (for doped BPLC). In line with our expectations, both effects are saturated, and their magnitude depends on the concentration of investigated nanodopants as well the BP phase type. Our research highlights the critical role of functionalization of Au NPs on the phase sequence of BPLCs. We show that inappropriate selection of surface ligands can destabilize BPs. Our BPLC and Au NPs are photochemically stable and exhibit great miscibility, preventing NP aggregation in the BPLC matrix over the long term. We believe that our findings will improve the fabrication of advanced nanomaterials into 3D periodic soft photonic structures.

By coating plasmonic nanoparticles (NPs) with thermally responsive liquid crystals (LCs) it is possible to prepare reversibly reconfigurable plasmonic nanomaterials with prospective applications in optoelectronic devices. However, simple and versatile methods to precisely tailor properties of liquid-crystalline nanoparticles (LC NPs) are still required. Here, we report a new method for tuning structural properties of assemblies of nanoparticles grafted with a mixture of promesogenic and alkyl thiols, by varying design of the latter. As a model system, we used Ag and Au nanoparticles that were coated with three-ring promesogenic molecules and dodecanethiol ligand. These LC NPs self-assemble into switchable lamellar (Ag NPs) or tetragonal (Au NPs) aggregates, as determined with small angle X-ray diffraction and transmission electron microscopy. Reconfigurable assemblies of Au NPs with different unit cell symmetry (orthorombic) are formed if hexadecanethiol and 1H,1H,2H,2H-perfluorodecanethiol were used in the place of dodecanethiol; in the case of Ag NPs the use of 11-hydroxyundecanethiol promotes formation of a lamellar structure as in the reference system, although with substantially broader range of thermal stability (140 vs. 90 °C). Our results underline the importance of alkyl ligand functionalities in determining structural properties of liquid-crystalline nanoparticles, and, more generally, broaden the scope of synthetic tools available for tailoring properties of reversibly reconfigurable plasmonic nanomaterials.

A Janus-type lamellar structure is formed from gold nanoparticles grafted with chemically incompatible mesogenic ligands. Metallic NP-rich sublayers are separated by ligand-rich sublayers of various composition due to the ligand segregation.

Abstract

Correction for ‘Gold nanoparticles grafted with chemically incompatible ligands’ by Joanna M. Wolska et al., RSC Adv., 2021, 11, 9568–9571, DOI: 10.1039/D1RA00547B.