Disentangling optical effects in 3D spiral-like, chiral plasmonic assemblies templated by a dark conglomerate liquid crystal.

Chiral thin films showing electronic and plasmonic circular dichroism (CD) are intensively explored for optoelectronic applications. The most studied chiral organic films are the composites exhibiting a helical geometry, which often causes entanglement of circular optical properties with unwanted linear optical effects (linearly polarized absorption or refraction). This entanglement limits tunability and often translates to a complex optical response. This paper describes chiral films based on dark conglomerate, sponge-like, liquid crystal films, which go beyond the usual helical type geometry, waiving the problem of linear contributions to chiroptical electronic and plasmonic properties. First, we show that purely organic films exhibit high electronic CD and circular birefringence, as studied in detail using Mueller matrix polarimetry. Analogous linear properties are two orders of magnitude lower, highlighting the benefits of using the bi-isotropic dark conglomerate liquid crystal for chiroptical purposes. Next, we show that the liquid crystal can act as a template to guide the assembly of chemically compatible gold nanoparticles into 3D spiral-like assemblies. The Mueller matrix polarimetry measurements confirm that these composites exhibit both electronic and plasmonic circular dichroisms, while nanoparticle presence is not compromising the beneficial optical properties of the matrix.

Unrestricted Chiral Patterning by Laser Writing in Liquid Crystalline and Plasmonic Nanocomposite Thin Films.

Obtaining hierarchical structures with arbitrarily controlled chirality remains a challenge. Here, thin films featuring chiroptically bipolar patterns are produced by a device utilizing microscale photothermal re-melting of materials exhibiting chirality synchronization. This device operates autonomously, guided by an algorithm that facilitates the homochiral growth of supramolecular organic helices through controlling their re-melting. The chirality synchronization phenomena of constitutionally achiral molecules grants availability of both handednesses of the helices, enabling unrestricted chiral writing in the film. The collective chiroptical response of assembled molecules is utilised to guide the patterning process, creating a foundation for optically secured information. The established methodology enables achieving dissymmetry factor values for circular dichroism (CD) a magnitude higher than previously reported, as confirmed with state-of-the-art, synchrotron-based Mueller matrix polarimetry (MMP). Moreover, the developed method is extended to nanocomposites comprising gold nanoparticles, providing the opportunity to tune the CD toward the plasmonic region. This strategic application of photothermal processing, specifically laser-directed melting, uncovers the potential to broaden the selection of nanostructured materials with precisely designed functionalities for photonic applications.

Light-Responsive Supramolecular Nanotubes-Based Chiral Plasmonic Assemblies.

We describe the fabrication of dual-responsive (thermo/light) chiral plasmonic films. The idea is based on using photoswitchable achiral liquid crystal (LCs) forming chiral nanotubes for templating helical assemblies of Au NPs. Circular dichroism spectroscopy (CD) confirms chiroptical properties coming from the arrangement of organic and inorganic components, with up to 0.2 dissymmetry factor (g-factor). Upon exposure to UV light, organic molecules isomerize, resulting in controlled melting of organic nanotubes and/or inorganic nanohelices. The process can be reversed using visible light and further modified by varying the temperature, offering a control of chiroptical response of the composite material. These properties can play a key role in the future development of chiral plasmonics, metamaterials, and optoelectronic devices.

Achiral Nanoparticle-Enhanced Chiral Twist and Thermal Stability of Blue Phase Liquid Crystals.

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.

Tunable Circularly Polarized Luminescence via Chirality Induction and Energy Transfer from Organic Films to Semiconductor Nanocrystals.

Circularly polarized luminescent (CPL) films with high dissymmetry factors hold great potential for optoelectronic applications. Herein, we propose a strategy for achieving strongly dissymetric CPL in nanocomposite films based on chirality induction and energy transfer to semiconductor nanocrystals. First, focusing on a purely organic system, aggregation-induced emission (AIE) and CPL activity of organic liquid crystals (LCs) forming helical nanofilaments was detected, featuring green emission with high dissymmetry factors glum ∼ 10-2. The handedness of helical filaments, and thus the sign of CPL, was controlled via minute amounts of a small chiral organic dopant. Second, nanocomposite films were fabricated by incorporating InP/ZnS semiconductor quantum dots (QDs) into the LC matrix, which induced the chiral assembly of QDs and endowed them with chiroptical properties. Due to the spectral matching of the components, energy transfer (ET) from LC to QDs was possible enabling a convenient way of tuning CPL wavelengths by varying the LC/QD ratio. As obtained, composite films exhibited absolute glum values up to ∼10-2 and thermally on/off switchable luminescence. Overall, we demonstrate the induction of chiroptical properties by the assembly of nonchiral building QDs on the chiral organic template and energy transfer from organic films to QDs, representing a simple and versatile approach to tune the CPL activity of organic materials.

Cellular automata approach to modeling self-organized periodic patterns in nanoparticle-doped liquid crystals.

Elementary cellular automata provide one of the simplest ways to generally describe the phenomena of pattern formation. However, they are considered too simple to be able to describe in detail the more complex phenomena occurring in real experimental systems. In this article, we demonstrate the an application of these methods to optical systems, providing an understanding of the mechanisms behind the formation of periodic patterns in nanoparticle-doped liquid crystals. Our extremely simplified model also explains the observed linear relationship between periodicity and system size.

Hydrophobic Gold Nanoparticles with Intrinsic Chirality for the Efficient Fabrication of Chiral Plasmonic Nanocomposites.

The development of plasmonic nanomaterials with chiral geometry has drawn extensive attention owing to their practical implications in chiral catalysis, chiral metamaterials, or enantioselective biosensing and medicine. However, due to the lack of effective synthesis methods of hydrophobic nanoparticles (NPs) showing intrinsic, plasmonic chirality, their applications are currently limited to aqueous systems. In this work, we resolve the problem of achieving hydrophobic Au NPs with intrinsic chirality by efficient phase transfer of water-soluble NPs using low molecular weight, liquid crystal-like ligands. We confirmed that, after the phase transfer, Au NPs preserve strong, far-field circular dichroism (CD) signals, attesting their chiral geometry. The universality of the method is exemplified by using different types of NPs and ligands. We further highlight the potential of the proposed approach to realize chiral plasmonic, inorganic/organic nanocomposites with block copolymers, liquid crystals, and compounds forming physical gels. All soft matter composites sustain plasmonic CD signals with electron microscopies confirming well-dispersed nanoinclusions. The developed methodology allows us to expand the portfolio of plasmonic NPs with intrinsic structural chirality, thereby broadening the scope of their applications toward soft-matter based systems.

Tuneable helices of plasmonic nanoparticles using liquid crystal templates: molecular dynamics investigation of an unusual odd-even effect in liquid crystalline dimers.

Liquid crystalline (LC) dimers formed helical nanofilaments depending on the parity of the alkyl linker, revealing an unusual odd-even effect. Molecular dynamics simulations were used to investigate the observed tendency. Elongation of the linker translates to an increase of the pitch of the helices, which allows achieving tuneable helical assemblies of Au nanoparticles doped to the LC matrix. The impact of the tuneable pitch of helices on the chiral optical properties of composites was investigated with full-wave simulations based on the T-matrix method.

Active Plasmonics with Responsive, Binary Assemblies of Gold Nanorods and Nanospheres.

Self-assembly of metal nanoparticles has applications in the fabrication of optically active materials. Here, we introduce a facile strategy for the fabrication of films of binary nanoparticle assemblies. Dynamic control over the configuration of gold nanorods and nanospheres is achieved via the melting of bound and unbound fractions of liquid-crystal-like nanoparticle ligands. This approach provides a route for the preparation of hierarchical nanoparticle superstructures with applications in reversibly switchable, visible-range plasmonic technologies.

STEM Tomography of Au Helical Assemblies.

Composite, helical nanostructures formed using cooperative interactions of liquid crystals and Au nanoparticles were studied using a scanning transmission electron microscopy (STEM) mode. The investigated helical assemblies exhibit long-range hierarchical order across length scales, as a result of the crystallization (freezing) directed growth mechanism of nanoparticle-coated twisted nanoribbons and their ability to form organized bundles. Here, STEM methods were used to reproduce the 3D structure of the Au nanoparticle double helix.

Understanding and Controlling the Crystallization Process in Reconfigurable Plasmonic Superlattices.

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.

Thermomechanically controlled fluorescence anisotropy in thin films of InP/ZnS quantum dots.

Macroscopic scale sources of polarized light play a fundamental role in designing light-emitting devices. In this communication we report the formation of nano- and macro-scale ordered, layered assemblies of InP/ZnS quantum dots (QDs) exhibiting fluorescence anisotropy (FA), as well as thermo- and mechano-responsive properties. The long-range organization of small, quasi-isotropic nanoparticles was achieved by introducing liquid crystal molecules to the surface of QDs, without the need to use an organic matrix. Melting/crystallization of the ligand at 95 deg. C translated to a reversible reconfiguration of QDs thin film between 2D layered and body-centered cubic structures, characteristic for a temperature range below and above the melting point, respectively. The low-temperature, layered structure exhibited mechano-responsiveness which was key to introduce and control the sample alignment. Interestingly, transverse and parallel alignment modes of QDs layers were achieved, depending on the temperature of mechanical shearing. As prepared QD samples exhibited fluorescence anisotropy strongly correlated to the macroscopic orientation of the layers. Correlated small-angle X-ray diffraction (SAXRD) and fluorescence spectroscopy studies confirmed the mm-scale alignment of the thin films of QDs. Such films may be advantageous for developing efficient, densely packed, and uniform macro-scale FA sources.

In Situ Tracking of Colloidally Stable and Ordered Assemblies of Gold Nanorods.

Solution-phase self-assembly of anisotropic nanoparticles into complex 2D and 3D assemblies is one of the most promising strategies toward obtaining nanoparticle-based materials and devices with unique optical properties at the macroscale. However, controlling this process with single-particle precision is highly demanding, mostly due to insufficient understanding of the self-assembly process at the nanoscale. We report the use of in situ environmental scanning transmission electron microscopy (WetSTEM), combined with UV/vis spectroscopy, small-angle X-ray diffraction (SAXRD) and multiscale modeling, to draw a detailed picture of the dynamics of vertically aligned assemblies of gold nanorods. Detailed understanding of the self-assembly/disassembly mechanisms is obtained from real-time observations, which provide direct evidence of the colloidal stability of side-to-side nanorod clusters. Structural details and the forces governing the disassembly process are revealed with single particle resolution as well as in bulk samples, by combined experimental and theoretical modeling. In particular, this study provides unique information on the evolution of the orientational order of nanorods within side-to-side 2D assemblies and shows that both electrostatic (at the nanoscale) and thermal (in bulk) stimuli can be used to drive the process. These results not only give insight into the interactions between nanorods and the stability of their assemblies, thereby assisting the design of ordered, anisotropic nanomaterials but also broaden the available toolbox for in situ tracking of nanoparticle behavior at the single-particle level.

Supramolecular Chirality Synchronization in Thin Films of Plasmonic Nanocomposites.

Mirror symmetry breaking in materials is a fascinating phenomenon that has practical implications for various optoelectronic technologies. Chiral plasmonic materials are particularly appealing due to their strong and specific interactions with light. In this work we broaden the portfolio of available strategies toward the preparation of chiral plasmonic assemblies, by applying the principles of chirality synchronization-a phenomenon known for small molecules, which results in the formation of chiral domains from transiently chiral molecules. We report the controlled cocrystallization of 23 nm gold nanoparticles and liquid crystal molecules yielding domains made of highly ordered, helical nanofibers, preferentially twisted to the right or to the left within each domain. We confirmed that such micrometer sized domains exhibit strong, far-field circular dichroism (CD) signals, even though the bulk material is racemic. We further highlight the potential of the proposed approach to realize chiral plasmonic thin films by using a mechanical chirality discrimination method. Toward this end, we developed a rapid CD imaging technique based on the use of polarized light optical microscopy (POM), which enabled probing the CD signal with micrometer-scale resolution, despite of linear dichroism and birefringence in the sample. The developed methodology allows us to extend intrinsically local effects of chiral synchronization to the macroscopic scale, thereby broadening the available tools for chirality manipulation in chiral plasmonic systems.

Chirality of Liquid Crystals Formed from Achiral Molecules Revealed by Resonant X-Ray Scattering.

Intensive research on chiral liquid crystals (LCs) has been fueled by their actively tunable physicochemical properties and structural complexity, comparable to those of sophisticated natural materials. Herein, recent progress in the discovery of new classes of chiral LCs, enabled by a combination of nano- and macroscale investigations is reviewed. First, an overview is provided of liquid crystalline phases, made of chiral and achiral low-weight molecules, that exhibit chiral structure and/or chiral morphology. Then, recent progress in the discovery of new classes of chiral LCs, particularly enabled by the application of resonant X-ray scattering is described. It is shown that the method is sensitive to modulations of molecular orientation and therefore provides information hardly accessible by means of other techniques, such as the sense of helical structures or chirality transfer across length scales. Finally, a perspective is presented on the future scope, opportunities, and challenges in the field of chiral LCs, in particular related to nanocomposites.

Size-Dependent Thermo- and Photoresponsive Plasmonic Properties of Liquid Crystalline Gold Nanoparticles.

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.

Shaping Liquid Crystals with Gold Nanoparticles: Helical Assemblies with Tunable and Hierarchical Structures Via Thin-Film Cooperative Interactions.

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.

Self-Organized, One-Dimensional Periodic Structures in a Gold Nanoparticle-Doped Nematic Liquid Crystal Composite.

Composite structures exhibiting a periodic arrangement of building blocks can be found in natural systems at different length scales. Recreating such systems in artificial composites using the principles of self-assembly has been a great challenge, especially for 1D microscale systems. Here, we present a purposely designed composite material consisting of gold nanoparticles and a nematic liquid crystal matrix that has the ability to self-create a periodic structure in the form of a one-dimensional photonic lattice through a phase separation process occurring in a confined space. Our strategy is based on the use of a thermoswitchable medium that reversibly and quickly responds to both heating and cooling. We find that the period of the structure is strongly related to the size of the confining space. We believe that our findings will allow us to not only better understand the phase separation process in multicomponent soft/colloid mixtures with useful optical properties but also improve our understanding of the precise assembly of advanced materials into one-dimensional periodic systems, with prospective applications in future photonic technologies.

Robust Synthesis of Gold Nanotriangles and their Self-Assembly into Vertical Arrays.

We report an efficient, seed-mediated method for the synthesis of gold nanotriangles (NTs) which can be used for controlled self-assembly. The main advantage of the proposed synthetic protocol is that it relies on using stable (over the course of several days) intermediate seeds. This stability translates into increasing time efficiency of the synthesis and makes the protocol experimentally less demanding ('fast addition' not required, tap water can be used in the final steps) as compared to previously reported procedures, without compromising the size and shape monodispersity of the product. We demonstrate high reproducibility of the protocol in the hands of different researchers and in different laboratories. Additionally, this modified seed-mediated method can be used to produce NTs with edge lengths between ca. 45 and 150 nm. Finally, the high 'quality' of NTs allows the preparation of long-range ordered assemblies with vertically oriented building blocks, which makes them promising candidates for future optoelectronic technologies.

Universal Method for Producing Reduced Graphene Oxide/Gold Nanoparticles Composites with Controlled Density of Grafting and Long-Term Stability.

In this study, we report a universal approach allowing the non-covalent deposition of gold nanoparticles on reduced graphene oxide surface in a controlled fashion. We used a modified Hummers method to obtain graphene oxide, which then underwent surficial functionalization with carboxyl moieties coupled with simultaneous reduction. Nanoparticles were synthesized ex-situ and capped with a thiolated poly-ethylene glycol (PEG) ligand. The interactions between the surface of modified graphene oxide and nanoparticle ligands enabled the formation of stable hybrid graphene-nanoparticles materials in the aqueous phase. Using this technique, we were able to cover the surface of graphene with gold nanoparticles of different shapes (spheres, rods, triangles, stars, and bipyramids), broad range of sizes (from 5 nm to 100 nm) and controlled grafting densities. Moreover, materials obtained with this strategy exhibited long-term stability, which coupled with the versatility and facility of preparation, makes our technique appealing in the light of increasing demand for new graphene-based hybrid nanostructures.