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The optical response of a two-dimensional supercrystal (monolayer) of quantum emitters with a doublet in the excited state to the action of a continuous external field was theoretically studied, considering the dephasing of the electronic states of the system. The secondary field acting on the V-emitter from other V-emitters of the system forms their nonlinearity and provides internal positive feedback, which leads to bistability and periodic and aperiodic self-oscillations, including chaotic behavior. In the presence of dephasing, the multistability of the optical response is preserved. Phase relaxation leads to a change in the scenario of the system dynamics from chaos to periodic oscillations of the field amplitude, i.e., to a chaos–limit cycle bifurcation and to a decrease in the reflectivity of the monolayer in linear and nonlinear modes. [ABSTRACT FROM AUTHOR]

Supercrystalline nanocomposites (SCNCs) are a new category of hybrid materials consisting of inorganic nanoparticles surface‐functionalized with organic ligands and with periodic nanostructures, featuring multi‐functionality and able to reach exceptional mechanical properties. Although efforts have been made to explore their mechanical behavior, their response to cyclic loading remains to be unveiled. Here, the fatigue behavior of SCNCs with different degrees of organic crosslinking is investigated via nanoindentation. The nanocomposites' fatigue life is assessed, and it emerges that SCNCs without crosslinking are more efficient in dissipating energy under cyclic loading and thus feature a longer fatigue life. Chipping is identified as the main fatigue failure mechanism, whereas different mechanisms, intrinsic or extrinsic, dominate in the indentation depth propagation, again depending on crosslinking. [ABSTRACT FROM AUTHOR]

Abstract Supercrystalline nanocomposites (SCNCs) are a new category of hybrid materials consisting of inorganic nanoparticles surface‐functionalized with organic ligands and with periodic nanostructures, featuring multi‐functionality and able to reach exceptional mechanical properties. Although efforts have been made to explore their mechanical behavior, their response to cyclic loading remains to be unveiled. Here, the fatigue behavior of SCNCs with different degrees of organic crosslinking is investigated via nanoindentation. The nanocomposites’ fatigue life is assessed, and it emerges that SCNCs without crosslinking are more efficient in dissipating energy under cyclic loading and thus feature a longer fatigue life. Chipping is identified as the main fatigue failure mechanism, whereas different mechanisms, intrinsic or extrinsic, dominate in the indentation depth propagation, again depending on crosslinking.

Supercrystalline nanocomposites (SCNCs) are inorganic-organic hybrid materials with a unique periodic nanostructure, and thus they have been gaining growing attention for their intriguing functional properties and parallelisms with hierarchical biomaterials. Their mechanical behavior remains, however, poorly understood, even though its understanding and control are important to allow SCNCs’ implementation into devices. An important aspect that has not been tackled yet is their time-dependent deformation behavior, which is nevertheless expected to play an important role in materials containing such a distribution of organic phase. Hereby, we report on the creep of ceramic-organic SCNCs with varying degrees of organic crosslinking, as assessed via nanoindentation. Creep strains and their partial recoverability are observed, hinting at the co-presence of viscoelasticity and viscoplasticity, and a clear effect of crosslinking in decreasing the overall material deformability emerges. We rationalize our experimental observations with the analysis of stress exponent and activation volume, resulting in a power-law breakdown behavior and governing deformation mechanisms occurring at the organic sub-nm interfaces scale, as rearrangement of organic ligands. The set of results is reinforced by the evaluation of the strain rate sensitivity via strain rate jump tests, and the assessment of the effect of oscillations during continuous stiffness measurement mode.

Mott metal-insulator transitions possess electronic, magnetic, and structural degrees of freedom promising next-generation energy-efficient electronics. A previously unknown, hierarchically ordered, and anisotropic supercrystal state is reported and its intrinsic formation characterized in-situ during a Mott transition in a Ca 2 RuO 4 thin film. Machine learning-assisted X-ray nanodiffraction together with cryogenic electron microscopy reveal multi-scale periodic domain formation at and below the film transition temperature (T Film  ≈ 200-250 K) and a separate anisotropic spatial structure at and above T Film . Local resistivity measurements imply an intrinsic coupling of the supercrystal orientation to the material's anisotropic conductivity. These findings add a new degree of complexity to the physical understanding of Mott transitions, opening opportunities for designing materials with tunable electronic properties., (© 2024 Wiley‐VCH GmbH.)

Self-assembly of nanoparticles into supercrystals represents a powerful approach to create unique and complex superstructures with fascinating properties and novel functions, but the complexity in spatial configuration, and the tunability in lattice structure are still quite limited compared to the crystals formed by atoms and molecules. Herein, shallowly concave gold nanoarrows with a unique concave-convex geometry are synthesized and employed as novel building blocks for shape-directed self-assembly of a wealth of complex 3D supercrystals with unprecedented configurations. The obtained diverse superstructures including six Interlocking-type supercrystals and three Packing-type supercrystals exhibit four types of Bravais lattices (i.e., tP, oI, tI, and oF) and six types of crystallographic space groups (i.e., Pmmm, I222, Pnnm, Ibam, I4/mmm, and Fmmm), which have not been documented in the mesoscale self-assembled systems. It has been revealed that the relative yield of different supercrystal structures is mainly determined by the packing density and deformability of the supercrystals, which are closely related to the tailored concavity of the nanoparticles and is affected by the particle concentration, thus allowing for programmable self-assembly into specific supercrystals through particle shape modulation. The concavity-enabled supercrystal engineering may open a new avenue toward unconventional nanoparticle superstructures with expanded complexity, tunability, and functionality., (© 2024 Wiley‐VCH GmbH.)

Organizing nanoparticles (NPs) into periodic structures is a central goal in materials science. Despite progress in the last decades, it is still challenging to produce macroscopic assemblies reliably. In this work, the analysis of the pervaporation‐induced organization of gold octahedra into supercrystals within microfluidic channels using a combination of X‐ray scattering techniques and FIB‐SEM tomography is reported. The results reveal the formation of a single‐domain supercrystal with a monoclinic C2/m symmetry and long‐range order extending over the dimensions of the microfluidic channel, covering at least 1.7 × 0.3 mm2. Time‐resolved small angle X‐ray scattering analysis shows that the formation of the superlattice involves an accumulation of the NPs within the channel before the nucleation and growth of the supercrystal. The orientation of the crystal remains unchanged during its formation, suggesting a growth mechanism directed by the channel interface. Together, these results show the potential application of the pervaporation strategy to providing spatially determined control over NP crystallization, which can be used for the rational fabrication of nanomaterial architectures. [ABSTRACT FROM AUTHOR]

Meta-atoms are the building blocks of metamaterials, which are employed to control both generation and propagation of light as well as provide novel functionalities of localization and directivity of electromagnetic radiation. In many cases, simple dielectric or metallic resonators are employed as meta-atoms to create different types of electromagnetic metamaterials. Here, we fabricate and study supercrystal meta-atoms composed of coupled perovskite quantum dots. We reveal that these multiscale structures exhibit specific emission properties, such as spectrum splitting and polaritonic effects. We believe that such multiscale supercrystal meta-atoms will provide novel functionalities in the design of many novel types of active metamaterials and metasurfaces.

Supercrystals composed of plasmonic nanoparticles constitute a promising material platform for tailored light‐matter interactions. The optimization of their optical properties requires precise syntheses and a detailed structural characterization that addresses not only the basic geometrical parameters but also the degree of order. Herein, plasmonic supercrystals with a well‐defined layered structure are studied by a combined transmission electron microscopy, small‐angle X‐ray scattering and X‐ray cross‐correlation analysis (TEM‐SAXS‐XCCA) approach. It is demonstrated that scanning small‐angle x‐ray scattering (SAXS) data can unambiguously be assigned to the number of crystalline layers by comparison with complementary transmission electron microscopy (TEM) experiments on the same regions of interest. A small but significant increase of the lattice constant with increasing number of layers and a high degree of orientational order irrespective of the number of layers is found. This points to specifics of the supercrystal formation mechanism that could be utilized to improve the control of self‐assembly for supercrystal geometries with subnanometer precision. [ABSTRACT FROM AUTHOR]

To translate the exceptional properties of colloidal nanoparticles (NPs) to macroscale geometries, assembly techniques must bridge a 106‐fold range of length. Moreover, for successfully attaining a final mechanically robust nanocomposite macroscale material, some of the intrinsic NPs' properties have to be maintained while minimizing the density of strength‐limiting defects. However, the assembly of nanoscale building blocks into macroscopic dimensions, and their effective macroscale properties, are inherently affected by the precision of the conditions required for assembly and emergent flaws including point defects, dislocations, grain boundaries, and cracks. Herein, a direct‐write self‐assembly technique is used to construct free‐standing, millimeter‐scale columns comprising spherical iron oxide NPs (15 nm diameter) surface functionalized with oleic acid (OA), which self‐assemble into face‐centered cubic (FCC) supercrystals in minutes during the direct‐writing process. The subsequent crosslinking of OA molecules results in nanocomposites with a maximum strength of 110 MPa and elastic modulus up to 58 GPa. These mechanical properties are interpreted according to the flaw size distribution and are as high as newly engineered platelet‐based nanocomposites. The findings indicate a broad potential to create mechanically robust, multifunctional 3D structures by combining additive manufacturing with colloidal assembly. [ABSTRACT FROM AUTHOR]

In this paper, we report the first local magnetic study, performed by magneto-optical Kerr effect (MOKE), of supercrystals made of magnetic nanoparticles. The supercrystals are characterized by a film morphology and contain several hundred layers of 7.7 nm-Co NPs, ordered in a face-centered cubic (fcc) superstructure. Conversely to the standard superconducting quantum interference device (SQUID) technique, which provides only a global measurement over an entire sample, the utilization of MOKE enables magnetic measurements of individual localized areas of c.a. 30 µm x 30 µm, from which we can draw conclusions regarding the uniformity of the magnetic properties of the sample, and therefore on the high uniformity of its structure. The latter conclusion is supported by Monte Carlo simulation performed on a model system composed of spherical particles interacting through the dipole-dipole interactions (DDI) and exhibiting a uniaxial magneto-crystalline anisotropy energy (MAE). In addition, by combining these results, with those obtained by SQUID and by grazing incidence small-angle X-ray scattering (GISAXS), we show that magnetic and super-structural properties of supercrystals can be accurately determined. [Display omitted] [ABSTRACT FROM AUTHOR]

The focus of this work is on matrix-inclusion nanocomposites and their mechanical behavior, particularly taking into account inelasticity and damage. We propose a nonlocal damage model based on a micropolar continuum theory which captures the heterogeneous interphases in the nanostructure. The model is valid for a large range of matrix-inclusion nanocomposites. The effects of the interaction between nanoparticles, the thickness of the interphase and the size of nanoparticles on the overall mechanical properties of the nanocomposite are analyzed to optimize the microstructure of the nanocomposites. 3D micromechanical simulations are conducted for the particular example of a tailored, ultrastrong nanocomposite. It has extraordinary mechanical properties, and to date, is the strongest synthetic inorganic-organic nanocomposite. The simulation results are compared to experimental data from microcantilever beams for different process temperatures. [ABSTRACT FROM AUTHOR]

The lattice dynamics of natural crystals, artificial superlattices, or self‐organized nanocrystals intimately mix confinement, coupling, periodicity, and dissipative effects. The low wavenumber vibrational response of the new class of nanomaterials called "supercrystals" does contain relevant information concerning finite size effects on atomic movements inside each nanocrystal, mechanical coupling between adjacent nanocrystals, coherent behavior of the total assembly due to its superperiodicity, and finally finite‐time effects due to damping. All these aspects concerning the dynamical behavior of silver supercrystals has been analyzed using plasmon resonance Raman scattering. Owing to the highly uniform size and chemical environment of the nanocrystals, the confinement and homogeneous damping of their fundamental vibrations are carefully analyzed. The signature of their internal atomic arrangements, as a reminiscence of bulk phonons, is also explored. It is shown that for low particles diameter (≲5 nm), deviations from the continuum elastic approximation occur and that the vibrational response is more sensitive to atomic arrangements and surface effects inside the nanocrystals than to spatial coherence effects between them. Using plasmon resonance and low‐wavenumber Raman scattering from periodic arrangements of silver nanocrystals, information concerning finite size effects on atomic movements inside each nanocrystal, mechanical coupling between adjacent nanocrystals, coherent behavior of the total assembly due its superperiodicity, and finally finite‐time effects due to damping, have been analyzed. A theoretical support is given through atomic‐scale simulations. [ABSTRACT FROM AUTHOR]

Gas nanobubbles are directly linked to many important chemical reactions. While they can be detrimental to operational devices, they also reflect the local activity at the nanoscale. Here, supercrystals made of highly monodisperse Ag@Pt core-shell nanoparticles are first grown onto a solid support and fully characterized by electron microscopies and X-ray scattering. Supercrystals are then used as a plasmonic photocatalytic platform for triggering the hydrogen evolution reaction. The catalytic activity is measured operando at the single supercrystal level by high-resolution optical microscopy, which allows gas nanobubble nucleation to be probed at the early stage with high temporal resolution and the amount of gas molecules trapped inside them to be quantified. Finally, a correlative microscopy approach and high-resolution electron energy loss spectroscopy help to decipher the mechanisms at the origin of the local degradation of the supercrystals during catalysis, namely nanoscale erosion and corrosion., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

[Display omitted] • The creep behavior of ceramic-organic supercrystalline nanocomposites is assessed for the first time, via nanoindentation. • The organic phase, even though less than 10 wt%, plays a dominant role in the nanocomposites' deformation. • Partial recovery of creep after unloading reveals that supercrystals feature both viscoelasticity and viscoplasticity. • Ligands-facilitated rearrangement of the ceramic nanoparticles is proposed as dominating creep mechanism of supercrystals. • The applicability of nanoindentation methodologies, single loading and continuous stiffness measurement, is analyzed. Supercrystalline nanocomposites (SCNCs) are inorganic-organic hybrid materials with a unique periodic nanostructure, and thus they have been gaining growing attention for their intriguing functional properties and parallelisms with hierarchical biomaterials. Their mechanical behavior remains, however, poorly understood, even though its understanding and control are important to allow SCNCs' implementation into devices. An important aspect that has not been tackled yet is their time-dependent deformation behavior, which is nevertheless expected to play an important role in materials containing such a distribution of organic phase. Hereby, we report on the creep of ceramic-organic SCNCs with varying degrees of organic crosslinking, as assessed via nanoindentation. Creep strains and their partial recoverability are observed, hinting at the co-presence of viscoelasticity and viscoplasticity, and a clear effect of crosslinking in decreasing the overall material deformability emerges. We rationalize our experimental observations with the analysis of stress exponent and activation volume, resulting in a power-law breakdown behavior and governing deformation mechanisms occurring at the organic sub-nm interfaces scale, as rearrangement of organic ligands. The set of results is reinforced by the evaluation of the strain rate sensitivity via strain rate jump tests, and the assessment of the effect of oscillations during continuous stiffness measurement mode. [ABSTRACT FROM AUTHOR]

Supramolecularly assembled high-order supercrystals (SCs) help control the dielectric, electronic, and excitonic properties of semiconductor nanocrystals (NCs) and quantum dots (QDs). Ligand-engineered perovskite NCs (PNCs) assemble into SCs showing shorter excitonic lifetimes than strongly dielectric PNC films showing long photoluminescence (PL) lifetimes and long-range carrier diffusion. Monodentate to bidentate ligand exchange on ≈ 8 nm halide perovskite (APbX 3 ; A:Cs/MA, X:Br/I) PNCs generates mechanically stable SCs with close-packed lattices, overlapping electronic wave functions, and higher dielectric constant, providing distinct excitonic properties from single PNCs or PNC films. From Fast Fourier Transform (FFT) images, time-resolved PL, and small-angle X-ray scattering, structurally and excitonically ordered large SCs are identified. An Sc shows a smaller spectral shift (<35 meV) than a PNC film (>100 meV), a microcrystal (>100 meV), or a bulk crystal (>100 meV). Also, the exciton lifetime (<10 ns) of an SC is excitation power-independent in the single exciton regime 〈N〉<1, comparable to an isolated PNC. Therefore, bidentate-ligand-assisted SCs help overcome delayed exciton or carrier recombination in halide perovskite nanocrystal assemblies or films., (© 2023 Wiley-VCH GmbH.)

Supracrystals are highly symmetrical ordered superstructures built up from nanoparticles (NPs) via self-assembly. While the NP assembly has been intensively investigated, the formation mechanism is still not understood. To shed some light onto the formation mechanism, one of the most common supracrystal morphologies, the trigonal structures, as a model system is being used to investigate the formation process in solution. To explain the formation of the trigonal structures and determining the size of the supracrystal seeds formed in solution, the concept of substrate-affected growth is introduced. Furthermore, the influence of the NP concentration on the seed size is shown and our investigations from Ag toward Au are extended. [ABSTRACT FROM AUTHOR]

The assembly of nanocrystals into ordered structures called supercrystals or superstructures has become a pivotal frontier owing to numerous useful applications such as correlating the arrangements of atoms in macroscopic crystals and tuning the collective properties to meet the demands of various applications. In this article, recent progress in the preparation of three-dimensional superlattices of nanocrystals is outlined, with a particular emphasis on the driving forces and evolutionary routes beyond orderly assembly. First, the leading or repulsive forces that internally and externally govern the formation of three-dimensional supercrystals are systematically identified and discussed with respect to their origins and functions in three-dimensional self-organization. Then a synoptic introduction of commonly applied means of nanocrystal self-assembly based on growth scenarios such as droplet evaporation and a liquid/liquid interface is presented with specific cases and detailed analyses. Finally, the existing challenges and prospects for this field are briefly highlighted. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Summary Compared to the number of reports on the self-assembly of spherical nanoparticles forming superlattices, relatively fewer studies have addressed the assembly of polyhedral metal and semiconductor nanocrystals for the formation of supercrystals with well-defined geometric shapes. These polyhedral supercrystals are considered as a new class of superlattice structures in which particle morphology strongly dictates the shapes of resulting supercrystals if the particles are larger than 20 nm. This review provides examples and advances in fabricating supercrystals on a substrate during the process of solvent evaporation and through diffusion transport of surfactant to generate free-standing supercrystals. The diversity of supercrystal morphologies observed is illustrated. In many cases, the supercrystal formation process has been found to be surfactant-mediated with surfactant molecules residing between adjacent nanocrystals. Polyhedral nanocrystal assembly was found to be strongly shape-guided. Thus, the formation of polyhedral supercrystals offers a unique opportunity to reconsider the forces involved from a more global perspective instead of focusing on mainly local interactions. Efforts have been made to record the entire supercrystal formation process. Finally, some results of properties of supercrystals and future directions for supercrystal research are provided. [ABSTRACT FROM AUTHOR]

Nanocrystal assembly into ordered structures provides mesostructural functional materials with a precise control that starts at the atomic scale. However, the lack of understanding on the self-assembly itself plus the poor structural integrity of the resulting supercrystalline materials still limits their application into engineered materials and devices. Surface functionalization of the nanobuilding blocks with organic ligands can be used not only as a means to control the interparticle interactions during self-assembly but also as a reactive platform to further strengthen the final material via ligand cross-linking. Here, we explore the influence of the ligands on superlattice formation and during cross-linking via thermal annealing. We elucidate the effect of the surface functionalization on the nanostructure during self-assembly and show how the ligand-promoted superlattice changes subsequently alter the cross-linking behavior. By gaining further insights on the chemical species derived from the thermally activated cross-linking and its effect in the overall mechanical response, we identify an oxidative radical polymerization as the main mechanism responsible for the ligand cross-linking. In the cascade of reactions occurring during the surface-ligands polymerization, the nanocrystal core material plays a catalytic role, being strongly affected by the anchoring group of the surface ligands. Ultimately, we demonstrate how the found mechanistic insights can be used to adjust the mechanical and nanostructural properties of the obtained nanocomposites. These results enable engineering supercrystalline nanocomposites with improved cohesion while preserving their characteristic nanostructure, which is required to achieve the collective properties for broad functional applications.

Summary: The fabrication of highly optically active supercrystals of anisotropic nanorods exploiting the electric field concentration and the nanoantenna effects provides a new family of optical sensors with the potential to maximize the SERS signal and thereby the possibility of detecting and quantifying the disease markers with low SERS cross-sections at ultralow concentrations. The capabilities of the new self-assembled nanorod SERS substrates have been demonstrated for real-time sensing of prions in real blood. It may also be possible to functionalize the top layers of supercrystals with specific recognition molecules for sensing many other disease markers, or even its integration into on-line devices, for the ultrasensitive screening of analytical targets relevant to medical science, environment, and homeland security. [ABSTRACT FROM AUTHOR]

Pentagonal packing is a long-standing issue and a rich mathematical topic, brought to the fore by recent progress in nanoparticle design. Gold pentagonal bipyramids combine fivefold symmetry and anisotropy and their section varies along the length. In this work, colloidal supercrystals of pentagonal gold bipyramids are obtained in a compact arrangement that generalizes the optimal packing of regular pentagons in the plane. Multimodal investigations reveal a two-particle unit cell with triclinic symmetry, a lower symmetry than that of the building blocks. Monte Carlo computer simulations show that this lattice achieves the densest possible packing. Going beyond pentagons, further simulations show an odd-even effect of the number of sides on the packing: odd-sided bipyramids are non-centrosymmetric and require the double-lattice arrangement to recover inversion symmetry. The supercrystals display a facet-dependent optical response that is promising for sensing, metamaterials applications, and for fundamental studies of self-assembly processes., (© 2022 Wiley-VCH GmbH.)

Understanding the phase transitions and domain evolutions of mesoscale topological structures in ferroic materials is critical to realizing their potential applications in next-generation high-performance storage devices. Here, the behaviors of a mesoscale supercrystal are studied with 3D nanoscale periodicity and rotational topology phases in a PbTiO 3 /SrTiO 3 (PTO/STO) superlattice under thermal and electrical stimuli using a combination of phase-field simulations and X-ray diffraction experiments. A phase diagram of temperature versus polar state is constructed, showing the formation of the supercrystal from a mixed vortex and a-twin state and a temperature-dependent erasing process of a supercrystal returning to a classical a-twin structure. Under an in-plane electric field bias at room temperature, the vortex topology of the supercrystal irreversibly transforms to a new type of stripe-like supercrystal. Under an out-of-plane electric field, the vortices inside the supercrystal undergo a topological phase transition to polar skyrmions. These results demonstrate the potential for the on-demand manipulation of polar topology and transformations in supercrystals using electric fields. The findings provide a theoretical understanding that may be utilized to guide the design and control of mesoscale polar structures and to explore novel polar structures in other systems and their topological nature., (© 2022 Wiley-VCH GmbH.)

Building chemical structures of complexity and functionality approaching the level of biological systems is an ongoing challenge. A general synthetic strategy is proposed by which progressive levels of complexity are achieved through the building block approach whereby molecularly defined constructs at one level serve as constituent units of the next level, all being linked through strong bonds-"augmented reticular chemistry". Specifically, current knowledge of linking metal complexes and organic molecules into reticular frameworks is applied here to linking the crystals of these frameworks into supercrystals (superframeworks). This strategy allows for the molecular control exercised on the molecular regime to be translated into higher augmentation levels to produce systems capable of dynamics and complex functionality far exceeding current materials., (© 2021 Wiley-VCH GmbH.)

With the ever-expanding functional applications of supercrystalline nanocomposites (a relatively new category of materials consisting of organically functionalized nanoparticles arranged into periodic structures), it becomes necessary to ensure their structural stability and understand their deformation and failure mechanisms. Inducing the cross-linking of the functionalizing organic ligands, for instance, leads to a remarkable enhancement of the nanocomposites' mechanical properties. It is however still unknown how the cross-linked organic phase redistributes applied loads, how the supercrystalline lattice accommodates the imposed deformations, and thus in general what phenomena govern the overall material's mechanical response. This work elucidates these aspects for cross-linked supercrystalline nanocomposites through an in situ small- and wide-angle X-ray scattering study combined with uniaxial pressing. Because of this loading condition, it emerges that the cross-linked ligands effectively carry and distribute loads homogeneously throughout the nanocomposites, while the superlattice deforms via rotation, slip, and local defects generation.

Surface-enhanced vibrational spectroscopy strongly increases the cross section of Raman scattering and infrared absorption, overcoming the limited sensitivity and resolution of these two powerful analytic tools. While surface-enhanced setups with maximum enhancement have been studied widely in recent years, substrates with reproducible, uniform enhancement have received less attention although they are required in many applications. Here, we show that plasmonic supercrystals are an excellent platform for enhanced spectroscopy because they possess a high density of hotspots in the electric field. We describe the near field inside the supercrystal within the framework of plasmon polaritons that form due to strong light-matter interaction. From the polariton resonances we predict resonances in the far-field enhancement for Raman scattering and infrared absorption. We verify our predictions by measuring the vibrations of polystyrene molecules embedded in supercrystals of gold nanoparticles. The intensity of surface-enhanced Raman scattering is uniform within 10% across the crystal with a peak integrated enhancement of up to 300 and a peak hotspot enhancement of 10 5 . The supercrystal polaritons induce pairs of incoming and outgoing resonances in the enhanced cross section as we demonstrate experimentally by measuring surface-enhanced Raman scattering with multiple laser wavelengths across the polariton resonance. The infrared absorption of polystyrene is likewise enhanced inside the supercrystals with a maximum enhancement of 400%. We show with a coupled oscillator model that the increase originates from the combined effects of hotspot formation and the excitation of standing polariton waves. Our work clearly relates the structural and optical properties of plasmonic supercrystals and shows that such crystals are excellent hosts and substrates for the uniform and predictable enhancement of vibrational spectra.

Semiconductor nanocrystals, or quantum dots (QDs), simultaneously benefit from inexpensive low-temperature solution processing and exciting photophysics, making them the ideal candidates for next-generation solar cells and photodetectors. While the working principles of these devices rely on light absorption, QDs intrinsically belong to the Rayleigh regime and display optical behavior limited to electric dipole resonances, resulting in low absorption efficiencies. Increasing the absorption efficiency of QDs, together with their electronic and excitonic coupling to enhance charge carrier mobility, is therefore of critical importance to enable practical applications. Here, we demonstrate a general and scalable approach to increase both light absorption and excitonic coupling of QDs by fabricating hierarchical metamaterials. We assemble QDs into crystalline supraparticles using an emulsion template and demonstrate that these colloidal supercrystals (SCs) exhibit extended resonant optical behavior resulting in an enhancement in absorption efficiency in the visible range of more than 2 orders of magnitude with respect to the case of dispersed QDs. This successful light trapping strategy is complemented by the enhanced excitonic coupling observed in ligand-exchanged SCs, experimentally demonstrated through ultrafast transient absorption spectroscopy and leading to the formation of a free biexciton system on sub-picosecond time scales. These results introduce a colloidal metamaterial designed by self-assembly from the bottom up, simultaneously featuring a combination of nanoscale and mesoscale properties leading to simultaneous photonic and excitonic coupling, therefore presenting the nanocrystal analogue of supramolecular structures.

Inorganic perovskites display an enticing foreground for their wide range of optoelectronic applications. Recently, supercrystals (SCs) of inorganic perovskite nanocrystals (NCs) have been reported to possess highly ordered structure as well as novel collective optical properties, opening new opportunities for efficient films. Here, we report the large-scale assembly control of spherical, cubic, and hexagonal SCs of inorganic perovskite NCs through templating by oil-in-oil emulsions. We show that an interplay between the roundness of the cubic NCs and the tension of the confining droplet surface sets the superstructure morphology, and we exploit this interplay to design dense hyperlattices of SCs. The SC films show strongly enhanced stability for at least two months without obvious structural degradation and minor optical changes. Our results on the controlled large-scale assembly of perovskite NC superstructures provide new prospects for the bottom-up production of optoelectronic devices based on the microfluidic production of mesoscopic building blocks.

Mesoscale self-assembly of particles into supercrystals is important for the design of functional materials such as photonic and plasmonic crystals. However, while much progress has been made in self-assembling supercrystals adopting diverse lattices and using different types of particles, controlling their growth orientation on surfaces has received limited success. Most of the latter orientation control has been achieved via templating methods in which lithographic processes are used to form a patterned surface that acts as a template for particle assembly. Herein, a template-free method to self-assemble (111)-, (100)-, and (110)-oriented face-centered cubic supercrystals of the metal-organic framework ZIF-8 particles by adjusting the amount of surfactant (cetyltrimethylammonium bromide) used is described. It is shown that these supercrystals behave as photonic crystals whose properties depend on their growth orientation. This control on the orientation of the supercrystals dictates the orientation of the composing porous particles that might ultimately facilitate pore orientation on surfaces for designing membranes and sensors., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

When narrowly distributed silver nanoparticles (NPs) are functionalized by dodecanethiol, they acquire the ability to self-organize in organic solvents into 3D supercrystals (SCs). The NP surface chemistry is shown to introduce a light-driven thermomigration effect, thermophoresis. Using a laser beam to heat the NPs and generate steep thermal gradients, the migration effect is triggered dynamically, leading to tailored structures with high density of plasmonic hot spots. This work describes how to manipulate the hot spots and monitor the effect by holography, thus providing a complete characterization of the migration process on a single object basis. Extensive single object tracking strategies are employed to measure the SCs trajectories, evaluate their size, drift velocity magnitude and direction, allowing the identification of the physical chemical origins of the migration. The phenomenon is shown to happen as a result of the combination of thermophoresis (at short length scales) and convection (long-range), and does not require a metallic substrate. This constitutes a fully optical method to dynamically generate plasmonic platforms in situ and on demand, without requiring substrate nanostructuration and with minimal interference on the chemistry of the system. The importance of the proof-of-concept herein described stems from the numerous potential applications, spanning over a variety of fields such as microfluidics and biosensing.

The assembly of semiconductor nanoparticles, quantum dots (QDs), into dense crystalline nanostructures holds great promise for future optoelectronic devices. However, knowledge of the sub-nanometer scale driving forces underlying the kinetic processes of nucleation, growth, and final densification during QD assembly remains poor. Emulsion-templated assembly has recently been shown to provide good control over the bulk condensation of QDs into highly ordered 3D supercrystals. Here, emulsion-templated assembly is combined with in situ small-angle X-ray scattering to obtain direct insight into the nanoscale interactions underlying the nucleation, growth, and densification of QD supercrystals. At the point of supercrystal nucleation, nanoparticles undergo a hard-sphere-like crystallization into a hexagonal-close-packed lattice, slowly transforming into a face-centered-cubic lattice. The ligands play a crucial role in balancing steric repulsion against attractive van der Waals forces to mediate the initial equilibrium assembly, but cause the QDs to be progressively destabilized upon densification. The rich detail of this kinetic study elucidates the assembly and thermodynamic properties that define QD supercrystal fabrication approaching single-crystal quality, paving the way toward their use in optoelectronic devices., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Self-assembly of nanoscale building blocks into ordered nanoarchitectures has emerged as a simple and powerful approach for tailoring the nanoscale properties and the opportunities of using these properties for the development of novel optoelectronic nanodevices. Here, the one-pot synthesis of CsPbBr 3 perovskite supercrystals (SCs) in a colloidal dispersion by ultrasonication is reported. The growth of the SCs occurs through the spontaneous self-assembly of individual nanocrystals (NCs), which form in highly concentrated solutions of precursor powders. The SCs retain the high photoluminescence (PL) efficiency of their NC subunits, however also exhibit a redshifted emission wavelength compared to that of the individual nanocubes due to interparticle electronic coupling. This redshift makes the SCs pure green emitters with PL maxima at ≈530-535 nm, while the individual nanocubes emit a cyan-green color (≈512 nm). The SCs can be used as an emissive layer in the fabrication of pure green light-emitting devices on rigid or flexible substrates. Moreover, the PL emission color is tunable across the visible range by employing a well-established halide ion exchange reaction on the obtained CsPbBr 3 SCs. These results highlight the promise of perovskite SCs for light emitting applications, while providing insight into their collective optical properties., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

One of the ultimate goals of nanocrystal self-assembly is to transform nanoscale building blocks into a material that displays enhanced properties relative to the sum of its parts. Herein, we demonstrate that 1D needle-shaped assemblies composed of Fe 3-δ O 4 nanocubes display a significant augmentation of the magnetic susceptibility and dissipation as compared to 0D and 2D systems. The performance of the nanocube needles is highlighted by a colossal anisotropy factor defined as the ratio of the parallel to the perpendicular magnetization components. We show that the origin of this effect cannot be ascribed to shape anisotropy in its classical sense; as such, it has no analogy in bulk magnetic materials. The temperature-dependent anisotropy factors of the in- and out-of-phase components of the magnetization have an extremely strong particle size dependence and reach values of 80 and 2500, respectively, for the largest nanocubes in this study. Aided by simulations, we ascribe the anisotropy of the magnetic susceptibility, and its strong particle-size dependence to a synergistic coupling between the dipolar interaction field and a net anisotropy field resulting from a partial texture in the 1D nanocube needles.

Aqueous phase synthesis of small Au-Ag core-shell nanocubes, cuboctahedra, and octahedra is achieved through the deposition of Ag shells on small octahedral Au cores. These nanocrystals show efficient photothermal activity and can assemble into supercrystals., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)