Prismatic Confinement Induces Tunable Orientation in Plasmonic Supercrystals.

Throughout history scientists have looked to Nature for inspiration and attempted to replicate intricate complex structures formed by self-assembly. In the context of synthetic supercrystals, achieving such complexity remains a challenge due to the highly symmetric nature of most nanoparticles (NPs). Previous works have shown intricate coupling between the self-assembly of NPs and confinement in templates, such as emulsion droplets (spherical confinement) or tubes (cylindrical confinement). This study focuses on the interplay between anisotropic NP shape and tunable "prismatic confinement" leading to the self-assembly of supercrystals in cavities featuring polygonal cross sections. A multiscale characterization strategy is employed to investigate the orientation and structure of the supercrystals locally and at the ensemble level. Our findings highlight the role of the mold interface in guiding the growth of distinct crystal domains: each side of the mold directs the formation of a monodomain that extends until it encounters another, leading to the creation of grain boundaries. Computer simulations in smaller prismatic cavities were conducted to predict the effect of an increased confinement. Comparison between prismatic and cylindrical confinements shows that flat interfaces are key to orienting the growth of supercrystals. This work shows a method of inducing orientation in plasmonic supercrystals and controlling their textural defects, thus offering insight into the design of functional metasurfaces and hierarchically structured devices.

Confinement Effects on the Structure of Entropy-Induced Supercrystals.

Depletion-induced self-assembly is routinely used to separate plasmonic nanoparticles (NPs) of different shapes, but less often for its ability to create supercrystals (SCs) in suspension. Therefore, these plasmonic assemblies have not yet reached a high level of maturity and their in-depth characterization by a combination of in situ techniques is still very much needed. In this work, gold triangles (AuNTs) and silver nanorods (AgNRs) are assembled by depletion-induced self-assembly. Small Angle X-ray Scattering (SAXS) and scanning electron microscopy (SEM) analysis shows that the AuNTs and AgNRs form 3D and 2D hexagonal lattices in bulk, respectively. The colloidal crystals are also imaged by in situ Liquid-Cell Transmission Electron Microscopy. Under confinement, the affinity of the NPs for the liquid cell windows reduces their ability to stack perpendicularly to the membrane and lead to SCs with a lower dimensionality than their bulk counterparts. Moreover, extended beam irradiation leads to disassembly of the lattices, which is well described by a model accounting for the desorption kinetics highlighting the key role of the NP-membrane interaction in the structural properties of SCs in the liquid-cell. The results shed light on the reconfigurability of NP superlattices obtained by depletion-induced self-assembly, which can rearrange under confinement.

Polymorphous Packing of Pentagonal Nanoprisms.

Packing solid shapes into regular lattices can yield very complex assemblies, not all of which achieve the highest packing fraction. In two dimensions, the regular pentagon is paradigmatic, being the simplest shape that does not pave the plane completely. In this work, we demonstrate the packing of plasmonic nanoprisms with pentagonal cross section, which form extended supercrystals. We do encounter the long-predicted ice-ray and Dürer packings (with packing fractions of 0.921 and 0.854, respectively) but also a variety of novel polymorphs that can be obtained from these two configurations by a continuous sliding transformation and exhibit an intermediate packing fraction. Beyond the fundamental interest of this result, fine control over the density and symmetry of such plasmonic assemblies opens the perspective of tuning their optical properties, with potential applications in metamaterial fabrication, catalysis, or molecular detection.

Double-Lattice Packing of Pentagonal Gold Bipyramids in Supercrystals with Triclinic Symmetry.

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.

Highly sensitive optical temperature sensing based on pump-power-dependent upconversion luminescence in LiZnPO4:Yb3+-Er3+/Ho3+ phosphors.

In this work, various LiZnPO4:0.5 mol% Ln3+ (Ln = Ho, Er) phosphors with different Yb3+ ion doping concentrations were synthesized by a sol-gel/Pechini method. X-ray diffraction (XRD) and scanning electron microscope (SEM) techniques were used to evaluate the phase and morphology of the samples. The UC process was mentioned as the typical emission peaks of Er3+ and Ho3+. For Er3+ and Ho3+, different optical temperature sensing methods are included. The Boltzmann distribution was accompanied by the fluorescence intensity ratio (FIR) for the two green Er3+ emissions originating from thermally-coupled levels. The effect of pump power on sensor sensitivities was extensively studied. The temperature uncertainty is also evaluated. The red and green emissions generated from non-thermally-coupled levels were used for temperature sensing in the Ho3+-activated LiZnPO4. High sensitivities were obtained in the phosphors, and the LiZnPO4:Yb3+/Ho3+ showed the largest absolute sensitivities. LiZnPO4:Yb3+-Er3+/Ho3+ phosphors may be useful in the development of new luminescent materials for optical temperature sensing.

Large-Scale and Low-Cost Fabrication of Silicon Mie Resonators.

High index dielectric nanoparticles have been proposed for many different applications. However, widespread utilization in practice also requires large-scale production methods for crystalline silicon nanoparticles, with engineered optical properties in a low-cost manner. Here, we demonstrate a facile, low-cost, and large-scale fabrication method of crystalline silicon colloidal Mie resonators in water, using a blender. The obtained nanoparticles are polydisperse with an almost spherical shape and the diameters controlled in the range 100-200 nm by a centrifugation process. Then the size distribution of silicon nanoparticles enables broad extinction from UV to near-infrared, confirmed by Mie theory when considering the size distribution in the calculations. Thanks to photolithographic and drop-cast deposition techniques to locate the position on a substrate of the colloidal nanoparticles, we experimentally demonstrate that the individual silicon nanoresonators show strong electric and magnetic Mie resonances in the visible range.