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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Nanocrystal Assemblies: Current Advances and Open Problems

Here we explore the potential of nanocrystals (a term used equivalently to nanoparticles) as building blocks for nanomaterials, and the current advances and open challenges for fundamental science developments and applications. Nanocrystal assemblies are inherently multiscale, and the generation of revolutionary material properties requires a precise understanding of the relationship between structure and function, the former being determined by classical effects and the latter often by quantum effects. With an emphasis on theory and computation, we discuss challenges that hamper current assembly strategies and to what extent nanocrystal assemblies represent thermodynamic equilibrium or kinetically trapped metastable states. We also examine dynamic effects and optimization of assembly protocols. Finally, we discuss promising material functions and examples of their realization with nanocrystal assemblies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Symmetry-specific orientational order parameters for complex structures

A comprehensive framework of characterizing complex self-assembled structures with a set of orientational order parameters is presented. It is especially relevant in the context of using anisotropic building blocks with various symmetries. Two classes of tensor order parameters are associated with polyhedral nematic and bond orientational order. For the latter, a variation of classical bond order parameters (BOPs) is introduced, which takes advantage of the symmetry of constituent particles and/or expected crystalline phases. These symmetrized BOPs can be averaged over an entire system or assigned locally to an individual bond. By combining that with the bond percolation procedure, one is able to identify coherent domains within a self-assembled structure. As a demonstration of the proposed framework, we apply it to a simulated hybrid system that combines isotropic and patchy particles with octahedral symmetry. In conclusion, not only does the methodology allow one to identify individual crystalline domains but also it detects coherent clusters of a peculiar compact amorphous structure that is not space-filling and lacks any long-range order.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Photo-printing of faceted DNA patchy particles

Patchy particles with shape complementarity can serve as building blocks for assembling colloidal superstructures. Alternatively, encoding information on patches using DNA can direct assembly into a variety of crystalline or other preprogrammed structures. Here, we present a tool where DNA is used both to engineer shape and to encode information on colloidal particles. Two reactive oil emulsions with different but complementary DNA (cDNA) brushes are assembled into CsCl-like crystalline lattices. The DNA brushes are recruited to and ultimately localized at the junctions between neighboring droplets, which gives rise to DNA-encoded faceted patches. The emulsions are then solidified by ultraviolet (UV) polymerization, producing faceted patchy particles. The facet size and DNA distribution are determined by the balance between the DNA binding energy and the elastic deformation energy of droplets. This method leads to a variety of new patchy particles with directional interactions in scalable quantities.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Tuning Stoichiometry to Promote Formation of Binary Colloidal Superlattices

The self-assembly of binary nanoparticle superlattices from colloidal mixtures is a promising method for the fabrication of complex colloidal cocrystal structures. However, binary mixtures often form amorphous or metastable phases instead of the thermodynamically stable phase. Here we show that in binary mixtures of differently sized spherical particles, an excess of the smaller component can promote—and, in some cases, may be necessary for—the self-assembly of a binary cocrystal. Using computer simulations, we identify two mechanisms responsible for this phenomenon. First, excess small particles act like plasticizers and enable systems to reach a greater supersaturation before kinetic arrest occurs. Second, they can disfavor competing structures that may interfere with the growth of the target structure. We find the phase behavior of simulated mixtures of nearly hard spheres closely matches published experimental results. We demonstrate the generality of our findings for mixtures of particles of arbitrary shape by presenting a binary mixture of hard shapes that only self-assembles with an excess of the smaller component.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Nanoparticle self-assemblies with modern complexity

Thanks to decades of tireless efforts, nanoparticle assemblies have reached at an extremely high level of controllability, sophistication, and complexity, with new insights provided by integration with graph theory, cutting-edge characterization, and machine learning (ML)-based computation and modeling, as well as with ever-diversifying applications in energy, catalysis, biomedicine, optics, electronics, magnetics, organic biosynthesis, and quantum technology. Nanoparticle assemblies can be crystalline, known as superlattices or supracrystals. Their assembly entails a transition from disorder—dispersed nanoparticles—to order, which can be achieved through classical nucleation pathways or nonclassical pathways via prenucleation precursors or particle aggregation. Further, the periodic lattices allow facile manipulations of electrons, phonons, photons, and even spins, leading to advanced device components and metamaterials. Meanwhile, aperiodic assemblies out of nanoparticles, such as gels, networks, and amorphous solids, also start to attract attentions. Despite the loss of periodicity, symmetry-lowering or symmetry-breaking three-dimensional (3D) structures emerge with unique properties, such as chiroptical activity, topological mechanical strength, and quantum entanglement. Real-space imaging such as electron microscopy and X-ray based tomography methods are utilized to characterize these complex structures, while mathematical tools such as graph theories are in need to describe such complex structures. This issue aims to provide a timely review of the efforts in this greatly broadened materials design space including experiment, simulation, theory, and applications. Nine top experts (and their teams) from four countries deliver six review papers, summarizing fundamental mechanistic understandings of nanoparticle assemblies, highlighted with the developments of state-of-the-art in situ characterization tools and ML-assisted reverse engineering, and newly emergent applications of nanoarchitectures.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Entropically engineered formation of fivefold and icosahedral twinned clusters of colloidal shapes

Fivefold and icosahedral symmetries induced by multiply twinned crystal structures have been studied extensively for their role in influencing the shape of synthetic nanoparticles, and solution chemistry or geometric confinement are widely considered to be essential. Here we report the purely entropy-driven formation of fivefold and icosahedral twinned clusters of particles in molecular simulation without geometric confinement or chemistry. Hard truncated tetrahedra self-assemble into cubic or hexagonal diamond colloidal crystals depending on the amount of edge and vertex truncation. By engineering particle shape to achieve a negligible entropy difference between the two diamond phases, we show that the formation of the multiply twinned clusters is easily induced. The twinned clusters are entropically stabilized within a dense fluid by a strong fluid-crystal interfacial tension arising from strong entropic bonding. Our findings provide a strategy for engineering twinning behavior in colloidal systems with and without explicit bonding elements between particles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Ligand-Mediated Phase Control in Colloidal AgInSe 2 Nanocrystals

Synthetic studies of colloidal nanoparticles that crystallize in metastable structures represent an emerging area of interest in the development of novel functional materials, as metastable nanomaterials may exhibit unique properties when compared to their counterparts that crystallize in thermodynamically preferred structures. Herein, we demonstrate how phase control of colloidal AgInSe 2 nanocrystals can be achieved by performing reactions in the presence, or absence, of coordinating ligands that can act as cation exchange mediators (i.e., oleylamine or 1-dodecanethiol). These coordinating ligands play a crucial role in formation of metastable AgInSe 2 nanocrystals, as they mediate in-situ topotactic conversion of an orthorhombic Ag2Se intermediate to a metastable orthorhombic phase of AgInSe 2 . We pro-vide a detailed mechanistic crystal chemistry description of this process to structurally elucidate how the orthorhombic phase of AgInSe 2 forms. Density functional theory calculations suggest that the metastable orthorhombic phase of AgInSe 2 is metastable by a small margin, at 10 meV/atom above the thermodynamic ground state. In the absence of oleylamine or 1-dodecanethiol, Ag 2 Se nanocrystal intermediates convert through kinetically slow, non-topotactic conversion processes to yield the thermodynamically preferred chalcopyrite structure of AgInSe 2 . Furthermore, on the basis of these discoveries, we offer new insight into the prediction of novel metastable multinary nanocrystal phases that do not exist on bulk phase diagrams.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Tunable assembly of hybrid colloids induced by regioselective depletion

Assembling colloidal particles using site-selective directional interactions into predetermined colloidal superlattices with desired properties is broadly sought-after, but challenging to achieve. Here in this paper, we exploit regioselective depletion interactions to engineer the directional bonding and assembly of non-spherical colloidal hybrid microparticles. We report that the crystallization of a binary colloidal mixture can be regulated by tuning the depletion conditions. Subsequently, we fabricate triblock biphasic colloids with controlled aspect ratios to achieve regioselective bonding. Without any surface treatment, these biphasic colloids assemble into various colloidal superstructures and superlattices featuring optimized pole-to-pole or center-to-center interactions. Additionally, we observe polymorphic crystallization, quantify the abundancy of each form using algorithms we developed, and investigate the crystallization process in real time. We demonstrate selective control of attractive interactions between specific regions on an anisotropic colloid with no need of site-specific surface functionalization, leading to a general method for achieving colloidal structures with yet unforeseen arrangements and properties.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Two-dimensional non-equilibrium melting of charged colloids

Thermodynamic two-dimensional melting has been extensively studied in experiments and simulations, and is well predicted by theory. For systems in equilibrium, this transition is well described by the Kosterlitz–Thouless–Halperin–Nelson–Young theory, where melting is directly linked to the unbinding of topological defects. For driven, non-equilibrium melting and other non-equilibrium phase transitions, the picture is less clear. Here, in this work, we study the two-dimensional melting of a crystal of charged colloids. By randomly replacing some charged colloids with magnetic colloids, we can melt our system by rotating a fraction of the particles to create non-equilibrium, hydrodynamic random flows and local stresses. We can also melt it thermally by changing the particle number density. We find that an effective temperature approach cannot explain the results of our driven system. Rather, in both experiments and simulations, we observe that plotting the hexatic order parameter and the hexatic correlation’s exponent versus the density of disclinations and dislocations, respectively, yields universal curves. This implies that in our systems, two-dimensional melting depends directly on the density of topological defects and is independent of whether thermal or non-equilibrium forces generate them.

critical phenomena↗
DOE OSTI2021

Colloidal Synthesis of Single-Layer Quasi-Ruddlesden–Popper Phase Bismuth-Based Two-Dimensional Perovskite Nanosheets with Controllable Optoelectronic Properties

Single- and few-layered two-dimensional (2D) nanomaterials have attracted intense research interest in the last two decades due to their unique electronic and optoelectronic properties leading to various potential applications. Herein, we report the colloidal synthesis of Bi-based 2D perovskite nanosheets (PEG6-NH 3 +) n Cs 3-n Bi 2 X 9 , where X = CI, Br, and I, through careful design of reaction conditions and selection of poly(ethylene glycol) (PEG6) surface passivating ligands. The 2D nanosheets are similar to 5 nm in thickness with micron-sized lateral dimensions and display composition-dependent band gap and work function modulation. Furthermore, small-angle X-ray scattering analysis substantiates that the individual inorganic crystal layer, Cs 3-n Bi 2 X 9 , is separated by the spacer, PEG6 ligand. Additionally, we determined that PEG6-NH 2 is an essential passivating ligand and spacer for the formation of Bi-based 2D nanosheets. Most importantly, controlled crystallization of the colloidal dispersion of nanosheets results in the formation of superlattice microstructures of the quasi-Ruddlesden-Popper phase. These microstructures can be exfoliated to ultrathin nanosheets by overcoming the van der Waals interaction between the organic passivating layers. The controlled synthesis of lead-free 2D perovskite nanosheets presented here can expand their utility to photocatalytic and optoelectronic applications with reduced toxicity.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Geometric transformation and three-dimensional hopping of Hopf solitons

Arising in many branches of physics, Hopf solitons are three-dimensional particle-like field distortions with nontrivial topology described by the Hopf map. Despite their recent discovery in colloids and liquid crystals, the requirement of applied fields or confinement for stability impedes their utility in technological applications. Here we demonstrate stable Hopf solitons in a liquid crystal material without these requirements as a result of enhanced stability by tuning anisotropy of parameters that describe energetic costs of different gradient components in the molecular alignment field. Nevertheless, electric fields allow for inter-transformation of Hopf solitons between different geometric embodiments, as well as for their three-dimensional hopping-like dynamics in response to electric pulses. Numerical modelling reproduces both the equilibrium structure and topology-preserving out-of-equilibrium evolution of the soliton during switching and motions. Our findings may enable myriads of solitonic condensed matter phases and active matter systems, as well as their technological applications.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Soft matter roadmap

Soft materials are usually defined as materials made of mesoscopic entities, often self-organised, sensitive to thermal fluctuations and to weak perturbations. Archetypal examples are colloids, polymers, amphiphiles, liquid crystals, foams. The importance of soft materials in everyday commodity products, as well as in technological applications, is enormous, and controlling or improving their properties is the focus of many efforts. From a fundamental perspective, the possibility of manipulating soft material properties, by tuning interactions between constituents and by applying external perturbations, gives rise to an almost unlimited variety in physical properties. Together with the relative ease to observe and characterise them, this renders soft matter systems powerful model systems to investigate statistical physics phenomena, many of them relevant as well to hard condensed matter systems. Understanding the emerging properties from mesoscale constituents still poses enormous challenges, which have stimulated a wealth of new experimental approaches, including the synthesis of new systems with, e.g. tailored self-assembling properties, or novel experimental techniques in imaging, scattering or rheology. Theoretical and numerical methods, and coarse-grained models, have become central to predict physical properties of soft materials, while computational approaches that also use machine learning tools are playing a progressively major role in many investigations. This Roadmap intends to give a broad overview of recent and possible future activities in the field of soft materials, with experts covering various developments and challenges in material synthesis and characterisation, instrumental, simulation and theoretical methods as well as general concepts.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Design and Preparation of Nematic Colloidal Particles

Colloidal systems are abundant in technology, in biomedical settings, and in our daily life. The so-called “colloidal atoms” paradigm exploits interparticle interactions to self-assemble colloidal analogs of atomic and molecular crystals, liquid crystal glasses, and other types of condensed matter from nanometer- or micrometer-sized colloidal building blocks. Nematic colloids, which comprise colloidal particles dispersed within an anisotropic nematic fluid host medium, provide a particularly rich variety of physical behaviors at the mesoscale, not only matching but even exceeding the diversity of structural and phase behavior in conventional atomic and molecular systems. This feature article, using primarily examples of works from our own group, highlights recent developments in the design, fabrication, and self-assembly of nematic colloidal particles, including the capabilities of preprogramming their behavior by controlling the particle’s surface boundary conditions for liquid crystal molecules at the colloidal surfaces as well as by defining the shape and topology of the colloidal particles. Here recent progress in defining particle-induced defects, elastic multipoles, self-assembly, and dynamics is discussed along with open issues and challenges within this research field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Sculpting crystals one Burgers vector at a time: Toward colloidal lattice robot swarms

Plastic deformation of crystalline materials with isotropic particle attractions proceeds by the creation and migration of dislocations under the influence of external forces. If dislocations are produced and migrated under the action of local forces, then material shape change can occur without the application of surface forces. We investigate how particles with variable diameters can be embedded in colloidal monolayers to produce dislocations on demand. Additionally, we find in simulation that when embedded clusters of variable diameter particles are taken through multiple cycles of swelling and shrinking, large cumulative plastic slip is produced by the creation and biased motion of dislocation pairs in the solid for embedded clusters of particular geometries. In this way, dislocations emitted by these clusters (biased “dislocation emitters”) can be used to reshape colloidal matter. Our results are also applicable to larger-scale swarms of robotic particles that organize into dense ordered two-dimensional (2D) arrangements. We conclude with a discussion of how dislocations fulfill for colloids the role sought by “metamodules” in lattice robotics research and show how successive applications of shear as a unit operation can produce shape change through slicing and swirling.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Electrical Switching of Nematic Plasmonic Nanocolloids for Infrared Solar Gain Control

Controlling solar gain is essential to reduce the energy consumption by residential and commercial buildings, which are responsible for ≈40% of all energy generated globally. However, the dynamic control of solar gain in the near-infrared that corresponds to ≈50% of the overall Sun's energy at the Earth's surface, separately from the visible spectral range has been a challenge, albeit commercial coatings provide passive control while retaining highly visible transmission. To address this problem, in this paper switchable silver colloids (SSCs) are demonstrated, colloidal analogs of the common silver coatings used for solar gain control. When dispersed in a nematic liquid crystal, orientations of such plasmonic silver nanoplates are controlled by ≈1 V low-voltage electric fields, allowing for sub-second switching of the near-infrared-based solar gain. Installed and retrofit products made from thin films of such nanoplate dispersions confined between glass and plastic substrates, respectively, exhibit electrically controlled infrared-based solar gain while retaining high visible-range transparency, low haze, and high color rendering index. Furthermore, this study's findings reveal a great potential of soft-matter systems in addressing energy-related problems.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Out-of-equilibrium interactions and collective locomotion of colloidal spheres with squirming of nematoelastic multipoles

Many living and artificial systems show similar emergent behavior and collective motions on different scales, starting from swarms of bacteria to synthetic active particles, herds of mammals, and crowds of people. What all these systems often have in common is that new collective properties like flocking emerge from interactions between individual self-propelled or driven units. Such systems are naturally out-of-equilibrium and propel at the expense of consumed energy. Mimicking nature by making self-propelled or externally driven particles and studying their individual and collective motility may allow for deeper understanding of physical underpinnings behind collective motion of large groups of interacting objects or beings. Here, in this work, using a soft matter system of colloids immersed into a liquid crystal, we show that resulting so-called nematoelastic multipoles can be set into a bidirectional locomotion by external oscillating electric fields. Out-of-equilibrium elastic interactions between such colloidal objects lead to collective flock-like behaviors emerging from time-varying elasticity-mediated interactions between externally driven propelling particles. Repulsive elastic interactions in the equilibrium state can be turned into attractive interactions in the out-of-equilibrium state under applied external electric fields. We probe this behavior at different number densities of colloidal particles and show that particles in dense dispersions collectively select the same direction of a coherent motion due to elastic interactions between near neighbors. In our experimentally implemented design, their motion is highly ordered and without clustering or jamming often present in other colloidal transport systems, which is promising for technological and fundamental-science applications, like nano-cargo transport, out-of-equilibrium assembly, and microrobotics.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗