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At least 91 records · Page 5

Interfacial-Strain-Controlled Ferroelectricity in Self-Assembled BiFeO 3 Nanostructures

Self-assembled BiFeO 3 -CoFe 2 O 4 (BFO-CFO) vertically aligned nanocomposites are promising for logic, memory, and multiferroic applications, primarily due to the tunability enabled by strain engineering at the prodigious epitaxial vertical interfaces. However, local investigations directly revealing functional properties in the vicinity of such critical interfaces are often hampered by the size, geometry, microstructure, and concomitant experimental artifacts. Ferroelectric switching in the presence of lateral distributions of vertical strain thus remains relatively unexplored, with broader implications for all strain-engineered functional devices. Additionally, by implementing tomographic atomic force microscopy, 3D domain orientation mapping, and spatially-resolved ferroelectric switching movies, local tensile strain significantly impacts the ferroelectric switching, principally by retarding domain nucleation in the BFO nearest to the vertically epitaxial tensile-strained interfaces. The relaxed centers of the BFO pillars become preferred domain nucleation and growth sites for low biases, with up to an order of magnitude change in the edge:center switching ratio for high biases. The new, multi-dimensional imaging approach—and its corresponding insights especially for directly strained interface effects on local properties—thereby advances the fundamental understanding of polarization switching and provides design principles for optimizing functional response in confined nanoferroic systems.

36 MATERIALS SCIENCE↗

Self‐Assembled LuFeO 3 /LuFe 2 O 4 Heterostructure with Emergent Ferroic Orderings

Abstract Achieving self‐assembling structures that exhibit emergent properties and functionalities is one of the holy grails in nanotechnology and holds great promise for a wide range of potential applications. Herein, a self‐assembled LuFeO 3 –(1/3)LuFe 2 O 4 –LuFeO 3 heterostructure that consists of two model multiferroics, i.e., hexagonal LuFeO 3 and rhombohedral LuFe 2 O 4 , is reported in single‐layer epitaxial LuFeO 3 thin films. Atomic‐scale electron microscopy investigations reveal the spontaneous organization of ferroelectric polarization in each building block, which forms a series of polar configurations. Specifically, the charge and lattice of neighboring LuFeO 3 and LuFe 2 O 4 blocks are closely coupled with competing degrees of freedom. A combination of the quantitative analysis of atomically resolved images and spectroscopy with theoretical calculations determines how charge‐ordering‐induced polarization accommodates charge naturality across the interfaces to reduce the system energy and unravels the formation mechanism of this heterostructure. The results point to the possibilities of generation and control of multiferroic self‐assembled systems, which may provide a basis for engineering novel materials with emergent properties.

Deng, Shiqing↗

Hierarchical Self-Assembly of Carbon Dots into High-Aspect-Ratio Nanowires

Here, we report a spontaneous and hierarchical self-assembly mechanism of carbon dots prepared from citric acid and urea into nanowire structures with large aspect ratios (>50). Scattering-type scanning near-field optical microscopy (s-SNOM) with broadly tunable mid-IR excitation was used to interrogate details of the self-assembly process by generating nanoscopic chemical maps of local wire morphology and composition. s-SNOM images capture the evolution of wire formation and the complex interplay between different chemical constituents directing assembly over the nano- to microscopic length scales. We propose that residual citrate promotes tautomerization of melamine surface functionalities to produce supramolecular shape synthons comprised of melamine-cyanurate adducts capable of forming long-range and highly directional hydrogen-bonding networks. This intrinsic, heterogeneity-driven self-assembly mechanism reflects synergistic combinations of high chemical specificity and long-range cooperativity that may be harnessed to reproducibly fabricate functional structures on arbitrary surfaces.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Self-Assembly Driven Microlithography via Near-Infrared Light Activation

Current vat photopolymerization (VP) relies on UV or visible light to start the rapid crosslinking of liquid photocurable resins into 3D-printed structures. Here, we develop a self-assembly-driven photopatterning approach to photothermally generate polymeric solids by combining thermoplasmonic nanoparticles and thermoresponsive polymers, in which near-infrared (NIR) light activates thermoplasmonic heating of nanoparticles, triggering the irreversible self-assembly of thermoresponsive polymers into insoluble mesoglobules. A small amount of thermal initiator and crosslinker leads to irreversible self-assembly of polymer nanocomposites. NIR light offers deeper penetration and reduced scattering compared to UV, enabling more uniform curing of thicker or filled materials and expanded process control for composites or opaque systems. Thermoplasmonic heat generation is achieved using surface-modified gold nanorods (AuNRs) with a longitudinal localized surface plasmon resonance peak in the NIR region. Key variables such as polymer composition, molecular weight, physical interactions at the nanoparticle–polymer interface, which can be tuned by surface functionalization, AuNR concentration, and pH can be used to tailor the assembly behavior of these systems, including photothermal effect, flocculation, and cloud point temperature, and the mechanical properties of the final structures. Collectively, these results highlight a platform for photothermally-driven microlithography of polymer solids with diverse, tunable macroscopic properties, enabled by low-energy NIR light-activated self-assembly.

36 MATERIALS SCIENCE↗

Toward controlling wetting hysteresis with nanostructured surfaces derived from block copolymer self-assembly

The synthesis of nanostructured surfaces via block copolymer (BCP) self-assembly enables a precise control of the surface feature shape within a range of dimensions of the order of tens of nanometers. Herein, this work studies how to exploit this ability to control the wetting hysteresis and liquid adhesion forces as the substrate undergoes chemical aging and changes in its intrinsic wettability. Via BCP self-assembly we fabricate nanostructured surfaces on silicon substrates with a hexagonal array of regular conical pillars having a fixed period (52 nm) and two different heights (60 and 200 nm), which results in substantially different lateral and top surface areas of the nanostructure. The wetting hysteresis of the fabricated surfaces is characterized using force–displacement measurements under quasistaic conditions and over sufficiently long periods of time for which the substrate chemistry and surface energy, characterized by the Young contact angle, varies significantly. The experimental results and theoretical analysis indicate that controlling the lateral and top area of the nanostructure not only controls the degree of wetting hysteresis but can also make the advancing and receding contact angles less susceptible to chemical aging. These results can help rationalize the design of nanostructured surfaces for different applications such as self-cleaning, enhanced heat transfer, and drag reduction in micro/nanofluidic devices.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Self-assembly of solid nanoclusters in molybdenum under gas ion implantation

The self-assembly of defects in materials could create unique physical and chemical properties. In nuclear fuels, the formation of self-assembled fission products mitigates fission-gas-release and swelling. In this work, we report the formation of a solid nanocluster superlattice in molybdenum, an important constituent in metallic fuels, under krypton gas ion implantation. X-ray absorption near edge structure measurements coupled with density functional theory calculations show that the pressure of krypton nanoclusters in molybdenum is ~2 GPa and molecular dynamic simulations reveal that the krypton atoms are solid in the nanoclusters with a krypton-to-vacancy ratio of ~0.28 at 300 K.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Self-assembled InAsSb quantum dots on (001) InP substrates

Self-assembled InAsSb quantum dots (QD) on (001) InP substrates have been grown using metalorganic vapor phase epitaxy. The dot density and size are found to be strongly dependent on the presence of arsine. Direct deposition of InSb on InP and GaSb substrates formed large islands of InSb with low density of less than 53109/cm², however, InAsSb QDs of density as high as 4 X10¹º/cm² could be self-assembled by alternating group III and group V precursors, and high density almost pure InSb QDs were achieved on In0.53Ga0.47As/InP. The formation of high density InAsSb QDs is a result of a local nonequilibrium process and a reduction in mobility of In adatoms on the growth surface due to the presence of arsenic atoms, and in the case of high density almost pure InSb QDs on InGaAs/InP, the InAs interface layer is believed to be responsible. Photoluminescence shows that InSb QDs emit light at room temperature in the range of 1.7–2.2µm.

Uhl, David↗

Diversifying self-assembled phases in block copolymer thin films via blending

Block copolymer (BCP) thin films readily self-assemble into intricate nanoscale morphologies, with structure dictated by chain architecture. As the field searches for more control over structure formation, it is natural to investigate more sophisticated control mechanisms, such as synthesizing more complex chain architectures or applying directing fields. We review the use of a simple but powerful method for controlling self-assembly: blending of BCPs with homopolymers or other BCPs. Blending enables tailoring ordering kinetics, the spatial distribution of chains throughout the film thickness, and the nanoscale morphology itself. Blending is thus emerging as a remarkably simple and powerful means of tailoring self-assembled morphologies.

36 MATERIALS SCIENCE↗

Aging of Self-Assembled Lead Halide Perovskite Nanocrystal Superlattices: Effects on Photoluminescence and Energy Transfer

Excitonic coupling, electronic coupling, and cooperative interactions in self-assembled lead halide perovskite nanocrystals were reported to give rise to a red-shifted collective emission peak with accelerated dynamics. Here we report that similar spectroscopic features could appear as a result of the nanocrystal reactivity within the self-assembled superlattices. This is demonstrated by studying CsPbBr 3 nanocrystal superlattices over time with room-temperature and cryogenic micro-photoluminescence spectroscopy, X-ray diffraction, and electron microscopy. It is shown that a gradual contraction of the superlattices and subsequent coalescence of the nanocrystals occurs over several days of keeping such structures under vacuum. As a result, a narrow, low-energy emission peak is observed at 4 K with a concomitant shortening of the photoluminescence lifetime due to the energy transfer between nanocrystals. When exposed to air, self-assembled CsPbBr 3 nanocrystals develop bulk-like CsPbBr 3 particles on top of the superlattices. At 4 K, these particles produce a distribution of narrow, low-energy emission peaks with short lifetimes and excitation fluence-dependent, oscillatory decays. Overall, the aging of CsPbBr 3 nanocrystal assemblies dramatically alters their emission properties and that should not be overlooked when studying collective optoelectronic phenomena nor confused with superfluorescence effects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Vibrational Sum-Frequency Generation Hyperspectral Microscopy for Molecular Self-Assembled Systems

In this review, we discuss the recent developments and applications of vibrational sum-frequency generation (VSFG) microscopy. This hyperspectral imaging technique can resolve systems without inversion symmetry, such as surfaces, interfaces and noncentrosymmetric self-assembled materials, in the spatial, temporal, and spectral domains. We discuss two common VSFG microscopy geometries: wide-field and confocal point-scanning. We then introduce the principle of VSFG and the relationships between hyperspectral imaging with traditional spectroscopy, microscopy, and time-resolved measurements. We further highlight crucial applications of VSFG microscopy in self-assembled monolayers, cellulose in plants, collagen fibers, and lattice self-assembled biomimetic materials. In these systems, VSFG microscopy reveals relationships between physical properties that would otherwise be hidden without being spectrally, spatially, and temporally resolved. Lastly, we discuss the recent development of ultrafast transient VSFG microscopy, which can spatially measure the ultrafast vibrational dynamics of self-assembled materials. The review ends with an outlook on the technical challenges of and scientific potential for VSFG microscopy.

Chemistry↗

Spatially dependent H-bond dynamics at interfaces of water/biomimetic self-assembled lattice materials

Significance It is challenging to develop biomimetic lattice self-assemblies because such materials need to resemble the flexibility and crystallinity of their biological analog. We show that these materials exhibit unique micro- and mesoscopic-ordered ultrafast hydrogen-bond dynamics, which could be a key feature in the lattice self-assembly: the ultrafast dynamics ensure flexibility, whereas the domain-level ordering reflects crystallinity. This scientific insight cannot be revealed without the ultrafast transient vibrational sum-frequency generation microscope, which integrates ultrafast interfacial spectroscopy with interfacial molecular vibrational imaging––a state-of-the-art development.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Supramolecular bending and twisting in the hierarchical self-assembly of monodisperse mesogenic oligomers

Understanding how different forms of supramolecular curvature arise during assembly is crucial to designing and tuning the microstructure of hierarchically self-assembled materials. Here, we show that in crystalline phases of mesogenic oligomers, the oligomer length is a critical parameter that determines the type of curvature (Gaussian or cylindrical) exhibited by the self-assembled structures. We use iterative exponential growth to synthesize monodisperse mesogenic oligomers ranging from dimer to octamer. By analyzing their phase behavior and microstructure, we elucidate how length-dependent thermodynamic and kinetic effects tune their hierarchical degree of ordering. The oligomers’ length-dependent crystalline order drives the formation of scrolled sheets in shorter oligomers and twisted ribbons in longer oligomers. These studies highlight how oligomer length interplays with mesogen geometry and crystalline packing to drive self-assembly, introducing oligomer length as a powerful design parameter toward tailored applications of mesogenic systems.

36 MATERIALS SCIENCE↗

Designing sequence-defined peptoids for fibrillar self-assembly and silicification

In the biological environment, mineral crystals exquisitely controlled by biomacromolecules often show intricate hierarchical structures and superior mechanical properties. Among these biominerals, spicules, hybrid silica/protein superstructures serving as skeletal elements in demosponges, represent an excellent example for motivating the synthesis of silica materials. Herein, by designing sequence-defined peptoids containing side chains with a strong binding to silica, we demonstrated that self-assembly of these peptoids into fiber structures enables the mimicking of both biocatalytic and templating functions of silicatein filaments for the formation of silica fibers at near-neutral pH and ambient temperature. We further showed that the presence of amino groups is significant for the nucleation of silica on self-assembled peptoid nanofibers. Molecular dynamics simulation further confirmed that having silica-binding of amino side chains is critical for self-assembled peptoid fibers in triggering silica formation. Here, we demonstrated that tuning inter-peptoid interactions by varying carboxyl and amino side chains significantly influences the assembly kinetics and final morphologies of peptoid assemblies as scaffolds for directing silica mineralization to form silica spheres, fibers, and sheets. The formation of silica shell on peptoid fibers increased the mechanical property of peptoid hydrogel materials by nearly 1000-fold, highlighting the great potential of using silicification to enhance the mechanical property of hydrogel materials for applications including tissue engineering. Since peptoids are highly robust and programmable, we expect that self-assembly of peptoids containing solid-binding side chains into hierarchical materials opens new opportunities in the design and synthesis of highly tunable scaffolds that direct the formation of composite nanomaterials.

59 BASIC BIOLOGICAL SCIENCES↗

Electronic Transport through Self Assembled Thiol Molecules: Effect of Monolayer Order, Dynamics and Temperature

We present the charge transport and tunneling conductance of self assembled organic thiol molecules and discuss the influence of order and dynamics in the monolayer on the transport behavior and the effect of temperature. Conjugated thiol molecular wires and organometals such as terpyridine metal complexes provide a new platform for molecular electronic devices and we study their self assembly on Au(111) substrates by the scanning tunneling microscope. Determining the organization of the molecule and the ability to control the nature of its interface with the substrate is important for reliable performance of the molecular electronic devices. By concurrent scanning tunneling microscopy and spectroscopy studies on SAMs formed from oligo (phenelyne ethynelyne) monolayers with and without molecular order, we show that packing and order determine the response of a self assembled monolayer (SAM) to competing interactions. Molecular resolution STM imaging in vacuum shows that the OPES adopt an imcommensurate SAM structure on Au(111) with a rectangular unit cell. Tunneling spectroscopic measurements were performed on the SAM as a function of junction resistance. STS results show that the I-Vs are non linear and asymmetric due to the inherent asymmetry in the molecular structure, with larger currents at negative sample biases. The asymmetry increases with increasing junction resistance due to the asymmetry in the coupling to the leads. This is brought out clearly in the differential conductance, which also shows a gap at the Fermi level. We also studied the effect of order and dynamics in the monolayer on the charge transport and found that competing forces between the electric field, intermolecular interactions, tip-molecule physisorption and substrate-molecule chemisorption impact the transport measurements and its reliability and that the presence of molecular order is very important for reproducible transport measurements. Thus while developing new electronic platforms based on molecules, it is important to have a good control of the molecule-substrate interface, for the devices to perform reliably. While such a control would minimize fluctuations and dynamics in the ensemble, the real challenge is to develop device architectures that are tolerant to fluctuations, since they cannot be totally eliminated in these low dimensional soft systems. Results of temperature dependent STS measurements will also be discussed.

Dholakia, Geetha↗

Controlling the Self-Assembly of DNA Origami Octahedra via Manipulation of Inter-Vertex Interactions

Recent studies have demonstrated novel strategies for the organization of nanomaterials into three-dimensional (3D) ordered arrays with prescribed lattice symmetries using DNA-based self-assembly strategies. In one approach, the nanomaterial is sequestered into DNA origami frames or “material voxels” and then coordinated into ordered arrays based on the voxel geometry and the corresponding directional interactions based on its valency. While the lattice symmetry is defined by the valency of the bonds, a larger-scale morphological development is affected by assembly processes and differences in energies of anisotropic bonds. To facilely model this assembly process, we investigate the self-assembly behavior of hard particles with six interacting vertices via theory and Monte Carlo simulations and exploration of corresponding experimental systems. We demonstrate that assemblies with different 3D crystalline morphologies, but the same lattice symmetry can be formed depending on the relative strength of vertex-to-vertex interactions in orthogonal directions. We observed three distinct assembly morphologies for such systems: cube-like, sheet-like, and cylinder-like. A simple analytical theory inspired by well-established ideas in the areas of protein crystallization, based on calculating the second virial coefficient of patchy hard spheres, captures the simulation results and thus represents a straightforward means of modeling this self-assembly process. To complement the theory and simulations, experimental studies were performed to investigate the assembly of octahedral DNA origami frames with varying binding energies at their vertices. In conclusion, x-ray scattering confirms the robustness of the formed nanoscale lattices for different binding energies, while both optical and electron microscopy imaging validated the theoretical predictions on the dependence of the distinct morphologies of assembled state on the interaction strengths in the three orthogonal directions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A coarse-grained simulation model for colloidal self-assembly via explicit mobile binders

Colloidal particles with mobile binding molecules constitute a powerful platform for probing the physics of self-assembly. Binding molecules are free to diffuse and rearrange on the surface, giving rise to spontaneous control over the number of droplet–droplet bonds, i.e., valence, as a function of the concentration of binders. This type of valence control has been realized experimentally by tuning the interaction strength between DNA-coated emulsion droplets. Optimizing for valence two yields droplet polymer chains, termed ‘colloidomers’, which have recently been used to probe the physics of folding. To understand the underlying self-assembly mechanisms, here we present a coarse-grained molecular dynamics (CGMD) model to study the self-assembly of this class of systems using explicit representations of mobile binding sites. Further, we explore how valence of assembled structures can be tuned through kinetic control in the strong binding limit. More specifically, we optimize experimental control parameters to obtain the highest yield of long linear colloidomer chains. Subsequently tuning the dynamics of binding and unbinding via a temperature-dependent model allows us to observe a heptamer chain collapse into all possible rigid structures, in good agreement with recent folding experiments. Our CGMD platform and dynamic bonding model (implemented as an open-source custom plugin to HOOMD-Blue) reveal the molecular features governing the binding patch size and valence control, and opens the study of pathways in colloidomer folding. This model can therefore guide programmable design in experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanotubes Growth by Self-Assembly of DNA Strands at Room Temperature

Artificial biomolecular nanotubes are a promising approach to building materials mimicking the capacity of the cellular cytoskeleton to grow and self-organize dynamically. Nucleic acid nanotechnology has demonstrated a variety of self-assembling nanotubes with programmable, robust features and morphological similarities to actual cytoskeleton components. However, their production typically requires thermal annealing, which not only poses a general constraint on their potential applications but is also incompatible with physiological conditions. Here, we demonstrate that DNA nanotubes can self-assemble from a simple mixture of five short DNA strands at constant room temperature, growing for extended periods of time in bulk conditions as well as under confinement. Assembly is achieved using a monovalent salt buffer, which ensures a faithful nanoscale arrangement and avoids nanotube aggregation. We observe the formation of individual nanotubes up to 20 days with a diameter of 22 ± 4 nm and length of several tens of micrometers. We finally encapsulate the strands in microsized compartments, such as water-in-oil microdroplets and giant unilamellar vesicles serving as simple cell models. Notably, nanotubes not only isothermally self-assemble directly inside the microcompartments but also self-organize into dynamic higher-order structures resembling rings and dynamic networks. Our study provides an advantageous method for in situ assembly of programmable biomolecular scaffolds and materials using synthetic DNA strands without requirements of thermal treatment.

Chemistry↗

Homopolymer self-assembly of poly(propylene sulfone) hydrogels via dynamic noncovalent sulfone-sulfone bonding

Natural biomolecules such as peptides and DNA can dynamically self-organize into diverse hierarchical structures. Mimicry of this homopolymer self-assembly using synthetic systems has remained limited but would be advantageous for the design of adaptive bio/nanomaterials. Here, we report both experiments and simulations on the dynamic network self-assembly and subsequent collapse of the synthetic homopolymer poly(propylene sulfone). The assembly is directed by dynamic noncovalent sulfone–sulfone bonds that are susceptible to solvent polarity. The hydration history, specified by the stepwise increase in water ratio within lower polarity water-miscible solvents like dimethylsulfoxide, controls the homopolymer assembly into crystalline frameworks or uniform nanostructured hydrogels of spherical, vesicular, or cylindrical morphologies. These electrostatic hydrogels have a high affinity for a wide range of organic solutes, achieving >95% encapsulation efficiency for hydrophilic small molecules and biologics. This system validates sulfone–sulfone bonding for dynamic self-assembly, presenting a robust platform for controllable gelation, nanofabrication, and molecular encapsulation.

59 BASIC BIOLOGICAL SCIENCES↗