Observation of an Orientational Glass in a Superlattice of Elliptically-Faceted CdSe Nanocrystals.

Extensive prior work has shown that colloidal inorganic nanocrystals coated with organic ligand shells can behave as artificial atoms and, as such, form superlattices with different crystal structures and packing densities. Although ordered superlattices present a high degree of long-range positional order, the relative crystallographic orientation of the inorganic nanocrystals with respect to each other tends to be random. Recent works have shown that superlattices can achieve orientational alignment through combinations of nanocrystal faceting and ligand modification, as well as selective metal particle attachment to particular facets. These studies have focused on the assembly of high-symmetry nanocrystals, such as cubes and cuboctahedra. Here, we study the assembly of elliptically faceted CdSe/CdS core/shell nanocrystals with one distinctive crystallographic orientation along the major elliptical axis. We show that the nanocrystals form an unexpectedly well-ordered translational superlattice, with a degree of order comparable to that achieved with higher-symmetry nanocrystals. Additionally, we show that, due to the particles' faceted shape, the superlattice is characterized by an orientational glass phase in which only certain orientations are possible due to entropically frustrated crystallization. In this phase, the nanocrystals do not exhibit a local orientational ordering but rather have distinct orientations that emerge at different locations within the same domain. The distinct orientations are a result of a facet-to-facet lock-in mechanism that occurs during the self-assembly process. These facet-to-facet alignments force the nanocrystals to tilt on different lattice planes forming different projections that we termed apparent polydispersity. Our experimental realization of an orientational glass phase for multifaceted semiconducting nanocrystals can be used to investigate how this phase is formed and how it can be utilized for potential optical, electrical, and thermal transport applications.

Anomalous nanoparticle surface diffusion in LCTEM is revealed by deep learning-assisted analysis.

The motion of nanoparticles near surfaces is of fundamental importance in physics, biology, and chemistry. Liquid cell transmission electron microscopy (LCTEM) is a promising technique for studying motion of nanoparticles with high spatial resolution. Yet, the lack of understanding of how the electron beam of the microscope affects the particle motion has held back advancement in using LCTEM for in situ single nanoparticle and macromolecule tracking at interfaces. Here, we experimentally studied the motion of a model system of gold nanoparticles dispersed in water and moving adjacent to the silicon nitride membrane of a commercial LC in a broad range of electron beam dose rates. We find that the nanoparticles exhibit anomalous diffusive behavior modulated by the electron beam dose rate. We characterized the anomalous diffusion of nanoparticles in LCTEM using a convolutional deep neural-network model and canonical statistical tests. The results demonstrate that the nanoparticle motion is governed by fractional Brownian motion at low dose rates, resembling diffusion in a viscoelastic medium, and continuous-time random walk at high dose rates, resembling diffusion on an energy landscape with pinning sites. Both behaviors can be explained by the presence of silanol molecular species on the surface of the silicon nitride membrane and the ionic species in solution formed by radiolysis of water in presence of the electron beam.

Enhanced ordering in length-polydisperse carbon nanotube solutions at high concentrations as revealed by small angle X-ray scattering.

Carbon nanotubes (CNTs) are stiff, all-carbon macromolecules with diameters as small as one nanometer and few microns long. Solutions of CNTs in chlorosulfonic acid (CSA) follow the phase behavior of rigid rod polymers interacting via a repulsive potential and display a liquid crystalline phase at sufficiently high concentration. Here, we show that small-angle X-ray scattering and polarized light microscopy data can be combined to characterize quantitatively the morphology of liquid crystalline phases formed in CNT solutions at concentrations from 3 to 6.5% by volume. We find that upon increasing their concentration, CNTs self-assemble into a liquid crystalline phase with a pleated texture and with a large inter-particle spacing that could be indicative of a transition to higher-order liquid crystalline phases. We explain how thermal undulations of CNTs can enhance their electrostatic repulsion and increase their effective diameter by an order of magnitude. By calculating the critical concentration, where the mean amplitude of undulation of an unconstrained rod becomes comparable to the rod spacing, we find that thermal undulations start to affect steric forces at concentrations as low as the isotropic cloud point in CNT solutions.

In Situ Quantification of Interactions between Charged Nanorods in a Predefined Potential Energy Landscape.

Quantitative understanding of nanoscale interactions is a prerequisite for harnessing the remarkable collective properties of nanoparticle systems. Here, we report the combined use of liquid-phase transmission electron microscopy and electron beam lithography to elucidate the interactions between charged nanorods in a predefined potential energy landscape. In situ site-selective lift-off of surface-functionalized lithographed gold nanorods is achieved by patterning them with adhesion layer materials that undergo etching at different rates. Analysis of the subsequent nanorod motion, which is two-dimensionally confined as a result of the particle-substrate attraction, allows quantification of interparticle interactions in a lithographically engineered environment. For lithographed nanorods patterned with the same adhesion layer material, their self-assembly behavior following lift-off is tuned by changing their starting spatial arrangement. Our approach facilitates investigation of interparticle interactions in designed nanoparticle systems and affords fundamental insights into the role of the potential energy landscape in determining the kinetic pathway for nanoparticle self-assembly.

Perovskite-Carbon Nanotube Light-Emitting Fibers.

Active fibers with electro-optic functionalities are promising building blocks for the emerging and rapidly growing field of fiber and textile electronics. Yet, there remains significant challenges that require improved understanding of the principles of active fiber assembly to enable the development of fiber-shaped devices characterized by having a small diameter, being lightweight, and having high mechanical strength. To this end, the current frameworks are insufficient, and new designs and fabrication approaches are essential to accommodate this unconventional form factor. Here, we present a first demonstration of a pathway that effectively integrates the foundational components meeting such requirements, with the use of a flexible and robust conductive core carbon nanotube fiber and an organic-inorganic emissive composite layer as the two critical elements. We introduce an active fiber design that can be realized through an all solution-processed approach. We have implemented this technique to demonstrate a three-layered light-emitting fiber with a coaxially coated design.

Effect of Carbon Nanotube Diameter and Stiffness on Their Phase Behavior in Crowded Solutions.

The unique carbon nanotube (CNT) properties are mainly determined by their geometry, e.g., their aspect ratio, diameter, and number of walls. So far, chlorosulfonic acid is the only practical true solvent for carbon nanotubes, forming thermodynamically stable molecular solutions. Above a critical concentration the system forms an ordered, nematic liquid-crystalline phase. That phase behavior is the basis for liquid-phase processing and the optimal translation of the carbon nanotube molecular properties to the macroscopic scale. The final material properties depend on the phase behavior of the "dope" from which it is prepared, which depends on the CNT parameters themselves. Earlier work determined that CNT aspect ratio controls the phase behavior, in accordance with classical rigid-rod theories. Here we use cryogenic transmission electron microscopy and Raman spectroscopy to understand the relation between the geometry of the CNTs, the chemical interaction with chlorosulfonic acid, and the phase behavior of crowded solutions. We show that the CNT diameter and number of walls also play an independent role in the phase transition and phase morphology of the system because of their effect on the CNT bending stiffness.

Purification and Dissolution of Carbon Nanotube Fibers Spun from the Floating Catalyst Method.

In this study, we apply a simple but effective oxidative purification method to purify carbon nanotube (CNT) fibers synthesized via a floating catalyst technique. After the purification treatment, the resulting CNT fibers exhibited significant improvements in mechanical and electrical properties with an increase in strength, Young's modulus, and electrical conductivity by approximately 81, 230, and 100%, respectively. With the successful dissolution of the CNT fibers in superacid, an extensional viscosity method could be applied to measure the aspect ratio of the CNTs constituting the fibers, whereas high-purity CNT thin films could be produced with a low resistance of 720 Ω/sq at a transmittance of 85%. This work suggests that the oxidative purification approach and dissolution process are promising methods to improve the purity and performance of CNT macroscopic structures.

Line Tension of Twist-Free Carbon Nanotube Lyotropic Liquid Crystal Microdroplets on Solid Surfaces.

Line tension, i.e., the force on a three-phase contact line, has been a subject of extensive research due to its impact on technological applications including nanolithography and nanofluidics. However, there is no consensus on the sign and magnitude of the line tension, mainly because it only affects the shape of small droplets, below the length scale dictated by the ratio of line tension to surface tension σ/τ. This ratio is related to the size of constitutive molecules in the system, which translates to a nanometer for conventional fluids. Here, we show that this ratio is orders of magnitude larger in lyotropic liquid crystal systems comprising micrometer-long colloidal particles. Such systems are known to form spindle-shaped elongated liquid crystal droplets in coexistence with the isotropic phase, with the droplets flattening when in contact with flat solid surfaces. We propose a method to characterize the line tension by fitting measured droplet shape to a macroscopic theoretical model that incorporates interfacial forces and elastic deformation of the nematic phase. By applying this method to hundreds of droplets of carbon nanotubes dissolved in chlorosulfonic acid, we find that σ/τ ∼ -0.84 ± 0.06 µm. This ratio is 2 orders of magnitude larger than what has been reported for conventional fluids, in agreement with theoretical scaling arguments.

Increased solubility and fiber spinning of graphenide dispersions aided by crown-ethers.

Graphenide solutions in NMP have been prepared by dispersing potassium intercalated graphite with the assistance of 18-crown-6. The highest graphenide solubility achieved is 1.5 mg mL-1. Graphenide solutions have been applied to spin graphene/SWCNT hybrid fibers.

Experimental realization of crossover in shape and director field of nematic tactoids.

Spindle-shaped nematic droplets (tactoids) form in solutions of rod-like molecules at the onset of the liquid crystalline phase. Their unique shape and internal structure result from the interplay of the elastic deformation of the nematic and anisotropic surface forces. The balance of these forces dictates that tactoids must display a continuous variation in aspect ratio and director-field configuration. Yet, such continuous transition has eluded observation for decades: tactoids have displayed either a bipolar configuration with particles aligned parallel to the droplet interface or a homogeneous configuration with particles aligned parallel to the long axis of the tactoid. Here, we report the first observation of the continuous transition in shape and director-field configuration of tactoids in true solutions of carbon nanotubes in chlorosulfonic acid. This observation is possible because the exceptional length of carbon nanotubes shifts the transition to a size range that can be visualized by optical microscopy. Polarization micrographs yield the interfacial and elastic properties of the system. Absorbance anisotropy measurements provide the highest nematic order parameter (S=0.79) measured to date for a nematic phase of carbon nanotubes at coexistence with its isotropic phase.