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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Monitoring the dynamics of miscible P3HT:PCBM blends: A quasi elastic neutron scattering study of organic photovoltaic active layers

Our work reports on the detailed molecular dynamic behavior of miscible blends of Poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) and their pure counterparts by quasi-elastic neutron scattering measurements (QENS). The study provides the measure of relaxation processes on pico-to-nanosecond time scales. A single relaxation process was observed in pure P3HT and PCBM while two relaxation processes, one fast and one slow, were observed in the blends. The fast process was attributed to the dynamics of P3HT while the slow process was correlated to the dynamics of PCBM. The results show that the relaxation process is a balance between two opposing effects: increased mobility due to thermal activation of P3HT molecules and decrease mobility due to the presence of PCBM which is correlated to the percent crystallinity of P3HT and local packing density of PCBM in the amorphous phase. The threshold for the domination of the thermally activated relaxation is between 5 and 9 vol.% of PCBM loading. Two distinct spatial dependences of the relaxation processes, in which the crossover length scale depends neither on temperature nor composition, were observed for all the samples. They were attributed to the collective motions of the hexyl side chains and the rotational motions of the C-C single bonds of the side chains. Finally, these results provide an understanding of the effects of PCBM loading and temperature on the dynamics of the polymer-fullerene blends which provides a tool to optimize the efficiency of charge carrier and exciton transport within the organic photovoltaic (OPV) active layer to improve the high performance of organic solar cells.

14 SOLAR ENERGY↗
DOE OSTI2018

Direct Imaging of Low-Dimensional Nanostructures

Low-dimensional nanostructures are technologically desirable for their novel physical properties, as well as the benefits of packing density due to scale. In quantum computing, an ideal structure might consist of single dopant atoms precisely positioned a few nanometers below a surface [1]. There is also a need for truly atomic-scale interconnects and ancillary structures. However, due to their nanoscale dimensions, the physical properties of nanowires and related structures will depend on the environment in which they are embedded as well as their composition. This problem is particularly relevant for samples grown on ultra-clean surfaces, which may not survive outside of high-vacuum systems or which might be substantially affected by adatoms. The question then arises as to what happens to surface nanostructures or single dopant atoms during encapsulation or overgrowth.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Hydrogen Storage Performance of Preferentially Oriented Mg/rGO Hybrids

Chemical interactions on the surface of a functional nanoparticle are closely related to its crystal facets, which can regulate the corresponding energy storage properties like hydrogen absorption. In this study, we reported a one-step growth of magnesium (Mg) particles with both close- and nonclose-packed facets, that is, {0001} and {$2\overline{116}$} planes, on atomically thin reduced graphene oxide (rGO). The detailed microstructures of Mg/rGO hybrids were revealed by X-ray diffraction, selected-area electron diffraction, high-resolution transmission electron microscopy, and fast Fourier transform analysis. Hydrogen storage performance of Mg/rGO hybrids with different orientations varies: Mg with preferential high-index {$2\overline{116}$} crystal surface shows remarkably increased hydrogen absorption up to 6.2 wt % compared with the system exposing no preferentially oriented crystal surfaces showing inferior performance of 5.1 wt % within the first 2 h. First-principles calculations revealed improved hydrogen sorption properties on the {$2\overline{116}$} surface with a lower hydrogen dissociation energy barrier and higher stability of hydrogen atoms than those on the {0001} basal plane, supporting the hydrogen uptake experiment. In addition, the hydrogen penetration energy barrier is found to be much lower than that of {0001} because of low surface atom packing density, which might be the most critical process to the hydrogenation kinetics. Here, the experimental and calculation results present a new handle for regulating the hydrogen storage of metal hydrides by controlled Mg facets.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Star Block Copolymers at Homopolymer Interfaces: Conformation and Compatibilization

Star block copolymers (s-BCPs), comprised of multiple linear diblock copolymers joined at a central point, are shown to segregate to the interface between two immiscible homopolymers that are identical to the blocks of the s-BCPs. The s-BCPs undergo a configurational transition at the interface, with different blocks of copolymers being embedded in their respective homopolymers, thereby bridging the interface and promoting adhesion. A series of 4-arm s-BCPs were synthesized with hydrogenated or deuterated polystyrene (PS/dPS) as the core block and poly(2-vinylpyridine) (P2VP) as the corona block, which was directly placed at the interface between the two homopolymers. Neutron reflectivity (NR) was used to determine the concentration profiles of the PS homopolymer, s-BCP core blocks, and P2VP total segments under equilibrium. The investigation varies the molecular weight (MW) and the total number of s-BCPs at the interface. Self-consistent-field theory (SCFT) was also employed to calculate the concentration profiles of the components at the interface, which were in excellent agreement with experimental results. The NR showed that the interfacial width between the homopolymers increased with the increasing number of s-BCPs at the interface up to a saturation limit. Beyond this limit, additional s-BCPs were released into the corona-miscible phase as unimolecular micelles. For a comparable interlayer thickness of s-BCPs at the interface, lower MW s-BCPs generated a broader interface. SCFT analysis suggested that, at the same packing density, the arms of the low MW s-BCPs align more parallel to the interface, while the arms of high MW s-BCPs adopt a more normal orientation, like their linear BCP counterparts. Furthermore, it was also observed that the core blocks, constrained by the junction points, were oriented more parallel and closer to the interface than the corona blocks. The phase behavior of the polymer blends revealed that s-BCP additives can efficiently reduce the domain size, with the low MW yielding smaller domain sizes due to the greater reduction in the interfacial energy and the high MW arresting phase separation due to their higher binding energy and a jamming of the interfacial assemblies. Asymmetric double cantilever beam (ADCB) tests demonstrated that s-BCPs promoted adhesion more efficiently than their linear BCP counterparts due to stronger binding energy per molecule, suggesting a more efficient compatibilizer for polymer upcycling. In conclusion, the results from these studies provide fundamental insights into the assembly of s-BCPs at homopolymer interfaces, the reduction of domain size, and promotion of adhesion, providing a strategy for the use of s-BCPs as stealth surfactants and universal compatibilizers.

interface↗
DOE OSTI2017

Tunable Anisotropic Photon Emission from Self-Organized CsPbBr 3 Perovskite Nanocrystals

In this paper, we report controllable anisotropic light emission of photons originating from vertically aligned transition dipole moments in spun-cast films of CsPbBr 3 nanocubes. By depositing films of nanocrystals on precoated substrates we can control the packing density and resultant radiation pattern of the emitted photons. We develop a technical framework to calculate the average orientation of light emitters, i.e., the angle between the transition dipole moment vector (TDM) and the substrate. This model is applicable to any emissive material with a known refractive index. Theoretical modeling indicates that oriented emission originates from an anisotropic alignment of the valence band and conduction band edge states on the ionic crystal lattice and demonstrates a general path to model the experimentally less accessible internal electric field of a nanosystem from the photoluminescent anisotropy. The uniquely accessible surface of the perovskite nanoparticles allows for perturbation of the normally isotropic emissive transition. Finally, the reported sensitive and tunable TDM orientation and control of emitted light will allow for applications of perovskite nanocrystals in a wide range of photonic technologies inaccessible to traditional light emitters.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2017

Altering DNA-Programmable Colloidal Crystallization Paths by Modulating Particle Repulsion

Colloidal crystal engineering with DNA can be used to realize precise control over nanoparticle (NP) arrangement. Here, we investigate a case of DNA-based assembly where the properties of DNA as a polyelectrolyte brush are employed to alter a hybridization-driven NP crystallization pathway. Using the co-assembly of DNA-conjugated proteins and spherical gold 2 nanoparticles (AuNPs) as a model system, we explore how steric repulsion between non-complementary, neighboring DNA-NPs due to overlapping DNA shells can influence their ligand-directed behavior. Specifically, our experimental data coupled with coarse-grained molecular dynamics (MD) simulations reveal that by changing factors related to NP repulsion, two structurally distinct outcomes can be achieved. When steric repulsion between DNA-AuNPs is significantly greater than that between DNA-proteins, a lower packing density crystal lattice is favored over the structure that is predicted by design rules based on DNA-hybridization considerations alone. This is enabled by the large difference in DNA density on AuNPs versus proteins and can be tuned by modulating the flexibility, and thus conformational entropy, of the DNA on the constituent particles. At intermediate ligand flexibility, the crystallization pathways are energetically similar and the structural outcome can be adjusted using the density of DNA duplexes on DNA-AuNPs and by screening the Coulomb potential between them. Such lattices are shown to undergo dynamic reorganization upon changing salt concentration. These data help elucidate the structural considerations necessary for understanding repulsive forces in DNA-assembly and lay the groundwork for using them to increase architectural diversity in engineering colloidal crystals.

colloidal crystals↗
DOE OSTI2018

The Interfacial Assembly of Polyoxometalate Nanoparticle Surfactants

Polyoxometalates (POMs) using {Mo 72 V 30 } as an example, dissolved in water, can interact with amine-terminated polydimethylsiloxane (PDMS-NH 2 ) dissolved in toluene at the water/toluene interface to form POM-surfactants that significantly lower the interfacial tension and can be used to stabilize liquids via interfacial elasticity. The jamming of the POM-surfactants at the water/oil interface with consequent wrinkling occurs with a decrease in the interfacial area. Furthermore, the packing density of the POM-surfactants at the interface can be tuned by varying the strength of screening with the addition of cations with differing hydrated radii.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2026

Pseudocapacitive Titanium Oxynitride Nanowires for Ultrahigh Capacitance Supercapacitors

High-quality, multifunctional two-dimensional (2D) titanium oxynitide (TiNO) thin films and one-dimensional (1D) TiNO nanowires have been synthesized using a pulsed laser deposition, a simple, fast, and congruent evaporation method. First-principles calculations as a function of surface orientation and termination indicate that surface oxidation of TiNO nanowires can stabilize the (110) orientation observed experimentally. The specific capacitance value for the TiNO nanowire samples (2725 mF/cm 2 ) has been found to be nearly six times more than that of the TiNO thin film samples (400 mF/cm 2 ), which is attributed to the high packing density of TiNO nanowires over a given area. The nanowire samples have also been found to exhibit a significantly higher energy density (1.35 μWh/cm 2 ) than the TiNO thin-film samples (0.33 μWh/cm 2 ). Thus, the TiNO material system in thin-film and nanowire forms has been demonstrated to be a promising candidate for use as an electrode material in supercapacitors and other charge-storage applications.

capacitors↗
DOE OSTI2022

CO 2 Laser Sintering of Garnet-Type Solid-State Electrolytes

We report the processing of garnet-type solid-state electrolytes remains challenging as densification conventionally requires high sintering temperatures and long processing times, which can result in severe Li loss, the formation of secondary phases, and thus high porosity and low ionic conductivity. Here, we report an ultrafast sintering method based on CO 2 laser scanning with the assistance of a heating stage. We demonstrate the rapid densification of low-packing-density Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) films, which are difficult to densify by conventional furnace sintering methods. This unique approach has three fingerprint characteristics: (1) mitigation of Li loss through ultrafast sintering (dwelling time $\ll$1 s); (2) a unique anisotropic shrinkage behavior that greatly reduces film thickness; (3) wave-like surface topology from point scanning strategy that enables 3D interfacial contacts with electrode materials. Herein, highly dense (95.68%) and highly conductive (0.26 mS·cm –1 at 25 °C) LLZTO films are obtained through CO2 laser sintering. This work provides a unique, scalable, and widely applicable ultrarapid laser sintering technique to overcome the difficulties associated with classic methods for the integration of SSEs for practical all-solid-state Li-metal battery applications.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Architecting the Third Dimension of Electrochemical Energy Storage

Three-dimensional (3D) architectural design has emerged as a powerful strategy to push electrochemical energy storage (EES) devices beyond the intrinsic limitations of conventional two-dimensional (2D) electrodes. While planar architectures enable high packing density and mature manufacturing, they suffer from limited ion transport and low active-material loading. In contrast, 3D architectures introduce low-tortuosity networks and high surface area that enhance charge and mass transport while supporting thick, high mass-loading electrodes. However, their practicality remains hindered by challenges in volumetric density, mechanical stability, and large-scale manufacturability. Here, this Perspective examines the key evaluation and design principles that govern 3D device performance. We discuss the fundamental trade-offs between porosity, volumetric density, and mechanical stability that shape 3D design and highlight emerging strategies for integrating materials engineering, structural optimization, device integration, computational modeling, and scalable manufacturing. By aligning structural functionality with manufacturability, 3D architectures can evolve from laboratory prototypes to commercially viable energy storage systems.

25 ENERGY STORAGE↗
DOE OSTI2022

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. In this work, 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.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Ultrathin Gold Nanowires with the Polytetrahedral Structure of Bulk Manganese

Despite the intensive interest in thin gold nanowires for a variety of technologically important applications, key details of the mechanism of their formation and atomic-scale structure remain unknown. In this work we synthesize highly uniform, very long, and ultrathin gold nanowires in a liquid-phase environment and study their nucleation and growth using in situ high-energy synchrotron X-ray diffraction. By controlling the type of solvents, reducing agents, and gold precursor concentration, it is shown that the nucleation and growth of gold nanowires involve the emergence and self-assembly of transient linear gold complexes, respectively. In sharp contrast with the face-centered-cubic bulk gold, the evolved nanowires are found to possess a tetrahedrally close packed structure incorporating distorted icosahedra and larger size coordination polyhedra of the type observed with the room-temperature phase of bulk manganese. We relate the complexes to synergistic effects between the selected precursor and reducing agents that become appreciable over a narrow range of their molar ratios. We attribute the unusual structural state of gold nanowires to geometrical frustration effects arising from the conflicting tendencies of assemblies of metal atoms to evolve toward attaining high atomic packing density while keeping the atomic-level stresses low, ultimately favoring the growth of cylindrical nanowires with a well-defined diameter and atomically smooth surface. Our work provides a roadmap for comprehensive characterization and, hence, better understanding of 1D metallic nanostructures with an unusual atomic arrangement and may have important implications for their synthesis and performance in practical applications.

1D nanomaterials↗
DOE OSTI2023

Optimal Binding Affinity for Sieving Separation of Propylene from Propane in an Oxyfluoride Anion-Based Metal–Organic Framework

Highly efficient adsorptive separation of propylene from propane offers an ideal alternative method to replace the energy-intensive cryogenic distillation technology. Molecular sieving-type separation via high-performance adsorbents is targeted for superior selectivity, but the limit in adsorption capacity remains a great challenge. Here, we report an oxyfluoride-based ultramicroporous metal–organic framework UTSA-400, [Ni(WO 2 F 4 )(pyz) 2 ] (pyz = pyrazine), featuring one-dimensional pore channels that can accommodate the propylene molecules with optimal binding affinity while specifically excluding the propane molecules. The exposed oxide/fluoride pairs in UTSA-400 serve as strong functional sites for strengthened propylene–host interactions, accounting for a significantly enhanced propylene uptake, while the propane molecules are excluded due to the regulated host framework dynamics. The strong propylene binding enables near-saturation of propylene in the pore confinement at ambient conditions, leading to full utilization of pore space and superior packing density. Combined in situ infrared spectroscopy measurements and dispersion-corrected density functional theory calculations clearly unveil the nature of boosted host–guest binding. Direct production of polymer-grade (>99.5%) propylene with remarkable dynamic productivity is demonstrated by column breakthrough experiments. Furthermore, this work presents an example of pore engineering with atomic precision to break the trade-off in adsorptive separation through guest binding optimization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Framework-Topology-Controlled Singlet Fission in Metal–Organic Frameworks

Singlet fission (SF) has been explored as a viable route to improve photovoltaic performance by producing more excitons. Efficient SF is achieved through a high degree of interchromophoric coupling that facilitates electron super exchange to generate triplet pairs. However, strongly coupled chromophores often form excimers that can serve as an SF intermediate or a low-energy trap site. The succeeding decoherence process, however, requires an optimum electronic coupling to facilitate the isolation of triplet production from the initially prepared correlated triplet pair. Conformational flexibility and dielectric modulation can provide a means to tune the SF mechanism and efficiency by modulating the interchromophoric electronic interaction. Such a strategy cannot be easily adopted in densely stacked traditional organic solids. Here, we show that the assembly of the SF-active chromophores around well-defined pores of solution-stable metal-organic frameworks (MOFs) can be a great platform for a modular SF process. A series of three new MOFs, built out from 9,10-bis(ethynylenephenyl)anthracene-derived struts, show a topology-defined packing density and conformational flexibility of the anthracene core to dictate the SF mechanism. Various steady-state and transient spectroscopic data suggest that the initially prepared singlet population can prefer either an excimer-mediated SF or a direct SF (both through a virtual charge-transfer (CT) state). Finally, these solution-stable frameworks offer the tunability of the dielectric environment to facilitate the SF process by stabilizing the CT state. Given that MOFs are a great platform for various photophysical and photochemical developments, generating a large population of long-lived triplets can expand their utilities in various photon energy conversion schemes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Investigation of Metal Free Naphthalocyanine Vapor Deposited on Au(111)

Naphthalocyanines (Ncs) are promising candidates for future components in electronic devices and applications. To maximize the efficiency of Nc devices, it is critical to understand their structural and electronic properties and how these are impacted by deposition methods. The formation of a metal free naphthalocyanine (H2Nc) self-assembled monolayer on a Au(111) crystal was investigated by scanning tunneling microscopy under ultra-high-vacuum conditions at room temperature. A rigorous purification and processing procedure was developed to produce high purity, low defect, and well-ordered monolayers. High-resolution STM images reveal epitaxial growth of H2Nc on Au(111) with the observed structure having a molecular spacing of 1.6 ± 0.05 nm, with molecules orientated slightly off (roughly 2.5°) the low density packing direction of Au(111). A commensurate structure having 4 molecules per unit cell and unit cell parameters of A = 3.25 ± 0.05 nm, B = 3.17 ± 0.05 nm, and α = 87.5 ± 2° is proposed. Orbital-mediated tunneling spectroscopy was used to examine the electronic properties of individual molecules within the thin film. The first ionization potential and electron affinity of H2Nc adsorbed on Au(111) were measured to be -0.68 ± 0.03 and 1.12 ± 0.02 eV, relative to the Fermi energy.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2018

Niobium tungsten oxides for high-rate lithium-ion energy storage

Here, the maximum power output and minimum charging time of a lithium-ion battery – key parameters for its use in, for example, transportation applications – depend on mixed ionic– electronic diffusion. While the discharge/charge rate and capacity can be tuned by varying the composite electrode structure, ionic transport within the active particles represents a fundamental limitation. Thus, to achieve high rates, particles are frequently reduced to nanosize dimensions despite this being disadvantageous in terms of volumetric packing density as well as cost, stability, and sustainability considerations. As an alternative to nanoscaling, we show that complex niobium tungsten oxides with topologically frustrated polyhedral arrangements and dense µm-scale particle morphologies can rapidly and reversibly intercalate large quantities of lithium. Multielectron redox, buffered volume expansion, and extremely fast lithium transport approaching that of a liquid lead to extremely high volumetric capacities and rate performance for both crystallographic shear structure and bronze-like niobium tungsten oxides. The active materials Nb 16 W 5 O 55 and Nb 18 W 16 O 93 offer new strategies toward designing electrodes with advantages in energy density, scalability, electrode architecture/complexity and cost as alternatives to the state-ofthe art high-rate anode material Li 4 Ti 5 O 12 . The direct measurement of solid-state lithium diffusion coefficients (DLi) with pulsed field gradient NMR demonstrates room temperature DLi values of 10–12–10–13 m 2 × s -1 in the niobium tungsten oxides, which is several orders-ofmagnitude faster than typical electrode materials and corresponds to a characteristic diffusion length of ~10 µm for a 1 minute discharge. Materials and mechanisms that enable lithiation of µm particles in minutes have implications for high power applications, fast charging devices, all-solid-state batteries, and general approaches to electrode design and material discovery.

25 ENERGY STORAGE↗
DOE OSTI2016

Microstructural characterization of random packings of cubic particles

Understanding the properties of random packings of solid objects is of critical importance to a wide variety of fundamental scientific and practical problems. The great majority of the previous works focused, however, on packings of spherical and sphere-like particles. We report the first detailed simulation and characterization of packings of non-overlapping cubic particles. Such packings arise in a variety of problems, ranging from biological materials, to colloids and fabrication of porous scaffolds using salt powders. In addition, packing of cubic salt crystals arise in various problems involving preservation of pavements, paintings, and historical monuments, mineral-fluid interactions, CO 2 sequestration in rock, and intrusion of groundwater aquifers by saline water. Not much is known, however, about the structure and statistical descriptors of such packings. We have developed a version of the random sequential addition algorithm to generate such packings, and have computed a variety of microstructural descriptors, including the radial distribution function, two-point probability function, orientational correlation function, specific surface, and mean chord length, and have studied the effect of finite system size and porosity on such characteristics. Here, the results indicate the existence of both spatial and orientational long-range order in the packing, which is more distinctive for higher packing densities.

36 MATERIALS SCIENCE↗