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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 127 records · Page 7

Stable Cuprous Hydroxide Nanostructures by Organic Ligand Functionalization

Abstract Copper compounds have been extensively investigated for diverse applications. However, studies of cuprous hydroxide (CuOH) have been scarce due to structural metastability. Herein, a facile, wet‐chemistry procedure is reported for the preparation of stable CuOH nanostructures via deliberate functionalization with select organic ligands, such as acetylene and mercapto derivatives. The resulting nanostructures are found to exhibit a nanoribbon morphology consisting of small nanocrystals embedded within a largely amorphous nanosheet‐like scaffold. The acetylene derivatives are found to anchor onto the CuOH forming CuC linkages, whereas CuS interfacial bonds are formed with the mercapto ligands. Effective electronic coupling occurs at the ligand‐core interface in the former, in contrast to mostly non‐conjugated interfacial bonds in the latter, as manifested in spectroscopic measurements and confirmed in theoretical studies based on first principles calculations. Notably, the acetylene‐capped CuOH nanostructures exhibit markedly enhanced photodynamic activity in the inhibition of bacteria growth, as compared to the mercapto‐capped counterparts due to a reduced material bandgap and effective photocatalytic generation of reactive oxygen species. Results from this study demonstrate that deliberate structural engineering with select organic ligands is an effective strategy in the stabilization and functionalization of CuOH nanostructures, a critical first step in exploring their diverse applications.

Liu, Qiming↗

Self-assembly of co-continuous nanostructured copolymer templates with compositional and architectural dispersity

In our previous DOE-supported project (DE-SC0016208), we demonstrated that a particular architecture dubbed ‘randomly end-linked copolymer networks’ (RECNs) led to especially robust self-assembly of disordered cocontinuous nanostructures. Such structures, wherein both microphases are fully percolating in three dimensions, are attractive for a wide-variety of energy-relevant applications including purification membranes, separators in batteries and fuel cells, catalyst supports, and high surface area electrodes. In the current project we sought to substantially extend our fundamental understanding of how different types of randomness in blocky copolymer architecture contribute to the robust formation of disordered cocontinuous nanostructures. To do so, we filled in the sizable gap between the previously studied cases of randomly linked linear multiblock copolymers and RECNs by studying two intermediate cases: (i) random miktoarm star polymers, which contain dispersity in the number of the two chemically-incompatible strands located at each junction and therefore the preferred interfacial curvature of each polymer, and (ii) randomly branched copolymers, which also possess bridging strands that stretch across domains and apply local ‘elastic’ forces to the interfaces. In addition, we studied a different network architecture, statistically crosslinked copolymer networks, that is more straightforward to prepare using chain growth polymerization methods, enabling more facile formation of cocontinuous nanostructures. Finally, we extended our approaches from model systems based on polystyrene and poly(lactic acid) to copolymer architectures containing either (i) polysulfone, an engineering polymer that provides excellent mechanical properties for membrane applications, or (ii) polyacrylonitrile, providing a convenient route to nanoporous carbon materials.

36 MATERIALS SCIENCE↗

Hierarchical thermal-conductive polymer nanocomposites for thermal management

Managing heat in electrical conductors is a major challenge to meet the demands for sustainable energy use and electrical reliability, most notably power electronics and energy-critical electrical machines. Achieving such disparate functionalities, such as high temperature thermal and electrical reliability, require rational design and manufacturing of thermal conductor material and its hierarchical structures. Here we present hierarchical thermal-conductive nanocomposites, consisting of nanostructured ceramic conformal coating and aligned ultrahigh molecular weight polyethylene fiber, to tailor heat dissipation in electric conductors. The hybrid aligned thermal interface exhibits a highly desirable temperature dependent anisotropic high thermal conductivity with 0.98W m –1 K –1 and dielectric strength with 3.4. In addition, electrically insulating thermal interfaces demonstrate high-performing and reliable electrical systems under the dynamic load conditions. The surface temperature of heterogeneous ceramic-polymer encapsulated conductor is 17.8 °C lower than that of polymer-encapsulated conductor at the same electrical load. Consequently, the findings shown here hold great promises for directing heat extraction in electrical machine systems, advancing thermal management for emerging electronic applications.

36 MATERIALS SCIENCE↗

Tailoring Charge Transport and Magnetism in Complex Half-Heusler/Full-Heusler Nanocomposites (Final Report)

This project exploits (1) the facile co-crystallization of the half-Heusler (HH) and full-Heusler (FH) structures, (2) the high coherency and stability of the HH/FH interfaces, and (3) the solid-state inter-conversion between HH and FH structures through local atomic diffusion, to investigate, for selected compositions of the HH and FH phases, the effect of size, dimensionality, dispersion and volume fraction of FH nanostructures on the electronic, phonon and magnetic behavior of the resulting HH/FH nanocomposites. Our goal is to identify and control key material and growth parameters governing phase formation, microstructural evolution, and to understand the mechanism by which these changes of the internal structure modify the material’s performance. To elucidate the mechanism by which the FH nanostructures regulate electronic charge transport and induce ferromagnetism within non-magnetic and magnetic semiconducting HH matrices, suitable series of HH/0D-FH and HH/2D-FH nanocomposites will be fabricated using synthesis conditions suggested by theoretical calculations of the formation energy and stability of various FH phases (varying M) in HH matrices with known chemical composition. The structure of the HH/FH interfaces (size, chemical composition, volume fraction and dispersion) will be investigated along with the evaluation of the electronic (carrier density, mobility, thermopower, electrical conductivity, effective mass), thermal and magnetic (susceptibility, magnetization etc.) properties of the resulting HH/FH nanocomposites.

36 MATERIALS SCIENCE↗

One-dimensional twisted and tubular structures of zinc oxide by semiconductor-catalyzed vapor–liquid–solid synthesis

The exploration of unconventional catalysts for the vapor-liquid-solid synthesis of one-dimensional materials promises to yield new morphologies and functionality. Here, we show, for the model ZnO system, that unusual nanostructures can be produced via a semiconductor (Ge) catalyst. As well as the usual straight nanowires, we describe two other distinct morphologies: twisted nanowires and twisted nanotubes. The twisted nanotubes show large hollow cores and surprisingly high twisting rates, up to 9°/μm, that cannot be easily explained through the Eshelby twist model. A combination of ex situ and in situ transmission electron microscopy measurements suggest that the hollow core results from a competition between growth and etching at the Ge-ZnO interface during synthesis. The twisting rate is consistent with a softening of elastic rigidity. Finally, these results indicate that the use of unconventional, nonmetallic catalysts provides opportunities to synthesize unusual oxide nanostructures with potentially useful properties.

36 MATERIALS SCIENCE↗

Localized Orbital Excitation Drives Bond Formation in Plasmonic Catalysis

Localized surface plasmons generated on metallic nanostructures can be used to accelerate molecular transformations; however, the efficiency is limited by the challenge to control the energy/charge transfer at the interfaces. Here, we combine density functional theory (DFT) calculations and experiments to reveal the mechanism of nitrophenol reduction on Au nanoparticles under visible-light irradiation and propose a strategy to further enhance the reaction rates. DFT calculations show a reduced activation barrier under electronic excitation on Au(111), thus explaining the measured higher rates under visible-light irradiation. Furthermore, we propose a heterostructure with Au nanoparticles covered by a thin film of hexagonal boron nitride; the latter is used to decouple the molecular orbitals from the metal to enable charge localization in the molecule. DFT calculations show that, by this electronic decoupling, the activation barrier can be lowered by a factor of five. Furthermore, this work thus provides a valuable strategy for optimizing catalytic efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantized electronic transitions in electrodeposited copper indium selenide nanocrystalline homojunctions

Pairing semiconductors with electrochemical processing offers an untapped opportunity to create novel nanostructures for practical devices. Here we report the results of one such pairing: the in-situ formation of highly-doped, interface-matched, sharp nanocrystalline homojunctions (NHJs) with single step electrodeposition of two copper-indium-selenide (CISe) compounds on flexible foil. It produces a homogenous film, comprising inherently ordered, 3-dimensional interconnected network of pn -CISe NHJs. These CISe NHJs exhibit surprising non-linear emissions, quantized transitions, large carrier mobility, low trap-state-density, long carrier lifetime and possible up-conversion. They facilitate efficient separation of minority carriers, reduce recombination and essentially function like quantum materials. This approach mitigates the material issues and complex fabrication of incumbent nanoscale heterojunctions; it also overcomes the flexibility and scale-up challenges of conventional planar pn junctions. The self-stabilized CISe NHJ film can be roll-to-roll processed in ambient atmosphere, thus providing a promising platform for a range of optoelectronic technologies. This concept exemplified by CISe compounds can be adapted to create nano-scale pn junctions with other inorganic semiconductors.

36 MATERIALS SCIENCE↗

NanoMechanics: Elasticity and Friction in Nano‐Objects

A large scientific and technological effort is underway to investigate the properties of two‐dimensional (2D) materials to become building blocks in integrated nano‐electronic and photonic circuits, composites, coatings, energy harvesting nano‐ systems, nano‐sensors, and nano‐electro‐mechanical systems (NEMS).While several experiments and calculations have revealed exciting novel phenomena in these nanostructures, many scientific and technological questions remain open. In particular, understanding and controlling the structure and mechanical properties of 2D materials at the interface with a solid surface is of key importance to enable the aforementioned nanotechnologies, as well as to fulfill the potential of strain engineering to tailor their properties. The vision of this DoE research program was to investigate novel mechanical properties and phenomena in 1D and 2D materials with the overarching goal of defining a new basic understanding of mechanical behavior in nano and quantum systems. The group of the PI has developed in the last years several studies on the mechanical properties of Carbon nanotubes and oxide nanobelts, more recently the PI has focused her attention on the properties of two‐dimensional materials, such as graphene and MoS 2 , which are a few‐atomic‐layer thick films and hold a great potential for technological and energy applications. The most studied 2D material is graphene, existing as a single layer of graphite or a few‐layer thick epitaxial graphene film. Graphene possesses a large in‐plane Young’s modulus as well as high intrinsic carrier mobility, and high in‐plane thermal conductivity. Besides graphene, also 2D films of graphene oxide (GO), hexagonal Boron Nitride (h‐BN), and transition metal dichalcogenides such as MoS 2 exhibit unique and excellent properties and hold great promise for nanotechnology applications. This research program was aimed at developing a new basic understanding of the mechanical properties of 1D and 2D materials at the interface with solid substrates, with a focus on the role of defects, materials structure, and substrate interaction. Ultimately, we aimed at developing the basic knowledge and experimental tools for manipulating 1D and 2D materials’ structure, stacking, substrate interaction, defects, and number of layers to realize an entirely new class of ultra‐hard, ultra‐thin, and ultra‐light active materials with ad‐ hoc mechanical properties for a variety of applications.

2D Materials↗

Optimization of La 2–x Sr x CuO 4 Single Crystal Film Growth via Molecular Beam Epitaxy

Atomic layer-by-layer molecular beam epitaxy (ALL-MBE) combined with ozone is one of the best methods to fabricate single-crystal thin films of complex oxides. Cuprate such as La 2-x Sr x CuO 4 (LSCO) is a representative complex-oxide high-temperature superconductor (HTS) material. Our group utilizes this method to produce high-quality single-crystal HTS films with atomically smooth surfaces and interfaces. In addition, ALL-MBE enables us to engineer multilayer heterostructures with atomic precision. This allows the fabrication of tunnel junctions, various nanostructures, and other HTS devices of interest for superconducting electronics. We have synthesized over three thousand LSCO thin films in the past two decades. These films’ structural and electronic properties have been studied and characterized by various methods. Here, we distill the extensive experience we accumulated into a step-by-step protocol to fabricate atomically perfect LSCO films. The recipe includes substrate preparation, ozone generation and distillation, source calibration, the in situ monitoring of the film synthesis, post-growth annealing, and ex situ characterization. It discloses a reproducible way to fabricate single-crystal LSCO films for basic research and HTS electronic applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Scaling Laws of Exciton Recombination Kinetics in Low Dimensional Halide Perovskite Nanostructures

Carrier recombination is a crucial process governing the optical properties of a semiconductor. Although various theoretical approaches have been utilized to describe carrier behaviors, a quantitative understanding of the impact of defects and interfaces in low dimensional semiconductor systems is still elusive. Here, we develop a model system consisting of chemically tunable, highly luminescent halide perovskite nanocrystals to illustrate the role of carrier diffusion and material dimensionality on the carrier recombination kinetics and luminescence efficiency. Our advanced synthetic methods provide a well-controlled colloidal system consisting of nanocrystals with different aspect ratios, halide compositions, and surface conditions. Using this system, we reveal the scaling laws of photoluminescence quantum yield and radiative lifetime with respect to the aspect ratio of nanocrystals. The scaling laws derived herein are not only a phenomenological observation but proved a powerful tool disentangling the carrier dynamics of microscopic systems in a quantitative and interpretable manner. The investigation of our model system and theoretical formulation bring to light the dimensionality, as a hidden constraint on carrier dynamics, and identify the diffusion length as an important parameter that distinguishes nanoscale and macroscale carrier behaviors. Furthermore, the conceptual distinction in carrier dynamics in different dimensionality regimes informs new design rules for optical devices where complex microstructures are involved.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Defect‐Free Nanowelding of Bilayer SnSe Nanoplates

Nanowelding is a bottom‐up technique to create custom‐designed nanostructures and devices beyond the precision of lithographic methods. Here, a new technique is reported based on anisotropic lubricity at the van der Waals interface between monolayer and bilayer SnSe nanoplates and a graphene substrate to achieve precise control of the crystal orientation and the interface during the welding process. As‐grown SnSe monolayer and bilayer nanoplates are commensurate with graphene's armchair direction but lack commensuration along graphene's zigzag direction, resulting in a reduced friction along that direction and a rail‐like, 1D movement that permits joining nanoplates with high precision. This way, molecular beam epitaxially grown SnSe nanoplates of lateral sizes 30–100 nm are manipulated by the tip of a scanning tunneling microscope at room temperature. In situ annealing is applied afterward to weld contacting nanoplates without atomic defects at the interface. This technique can be generalized to any van der Waals interfaces with anisotropic lubricity and is highly promising for the construction of complex quantum devices, such as field effect transistors, quantum interference devices, lateral tunneling junctions, and solid‐state qubits.

2D ferroelectrics↗

Unraveling the multi-step crystallization mechanism of polytetrafluoroethylene, modified polytetrafluoroethylene, and their nanocomposites with boron nitride nanobarbs: Experimental insights and theoretical analysis

The non-isothermal crystallization behavior and kinetics of polytetrafluoroethylene (PTFE) composites with boron nitride nanobarb (BNNB), a new generation nanostructure with unique surface morphology and mechanical “barbs” have been analyzed, understanding these properties is essential for their high-end applications as thermal interface materials (TIM) for microwave, 5G and microelectronic devices. The analysis of the crystallization parameters includes crystallization onset, peak and end temperatures, crystallization half-life and overall crystallinity of PTFE, modified PTFE and their BNNB composites. The results were further analyzed using theoretical models such as the combined Avrami-Ozawa model. It was found that BNNB supports crystallization in the modified PTFE but shows minimal effect on the crystallization of PTFE. Due to the limitation of the classical theoretical models used above in fully characterizing the multi-step crystallization process of PTFE, an in-depth analysis using the model-free advanced isoconversional computation was used to characterize the PTFE crystallization based on the evolution of activation energy with fractional crystallinity and for the first time with temperature. Three kinetic regions were identified in the crystallization mechanism. Here, this study investigated the molecular organization and microstructural evolution of PTFE, modified PTFE and their composites during non-isothermal crystallization using advanced X-ray scattering measurements. An insight into the changes undergone by the material's microstructural units including crystallite size and morphology, lamellar thickness and lamellar interfacial layer thickness, and crystallographic phase dynamics during non-isothermal cooling from the melt, was provided here in this work. The effect of copolymer modification of PTFE and the inclusion of pristine and functionalized BNNB (a thermally conductive and electrically insulating ceramic) are both new investigations that provide valuable knowledge for the development of materials with strong matrix-nanofiller interaction and guidance for optimizing sintering and cooling cycles, two key steps in PTFE processing that largely affect the material microstructural features. Overall, the result of the three-part investigation demonstrates that BNNB supports crystallization in the modified PTFE up to 20 wt% concentration and at low and high cooling rates typically used in the industrial processing of PTFE.

36 MATERIALS SCIENCE↗

Energy Funneling in a Noninteger Two-Dimensional Perovskite

Energy funneling is a phenomenon that has been exploited in optoelectronic devices based on low-dimensional materials to improve their performance. Here, we introduce a new class of two-dimensional semiconductor, characterized by multiple regions of varying thickness in a single confined nanostructure with homogeneous composition. This "noninteger 2D semiconductor" was prepared via the structural transformation of two-octahedron-layer-thick (n = 2) 2D cesium lead bromide perovskite nanosheets; it consisted of a central n = 2 region surrounded by edge-lying n = 3 regions, as imaged by electron microscopy. Thicker noninteger 2D CsPbBr 3 nanostructures were obtained as well. Finally, these noninteger 2D perovskites formed a laterally coupled quantum well band alignment with virtually no strain at the interface and no dielectric barrier, across which unprecedented intramaterial funneling of the photoexcitation energy was observed from the thin to the thick regions using time-resolved absorption and photoluminescence spectroscopy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In-situ resonant band engineering of solution-processed semiconductors generates high performance n-type thermoelectric nano-inks

Thermoelectric devices possess enormous potential to reshape the global energy landscape by converting waste heat into electricity, yet their commercial implementation has been limited by their high cost to output power ratio. No single “champion” thermoelectric material exists due to a broad range of material-dependent thermal and electrical property optimization challenges. While the advent of nanostructuring provided a general design paradigm for reducing material thermal conductivities, there exists no analogous strategy for homogeneous, precise doping of materials. Here, we demonstrate a nanoscale interface-engineering approach that harnesses the large chemically accessible surface areas of nanomaterials to yield massive, finely-controlled, and stable changes in the Seebeck coefficient, switching a poor nonconventional p- type thermoelectric material, tellurium, into a robust n -type material exhibiting stable properties over months of testing. These remodeled, n -type nanowires display extremely high power factors (~500 µW m -1 K -2 ) that are orders of magnitude higher than their bulk p -type counterparts.

42 ENGINEERING↗

Screw-Dislocation-Driven Growth of 2D Perovskite Spiral Microplates

Two-dimensional (2D) organic–inorganic halide perovskites are solution-processable semiconductors that are promising for optoelectronic applications. Understanding crystallization mechanisms to achieve control over nanostructures is important for optimizing desired properties. Here we introduce a versatile strategy to synthesize spiral microplates of diverse 2D perovskites at the air–water interface through screw-dislocation-driven growth. Spirals of 11 2D perovskite compositions (LA) 2 (A) n−1 Pb n X 3n+1 with different spacer (LA) cations, A-cations, halide (X) anions, and n-number can be grown. They typically consist of single- or few-layer perovskite step heights but exhibit stacking complexity when multiple dislocations interact. The spiral microplates exhibit the characteristic optical properties (photoluminescence and second-harmonic generation) of the underlying 2D perovskites. Fluorescence-detected circular dichroism imaging shows that the chirality of the spiral center does not translate to the observed chiroptical properties of the microplate, consistent with the length scale of the chiral distortion. Furthermore, this solution growth of perovskite spirals diversifies the perovskite microstructures for optoelectronics and other applications.

2D halide perovskites↗

Role of Intra-Domain Heterogeneity on Ion and Polymer Dynamics in Block Polymer Electrolytes: An Approach for Spatially Resolving Dynamics and Ion Transport

The design of safe and high-performance, nanostructured, block polymer (BP) electrolytes for lithium-ion batteries requires a thorough understanding of the key parameters that govern local structure and dynamics. Yet, the interfaces between microphase separated domains can introduce complexities in this local behavior that can be challenging to quantify. Herein, the local polymer, cation (Li + ), and anion dynamics were described in salt-doped polystyrene block poly(oligo-oxyethylene methyl ether methacrylate) (PS-b-POEM) through a quantitative framework that considered the effects of polymer architecture, segmental mixing, chain stretching, and confinement on polymer mobility and ion transport. This framework was validated through nuclear magnetic resonance (NMR) spectroscopy measurements on solid (dry) polymer electrolyte samples. Notably, a mobility transition temperature (T mobility ) was identified through NMR spectroscopy that captured the local dynamics more accurately than the thermal glass transition temperature. Additionally, the approach quantitatively described the mobility gradient across a domain when segmental mixing effects were combined with chain stretching and confinement information, especially at higher segregation strengths – facilitating the assessment of local ion diffusion and conductivity. As a result, spatially averaged local ion diffusion predictions quantitatively matched NMR-measured ion diffusivities in the BP samples, while spatially summed ionic conductivity predictions across a domain qualitatively captured trends in the measured ionic conductivities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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↗

Tailoring Cu-Zr gradient nanoglass structures: Influence of nanoparticle size and cooling rates on glass-glass interfaces

The study of gradient nanoglasses (GNGs) has gained attention due to their unique mechanical properties and potential applications in advanced materials. This study employs molecular dynamics simulations to synthesize a GNG using Cu-Zr metallic glass nanoparticles (NPs) sized from 3 to 15 nm. The NPs were produced by melting and quenching metallic clusters at a relatively slow quench rate of 10 9 K/s. The synthesis of GNG is elucidated along with the characterization of its heterogeneous metallic glass nanostructure. A seamless GNG structure is formed through cold compression of Cu 64 Zr 36 amorphous NPs of varying sizes. The influence of NP size on the GNG structure is investigated, utilizing deeply relaxed NPs, which exhibit a characteristic Cu segregation pattern on their surfaces. The results highlight an increase in structural heterogeneity due to heterogeneous mass transport and the development of local composition and density variations caused by Cu segregation at glass-glass interfaces (GGIs). A reduction in NP size is correlated with decreased Cu atomic displacements and local density at GGIs, suggesting that larger NPs may produce stronger GGIs. This research presents a novel methodology for synthesizing heterogeneous metallic glasses, demonstrating the capacity to control and customize nanostructure heterogeneity through the manipulation of NP sizes and cooling rates. Furthermore, these findings enhance our understanding of structural evolution during nanoglass synthesis and lay the foundation for further exploration in nanomaterial synthesis and characterization.

36 MATERIALS SCIENCE↗