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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 55 records · Page 3

Autonomous discovery of emergent morphologies in directed self-assembly of block copolymer blends

The directed self-assembly (DSA) of block copolymers (BCPs) is a powerful approach to fabricate complex nanostructure arrays, but finding morphologies that emerge with changes in polymer architecture, composition, or assembly constraints remains daunting because of the increased dimensionality of the DSA design space. Here, we demonstrate machine-guided discovery of emergent morphologies from a cylinder/lamellae BCP blend directed by a chemical grating template, conducted without direct human intervention on a synchrotron x-ray scattering beamline. This approach maps the morphology-template phase space in a fraction of the time required by manual characterization and highlights regions deserving more detailed investigation. These studies reveal localized, template-directed partitioning of coexisting lamella- and cylinder-like subdomains at the template period length scale, manifesting as previously unknown morphologies such as aligned alternating subdomains, bilayers, or a “ladder” morphology. This work underscores the pivotal role that autonomous characterization can play in advancing the paradigm of DSA.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Arrays of high-aspect-ratio germanium nanostructures with nanoscale pitch and methods for the fabrication thereof

Methods for fabricating thin, high-aspect-ratio Ge nanostructures from high-quality, single-crystalline Ge substrates are provided. Also provided are grating structures made using the methods. The methods utilize a thin layer of graphene between a surface of a Ge substrate, and an overlying resist layer. The graphene passivates the surface, preventing the formation of water-soluble native Ge oxides that can result in the lift-off of the resist during the development of the resist.

Lagally, Max G.↗

Reactive Oxygen Ion Beam-Induced Deposition for Concurrent Purification of Platinum Nanostructures

Oxygen-focused ion beam induced deposition (O-FIBID) enables the direct-write fabrication of Pt nanostructures while simultaneously enhancing purity concurrently through reactive oxygen–deposit interactions. By systematically varying the dwell time, accelerating voltage, and precursor pressure, the Pt content and conductivity can be controlled. Under optimum conditions, the Pt content reached 63 at.%. Across the dwell-time range used for resistivity measurements, the Pt content increased from 20 to 33 at.%, while the resistivity decreased from 2.9 × 10 4 μΩ·cm to 1.2 × 10 3 μΩ·cm, which is consistent with enhanced percolation through Pt grains and the lower intrinsic resistivity of the purer Pt deposit. The simulation results support a purification mechanism driven by the beam-induced activation of implanted oxygen balanced against the preferential sputtering of Pt. These results demonstrate O-FIBID as a viable method for the nanoscale direct write of conductive Pt without post-processing, and some deviations from conventional FIBID wisdom are observed. These results serve as a foundation for exploring nascent, reactive focused ion beam-induced deposition processes.

deposit purification↗

Scalable fabrication of Chip-integrated 3D-nanostructured electronic devices via DNA-programmable assembly

DNA-based self-assembly methods have demonstrated powerful and unique capabilities to encode nanomaterial structures through the prescribed placement of inorganic and biological nanocomponents. However, the challenge of selectively growing DNA superlattices on specific locations of surfaces and their integration with conventional nanofabrication has hindered the fabrication of three-dimensional (3D) DNA-assembled functional devices. Here, we present a scalable nanofabrication technique that combines bottom-up and top-down approaches for selective growth of 3D DNA superlattices on gold microarrays. This approach allows for the fabrication of self-assembled 3D-nanostructured electronic devices. DNA strands are bound onto the gold arrays, which anchor DNA origami frames and promote ordered framework growth on the specific areas of the surface, enabling control of the lateral placement and orientation of superlattices. DNA frameworks selectively grown on the pads are subsequently templated to nanoscale silica and tin oxide (SnO x ) that follow the architecture, as confirmed by structural and chemical characterizations. The fabricated SnO x superlattices are integrated into devices that demonstrate photocurrent response.

36 MATERIALS SCIENCE↗

Dual‐Scale Nanostructures via Evaporative Assembly

Abstract Dual‐scale hierarchical structures with regular microscale patterns and varying degree of nanoscale crystalline order are synthesized on physically and chemically homogeneous substrates by evaporative self‐assembly with a suspension of DNA‐functionalized nanoparticles (NPs) with a charged core shell. For a certain NP concentration range, periodic concentric rings in a stripe‐like micropattern are produced over macroscale surface areas by an NP monolayer with hexagonal lattice structure at the nanoscale. The stripe width, spacing, and nanoparticle ordering can be controlled by varying the NP concentration. The results indicate that the interplay between “stick‐slip” motion of the droplet contact line and coulombic and steric NP interactions control the formation of the observed structures. A simple analytical model is proposed to account for the experimental observations and guide the future design of different nanostructure morphologies. This work demonstrates a simple cost‐effective mask‐free method for fabricating large‐area nanostructured 2D materials and metasurfaces for applications ranging from energy conversion/storage to optoelectronics and nanophotonics.

Srivastava, Sunita↗

Template-free fabrication of fractal porous Y 2 O 3 monolithic foam and its functional modification by Ni-doping

Fractal structures which display nearly the same character at every scale exist widely in nature, however, it is still a great challenge to fabricate a fractal nanostructure. Herein, a Y 2 O 3 monolith with unique hierarchically fractal porous structure was fabricated via calcination of a fractal porous coordination polymer precursor. The monolith exhibits porous feature with the pore-size ranging from micrometers to nanometers. Interestingly, each level of the pore-wall is composed of secondary porous structures, whose pore-wall is composed of sub-level self-similar porous feature. Moreover, by Ni-doping in the coordination polymer precursor, fractal porous Ni@Y 2 O 3 was prepared, and exhibited enhanced activity in ethanol steam reforming compared with that of a common supported NiO catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Doping of Cr in Graphene Using Electron Beam Manipulation for Functional Defect Engineering

Chromium atoms in graphene have been proposed to exhibit magnetic moments and spin-selective conducting states depending on the local bonding geometry within the graphene structure, which could lead to interesting applications in spintronics. Despite this interest, there are few direct experimental reports of Cr dopants in graphene even though it is theorized to be stable. Here, we demonstrate the introduction of single Cr dopant atoms into the graphene lattice and onto graphene edges through the controlled use of a focused electron beam in a scanning transmission electron microscope. Here, we show local control of doping locations, and when coupled with targeted in situ milling during scanning of the e-beam, these strategies demonstrate an important component of the fabrication of tailored nanostructured devices in the electron microscope. The approach is validated with first-principles calculations to understand synthesis pathways during fabrication and reveal the energetics and local properties of Cr atoms embedded in graphene; for example, Cr doping can convert graphene into a magnetic and semiconducting material, which suggests Cr-doped graphene can be used as a building block for potential electronic devices and a means to construct them.

36 MATERIALS SCIENCE↗

High-temperature nanoindentation creep studies on castable and sintered nanostructured low-activation ferritic-martensitic alloys

In this article, we present the creep characteristics of two reduced activation ferritic-martensitic steels of identical starting compositions formed by different fabrication routes: a nanostructured ferritic alloy commonly referred to as a castable nanostructured alloy (CNA) and a sintered nanostructured alloy (SNA) variant. Through a series of nanoindentation experiments spanning a temperature range of 25 °C to 650 °C, with a maximum load of 100 mN, we find creep behaviors in the cast and sintered materials to be remarkably similar. The creep stress exponent (n) for CNA and SNA were found to be in the range of 8–35 and the activation volume was ∼14–42b 3 , underscoring a dominance of dislocation-mediated mechanisms in both alloys. Notably, we observed a decline in the creep stress exponent with increasing temperature, attributable to the heightened influence of thermally activated dislocations. This phenomenon suggests a potential transition in the deformation mechanism towards a thermally activated dislocation climb process, significantly impacting the observed creep behavior.

36 MATERIALS SCIENCE↗

Large-area nanostructured surfaces with tunable zeta potentials

Through a refined fabrication protocol based on block-copolymer self-assembly we synthesize nanostructured surfaces with conical nanopillars of different height (60, 120, and 200 nm) in hexagonal arrays with uniform spacing (~50 nm) over large areas (>cm 2 ). While the nanostructured surfaces fabricated on silicon substrates display superhydrophilic behavior, superhydrophobic properties are attained by coating with octadecyltrichlorosilane (OTS). Negative zeta potentials for all the studied surfaces are reported by electrokinetic flow measurements with aqueous KCl solutions at different concentrations (1 and 10 mM) and pH values between 4 and 8. While the surface nanostructure reduces the zeta potential magnitude, the hydrophobic OTS coating enhances it. Experimental results can be accounted for by a site-dissociation model for the surface charge density. The reported wetting properties and zeta potential tunability makes the studied surfaces particularly relevant for applications such as energy conversion and storage, membrane-based water treatment and molecular separation.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Using block-copolymer nanolithography as a tool to sensitively evaluate variation in chemical dry etching rates of semiconductor materials with sub-5 nm resolution

Ion implantation is a robust and established method to customize the electronic properties of Si. However, fabricating doped, ultrafine semiconductor nanostructures can be challenging. Ion implantation has well-established effects on the dry etch rates of Si, which becomes increasingly consequential as the target dimension shrinks below a few tens of nanometers. While dry etching arrays of block copolymer-templated nanoscale holes (pitch = 37.5 nm, diameter ~25 nm) into p-type, n-type, and undoped Si, we observed that the lateral etch rate was notably larger for the n-type regions than p-type or undoped regions. By doing image analyses on high resolution electron micrographs of the nanostructured hole arrays, we were able to extract the porosity and average radii of the holes with subnanometer sensitivity and compare the relative etch rates between different doping conditions. We found that degenerately doped n-type silicon consistently etches between approximately 17% and 27% faster in the lateral direction than p-type Si, resulting in significantly larger porosity and, consequently, less mechanical stability. Here, we demonstrate that top-down dimensional analysis of a densely packed porous nanostructure is a robust method for assessing extremely small differences in the lateral, chemical etch rate of doped Si to a degree of sensitivity that was previously unachievable. The minute, dense-packed nature of block copolymer self-assembled nanostructures is shown to be ideal for this application. This proposed method could be useful for designing fabrication processes for heterogeneous nanostructures, as slight dry etch rate variations that may be within process tolerance at the micrometer-scale appear to have nontrivial consequences at the nanometer scale.

42 ENGINEERING↗

Gradient nanostructuring via compositional means

Nanocrystalline metals are inherently unstable against thermal and mechanical stimuli, commonly resulting in significant grain growth. Also, while these metals exhibit substantial Hall-Petch strengthening, they tend to suffer from low ductility and fracture toughness. With regard to the grain growth problem, alloying elements have been employed to stabilize the microstructure through kinetic and/or thermodynamic mechanisms. And to address the ductility challenge, spatially-graded grain size distributions have been developed to facilitate heterogeneous deformation modes: high-strength at the surface and plastic deformation in the bulk. In the present work, we combine these two strategies and present a new methodology for the fabrication of gradient nanostructured metals via compositional means. Here, we have demonstrated that annealing a compositionally stepwise Pt-Au film with a homogenous microstructure results in a film with a spatial microstructural gradient, exhibiting grains which can be twice as wide in the bulk compared to the outer surfaces. Additionally, phase-field modeling was employed for the comparison with experimental results and for further investigation of the competing mechanisms of Au diffusion and thermally induced grain growth. This fabrication method offers an alternative approach for developing the next generation of microstructurally stable gradient nanostructured films.

36 MATERIALS SCIENCE↗

Rationally Programming Nanomaterials with DNA for Biomedical Applications

Abstract DNA is not only a carrier of genetic information, but also a versatile structural tool for the engineering and self‐assembling of nanostructures. In this regard, the DNA template has dramatically enhanced the scalability, programmability, and functionality of the self‐assembled DNA nanostructures. These capabilities provide opportunities for a wide range of biomedical applications in biosensing, bioimaging, drug delivery, and disease therapy. In this review, the importance and advantages of DNA for programming and fabricating of DNA nanostructures are first highlighted. The recent progress in design and construction of DNA nanostructures are then summarized, including DNA conjugated nanoparticle systems, DNA‐based clusters and extended organizations, and DNA origami‐templated assemblies. An overview on biomedical applications of the self‐assembled DNA nanostructures is provided. Finally, the conclusion and perspectives on the self‐assembled DNA nanostructures are presented.

59 BASIC BIOLOGICAL SCIENCES↗

Probing and Understanding the Spatial and Energy Distributions of Plasmonic Hot Carriers via Single-Molecule Quantum Transport

The generation of hot carriers in plasmonic nanostructures offers new transformative opportunities for a range of applications, including solar energy harvesting, photochemistry, and photodetection. To better understand such phenomena, this project aims to develop an experimental approach to study and understand hot carrier distributions in photoexcited plasmonic nanostructures. The developed experimental approach, combining scanning probe-based single-molecule quantum transport measurements with plasmonic excitation methods, leverages nanoscopic single molecules as quantum energy filters to selectively access hot carriers in a variety of plasmonic nanostructures. This report summarizes the key outcomes, impacts, and lessons learned in the first two years of the project. Over the past two years, important progress was made in achieving the project's goals, including the development of the scanning probe-based experimental platform, fabrication of plasmonic nanostructures, and design and synthesis of the desired molecular candidates. Insights from this research will pave the path toward the development of technologies that will improve the way we harvest solar energy and drive chemical reactions and ultimately help transition the U.S. to a clean and sustainable society.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Synthesis of bulk reactive Ni–Al composites using high pressure torsion

Self-propagating exothermic reactions, for instance in the nickel-aluminum (Ni-Al) system, have been widely studied to create high performance intermetallic compounds or for in-situ welding. Their easy ignition once the phase spacing is reduced below the micron scale, makes top-down methods like high-energy ball milling, ideal to fabricate such reactive nanostructures. A major drawback of ball milling is the need of a sintering step to form bulk pieces of the reactive material. However, this is not possible, as the targeted reactions would already proceed. Therefore, we investigate the ability of high pressure torsion as an alternative process, capable to produce bulk nanocomposites from powder mixtures. Severe straining of powder mixtures with a composition of 50 wt% Ni and 50 wt% Al enables fabrication of self-reactive bulk samples with microstructures similar to those obtained from ball milling or magnetron sputtering. Additionally, samples deformed at ambient temperature are highly reactive and can be ignited significantly below the Al melting point, finally predominantly consisting of Al 3 Ni 2 and Al 3 Ni, independent of the applied strain. Although the reaction proceeds first at the edge of the disk, the strain gradient present in the disks does not prevent reaction of the whole sample.

36 MATERIALS SCIENCE↗

Scalable Graphene Oxide Hollow Fiber Membranes for Dye Desalination Enabled by Multi‐Purpose Polyamine Functionalization

2D nanosheets such as graphene oxide (GO) can be stacked to construct membranes with fine-tuned nanochannels to achieve molecular sieving ability. These membranes are often thin to achieve high water permeance, but their fabrication with consistent nanostructures on a large scale presents an enormous challenge. Herein, GO-based hollow fiber membranes (HFMs) are developed for dye desalination by synergistically combining chemical etching to form in-plane nanopores (10–30 nm) to increase water permeance and polyamine functionalization to improve underwater stability and enable facile large-scale production using existing membrane manufacturing processes. HFM modules with areas of 88 cm 2 and GO layer thicknesses of ≈500 nm are fabricated, and they exhibited a stable dye water permeance of 75 L m −2 h −1 bar −1 , rejection of >99.5% for Direct red and Congo red, and Na 2 SO 4 /dye separation factor of 300–500, superior to state-of-the-art commercial membranes. Furthermore, the versatility of this approach is also demonstrated using different short polyamines and porous substrates. This study reveals a scalable way of designing 2D materials into high-performance robust membranes for practical applications.

amine functionalization↗

Depolymerization as a Design Strategy: Depolymerization Etching of Polymerization-Induced Microphase Separations

Thermally triggered depolymerization has traditionally been viewed through the lens of sustainability and recycling, not as a constructive tool for materials design. Herein, we show that selective, thermally triggered depolymerization to gaseous monomer serves as a solvent-free strategy for generating porosity in nanostructured polymer materials, offering a means to bypass the mass transport limitations inherent in conventional solution-based etching. As a demonstration platform, we employed polymerization-induced microphase separation (PIMS) to generate disordered bicontinuous block copolymer structures with embedded depolymerizable domains. By incorporating a methacrylate block susceptible to thermal depolymerization within a cross-linked, depolymerization-resistant styrenic matrix, we developed a process we term depolymerization etching of polymerization-induced microphase separations (DEPIMS). This approach enables highly selective and efficient domain removal via reversion to monomer to produce mesoporous materials with high surface areas (>200 m 2 /g). Subsequent surface functionalization yielded mesoporous adsorbents with tunable uptake kinetics and among the highest dye adsorption capacities reported for PIMS-derived materials, demonstrating the adaptability of the DEPIMS platform for chemical separations. DEPIMS can also be extended to a gram-scale, one-pot approach to yield mesoporous materials with recoverable monomer in under 12 h. These findings reposition thermal depolymerization from a sustainability tool to a broadly enabling strategy for scalable, on-demand fabrication of functional nanostructured materials.

Depolymerization↗

Alignment frustration in block copolymer films with block copolymer grafted TiO 2 nanoparticles under soft-shear cold zone annealing

Block copolymers (BCPs) have received significant attention as promising candidates for sequestering nanoparticles and fabrication of aligned nanostructures with optimal optical or electrical properties. We investigate the influence of static and dynamic thermal field on the alignment of polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) BCP morphology with the loading of novel poly(methyl methacrylate-block-Polystyrene) (PMMA-b-PS)-grafted-TiO 2 nanoparticles (BCP-g-TiO 2 ). Observation of characteristics IR peaks for PMMA and PS in BCP-g-TiO 2 nanoparticles and Transmission Electron Microscopy (TEM) results of the outer coating of core nanoparticle, validate the grafting to approach in synthesizing BCP-g-TiO 2 . In this work, we report that under the sharp dynamic thermal field, at low loading of BCP-g-TiO 2 , there is good dispersion of nanoparticles in unidirectionally aligned BCP matrix in film interior probed by GISAXS, while, at high nanoparticle loading (~10 wt%), there is local frustration in the unidirectional alignment of the BCP matrix due to aggregation of BCP-g-TiO 2 nanoparticles. However, Grazing incidence small angle X-ray scattering (GISAXS) shows clearly that the BCP films remain largely locally ordered at the domain scale, despite these large perturbations to long-range ordering even at high loading level, while bringing in new TiO 2 functionality to the BCP films, such as UVO absorptivity or biofouling prevention, important to potential new applications of such membranes.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Raspberry colloid-templated approach for the synthesis of palladium-based oxidation catalysts with enhanced hydrothermal stability and low-temperature activity

It is becoming increasingly urgent to develop and utilize novel, more efficient and stable materials for mobile and stationary emission control applications as the deleterious consequences of anthropogenic air pollution are becoming more evident and pressing. Tightening regulations, particularly related to automotive exhaust treatment, together with continued improvements in engine design, that result in lowering the engine operating temperatures and inadvertently lead to the release of an overwhelming proportion of pollutants during the cold start, present new challenges for materials design, specifically for oxidation catalysts. In particular, improvements in the low-temperature activity while maintaining catalyst stability at high temperatures are required from the next-generation catalyst. Typical catalysts for removal of pollutants from automotive exhaust streams incorporate platinum group metals (PGMs). They tend to be inefficient at low temperatures (below 250 °C), thus accounting for the cold start problem, yet sinter and lose their activity at high temperatures that are frequently encountered during catalyst operation. High PGM loadings are often employed to compensate for catalyst inefficiencies and fast degradation, ultimately resulting in high-cost catalytic converters. Here, we have developed a new approach for the design and formation of catalytic materials that allows for both significantly more efficient PGM incorporation and improved overall catalyst performance at reduced PGM loadings. The method provides control over the composition and geometry of the support through self-assembly of sacrificial composite template — “raspberry” polymeric colloids decorated with catalytic particles — accompanied by infiltration with metal-oxide precursor and subsequent removal of the colloids. This method simultaneously structures the porous network and organizes the catalytic particles within it. Uniquely, the resulting catalytic particles are partially embedded in the support matrix and partially exposed to the pore interior, producing catalytic sites that are both stable and accessible. Herein, the feasibility of this novel and versatile approach for automotive catalytic conversion is demonstrated: the studies include testing alumina-based raspberry-colloid-templated (RCT) catalysts containing Pd nanoparticles (RCT Pd/Al2O3) for oxidation of propane and carbon monoxide under simulated diesel exhaust conditions and hydrothermal aging at 800 °C for 50 h in the simulated stream. The RCT Pd/Al2O3 catalysts exhibit exceptional activity toward CO oxidation, reduced reaction onset temperature, and high stability to elevated temperatures (demonstrated through prolonged exposure to temperatures up to 950 °C) and reactive gas streams, without migration, sintering or loss of the precious metal NPs. Notably, the novel catalyst shows the same or slightly better performance than the commercial catalysts even when the PGM load is reduced by ~80 % compared to the commercial counterparts. These results provide confidence for the utilization of the RCT approach for the fabrication of robust nanostructured catalysts for next-generation, energy-efficient catalytic converters with improved performance at low and high temperatures and reduced costs. The RCT methodology is, in addition, highly generalizable, and can thus be applied for the design of a wide range of catalytic systems in the automotive sector and beyond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗