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At least 415 records · Page 23

Solutions Are the Problem: Ordered Two-Dimensional Covalent Organic Framework Films by Chemical Vapor Deposition

Covalent organic frameworks (COFs) are a promising class of crystalline polymer networks that are useful due to their high porosity, versatile functionality, and tunable architecture. Conventional solution-based methods of producing COFs are marred by slow reactions that produce powders that are difficult to process into adaptable form factors for functional applications, and there is a need for facile and fast synthesis techniques for making crystalline and ordered covalent organic framework (COF) thin films. In this work, we report a chemical vapor deposition (CVD) approach utilizing co-evaporation of two monomers onto a heated substrate to produce highly crystalline, defect-free COF films and coatings with hydrazone, imine, and ketoenamine COF linkages. Further, this all-in-one synthesis technique produces highly crystalline, 40 nm–1 μm-thick COF films on Si/SiO2 substrates in less than 30 min. Crystallinity and alignment were proven by using a combination of grazing-incidence wide-angle X-ray scattering (GIWAXS) and transmission electron microscopy (TEM), and successful conversion of the monomers to produce the target COF was supported by Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and UV–vis measurements. Additionally, we used atomic force microscopy (AFM) to investigate the growth mechanisms of these films, showing the coalescence of triangular crystallites into a smooth film. To show the wide applicability and scope of the CVD process, we also prepared crystalline ordered COF films with imine and ketoenamine linkages. These films show potential as high-quality size exclusion membranes, catalytic platforms, and organic transistors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantum light: creation, integration, and applications

In today’s rapidly evolving quantum landscape, the generation and manipulation of quantum light not only represent fundamental challenges but also herald unprecedented opportunities in communication, computing, sensing, and imaging. This special issue brings together a collection of contributions that span the entire journey, from the creation of quantum light using novel materials and emitters to its seamless integration into photonic architectures and eventual deployment in advanced quantum applications. This special issue, “Quantum Light: Creation, Integration, and Applications,” features a collection of three review articles, five perspectives, and 23 original research papers, highlighting both the timeliness of the topic and the remarkable breadth and richness of ongoing advancements in the field.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

A Digital System-On-Chip CO 2 Sensor (Final Report)

The overall goal of the project was to build a low-cost digital CO 2 sensor made of N5’s patented sensing architecture using a digital application specific integrated circuit (ASIC) to reduce the amount of energy usage in residential and commercial buildings. The proposed small form-factor CO 2 monitoring device contains a molecular sieve membrane filter capable of monitoring indoor air quality which indicates the content of CO 2 inside a residential or commercial building.

36 MATERIALS SCIENCE↗

Gate-tunable superconducting diode effect in a three-terminal Josephson device

Abstract The phenomenon of non-reciprocal critical current in a Josephson device, termed the Josephson diode effect, has garnered much recent interest. Realization of the diode effect requires inversion symmetry breaking, typically obtained by spin-orbit interactions. Here we report observation of the Josephson diode effect in a three-terminal Josephson device based upon an InAs quantum well two-dimensional electron gas proximitized by an epitaxial aluminum superconducting layer. We demonstrate that the diode efficiency in our devices can be tuned by a small out-of-plane magnetic field or by electrostatic gating. We show that the Josephson diode effect in these devices is a consequence of the artificial realization of a current-phase relation that contains higher harmonics. We also show nonlinear DC intermodulation and simultaneous two-signal rectification, enabled by the multi-terminal nature of the devices. Furthermore, we show that the diode effect is an inherent property of multi-terminal Josephson devices, establishing an immediately scalable approach by which potential applications of the Josephson diode effect can be realized, agnostic to the underlying material platform. These Josephson devices may also serve as gate-tunable building blocks in designing topologically protected qubits.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Photoluminescence as a probe of phosphorene properties

Abstract Here, we provide a detailed evaluation of photoluminescence (PL) as a comprehensive tool for phosphorene characterization with the emphasis on a prominent quantitative role of PL in providing fingerprint-like features due to its extreme sensitivity to the band structure details, anisotropy, disorder, external fields, etc. Factors such as number of layers, dimensionality, structural and chemical disorder, and environmental factors and their effect on phosphorene’s PL signal are reviewed and discussed. Applications of PL in monitoring phosphorene and its modifications, as well as potential impacts on the fields of chemical and biosensing, nanomedicine, and solar energy harvesting, are also elaborated.

2D materials↗

An Interim Report on NASA's Draft Space Technology Roadmaps

NASA has developed a set of 14 draft roadmaps to guide the development of space technologies under the leadership of the NASA Office of the Chief Technologist (OCT). Each of these roadmaps focuses on a particular technology area (TA). The roadmaps are intended to foster the development of advanced technologies and concepts that address NASA's needs and contribute to other aerospace and national needs. OCT requested that the National Research Council conduct a study to review the draft roadmaps, gather and assess relevant community input, and make recommendations and suggest priorities to inform NASA's decisions as it finalizes its roadmaps. The statement of task states that "based on the results of the community input and its own deliberations, the steering committee will prepare a brief interim report that addresses high-level issues associated with the roadmaps, such as the advisability of modifying the number or technical focus of the draft NASA roadmaps." This interim report, which does not include formal recommendations, addresses that one element of the study charge. NASA requested this interim report so that it would have the opportunity to make an early start in modifying the draft roadmaps based on feedback from the panels and steering committee. The final report will address all other tasks in the statement of task. In particular, the final report will include a prioritization of technologies, will describe in detail the prioritization process and criteria, and will include specific recommendations on a variety of topics, including many of the topics mentioned in this interim report. In developing both this interim report and the final report to come, the steering committee draws on the work of six study panels organized by technical area, loosely following the organization of the 14 roadmaps, as follows: A Panel 1: Propulsion and Power TA01 Launch Propulsion Systems TA02 In-Space Propulsion Technologies TA03 Space Power and Energy Storage Systems TA13 Ground and Launch Systems Processing B Panel 2: Robotics, Communications, and Navigation TA04 Robotics, TeleRobotics, and Autonomous Systems TA05 Communication and Navigation Systems C Panel 3: Instruments and Computing TA08 Science Instruments, Observatories, and Sensor Systems TA11 Modeling, Simulation, Information Technology, and Data Processing D Panel 4: Human Health and Surface Exploration TA06 Human Health, Life Support, and Habitation Systems TA07 Human Exploration Destination Systems E Panel 5: Materials Panel TA10 Nanotechnology TA12 Materials, Structures, Mechanical Systems, and Manufacturing TA14 Thermal Management Systems F Panel 6: Entry, Descent, and Landing Panel TA09 Entry, Descent, and Landing Systems In addition to drawing on the expertise represented on the steering committee and panels, the committee obtained input from each of 14 public workshops held on each of the 14 roadmaps. At these 1-day workshops, invited speakers, guests, and members of the public engaged in discussions on the different technology areas and their value to NASA. Broad community input was also solicited from a public website, where more than 240 public comments were received on the draft roadmaps in response to application of criteria (such as benefit, risk and reasonableness, and alignment with NASA and national goals) that the steering committee established. This interim report reflects the results of deliberations by the steering committee in light of these public inputs as well as additional inputs from the six panels. The steering committee's final report will be completed early in 2012. That report will prioritize the technologies that span the entire scope of the 14 roadmaps and provide additional guidance on crosscutting themes and other relevant topics.

Source record↗

Coherent Erbium Spin Defects in Colloidal Nanocrystal Hosts

We demonstrate nearly a microsecond of spin coherence in Er 3+ ions doped in cerium dioxide nanocrystal hosts, despite a large gyromagnetic ratio and nanometric proximity of the spin defect to the nanocrystal surface. The long spin coherence is enabled by reducing the dopant density below the instantaneous diffusion limit in a nuclear spin-free host material, reaching the limit of a single erbium spin defect per nanocrystal. We observe a large Orbach energy in a highly symmetric cubic site, further protecting the coherence in a qubit that would otherwise rapidly decohere. Spatially correlated electron spectroscopy measurements reveal the presence of Ce 3+ at the nanocrystal surface, which likely acts as extraneous paramagnetic spin noise. Even with these factors, defect-embedded nanocrystal hosts show tremendous promise for quantum sensing and quantum communication applications, with multiple avenues, including core-shell fabrication, redox tuning of oxygen vacancies, and organic surfactant modification, available to further enhance their spin coherence and functionality in the future.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Intercalation as a versatile tool for fabrication, property tuning, and phase transitions in 2D materials

Recent advances in two-dimensional (2D) materials have led to the renewed interest in intercalation as a powerful fabrication and processing tool. Intercalation is an effective method of modifying the interlayer interactions, doping 2D materials, modifying their electronic structure or even converting them into starkly different new structures or phases. Herein, we discuss different methods of intercalation and provide a comprehensive review of various roles and applications of intercalation in next-generation energy storage, optoelectronics, thermoelectrics, catalysis, etc. The recent progress in intercalation effects on crystal structure and structural phase transitions, including the emergence of quantum phases are also reviewed.

2D materials↗

Anisotropic Transient Disordering of Colloidal, Two-Dimensional CdSe Nanoplatelets upon Optical Excitation

Nanoplatelets (NPLs)-colloidally synthesized, spatially anisotropic, two-dimensional semiconductor quantum wells-are of intense interest owing to exceptionally narrow transition line widths, coupled with solution processability and bandgap tunability. However, given large surface areas and undercoordinated bonding at facet corners and edges, excitation under sufficient intensities may induce anisotropic structural instabilities that impact desired properties. We employ time-resolved X-ray diffraction to study the crystal structure of CdSe NPLs in response to optical excitation. Photoexcitation induces greater out-of-plane than in-plane disordering in 4 and 5 monolayer (ML) NPLs, while 3 ML NPLs display the opposite behavior. Recovery dynamics suggest that out-of-plane cooling slightly outpaces in-plane cooling in 5 ML NPLs with recrystallization occurring on indistinguishable time scales. In comparison, for zero-dimensional CdSe nanocrystals, disordering is isotropic and recovery is faster. These results favor the use of NPLs in optoelectronic applications, where they are likely to exhibit superior performance over traditional, zero-dimensional nanocrystals.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Multi-element metasurface system for imaging in the near-infrared

Metasurfaces are optically thin 2D arrays of subwavelength scatterers that modify scalar and vector properties of incident electromagnetic fields. Metasurface lenses are of particular interest for imaging applications for their flat form factor, compatibility with CMOS fabrication processes, and potential for correcting aberrations with a small number of elements. Here, we advance this capability by realizing a millimeter-diameter, polarization-independent metalens triplet system with chromatic aberration correction over the wavelength range of 1.30–1.60 μm and monochromatic aberration correction enabling a field of view of 50°.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Self-assembled nanofiltration membranes with thermo- and pH-responsive behavior

We produce controlled nanostructured membranes from cross-linking of self-assembled diacrylated poloxamers. At sufficiently high concentrations, poloxamers form lyotropic liquid crystals (LLCs), such as lamellar (L α ), cubic packing of spherical micelles, and hexagonal packing of rod-like micelles in water (H 1 ). We use the H 1 phase as a template to produce orderly packed nanofibrous membranes. The obtained membrane has a continuous 3D transport pathway and can alter its nanofiltration (NF) properties in response to changes in temperature and pH. The formulation includes Pluronic P84-diacrylate (P84DA), a thermoresponsive component that acts as both macromer and structure-directing amphiphile. P84DA facilitates changes in membrane pore size with temperature due to its thermoresponsiveness when it is in contact with water. Furthermore, the precursor contains acrylic acid (AAc) as the charged component, which upon copolymerization with P84DA, not only enables ion separation through Donnan exclusion but also imparts pH-responsive behavior for the separation of ionic species. The membrane performance is studied and compared with a commercial NF membrane (NF270). We show that the synthesized NF membrane has separation properties adjustable with temperature and pH with exceptional resistance to fouling by various solutes due to its highly hydrophilic surface. Furthermore, the membrane shows an outstanding sulfate over chloride ion selectivity, which is a requirement for salt fractionation applications. Deducted from separate experiments, the ideal chloride/sulfate selectivity for magnesium cation is about 2.38 at low ionic strengths. This study is done on a model system to show the capability of incorporating pH-responsiveness in LLC templated membranes, in which the pH-responsive range can be designed by changing the charged groups of comonomer in the formulation.

36 MATERIALS SCIENCE↗

Structural and compositional complexities of hierarchical self-assembly: A hypergraph approach

Programmable self-assembly enables the construction of complex molecular, supramolecular, and crystalline architectures from well-designed building blocks. In this work, we introduce a hypergraph-based formalism, Blocks & Bonds (B&B), which generalizes classical chemical graph theory by incorporating directed and multicolored interactions, internal symmetries, and hierarchical organization. Within this framework, we develop the Structure Code (SC), a compact and versatile language for describing self-assembled architectures. We define a Kolmogorov-style structural complexity as the total information content of SC, obtained through its tokenization and Shannon information assignment. Complementing this encoding-based measure, we introduce a much simpler quantity, the compositional complexity, which depends only on the number and cumulative usage of block and bond types in the construction set. A central result of this work is a strong empirical correlation between the token-based structural complexity and the compositional complexity across all examined systems. Owing to this agreement, the compositional complexity emerges as the most practical and broadly applicable measure: it is easy to compute, requires no explicit encoding, and yet closely tracks the actual information content of structurally diverse architectures. Applications to molecular systems (ethylene glycol and glucose), DNA-origami lattices, and crystalline assemblies show that B&B hypergraphs provide a unified, scalable, and information-efficient representation of structural organization, naturally capturing symmetry, modularity, and stereochemistry. This framework establishes a quantitative foundation for complexity-aware classification and inverse design of programmable matter.

36 MATERIALS SCIENCE↗

Engineering of niobium surfaces through accelerated neutral atom beam technology for quantum applications

A major roadblock to scalable quantum computing is phase decoherence and energy relaxation caused by qubits interacting with defect-related two-level systems (TLSs). Native oxides present on the surfaces of superconducting metals used in quantum devices are acknowledged to be a source of TLS that decrease qubit coherence times. Reducing microwave loss by “surface engineering” (i.e., replacing the uncontrolled native oxide of superconducting metals with a thin, stable surface with predictable characteristics) can be a key enabler for pushing performance forward with devices of higher intrinsic quality factor. In this work, we present a novel approach to replace the native oxide of niobium (typically formed in an uncontrolled fashion when its pristine surface is exposed to air) with an engineered oxide, using a room-temperature process that leverages accelerated neutral atom beam (ANAB) technology at 300 mm wafer scale. This ANAB is composed of a mixture of argon and oxygen, with tunable energy per atom, which is rastered across the wafer surface. The ANAB-engineered Nb-oxide thickness was found to vary from 2 to 6 nm depending on ANAB process parameters. The modeling of variable-energy x-ray photoelectron spectroscopy data confirms the thickness and compositional control of Nb surface oxide by the ANAB process. Furthermore, these results correlate well with those from transmission electron microscopy and x-ray reflectometry. Since ANAB is broadly applicable to material surfaces, the present study indicates its promise for modification of the surfaces of superconducting quantum circuits to achieve longer coherence times.

36 MATERIALS SCIENCE↗

Fabrication and Characterization of Non-Equilibrium Plasma-Treated PVDF Nanofiber Membrane-Based Sensors

The effect of a self-pulsing non-equilibrium plasma discharge on piezoelectric PVDF nanofiber membrane was investigated. The plasma discharge was generated in air with a DC power source, with a discharge current of 0.012 mA, a nominal interelectrode separation of 1 mm, and discharge voltage of ~970 V. In a continuous fabrication process, the electrospinning method was used to generate thin nanofiber membrane with a flow rate of 0.7–1 mL h -1 and 25–27 kV voltage to obtain the nanofiber with high sensitivity and a higher degree of alignment and uniformity over a larger area. Plasma treatment was applied on both single layer and multi-layer (three layers) nanomembranes. In addition, simultaneously, the nanofiber membranes were heat-treated at a glass transition temperature (80–120 °C) and then underwent plasma treatment. Fourier-transform infrared (FTIR) spectroscopy showed that the area under the curve at 840 and 1272 cm -1 (β phase) increased due to the application of plasma and differential scanning calorimeter (DSC) indicated an increase in the degree of crystallinity. Finally, PVDF sensors were fabricated from the nanofibers and their piezoelectric properties were characterized. The results suggested that compared to the pristine samples the piezoelectric properties in the plasma and plasma-heat-treated sensors were enhanced by 70% and 85% respectively.

42 ENGINEERING↗

Progress of Nanotechnology for Lithium-Sulfur Batteries

Lithium-Sulfur (Li-S) battery has been proposed and investigated since the 1960s as an effective energy storage device via reversible electrochemical reactions. As the fast development and commercialization of Li-ion battery (LIB) technology kept moving forward, no breakthroughs have been attained to solve critical technical issues facing Li-S batteries during the following decades. In the year 2000s, Li-S batteries reattracted significant interests in the research field owing to their low-cost advantages, high theoretical specific energy of 2600 Wh kg -1 , which is at least 3 times higher than the current LIB technology. The low-cost and high abundance of sulfur (i.e., the cathode active material), make Li-S batteries more appealing than LIBs given the fact that the latter use critical materials such as cobalt and nickel in the manufacturing of the cathodes. Moreover, the high-energy and low-cost features make the Li-S battery a promising energy storage technology in practical applications such as portable devices, electric vehicles, and grid storage when coupled with the harvesting of solar or wind renewable energies. For example, since 2007, SION Power Corporation (Tucson, USA) and Oxis Energy (UK) made progress towards the commercialization of Li-S batteries with products showing specific energies over 350 Wh kg -1 for powering electric vehicles. To be on a par with the current LIB technology, the ultimate goal of achieving 500 Wh kg -1 for Li-S battery will make it more competitive for widespread commercialization.

Li, Mengya↗

Scalable Nano-Scaffold SOFC Anode Architecture Enabling Direct Hydrocarbon Utilization

This project is based on WVU’s pending patents, technology and aims to design and modify the internal surfaces of the Ni/YSZ anode from currently commercially viable Solid Oxide Fuel Cells (SOFCs) using the additive manufacturing process of Atomic Layer Deposition (ALD). The surface architecture/scaffold added onto the internal surface of the anode possesses an engineered nanostructure but it features only commonly-used oxide conductors and electro-catalyst materials. The surface layer possesses a minimum thickness of ~2-40 nm and is solely designed to control the surface reforming reactions and to increase catalytic activity. Three-dimensional (3D) nano scaffold architectures with the noble metal nano-catalyst, low-cost bimetallic catalytic alloys, and nano-scale ionic conducting oxide fully compatible with the state-of-the-art Ni/YSZ anode, were applied to the internal surface of the entire porous SOFC anode using ALD. In the present work, the surface scaffold architecture is essentially multi-functional at the nano-scale, facilitated by the multiple heterostructured interfaces. It will significantly enhance the power density and cell durability for direct hydrocarbon utilization by (1) increasing the number of electrochemical reaction sites to enhance the hydrogen/hydrocarbon oxidation reactions; (2) reducing carbon formation; (3) mitigating the coarsening of backbone Ni phase and the oxidation attack of Ni from oxidants (e.g., H2O, CO2); and (4) promoting the internal reforming capabilities, especially for natural gas applications. ALD is employed to generate stable anode surface architectures that are uniform, precisely controllable at the atomic scale, and accurately repeatable for processing. The engineered anode surface nano-scaffold architecture was cataloged and analyzed using High-resolution Transmission Electron Microscopy (TEM), and cell power/durability performance assessed via comprehensive electrochemical performance testing with commercial specimens and relevant environments using hydrocarbon fuels. To the best of our knowledge, this project is the First Report on ALD of Ni/YSZ. The actual achievement of this Project includes (1). Successful demonstration of 7 types of ALD layers on Ni/YSZ anode, including Co, Ni, Mn, Pt, Ru, ZrOx and multi-functional nano-composite. (1). Conformal coating and subsequently spontaneously pinning the discrete nano-catalyst, including the precious metal nano-catalyst and the Ni and Co catalysts, on the YSZ surface upon the electrochemical operation in the reduced atmosphere. Those nano-catalysts on the ionic-conducting YSZ provided excellent sites for promoting internal reforming; (2). Demonstrated ALD coating increased both catalytic activity and conductivity of Ni/YSZ. Conformal coating provided dopants and introduced additional electrical conducting pathways on the YSZ ionic conductor. The doped surface layer of YSZ with mixed conductivity thus further introduces the active triple phase boundaries adjacent to the ALD-coated nano-catalysts such as Pt, Co, and Ni that are pinned on the YSZ surface. The nano-composite ALD coating on Ni/YSZ anode has significantly increased cell durability; and (3). ALD coating of Ni/YSZ anode increased the power density of the entire cell by 300%. For a long time, the SOFC performance, such as the power density, was deemed hindered by the cathode. The sluggish oxygen reduction reaction (ORR) in the cathode was deemed as hindering the power density of the SOFCs. For the anode-supported commercial SOFCs, the cell performance is considered to be limited by the cathode's performance. For the first time in the field of SOFC, this project has demonstrated that (1). the performance of commercial SOFCs can be further increased by the ALD coating on Ni/YSZ anode backbone. (2). ALD coating on Ni/YSZ fuel electrodes results in the enhancement of power density, and increased reliability, robustness, and endurance of SOFCs, for their application using both hydrogen and hydrocarbon fuels over the entire operating temperature range of 650-800ºC for the inherently functional commercial cells. (3). ALD coating provides alternative approaches of exsolutions for introducing the stable catalyst onto the internal surface of the Ni/YSZ electrode. ALD coating could be much more versatile than exsolution in employing the catalysts with various chemistries onto the various backbones. (4). Due to the negligible amount of ALD materials coated onto the internal surface of the porous cathode of the as-fabricated cells, a peak power density increase up to 300 % induced by ALD coating was simultaneously achieved in terms of both power density and specific power. (5). The ALD coating developed through this project was applied to both the SOFC and Solid Oxide Electrolysis Cells (SOEC). SOEC’s face a similar but more demanding need to improve the fuel electrode's performance. It opens further research directions for electrocatalytic surface nanoionics with a wide range of chemistry. It will revolutionize our ability to render the formation of a nanostructured electrode that has been constantly pursued yet barely achieved for practical SOFC/SOEC applications. The research is also immediately transformative since both the preliminary data and the proposed work are on the direct implantation of nanoionics into the state-of-the-art inherently functional SOCs. It represents an immediate impact on the commercial sectors in SOC technology since the applied ALD processing is computer-controlled ALD coating using the commercial ALD systems, and it is scalable to both the single cells and SOC stacks.

36 MATERIALS SCIENCE↗

Current-Phase Relations of Superconducting PtSi Constriction Josephson Junctions

Here, we study the current-phase relations of superconductor–constriction–superconductor Josephson junctions made from platinum silicide thin films by fabricating dc-superconducting quantum interference devices incorporating pairs of junctions and measuring their magnetic-field-dependent electrical transport. By comparing the supercurrent interference patterns with numerical Ginzburg–Landau simulations, we extract the current-phase relations of individual junctions and quantify the degree of nonlinearity. These measurements show that while the constrictions themselves sustain substantial nonlinearity, the effect is moderated by the kinetic inductance of the device leads, which is an important consideration for practical superconducting circuit applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗