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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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50 records · Page 3

Strain and Defect-Tailored Magnetotransport in NiCo 2 O 4 Thin Films and Freestanding Membranes

Magnetic spinel NiCo 2 O 4 is promising for developing spintronic applications due to its high magnetic Curie temperature, high spin polarization, fast spin dynamics, and strain-tunable magnetic anisotropy, while its electronic and magnetic properties depend sensitively on epitaxial strain and disorder. Here, in this study, we use epitaxial NiCo 2 O 4 thin films and freestanding NiCo 2 O 4 membranes as model systems to reveal the complex interplay of strain and defects in determining the metallicity and magnetotransport properties of the ferrimagnetic spinel. NiCo 2 O 4 on perovskite substrates and NiCo 2 O 4 membranes exhibit insulating behaviors and spin canting, in sharp contrast to the metallic NiCo 2 O 4 films on spinel substrates that possess strong perpendicular magnetic anisotropy. Anisotropic magnetoresistance studies provide critical information about disorder-induced spin scattering and strain-induced tetragonal magnetocrystalline anisotropy, which is corroborated by comprehensive electron microscopy characterizations. Our study presents a promising venue for designing flexible magnetic memory, sensor, and spintronic applications.

36 MATERIALS SCIENCE↗

New Aptes Cross-linked Polymers from Poly(ethylene oxide)s and Cyanuric Chloride for Lithium Batteries

A new series of polymer electrolytes for use as membranes for lithium batteries are described. Electrolytes were made by polymerization between cyanuric chloride and diamino-terminated poly(ethylene oxide)s, followed by cross-linking via a sol-gel process. Thermal analysis and lithium conductivity of freestanding polymer films were studied. The effects of several variables on conductivity were investigated, such as length of backbone PEO chain, length of branching PEO chain, extent of branching, extent of cross-linking, salt content, and salt counterion. Polymer films with the highest percentage of PEO were found to be the most conductive, with a maximum lithium conductivity of 3.9 x 10(exp -5) S/cm at 25 C. Addition of plasticizer to the dry polymers increased conductivity by an order of magnitude.

Tigelaar, Dean M.↗

Chemical Sharpening, Shortening, and Unzipping of Boron Nitride Nanotubes

Boron nitride nanotubes (BNNTs), the one-dimensional member of the boron nitride nanostructure family, are generally accepted to be highly inert to oxidative treatments and can only be covalently modifi ed by highly reactive species. Conversely, it is discovered that the BNNTs can be chemically dispersed and their morphology modifi ed by a relatively mild method: simply sonicating the nanotubes in aqueous ammonia solution. The dispersed nanotubes are significantly corroded, with end-caps removed, tips sharpened, and walls thinned. The sonication treatment in aqueous ammonia solution also removes amorphous BN impurities and shortened BNNTs, resembling various oxidative treatments of carbon nanotubes. Importantly, the majority of BNNTs are at least partially longitudinally cut, or "unzipped". Entangled and freestanding BN nanoribbons (BNNRs), resulting from the unzipping, are found to be approximately 5-20 nm in width and up to a few hundred nanometers in length. This is the fi rst chemical method to obtain BNNRs from BNNT unzipping. This method is not derived from known carbon nanotube unzipping strategies, but is unique to BNNTs because the use of aqueous ammonia solutions specifi cally targets the B-N bond network. This study may pave the way for convenient processing of BNNTs, previously thought to be highly inert, toward controlling their dispersion, purity, lengths, and electronic properties.

Liao, Yunlong↗

Sintering and Interface Strain Tolerance of Plasma-Sprayed Thermal and Environmental Barrier Coatings

Ceramic thermal and environmental barrier coatings will be more aggressively designed to protect gas turbine engine hot section SiC/SiC Ceramic Matrix Composite (CMC) components in order to meet future engine higher fuel efficiency and lower emission goals. A coating system consisting of a zirconia-based oxide topcoat (thermal barrier) and a mullite/BSAS silicate inner coat (environmental barrier) is often considered a model system for the CMC applications. However, the coating sintering, and thermal expansion mismatch between the zirconia oxide layer and the silicate environmental barrier/CMC substrate will be of major concern at high temperature and under thermal cycling conditions. In this study, the sintering behavior of plasma-sprayed freestanding zirconia-yttria-based thermal barrier coatings and mullite (and/or barium-strontium-aluminosilicate, i.e., BSAS) environmental barrier coatings was determined using a dilatometer in the temperature range of 1200-1500 C. The effects of test temperature on the coating sintering kinetics were systematically investigated. The plasma-sprayed zirconia-8wt.%yttria and mullite (BSAS) two-layer composite coating systems were also prepared to quantitatively evaluate the interface strain tolerance of the coating system under thermal cycling conditions based on the dilatomentry. The cyclic response of the coating strain tolerance behavior and interface degradation as a function of cycle number will also be discussed.

Zhu, Dongming↗

Highly confined epsilon-near-zero and surface phonon polaritons in SrTiO 3 membranes

Recent theoretical studies have suggested that transition metal perovskite oxide membranes can enable surface phonon polaritons in the infrared range with low loss and much stronger subwavelength confinement than bulk crystals. Such modes, however, have not been experimentally observed so far. Here, using a combination of far-field Fourier-transform infrared (FTIR) spectroscopy and near-field synchrotron infrared nanospectroscopy (SINS) imaging, we study the phonon polaritons in a 100 nm thick freestanding crystalline membrane of SrTiO 3 transferred on metallic and dielectric substrates. We observe a symmetric-antisymmetric mode splitting giving rise to epsilon-near-zero and Berreman modes as well as highly confined (by a factor of 10) propagating phonon polaritons, both of which result from the deep-subwavelength thickness of the membranes. Theoretical modeling based on the analytical finite-dipole model and numerical finite-difference methods fully corroborate the experimental results. Our work reveals the potential of oxide membranes as a promising platform for infrared photonics and polaritonics.

36 MATERIALS SCIENCE↗

Magnetic La 0.7 Sr 0.3 MnO 3 Membranes Synthesized by Etching a Sr 3 Al 2 O 6 Sacrificial Layer Using an Intermediary Manganite Protection Layer

The integration of perovskite oxides onto flexible substrates has witnessed significant advancements owing to the development of an epitaxial lift-off technique utilizing a Sr 3 Al 2 O 6 sacrificial layer. However, Sr 3 Al 2 O 6 is susceptible to instability in both air and high-temperature oxygen atmospheres, potentially leading to degradation during the growth of the functional oxide layer. In this study, we investigate the use of an oxygen-deficient La 0.7 Sr 0.3 MnO 3 as capping layer, and demonstrate its ability to stabilize Sr 3 Al 2 O 6 films in ambient air. We successfully synthesized freestanding La 0.7 Sr 0.3 MnO 3 membranes by etching this sacrificial layer and transferring them onto flexible polymer substrates. Importantly, the magnetic properties of the La 0.7 Sr 0.3 MnO 3 films are preserved in these membranes. Furthermore, our results underline that employing a thin manganite capping layer ensures both high structural quality and the preservation of functional properties in the resulting membranes.

Deposition↗

Low‐Loss Far‐Infrared Surface Phonon Polaritons in Suspended SrTiO 3 Nanomembranes

Phonon polaritons (PhPs), excitations arising from the coupling of light with lattice vibrations, enable light confinement and local field enhancement, which is essential for various photonic and thermal applications. To date, PhPs with high confinement and low loss are mainly observed in the mid-infrared regime and mostly in manually exfoliated flakes of van der Waals (vdW) materials. In this work, the existence of low-loss, thickness-tunable phonon polaritons in the far-infrared regime within transferable freestanding SrTiO 3 membranes synthesized through a scalable approach, achieving high figures of merit is demonstrated, which are comparable to the previous record values from the vdW materials. Leveraging atomic precision in thickness control, large dimensions, and compatibility with mature oxide electronics, functional oxide membranes present a promising large-scale 2D platform alternative to vdW materials for on-chip polaritonic technologies in the infrared regime.

functional oxide membranes↗

Electrochemical chlor-iron process for iron production from iron oxide and salt water

The iron and steel industry accounts for ~8% of global greenhouse gas emissions. Electrochemical reduction of iron ore to metal for electric arc furnaces can enable sustainable steel production, but existing electrochemical processes require expensive capital or electrolytes. Here we report a low-temperature, electrochemical cell that consumes low-cost and abundant iron oxide and aqueous sodium chloride, while co-producing sodium hydroxide and chlorine. Industrially relevant current densities and Faradaic efficiencies for iron production were demonstrated, with 94% selectivity to iron metal at an applied current density of 200 mA cm –2 . Freestanding films of phase-pure iron were formed after 4h of continuous, stable electrolysis. The process can lead to levelized costs of iron that are competitive with iron produced in fossil-fuel-powered blast furnaces, and the co-produced sodium hydroxide can be used for CO 2 capture from the air or ocean, creating a net-negative-emission process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Size-Induced Ferroelectricity in Antiferroelectric Oxide Membranes (Adv. Mater. 17/2023)

Thin Films. In article number 2210562, Ruijuan Xu, Kevin J. Crust, Varun Harbola, and co-workers report intrinsic size-driven scaling in lead-free antiferroelectric thin films. They demonstrate an intriguing antiferroelectric-to-ferroelectric transition upon reducing the thickness of antiferroelectric NaNbO 3 membranes. Here, the image shows the coexistence of ferroelectric and antiferroelectric phases in freestanding NaNbO 3 membranes.

36 MATERIALS SCIENCE↗

Control of ternary alloy composition during remote epitaxy on graphene

Understanding the sticking coefficient σ, i.e., the probability of an adatom sticking to a surface, is essential for controlling the stoichiometry during epitaxial film growth. However, σ on monolayer graphene-covered surfaces and its impact on remote epitaxy are not understood. Here, using molecular-beam epitaxial growth of the magnetic shape memory alloy Ni 2 MnGa, we show that the sticking coefficients for metals on graphene-covered MgO (001) are less than one and are temperature and element dependent, as revealed by ion backscattering spectrometry and energy-dispersive x-ray spectroscopy. This lies in stark contrast with most transition metals sticking on semiconductor and oxide substrates, for which σ is near unity at typical growth temperatures (T < 800°C). By initiating growth below 400°C, where the sticking coefficients are closer to unity and wetting on the graphene surface is improved, we demonstrate the epitaxy of Ni 2 MnGa films with controlled stoichiometry that can be exfoliated to produce freestanding membranes. Straining these membranes tunes the magnetic coercive field. Finally, our results provide a route to synthesize membranes with complex stoichiometries whose properties can be manipulated via strain.

36 MATERIALS SCIENCE↗

Role of transferred graphene on atomic interaction of GaAs for remote epitaxy

Remote epitaxy is a recently discovered type of epitaxy, wherein single-crystalline thin films can be grown on graphene-coated substrates following the crystallinity of the substrate via remote interaction through graphene. Although remote epitaxy provides a pathway to form freestanding membranes by controlled exfoliation of grown film at the graphene interface, implementing remote epitaxy is not straightforward because atomically precise control of interface is required. Here, we unveil the role of the graphene–substrate interface on the remote epitaxy of GaAs by investigating the interface at the atomic scale. By comparing remote epitaxy on wet-transferred and dry-transferred graphene, we show that interfacial oxide layer formed at the graphene–substrate interface hinders remote interaction through graphene when wet-transferred graphene is employed, which is confirmed by an increase of interatomic distance through graphene and also by the formation of polycrystalline films on graphene. On the other hand, when dry-transferred graphene is employed, the interface is free of native oxide, and single-crystalline remote epitaxial films are formed on graphene, with the interatomic distance between the epilayer and the substrate matching with the theoretically predicted value. The first atomic layer of the grown film on graphene is vertically aligned with the top layer of the substrate with these atoms having different polarities, substantiating the remote interaction of adatoms with the substrate through graphene. These results directly show the impact of interface properties formed by different graphene transfer methods on remote epitaxy.

36 MATERIALS SCIENCE↗

Fabrication of ultrathin suspended membranes from atomic layer deposition films

In this report, ultrathin films suspended as freestanding membranes are critical to many microelectronic and materials science applications. However, fabrication methods are currently limited in either their flexibility, due to material selectivity issues during the final membrane release, or their scalability. Here, we demonstrate a novel fabrication process for suspending ultrathin films with thicknesses as low as 4 nm and lateral dimensions up to 20 x 1000 μm from a variety of materials grown by atomic layer deposition. A silicon nitride membrane serves as the support for a sacrificial polymer layer and an ultrathin atomic layer deposition film which, after plasma etching, will form the membrane. The high chemical selectivity between atomic layer deposition-grown transition metal nitrides and oxides and the sacrificial polymer means that ultrathin films of a variety of materials can be released without damage using a single process. Electrically conductive titanium nitride membranes can be produced by this method and are of significant interest for electron microscopy applications. Electron transparency of titanium nitride membranes was found to be ~14% higher than silicon nitride of the same thickness, and of similar conductivity to graphite, meaning that ultrathin, conductive, and electron transparent membranes can be fabricated at scale. These membranes are ideal supports for electron and photon characterization techniques, as well as microelectromechanical system applications that require a conductive membrane.

36 MATERIALS SCIENCE↗

Methods of making lithium ion conducting sulfide glass

A lithium ion-conductive solid electrolyte including a freestanding inorganic vitreous sheet of sulfide-based lithium ion conducting glass is capable of high performance in a lithium metal battery. Such an electrolyte is also manufacturable, and readily adaptable for battery cell and cell component manufacture, in a cost-effective, scalable manner using an automated machine based system, apparatus and methods based on inline spectrophotometry to assess and inspect the quality of such vitreous solid electrolyte sheets and associated components. Suitable manufacturing methods can involve providing a sulfur precursor, providing a boron precursor material having lithium as a second constituent, combining the sulfur and boron precursor materials to form a precursor mixture, melting the mixture, and cooling the melt to form a solid lithium ion conducting glass. The glass may have a Li+ conductivity of at least 10 −5 S/cm. The boron precursor material may be synthesized by reducing boron oxide to boron metal by heating the boron oxide in direct contact with lithium metal.

Visco, Steven J.↗

Deviation from Debye-Waller behavior in single crystalline freestanding Ni⁢ O membranes studied via ultrafast electron diffraction

Here, we realize single-crystal freestanding Ni⁢O films on Si⁢N membranes, enabling thin-film scattering experiments with little or no substrate background signal. These membrane samples provide a critical platform for performing ultrafast electron diffraction (UED) to probe the response of the lattice to laser excitation. We show that epitaxial Ni⁢O films on a water-soluble Sr 2 ⁢Ca⁢Al 2⁢ O 6 buffer layer on Sr⁢Ti⁢O 3 substrates can be transferred as freestanding films to the Si⁢N membranes while maintaining the epitaxial character of the films. An above-gap photoexcitation (𝜆 =266 nm) incident on the sample stimulates an initial lattice response of the order of 1.1 ps, followed by the persistence of this state for more than 20 ps. We observe typical Debye-Waller behavior in peaks with 𝑞 above the (220) family, but a distinct deviation from this behavior is seen in low-𝑞 peaks. We relate this behavior to a dynamic decrease in sample mosaicity in response to the optical pump of the order of 3% that endures for approximately 4 ps. We suspect that this dynamic mosaicity is due to laser-induced strain propagation. This work demonstrates the viability of the thin-film transfer method for UED and paves the way for the study of the dynamic response of antiferromagnetic thin-film oxides.

Wisser, Jacob J. [Stanford Univ., CA (United State↗