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At least 1,207 records · Page 67

An impermeable copper surface monolayer with high-temperature oxidation resistance

Despite numerous efforts involving surface coating, doping, and alloying, maintaining surface stability of metal at high temperatures without compromising intrinsic properties has remained challenging. Here, we present a pragmatic method to address the accelerated oxidation of Cu, Ni, and Fe at temperatures exceeding 200 °C. Inspired by the concept that oxygen (O) itself can effectively obstruct the pathway of O infiltration, this study proposes the immobilization of O on the metal surface. Through extensive calculations considering various elements (C, Al, Si, Ge, Ga, In, and Sn) to anchor O on Cu surfaces, Si emerges as the optimal element. The theoretical findings are validated through systematic sputtering deposition experiments. The introduction of anchoring elements to reinforce Cu–O bonds enables the formation of an atomically thin barrier on the Cu surface, rendering it impermeable to O even at high temperatures (400 °C) while preserving its intrinsic conductivity. This oxidation resistance, facilitated by the impermeable atomic monolayer, opens promising opportunities for researchers and industries to overcome limitations associated with the use of oxidizable metal films.

36 MATERIALS SCIENCE↗

In-situ integrated processing and characterization of thin films of high temperature superconductors, dielectrics and semiconductors by MOCVD

In this strategy of depositing the basic building blocks of superconductors, semiconductors, and dielectric having common elements, researchers deposited superconducting films of Y-Ba-Cu-O, semiconductor films of Cu2O, and dielectric films of BaF2 and Y2O3 by metal oxide chemical vapor deposition (MOCVD). By switching source materials entering the chamber, and by using direct writting capability, complex device structures like three-terminal hybrid semiconductors/superconductors transistors can be fabricated. The Y-Ba-Cu-O superconducting thin films on BaF2/YSZ substrates show a T(sub c) of 80 K and are textured with most of the grains having their c-axis or a-axis perpendicular to the substrate. Electrical characteristics as well as structural characteristics of superconductors and related materials obtained by x-ray defraction, electron microscopy, and energy dispersive x-ray analysis are discussed.

Singh, R.↗

Deposition and characterization of α-Fe 2 O 3 /Pd thin films for neutron reflectometry studies

Here, we report deposition of hematite/Pd thin films on silicon wafers via radio frequency (RF) magnetron sputtering and subsequent characterization for future in situ neutron reflectometry studies. Following deposition, the hematite/Pd thin films were characterized as prepared and after annealing in air for 2h at 400, 500, and 600 °C, respectively. Raman spectroscopy, grazing incidence x-ray diffraction, and neutron reflectometry (NR) were used to characterize the structure and chemical compositions of the thin films. The results indicate that pure α-Fe 2 O 3 (hematite) films were produced, free from other iron oxide phases and impurities. NR data reveal that one intermediate layer between the Pd layer and the hematite layer was formed during sputtering deposition processes. The fitted scattering length density (SLD) of the as-deposited hematite layer is 70% of the theoretical SLD value, indicating that the grains are loosely packed in the RF-deposited hematite films. After annealing at elevated temperatures, the hematite films show increased SLD values but remain comparable to that of preannealed.

36 MATERIALS SCIENCE↗

Monovalent ion–graphene oxide interactions are controlled by carboxylic acid groups: Sum frequency generation spectroscopy studies

Graphene oxide (GO) is a two-dimensional, mechanically strong, and chemically tunable material for separations. Elucidating GO–ion–water interactions at the molecular scale is highly important for predictive understanding of separation systems. However, direct observations of the nanometer region by GO surfaces under operando conditions are not trivial. Therefore, thin films of GO at the air/water interface can be used as model systems. With this approach, we study the effects of alkali metal ions on water organization near graphene oxide films at the air/water interface using vibrational sum frequency generation (SFG) spectroscopy. Here, we also use an arachidic acid Langmuir monolayer as a benchmark for a pure carboxylic acid surface. Theoretical modeling of the concentration-dependent sum frequency signal from graphene oxide and arachidic acid surfaces reveals that the adsorption of monovalent ions is mainly controlled by the carboxylic acid groups on graphene oxide. An in-depth analysis of sum frequency spectra reveals at least three distinct water populations with different hydrogen bonding strengths. The origin of each population can be identified from concentration dependent variations of their SFG signal. Interestingly, an interfacial water structure seemed mostly insensitive to the character of the alkali cation, in contrast to similar studies conducted at the silica/water interface. However, we observed an ion-specific effect with lithium, whose strong hydration prevented direct interactions with the graphene oxide film.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Observation of well-defined Kohn-anomaly in high-quality graphene devices at room temperature

Abstract Due to its ultra-thin nature, the study of graphene quantum optoelectronics, like gate-dependent graphene Raman properties, is obscured by interactions with substrates and surroundings. For instance, the use of doped silicon with a capping thermal oxide layer limited the observation to low temperatures of a well-defined Kohn-anomaly behavior, related to the breakdown of the adiabatic Born–Oppenheimer approximation. Here, we design an optoelectronic device consisting of single-layer graphene electrically contacted with thin graphite leads, seated on an atomically flat hexagonal boron nitride substrate and gated with an ultra-thin gold layer. We show that this device is optically transparent, has no background optical peaks and photoluminescence from the device components, and no generation of laser-induced electrostatic doping (photodoping). This allows for room-temperature gate-dependent Raman spectroscopy effects that have only been observed at cryogenic temperatures so far, above all the Kohn-anomaly phonon energy normalization. The new device architecture, by decoupling graphene optoelectronic properties from the substrate effects, allows for observing quantum phenomena at room temperature.

Materials Science↗

Edge geometry superconducting tunnel junctions utilizing an NbN/MgO/NbN thin film structure

An edge defined geometry is used to produce very small area tunnel junctions in a structure with niobium nitride superconducting electrodes and a magnesium oxide tunnel barrier. The incorporation of an MgO tunnel barrier with two NbN electrodes results in improved current-voltage characteristics, and may lead to better junction noise characteristics. The NbN electrodes are preferably sputter-deposited, with the first NbN electrode deposited on an insulating substrate maintained at about 250 to 500 C for improved quality of the electrode.

Hunt, Brian D.↗

Edge geometry superconducting tunnel junctions utilizing an NbN/MgO/NbN thin film structure

An edge defined geometry is used to produce very small area tunnel junctions in a structure with niobium nitride superconducting electrodes and a magnesium oxide tunnel barrier. The incorporation of an MgO tunnel barrier with two NbN electrodes results in improved current-voltage characteristics, and may lead to better junction noise characteristics. The NbN electrodes are preferably sputter-deposited, with the first NbN electrode deposited on an insulating substrate maintained at about 250 C to 500 C for improved quality of the electrode.

Hunt, Brian D.↗

Large-area YBa2Cu3O(7-delta) thin films on sapphire for microwave applications

We have deposited YBa2Cu3O(7-delta) (YBCO) films with low microwave surface resistance (Rs) on 5-cm-diam, oxide-buffered sapphire substrates by planar magnetron sputtering. MgO buffer layers are used on M-plane (1 0 -1 0) sapphire, and R-plane (1 -1 0 2) sapphire is buffered by CeO2. Rs values of 450-620 microhms at 77 K and 10 GHz were measured across an entire 5-cm diam YBCO film on M-plane sapphire. For YBCO on R-plane sapphire, Rs values at 77 K and 10 GHz were 950 microohms for a 5-cm-diam wafer and 700 microohms for 1 x 1 sq cm samples.

Cole, B. F.↗

Memristive Behavior Enabled by Amorphous–Crystalline 2D Oxide Heterostructure

The emergence of memristive behavior in amorphous–crystalline 2D oxide heterostructures, which are synthesized by atomic layer deposition (ALD) of a few-nanometer amorphous Al 2 O 3 layers onto atomically thin single-crystalline ZnO nanosheets, is demonstrated. The conduction mechanism is identified based on classic oxygen vacancy conductive channels. ZnO nanosheets provide a 2D host for oxygen vacancies, while the amorphous Al 2 O 3 facilitates the generation and stabilization of the oxygen vacancies. The conduction mechanism in the high-resistance state follows Poole–Frenkel emission, and in the the low-resistance state is fitted by the Mott–Gurney law. From the slope of the fitting curve, the mobility in the low-resistance state is estimated to be ≈2400 cm 2 V -1 s -1 , which is the highest value reported in semiconductor oxides. When annealed at high temperature to eliminate oxygen vacancies, Al is doped into the ZnO nanosheet, and the memristive behavior disappears, further confirming the oxygen vacancies as being responsible for the memristive behavior. The 2D heterointerface offers opportunities for new design of high-performance memristor devices.

2D heterostructures↗

Effect of prior creep at 1365 K on the room temperature tensile properties of several oxide dispersion strengthened alloys

An experimental study was conducted to determine whether oxide dispersion-strengthened (ODS) Ni-base alloys in wrought bar form are subject to creep degradation effects similar to those found in thin-gage sheet. The bar products evaluated included ODS-Ni, ODS-NiCr, and advanced ODS-NiCrAl types; the alloys included microstructures ranging from an essentially perfect single crystal to a structure consisting of very small elongated grains. Tensile test specimens were exposed to creep at various stress levels at 1365 K and then tensile tested at room temperature. Low residual tensile properties, change in fracture mode, appearance of dispersoid free bands, grain boundary cavitation, and/or internal oxidation are interpreted as creep degradation effects. The amount of degradation depends on creep strain, and degradation appears to be due to diffusional creep which produces dispersoid free bands around grain boundaries acting as vacancy sources.

Whittenberger, J. D.↗

Synthesis and Physical Properties of Manganese Chromium Nitride Thin Films Grown via Molecular Beam Epitaxy

Here, we demonstrate the ability to grow epitaxial thin films of manganese–chromium nitride (Mn x Cr 1–x N) across the entire composition range on magnesium oxide (MgO) (1 0 0) surfaces by molecular beam epitaxy. By independently controlling the ratio of the atomic fluxes of manganese and chromium, the compositional dependence of structural and electrical transport properties is determined. Soft X-ray absorption shows that the valence states of Cr( 3+ ) and Mn( 3+ ) remain identical among these MnCrN epitaxial films. The metallic transport behavior of binary manganese nitride (MnN) and chromium nitride (CrN) is suppressed in the ternary alloys. Changes in room temperature electrical resistivity of up to 100 times and 5 orders of magnitude at cryogenic temperatures are observed. This work expands the variety of nitride compounds available for epitaxial integration and could provide additional flexibility for the development of metal–semiconductor–insulator junctions for spintronic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Coherent growth and characterization of van der Waals 1T-VSe2 layers on GaAs(111)B using molecular beam epitaxy

We report epitaxial growth of vanadium diselenide (VSe₂) thin films in the octahedrally coordinated (1T) structure on GaAs(111)B substrates by molecular beam epitaxy. Film thickness from a single monolayer (ML) up to 30 ML is demonstrated. Structural and chemical studies using x-ray diffraction, transmission electron microscopy, scanning tunneling microscopy, and x-ray photoelectron spectroscopy indicate high-quality thin films. Further studies show that monolayer VSe₂ films on GaAs are not air stable and are susceptible to oxidation within a matter of hours, which indicates that a protective capping layer should be employed for device applications. This work demonstrates that VSe₂, a candidate van der Waals material for possible spintronic and electronic applications, can be integrated with III-V semiconductors via epitaxial growth for two- and three-dimensional hybrid devices.

2D materials↗

Permeation Properties of Disordered Metal-Organic Framework Membranes Made by Vapor Phase Ligand Treatment

Zeolitic imidazolate frameworks (ZIFs) are nanoporous molecular sieves offering exciting opportunities for membrane- and adsorption-based gas separations. The Tsapatsis group developed an all-vapor-phase ligand induced permselectivation (LIPS) method for the fabrication of ZIF nanocomposite membranes. The LIPS method consists of a combination of atomic layer deposition of a dense oxide inside the mesopores of a porous support followed by transformation of the dense oxide deposit to nanoporous ZIF by exposure to sublimated vapors of an imidazolate ligand. It enables the formation of thin nanocomposite films consisting of ZIF deposited inside pores with diameters smaller than 10 nm. Vapor-phase conversion of the impermeable ZnO to ZIF increases flux of certain gases more than others. Vapor phase linker/ligand treatment (VPLT) can further modify the properties of LIPS and other membranes. The combination of LIPS with VPLT provides an all-vapor methodology for making and modifying ZIF membranes with the ability to control the ZIF deposit composition and the level of confinement in a variety of mesoporous supports. The propylene/propane separation performance of LIPS/VPLT ZIF membranes confined (entirely or partially) inside mesopores is remarkably superior to that of most conventional ZIF membranes consisting of unconfined (deposited on the external surface of porous supports) polycrystalline films. The accomplishments of this award are: (i) understanding of the LIPS process using mathematical models of atomic layer deposition (ALD), (ii) development of surface modification methods (vapor, e-beam, plasma, and X-ray treatments) to tune permeation properties, (iii) microstructural control of ZIF-8 films using ALD (support modification, direct ALD, and by use of in situ permeability monitoring), (iv) molecular simulations, and (v) thin film characterization and adsorption measurements using spectroscopy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis of epitaxial TaO$_2$ thin films on Al$_2$O$_3$ by suboxide molecular-beam epitaxy and thermal laser epitaxy

Tantalum dioxide (TaO2) is a metastable tantalum compound. Here, we report the epitaxial stabilization of TaO2 on Al2O3 (1-102) (r-plane sapphire) substrates using suboxide molecular-beam epitaxy (MBE) and thermal laser epitaxy (TLE), demonstrating single-oriented, monodomain growth of anisotropically strained thin films. Microstructural investigation is performed using synchrotron X-ray diffraction and scanning transmission electron microscopy. The tetravalent oxidation state of tantalum is confirmed using X-ray absorption and photoemission spectroscopy as well as electron energy-loss spectroscopy. Optical properties are investigated via spectroscopic ellipsometry and reveal a 0.3 eV Mott gap of the tantalum 5d electrons. Density-functional theory and group theoretical arguments are used to evaluate the limited stability of the rutile phase and reveal the potential to unlock a hidden metal-insulator transition concomitant with a structural phase transition to a distorted rutile phase, akin to NbO2. Our work expands the understanding of tantalum oxides and paves the way for their integration into next-generation electronic and photonic devices.

FOS: Physical sciences↗

Sputtering and ion plating for aerospace applications

Sputtering and ion plating technologies are reviewed in terms of their potential and present uses in the aerospace industry. Sputtering offers great universality and flexibility in depositing any material or in the synthesis of new ones. The sputter deposition process has two areas of interest: thin film and fabrication technology. Thin film sputtering technology is primarily used for aerospace mechanical components to reduce friction, wear, erosion, corrosion, high temperature oxidation, diffusion and fatigue, and also to sputter-construct temperature and strain sensors for aircraft engines. Sputter fabrication is used in intricate aircraft component manufacturing. Ion plating applications are discussed in terms of the high energy evaporant flux and the high throwing power. Excellent adherence and 3 dimensional coverage are the primary attributes of this technology.

Spalvins, T.↗

Sputtering and ion plating for aerospace applications

Sputtering and ion plating technologies are reviewed in terms of their potential and present uses in the aerospace industry. Sputtering offers great universality and flexibility in depositing any material or in the synthesis of new ones. The sputter deposition process has two areas of interest: thin film and fabrication technology. Thin film sputtering technology is primarily used for aerospace mechanical components to reduce friction, wear, erosion, corrosion, high temperature oxidation, diffusion and fatigue, and also to sputter-construct temperature and strain sensors for aircraft engines. Sputter fabrication is used in intricate aircraft component manufacturing. Ion plating applications are discussed in terms of the high energy evaporant flux and the high throwing power. Excellent adherence and 3-dimensional coverage are the primary attributes of this technology.

Spalvins, T.↗

Oxide-dispersion-strengthened turbine blades, volume 1

The objective of Project 4 was to develop a high-temperature, uncooled gas turbine blade using MA6000 alloy. The program objectives were achieved. Production scale up of the MA6000 alloy was achieved with a fair degree of tolerance to nonoptimum processing. The blade manufacturing process was also optimized. The mechanical, environmental, and physical property evaluations of MA6000 were conducted. The ultimate tensile strength, to about 704 C (130 F), is higher than DS MAR-M 247 but with a corresponding lower tensile elongation. Also, above 982 C (180 F) MA6000 tensile strength does not decrease as rapidly as MAR-M 247 because the ODS mechanism still remains active. Based on oxidation resistance and diffusional stability considerations, NiCrAlY coatings are recommended. CoCrAly coating should be applied on top of a thin NiCrAlY coating. Vibration tests, whirlpit tests, and a high-rotor-rig test were conducted to ensure successful completion of the engine test of the MA6000 TFE731 high pressure turbine blades. The results of these tests were acceptable. In production quantities, the cost of the Project 4 MA6000 blade is estimated to be about twice that of a cast DS MAR-M 247 blade.

Millan, P. P., Jr.↗

Friction and Wear of Monolithic and Fiber Reinforced Silicon-Ceramics Sliding Against IN-718 Alloy at 25 to 800 C in Atmospheric Air at Ambient Pressure

The friction and wear of monolithic and fiber reinforced Si-ceramics sliding against the nickel base alloy IN-718 at 25 to 800 C was measured. The monolithic materials tested were silicon carbide (SiC), fused silica (SiO2), syalon, silicon nitride (Si3N4) with W and Mg additives, and Si3N4 with Y2O3 additive. At 25 C fused silica had the lowest friction while Si3N4 (W,Mg type) had the lowest wear. At 800 C syalon had the lowest friction while Si3N4 (W,Mg type) and syalon had the lowest wear. The SiC/IN-718 couple had the lowest total wear at 25 C. At 800 C the fused silica/IN-718 couple exhibited the least total wear. SiC fiber reinforced reaction bonded silicon nitride (RBSN) composite material with a porosity of 32 percent and a fiber content of 23 vol percent had a lower coefficient of friction and wear when sliding parallel to the fiber direction than in the perpendicular at 25 C. The coefficient of friction for the carbon fiber reinforced borosilicate composite was 0.18 at 25 C. This is the lowest of all the couples tested. Wear of this material was about two decades smaller than that of the monolithic fused silica. This illustrates the large improvement in tribological properties which can be achieved in ceramic materials by fiber reinforcement. At higher temperatures the oxidation products formed on the IN-718 alloy are transferred to the ceramic by sliding action and forms a thin, solid lubricant layer which decreases friction and wear for both the monolithic and fiber reinforced composites.

Deadmore, Daniel L.↗