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At least 271 records · Page 15

Searching for a route to synthesize in situ epitaxial Pr 2 Ir 2 O 7 thin films with thermodynamic methods

In situ growth of pyrochlore iridate thin films has been a long-standing challenge due to the low reactivity of Ir at low temperatures and the vaporization of volatile gas species such as IrO 3 (g) and IrO 2 (g) at high temperatures and high P O2 . To address this challenge, we combine thermodynamic analysis of the Pr-Ir-O 2 system with experimental results from the conventional physical vapor deposition (PVD) technique of co-sputtering. Our results indicate that only high growth temperatures yield films with crystallinity sufficient for utilizing and tailoring the desired topological electronic properties and the in situ synthesis of Pr 2 Ir 2 O 7 thin films is fettered by the inability to grow with P O2 on the order of 10 Torr at high temperatures, a limitation inherent to the PVD process. Thus, we suggest techniques capable of supplying high partial pressure of key species during deposition, in particular chemical vapor deposition (CVD), as a route to synthesis of Pr 2 Ir 2 O 7 .

Chemistry↗

Magnetic pinning in a superconducting film by a ferromagnetic layer with stripe domains

A magnetic study of superconductor/ferromagnet bilayers was performed by hysteresis loops and temperature-dependent magnetization measurements. The superconductor/ferromagnet bilayers consist of a Nb film deposited on a Py film with weak perpendicular magnetic anisotropy. By comparing the temperature-dependent magnetization data obtained on samples with different ferromagnetic layer thickness, a decrease of the magnetic pinning with increasing thickness of the ferromagnetic layer has been found. This is confirmed by the reduction of the Nb film critical current density at low fields extracted by using the magnetic irreversibility of the hysteresis loops. Here, the reduction of the pinning can be related to the increase of the stripe width in the ferromagnetic layer observed by magnetic force microscopy (MFM) measurements.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Magnetic field, frequency and temperature dependence of complex conductance of ultrathin La1.65Sr0.45CuO4/La2CuO4 films and the organic superconductors κ-(BEDT-TTF)2Cu[N(CN)2]Br

We used atomic-layer molecular beam epitaxy (ALL-MBE) to synthesize bilayer films of a cuprate metal (La1.65Sr0.45CuO4La1.65Sr0.45CuO4, LSCO) and a cuprate insulator (La2CuO4La2CuO4, LCO), in which interface superconductivity occurs in a layer that is just one-half unit cell thick. We have studied the magnetic field and temperature dependence of the complex sheet conductance, σ(ω)σ(ω), of these films, and compared them to κκ-(BEDT-TTF)2Cu[N(CN)2]Br2Cu[N(CN)2]Br single crystals. The magnetic field HH was applied both parallel and perpendicular to the 2D conducting layers. Experiments have been carried out at frequencies between 23 kHz and 50 MHz using either two-coil mutual inductance technique, or the LC resonators with spiral or rectangular coils. The real and the imaginary parts of the mutual-inductance M(T,ω)M(T,ω) between the coil and the sample were measured and converted to complex conductivity. For HH perpendicular to the conducting layers, we observed almost identical behavior in both films and κκ-Br single crystals: (i) the transition onset in the inductive response, L-1kLk-1(T) occurs at a temperature lower by 2 K than in Reσ(T)Reσ(T), (ii) this shift is almost constant with magnetic field up to 8 T; (iii) the vortex diffusion constant D(T)D(T) is exponential due to pinning of vortex cores. These results can be described by the extended dynamic theory of the Berezinski–Kosterlitz–Thouless (BKT) transition and dynamics of bound vortex–antivortex pairs with short separation lengths.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Film breakdown and nano-porous Mg(OH) 2 formation from corrosion of magnesium alloys in salt solutions

In this paper, small angle neutron scattering (SANS) and scanning transmission electron microscopy (STEM) were used to study film formation by magnesium alloys AZ31B (Mg-3Al-1Zn base) and ZE10A (Elektron 717, E717: Mg-1Zn + Nd, Zr) in H 2 O and D 2 O with and without 1 or 5 wt% NaCl. No SANS scattering changes were observed after 24 h D 2 O or H 2 O exposures compared with as-received (unreacted) alloy, consistent with relatively dense MgO-base film formation. However, exposure to 5 wt% NaCl resulted in accelerated corrosion, with resultant SANS scattering changes detected. The SANS data indicated both particle and rough surface (internal and external) scattering, but with no preferential size features. The films formed in 5 wt% NaCl consisted of a thin, inner MgO-base layer, and a nano-porous and filamentous Mg(OH) 2 outer region tens of microns thick. Chlorine was detected extending to the inner MgO-base film region, with segregation of select alloying elements also observed in the inner MgO, but not the outer Mg(OH) 2 . Modeling of the SANS data suggested that the outer Mg(OH) 2 films had very high surface areas, consistent with loss of film protectiveness. Finally, implications for the NaCl corrosion mechanism, and the potential utility of SANS for Mg corrosion, are discussed.

36 MATERIALS SCIENCE↗

X-Ray Spectroscopy of Ultra-Thin Oxide/Oxide Heteroepitaxial Films: A Case Study of Single-Nanometer VO2/TiO2

Epitaxial ultra-thin oxide films can support large percent level strains well beyond their bulk counterparts, thereby enabling strain-engineering in oxides that can tailor various phenomena. At these reduced dimensions (typically < 10 nm), contributions from the substrate can dwarf the signal from the epilayer, making it difficult to distinguish the properties of the epilayer from the bulk. This is especially true for oxide on oxide systems. Here, we have employed a combination of hard X-ray photoelectron spectroscopy (HAXPES) and angular soft X-ray absorption spectroscopy (XAS) to study epitaxial VO2/TiO2 (100) films ranging from 7.5 to 1 nm. We observe a low-temperature (300 K) insulating phase with evidence of vanadium-vanadium (V-V) dimers and a high-temperature (400 K) metallic phase absent of V-V dimers irrespective of film thickness. Our results confirm that the metal insulator transition can exist at atomic dimensions and that biaxial strain can still be used to control the temperature of its transition when the interfaces are atomically sharp. More generally, our case study highlights the benefits of using non-destructive XAS and HAXPES to extract out information regarding the interfacial quality of the epilayers and spectroscopic signatures associated with exotic phenomena at these dimensions.

Quackenbush, Nicholas↗

Technical Note: Characterization of Corrosion Films Formed on Austenitic Stainless Steel in Supercritical CO 2 Containing H 2 O and O 2

Future technologies require structural alloys resistant to corrosion in supercritical CO 2 (sCO 2 ) fluids containing impurities such as H 2 O and O 2 . Traditional pipeline steels are potentially unsuitable for these environments and more corrosion resistant alloys such as stainless steels might be required. Little is known about the corrosion products formed on, and hence the processes which control corrosion of, stainless steels in impure sCO 2 environments. In this study, austenitic stainless steel 347H (UNS S34709) was exposed to sCO 2 containing H 2 O and O 2 at 8 MPa and 50°C or 250°C, and separately to the aqueous phase in equilibrium with the sCO 2 at 50°C, to simulate conditions expected in sCO 2 -based power cycles and carbon capture and storage pipelines. Only thin (< 20 nm) surface films formed after 500 h resulting in small mass changes and corrosion rates < 10 –4 mm/y, suggesting the material resists significant degradation in these environments. X-ray photoelectron spectroscopy and transmission electron microscopy were used to characterize the corrosion films in detail. Here, the exposure to the aqueous phase resulted in a thin (< 5 nm) Cr-oxide and/or -hydroxide passive film, while exposure to sCO 2 phases resulted in a multilayer Fe-rich oxide structure characteristic of a gas-phase oxidation process.

36 MATERIALS SCIENCE↗

Effect of thermal aging on the tribological properties of polyimide films and polyimide-bonded graphite fluoride films

The effect of thermal aging on the weight loss, adherence, friction and wear of polyimide films and polyimide-bonded graphite fluoride films applied to 440C-HT stainless steel disks and to 304 stainless steel thin foils was studied. The films were exposed at temperatures of 315, 345, 370 or 400 C for 100 hours or more and then evaluated at temperatures of 25, 315 or 345 C in atmospheres of dry or moist air. Polyimide films were found to be brittle after thermal exposure; but polyimide-bonded graphite fluoride films possessed good adherence and gave low friction and wear results. Thus, polyimide-bonded graphite fluoride films appear to be good candidates for solid lubrication applications where long thermal soaks are prevalent.

Fusaro, R. L.↗

Development of self-healing films to improve durability of VIPs by in-situ remediation of film defects

The integrity of the VIP barrier film or envelope is a critical for maintaining the ultra-low thermal conductivity of VIPs. Here, the concept of a self-healing barrier film is described and demonstrated. The self-healing concept is based on an addition reaction between two chemicals, without the need for any external stimuli. The chemicals are incorporated as coatings in a multi-layered film and are initially kept separate with a partition layer. In case of damage, the chemicals would mix, react and heal the damage. Tests of small-scale film samples in a custom vacuum pump apparatus by puncturing the samples demonstrated the proof-of-concept. The tests indicated that the chemicals reacted and healed the puncture immediately to maintain the system vacuum. The intact and punctured self-healing films showed near-identical behaviour, while a control sample allowed the pressure to rise to atmospheric levels on puncturing. Development of films with coated chemicals using tape casting and slot die coating methods is also described. These are low-cost and mature technologies, which are commonly used by various industries. The proposed chemicals are low-cost, commercially available materials. Thus, the self-healing technology is expected to be inexpensive and scalable.

Biswas, Kaushik↗

Atmospheric-Pressure Chemical Vapor Deposition of Iron Pyrite Thin Films

Iron pyrite (cubic FeS{sub 2}) is a promising candidate absorber material for earth-abundant thin-film solar cells. In this report, single-phase, large-grain, and uniform polycrystalline pyrite thin films are fabricated on glass and molybdenum-coated glass substrates by atmospheric-pressure chemical vapor deposition (AP-CVD) using the reaction of iron(III) acetylacetonate and tert-butyl disulfide in argon at 300 C, followed by sulfur annealing at 500--550 C to convert marcasite impurities to pyrite. The pyrite-marcasite phase composition depends strongly on the concentration of sodium in the growth substrate and the sulfur partial pressure during annealing. Phase and elemental composition of the films are characterized by X-ray diffraction, Raman spectroscopy, Auger electron spectroscopy, secondary ion mass spectrometry, Rutherford backscattering spectrometry, and X-ray photoelectron spectroscopy. The in-plane electrical properties are surprisingly insensitive to phase and elemental impurities, with all films showing p-type, thermally activated transport with a small activation energy ({approx}30 meV), a room- temperature resistivity of {approx}1 {Omega} cm, and low mobility. These ubiquitous electrical properties may result from robust surface effects. These CVD pyrite thin films are well suited to fundamental electrical studies and the fabrication of pyrite photovoltaic device stacks.

14 SOLAR ENERGY↗

Magnetic stability of He{sup +} ion irradiated FeO+Fe{sub 3}N granular films

Ion irradiation effects on the magnetic properties of FeO+Fe{sub 3}N (iron oxide/iron nitride) granular films are investigated in this study. The FeO+Fe{sub 3}N granular films were prepared using a nanocluster deposition system. The x-ray diffraction data confirm the presence of FeO and Fe{sub 3}N compounds in the prepared granular films. The saturation magnetization (30 emu/g), coercivity (87.9 Oe), and remanence (3.2 emu/g) of these granular films remain unaltered after irradiation with 2 MeV He{sup +} ions to a fluence of 3 x 10{sup 15} ions/cm{sup 2} at room temperature, indicating that the magnetic properties of these granular films are not affected in a highly radioactive environment. This unique property of the magnetic stability may provide promising applications for advanced data storage.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Nano-structural Characteristics of N-doped ZnO Thin Films and Fabrication of Film Bulk Acoustic Resonator Devices

N-doped ZnO thin films (ZnO:N) with c-axis preferred orientation were prepared on p-Si(100) wafers, using an RF magnetron sputter deposition. For ZnO deposition, N{sub 2}O gas was employed as a dopant source and various deposition conditions such as N{sub 2}O gas fraction and RF power were applied. In addition, the film bulk acoustic resonator (FBAR) devices with three kinds of top electrodes patterns were fabricated by using the N-doped ZnO thin films as the piezoelectric layers. The depth profiles of the nitrogen [N] atoms incorporated into the ZnO thin films were investigated by an Auger Electron Spectroscopy (AES) and the nano-scale structural characteristics of the N-doped ZnO (ZnO:N) thin films were also investigated by a scanning electron microscope (SEM) technique. The fabricated resonators were evaluated by measuring the return loss (S{sub 11}) characteristics using a probe station and E8361A PNA Network Analyzer.

36 MATERIALS SCIENCE↗

In Situ Real-Time Radiographic Study of Thin Film Formation Inside Rotating Hollow Spheres

Hollow spheres with uniform coatings on the inner surface have applications in optical devices, time- or site controlled drug release, heat storage devices, and target fabrication for inertial confinement fusion experiments. The fabrication of uniform coatings, which is often critical for the application performance, requires precise understanding and control over the coating process and its parameters. Here, we report on in-situ real-time radiography experiments that provide critical spatio-temporal information about the distribution of fluids inside hollow spheres during uniaxial rotation. Image analysis and computer fluid dynamics simulations were used to explore the effect of liquid viscosity and rotational velocity on the film uniformity. The data were then used to demonstrate the fabrication of uniform sol-gel chemistry derived porous polymer films inside 2mm inner diameter diamond shells.

aerogel↗

Control of Domain Structures in Multiferroic Thin Films through Defect Engineering

Domain walls (DWs) have become an essential component in nanodevices based on ferroic thin films. The domain configuration and DW stability, however, are strongly dependent on the boundary conditions of thin films, which make it difficult to create complex ordered patterns of DWs. Here, it is shown that novel domain structures, that are otherwise unfavorable under the natural boundary conditions, can be realized by utilizing engineered nanosized structural defects as building blocks for reconfiguring DW patterns. It is directly observed that an array of charged defects, which are located within a monolayer thickness, can be intentionally introduced by slightly changing substrate temperature during the growth of multiferroic BiFeO 3 thin films. These defects are strongly coupled to the domain structures in the pretemperature-change portion of the BiFeO 3 film and can effectively change the configuration of newly grown domains due to the interaction between the polarization and the defects. Thus, two types of domain patterns are integrated into a single film without breaking the DW periodicity. The potential use of these defects for building complex patterns of conductive DWs is also demonstrated.

36 MATERIALS SCIENCE↗

Creating Functional Oxynitride–Silicon Interfaces and SrNbO 2 N Thin Films for Photoelectrochemical Applications

Photoelectrochemical performance dependence upon absorption length, carrier diffusion length, and surface area of an oxynitride photoabsorber is investigated. How best to fabricate optical-quality thin films of bandgap-tunable oxynitrides is also discussed. We targeted the stoichiometric compound SrNbO 2 N as an optimal wide-bandgap photoabsorber (1.9 eV) for use with silicon (1.1 eV) in a tandem structure photoelectrochemical cell. Preparation of perovskite oxynitrides at high-temperature as isolated powders is often straightforward, but it is difficult to integrate them as thin films in tandem junction devices with low-temperature materials. Here we develop the first method to prepare optical-quality SrNbO 2 N thin-films of tunable thickness and roughness on single-crystal silicon substrate. This achievement required an interfacial layer of ultra-thin TaN to be used as a barrier to reduce the inter-diffusion of silicon and oxygen during oxynitride syn-thesis. We produced a variety of SrNbO 2 N film thicknesses (20-440 nm) on n + -Si(100) surfaces. Roughness factor (0.14-21) scaled with thickness. The intrinsic photoelectrochemical activity of these devices was evaluated using a low-barrier sacrificial electron donor. Photocurrent density and photovoltage revealed a significant (and non-linear) dependence on film thickness and roughness. Furthermore, absorption length, carrier diffusion length, and surface area were each found to play key roles. Balancing these is required for optimally performing devices.

08 HYDROGEN↗