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At least 37 records · Page 2

Thin film combinatorial sputtering of Al-Ce alloys: Investigating the phase separation of as-deposited solid solutions and determining the coefficient of thermal expansion

Al x Ce 100–x thin films with a composition range of ~75.0 < x < 99.5 at% (36.5 < x < 97.5 wt%) were synthesized via combinatorial co-sputtering from an Al and an Al 50 Ce 50 target. The crystal structure, phase fraction, film morphology, electrical resistivity, and temperature-dependent coefficients of thermal expansion (CTE) are all correlated to the Al x Ce 100–x composition. The as-deposited films form a metastable solid-solution, and annealing leads to the formation of the thermodynamically stable two-phase system of Al and the α-Al 11 Ce 3 intermetallic. Temperature dependent x-ray diffraction (XRD) reveals that the two phases expand independently of one another, and the thin film Al temperature-dependent CTE is similar to bulk Al. The thin film Al 11 Ce 3 intermetallic phase has a nearly constant CTE of ~1.5 × 10 –5 /°C within the temperature range studied (25–550 °C). To confirm the thin film Al 11 Ce 3 results, bulk stoichiometric Al 11 Ce 3 and +/- 1 wt% Ce samples were prepared and the CTE of each was measured with the same conditions. A Rietveld analysis of the bulk data enabled an estimation of the CTE in each of the 3 orthorhombic lattice parameters, which displayed anisotropic behavior. The thin film and bulk CTE measurements were in very good agreement. Estimations of the temperature dependent CTE of the two-phase alloys are made via the Reuss and Voigt models. Finally, by demonstrating the efficacy of the approach, more complex multi-component rapid materials discovery of low CTE Al-alloys can be pursued via the combinatorial thin film synthesis and XRD measurement.

36 MATERIALS SCIENCE↗

Metal DiSulfide thin films synthesized by pulsed ion beam ablation: Self-assembled structures with improved mechanical properties in humid conditions

Thin films composed of transition metal dichalcogenides such as molybdenum disulfide (MoS 2 ) or tungsten disulfide (WS 2 ) are well known for their solid lubricating behavior in dry environments such as space, but deteriorate rapidly in environments where oxygen is present. There have been many attempts over recent decades to improve MoS 2 lubricating performance in humid environments by addition of metals such as titanium to the film. The additions have come in the form of co-sputtering with the MoS 2 , or formation of nano multilayer coatings. We have previously reported on the synthesis of MoS 2 films by high-power ion beam ablation [Prasad et al, Matls. Lett. 65 (2010) 4–6]. The resulting films are observed to contain spheres of pure Mo of 10–100 nm size evenly dispersed throughout the ~1 μm-thick film, a form of self-assembly not before seen in films produced by sputtering or by pulsed laser deposition (PLD). The remaining Mosingle bondS matrix was observed to crystalize in situ under frictional contact into MoS 2 with the basal planes orienting themselves in the direction of sliding underneath the wear surface. The present study concerns metal additions in the form of alternating layers with MoS 2 deposited in between from an ablation target. The addition of Ti resulted in the extension of good tribological performance to humid air conditions, but the path to good performance appears to be relatively narrow. The same distributed Mo spheres were present in the new film, and similar self-assembled morphologies when V was substituted for the Ti, and when multilayers were formed of WS 2 with Zr additions. Furthermore, it appears that addition of Ti resulted in improvements in mechanical film strength that contributed to the wear ability in humid conditions.

Intense ion beams↗

Sputter deposition of high electrical resistivity Au-Ta alloy coatings on rotating substrates

Sputter deposition of gold-tantalum alloy coatings is a key process for manufacturing hohlraums for magnetically-assisted inertial confinement fusion implosions. In this report we describe direct current magnetron sputter deposition of ~ 10 - μ~ 10 - μm-thick films of Au-80 at.% Ta onto rotating sphero-cylindrical hohlraum and planar Si witness substrates. Emphasis is given to how film microstructure and properties are affected by main deposition parameters, including argon working gas pressure, substrate bias, and the source composition (a single alloyed target compared to co-sputtering from two elemental targets). Experimental findings are correlated with distributions of landing energies and incident angles of depositing species calculated by Monte Carlo simulations of ballistic collisions and gas phase atomic transport. Deposition conditions characterized by low energetics of depositing species favor the formation of a β-Ta-like phase. Implications of these results to hohlraum fabrication are discussed.

36 MATERIALS SCIENCE↗

WO 3 /CuWO 4 Ratio Controls Open-Circuit Photovoltage and Photocurrent in Type II Heterojunction Solar Fuel Photoelectrodes

WO 3 /CuWO 4 photoelectrodes for the oxygen evolution reaction benefit from a type II heterojunction for charge separation. However, the impact of the WO 3 /CuWO 4 ratio on the photocurrent and the photovoltage is not clear. To probe the effect of composition, Cu x W 1-x O y thin films with variable W:Cu ratio were prepared on FTO by reactive magnetron co-sputtering of W and Cu, followed by air annealing at 500ºC. EDS, XRD, Rietveld refinement, and Raman spectroscopy confirm the presence of crystalline WO 3 and CuWO 4 in the W rich films and increasing amounts of amorphous copper oxides in the Cu rich films. Bandgaps were determined by optical absorption spectroscopy, surface photovoltage spectroscopy (SPS), and photoaction spectra and are found to decrease from 2.7 eV to 1.2 eV with increasing copper oxide content. SPS reveals n-type semiconductor photoanode behavior for WO 3 /CuWO 4 samples and p-type photocathode behavior for CuO x rich films. Photoelectrochemical experiments confirm stable water oxidation with Faraday efficiency near unity for all W rich films and photocurrents that are increasing with CuWO 4 content. Optimal performance is seen for WO 3 /CuWO 4 mixed phases containing 47-75 mass% CuWO 4 . These compositions maximize charge separation at the type II heterojunction interface between the two materials. Additionally, according to incident photon to current efficiency (IPCE) data, the WO 3 improves photon conversion below 350 nm, while CuWO 4 improves conversion at 450-525 nm. Overall, this work shows for the first time how the WO 3 /CuWO 4 ratio controls the photovoltage and the photocurrent in type II heterojunction solar fuel photoelectrodes, and how copper oxides in the copper rich films severely degrade the performance. Furthermore, these results are useful in the context of bulk-heterojunction electrodes for the conversion of solar energy into fuels.

CuWO4↗

Tunable multistate field-free switching and ratchet effect by spin-orbit torque in canted ferrimagnetic alloy

Spin-orbit torque is not only a useful probe to study manipulation of magnetic textures and magnetic states at the nanoscale but also it carries great potential for next-generation computing applications. Here we report the observation of rich spin-orbit torque switching phenomena such as field-free switching, multistate switching, memristor behavior and ratchet effect in a single shot, co-sputtered, rare earth-transition metal Gd x Co 100-x . Notably such effects have only been observed in antiferromagnet/ferromagnet bi-layer systems previously. We show that these effects can be traced to a large anistropic canting, that can be engineered into the Gd x Co 100-x system. Further, we show that the magnitude of these switching phenomena can be tuned by the canting angle and the in-plane external field. The complex spin-orbit torque switching observed in canted Gd x Co 100-x not only provides a platform for spintronics but also serves as a model system to study the underlying physics of complex magnetic textures and interactions.

36 MATERIALS SCIENCE↗

One-step sputtering of MoSSe metastable phase as thin film and predicted thermodynamic stability by computational methods

Abstract We present the fabrication of a MoS 2−x Se x thin film from a co-sputtering process using MoS 2 and MoSe 2 commercial targets with 99.9% purity. The sputtering of the MoS 2 and MoSe 2 was carried out using a straight and low-cost magnetron radio frequency sputtering recipe to achieve a MoS 2−x Se x phase with x = 1 and sharp interface formation as confirmed by Raman spectroscopy, time-of-flight secondary ion mass spectroscopy, and cross-sectional scanning electron microscopy. The sulfur and selenium atoms prefer to distribute randomly at the octahedral geometry of molybdenum inside the MoS 2−x Se x thin film, indicated by a blue shift in the A 1g and E 1 g vibrational modes at 355 cm −1 and 255 cm −1 , respectively. This work is complemented by computing the thermodynamic stability of a MoS 2−x Se x phase whereby density functional theory up to a maximum selenium concentration of 33.33 at.% in both a Janus-like and random distribution. Although the Janus-like and the random structures are in the same metastable state, the Janus-like structure is hindered by an energy barrier below selenium concentrations of 8 at.%. This research highlights the potential of transition metal dichalcogenides in mixed phases and the need for further exploration employing low-energy, large-scale methods to improve the materials’ fabrication and target latent applications of such structures.

36 MATERIALS SCIENCE↗

Thin Film Synthesis of SrZn2P2 with SrI2 Post-Annealing for Enhanced Crystallinity and Optoelectronic Quality

Ternary Zintl phosphides are promising light-absorbing semiconductors for thin-film optoelectronic applications, but strategies for controlling their microstructure and optoelectronic quality remain underexplored. Here, we report the synthesis of phase-pure SrZn2P2 thin films using radio-frequency co-sputtering in a PH3 + Ar atmosphere and investigate the impact of post-growth processing on their structural and optical properties. Grazing-incidence X-ray scattering and Raman spectroscopy confirm the formation of crystalline SrZn2P2 films over a finite compositional window. Optical measurements reveal clear absorption near the direct-band-gap energy (~1.8 eV) and near-band-edge photoluminescence. Further, we have studied the effects of chemically compatible halide-assisted annealing. It is found that SrI2 treatments lead to pronounced grain growth and reduced diffraction peak broadening while preserving phase purity, in contrast to rapid thermal or forming-gas annealing. Notably, annealing with SrI2 at 450 degrees C significantly enhances both the intensity and spatial uniformity of the photoluminescence, thus connecting the observed microstructural consolidation with improved radiative recombination. Our study demonstrates that halide-assisted annealing provides an effective pathway for microstructural control in SrZn2P2 thin films and highlights a generalizable processing strategy for advancing Zintl phosphide semiconductors toward optoelectronic applications.

14 SOLAR ENERGY↗

Autonomous sputter synthesis of thin film nitrides with composition controlled by Bayesian optimization of optical plasma emission

Autonomous experimentation has emerged as an efficient approach to accelerate the pace of material discovery. Although instruments for autonomous synthesis have become popular in molecular and polymer science, solution processing of hybrid materials, and nanoparticles, examples of autonomous tools for physical vapor deposition are scarce yet important for the semiconductor industry. Here, we report the design and implementation of an autonomous workflow for sputter deposition of thin films with controlled composition, leveraging a highly automated sputtering reactor custom-controlled by Python, optical emission spectroscopy (OES), and a Bayesian optimization algorithm. We modeled film composition, measured by x-ray fluorescence, as a linear function of plasma emission lines monitored during co-sputtering from elemental Zn and Ti targets in an N 2 and Ar atmosphere. A Bayesian control algorithm, informed by OES, navigates the space of sputtering power to fabricate films with user-defined compositions by minimizing the absolute error between desired and measured optical emission signals. We validated our approach by autonomously fabricating Zn x Ti 1-x N y films that deviate from the targeted cation composition by a relative ±3.5%, even for 15 nm thin films, demonstrating that the proposed approach can reliably synthesize thin films with a specific composition and minimal human interference. Moreover, the proposed method can be extended to more difficult synthesis experiments where plasma intensity lines depend non-linearly on pressure, or the elemental sticking coefficients strongly depend on the substrate temperature.

36 MATERIALS SCIENCE↗

Superior plastic flow stability of self-patterned carbide – amorphous ceramic nanostructures

Amorphous ceramics and carbides exhibit superb strength but poor plasticity. Here, we synthesized TiC-SiOC nanostructures with TiC-nanocarbides embedded in amorphous ceramic SiOC by co-sputtering followed by high-temperature annealing and/or irradiation. TiC-SiOC nanostructures exhibit high strength and good plastic flow stability even after heavy irradiation, 7 GPa at room temperature and 3.6 GPa at 700 ℃ with a uniform strain of about 10%∼18%. The uniform deformation is accommodated by the shearing of amorphous ceramic and the rotation of nanocarbides. Nanocarbides inhibit the propagation of shear banding in amorphous SiOC, and amorphous-crystal interfaces act as sinks to manage irradiation-induced defects.

36 MATERIALS SCIENCE↗

Combinatorial sputter deposition of ultrathick Au-Bi alloy films

We report gold-bismuth alloys are of interest as catalysts and catalytic sensing systems, electrochemical sensors, superconductors, and hohlraums for magnetically assisted inertial confinement fusion implosions. Radiation-hydrodynamics simulations with the Lasnex code of laser-driven hohlraums predict higher x-ray drive from Au-Bi alloys compared with cases of Au-Ta or pure Au and Bi hohlraums. Here, we use direct current magnetron sputtering in Ar gas, with co-sputtering from two elemental targets, to deposit Au-Bi alloys with Bi content of 9–77 at.% and thicknesses up to ~20 µm. Films are characterized by a combination of x-ray diffraction, Rutherford backscattering, scanning electron microscopy, substrate-curvature-based residual stress, and electronic transport measurements. Experiments are complemented by Monte Carlo simulations of ballistic sputtering and gas phase transport of depositing species and Ar gas atoms. Results show that all films are polycrystalline, with three distinct compositional regimes dominated by Au, Au 2 Bi, and Bi crystallographic phases. A metallic behavior of the temperature dependence of electrical resistivity is observed for all the films. Films with Bi content above ~30 at.% exhibit porosity, which is tolerable to hohlraum x-ray drive based on Lasnex simulations.

36 MATERIALS SCIENCE↗

The effect of metal–insulator interface interactions on electrical transport in granular metals

Here, we present an in-depth study of metal–insulator interfaces within granular metal (GM) films and correlate their interfacial interactions with structural and electrical transport properties. Nominally 100 nm thick GM films of Co and Mo dispersed within yttria-stabilized zirconia (YSZ), with volumetric metal fractions (φ) from 0.2–0.8, were grown by radio frequency co-sputtering from individual metal and YSZ targets. Scanning transmission electron microscopy and DC transport measurements find that the resulting metal islands are well-defined with 1.7–2.6 nm average diameters and percolation thresholds between φ = 0.4–0.5. The room temperature conductivities for the φ = 0.2 samples are several orders of magnitude larger than previously-reported for GMs. X-ray photoemission spectroscopy indicates both oxygen vacancy formation within the YSZ and band-bending at metal–insulator interfaces. The higher-than-predicted conductivity is largely attributed to these interface interactions. In agreement with recent theory, interactions that reduce the change in conductivity across the metal–insulator interface are seen to prevent sharp conductivity drops when the metal concentration decreases below the percolation threshold. These interface interactions help interpret the broad range of conductivities reported throughout the literature and can be used to tune the conductivities of future GMs.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Exploring Structural Anisotropy in Amorphous Tb-Co via Changes in Medium-Range Ordering

Amorphous thin films grown by magnetron co-sputtering exhibit changes in atomic structure with varying growth and annealing temperatures. Structural variations influence the bulk properties of the films. Scanning nanodiffraction performed in a transmission electron microscope (TEM) is applied to amorphous Tb 17 Co 83 (a-Tb-Co) films deposited over a range of temperatures to measure relative changes in medium-range ordering (MRO). These measurements reveal an increase in MRO with higher growth temperatures and a decrease in MRO with higher annealing temperatures. The trend in MRO indicates a relationship between the growth conditions and local atomic ordering. By tilting select films, the TEM measures variations in the local atomic structure as a function of orientation within the films. The findings support claims that preferential ordering along the growth direction results from temperature-mediated adatom configurations during deposition, and that oriented MRO correlates with increased structural anisotropy, explaining the strong growth-induced perpendicular magnetic anisotropy found in rare earth–transition metal films. Beyond magnetic films, we propose the tilted FEM workflow as a method of extracting anisotropic structural information in a variety of amorphous materials with directionally dependent bulk properties, such as films with inherent bonding asymmetry grown by physical vapor deposition.

36 MATERIALS SCIENCE↗

A15 phase Ta 3⁢ Sb thin films: Direct synthesis, charge transport, and spin-orbit torque

Ta 3 ⁢Sb is one of the A15 compounds that have been predicted to have giant spin Hall conductivities due to the gapped Dirac-like band crossings in their electronic structures. We use co-sputtering to directly synthesize thin films of Ta 3 ⁢Sb and identify a large window of Ta:Sb flux ratio that permits the formation of single-phase A15 structure. These sputtered films have an actual Ta:Sb atomic ratio of 4:1, as determined from Rutherford backscattering spectrometry. Their high resistivity, at the Mott-Ioffe-Regel limit, suggests that the electron mean free path is comparable to interatomic distances. From harmonic Hall and spin-torque ferromagnetic resonance measurements, the intrinsic spin Hall conductivity of thin film Ta 3 ⁢Sb is estimated to be in the range of −526 to −1230⁢(ℏ/𝑒)S/cm at 300 K, lower in magnitude than the predicted value of −1400⁢(ℏ/𝑒)S/cm . Here, first-principles calculations of the electronic structure show that the discrepancy is consistent with an increase of the Fermi level due to the nonideal stoichiometry needed to stabilize the A15 structure.

Density functional theory↗

Impact of high-temperature annealing on hafnia-silica composite coatings deposited via ion beam sputtering for high-peak power 1064 nm lasers

The maximum power handling fluence of high-peak and average power laser systems is often limited by the laser damage of the coatings on optical components. Furthermore, these multilayer dielectric coatings are limited in their maximum power handling due to laser-damage-prone defects in the lower optical bandgap, higher optical index material. Some of these defects can be mitigated by thermal annealing to high temperatures, which can greatly reduce the linear absorbative precursors. Typically, hafnia and silica are the materials of choice for high-peak and average power laser systems in the ultraviolet through infrared spectral range; however, hafnia crystalizes readily when annealed at high temperatures. In this study, we prepare composite HfO 2 -SiO 2 coatings by co-sputtering hafnia and silica in an ion beam sputtering system and compare them to pure hafnia-based coatings. We demonstrate that crystallinity in hafnia can be completely suppressed when it is mixed with silica, such as the composite coatings in this study. High reflectors were fabricated and annealed, demonstrating that the multilayer dielectric stacks can survive high-temperature annealing and exhibit an excellent linear absorption of 0.2 +/- 1 ppm at 1064 nm. Short- and long-pulse laser damage was explored, demonstrating the complex relationship between linear absorption and the non-linear absorption which drives pulsed laser damage. These results provide an excellent route to the creation of very low linear absorption optical coatings, which also utilize low scattering materials that are best suited for high-peak and average power applications.

Harthcock, Colin [Lawrence Livermore National Labo↗

Cylindrical Magnetron Development for Nb3sn Deposition via Magnetron Sputtering

Due to its better superconducting properties (critical temperature Tc~ 18.3 K, superheating field Hsh~ 400 mT), Nb₃Sn is considered as a potential alternative to niobium (Tc~ 9.25 K, Hsh~ 200 mT) for superconducting radiofrequency (SRF) cavities for particle acceleration. Magnetron sputtering is an effective method to produce superconducting Nb₃Sn films. We deposited superconducting Nb₃Sn films on samples with magnetron sputtering using co-sputtering, sequential sputtering, and sputtering from a stoichiometric target. Nb₃Sn films produced by magnetron sputtering in our previous experiments have achieved DC superconducting critical temperature up to 17.93 K and RF superconducting transition at 17.2 K. A magnetron sputtering system with two identical cylindrical cathodes that can be used to sputter Nb₃Sn films on cavities has been designed and is under development now. We report on the design and the current progress on the development of the system.

43 PARTICLE ACCELERATORS↗

Micro-Mechanically Guided High-Throughput Alloy Design Exploration Towards Metastability-Induced H Embrittlement Resistance

We develop a high-throughput approach for studying H embrittlement (HE)-resistance in alloys, which is based on combinatorial compositional screening of metastability effects by in situ scanning electron microscopy H-analyses. The project objective included: (i) technique development of high-throughput screening (HTS) for HE-resistance, (ii) discovery of new metallic materials with superior HE-resistance, (iii) Multiscale verification of HE-resistance of the new alloys and H-barrier layers, from atomic scale to an engineering scale. The investigation focused on a model system that enables exploration of different metastable states in Fe-based complex-concentrated alloys. Composition spread islands with hundreds of varying compositions are fabricated on a single substrate using a combinatorial co-sputtering technique. To screen these alloys, we developed and employed a home-built SEM-based integrated analysis system capable of characterizing H-permeability, H-trapping, H-influence on mechanical properties, and other material properties, as well as atomistic to continuum simulations to study the underlying physics.

08 HYDROGEN↗

Combinatorial Cu-Ni Alloy Thin-Film Catalysts for Layer Number Control in Chemical Vapor-Deposited Graphene

We synthesized a combinatorial library of CuxNi1−x alloy thin films via co-sputtering from Cu and Ni targets to catalyze graphene chemical vapor deposition. The alloy morphology, composition, and microstructure were characterized via scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDS), and X-ray diffraction (XRD), respectively. Subsequently, the CuxNi1−x alloy thin films were used to grow graphene in a CH4-Ar-H2 ambient at atmospheric pressure. The underlying rationale is to adjust the CuxNi1−x composition to control the graphene. Energy dispersive x-ray spectroscopy (EDS) analysis revealed that a continuous gradient of CuxNi1−x (25 at. % < x < 83 at.%) was initially achieved across the 100 mm diameter substrate (~0.9%/mm composition gradient). The XRD spectra confirmed a solid solution was realized and the face-centered cubic lattice parameter varied from ~3.52 to 3.58 A˙, consistent with the measured composition gradient, assuming Vegard’s law. Optical microscopy and Raman analysis of the graphene layers suggest single layer growth occurs with x > 69 at.%, bilayer growth dominates from 48 at.% < x < 69 at.%, and multilayer (≥3) growth occurs for x < 48 at.%, where x is the Cu concentration. Finally, a large area of bi-layer graphene was grown via a CuxNi1−x catalyst with optimized catalyst composition and growth temperature.

2D materials↗