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At least 1,045 records · Page 58

Grain Growth in Nanocrystalline Mg-Al Thin Films

An improved understanding of grain growth kinetics in nanocrystalline materials, and in metals and alloys in general, is of continuing interest to the scientific community. In this study, Mg - Al thin films containing ~10 wt.% Al and with 14.5 nm average grain size were produced by magnetron-sputtering and subjected to heat-treatments. The grain growth evolution in the early stages of heat treatment at 423 K (150 °C), 473 K (200 °C) and 573K (300 °C) was observed with transmission electron microscopy and analyzed based upon the classical equation developed by Burke and Turnbull. The grain growth exponent was found to be 7±2 and the activation energy for grain growth was 31.1±13.4 kJ/mol, the latter being significantly lower than in bulk Mg-Al alloys. The observed grain growth kinetics are explained by the Al supersaturation in the matrix and the pinning effects of the rapidly forming beta precipitates and possibly shallow grain boundary grooves. The low activation energy is attributed to the rapid surface diffusion which is dominant in thin film systems.

activation energy↗

Effect of Deposition Pressure, Nitrogen Content and Substrate Temperature on Optical and Mechanical Behavior of Nanocomposite Al-Si-N Hard Coatings for Solar Thermal Applications

Hard and optically transparent nanocomposite Al-Si-N thin films were deposited using DC magnetron sputtering at different process parameters. There was a significant effect of these parameters on the film properties affecting its mechanical and optical behavior. The nitrogen content or pressure, deposition pressure and substrate temperature strongly influence the phase formation which governs the hardness and optical transparency of the coating. Hardness was measured between 18 and 30 GPa. The band gap could be varied in the range of 3.8-4.2 eV by varying nitrogen pressures in the chamber during deposition. The films showed (0-80)% transparency in UV and visible region depending on the sputtering conditions.

36 MATERIALS SCIENCE↗

Investigation into the Wear and Dent Resistance of Ni/Ti Nanolaminates and Superelastic NiTi Coating

Metallic wear-resistant coatings, such as chromium based, are desired to prevent premature failure of working parts and are widely used in the oil and gas and aerospace industries. These coatings are extremely hard; however, researchers have found that an optimal coating will also be resilient. Bulk NiTi possesses a superelasticity effect that can provide wear resistance to parts that will experience impact, wear, and erosion daily. Yet, NiTi as a surface coating has not been fully exploited in industrial applications. Bulk NiTi production presents significant challenges, such as poor formability and machinability. This study attempts to fabricate NiTi through a heat treatment process of sputter-deposited alternating nanosized Ni and Ti layers. After annealing, the nanolaminate coatings contained the austenitic NiTi phase. The elastic modulus to hardness ratio and wear resistance showed that the nanolaminate annealed at 650 °C is comparable to the sputtered superelastic NiTi coating. The annealed nanolaminate coating is found to exhibit higher hardness than the monolayered NiTi, as well as, comparable elastic modulus to hardness values and dent resistance. The findings in this study reveal the superiority of 650 °C annealed nanolaminate NiTi coating over the monolayer NiTi.

36 MATERIALS SCIENCE↗

ToF-SIMS Depth Profiling of Organic Delta Layers with Low-Energy Cesium Ions: Depth Resolution Assessment

The advent of cluster ion beams has paved the way to the routine 3D analysis of organic heterojunctions. Alternatively, organic thin layers have also been successfully depth profiled with a low-energy cesium ion beam (Cs{sup +}), to exploit the high chemical reactivity of cesium atoms, acting as free-radical scavengers. Despite of this, little is known about the depth resolution associated with low-energy Cs{sup +} sputtering on organic multilayers. In this work, amino acids multilayers, consisting of phenylalanine delta layers alternated with tyrosine spacers, were used as model systems to assess the depth resolution associated with 500 eV Cs{sup +} depth profiles. High yields were obtained for quasi-molecular ions from both amino acids, and no significant chemical alteration was noticed under the monoatomic bombardment. A depth resolution as low as 4 nm is demonstrated without sensible degradation on a rather long profile depth (300 nm). Limited depth resolution (> 10 nm) along with high molecular degradation was previously reported on similar systems by combining low-energy Cs{sup +} with Ga{sup +} analysis beam. The use of the Bi{sub 3}{sup +} analysis beam results in a dramatic improvement of both the characteristic molecular signal intensities and the depth resolution. Even though the analysis beam fluence is very low compared to the sputtering beam fluence, data suggest that further reducing the analysis Bi{sub 3}{sup +} fluence could improve the depth resolution by ~ 1 nm. .

74 ATOMIC AND MOLECULAR PHYSICS↗

Measurement and analysis of the Doppler broadened energy spectra of gamma radiation originating from the annihilation of positrons incident on clean and adsorbate-covered surfaces

We present measurements and theoretical modeling demonstrating the capability of coincidence Doppler broadened (CDB) annihilation gamma spectroscopy to provide element-specific information from the topmost atomic layer of surfaces. Our measurements show that the energy spectra of Doppler-shifted annihilation gamma photons emitted following the annihilation of positrons from the topmost atomic layers of clean and adsorbate covered surfaces of gold (Au), silver (Ag) and copper (Cu) differ significantly. The shape of the Doppler-broadened gamma spectrum, as analyzed using ratio curves, indicates that the elemental composition of the surface can still be identified despite contributions from positronium annihilation and a significant reduction in core electron annihilation. We estimate the chemical composition of the various probed surfaces by modeling the ratios of the measured Doppler spectra with respect to the Doppler spectra from a clean Cu surface using a linear combination of calculated ratio curves. The fitting of the experimental ratio curves was used to obtain an estimate of the elemental composition of Cu surfaces with sulfur segregation, oxygen adsorption, a thin film of Selenium (Se), and a single layer of graphene (SLG). A similar analysis was performed on the Ag surface with environmental adsorbates, the same surface after argon ion sputtering, as well as a sputter cleaned Au surface. The surface compositions obtained from the analysis of the CDB data were compared to the compositions obtained using positron annihilation induced Auger electron spectroscopy (PAES). Our results show that CDB can detect, identify, and quantify, sub-monolayer adsorbates and a single atomic layer deposited on metal substrates.

Lotfimarangloo, Sima [Univ. of Texas, Arlington, T↗

Parabolic oxidation kinetics of a plutonium alloy at room temperature

Auger electron spectroscopy (AES) was used to characterize the oxide scale formed on an ~0.5 wt. % Ga plutonium metal alloy. Analysis of changes to the characteristic Auger transitions for Pu and O during sputter depth profiles were used in combination with previously measured sputter yields to determine the thickness of the oxide scale and provide insight into its chemistry. From this data, the parabolic kinetics for the Pu-Ga alloy were determined as a function of relative humidity, RH = 14–92%, and oxygen partial pressure, p(O 2 ) = 31–157 Torr, at 25°C. For each relative humidity investigated, the parabolic rate constant was found to be independent of oxygen partial pressure. Furthermore, power-law fits to the relative humidity effect on the rate constant was found to have a power of n = 1.265, indicating the diffusion species which rate-limits the reaction isn’t molecular water, which subsequent dissociates at the oxide-metal interface, or hydroxyl from dissociation at the gas-surface interface.

36 MATERIALS SCIENCE↗

Controlled optical properties via chemical composition tuning in molybdenum-incorporated β-Ga 2 O 3 nanocrystalline films

An approach is presented to design refractory-metal incorporated Ga2O3-based materials with controlled structural and optical properties. The molybdenum (Mo)-content in Ga2O3 was varied from 0 to 11 at% in the sputter-deposited Ga-Mo-O films. Molybdenum was found to significantly affect the structure and optical properties. While low Mo-content (≤4 at%) results in the formation of single-phase (β-Ga2O3), higher Mo-content results in amorphization. Chemically-induced band gap variability (Eg~1 eV) coupled with structure-modification indicates the electronic-structure changes in Ga-Mo-O. The linear relationship between chemical-composition and optical properties suggests that tailoring the optical-quality and performance of Ga-Mo-O films is possible by tuning the Mo-content.

Environmental Molecular Sciences Laboratory↗

Characterization data of an (AlFeNiTiVZr) 1-x Cr x multi-principal element alloy continuous composition spread library

The data provided in this article is related to the research article entitled “Phase stabilization and oxidation of a continuous composition spread multi-principal element (AlFeNiTiVZr) 1-x Cr x alloy”. This data article describes the high-throughput synthesis and characterization processes of an (AlFeNiTiVZr) 1-x Cr x alloy system. Continuous composition spread (CCS) thin-film libraries were synthesized by co-depositing an AlFeNiTiVZr metal alloy target and Cr target via magnetron sputtering. Post-processing was performed on the sample libraries with a vacuum anneal at 873 K and an air anneal at 873 K. Compositional data was determined via WDS in order to verify parameters provided by an in-house sputter model. Crystallographic data was captured via synchrotron diffraction and diffractograms were compared as a function of the change in Cr concentration. These measurements were taken in order to observe phase behavior after oxidation throughout the composition library. Furthermore, vibrational spectrographic data is provided of the oxidized library to show surface speciation along the composition gradient of the alloy system. The structural and oxidative behavior of the (AlFeNiTiVZr) 1-x Cr x alloy can be analysed using the data provided in this article. Additionally, this characterization dataset can be utilized in machine learning algorithms for determining important features and parameters for future hypothesis generation of functional multi-principal element alloys (MPEAs).

36 MATERIALS SCIENCE↗

Relative phase stability of L1 2 and DO 22 /DO 23 structures in Al 3 Nb, Al 3 Zr and Al 3 V compounds

The relative stability of the different tri-aluminide (Al 3 M) phases in three binary systems (M = Zr, Nb and V) was assessed for their potential to form fine cubic L1 2 precipitates in additively manufactured alloys. Supersaturated thin films of Al-(8–30) at% M were sputtered and heat treated during in-situ x-ray diffraction (XRD) measurements to observe the temperature ranges of stability for each phase. As-sputtered films were then processed with laser tracks simulating additive manufacturing solidification conditions, and the formation of phases in the laser tracks was correlated with density functional theory (DFT) and nucleation rate calculations. We found that the metastable L1 2 structure is highly competitive with the stable DO 23 structure in the Al-Zr system, but much less stable than the DO 22 structure in the Al-Nb system, and both the DO 22 and Al 8 V 5 structure in the Al-V system. Furthermore, these experimental results were found to be in good agreement with the DFT and kinetic calculations, as we determined that the metastable L1 2 in Al-Zr only requires a small amount of undercooling to favor its nucleation over the stable DO 23 , suggesting additive manufacturing can be a viable pathway to develop Al-Zr alloys strengthened by a high volume fraction of L1 2 Al 3 Zr phase.

Perrin, Alice E. [Oak Ridge National Laboratory (O↗

Ni coating on 316L stainless steel using cage plasma treatment: Feasibility and swelling studies

A modified cage plasma nitriding technique is used to coat a Ni film onto a 316L substrate as a protective layer for austenitic steels in molten fluoride salts. The coating is achieved by deposition of Ni atoms sputtered from a Ni cage with a 316L substrate floated at the same potential as the cage to reduce plasma sputtering on the substrate. The Ni coating is porosity-free and precipitation-free and forms a γ-(Fe, Ni) phase due to interdiffusion from the substrate. Beneath the interdiffusion layer exists a thick γ-phase layer mainly affected by long-range nitrogen diffusion along the grain boundary. This layer develops grain boundary Cr nitride precipitates. Ion irradiation on the polished cross-section of the plasma-treated sample shows no void swelling in the surface-deposited Ni layer, very limited void formation in N diffusion layer, and significant void swelling in bulk unaffected by nitrogen. The studies demonstrate the feasibility of the technique for Ni coating and show good swelling resistance of the coating layer and N diffusion-affected layer. Mechanisms are discussed in this paper.

36 MATERIALS SCIENCE↗

Effects of elevated temperature exposure on the residual stress state and microstructure of PVD Cr coatings on SiC investigated via in situ X-ray diffraction and transmission electron microscopy

Pure Cr coatings are being considered as corrosion-resistant layers for SiC-SiC f composite fuel cladding in light water reactors. The residual stress state and interdiffusion behavior of Cr coatings deposited on SiC substrates using bipolar high-power impulse magnetron sputtering (B-HiPIMS) and direct current impulse magnetron sputtering (DCMS) were studied using in situ X-ray diffraction experiments at 300 °C, 700 °C, and 1200 °C. After elevated temperature exposure, evolution of the coating microstructure and coating/substrate interdiffusion was characterized by transmission electron microscopy. The compressive residual stress of the dense B-HiPIMS coating at room temperature was gradually relieved at 300 °C, while the stress transitioned to a tensile state at 700 °C. Grain growth of the Cr coating and a Cr–SiC interdiffusion layer consisting of newly formed Cr–C and Cr–Si phases were observed in the B-HiPIMS coating after exposure at 700 °C. The phases in the interdiffusion layer were identified to be Cr 7 C 3 , Cr 3 Si, and Cr 5 Si 3 C x experimentally and by thermodynamic predictions. For the DCMS coating, however, changes in residual stress and microstructure at the elevated temperatures were limited by the inherent porosity and inhomogeneous structure of the as-deposited coating. At 1200 °C, both coating types interacted rapidly with the underlying SiC substrate in the early stages of the experiment. The results from this study suggest that the characteristics of the Cr coatings do not significantly change at the reactor operating temperature of 300 °C, while changes in microstructure and stress state are expected in off-normal conditions of 700 °C and 1200 °C. Finally the results from this study suggest the B-HiPIMS coating is best-suited as a protective coating for SiC fuel cladding.

36 MATERIALS SCIENCE↗

Over 11% Efficient Eco-Friendly Kesterite Solar Cell: Effects of S-Enriched Surface of Cu2ZnSn(S,Se)4 Absorber and Band Gap Controlled (Zn,Sn)O Buffer

For high efficiency kesterite Cu2ZnSn(S,Se)4 (CZTSSe) solar cell, CdS thin film was usually used as a buffer layer. However, due to the toxicity of Cd and pollution problems involved from the solution-based chemical bath deposition, eco-friendly high efficiency CZTSSe solar cell with Cd-free buffer is necessary. As an Cd-free buffer layer, we investigated (Zn,Sn)O (ZTO) film deposited by sputtering method. In order to achieve high power conversion efficiency, we controlled energy band gaps of CZTSSe absorber as well as ZTO buffer, which was required to optimize conduction band offset (CBO) between the absorber and the buffer and to increase open circuit voltage (Voc) and fill factor (FF). The CBO was optimized by controlling the band gap of ZTO. By varying the Sn/(Zn + Sn) ratio and its deposition temperature, band gap of ZTO was successfully adjusted. Experimental and computational calculation results showed that solar cell performance was strongly affected by the CBO between absorber and buffer. Besides CBO matching, larger band gap of ZTO improved short circuit current density (Jsc) with enhanced external quantum efficiency value in blue photon spectrum range. As an additional way to improve power conversion efficiency of solar cell, band graded CZTSSe absorber was developed by using spray-based two-step process. The sprayed CZTSSe film was engineered to have S-enriched surface, which makes surface band gap widened and surface passivated, and resultantly increases Voc, Jsc and fill factor (FF). By controlling band gaps of both CZTSSe absorber and ZTO buffer, we obtained 11.22% environment-friendly CZTSSe solar cell without MgF2 anti-reflection coating.

(Zn↗

Black textile with bottom metallized surface having enhanced radiative cooling under solar irradiation

We discuss the cooling performance of garments can play an important role of enabling comfortable human activities under extreme environments. Imparting extra cooling performance to a garment in a passive way is extremely challenging under the sunlight which provides a huge energy influx to the garment, especially made of black colored textile. In this study, a solar-adaptive-textile (SAT) has been designed and experimentally demonstrated. Near-infrared (NIR) transmittance to the human skin from the solar irradiance has been intercepted by incorporating a nanoscale sputtered thin aluminum metal film underneath the textile layer facing the skin. The high-pressure sputtering employed allows a deep penetration of aluminum into the fabric structure for enhanced solar-energy-blocking effect and film stability. The aluminum layer effectively reduces the solar irradiance as well as the thermal radiation from the textile, which gets heated in lieu of the human skin. The outdoor, under-the-sun measurements with a simulated skin showed an outstanding 2 °C cooling effect compared to the normal textile without the metal film, while preserving most of the given textile properties such as colors, air permeability and wicking behavior.

36 MATERIALS SCIENCE↗

Studies of lithiumization and boronization of ATJ graphite PFCs in NSTX-U

This work examines the effect of boron and lithium conditioned ATJ graphite surface bombarded by low-energy deuterium atoms on the deuterium retention and chemical sputtering. We use atomistic simulations and compare them with experimental in situ studies with x-ray photoelectron spectroscopy (XPS), to understand the effects of deuterium irradiation on the chemistry in lithiated, boronized and oxidized amorphous carbon surfaces. Our results are validated qualitatively by comparison with experiments and with quantum classical molecular dynamic simulations. We explain the important role of oxygen in D retention for lithiated surfaces and the suppression of oxygen role by boron in boronized surfaces. The calculated increase of the oxygen role in deuterium uptake after D accumulation in B–C–O surface configuration is discussed. The sputtering yield per low energy D impact is significantly smaller in boronized than in lithiated surfaces.

36 MATERIALS SCIENCE↗

Observation of tantalum deposition and growth on TiB2 and ZrB2 from PISCES-RF deuterium and helium plasma exposures

Deuterium and helium plasma exposures on bulk TiB2 and ZrB2 samples were performed using the PISCES-RF linear plasma device. 40 and 90 eV deuterium ion plasma exposures were performed at 240 and 800 °C sample temperatures, and 80 eV helium ion plasma exposures were performed at 800 °C sample temperatures. Following plasma exposures, it was discovered that two plasma conditions (90 eV deuterium and 80 eV helium at 800 °C) resulted in thick (>200 nm) tantalum-rich (>10 at%) surface features on the targets, presumably from tantalum sourced from a tantalum adapter mask or cap used as part of the target holder. This work aims to characterize these tantalum-rich features and examine the mechanisms of impurity deposition.Plasma-induced surface morphology of the tantalum-rich surface layers depends on plasma properties and target temperature and chemistry. Greater titanium sputtering compared to zirconium resulted in more distinct surface features in the TiB2 samples compared to the ZrB2 samples via increased, prompt deposition onto tantalum surface impurities. There is still uncertainty as to why thick tantalum deposition only occurred under some plasma exposure conditions but not others; it is likely due to tantalum sputtering by a combination of boron molecules from the targets and carbon-impurities in the tantalum mask or targets. Impurity driven surface features are a well-documented phenomena in samples exposed to plasma from linear plasma device facilities—this work confirms the occurrence of this and emphasizes the need for chemistry characterization of isolated post-mortem surface features in plasma-exposed samples.

Nuckols, Lauren↗

Initial design concepts for solid boron injection in ITER

As part of ITER’s consideration to change its first wall material from beryllium to tungsten, the ITER Organization has proposed studying the feasibility of real-time solid boron injection (SBI) into the plasma to coat the walls and divertor to supplement glow discharge boronization (GDB). Boron deposits getter oxygen and reduce sputtering of tungsten from plasma facing components (PFCs). Particularly in areas with significant plasma wall interactions, boron coatings are expected to be short-lived under high performance plasma conditions. The proposed SBI system aims to maintain boron layers in these areas to avoid excessive radiation from tungsten in the plasma as a risk mitigation to ensure ITER will be able to reach and sustain Q = 10 conditions. The system will be used sparingly, as redeposition of boron can lead to significant tritium retention, which must be minimized in ITER to comply with nuclear safety concerns. SBI is proposed to limit and precisely control the amount of boron injected in real-time during plasma operation. Here, some of the design requirements and initial concepts for an SBI system in ITER are presented based on previous results carried out with SBI systems on a number of tokamaks and stellarators around the world. Previous results using SBI systems installed by PPPL have injected boron particles from 5 µm–2 mm diameter at calibrated rates of 2–200 mg/s in real-time during plasma operation on AUG, DIII-D, EAST, KSTAR, LHD, TFTR, WEST, and W7-X, leading to improved wall conditions with reduced plasma impurity concentrations and radiated power and improved plasma performance. The boron is ionized in the plasma edge and then deposited on plasma-wetted surfaces. On AUG, EAST and WEST reduced tungsten sputtering sources were observed following several discharges with SBI. Extrapolation of these SBI results are presented to estimate the amount of boron needed for wall conditioning in ITER. Real-time SBI control requirements and plasma operation scenarios for ITER are also described.

36 MATERIALS SCIENCE↗

Optimized NiTe 2 /Ni back contacts via chemical deposition for high performance CdTe solar cells

The development of efficient and stable back contacts remains a major challenge in achieving high performance and long-term stability of CdTe thin-film solar cells. Here, this work revisits the formation of NiTe 2 by chemical bath deposition (CBD) as a back contact for CdTe devices. An optimized CBD recipe, based on high-purity precursors and the addition of copper chloride directly into the bath, was developed and applied to fabricate Cu-doped CdTe solar cells. A modified Cu-free methodology was also applied to Group V doped absorbers. The process included pinhole filling, ion milling, CBD, annealing, and sputtering to form a low-barrier back contact. Devices fabricated using this method achieved consistent open-circuit voltages (V oc ) above 800 mV and fill factors (FF) exceeding 70%. The best Cu-doped devices reached power conversion efficiencies (PCE) above 18 %, and preliminary results with Group V-doped material demonstrated compatibility of the method with high-efficiency, state-of-the-art CdTe devices. This study shows that NiTe 2 /Ni back contacts, formed via an optimized chemical process followed by sputtering of Ni, represent a promising pathway for achieving low-barrier and potentially stable back contacts in modern CdTe photovoltaics.

14 SOLAR ENERGY↗

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↗