Results for “deposition optimization” — Page 6

DOE OSTI2024

The surface chemistry of the atomic layer deposition of metal thin films

Abstract In this perspective we discuss the progress made in the mechanistic studies of the surface chemistry associated with the atomic layer deposition (ALD) of metal films and the usefulness of that knowledge for the optimization of existing film growth processes and for the design of new ones. Our focus is on the deposition of late transition metals. We start by introducing some of the main surface-sensitive techniques and approaches used in this research. We comment on the general nature of the metallorganic complexes used as precursors for these depositions, and the uniqueness that solid surfaces and the absence of liquid solvents bring to the ALD chemistry and differentiate it from what is known from metalorganic chemistry in solution. We then delve into the adsorption and thermal chemistry of those precursors, highlighting the complex and stepwise nature of the decomposition of the organic ligands that usually ensued upon their thermal activation. We discuss the criteria relevant for the selection of co-reactants to be used on the second half of the ALD cycle, with emphasis on the redox chemistry often associated with the growth of metallic films starting from complexes with metal cations. Additional considerations include the nature of the substrate and the final structural and chemical properties of the growing films, which we indicate rarely retain the homogeneous 2D structure often aimed for. We end with some general conclusions and personal thoughts about the future of this field.

Materials Science↗

DOE OSTI2025

Optimization of La 2 NiO 4+δ Electrolysis Cell Oxygen Electrode through Surfactant-Enabled LaCoO 3±δ Nanocatalyst Deposition

Lanthanum nickelate (LNO) has shown promise as a Cr-resistant air electrode material for SOECs but has suboptimal surface oxygen exchange properties. Nanocoating of the LNO surface with lanthanum cobaltite (LCO) was chosen to improve cell performance as a surface oxygen conductor. The work focused on the implementation of a two-step nano-LCO film deposition utilizing catechol molecules in a porous LNO electrode. The subgoals of the work were to maintain nanosized LCO particles/ grains to increase active surface area and to control the regularity/ homogeneity of the coating across the microstructure. To achieve these goals, a novel surfactant-enhanced liquid infiltration method was utilized, where nucleation sites were spread across the electrode structure to control the location and size of LCO particles. Various catechol surfactant compositions were evaluated for their ability to control the kinetics of nanoparticle deposition and the homogeneity of the coating. Chelated LCO was characterized by X-ray diffraction (XRD), which found a substantial improvement in LCO formation with surfactant addition and determined polymerized norepinephrine to be the best-performing surfactant, with 88.4% pure LCO formed at low temperature. X-ray photoelectron spectroscopy (XPS) confirmed LCO nanostructures formed by the two-step infiltration process, showing no impurities and a stable perovskite structure. Deposition kinetics were analyzed using atomic force microscopy (AFM), correlating infiltration times and solution molarity to nanoparticle size and distribution, the results of which were confirmed in symmetrical cell samples by scanning electron microscopy (SEM). Electrochemical impedance spectroscopy (EIS) testing demonstrated substantial improvements in polarization resistance, where the nanocoating reduced the resistance by ∼55% to 0.152 Ω·cm 2 at 700 °C and 0.039 Ω·cm 2 at 800 °C. Electrical conductivity relaxation (ECR) at this temperature confirmed an improved surface oxygen exchange coefficient of the LCO + LNO heterostructure predicted by the Bode data from EIS, alongside a reduction in activation energy by about 30%.

Deposition↗

DOE OSTI2024

Kinetics of low temperature plasma assisted NH 3 /H 2 oxidation in a nanosecond-pulsed discharge

Ammonia (NH 3 ) has been widely recognized as one of the carbon-neutral fuels. However, ammonia combustion suffers low reactivity and high N 2 O/NO x emissions. Here, to overcome these issues, this work reports plasma assisted NH 3 /H 2 oxidation and unveils the kinetics of fuel oxidation and N 2 O/NO x formation by combining time-resolved laser diagnostics with plasma modeling. Firstly, we found that the NH 3 consumption is promoted with a H 2 blending ratio of 0.3, due to enhancements of H and OH formation by plasma assisted H 2 dissociation. Secondly, at a high reduced electric field, when the H 2 blending ratio increases, the NH 3 oxidation is promoted due to both the HO 2 formation and strong NO kinetic enhancement via NO-HO 2 and NO 2 -H pathways. In the meantime, it is shown that the NO mole fraction also increases with H 2 blending ratio, because the NO formation is enhanced via N( 2 D)-O 2 pathways, and the DeNO x chemistry is weakened with less NH 2 production. By contrast, at a lower reduced electric field, when the H 2 blending ratio increases, the decreased N( 2 D) formation does not produce enough NO to replenish the NO formation drop caused by lower NH 3 concentration. Thirdly, the reduced electric field non-monotonically affects fuel consumption and N 2 O/NO x formation by manipulating electron energy deposition pathways. The NH 3 consumption is maximized with an optimal reduced electric field where N 2 * excitation and O 2 dissociation are most efficient. When the reduced electric field deviates from its optimum, the NH 3 consumption decreases due to the discharge energy deposition to either vibrational excitation or dissociation of N 2 . The N 2 O/NO x emissions governed by the NH 3 oxidation follow the above NH 3 consumption trend.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2025

Tailored Additive Design of Scaffold‐Free Porous Mg for Ultimate Hydrogen Storage

For hydrogen storage materials to become practically viable, comprehensive improvements in key properties—kinetics, thermodynamics, thermal transport, and durability—are crucial. Porous Mg structure has been proposed as a promising strategy due to its high storage capacity and ability to accommodate volume expansion. However, challenges such as sluggish kinetics and structural degradation resulting from instability due to vacant sites still remain. In this study, a tailored design of porous Mg structure with site-specific transition metal dual-doping and structure-reinforced carbon nanotube (CNT)-framework is presented for optimal hydrogen storage. Ti and Ni are strategically deposited on the surface to synergistically enhance hydrogen sorption kinetics by facilitating hydrogen dissociation and diffusion, while CNTs are interpenetrated into 3D Mg structure for improving thermal conductivity and maintaining the porous structure. The resulting composite demonstrates exceptional performance, achieving hydrogen absorption and desorption of 4.8 and 5.8 wt%, respectively, within 10 min with an impressively low activation energy for absorption of 46 kJ mol −1 H 2 . Even after 50 cycles, its capacity and porous structure are well preserved, showing excellent cyclability in comparison with previously reported materials. In conclusion, this delicate design strategy based on a comprehensive understanding of structural and chemical characteristics is key to maximizing the targeted performance.

CNT embedding↗

DOE OSTI2025

Additive manufacturing of high‐density silicon carbide ceramics through post‐processing spark plasma sintering

This research advances the field of additive manufacturing (AM) of silicon carbide (SiC) ceramics by integrating spark plasma sintering (SPS) to enhance material density, mechanical strength, and thermal properties. Traditional AM techniques struggle to achieve the high‐density SiC required for demanding applications, such as aerospace engineering, where high thermal conductivity and mechanical strength are paramount. Here, our study addresses these challenges by incorporating SPS as a post‐processing step, achieving near‐theoretical maximum densities and significantly reducing porosity, thereby resulting in outstanding thermal conductivity in SiC ceramics. We developed a specialized SiC ink optimized for 3D printing, ensuring structural integrity after deposition through tailored rheological properties. The application of SPS facilitates rapid, uniform sintering, essential for attaining superior density, mechanical properties, and thermal performance. Our experimental results, confirmed through scanning electron microscopy analysis, demonstrate significant microstructural properties, mechanical strength, and thermal conductivity, showcasing the effectiveness of integrating SPS in AM processes. This innovative approach not only expands the capabilities of AM in producing complex, high‐density ceramic structures but also broadens the potential applications of SiC in demanding environments.

36 MATERIALS SCIENCE↗

NASA NTRS1987

CuInSe2/ZnSe solar cells using reactively sputter-deposited ZnSe

Results on CuInSe2/ZnSe thin-film heterojunction photovoltaic devices are presented. By the use of reactive magnetron cosputtering of Zn and In dopant in Ar/H2Se, ZnSe thin films have been deposited on glass and conducting SnO2-coated glass substrates with resistivity as low as 20 ohm-cm at deposition temperatures as low as 120 C. Preliminary ZnSe depositions onto CuInSe2 films supplied by industrial laboratories are encouraging. Reactive-sputter-deposition parameters for ZnSe have yet to be optimized for CuInSe2 substrates; however, open-circuit voltages as high as 430 mV were obtained. The highest short-circuit current density, as determined by spectral response weighted for AM1.5 global insulation, was 37.4 mA/sq cm. In all cases, a highly conductive ZnO film was overcoated onto the ZnSe to reduce the overall sheet resistance.

Nouhi, A.↗

DOE OSTI2024

Comparative Study on the Photoelectrochemical Hydrogen Production from the Layout Optimization in a Unit Cell

Solar-driven water splitting is achieved by connecting photovoltaics with electrolysis. Recently, integrated approaches of the two configurations for photoelectrochemical reactions have shown great potential in a combined unit, but strategies to address further material and cell development face significant scientific challenges. Here, in this work, we present an experimental demonstration of photoelectrochemical (PEC) unit-cells with efficient separate dual compartments for oxygen evolution and hydrogen evolution reactions. The design and fabrication of cell architectures with various degrees of integration are investigated efficient and sustainable PEC processes. The effect of the nanostructured silicon (Si) photoelectrodes, including the adoption of layer architectures, surface protection layer deposition, and membrane electrode assembly is further studied to optimize the design parameters of the PEC unit-cells. This developed PEC cell with the Si photocathode achieved a photocurrent density of -4.8 mA cm –2 at -2.0 V cell and -2.87 mA cm –2 at -1.6 V cell . It clearly provides a critical milestone for unbiased solar water splitting. Practical solar to hydrogen (STH) can be directly estimated in investigating PEC performance in this unit-cell as assembled with a solar cell. It is a significantly meaningful step forward in practical solar fuel production.

08 HYDROGEN↗

NASA NTRS2012

Three-Dimensional Porous Particles Composed of Curved, Two-Dimensional, Nano-Sized Layers for Li-Ion Batteries

Thin Si films coated on porous 3D particles composed of curved 2D graphene sheets have been synthesized utilizing techniques that allow for tunable properties. Since graphene exhibits specific surface area up to 100 times higher than carbon black or graphite, the deposition of the same mass of Si on graphene is much faster in comparison -- a factor which is important for practical applications. In addition, the distance between graphene layers is tunable and variation in the thickness of the deposited Si film is feasible. Both of these characteristics allow for optimization of the energy and power characteristics. Thicker films will allow higher capacity, but slower rate capabilities. Thinner films will allow more rapid charging, or higher power performance. In this innovation, uniform deposition of Si and C layers on high-surface area graphene produced granules with specific surface area (SSA) of 5 sq. m/g.

Yushin, Gleb↗

DOE OSTI2026

Self-driving thin film laboratory: autonomous epitaxial atomic-layer synthesis via real-time computer vision analysis of electron diffraction

Emerging materials science platforms with the ability to make autonomous decisions on the fly are fundamentally changing the outlook and protocols for materials optimization and discovery. Because AI-driven self-navigating schemes can effectively reduce the total number of iterations needed to arrive at the "answer" (i.e. the best stochiometric composition for a desired physical property, optimum materials processing parameters, etc.) by significant margins, they have the potential to revolutionize materials and chemical manufacturing processes at large in research laboratory settings as well as in industrial plants. Here, we demonstrate a successful implementation of real-time closed-loop autonomous navigation of a multi-dimensional materials synthesis parameter space for fabricating phase-pure epitaxial films of a metastable phase of a functional oxide in a combinatorial pulsed laser deposition chamber. Sequential epitaxial growth iterations in search of the optimized recipe to stabilize the desired crystal phase were performed using frame-by-frame quantitative computer vision analysis of reflection high-energy electron diffraction (RHEED) images of the unit-cell level film being deposited. The autonomous scheme regularly resulted in > 30-fold reduction in the number of required experiments compared to a comprehensive mapping of the parameter space. The real-time workflow developed here can be readily extended to a variety of thin film synthesis platforms opening the door for self-driving atomic-level materials design as well as autonomous optimization of semiconductor manufacturing.

36 MATERIALS SCIENCE↗

NASA NTRS2023

Additive Manufacturing Process Development DOE for NASA HR-1 using Laser Blown Powder Directed Energy Deposition

NASA HR-1 is a Fe-Ni-Cr alloy that is used for high pressure hydrogen applications such as rocket engines, energy, and oil and gas. This investigation was focused on conducting a design of experiment program aimed at mapping the parameter process window for NASA HR-1 using the laser blown powder directed energy deposition (LP-DED) process. A two phased design of experiments (DOE), the first phase of the experiment was focused on optimizing single bead tracks while the second phase of the experiment was focused on optimizing bead overlap hatching in a multi pass bead build up. During the first phase of the deposition parameters, namely laser power, travel speed, and powder feed rate were varied. A down selection from the single bead parameter set was made and hatching experiments were conducted that focused on the overlap distance. In this paper the approach for conducting the DOE and results are discussed. The results focused on measurement of bead geometry, the as-built microstructural evolution, and porosity within the samples. The team at MSFC saw a variety of results across the process map created during the first phase of experimentation and were able to down select a parameter that created an optimal bead shape with a minimal amount of build porosity. It was determined that laser power and robot travel speed were the most sensitive parameters. The results from this investigation will inform future laser powder directed energy deposition parameter developments.

Parker Shake↗

DOE OSTI2025

Warpage-Resistant, Under-Extrusion-Free, High-Surface-Quality Additive Manufacturing Process for Polyethylene-Based Composite Radiation Shielding Material

Polyethylene (PE) is one of the best shielding materials for primary space radiation due to its high hydrogen content. For effective secondary neutron shielding, boron-rich fillers are incorporated to enhance performance. The semicrystalline nature and high thermal expansion coefficient of PE impede its adoption for in situ additive manufacture in space via the fused deposition modeling (FDM) 3D printing. Here, we developed an optimized PE blend to mitigate the effects of under-extrusion and warpage. Guided by studies on extrusion and warpage, we developed an optimal set of printing parameters for the proposed PE blend. The optimum PE blend─both in its pure form and when doped with fillers─has been tested on different FDM printers. The printed structures exhibit high and uniform density, smooth surfaces, no warpage, and competitive mechanical properties. The FDM-printed plates demonstrate efficient shielding from thermal neutrons, predicted via modeling and confirmed experimentally using extended Q-range small-angle neutron scattering.

additive manufacturing↗

NASA NTRSDate not supplied

Process Development and Hot-fire Testing of Additively Manufactured NASA HR-1 for Liquid Rocket Engine Applications

Additive manufacturing (AM) has provided new design and manufacturing opportunities to reduce cost and schedules, consolidate parts, and optimize performance. One technique being evaluated is Laser Powder Directed Energy Deposition (LP-DED), which provides a significant increase in scale compared to Laser Powder Bed Fusion (L-PBF). NASA along with industry partners have been developing the LP-DED process to demonstrate internal channel geometry and development components for use in liquid rocket engine channel cooled nozzles. Optimized materials in the extreme high pressure and hydrogen environment for liquid rocket engines remains a key challenge. NASA has advanced an enabling material called NASA HR-1 (Hydrogen Resistant -1) as a solution using AM techniques. NASA HR-1 is a high-strength Fe-Ni superalloy designed to resist high pressure, hydrogen environment embrittlement, oxidation, and corrosion. NASA HR-1 meets materials requirements for liquid rocket engine components, including good hydrogen resistance, high conductivity, good low cycle fatigue performance, and high elongation and strength for components in high heat flux environments. Material properties and process characterization have been completed on the high density thin-wall material in addition to advancements of the supply chain. NASA has also completed fabrication of several subscale and full-scale channel wall nozzles in LP-DED NASA HR-1 and completed hot-fire testing. This includes refinement of the process to produce thin-walls and various channel geometries to meet the requirements for channel wall nozzle applications. This paper will provide an overview of the LP-DED process development, material characterization and properties, component manufacturing, and hot-fire testing. Hot-fire testing was completed for a lander-class 7K-lbf thrust chamber using Liquid Oxygen (LOX)/Methane. The design overview and results from hot-fire testing will be presented in addition to hardware development for future testing on 2K-lbf and 35k-lbf thrust chambers and large-scale manufacturing technology demonstrators.

Additive Manufacturing↗

NASA NTRSDate not supplied

Process Development and Hot-fire Testing of Additively Manufactured NASA HR-1 for Liquid Rocket Engine Applications

Additive manufacturing (AM) has provided new design and manufacturing opportunities to reduce cost and schedules, consolidate parts, and optimize performance. One technique being evaluated is Laser Powder Directed Energy Deposition (LP-DED), which provides a significant increase in scale compared to Laser Powder Bed Fusion (L-PBF). NASA along with industry partners have been developing the LP-DED process to demonstrate internal channel geometry and development components for use in liquid rocket engine channel cooled nozzles. Optimized materials in the extreme high pressure and hydrogen environment for liquid rocket engines remains a key challenge. NASA has advanced an enabling material called NASA HR-1 (Hydrogen Resistant -1) as a solution using AM techniques. NASA HR-1 is a high-strength Fe-Ni superalloy designed to resist high pressure, hydrogen environment embrittlement, oxidation, and corrosion. NASA HR-1 meets materials requirements for liquid rocket engine components, including good hydrogen resistance, high conductivity, good low cycle fatigue performance, and high elongation and strength for components in high heat flux environments. Material properties and process characterization have been completed on the high density thin-wall material in addition to advancements of the supply chain. NASA has also completed fabrication of several subscale and full-scale channel wall nozzles in LP-DED NASA HR-1 and completed hot-fire testing. This includes refinement of the process to produce thin-walls and various channel geometries to meet the requirements for channel wall nozzle applications. This paper will provide an overview of the LP-DED process development, material characterization and properties, component manufacturing, and hot-fire testing. Hot-fire testing was completed for a lander-class 7K-lbf thrust chamber using Liquid Oxygen (LOX)/Methane. The design overview and results from hot-fire testing will be presented in addition to hardware development for future testing on 2K-lbf and 35k-lbf thrust chambers and large-scale manufacturing technology demonstrators.

DED↗

DOE OSTI2024

Investigation of Sub‐Bandgap Emission and Unexpected n‐Type Behavior in Undoped Polycrystalline CdSe x Te 1‐x

Abstract Se alloying has enabled significantly higher carrier lifetimes and photocurrents in CdTe solar cells, but these benefits can be highly dependent on CdSe x Te 1‐x processing. This work evaluates the optoelectronic, chemical, and electronic properties of thick (3 µm) undoped CdSe x Te 1‐x of uniform composition and varied processing conditions (CdSe x Te 1‐x evaporation rate, CdCl 2 anneal, Se content) chosen to reflect various standard device processing conditions. Sub‐bandgap defect emission is observed, which increased as Se content increased and with “GrV‐optimized CdCl 2 ” (i.e., CdCl 2 anneal conditions used for group‐V‐doped devices). Low carrier lifetime is found for GrV‐optimized CdCl 2 , slow CdSe x Te 1‐x deposition, and low‐Se films. Interestingly, all films (including CdTe control) exhibited n‐type behavior, where electron density increased with Se up to an estimated ≈10 17 cm −3 . This behavior appears to originate during the CdCl 2 anneal, possibly from Se diffusion leading to anion vacancy (e.g., V Se , V Te ) and Cl Te generation.

14 SOLAR ENERGY↗

NASA NTRS2014

Development and Performance Evaluations of HfO2-Si and Rare Earth-Si Based Environmental Barrier Bond Coat Systems for SiC/SiC Ceramic Matrix Composites

Ceramic environmental barrier coatings (EBC) and SiCSiC ceramic matrix composites (CMCs) will play a crucial role in future aircraft propulsion systems because of their ability to significantly increase engine operating temperatures, improve component durability, reduce engine weight and cooling requirements. Advanced EBC systems for SiCSiC CMC turbine and combustor hot section components are currently being developed to meet future turbine engine emission and performance goals. One of the significant material development challenges for the high temperature CMC components is to develop prime-reliant, high strength and high temperature capable environmental barrier coating bond coat systems, since the current silicon bond coat cannot meet the advanced EBC-CMC temperature and stability requirements. In this paper, advanced NASA HfO2-Si based EBC bond coat systems for SiCSiC CMC combustor and turbine airfoil applications are investigated. The coating design approach and stability requirements are specifically emphasized, with the development and implementation focusing on Plasma Sprayed (PS) and Electron Beam-Physic Vapor Deposited (EB-PVD) coating systems and the composition optimizations. High temperature properties of the HfO2-Si based bond coat systems, including the strength, fracture toughness, creep resistance, and oxidation resistance were evaluated in the temperature range of 1200 to 1500 C. Thermal gradient heat flux low cycle fatigue and furnace cyclic oxidation durability tests were also performed at temperatures up to 1500 C. The coating strength improvements, degradation and failure modes of the environmental barrier coating bond coat systems on SiCSiC CMCs tested in simulated stress-environment interactions are briefly discussed and supported by modeling. The performance enhancements of the HfO2-Si bond coat systems with rare earth element dopants and rare earth-silicon based bond coats are also highlighted. The advanced bond coat systems, when integrated with advanced EBC top coats, showed promise to achieve 1500 C temperature capability, helping enable next generation turbine engines with significantly improved engine component temperature capability and long-term durability.

HfO2-Si bond coat↗

NASA NTRS2014

Enhanced Fluoride Over-Coated Al Mirrors for FUV Astronomy

Astronomical observations in the Far Ultraviolet (FUV) spectral region are some of the more challenging due to the very distant and faint objects that are typically searched for in cosmic origin studies such as origin of large scale structure, the formation, evolution, and age of galaxies and the origin of stellar and planetary systems. These challenges are driving the need to improve the performance of optical coatings over a wide spectral range that would increase reflectance in mirrors and reduced absorption in dielectric filters used in optical telescope for FUV observations. This paper will present recent advances in reflectance performance for Al+MgF2 mirrors optimized for Lyman-alpha wavelength by performing the deposition of the MgF2 overcoat at elevated substrate temperatures. We will also present optical characterization of little studied rare-earth fluorides such as GdF3 and LuF3 that exhibit low-absorption over a wide wavelength range and could therefore be used as high refractive index alternatives for dielectric coatings at FUV wavelengths.

Reflectance↗

NASA NTRS2014

Recent Progress on 2012 SAT for UVOIR Coatings

Astronomical observations in the Far Ultraviolet (FUV) spectral region are some of the more challenging due to the very distant and faint objects that are typically searched for in cosmic origin studies such as origin of large scale structure, the formation, evolution, and age of galaxies and the origin of stellar and planetary systems. These challenges are driving the need to improve the performance of optical coatings over a wide spectral range that would increase reflectance in mirrors and reduced absorption in dielectric filters used in optical telescope for FUV observations. This paper will present recent advances in reflectance performance for Al+MgF2 mirrors optimized for Lyman-alpha wavelength by performing the deposition of the MgF2 overcoat at elevated substrate temperatures. We will also present optical characterization of little studied rare-earth fluorides such as GdF3 and LuF3 that exhibit low-absorption over a wide wavelength range and could therefore be used as high refractive index alternatives fordielectric coatings at FUV wavelengths.

LiF↗

NASA NTRS2016

FUV Reflectance of Recently Prepared Al Protected with AlF3: COR Program Technology Development

Astronomical observations in the Far Ultraviolet (FUV) spectral region are some of the more challenging due to the very distant and faint objects that are typically searched for in cosmic origin studies such as origin of large scale structure, the formation, evolution, and age of galaxies and the origin of stellar and planetary systems. These challenges are driving the need to improve the performance of optical coatings over a wide spectral range that would increase reflectance in mirrors and reduced absorption in dielectric filters used in optical telescope for FUV observations. This paper will present recent advances in reflectance performance for Al+AlF3 mirrors optimized for Lyman-alpha wavelength by performing the deposition of the AlF3 overcoat at elevated substrate temperatures.

MOS"↗