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At least 199 records · Page 11

Radio-frequency magnetron sputter deposition of ultrathick boron carbide films

The deposition of thick B 4 C films with low residual stress by conventional direct-current magnetron sputtering is accompanied by the formation of dust particulates contaminating the target, chamber, and substrates and leading to the formation of nodular defects in films. Here, we demonstrate that the formation of particulates is greatly reduced during radio-frequency magnetron sputtering (RFMS). We systematically study properties of B 4 C films deposited by RFMS with a substrate temperature of 330 °C, a target-to-substrate distance of 10 cm, Ar working gas pressure in the range of 4.5–12.0 mTorr (0.6–1.6 Pa), and substrate tilt angles of 0°–80°. All films are x-ray amorphous. A columnar structure develops with increasing either Ar pressure or substrate tilt. For columnar films, the column tilt angle decreases with increasing Ar pressure, which we attribute to a corresponding increase in the width of the distribution of impact angles of deposition flux. In contrast to the Keller–Simmons rule, the deposition rate increases with increasing Ar pressure, which suggests a better coupling of the RF energy to the plasma processes that lead to target sputtering at higher pressures. There is a critical substrate tilt angle above which the total residual stress is close to zero. This critical substrate tilt angle is ~0° for an Ar pressure of 12 mTorr (1.6 Pa). The lower residual stress state, necessary for depositing ultrathick films, is characterized by a larger concentration of nanoscale inhomogeneities and decreased mechanical properties. Based on these results, RFMS deposition of 60-μm-thick B 4 C films is demonstrated.

36 MATERIALS SCIENCE↗

Microbial ecology of acidic, biogenic gypsum: community structure and distribution of extremophiles on freshly formed and relict sulfate deposits in a hydrogen sulfide-rich cave

Sulfate minerals are abundant on the Martian surface, and many of these evaporite deposits are thought to have precipitated from acidic fluids. On Earth, gypsum (CaSO 4 •2H 2 O) and other sulfates sometimes form under acidic conditions, so exploring the extremophilic life that occurs in these mineral environments can help evaluate the astrobiological potential of acid sulfate depositional settings. Here, we characterized the microbial communities associated with acidic gypsum deposits in a sulfuric acid cave, where sulfate precipitation is driven by sulfide-oxidizing bacteria and archaea. We used 16S rRNA gene sequencing and cell counts to characterize gypsum-associated microorganisms in freshly formed and relict deposits throughout the cave, to test how microbial community composition and abundance would vary with distance from the sulfidic water table and with the concentration of H 2 S(g) and other gases in the cave atmosphere. We found that actively forming gypsum in the lower cave levels was colonized by low-diversity communities that have few cells compared to other environments in the cave. The most abundant taxa were Acidithiobacillus, Metallibacterium, Mycobacteria, and three different Thermoplasmatales-group archaea, which occupied distinct niches based on proximity to sulfidic streams and the concentration of gases in the cave air. By contrast, deposits in older cave levels had more diverse communities that were distinct from those associated with freshly formed gypsum and likely represent a community reliant on different energy resources. These findings show that acidic sulfate deposits serve as habitats for extremophilic microorganisms and broaden our knowledge of the life associated with terrestrial sulfates.

58 GEOSCIENCES↗

Adsorption Processes during Electrochemical Atomic Layer Deposition of Gold

Electrochemical atomic layer deposition (e-ALD) technique offers a simple and effective "wet chemistry" approach enabling high-precision monolayer-by-monolayer deposition of metal films. The process of e-ALD of Au involves lead underpotential deposition (PbUPD) followed by its redox replacement by a Au monolayer. The time evolution of the deposit mass during "one-pot" Au e-ALD is known to exhibit a unique three-stage response that is presently not well understood. In this work, we probe this response using voltammetry, electrochemical quartz crystal microgravimetry (e-QCM), and chronoamperometry to unravel the underlying mechanistic events during Au e-ALD. Furthermore, the presence of adsorbed Au +3 -ligand complex(es) (Au-L) on the Au surface is established. In stage I of e-ALD, this Au-L adsorbed layer is reduced to Au while a Pb UPD adlayer is formed. In stage II, the Pb UPD adlayer undergoes spontaneous surface-limited redox replacement by nobler Au under open-circuit conditions. Finally, in stage III, re-adsorption of the Au-L occurs on the newly deposited Au. Quantitative analysis of the deposit mass transients obtained under a variety of conditions provides an estimate of the Au-L mass and its molecular weight.

36 MATERIALS SCIENCE↗

Comparative analysis of energy deposition modes available in Serpent 2 within the framework of the supercritical water reactor - Fuel qualification test reactor physics benchmark

A joint European Canadian Chinese development of a supercritical water-cooled small modular reactor (SCW-SMR) technology is in progress since September 2020 in the framework of a Horizon 2020 project called ECC-SMART. As a main purpose of the project, proper estimates of energy deposition and its spatial distribution are prerequisites for the accurate analysis of safety related parameters of the SCW-SMR concept under development. A supercritical water reactor fuel computational benchmark model, provided by Canadian Nuclear Laboratories, was applied for detailed comparison of different energy deposition calculation options available in the Serpent 2 Monte Carlo code. The effect of energy deposition options on the normalization of the results as well as on the spatial distribution of the energy deposition are discussed. Consistent energy deposition calculation methods are presented between three Monte Carlo codes, viz., Serpent 2, MCNP6 and OpenMC. Although resource-intensive, the use of the coupled neutron-photon transport mode of Serpent 2 is recommended for accurate spatial and quantitative characterization of energy deposition in the SCW-SMR fuel assemblies, accounting for both neutron and photon heating of all the materials. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

From Deposition to Encapsulation: Roll-to-roll manufacturing of organic light emitting devices for lighting (Final Report)

Organic light emitting devices (OLEDs) are promising solid state light sources due to their high efficiency, high color quality and flexible form factors. The key to enable low cost OLED lighting, is to rapidly fabricate thin film organic layers on a continuous flexible roll, called R2R processing. This project aims to investigate the feasibility of mass production of OLED lighting using the R2R process, from deposition to encapsulation. A high efficiency white OLED is fabricated on 10 cm-wide substrate rolls in a pilot R2R tool comprising of two different organic deposition: vacuum thermal evaporation (VTE) and organic vapor phase deposition (OVPD). A high quality encapsulation process to package OLEDs is demonstrated using an atomic layer deposition tool integrated to the R2R system without air exposure. The method to achieve ultrahigh deposition rates required by R2R processing is demonstrated by OVPD. Uniform organic semiconductor thin films grown by OVPD at rates as high as 50 Å/s are achieved. A comprehensive numerical model that is capable of simulating complex, multilayer WOLED structures is developed to provide an alternative to experimental iterations of OLED design and tests. A cost estimate on the R2R production of WOLEDs for lighting is developed. Assuming a WOLED luminance of 10 klm/m 2 , the cost of a WOLED light engine is anticipated to be $\$ 12.5$ /klm. With incremental reduction in material and driver costs and improved luminance, the cost of WOLED lighting can be reduced to $\$ 6.3$ /klm in the near term. These findings suggest OLED lighting can be volume manufactured by R2R vapor deposition methods with much reduced costs compared to current batch processing methods, potentially positioning WOLEDs for use in numerous premium lighting applications.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Facies Analysis and Depositional Environments of the Upper Cambrian Eau Claire Formation in Central and Northern Illinois

The Cambrian Eau Claire Formation is a confining unit for geologic carbon dioxide (CO2) storage, and potentially a confining unit for hydrogen storage, within the underlying Mount Simon Sandstone in the Central and Northern Illinois Basin. However, extensive regional studies on lateral continuity, environment of deposition, and depositional fabric of the Eau Claire Formation in the Illinois Basin are minimal compared to studies of the underlying Mount Simon Sandstone. This study presents an integrated facies analysis using sedimentological, stratigraphic, ichnological, and mineralogical data to interpret the depositional environments of the Eau Claire Formation, emphasizing the dynamic nature of sedimentary systems. By combining core analyses, thin-section analysis, facies interpretation from geophysical logs, and regional stratigraphic framework interpretation, this work provides insights into the integrated depositional framework across diverse depositional environments. These findings suggest that the Eau Claire Formation in the Central and Northern Illinois Basin was deposited in a shallow marine environment, ranging from tidal flats to offshore settings. Its mixed siliciclastic-carbonate succession was primarily controlled by relative sea-level change.

58 GEOSCIENCES↗

Additive Friction Stir Deposition of a Tantalum–Tungsten Refractory Alloy

Additive friction stir deposition (AFSD) is a solid-state metal additive manufacturing technique, which utilizes frictional heating and plastic deformation to create large deposits and parts. Much like its cousin processes, friction stir welding and friction stir processing, AFSD has seen the most compatibility and use with lower-temperature metals, such as aluminum; however, there is growing interest in higher-temperature materials, such as titanium and steel alloys. In this work, we explore the deposition of an ultrahigh-temperature refractory material, specifically, a tantalum–tungsten (TaW) alloy. The solid-state nature of AFSD means refractory process temperatures are significantly lower than those for melt-based additive manufacturing techniques; however, they still pose difficult challenges, especially in regards to AFSD tooling. In this study, we perform initial deposition trials of TaW using twin-rod-style AFSD with a high-temperature tungsten–rhenium-based tool. Many challenges arise because of the high temperatures of the process and high mechanical demand on AFSD machine hardware to process the strong refractory alloy. Despite these challenges, successful deposits of the material were produced and characterized. Mechanical testing of the deposited material shows improved yield strength over that of the annealed reference material, and this strengthening is mostly attributed to the refined recrystallized microstructure typical of AFSD. These findings highlight the opportunities and challenges associated with ultrahigh-temperature AFSD, as well as provide some of the first published insights into twin-rod-style AFSD process behaviors.

36 MATERIALS SCIENCE↗

Surface Treatment Strategies for Mitigating Gas Hydrate & Asphaltene Formation, Growth, and Deposition in Flowloops

Abstract Numerous solids including gas hydrates, waxes, and asphaltenes have the potential to form in the production lines of gas and oil fields. This creates a highly non-ideal scenario as the accumulation of said species leads to flow assurance issues, especially with long-term processes like deposition. Since an ever-increasing amount of material is deposited in place at the pipe surface, production stoppage or active mitigation efforts become inevitable. The latter production issues result in increased safety risks and operational expenditures. Therefore, a cost-effective, passive deposition mitigation technology, such as a pipeline coating or surface treatment is especially appealing. The ability to address multiple pipeline flow assurance issues simultaneously without actively disrupting production would represent a dramatic step forward in this area. This study is part of a long-term ongoing effort that evaluates the performance and application of an omniphobic surface treatment for solids deposition prevention in industrially relevant systems. In particular, this specific work concentrates on the efficacy and robustness of the treatment under fully flowing conditions. The apparatuses utilized for this include two flowloops: a lab-scale, high-pressure flowloop for gas hydrate and surface treatment durability studies, and a bench-scale, atmospheric pressure loop for crude oil and asphaltene experiments. Film growth in high-pressure flowloop tests corroborated previous reports of delayed gas hydrate nucleation observed in rocking cells. Without the aid of the memory effect, treated oil-dominated experiments never experienced hydrate formation, spending upwards of a week in the hydrate stability zone (at the subcooled/fluid test conditions). Subsequent tests which utilized the memory effect then revealed that the hydrate formation rate reduced in the presence of the surface treatment compared to a bare stainless-steel surface. This testing was part of a larger set of trials conducted in the flowloop, which lasted about one year. The surface treatment durability under flowing conditions was evaluated during this time. Even after experiencing ∼4000 operating hours and 2 full pressure cycles, no evidence of delamination or damage was detected. Finally, as part of an extension to previous work, corroded surface asphaltene deposition experiments were performed in a bench-top flowloop. Treated experiments displayed an order of magnitude reduction in both total oil (all fractions of crude oil) and asphaltene fraction deposited.

03 NATURAL GAS↗

Measurement of Piston Deposit Thickness Using Laser Profilometer

In this work, a novel method of measuring the thickness of deposits on engine pistons, including within ring grooves, is described. A laser profilometer is used in conjunction with a rotary stage to measure a continuous profile of the piston with deposits, and the measurement is repeated after cleaning the deposits from the piston. Algorithms for aligning the scans and determining the differential thickness are described, and results are compared to deposit thickness measurements using a contact-type magnetic induction coating thickness gauge. This method allows continuous measurement of deposit thickness across the entire surface including lands and ring grooves as well as quantification of the volume of the deposits.

42 ENGINEERING↗

Metal-ion deposition regulator for suppressing dendrite formation in electrochemical cells

A metal-ion deposition regulator to regulate the flux and deposition of metal ions in an electrochemical cell. The regulator containing two membranes made of a polymer and a plurality of two-dimensional porous nanosheets sandwiched between the two membranes. The regulator is capable of distributing flux of metal ions passing through the metal-ion deposition regulator and regulating the deposition of the metal ions onto the cathode or anode thereby suppressing dendrite growth in the electrochemical cell. An electrochemical cell containing an anode, a cathode, a liquid electrolyte, and a metal-ion deposition regulator. A method of making a metal-ion deposition regulator. The method includes fabricating two-dimensional porous nanosheets utilizing graphene oxide as an expendable template, and sandwiching the porous nanosheets between two membranes made of a polymer such that the nanosheets are in contact with the two membranes.

Pol, Vilas Ganpat↗

PbI 2 Nanocrystal Growth by Atomic Layer Deposition from Pb(tmhd) 2 and HI

Atomic layer deposition (ALD) allows for fine control over the thickness, stoichiometry, and structural defects of materials. ALD provides a suitable route to deposit lead halides, which can further be converted to perovskites for photovoltaics, photoemission, and photodetection, among other applications. Deposition of lead halides by ALD has already begun to be explored; however, the precursors used in published processes are highly hazardous, require expensive fabrication processes, or contain impurities that can jeopardize the optoelectronic properties of metal halide perovskites after conversion. In this work, we deposited lead iodide (PbI 2 ) by a facile ALD process involving only two readily accessible and low-cost precursors. PbI 2 nanocrystals were grown on soda-lime glass (SLG), silicon dioxide support grids, and silicon wafer substrates and provided the groundwork for further investigation into developing lead halide perovskite processes by ALD. Further, the ALD-grown PbI 2 was characterized by annular dark-field scanning transmission electron microscopy (ADF-STEM), atomic force microscopy (AFM), high resolution transmission electron microscopy (HRTEM), X-ray fluorescence (XRF), and X-ray photoemission spectroscopy (XPS), among other methods. This work presents the first step to synthesize lead halide perovskites with atomic control for applications such as interfacial layers in photovoltaics and for deposition in microcavities for lasing.

36 MATERIALS SCIENCE↗

Controlling Structure and Properties of Vapor-Deposited Glasses of Organic Semiconductors: Recent Advances and Challenges

The past decade has seen great progress in manipulating the structure of vapor-deposited glasses of organic semiconductors. Upon varying the substrate temperature during deposition, glasses with a wide range of density and molecular orientation can be prepared from a given molecule. Here, we review recent studies that show the structure of vapor-deposited glasses can be tuned to significantly improve the external quantum efficiency and lifetime of organic light-emitting diodes (OLEDs). We highlight the ability of molecular simulations to reproduce experimentally observed structures, setting the stage for in silico design of vapor-deposited glasses in the coming decade. Finally, we identify research opportunities for improving the properties of organic semiconductors by controlling the structure of vapor-deposited glasses.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High Density Two-Component Glasses of Organic Semiconductors Prepared by Physical Vapor Deposition

Physical Vapor Deposition (PVD) is widely utilized for the production of organic semiconductor devices due to its ability to form thin layers with exceptional properties. Although the layers in the device usually consist of two or more components, there is limited understanding about the fundamental characteristics of such multi-component vapor-deposited glasses. Here, spectroscopic ellipsometry was employed to characterize the densities, thermal stabilities and optical properties of co-vapor deposited NPD and TPD glasses across the entire range of composition. We find that co-deposited NPD and TPD form high density glasses with enhanced thermal stability. The dependences of density and stability upon substrate temperature are correlated, and the birefringence of the co-deposited glasses is determined by the reduced substrate temperature of mixtures. Additionally, we observe that the transformation of a highly stable and dense two-component glass into its supercooled liquid initiates from the free surface and propagates into the bulk at constant velocity, like single component PVD glasses. As a result, all these features are consistent with the surface equilibration mechanism.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Lithium Deposition-Induced Fracture of Carbon Nanotubes and Its Implication to Solid-State Batteries

The increasing demand for safe and dense energy storage has shifted research focus from liquid electrolyte-based Li-ion batteries toward solid-state batteries (SSBs). However, the application of SSBs is impeded by uncontrollable Li dendrite growth and short circuiting, the mechanism of which remains elusive. Herein, we conceptualize a scheme to visualize Li deposition in the confined space inside carbon nanotubes (CNTs) to mimic Li deposition dynamics inside solid electrolyte (SE) cracks, where the high-strength CNT walls mimic the mechanically strong SEs. We observed that the deposited Li propagates as a creeping solid in the CNTs, presenting an effective pathway for stress relaxation. When the stress-relaxation pathway is blocked, the Li deposition-induced stress reaches the gigapascal level and causes CNT fracture. Mechanics analysis suggests that interfacial lithiophilicity critically governs Li deposition dynamics and stress relaxation. Furthermore, our study offers critical strategies for suppressing Li dendritic growth and constructing high-energy-density, electrochemically and mechanically robust SSBs.

25 ENERGY STORAGE↗

Dopamine-Mediated Polymer Coating Facilitates Area-Selective Atomic Layer Deposition

Area-selective atomic layer deposition (ALD) has the potential to significantly improve current fabrication approaches by introducing a bottom-up process in which robust and conformal thin films are selectively deposited onto patterned substrates. This bottom-up approach requires selective areas of the substrates to be masked to inhibit deposition. Spontaneous self-assembly and organization of a mask, incorporating adhesion and other functions, are particularly attractive for this role as they do not require a separate patterning step. In this work, we make use of the pH/light tunability of catechol adhesion to develop a catechol-functionalized polymer that exhibits tunable adhesion strengths on different materials based on their specific chemistry. Tunable selective deposition was shown between metal/metal oxide substrates by controlling the local pH. Moreover, by controlling the adhesion strength through UV light, the deposition of hafnium oxide (HfO 2 ) during ALD was successfully inhibited.

36 MATERIALS SCIENCE↗

Fast Organic Vapor Phase Deposition of Thin Films in Light-Emitting Diodes

Fast deposition of thin films is essential for achieving low-cost, high throughput phosphorescent organic light emitting diode (PHOLED) production. In this work, we demonstrate rapid and uniform growth of semiconductor thin films by organic vapor phase deposition (OVPD). A green PHOLED comprising an emission layer (EML) grown at 50 Å/s with bis[2-(2-pyridinyl-N)phenyl-C](acetylacetonato)iridium(III) (Ir(ppy)2(acac)) doped into 4,4 bis(N-carbazolyl)-1,1zolylld (CBP) exhibits a maximum external quantum efficiency of 20 ± 1%. The morphology, charge transport properties, and radiative efficiency under optical and electrical excitation of the PHOLED EML are investigated as functions of the deposition rate via both experimental and theoretical approaches. The EML shows no evidence for gas phase nucleation of the organic molecules at deposition rates as high as 50 Å/s. However, the roll-off in quantum efficiency at high current progressively increases with deposition rate due to enhanced triplet-polaron annihilation. The roll-off results from accumulation of stress within the PHOLED EML that generates a high density of defect states. Here, the defects, in turn, act as recombination sites for triplets and hole polarons, leading to enhanced triplet-polaron annihilation at high current. We introduce a void nucleation model to describe the film morphology evolution that is observed using electron microscopy.

42 ENGINEERING↗

Effect of substrate temperature on sputter-deposited boron carbide films

Sputter deposition of B4C films with tailored physical properties remains a challenge. Here, we systematically study how substrate temperature influences the properties of B4C films deposited by direct current magnetron sputtering onto planar substrates held at temperatures in the range of 100-510°C. Results show that all films are amorphous stoichiometric B4C, with low O content of ~1 at. %. Films deposited onto substrates at 100°C exhibit high compressive residual stress and decreased mechanical properties. Therefore, for elevated substrate temperatures in the range of 180-510°C, film mass density, surface roughness, Young’s modulus, and hardness are weakly dependent on substrate temperature. However, in this temperature range, an increase in substrate temperature leads to larger residual compressive stress accompanied by a corresponding reduction in the concentration of nanoscale inhomogeneities. At least for the landing atom ballistics conditions studied here, a substrate temperature range of ~185-250°C is optimum for growing films with near-zero intrinsic residual stress. The overall weak substrate temperature dependence of film properties revealed in this work is favorable for the development of a robust deposition process, particularly for the case of deposition onto non-planar substrates where temperature control is often challenging.

36 MATERIALS SCIENCE↗

Design of a custom vapor transport co-deposition system for scalable production of perovskite solar cells

Vacuum-deposited perovskites provide a more direct path to manufacturing large area solar cells because of ready compatibility with multilayered architectures and historic use in the electronics industry. However, vacuum compatible co-deposition of organic-inorganic perovskites remains difficult due to issues of precisely controlling the organic precursor flux. Here, we demonstrate a manufacturing prototype specifically designed for co-depositing organic-inorganic perovskites and evaluate it with respect to the influence of process parameters on film growth. Through depositing and characterizing methylammonium lead iodide (MAPbI3) perovskite films, we highlight the necessary design requirements while measuring the influence of film growth parameters on deposition rate and perovskite phases.

14 SOLAR ENERGY↗