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At least 361 records · Page 20

Atomically Precise Graphene Nanoribbon Transistors with Long-Term Stability and Reliability

Atomically precise graphene nanoribbons (GNRs) synthesized from the bottom-up exhibit promising electronic properties for high-performance field-effect transistors (FETs). The feasibility of fabricating FETs with GNRs (GNRFETs) has been demonstrated, with ongoing efforts aimed at further improving their performance. However, their long-term stability and reliability remain unexplored, which is as important as their performance for practical applications. In this work, we fabricated short-channel FETs with nine-atom-wide armchair GNRs (9-AGNRFETs). We revealed that the on-state (/ ON ) current performance of the 9-AGNRFETs deteriorates significantly over consecutive full transistor on and off logic cycles, which has neither been demonstrated nor previously considered. To address this issue, we deposited a thin ~10 nm thick atomic layer deposition (ALD) layer of aluminum oxide (Al 2 O 3 ) directly on these devices. The integrity, compatibility, electrical performance, stability, and reliability, of the GNRFETs before and/or after Al 2 O 3 deposition were comprehensively studied. The results indicate that the observed decline in electrical device performance is most likely due to the degradation of contact resistance over multiple measurement cycles. We successfully demonstrated that the devices with the Al 2 O 3 layer operate well up to several thousand continuous full cycles without any degradation. Our study offers valuable insights into the stability and reliability of GNR transistors, which could facilitate their large-scale integration into practical applications.

36 MATERIALS SCIENCE↗

Nature of Reactive Hydrogen for Ammonia Synthesis over a Ru/C12A7 Electride Catalyst

Recently, there have been renewed interests in exploring new catalysts for ammonia synthesis under mild conditions. Electride-based catalysts are among the emerging ones. Ruthenium particles supported on an electride composed of a mixture of calcium and aluminum oxides (C12A7) have attracted great attention for ammonia synthesis due to their facile ability in activating N2 under ambient pressure. However, the exact nature of the reactive hydrogen species and the role of electride support still remain elusive for this catalytic system. Here, we report for the first time that the surface-adsorbed hydrogen, rather than the hydride encaged in the C12A7 electride, plays a major role in ammonia synthesis over the Ru/C12A7 electride catalyst with the aid of in situ neutron scattering techniques. Combining in situ neutron diffraction, inelastic neutron spectroscopy, density functional theory (DFT) calculation, and temperature-programmed reactions, the results provide direct evidence for not only the presence of encaged hydrides during ammonia synthesis but also the strong thermal and chemical stability of the hydride species in the Ru/C12A7 electride. Steady state isotopic transient kinetic analysis (SSITKA) of ammonia synthesis showed that the coverage of reactive intermediates increased significantly when the Ru particles were promoted by the electride form (coverage up to 84%) of the C12A7 support rather than the oxide form (coverage up to 15%). Such a drastic change in the intermediate coverage on the Ru surface is attributed to the positive role of electride support where the H2 poisoning effect is absent during ammonia synthesis over Ru. The finding of this work has significant implications for understanding catalysis by electride-based materials for ammonia synthesis and hydrogenation reactions in general.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cationic Tantalum Hydrides Catalyze Hydrogenolysis and Alkane Metathesis Reactions of Paraffins and Polyethylene

Sulfated aluminum oxide (SAO), a high surface area material containing sulfate anions that behave like weakly coordinating anions, reacts with Ta(=CH t Bu)(CH 2 t Bu) 3 to form [Ta(CH 2 t Bu) 2 (O–) 2 ][SAO] (1). Subsequent treatment with H 2 forms Ta–H + sites supported on SAO that are active in hydrogenolysis and alkane metathesis reactions. In both reactions Ta–H + is more active than related neutral Ta–H sites supported on silica. This reaction chemistry extends to melts of high-density polyethylene (HDPE), where Ta–H + converts 30% of a low molecular weight HDPE (M n = 2.5 kg mol –1 ; D = 3.6) to low molecular weight paraffins under hydrogenolysis conditions. Under alkane metathesis conditions Ta–H + converts this HDPE to a high MW fraction (M n = 6.2 kDa; D = 2.3) and low molecular weight alkane products (C 13 –C 32 ). Furthermore, these results show that incorporating charge as a design element in supported d 0 metal hydrides is a viable strategy to increase the reaction rate in challenging reactions involving reorganization of C–C bonds in alkanes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enabling safe aqueous lithium ion open batteries by suppressing oxygen reduction reaction

Abstract Due to the non-flammable nature of water-based electrolytes, aqueous lithium-ion batteries are resistant to catching fire. However, they are not immune to the risk of explosion, since the sealing structure adopted by current batteries limits the dissipation of heat and pressure within the cells. Here, we report a safe aqueous lithium-ion battery with an open configuration using water-in-salt electrolytes and aluminum oxide coated anodes. The design can inhibit the self-discharge by substantially suppressing the oxygen reduction reaction on lithiated anodes and enable good cycle performance over 1000 times. Our study may open a pathway towards safer lithium-ion battery designs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Non-Markovian relaxation spectroscopy of fluxonium qubits

Recent studies have shown that parasitic two-level systems (TLS) in superconducting qubits, which are a leading source of decoherence, can have relaxation times longer than the qubits themselves. However, the standard techniques used to characterize qubit relaxation is only valid for measuring T 1 under the Born-Markov approximation and could mask environmental memory effects in practice. Here, we introduce two-timescale relaxometry, a technique to probe the qubit and environment relaxation simultaneously and efficiently. We apply it to high-coherence fluxonium qubits over a frequency range of 0.1-0.4 GHz, and reveal a discrete spectrum of TLS with millisecond lifetimes. Our analysis of the spectrum is consistent with a random distribution of TLS in the aluminum oxide tunnel barrier of the Josephson junction chain of the fluxonium, with a spectral and volumetric density and average electric dipole similar to previous TLS studies at much higher frequencies. Our study suggests that investigating and mitigating TLS in the junction chain is crucial to the development of various types of noise-protected qubits in circuit QED.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Molecular coupling competing with defects within insulator of the magnetic tunnel junction-based molecular spintronics devices

Nearly 70 years old dream of incorporating molecule as the device element is still challenged by competing defects in almost every experimentally tested molecular device approach. This paper focuses on the magnetic tunnel junction (MTJ) based molecular spintronics device (MTJMSD) method. An MTJMSD utilizes a tunnel barrier to ensure a robust and mass-producible physical gap between two ferromagnetic electrodes. MTJMSD approach may benefit from MTJ's industrial practices; however, the MTJMSD approach still needs to overcome additional challenges arising from the inclusion of magnetic molecules in conjunction with competing defects. Molecular device channels are covalently bonded between two ferromagnets across the insulating barrier. An insulating barrier may possess a variety of potential defects arising during the fabrication or operational phase. This paper describes an experimental and theoretical study of molecular coupling between ferromagnets in the presence of the competing coupling via an insulating tunnel barrier. We discuss the experimental observations of hillocks and pinhole-type defects producing inter-layer coupling that compete with molecular device elements. We performed theoretical simulations to encompass a wide range of competition between molecules and defects. Monte Carlo Simulation (MCS) was used for investigating the defect-induced inter-layer coupling on MTJMSD. Our research may help understand and design molecular spintronics devices utilizing various insulating spacers such as aluminum oxide (AlOx) and magnesium oxide (MgO) on a wide range of metal electrodes. This paper intends to provide practical insights for researchers intending to investigate the molecular device properties via the MTJMSD approach and do not have a background in magnetic tunnel junction fabrication.

36 MATERIALS SCIENCE↗

The crystal orientation of THF clathrates in nano-confinement by in situ polarized Raman spectroscopy

Gas hydrates form at high pressure and low temperatures in marine sediments and permafrost regions of the earth. Despite forming in nanoporous structures, gas hydrates have been extensively studied only in bulk. Understanding nucleation and growth of gas hydrates in nonporous confinement can help create ways for storage and utilization as a future energy source. Herein, we introduce a new method for studying crystal orientation/tilt during tetrahydrofuran (THF) hydrate crystallization under the influence of nano-confinement using polarized Raman spectroscopy. Uniform cylindrical nanometer size pores of anodic aluminum oxide (AAO) are used as a model nano-confinement, and hydrate experiments are performed in a glass microsystem for control of the flash hydrate nucleation kinetics and analysis via in situ polarized Raman spectroscopy. The average THF hydrate crystal tilt of 56 ± 1° and 30.5 ± 0.5° were observed for the 20 nm and 40 nm diameter pores, respectively. Crystal tilt observed in 20 and 40-nanometer-size pores was proportional to the pore diameter, resulting in lower tilt relative to the axis of the confinement at larger diameter pores. Finally, the results indicate that the hydrates nucleation and growth mechanism can depend on the nanoconfinement size. A 1.6 ± 0.01 °C to 1.8 ± 0.01 °C depression in melting point compared to the bulk is predicted using the Gibbs–Thomson equation as a direct effect of nucleation in confinement on the hydrate properties.

25 ENERGY STORAGE↗

A tungsten external heater for BX90 diamond anvil cells with a range up to 1700 K

Resistive heating of a sample in a diamond anvil cell (DAC) can generate a homogeneous temperature field across the sample chamber with reliable temperatures measured by a thermocouple. It is of importance in experiments aiming at exploring phase diagrams and quantifying thermoelastic properties of materials. Here, we present a ring-heater design developed for BX90 diamond anvil cells (DACs). Furthermore, it is made of a ring-shaped aluminum oxide holder hosting a tungsten wire coil inside and coupled with Ar + 2% H 2 gas to prevent oxidation during experiment. This modular plug-and-play design enables in situ studies of samples via x-ray diffraction up to a temperature of 1700 K. Temperature in the BX90 sample volume as measured through a thermocouple was calibrated using the melting point of gold. As an application of this design, we report the thermal expansion coefficient of MgO at 9.5(1) GPa.

47 OTHER INSTRUMENTATION↗

Thermal shock resistance of multilayer silicon carbide receiver tubes for 800°C molten salt concentrating solar power application

CSP power tower receiver systems during rapid transient weather periods can be vulnerable to thermal shock conditions from rain that which can facilitate the onset of leaks and failures that can have catastrophic consequences. Silicon carbide (SiC) materials have attractive receiver application characteristics for being light weight, having high-strength and excellent thermal shock resistance performance which make them a particularly good fit for receiver absorber materials in CSP. In this investigation, the performance characteristics of Ceramic Tubular Products (CTP) SiC ceramic matrix composite (CMC), multilayered tubes were explored with respect to thermal shock performance for solar receiver applications in next generation CSP plants. Here, thermal shock testing was performed at the Sandia National Laboratories (SNL) Solar Furnace facility using a dynamic stage and thermal shock tube test setup. The tubes tested under incident solar heat flux of 100 W/cm2 were heated with inner tube temperatures reaching approximately 800 °C, with outer temperatures exceeding or just reaching 1000 El for the multilayer and monolithic SiC tubes respectively. The tubes were then quenched with simulated rain. The tubes were then cooled and subjected to hoop stress analysis using an Instron device to assess their subsequent mechanical strength. Furthermore, the on-sun study experimental results indicate an average of 24.2% and 97% higher hoop strength for the CMC tubes than those composed of monolithic SiC and aluminum oxide (A1203) respectively.

14 SOLAR ENERGY↗

The influence of particle size on the fluid dynamics of a laser-induced plasma

The interaction of a laser-induced shock wave with nanoparticles and microparticles of aluminum oxide is investigated through experiments and modeling. The chemistry and physics of the interaction between the particles and plasma generated from laser ablation shows similarities and discrete differences for the two particle sizes. For both particle sizes, early stage (< 10 μs) ionization was dominant and evidenced by higher concentrations of Al II. While both sizes exhibit ionization over the same duration, the intensity of emission was greater for nanoparticles indicating greater concentrations of ionized species. Moreover, the dispersion of species was notably more elongated for microparticles while radial dispersion was more pronounced for nanoparticles with elevated drag forces. At later stages (i.e., > 10 μs), oxidation reactions were dominant for both particle sizes, but the same distinctions in flow field were observed and attributed to particle drag. In all stages of interaction, microparticles expand axially with less drag that suppresses their radial expansion. As a result, the dispersion of reactive species was mapped over an up to 80% larger area for nanoparticles relative to microparticles. Results shown here can be applied toward advancing experimental diagnostics and particle-shock wave modeling and simulation efforts for energetic materials.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Interface-independent sound speed and thermal conductivity of atomic-layer-deposition-grown amorphous AlN / Al 2 O 3 multilayers with varying oxygen composition

Dielectric amorphous multilayers (AMLs) play a critical role in a wide array of technologies such as optical coatings, nanoelectronics, energy harvesting, and recovery devices. However, despite their wide applications, a robust understanding of the effect of the interplay between chemical and structural disorder on the thermal properties of AMLs is still lacking. Therefore, in this paper, we experimentally and numerically investigate the effects of composition and interface density on the sound speed and thermal conductivity of a series of amorphous aluminum nitride and aluminum oxide multilayers grown via plasma-enhanced atomic layer deposition. To systematically change the composition, the oxygen content of the AMLs is proportionally varied with interface density during growth. We find that the longitudinal sound speed of these AMLs is dictated by the oxygen content instead of the number of interfaces. The thermal conductivity, in contrast, is dictated by both interface density and oxygen content. The interfaces act to decrease the thermal conductivity, whereas the oxygen content increases the thermal conductivity. Due to the competing influence of the interfaces and oxygen content, the thermal conductivity of the AMLs remains nearly constant as a function of interface density. Furthermore, our study provides crucial insights into the effect of the interplay of composition and interfaces on the sound speed and thermal conductivity of AMLs.

36 MATERIALS SCIENCE↗

Pool Boiling Reliability Tests and Degradation Mechanisms of Microporous Copper Inverse Opal (CuIOs) Structures

The rising power density in electronic systems requires thermal management solutions that are both high-performing and reliable. Porous materials such as Copper Inverse Opal (CuIOs) have unique structural features, including high permeability and high thermal conductivity, to enhance pool boiling performance. However, there is little understanding of the degradation mechanism of such porous materials under pool boiling conditions. In this study, samples of 10 ..mu..m thick CuIOs with 4.8 ..mu..m diameter, covering silicon substrate of area 11 mm x 11 mm, with various heated areas ranging from 2.5 mm x 2.5 mm to 10 mm x 10 mm, were tested in 100 degrees C deionized water at a constant heat flux of 110 Wcm -2 for 3-to-7 days. The combined effect of erosion and corrosion caused structural degradation of the CuIOs. The directly heated area had the most severe degradation while the edge of the heater and the unheated area showed progressively less degradation, maintaining some CuIOs structure even after the 7-day reliability test. Among all the tested samples with various heater sizes, the 2.5 mm x 2.5 mm heater sample - in which the heater size was designed to be comparable to the water bubble characteristic length - had the largest critical heat flux (CHF) up to 300 Wcm -2 with a superheat ~ 13 degrees C. Additionally, CuIOs with a smaller heated area performed better in terms of reliability. This study offers preliminary insights into CuIOs degradation mechanisms, contributing to the development of more robust thermal management solutions. We expect that electroless plating of CuIOs with gold (Au), nickel (Ni), and atomic layer deposition (ALD) aluminum oxide (Al 2 O 3 ) in combination with appropriate application-specific coolants will further improve the reliability and lifetime of the CuIOs.

boiling-induced degradation↗

Hydrogen Sulfide Passivation for p-Type Passivated Emitter and Rear Contact Solar Cells

This work reports on the application of sulfur (S)-passivation to passivated emitter and rear contact (PERC) solar cells. The emitter surface was passivated by hydrogen sulfide (H 2 S) gas phase reaction and capped by a hydrogenated amorphous silicon nitride (a-SiN x :H) layer. The sulfur passivation on a symmetrically n + diffused emitter is shown to lead to an emitter saturation current density (J 0n+ ) of 30 fA/cm 2 at R sheet,n+ ≈ 100 Ω/sq. The application of S-passivation to the emitter surface in the PERC cell structure, with the rear surface passivated by an aluminum oxide (Al 2 O 3 )/a-SiN x :H stack, showed a promising implied open-circuit voltage (iV OC ) of 686 mV before metallization. This iV OC was higher than that for the a-SiN x :H or SiO 2 /a-SiN x :H passivated emitter surfaces (675 and 674 mV, respectively) on PERC cells processed in the same run. However, a significant drop in cell V OC is observed for the S-passivated PERC cell after the completion of device fabrication with laser patterning, screen-printed metal contact deposition, and firing. Nonetheless, an efficiency of ~20% and a V OC of ~650 mV was achieved with an emitter surface passivated by sulfur. We identified that the 760°C contact firing process degrades the S-passivation quality. Furthermore, the surface morphology was studied, and a detailed surface analysis was performed to study the causes of the S-passivated surface degradation.

14 SOLAR ENERGY↗

Solid-State Sintering of Core-Shell Ceramic Powders Fabricated by Particle Atomic Layer Deposition

The properties of technical ceramics are highly dependent on their microstructure, which evolves during sintering. Sintering is the process by which ceramic parts are subjected to high temperatures to activate chemical diffusion and the consumption of porosity. During the initial stage of sintering, interparticle necks between neighboring particles form and subsequently increase in size, consuming porosity as the particle centers move closer together. To experimentally determine how this process depends on particle surface composition, particle atomic layer deposition (ALD) was used to deposit a thin film of amorphous aluminum oxide (Al2O3) onto yttria-stabilized tetragonal zirconia (3YSZ) particles, producing core-shell structured powders. The uniformity of the Al2O3 film was confirmed with transmission electron microscopy and energy dispersive spectroscopy. Scanning electron microscopy was used to observe microstructural evolution during sintering, and the dihedral angles of Al2O3 and 3YSZ grains were measured to determine the ratio of interfacial energies between the 3YSZ|3YSZ, 3YSZ|Al2O3, and Al2O3|Al2O3 interfaces. Analysis of the densification kinetics revealed that the initial stage of densification is dependent on the material at the surface of the particles (ie, the Al2O3 film) and is controlled by the diffusion of Al3+ cations through Al2O3. Once the Al2O3 film has coalesced, the sintering behavior is controlled by the densification of the core material (3YSZ). Thus, core-shell powders fabricated by particle ALD sinter by a two-step process where the kinetics are dependent on the material present at interparticle contacts.

alumina↗

Continuous polymer films deposited on top of porous substrates using plasma-enhanced atomic layer deposition and molecular layer deposition

Molecular layer deposition (MLD) is able to produce ultrathin polymer films with control over thickness, cross-linking, and chemical composition. With these capabilities, MLD should be useful in the fabrication of novel polymer membranes on porous supports. However, confining a continuous MLD film to the surface of porous substrates is difficult because of MLD film growth in the pores. The deposition in the pores lowers the conductance of the porous support. This paper presents a method to deposit continuous polymer films on top of porous substrates. In this method, Al2O3 plasma-enhanced atomic layer deposition (PE-ALD) using trimethylaluminum and oxygen plasma as the reactants was first used to cap the pores of the substrate. Subsequently, a polyamide MLD film was deposited on the Al2O3 PE-ALD capping layer using m-phenylenediamine and trimesoyl chloride as the reactants. The Al2O3 pore caps were then removed from the porous substrate by etching from the backside using a timed exposure to a dilute sodium hydroxide solution. This method was demonstrated using anodic aluminum oxide (AAO) and polyethersulfone (PES) porous substrates. Al2O3 PE-ALD film growth was limited to the top of the porous substrate, resulting in rapid surface recombination or high sticking coefficients for the reactive plasma species within the pores. Gas permeance measurements confirmed the pore capping of the AAO substrates. The reopening of the pores by dissolving the Al2O3 pore caps with a sodium hydroxide solution was monitored using gas permeance versus etch time. The removal of the Al2O3 pore caps from the PES substrates could also dissolve the Al2O3 layer underneath the MLD film. The loss of this Al2O3 layer led to the detachment of the MLD film from the PES substrate. However, the MLD film could be anchored to the PES support at fractures located in the Al2O3 film prior to the MLD. The Al2O3 film fracture allowed the MLD film to anchor firmly to the PES substrate by MLD in the pores of the PES porous substrate. The distance between the anchor points was a function of fracture density. This distance could be controlled by applying a tensile stress to the Al2O3 PE-ALD film to fracture the film through sample bending. This method produced firmly anchored polymer MLD films on top of the PES porous substrates.

Welch, Brian C. (ORCID:000000029747045X)↗

High temperature isotropic and anisotropic etching of silicon carbide using forming gas

Plasma-etched micropillars in 4H-SiC were etched in forming gas (4% H2, 96% N2) at 1500, 1550, and 1600 °C at 2.4 and 9.4 standard liters per min (slm). At 2.4 slm, oxygen from the aluminum oxide components of the tube furnace oxidized the SiC surface, and the pillars etched isotropically. Additionally, at 9.4 slm, the pillars etched crystallographically at 1500 and 1550 °C, and sharp 4H-SiC needless with tips as narrow as 15 nm were produced. The lateral etch rates of both 4H- and 6H-SiC were measured with the a-plane etching faster than the m-plane at 1500 and 1550 °C. At 1600 °C, the m-plane and a-plane etch at comparable rates. Due to the difference in etch rates between the m-plane and a-plane, convex surfaces tend to produce facets parallel to the a-plane, while concave surfaces produce facets parallel to the m-plane.

42 ENGINEERING↗

Vapor-phase grafting of functional silanes on atomic layer deposited Al 2 O 3

Fundamental studies are needed to advance our understanding of selective adsorption in aqueous environments and develop more effective sorbents and filters for water treatment. Vapor-phase grafting of functional silanes is an effective method to prepare well-defined surfaces to study selective adsorption. In this investigation, we perform vapor phase grafting of five different silane compounds on aluminum oxide (Al2O3) surfaces prepared by atomic layer deposition. These silane compounds have the general formula L3Si–C3H6–X where the ligand, L, controls the reactivity with the hydroxylated Al2O3 surface and the functional moiety, X, dictates the surface properties of the grafted layer. We study the grafting process using in situ Fourier transform infrared spectroscopy and ex situ x-ray photoelectron spectroscopy measurements, and we characterize the surfaces using scanning electron microscopy, atomic force microscopy, and water contact angle measurements. Here, we found that the structure and density of grafted aminosilanes are influenced by their chemical reactivity and steric constraints around the silicon atom as well as by the nature of the anchoring functional groups. Methyl substituted aminosilanes yielded more hydrophobic surfaces with a higher surface density at higher grafting temperatures. Thiol and nitrile terminated silanes were also studied and compared to the aminosilane terminated surfaces. Uniform monolayer coatings were observed for ethoxy-based silanes, but chlorosilanes exhibited nonuniform coatings as verified by atomic force microscopy measurements.

36 MATERIALS SCIENCE↗

Effect of pattern transfer process on roughness of block copolymer patterns from directed self-assembly

Block copolymer-directed self-assembly (DSA) remains promising for improving pattern quality and reducing the stochastic variations that challenge high numerical aperture extreme ultraviolet lithography. Equally critical is refining pattern transfer methods for accurately transferring the rectified DSA features to the underlying substrate. We compare two atomic layer deposition (ALD)-based techniques: sequential infiltration synthesis (SIS) and dry liftoff, applied to polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) DSA patterns. Both methods utilize aluminum oxide hard masks, with one synthesized through infiltration into the PMMA domains and the other through conformal ALD coating. High-resolution scanning electron micrographs were analyzed to measure line edge, width, and placement roughness for both the line (PMMA) and space (PS) features. Although both methods yielded similar overall 3σ rms roughness, they differed significantly in the frequency-dependent power spectral density (PSD) profiles. SIS reduced line placement roughness at length scales associated with the polymer pitch, but increased space width roughness at low frequencies, whereas dry liftoff mimicked the frequency content of the original guiding pattern. This study underscores the importance of PSD evaluation in selecting optimal pattern transfer strategies for specific applications.

Block copolymers↗