Large H2O solubility in dense silica and its implications for the interiors of water-rich planets
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99 GENERAL AND MISCELLANEOUS↗
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Ultrahigh-pressure disordered eight-coordinated phase of Mg 2 GeO 4 : Analogue for super-Earth mantles
Mg 2 GeO 4 is important as an analog for the ultrahigh-pressure behavior of Mg 2 SiO 4 , a major component of planetary interiors. In this study, we have investigated magnesium germanate to 275 GPa and over 2,000 K using a laser-heated diamond anvil cell combined with in situ synchrotron X-ray diffraction and density functional theory (DFT) computations. The experimental results are consistent with the formation of a phase with disordered Mg and Ge, in which germanium adopts eightfold coordination with oxygen: the cubic, Th 3 P 4 -type structure. DFT computations suggest partial Mg-Ge order, resulting in a tetragonal $I\bar{4}2d$ structure indistinguishable from $I\bar{4}3d$ Th 3 P 4 in our experiments. If applicable to silicates, the formation of this highly coordinated and intrinsically disordered phase may have important implications for the interior mineralogy of large, rocky extrasolar planets.
58 GEOSCIENCES↗
Partial PdAu nanoparticle embedding into TiO 2 support accentuates catalytic contributions from the Au/TiO 2 interface
Despite the broad catalytic relevance of metal–support interfaces, controlling their chemical nature, the interfacial contact perimeter (exposed to reactants), and consequently, their contributions to overall catalytic reactivity, remains challenging, as the nanoparticle and support characteristics are interdependent when catalysts are prepared by impregnation. Here, we decoupled both characteristics by using a raspberry-colloid-templating strategy that yields partially embedded PdAu nanoparticles within well-defined SiO 2 or TiO 2 supports, thereby increasing the metal–support interfacial contact compared to nonembedded catalysts that we prepared by attaching the same nanoparticles onto support surfaces. Between nonembedded PdAu/SiO 2 and PdAu/TiO 2 , we identified a support effect resulting in a 1.4-fold higher activity of PdAu/TiO 2 than PdAu/SiO 2 for benzaldehyde hydrogenation. Notably, partial nanoparticle embedding in the TiO 2 raspberry-colloid-templated support increased the metal–support interfacial perimeter and consequently, the number of Au/TiO 2 interfacial sites by 5.4-fold, which further enhanced the activity of PdAu/TiO 2 by an additional 4.1-fold. Theoretical calculations and in situ surface-sensitive desorption analyses reveal facile benzaldehyde binding at the Au/TiO 2 interface and at Pd ensembles on the nanoparticle surface, explaining the connection between the number of Au/TiO 2 interfacial sites (via the metal–support interfacial perimeter) and catalytic activity. Our results demonstrate partial nanoparticle embedding as a synthetic strategy to produce thermocatalytically stable catalysts and increase the number of catalytically active Au/TiO 2 interfacial sites to augment catalytic contributions arising from metal–support interfaces.
Lim, Kang Rui Garrick (ORCID:0000000321599844)↗
Tritium Breeding Ratio Evaluation of Solid Breeder Concepts for the FESS-FNSF
This paper presents a parametric study of the Fusion Energy System Studies-Fusion Nuclear Science Facility’s (FNSF’s) tritium breeding performance for several solid breeder concepts, neutron multiplying materials, and blanket materials, assuming volume fractions based on the most recent FNSF design as a realistically representative fusion facility. In this study, we initially surveyed the tritium breeding ratio (TBR) of several solid breeder concepts by employing a simplified but efficient one-dimensional (1-D) infinite cylinder reduced-order model (ROM). Parametric studies were performed with the ROMs for the full range of breeder-to-multiplier ratios to identify the optimum mixture compositions for each breeder type that would lead to a maximum TBR. These optimized breeder-multiplier combinations were then homogenized with FNSF blanket component materials to estimate their impacts on the TBR. Subsequently, as a validation step for the optimal designs, TBR calculations were performed using a more realistic modified 1-D ROM with inner and outer breeding regions, as well as with a fully detailed 22.5-deg three-dimensional (3-D) sector of the FNSF to assess the impact of geometry details on the TBR. The differences between the two 1-D models were negligible, while the ROMs were able to correctly predict trends and identify the maximum and minimum TBR cases, as well as show consistent biases relative to the results produced by the full 3-D, 22.5-deg sector for specific breeder/multiplier combinations. Solid breeder concepts such as Li 2 O, Li 4 SiO 4 , and Li 8 ZrO 6 outperformed all others in this study in terms of TBR performance when combined with all the neutron multiplier materials selected. Here, an underlying goal of this study was to develop and improve rapid and reliable ROMs to aid designers during parametric optimizations of highly complex and computationally expensive fusion models.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
Dielectric properties of neutron and proton irradiated polymeric nanocomposite insulation for superconducting magnets of fusion power plants
Studies on radiation-resistant electrical insulation for superconducting magnets of nuclear fusion power plants are discussed. Metal oxide nanoparticle-incorporated organic polymer composite (MONAP) insulation films were manufactured and studied for their dielectric breakdown strength after exposure to neutrons and proton radiation at varying levels. Samples with up to 5 wt% of nanoparticles (NPs) of SiO 2 , MgO, and ZrO 2 were studied. The samples were exposed to radiation of up to 2 × 10 16 neutrons/cm 2 and 200 Mrad of protons. The addition of the nanoparticles improved the radiation resistance of the MONAP, and the performance depended on the type of NPs and the radiation exposure. Dielectric breakdown measurements at 77 K showed little degradation. Enhancement of dielectric strength was observed in some instances.
36 MATERIALS SCIENCE↗
Plasma-assisted catalysis for ammonia synthesis in a dielectric barrier discharge reactor: key surface reaction steps and potential causes of low energy yield
Ammonia synthesis experiments were carried out in a coaxial dielectric barrier discharge (DBD) reactor packed with several different supports and metal catalysts. There was a marked increase in the reaction rate, over that obtained in an empty DBD plasma reactor, upon introduction of a packed bed of γ-Al 2 O 3 , Ru/γ-Al 2 O 3 , or SiO 2 particles. The difference in the reaction rates over γ-Al 2 O 3 and Ru/γ-Al 2 O 3 was minimal. Complementary zero-dimensional plasma kinetic model analysis was also performed using inputs from experimental data. This kinetic analysis allowed for gas phase reactions, Eley–Rideal (E–R) reactions, and direct adsorption of radical species on the γ-Al 2 O 3 surface. On the metal surface, dissociative adsorption of N 2 and H 2 , and Langmuir–Hinshelwood reactions were also included. This analysis revealed that, under the conditions of our experiments, ammonia synthesis proceeds principally by the formation of reactive radicals in the gas phase, which then adsorb and participate in E–R reactions on both the metal and support material surfaces. Furthermore, this finding illustrates a challenge for substantially increasing the energy yield for plasma-assisted ammonia synthesis in typical DBD reactors containing packed catalyst beads.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Characterization of plasma catalytic decomposition of methane: role of atomic O and reaction mechanism
In this work, we investigated atmospheric pressure plasma jet (APPJ)-assisted methane oxidation over a Ni-SiO 2 /Al 2 O 3 catalyst. We evaluated possible reaction mechanisms by analyzing the correlation of gas phase, surface and plasma-produced species. Plasma feed gas compositions, plasma powers, and catalyst temperatures were varied to expand the experimental parameters. Real-time Fourier-transform infrared spectroscopy was applied to quantify gas phase species from the reactions. The reactive incident fluxes generated by plasma were measured by molecular beam mass spectroscopy using an identical APPJ operating at the same conditions. A strong correlation of the quantified fluxes of plasma-produced atomic oxygen with that of CH 4 consumption, and CO and CO 2 formation implies that O atoms play an essential role in CH 4 oxidation for the investigated conditions. With the integration of APPJ, the apparent activation energy was lowered and a synergistic effect of 30% was observed. We also performed in-situ diffuse reflectance infrared Fourier-transform spectroscopy to analyze the catalyst surface. The surface analysis showed that surface CO abundance mirrored the surface coverage of CH n at 25 °C. This suggests that CH n adsorbed on the catalyst surface as an intermediate species that was subsequently transformed into surface CO. We observed very little surface CH n absorbance at 500 °C, while a ten-fold increase of surface CO and stronger CO 2 absorption were seen. This indicates that for a nickel catalyst at 500 °C, the dissociation of CH 4 to CHn may be the rate-determining step in the plasma-assisted CH 4 oxidation for our conditions. We also found the CO vibrational frequency changes from 2143 cm –1 for gas phase CO to 2196 cm –1 for CO on a 25 °C catalyst surface, whereas the frequency of CO on a 500 °C catalyst was 2188 cm –1 . Here, the change in CO vibrational frequency may be related to the oxidation of the catalyst.
methane oxidation↗
Tuning electrical and interfacial thermal properties of bilayer MoS2 via electrochemical intercalation
Layered two-dimensional (2D) materials such as MoS 2 have attracted much attention for nano- and opto-electronics. Recently, intercalation (e.g. of ions, atoms, or molecules) has emerged as an effective technique to modulate material properties of such layered 2D films reversibly. We probe both the electrical and thermal properties of Li-intercalated bilayer MoS 2 nanosheets by combining electrical measurements and Raman spectroscopy. Furthermore, we demonstrate reversible modulation of carrier density over more than two orders of magnitude (from 0.8 × 10 12 to 1.5 × 10 14 cm -2 ), and we simultaneously obtain the thermal boundary conductance between the bilayer and its supporting SiO 2 substrate for an intercalated system for the first time. This thermal coupling can be reversibly modulated by nearly a factor of eight, from 14 ± 4.0 MW m -2 K -1 before intercalation to 1.8 ± 0.9 MW m -2 K -1 when the MoS 2 is fully lithiated. These results reveal electrochemical intercalation as a reversible tool to modulate and control both electrical and thermal properties of 2D layers.
77 NANOSCIENCE AND NANOTECHNOLOGY↗
First demonstration of robust tri-gate β-Ga 2 O 3 nano-membrane field-effect transistors
Nano-membrane tri-gate β-gallium oxide (β-Ga 2 O 3 ) field-effect transistors (FETs) on SiO 2 /Si substrate fabricated via exfoliation have been demonstrated for the first time. By employing electron beam lithography, the minimum-sized features can be defined with the footprint channel width of 50 nm. For high-quality interface between β-Ga 2 O 3 and gate dielectric, atomic layer-deposited 15 nm thick aluminum oxide (Al 2 O 3 ) was utilized with tri-methyl-aluminum (TMA) self-cleaning surface treatment. The fabricated devices demonstrate extremely low subthreshold slope (SS) of 61 mV dec –1 , high drain current (I DS ) ON/OFF ratio of 1.5 × 10 9 , and negligible transfer characteristic hysteresis. Furthermore, we also experimentally demonstrated robustness of these devices with current–voltage (I–V) characteristics measured at temperatures up to 400 °C.
77 NANOSCIENCE AND NANOTECHNOLOGY↗
Exfoliating silica bilayers via intercalation at the silica/transition metal interface
The growth of the silica (SiO 2 ) bilayer (BL) films on transition metal (TM) surfaces creates a new class of two-dimensional (2D) crystalline, self-contained materials that interact weakly with the TM substrate. The BL-silica/TM heterojunction has shown unique physical and chemical properties that can lead to new chemical reaction mechanisms under the sub-nm confinement and broad potential applications ranging from surface protection, nano transistors, molecular sieves to nuclear waste removal. Novel applications of BL-silica can be further explored as a constituent of van der Waals assembly of 2D materials. Key to these applications is an unmet technical challenge to exfoliate and transfer BL-silica films in a large area from one substrate to another without material damage. In this study, we propose a new exfoliation mechanism based on gas molecule intercalation from density functional theory studies of the BL-silica/TM heterojunction. Here, we found that the intercalation of O atoms and CO molecules at the BL-silica/TM interface weakens the BL-silica—TM hybridization, which results in an exponential decrease of the exfoliation energy against the interface distance as the coverage of interfacial species increases. This new intercalation mechanism opens up the opportunity for non-damaging exfoliation and transfer of large area silica bilayers.
36 MATERIALS SCIENCE↗
Operando study of mechanical integrity of high-volume expansion Li-ion battery anode materials coated by Al 2 O 3
Group IV elements and their oxides, such as Si, Ge, Sn and SiO have much higher theoretical capacity than commercial graphite anode. However, these materials undergo large volume change during cycling, resulting in severe structural degradation and capacity fading. Al 2 O 3 coating is considered an approach to improve the mechanical stability of high-capacity anode materials. To understand the effect of Al 2 O 3 coating directly, we monitored the morphology change of coated/uncoated Sn particles during cycling using operando focused ion beam–scanning electron microscopy. Here, the results indicate that the Al 2 O 3 coating provides local protection and reduces crack formation at the early stage of volume expansion. The 3 nm Al 2 O 3 coating layer provides better protection than the 10 and 30 nm coating layer. Nevertheless, the Al 2 O 3 coating is unable to prevent the pulverization at the later stage of cycling because of large volume expansion.
25 ENERGY STORAGE↗
Mitigating challenges in aberration-corrected electron-beam lithography on electron-opaque substrates
Aberration-corrected electron-beam lithography (AC-EBL) using ultra-thin electron transparent membranes has achieved single-digit nanometer resolution in two widely used electron-beam resists: poly (methyl methacrylate) (PMMA) and hydrogen silsesquioxane. On the other hand, AC-EBL implementation on thick, electron-opaque substrates is appealing for conventional top-down fabrication of quantum devices with nanometer-scale features. To investigate the performance of AC-EBL on thick substrates, we measured the lithographic point spread function of a 200 keV aberration-corrected scanning transmission electron microscope by defining both positive and negative patterns in PMMA thin films, spin-cast on thick SiO 2 /Si substrates. We present the problems encountered during pre-exposure beam focusing and discuss methods to overcome them. In addition, applying some of these methods using commercial 50 nm thick SiN X membranes with thick Si support frames, we printed arrays of holes in PMMA with pitches around 26 nm on SiN X /Si substrates with increasing Si thickness. Here, our results show that proximity effects from even 50 nm thick SiN X membranes limit hole arrays to 20 nm pitch; however, down to this limit, the effect of the substrate thickness on the pattern quality is minimal. These results highlight the need for novel resists less susceptible to proximity effects, or resists which can be used directly, after development, as the dielectric material in periodic gates in 2D quantum devices.
2D quantum devices↗
Simulation studies of the interaction of laser radiation with additively manufactured foams
The interaction of laser radiation with foams of various porosities and low densities has been the subject of several numerical and experimental studies. In all cases, the modeling of low-Z under-dense foams as uniform gases of equivalent average density using standard radiation-hydrodynamics codes has resulted in heat-front velocities that are considerably faster than those observed experimentally. It has been theoretically conjectured that this difference may be attributed to the breakdown of the foam’s morphology, leading to a dynamics of filament expansion where the ion and electron energy partitions are significantly different from those calculated using the uniform gas model. We found that 3D computer simulations employing a disconnected representation of the foam’s microstructure which allowed for the dynamics of foam element heating, expansion, and stagnation largely supported the theoretical picture. Simulations using this model for laser experiments on under-dense 2 mg cc -1 SiO 2 aerogel foams reproduced the experimental data fairly well. We used the validated model in simulations of low-density structured foam-like materials (produced via additive manufacturing) with a variety of morphologies. We found that the log-pile configurations were consistent with the analytical propagation model of Gus’kov et al. Further validation of the model was obtained by simulating experiments performed at the Jupiter Laser Facility using the log-pile and octet-truss foam morphologies. Simulations of the foam-laser interaction using a wave propagation code showed that the microstructure was able to enhance stimulated Brillouin scattering (SBS) by concentrating the light energy into density holes. In turn, this promotes laser filamentation, reducing SBS and bringing the predicted values closer to the experimental data.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
Few-femtosecond resolved imaging of laser-driven nanoplasma expansion
Abstract The free expansion of a planar plasma surface is a fundamental non-equilibrium process relevant for various fields but as-yet experimentally still difficult to capture. The significance of the associated spatiotemporal plasma motion ranges from astrophysics and controlled fusion to laser machining, surface high-harmonic generation, plasma mirrors, and laser-driven particle acceleration. Here, we show that x-ray coherent diffractive imaging can surpass existing approaches and enables the quantitative real-time analysis of the sudden free expansion of laser-heated nanoplasmas. For laser-ionized SiO 2 nanospheres, we resolve the formation of the emerging nearly self-similar plasma profile evolution and expose the so far inaccessible shell-wise expansion dynamics including the associated startup delay and rarefaction front velocity. Our results establish time-resolved diffractive imaging as an accurate quantitative diagnostic platform for tracing and characterizing plasma expansion and indicate the possibility to resolve various laser-driven processes including shock formation and wave-breaking phenomena with unprecedented resolution.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
In-situ coating of silicon-rich films on tokamak plasma-facing components with real-time Si material injection
Abstract Experiments have been conducted in the DIII-D tokamak to explore the in-situ growth of silicon-rich layers as a potential technique for real-time replenishment of surface coatings on plasma-facing components (PFCs) during steady-state long-pulse reactor operation. Silicon (Si) pellets of 1 mm diameter were injected into low- and high-confinement (L-mode and H-mode) plasma discharges with densities ranging from 3.9– 7.5 × 10 19 m −3 and input powers ranging from 5.5 to 9 MW. The small Si pellets were delivered with the impurity granule injector at frequencies ranging from 4 to 16 Hz corresponding to mass flow rates of 5–19 mg s −1 (1– 4.2 × 10 20 Si s −1 ) at cumulative amounts of up to 34 mg of Si per five-second discharge. Graphite samples were exposed to the scrape-off layer and private flux region plasmas through the divertor material evaluation system to evaluate the Si deposition on the divertor targets. The Si II emission at the sample correlates with silicon injection and suggests net surface Si-deposition in measurable amounts. Post-mortem analysis showed Si-rich coatings containing silicon oxides, of which SiO 2 is the dominant component. No evidence of SiC was found, which is attributed to low divertor surface temperatures. The in-situ and ex-situ analysis found that Si-rich coatings of at least 0.4–1.2 nm thickness have been deposited at 0.4–0.7 nm s −1 . The technique is estimated to coat a surface area of at least 0.94 m 2 on the outer divertor. These results demonstrate the potential of using real-time material injection to form Si-enriched layers on divertor PFCs during reactor operation.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
A method to observe field-region oxide charge and inter-electrode isolation from CV-characteristics of n-on-p devices
Abstract N-on-psilicon sensors will be utilized in the Compact Muon Solenoid (CMS) detector's tracker and High Granularity Calorimeter (HGCAL) in the High Luminosity upgrade of the Large Hadron Collider (HL-LHC). Among their several advantages in terms of radiation hardness over the traditionalp-on-nsensors in the extreme radiation environment of the HL-LHC are electron collection instead of holes and overlapping maxima of weighting and electric fields at the charge-collecting electrodes. The disadvantage of the multi-channel SiO 2 -passivatedn-on-psensors is the generation of an inversion layer under the Si/SiO 2 -interface by a positive interface-oxide-charge (N ox ) that at high densities can compromise the position resolution by creating a conduction channel between the electrodes. This issue is typically addressed by including additional isolnts (p-stp,p-spray) between n + -electrodes. Focusing on the guard-ring regions ofn-on-psensors where no isolation implants are applied between the electrodes, a capacitance-voltage (CV) characterization study of both 6-inch wafer test diodes and 8-inch HGCAL prototype and pre-series sensors showed a distinct threshold voltage (V th,iso ) in theCV-characteristics of a biased n + -electrode when its enclosing guard-ring was left floating. When reproduced by simulations, the measuredV th,iso was found to contain information on the field-regionN ox and indicate the threshold where the two electrodes become electrically isolated by the influence of the reverse bias voltage. Together with previous studies on the inter-electrode isolation of irradiatedn-on-psensors, the results indicate that position sensitiven-on-psensors without isolation implants may be feasible in future HEP experiments.
Instruments & Instrumentation↗
In situ laser reflectivity to monitor and control the nucleation and growth of atomically thin 2D materials*
The growth of atomically thin two-dimensional (2D) layered and other quantum materials is typically performed without in situ monitoring or control. Here, a simple laser reflectivity approach is demonstrated to provide in situ control over sub-monolayer thickness and growth kinetics during pulsed laser deposition (PLD) of MoSe 2 layers. First, the general technique is presented with emphasis on designing the maximum sensitivity of the optical contrast through consideration of Fresnel's equations with proper choice of layer thickness, substrate, and laser monitoring wavelength, incidence angle, and laser polarization. Then the 632.8 nm optical reflectivity of MoSe 2 layers on SiO 2 /Si substrates was predicted and compared with in situ monitoring of MoSe 2 growth by PLD under actual growth conditions using a probe HeNe laser beam. The measurements showed high sensitivity and excellent agreement with MoSe 2 surface coverages calculated from atomic resolution STEM analysis of 2D layers deposited in arrested growth experiments. Finally, growth kinetics revealed by these measurements showed sigmoidal nucleation and growth stages in the formation of the 2D MoSe 2 layers that are described by a simple model, indicating the promise of the laser reflectivity technique for in situ monitoring and control of 2D materials deposition.
2D materials↗
Thickness-dependent phase transition kinetics in lithium-intercalated MoS 2
The phase transitions of two-dimensional (2D) materials are key to the operation of many devices with applications including energy storage and low power electronics. Nanoscale confinement in the form of reduced thickness can modulate the phase transitions of 2D materials both in their thermodynamics and kinetics. Here, using in situ Raman spectroscopy we demonstrate that reducing the thickness of MoS 2 below five layers slows the kinetics of the phase transition from 2H- to 1T'-MoS 2 induced by the electrochemical intercalation of lithium. In this study, we observe that the growth rate of 1T' domains is suppressed in thin MoS 2 supported by SiO 2 , and attribute this growth suppression to increased interfacial effects as the thickness is reduced below 5 nm. In this study, the suppressed kinetics can be reversed by placing MoS 2 on a 2D hexagonal boron nitride ( h BN) support, which readily facilitates the release of strain induced by the phase transition. Additionally, we show that the irreversible conversion of intercalated 1T'-MoS 2 into Li2S and Mo is also thickness-dependent and the stability of 1T'-MoS 2 is significantly increased below five layers, requiring a much higher applied electrochemical potential to break down 1T'-MoS 2 into Li 2 S and Mo nanoclusters.
36 MATERIALS SCIENCE↗