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At least 37 records · Page 2

Reduced trap state density in AlGaN/GaN HEMTs with low-temperature CVD-grown BN gate dielectric

In this Letter, low-temperature (400 °C) chemical vapor deposition-grown boron nitride (BN) was investigated as the gate dielectric for AlGaN/GaN metal–insulator–semiconductor high electron mobility transistors (MISHEMTs) on a Si substrate. Comprehensive characterizations using x-ray photoelectron spectroscopy, reflection electron energy loss spectroscopy, atomic force microscope, high-resolution transmission electron microscopy, and time-of-flight secondary ion mass spectrometry were conducted to analyze the deposited BN dielectric. Compared with conventional Schottky-gate HEMTs, the MISHEMTs exhibited significantly enhanced performance with 3 orders of magnitude lower reverse gate leakage current, a lower off-state current of 1 × 10−7 mA/mm, a higher on/off current ratio of 108, and lower on-resistance of 5.40 Ω mm. The frequency-dependent conductance measurement was performed to analyze the BN/HEMT interface, unveiling a low interface trap state density (Dit) on the order of 5 × 1011–6 × 1011 cm−2 eV−1. This work shows the effectiveness of low-temperature BN dielectrics and their potential for advancing GaN MISHEMTs toward high-performance power and RF electronics applications.

Physics↗

Morphology‐controlled synthesis of multi‐metal‐based spinel oxide nanocatalysts and their performance for oxygen reduction

Abstract We present a one‐pot colloidal synthesis method for producing monodisperse multi‐metal (Co, Mn, and Fe) spinel nanocrystals (NCs), including nanocubes, nano‐octahedra, and concave nanocubes. This study explores the mechanism of morphology control, showcasing the pivotal roles of metal precursors and capping ligands in determining the exposed crystal planes on the NC surface. The cubic spinel NCs, terminated with exclusive {100}‐facets, demonstrate superior electrocatalytic activity for the oxygen reduction reaction (ORR) in alkaline media compared to their octahedral and concave cubic counterparts. Specifically, at 0.85 V, (CoMn)Fe 2 O 4 spinel oxide nanocubes achieve a high mass activity of 23.9 A/g and exhibit excellent stability, highlighting the promising ORR performance associated with {100}‐facets of multi‐metal spinel oxides over other low‐index and high‐index facets. Motivated by exploring the correlation between ORR performance and surface atom arrangement (active sites), surface element composition, as well as other factors, this study introduces a prospective approach for shape‐controlled synthesis of advanced spinel oxide NCs. It underscores the significance of catalyst shape control and suggests potential applications as nonprecious metal ORR electrocatalysts.

Li, Can↗

Highly durable fuel cell electrocatalyst with low-loading Pt-Co nanoparticles dispersed over single-atom Pt-Co-N-Graphene nanofiber

The limited durability of Pt electrocatalysis toward cathodic oxygen reduction reaction remains challenging, yet crucial for the development of Proton Exchange Membrane Fuel Cell. Here, we present a rational design of a robust catalyst consisting of PtCo nanoparticles supported on Pt-Co-N-graphene nanofiber prepared through electrospun Cobalt-Metal-Organic-Framework. The catalyst delivers unprecedented mass activity of 2.48 A·mgPt -1 , and retains 80% of initial value after 60,000 Accelerated-Stress-Test cycles. Operando X-ray absorption spectroscopies show that the electronic configurations of Pt sites in PtCo and Co sites in Co-N4 in the hybrid catalyst are modified toward high catalytic activities. Density Functional Theory unveils that the enhanced curvature of the substrate induced by the morphology engineering lowers the reaction thermodynamic barrier on Co-N4 sites, favoring the formation of H2O and suppressing that of H2O2. This result along with the strong affinity of PtCo nanoparticles to the Pt-Co-N-graphene fiber endows the catalyst an exceptional durability.

acidic electrolyte↗

Unconventional low temperature decomposition of a saturated hydrocarbon over atomically-dispersed titanium-aluminum-boron catalyst

Sonochemically-synthesized atomically-dispersed titanium-aluminum-boron nanopowder (TiAlB NP) exhibits a remarkable low-temperature catalytic activation of aliphatic C-H bonds at 750 K followed by C-C bond activation thus emerging as a potent low-cost alternative to expensive platinum group metals. Here, the model saturated hydrocarbon, exo-tetrahydrodicyclopentadiene (C10H16), undergoes catalytic decomposition on TiAlB NPs in a chemical microreactor to produce 1,3-cyclopentadiene (c-C5H6), cyclopentene (c-C5H8), and molecular hydrogen (H2) as detected in situ via isomer-selective, single-photon ionization time-of-flight mass spectrometry. Extensive electronic structure theory calculations on model clusters of the catalyst decode a unique synergy among the atomic constituents of the catalyst and chemical bonding in this stepwise, retro Diels Alder reaction: Ti, although insensitive to C-H activation in its metallic state, initiates the catalysis via chemisorption of the hydrocarbon, adjacent B centers readily abstract hydrogen atoms and store them during the catalytic cycle, while Al stabilizes the catalyst structure yet providing space for critical docking sites for the departing hydrocarbons.

Biswas, Souvick↗

Ion beam sputter-deposited thin film coatings for protection of spacecraft polymers in low Earth orbit

Ion beam sputter-deposited thin films of Al2O3, SiO2, and a codeposited mixture of predominantly SiO2 with small amounts of a fluoropolymer were evaluated both in laboratory plasma ashing tests and in space on board shuttle flight STS-8 for effectiveness in preventing oxidation of polyimide Kapton. Measurements of mass loss and optical performance of coated and uncoated polyimide samples exposed to the low Earth orbital environment are presented. Optical techniques were used to measure loss rates of protective films exposed to atomic oxygen. Results of the analysis of the space flight exposed samples indicate that thin film metal oxide coatings are very effective in protecting the polyimide. Metal oxide coatings with a small amount of fluoropolymer codeposited have the additional benefit of great flexibility.

Banks, B. A.↗

Ion beam sputter-deposited thin film coatings for protection of spacecraft polymers in low earth orbit

Ion beam sputter-deposited thin films at Al2O3, SiO2, and a codeposited mixture of predominantly SiO2 with small amounts of fluoropolymer were evaluated both in laboratory plasma ashing tests and in space on board Shuttle flight STS-8 for effectiveness in preventing oxidation of polyimide Kapton. Measurements of mass loss and optical performance of coated and uncoated polyimide samples exposed to the low earth orbital environment are presented. Optical techniques were used to measure loss rates of protective films exposed to atomic oxygen. Results of the analysis of the space flight exposed samples indicate that thin film metal oxide coatings are very effective in protecting the polyimide. Metal oxide coatings with a small amount of fluoropolymer codeposited have the additional benefit of great flexibility.

Banks, B. A.↗

Yttrium Hydride Post Irradiation Examination Plan

The overarching goal of the Department of Energy Office of Nuclear Energy (DOE-NE) microreactor program is to develop technologies for the deployment of civilian microreactors by stakeholders1. Microreactors are expressed as advanced transportable nuclear reactors operating at low power (<20MWth) but high temperatures (>600°C), as well as plug-and-play and inherently safe designs. One prerequisite of a microreactor is the compactness, so that a truck can transport the reactor under safe conditions with the current road infrastructure1,2. The compactness of these reactors likely can be attainable by use of solid components for the essentials of the nuclear core, such as fuel, core heat removal components, reflectors, and moderators. Among these essentials, where fuel enrichment must remain < 20% to meet High Assay Low Enrichment Uranium criteria (HALEU), the largest contribution to the compactness is offered by use of solid moderators which benefit from light atomic weight elements, such as hydrogen, carbon, and beryllium2. Among these, hydrogen-bearing materials, such as metal hydrides, are superior to other options from the lowest critical mass standpoint. Noting that, factors other than critical mass should be considered for a specific reactor design. Yttrium- or zirconium-based metal hydrides have been down-selected due to their neutronic performance. In addition to the neutronic perspective, maintaining hydrogen within the metal hydride is important at the high operating temperatures proposed by advanced reactors. Yttrium hydride (YHx) is, therefore, a proposed moderator material that offers better hydrogen retention at higher operating temperatures than zirconium hydrides due to higher retention and thermal stability of hydrogen in the metal3. The irradiated materials properties of metal hydrides, in this case YHx, must be assessed for the qualification of these moderators. Material testing and inspection processes must illustrate that the effects of dimensional and property changes on thermophysical and mechanical properties do not cause any significant changes on the microreactor safety, and the moderating power is maintained within design limits. Thus, the effect of irradiation on the thermophysical and mechanical properties must be determined. This post-irradiation examination (PIE) plan specifically aims to determine these properties for YHx following Advanced Test Reactor (ATR) irradiation.

99 GENERAL AND MISCELLANEOUS↗

PLN-6268 Yttrium Hydride Post Irradiation Examination Plan

The overarching goal of the Department of Energy Office of Nuclear Energy (DOE-NE) microreactor program is to develop technologies for the deployment of civilian microreactors by stakeholders1. Microreactors are expressed as advanced transportable nuclear reactors operating at low power (<20MWth) but high temperatures (>600°C), as well as plug-and-play and inherently safe designs. One prerequisite of a microreactor is the compactness, so that a truck can transport the reactor under safe conditions with the current road infrastructure1,2. The compactness of these reactors likely can be attainable by use of solid components for the essentials of the nuclear core, such as fuel, core heat removal components, reflectors, and moderators. Among these essentials, where fuel enrichment must remain < 20% to meet High Assay Low Enrichment Uranium criteria (HALEU), the largest contribution to the compactness is offered by use of solid moderators which benefit from light atomic weight elements, such as hydrogen, carbon, and beryllium2. Among these, hydrogen-bearing materials, such as metal hydrides, are superior to other options from the lowest critical mass standpoint. Noting that, factors other than critical mass should be considered for a specific reactor design. Yttrium- or zirconium-based metal hydrides have been down-selected due to their neutronic performance. In addition to the neutronic perspective, maintaining hydrogen within the metal hydride is important at the high operating temperatures proposed by advanced reactors. Yttrium hydride (YHx) is, therefore, a proposed moderator material that offers better hydrogen retention at higher operating temperatures than zirconium hydrides due to higher retention and thermal stability of hydrogen in the metal3. The irradiated materials properties of metal hydrides, in this case YHx, must be assessed for the qualification of these moderators. Material testing and inspection processes must illustrate that the effects of dimensional and property changes on thermophysical and mechanical properties do not cause any significant changes on the microreactor safety, and the moderating power is maintained within design limits. Thus, the effect of irradiation on the thermophysical and mechanical properties must be determined. This post-irradiation examination (PIE) plan specifically aims to determine these properties for YHx following Advanced Test Reactor (ATR) irradiation.

99 GENERAL AND MISCELLANEOUS↗

The Importance of Decarbonylation Mechanisms in the Atomic Layer Deposition of High-Quality Ru Films by Zero-Oxidation State Ru(DMBD)(CO) 3

Achieving facile nucleation of noble metal films through atomic layer deposition (ALD) is extremely challenging. To this end, η 4 -2,3-dimethylbutadiene ruthenium tricarbonyl (Ru(DMBD)(CO) 3 ), a zero-valent complex, has recently been reported to achieve good nucleation by ALD at relatively low temperatures and mild reaction conditions. Here, we study the growth mechanism of this precursor by in situ quartz-crystal microbalance and quadrupole mass spectrometry during Ru ALD, complemented by ex situ film characterization and kinetic modeling. These studies reveal that Ru(DMBD)(CO) 3 produces high-quality Ru films with excellent nucleation properties. This results in smooth, coalesced films even at low film thicknesses, all important traits for device applications. However, Ru deposition follows a kinetically limited decarbonylation reaction scheme, akin to typical CVD processes, with a strong dependence on both temperature and reaction timescale. The non-self-limiting nature of the kinetically driven mechanism presents both challenges for ALD implementation and opportunities for process tuning. By surveying reports of similar precursors, we suggest that the findings can be generalized to the broader class of zero-oxidation state carbonyl-based precursors used in thermal ALD, with insight into the design of effective saturation studies.

chemical vapor deposition↗

Reactions between NO/+/ and metal atoms using magnetically confined afterglows

A new method of studying thermal energy ion-neutral collision processes involving nongaseous neutral atoms is described. A long magnetic field produced by a solenoid in a vacuum chamber confines a thermal-energy plasma generated by photoionization of gas at very low pressure. As the plasma moves toward the end of the field, it is crossed by a metal atom beam. Ionic products of ion-atom reactions are trapped by the field and both the reactant and product ions move to the end of the magnetic field where they are detected by a quadrupole mass filter. The cross sections for charge transfer between NO(+) and Na, Mg, Ca, and Sr and that for rearrangement between NO(+) and Ca have been obtained. The charge-transfer reaction is found strongly dominant over the rearrangement reaction that forms metallic oxide ions.

Lo, H. H.↗

Multipole polaron roams the devil’s staircase

We report Electron–boson interaction (EBI) has an important role in the properties of materials. Electron–phonon interaction in good metals can give rise to superconductivity, where electrons flow without dissipation below a critical temperature. In ionic crystals such as organic semiconductors, the coupling of low-energy electrons (or holes) with the atomic vibrations can drive the formation of polarons — an electron dressed with a phonon cloud, with lower mobility and heavy effective mass. The same notion can be applied to strongly correlated electron systems. Electron–spin fluctuation coupling drives unconventional superconductivity in high-temperature cuprates, iron-based superconductors and heavy-fermion systems. Magnetic polarons can form around charged dopants in an otherwise antiferromagnetic background of a Mott insulator, while an electron–polaron is also possible, via electron–plasmon coupling, when a Kondo hole is introduced in a heavy-fermion material, similar to a plasmaron in doped graphene.

36 MATERIALS SCIENCE↗

Sputtered coatings for protection of spacecraft polymers

Kapton polyimide oxidizes at significant rates (4.3x10(-24) gram/incident oxygen atom) when exposed in low Earth orbit to the ram atomic oxygen flux. Ion beam sputter deposited thin films of Al2O3 and SiO2 as well as a codeposited mixture of predominantly SiO2 with a small amount of polytetrafluoroethylene were evaluated and found to be effective in protecting Kapton from oxidation in both laboratory plasma ashing tests as well as in space on board shuttle flight STS-8. A protective film of or = 96 percent SiO2 and or = 4 percent polytetrafluoroethylene was found to be very flexible compared to the pure metal oxide coatings and resulted in mass loss rates that were 0.2 percent of that of the unprotected Kapton. The optical properties of Kapton for wavelengths investigated between 0.33 and 2.2 microns were not significantly altered by the presence of the coatings or changed by exposure of the coated Kapton to the low Earth orbital ram environment.

Banks, B. A.↗

Electrodepositing Textured Sn Film as a Highly Reversible Anode for Aqueous Batteries

Electrodepositing metal materials in large capacity, at low potential, and with high reversibility serves as the foundation for any aqueous rechargeable battery chemistry to realize the promises of high energy, low cost, and high safety. However, such a foundation is not solid because of the natural tendency of metals to form irregular, nonplanar, and often dendritic morphologies during electrochemical crystallization, which is further amplified in an acidic environment due to the faster kinetics of the coupled proton and mass-transport processes between hydrated metal ions and free metal atoms. As a typical representative, tin metal (Sn 0 ) has potential to achieve high energy in acidic batteries, but its nonuniform large-particle morphology, obtained from traditional electrodeposition, leads to dead Sn 0 formation and deteriorating reversibility, accompanied by the sustained hydrogen evolution reaction (HER) and active Sn 0 loss. Here, in this study, we report quaternary onium salts as effective interfacial cocations that, via selective adsorption, steadily texturize Sn 0 deposition along the (211) plane, which is intrinsically inert to the HER, thus regulating the film deposition process by favoring the formation of planar Sn 0 film. Such Sn 0 film brings exceptional reversibility in acidic electrolytes, which translates into sustained cycling stability at applicable areal capacities in both anode-half cells (similar to 1500 deposition/dissolution cycles at 5 mAh cm -2 ) and full cells (350 charge/discharge cycles at 5 mAh cm -2 ). Textured electrodeposition with intrinsic HER-suppression capability provides a universal solution for diverse metal anode materials in rechargeable energy-dense aqueous batteries.

Sn metal↗

Local Electric Field Effects on Water Dissociation in Bipolar Membranes Studied Using Core–Shell Catalysts

The local electric field strength is thought to affect the rate of water dissociation (WD) in bipolar membranes (BPMs) at the catalyst–nanoparticle surfaces. Here, we study core–shell nanoparticles, where the core is metallic, semiconducting, or insulating, to understand this effect. The nanoparticle cores were coated with a WD catalyst layer (TiO2 or HfO2) via atomic layer deposition (ALD), and the morphology was imaged with transmission electron microscopy. Irrespective of the core material, these core–shell catalysts displayed comparable WD overpotentials at optimal mass loading, despite the hypothesized differences in the electric field strength across the catalyst particle suggested by continuum electrostatic simulations. Substantial atomic interdiffusion between the core and shell was ruled out by X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and diffuse reflectance optical measurements. However, the optimal mass loading of catalyst was roughly 1 order of magnitude higher for the conductive and high dielectric core materials than for the low dielectric insulating cores. These findings are consistent with the hypothesis that electric field screening within the core material focuses the electric field drop between particles such that larger film thicknesses can be tolerated. Collectively, these data support the idea that it is the local electric field at the molecular level that controls proton-transfer rates and that the metal core/dielectric-shell constructs introduced here modulate that field. Further materials and synthetic design may enable optimization of the electric field strength across the proton-transfer trajectory at the material surface.

Sarma, Prasad V↗

Constraints on the Nature and Distribution of Iridium Host Phases at the Cretaceous-Tertiary Boundary: Implications for Projectile Identity and dispersal on impact

Among Cretaceous-Tertiary boundary sites worldwide, variations in the concentrations and ratios of elements commonly enriched in meteorites complicate traditional geochemical attempts at impactor identification. Yet they may provide constraints on the physical and chemical processes associated with large-body disruption and dispersal, as well as with diagenesis of projectile components. To this end, we continue our efforts to identify the mineral host-phases of projectile-derived elements, particularly for Ir, and to document their partitioning between crater deposits and ejecta resulting from the Chicxulub basin-forming impact. Building on earlier work, we used INAA to measure Ir concentrations in successively smaller splits of finely powdered impact melt breccia from the Chicxulub Crater in Mexico (sample Y6Nl9-R(b)), and K/T boundary fish clay from Stevns Klint, Denmark (sample FC-1, split from 40 kg of homogenized material intended as an analytical standard). Results for the Chicxulub sample show a heterogeneous Ir distribution and document that at least five discrete Ir-bearing host phases were isolated in subsequent splits, having Ir masses equivalent to pure Ir spheres from about 0.8 to about 3.5 mm in diameter. Three of these are within a sufficiently reduced mass of powder to warrant searching for them using backscattered electron microscopy. In contrast, successively smaller splits of the Stevns Klint fish clay show no statistically significant deviation from the reported value of 32 +/- 2 ng/g Ir, suggesting a uniform Ir host-phase distribution. For the smallest split obtained thus far (100 +/- 40 ng/g Ir), a pure Ir sphere of equivalent Ir mass would be <0.05 min in diameter. (n.b. Although homogenizing and sieving of FC-1 to <75 min obviously obscured variations in stratigraphic distribution, it is unlikely to have affected the size-frequency distribution of Ir host phases.) We previously identified micrometer-scale Ir host phases by electron microscopy in melt-rock samples from two widely separated drill holes at the Chicxulub Basin, including a replicate split of Y6-NI9-R. One is an aggregate of subhedral Ir metal grains enclosed in silicate, in which no other Pt group elements (PGE) were detected. A second particle with twice the mass as the first, concentrated predominantly in a single grain, is associated with minor concentrations of Os, Ru, and Pt, and with adhering particles of corundum and perovskite. A third Ir-rich particle, with a greater apparent Os concentration, was identified before being lost as a result of charging under the electron beam. In addition to demonstrating the preservation of projectile components within the Chicxulub Crater, analogous phase associations in Ca- and Al-rich inclusions (CAI) from C2 and C3 chondrites suggest to us that these melt-rock Ir host phases are relics from a carbonaceous chondrite K/T boundary impactor Although the obviously low Ru/Ir ratios of the Chicxulub Ir host phases are qualitatively consistent with suggested PGE fractionation with distance during condensation in an ejecta cloud, it seems difficult to explain the accumulation of the about 3 x 10(exp 11) Ir atoms required to form a about 10(exp -10) g nugget of pure Ir metal within a jet of vaporized projectile expanding at 1-4 km/s, or to effectively exclude or remove commonly alloyed PGE and siderophile elements by fractionation processes resulting from condensation, oxidation, sulfidization, exsolution, or autometamorphism during cooling of the melt. We do not dismiss the importance of these processes entirely; on the contrary, other geochemical and mineralogical aspects of the melt rocks require them, and condensation from the expanding ejecta cloud appears to best explain the primary Ir host-phase distribution in the fish clay, as well as the high Ir concentrations associated with spinel-bearing spheroids at the K/T boundary in the Pacific Ocean . If the "relict" hypothesis is correct, micronuggets of other PGEs and alloys, not detected by our INAA screening, should also occur in the melt rocks. Possibly, the discrete host phases with lesser Ir masses are such alloys with subordinate Ir, rather than simply smaller, predominantly Ir-bearing particles. A CAI source for the relics would be consistent with either a comet or an asteroid K/T impact at Chicxulub. (Additional information contained in the original.)

Schuraytz, B. C.↗

An Expanded Set of Los Alamos OPLIB Tables in MESA: Type-1 Rosseland-mean Opacities and Solar Models

Abstract We present a set of 1194 Type-1 Rosseland-mean opacity tables for four different metallicity mixtures. These new Los Alamos OPLIB atomic radiative opacity tables are an order of magnitude larger in number than any previous opacity table release, and span regimes where previous opacity tables have not existed. For example, the new set of opacity tables expands the metallicity range to Z = 10 −6 to Z = 0.2, which allows improved accuracy of opacities at low and high metallicity, increases the table density in the metallicity range Z = 10 −4 to Z = 0.1 to enhance the accuracy of opacities drawn from interpolations across neighboring metallicities, and adds entries for hydrogen mass fractions between X = 0 and X = 0.1 including X = 10 −2 , 10 −3 , 10 −4 , 10 −5 , 10 −6 that can improve stellar models of hydrogen deficient stars. We implement these new OPLIB radiative opacity tables in MESA and find that calibrated solar models agree broadly with previously published helioseismic and solar neutrino results. We find differences between using the new 1194 OPLIB opacity tables and the 126 OPAL opacity tables range from ≈20% to 80% across individual chemical mixtures, up to ≈8% and ≈15% at the bottom and top of the solar convection zone respectively, and ≈7% in the solar core. We also find differences between standard solar models using different opacity table sources that are on par with altering the initial abundance mixture. We conclude that this new, open-access set of OPLIB opacity tables does not solve the solar modeling problem, and suggest the investigation of physical mechanisms other than the atomic radiative opacity.

79 ASTRONOMY AND ASTROPHYSICS↗

A far-infrared spectral line survey of 23 infrared-bright Galaxy nuclei

We present results from a KAO survey of fine-structure lines observed in 23 infrared-luminous galaxies. One or more of the following lines was observed and/or detected in each galaxy: (S III) 19, 33 microns, (Ne V) 24 microns, (O IV) 26 microns, (Fe II) 26 microns, (Si II) 35 microns, (O III) 52, 88 microns, (0 I) 63, 146 microns, (N III) 57 micro ns, (N II) 122, 205 microns, (C II) 158 microns. The galaxies span a wide range of morphologies (irregular to grand design), have varying metallicities, and include mergers, AGN's, and starburst systems. The observations were made beginning in 1988 using the facility Cryogenic Grating Spectrometer onboard the KAO at a typical resolution of approximately 60-140 km/s and with a 30-44 deg beam. We interpret the (C II) and (O I) fluxes, along with previous measurements of the IR continuum fluxes, in the context of photo dissociation region (PDR) models (Tielens & Hollenbach 1985; Wolfire et al. 1990). With these models, we obtain estimates of the typical interstellar UV fields incident on the line emitting regions (102-104 times the local interstellar radiation field) and the total masses (10(exp 7)-10(exp 8) Solar Mass), densities (10(exp 3)-10(exp 4)/cu cm), and temperatures (100-250 K) of the warm atomic gas. The (O III) (52/88) and (S III) (33/19) line flux ratios constrain the range of electron densities and pressures found within the ionized regions. The (O III) and (S III) lines also provide estimates of the effective temperature of the ionizing stars and elemental abundances within the ionized regions of these galactic nuclei. Our measurements imply typical gas pressures of nT approximately 5 x 10(exp 6)/cu cm K and typical upper mass cutoffs of 25-35 Solar Mass. The low-metallicity systems show high (C II)/CO and (O I)/CO flux ratios, 3-5 times the Milky Way value, indicating that they contain a larger fraction of photodissociated gas relative to the molecular material.

Lord, Steven D.↗

tert-butoxides as precursors for atomic layer deposition of alkali metal containing thin films

Alkali metal containing materials have become increasingly attractive in a world hunting for sustainable energy materials and green functional devices. Lithium- and sodium battery technology, lead-free piezo- and ferroelectric devices, and record-breaking alkali doped tandem perovskite solar cells are among the applications where alkali metal-containing thin films get increasing attention. Atomic layer deposition (ALD) is one of the enabling thin film deposition techniques that offer chemical and geometrical versatility to realize the implementation of such thin films on an applicable scale. The drawback has until recently been a lack of available precursor chemistry that offers self-limiting growth that is fundamental to ALD. The alkali metal tert-butoxides have been shown to exhibit the necessary properties to facilitate saturating growth for Li-, Na-, K-, and Rb-containing compounds. However, the behavior of the tert-butoxides in ALD-growth has been considered difficult to unravel, with processes exhibiting limited control and low reproducibility. Very little has been reported on trends in reaction mechanisms as the mass of the alkali metal increases. Herein, we summarize the existing literature on the use of alkali metal tert-butoxides as precursors in ALD. We consider differences in the structure and behavior of the tert-butoxides as the alkali metal cation becomes heavier. In addition, we present precursor synthesis routes and key information on precursor structure, stability, and mechanistic behavior. Finally, we provide the first ever report of Cs-containing films by ALD to complement previous work on its lighter counterparts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗