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Ceramic membranes are a promising alternative to polymeric membranes for selective separations, given their ability to operate under harsh chemical conditions. However, current fabrication technologies fail to construct ceramic membranes suitable for selective molecular separations. Herein, we demonstrate a molecular-level design of ceramic thin-film composite membranes with tunable subnanometer pores for precise molecular sieving. Through burning off the distributed carbonaceous species of varied dimensions within hybrid aluminum oxide films, we created membranes with tunable molecular sieving. Specifically, the membranes created with methanol showed exceptional selectivity toward monovalent and divalent salts. We attribute this observed selectivity to the dehydration of the large divalent ions within the subnanometer pores. As a comparison, smaller monovalent ions can rapidly permeate with an intact hydration shell. Lastly, the flux of neutral solutes through each fabricated aluminum oxide membrane was measured for the demonstration of tunable separation capability. Overall, our work provides the scientific basis for the design of ceramic membranes with subnanometer pores for molecular sieving using atomic layer deposition. Ceramic membranes are a promising alternative to polymeric membranes for selective separations, given their ability to operate under harsh chemical conditions. Here authors demonstrate a molecular-level design of ceramic membranes with tunable subnanometer pores. [ABSTRACT FROM AUTHOR]

Polymer membranes have a wide variety of applications, ranging from water treatment to energy storage. Many of these applications require precise control over the membrane porosity and surface chemistry. In this study, we explore the modification of isoporous polycarbonate (PC) track-etched membranes (PCTEs) by atomic layer deposition (ALD) and sequential infiltration synthesis (SIS) to tune the pore size and the pore wall surface chemistry. We first performed a detailed study of Al2O3 ALD and SIS in PCTE using a variety of in situ and ex situ measurements. We discovered that short precursor exposure times are critical to achieve conformal Al2O3 ALD in the PCTE nanopores, while longer precursor exposure times resulted in Al2O3 SIS within the bulk of the PC leaving the membranes brittle. Next, we tuned the PCTE pore size via Al2O3 ALD and studied its effect on the water contact angle and the water permeance. We found that the membranes became more hydrophilic, and the permeance decreased with increasing ALD Al2O3 cycles. Finally, we studied the effect of hydrophilic (SnO2)/hydrophobic (In2O3) ALD metal oxide coatings on membrane properties. We found that the most hydrophilic SnO2 showed the highest water flux and the least hydrophilic In2O3 showed the lowest water flux through the PCTE membranes. Our results demonstrate that ALD is an effective method to tune the surface and transport properties of PCTE membranes, but care must be exercised to avoid SIS and bulk modification of the polymer. [ABSTRACT FROM AUTHOR]

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. 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. [ABSTRACT FROM AUTHOR]

To enable greater control over thermal atomic layer deposition (ALD) of molybdenum disulfide (MoS2), here we report studies of the reactions of molybdenum hexafluoride (MoF6) and hydrogen sulfide (H2S) with metal oxide substrates from nucleation to few-layer films. In situ quartz crystal microbalance experiments performed at 150, 200, and 250 °C revealed temperature-dependent nucleation behavior of the MoF6 precursor, which is attributed to variations in surface hydroxyl concentration with temperature. In situ Fourier transform infrared spectroscopy coupled with ex situ x-ray photoelectron spectroscopy (XPS) indicated the presence of molybdenum oxide and molybdenum oxyfluoride species during nucleation. Density functional theory calculations additionally support the formation of these species as well as predicted metal oxide to fluoride conversion. Residual gas analysis revealed reaction by-products, and the combined experimental and computational results provided insights into proposed nucleation surface reactions. With additional ALD cycles, Fourier transform infrared spectroscopy indicated steady film growth after ∼13 cycles at 200 °C. XPS revealed that higher deposition temperatures resulted in a higher fraction of MoS2 within the films. Deposition temperature was found to play an important role in film morphology with amorphous films obtained at 200 °C and below, while layered films with vertical platelets were observed at 250 °C. These results provide an improved understanding of MoS2 nucleation, which can guide surface preparation for the deposition of few-layer films and advance MoS2 toward integration into device manufacturing. [ABSTRACT FROM AUTHOR]

Overcoating layers deposited on the surface of heterogeneous catalysts using atomic layer deposition (ALD) have been shown to increase catalyst activity, lifetime, and selectivity. In this study, we performed Al2O3 ALD and Pd ALD in a commercial fluidized bed reactor on high surface area mesoporous powder supports to create overcoated catalysts with high precursor utilization. We investigated the reaction mechanism for both Al2O3 ALD and Pd ALD using in situ mass spectrometry and developed a mathematical model to understand the precursor saturation behaviors. We characterized the catalyst samples using a variety of techniques to measure the surface area, porosity, composition, and surface chemistry of the overcoated catalysts. Finally, we used propane dehydrogenation as a probe reaction to evaluate the performance of the catalysts prepared by fluidized bed ALD. [ABSTRACT FROM AUTHOR]

The need for advanced energy conversion and storage devices remains a critical challenge amid the growing worldwide demand for renewable energy. Metal fluoride thin films are of great interest for applications in lithium-ion and emerging rechargeable battery technologies, particularly for enhancing the stability of the electrode-electrolyte interface and thereby extending battery cyclability and lifetime. Reported within, sodium fluoride (NaF) thin films were synthesized via atomic layer deposition. NaF growth experiments were carried out at reactor temperatures between 175 and 250 °C using sodium tert-butoxide and HF-pyridine solution. The optimal deposition temperature range was 175–200 °C, and the resulting NaF films exhibited low roughness (Rq ≈ 1.6 nm for films of ∼8.5 nm), nearly stoichiometric composition (Na:F = 1:1.05) and a growth per cycle value of 0.85 Å/cycle on SiO2 substrates. These results are encouraging for future applications of NaF thin films in the development of improved energy capture and storage technologies. [ABSTRACT FROM AUTHOR]

A new strategy for electrochemical interfaces that utilizes multilayer films deposited by atomic layer deposition (ALD) is introduced. Manganese-rich and nickel-rich cathode oxides were coated with a novel bilayer film of metal fluorides. Subsequent exposure to prolonged, high-voltage electrochemical cycling vs graphite electrodes revealed that the bilayer film can greatly enhance the high-voltage stability of cathode oxides. In particular, in manganese-rich cells, capacity fade due to manganese dissolution was substantially reduced and impedance rise was virtually eliminated. Furthermore, in nickel-rich NMC-811 cells, impedance rise was reduced by ∼80%, compared to the NMC-811 baseline, after ∼300 h of high-voltage exposure during cycling. The multilayer film strategy presents an exciting opportunity for tailoring designs and materials for electrochemical interfaces in advanced lithium-ion batteries and beyond. [ABSTRACT FROM AUTHOR]

Atomic layer deposition (ALD) is uniquely capable of providing uniform thin-film coatings on powder substrates, but powder processing has historically required an ALD reactor designed specifically for powders—e.g., a fluidized bed. Tubular hot-walled viscous-flow reactors commonly employed in laboratory-scale ALD research for coating planar substrates such as silicon have been employed previously to coat gram quantities of powder spread out in a thin layer on a tray, but larger quantities of powder introduce long diffusion pathways where reactants are unable to percolate to the bottom of the powder bed to provide uniform coating in reasonable time periods. In this work, we report a rotary drum with a capacity of 100s of grams that is compatible with conventional tubular hot-walled ALD reactors and provides uniform coatings on powders in viscous flow operation. We benchmark this system using Al2O3 ALD with trimethylaluminum and water. We examine the effect of rotation speed and powder quantity on saturation time via in situ quadrupole mass spectroscopy measurements and gravimetric analysis. The rotary drum we report is able to provide homogenous coating of up to 75 g of silica gel powder with a total surface area of ∼1500 m2 in viscous flow operation with precursor utilization as high as 70%. [ABSTRACT FROM AUTHOR]

Membranes are among the most promising means of delivering increased supplies of fit‐for‐purpose water, but membrane fouling remains a critical issue restricting their widespread application. Coupling photocatalysis with membrane separation has been proposed as a potentially effective approach to reduce membrane fouling. However, commonly used materials in photocatalysis limit use of low‐cost sources such as sunlight due to their large bandgaps. There are few examples of in situ photocatalytic self‐cleaning of membranes, with removal from the filtration system and ex situ illumination being more common. In this work, a visible‐light‐activated photocatalytic film prepared by nitrogen doping into the lattice of TiO2 is deposited on commercial ceramic membranes via atomic layer deposition. The synergy between membrane separation and redox reactions between organic pollutants and reactive oxygen species produced by the visible‐light‐activated layer offers a possibility for stable and sustainable membrane operation under in situ solar irradiation. [ABSTRACT FROM AUTHOR]

Thin hafnium oxide films were prepared by atomic layer deposition using a carbon-free precursor, tetrakis(tetrahydroborato)hafnium [Hf(BH4)4], and H2O. Film growth was studied using an in situ quartz crystal microbalance and Fourier transform infrared spectroscopy measurements. Self-limiting growth was observed between 100 and 175 °C, but the thermal decomposition of the Hf precursor occurred at higher temperatures. The film properties were investigated using x-ray photoelectron spectroscopy, x-ray reflectivity, x-ray diffraction, ellipsometry, time-of-flight secondary ion mass spectrometry, and x-ray absorption spectroscopy. The as-deposited films were found to consist of an amorphous mixture of HfO2 and B2O3, and had a lower density and lower refractive index compared to pure HfO2 thin films. Annealing the films to >750 °C yielded crystalline monoclinic HfO2 with a density of 9 g/cm3 and a refractive index of 2.10. [ABSTRACT FROM AUTHOR]

Improvements in energy–water systems will necessitate fabrication of high‐performance separation membranes. To this end, interface engineering is a powerful tool for tailoring properties, and atomic layer deposition (ALD) has recently emerged as a promising and versatile approach. However, most non‐polar polymeric membranes are not amenable to ALD processing due to the absence of nucleation sites. Here, a sensitization strategy for ALD‐coating is presented, illustrated by membrane interface hydrophilization. Facile dip‐coating with polyphenols effectively sensitizes hydrophobic polymer membranes to TiO2 ALD coating. Tannic acid‐sensitized ALD‐coated membranes exhibit outstanding underwater crude oil repulsion and rigorous mechanical stability through bending and rinsing tests. As a result, these membranes demonstrate outstanding crude oil‐in‐water separation and reusability compared to untreated membranes or those treated with ALD without polyphenol pretreatment. A possible polyphenol‐sensitized ALD mechanism is proposed involving initial island nucleation followed by film intergrowth. This polyphenol sensitization strategy enriches the functionalization toolbox in material science, interface engineering, and environmental science. [ABSTRACT FROM AUTHOR]

This study reports on the secondary electron emission (SEE) performance of atomic layer deposited MgO films, with thicknesses in the range from 5 to 25 nm, for the application in the Timed Photon Counter. In this novel, photodetector MgO is utilized as a material for the fabrication of ultrathin transmission dynodes (tynodes). Two different types of PECVD silicon oxide films are applied on top of MgO, in order to protect it against etching steps in the fabrication of tynodes and also as a prevention against aging. Applicability of these two materials as capping films is evaluated in terms of achieved secondary electron yield (SEY) of MgO after their removal. Emission of secondary electrons is known to depend on numerous physical and chemical properties of the material, such as surface roughness and chemical composition. On that account, morphological and structural properties of modified MgO are determined by atomic force microscope and x-ray photoelectron spectrometer and linked to the changes in SEE behavior. The authors demonstrate that the application of a suitable capping layer followed by its removal provides an SEY of 6.6, as opposed to the value of 4.8 recorded from the as-deposited MgO film. Furthermore, in a following experiment, they showed that annealing of MgO films at high temperatures (up to 1100 °C) significantly improved the secondary electron emission, elevating the SEY to 7.2. [ABSTRACT FROM AUTHOR]

Molybdenum sulfide films were grown by atomic layer deposition on silicon and fused silica substrates using molybdenum hexafluoride (MoF6) and hydrogen sulfide at 200 °C. In situ quartz crystal microbalance (QCM) measurements confirmed linear growth at 0.46Å /cycle and selflimiting chemistry for both precursors. Analysis of the QCM step shapes indicated that MoS2 is the reaction product and this finding is supported by x-ray photoelectron spectroscopy measurements showing that Mo is predominantly in the Mo(IV) state. However, Raman spectroscopy and x-ray diffraction measurements failed to identify crystalline MoS2 in the as-deposited films and this might result from unreacted MoFx residues in the films. Annealing the films at 350 °C in a hydrogen rich environment yielded crystalline MoS2 and reduced the F concentration in the films. Optical transmission measurements yielded a bandgap of 1.3 eV. Finally, the authors observed that the MoS2 growth per cycle was accelerated when a fraction of the 6 pulses were substituted with diethyl zinc. [ABSTRACT FROM AUTHOR]

Selectivity is a critical attribute of catalysts used in manufacturing of essential and fine chemicals. An excellent way to induce selectivity in catalysts is by using ultrathin films with tailored nanoporosity. For instance, nanopores can be created in atomic layer deposition (ALD) ultrathin over-coatings on supported metal nanoparticles by subjecting the coatings to high temperature annealing. These nanopores expose the active surface of the underlying metal nanoparticles. The dimensions of these nanopores can be tuned to impart shape selectivity: only reactants or products with a specific size or shape can fit inside the pore. In this work, the authors explore the underlying mechanism driving nanopore formation in ALD films. Ultrathin films of ALD TiO2 (∼2.5 nm thick) and ALD Al2O3 (∼4.9 nm thick) were deposited on nonporous γ-Al2O3 nanoparticles. The pore formation and evolution were monitored in situ during thermal annealing using small-angle x-ray scattering (SAXS) and the crystallinity was monitored by in situ x-ray diffraction. A correlation between the nanopore formation and amorphous to crystalline phase transitions in the ALD layers was observed. The authors hypothesize that the pores form through the relaxation of stress induced by densification of the ALD films during the phase transitions. The authors developed a mathematical model to evaluate this hypothesis and found remarkable agreement between the model and the SAXS measurements. [ABSTRACT FROM AUTHOR]

New complexes MoO2(tBuAMD)2 (1) and WO2(tBuAMD)2 (2) (AMD = acetamidinato) are synthesized and fully characterized as precursors for atomic layer deposition (ALD). They contain metal-oxo functionalities not previously utilized in ALD-type growth processes and are fully characterized by 1H and 13C NMR, X-ray diffraction (XRD), Fourier transform infrared, thermogravimetric analysis, single-crystal XRD, and elemental analysis. Guided by quartz-crystal microbalance studies, ALD growth methodologies for both complexes have been developed. Remarkably, these isostructural compounds exhibit dramatic differences in ALD properties. Using 1 and O3, amorphous, ultrathin molybdenum oxynitride (MoON) films are grown on Si(100) wafers. Using 2 and H2O yields amorphous WO3 films on Si(100) wafers that crystallize as WO3 nanowires upon annealing. Although 1/H2O and 2/O3 growth was attempted, effective ALD growth could only be obtained with 1/O3 and 2/H2O, underscoring reactivity differences in these precursors. Film thicknesses, compositions, and optical and electrical parameters are characterized by variable angle spectroscopic ellipsometry, X-ray reflectivity, grazing incidence X-ray diffraction, X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and atomic force microscopy techniques. The hitherto unknown ALD chemistry of group VI metal-oxo compounds lays a foundation for their use in the ALD synthesis of heterogeneous catalysts. [ABSTRACT FROM AUTHOR]

Ultrathin and conformal boron-containing atomic layer deposition (ALD) films could be used as a shallow dopant source for advanced transistor structures in microelectronics manufacturing. With this application in mind, diboron tetrafluoride (B2F4) was explored as an ALD precursor for the deposition of boron containing films. Density functional theory simulations for nucleation on silicon (100) surfaces indicated better reactivity of B2F4 in comparison to BF3. Quartz crystal microbalance experiments exhibited growth using either B2F4-H2O for B2O3 ALD, or B2F4-disilane (Si2H6) for B ALD, but in both cases, the initial growth per cycle was quite low (⩽0.2A ° /cycle) and decreased to near zero growth after 8-30 ALD cycles. However, alternating between B2F4-H2O and trimethyl aluminum (TMA)-H2O ALD cycles resulted in sustained growth at ~0.65A ° /cycle, suggesting that the dense -OH surface termination produced by the TMA-H2O combination enhances the uptake of B2F4 precursor. The resultant boron containing films were analyzed for composition by x-ray photoelectron spectroscopy, and capacitance measurements indicated an insulating characteristic. Finally, diffused boron profiles less than 100A ° were obtained after rapid thermal anneal of the boron containing ALD film. [ABSTRACT FROM AUTHOR]

The technique of atomic layer deposition (ALD) has enabled the development of alternative glass microchannel plates (MCPs) with independently tunable resistive and emissive layers, resulting in excellent thickness uniformity across the large area (20×20 cm), high aspect ratio (60:1 L/d) glass substrates. Furthermore, the use of ALD to deposit functional layers allows the optimal substrate material to be selected, such as borosilicate glass, which has many benefits compared to the lead-oxide glass used in conventional MCPs, including increased stability and lifetime, low background noise, mechanical robustness, and larger area (at present up to 400 cm2). Resistively stable, high gain MCPs are demonstrated due to the deposition of uniform ALD resistive and emissive layers on alternative glass microcapillary substrates. The MCP performance characteristics reported include increased stability and lifetime, low background noise (0.04 events cm-2 s-1), and low gain variation (±5%). [ABSTRACT FROM AUTHOR]

We have synthesized a material consisting of conducting metal oxide (MoO3-x) nanoclusters embedded in a high-dielectric-strength insulator (Al2O3) matrix. The resistivity of this material can be customized by varying the concentration of the MoO3-x nanoclusters. The Al2O3 protects the MoO3-x from stoichiometry change, thus conserving the number of carriers and maintaining a high dielectric strength. This composite material is grown by atomic layer deposition, a thin film deposition technique suitable for coating 3D structures. We applied these atomic layer deposition composite films to our 3D electron-optical micro electrical mechanical systems devices and greatly improved their performance. [ABSTRACT FROM AUTHOR]

Nanocomposite tungsten-aluminum oxide (W:Al2O3) thin films were prepared by atomic layer deposition (ALD) using tungsten hexafluoride (WF6) and disilane (Si2H6) for the W ALD and trimethyl aluminum (TMA) and H2O for the Al2O3 ALD. Quartz crystal microbalance (QCM) measurements performed using various W cycle percentages revealed that the W ALD inhibits the Al2O3 ALD and vice versa. Despite this inhibition, the relationship between W content and W cycle percentage was close to that predicted by theoretical calculations based on the growth per cycle values of binary compounds. Depth profiling XPS showed that the (W:Al2O3) films were uniform in composition and contained Al, O, and metallic W as expected, but also included significant F and C. Cross-sectional TEM revealed the composite film structure to be metallic nanoparticles (∼1 nm) embedded in an amorphous matrix. The resistivity of these composite films could be tuned in the range of 1012-108 Ω cm by adjusting the W cycle percentage between 10% and 30%W. These films have applications in electron multipliers as well as electron and ion optics. [ABSTRACT FROM AUTHOR]

Abstract: The ongoing development of Atomic Layer Deposition (ALD) enables the use of relatively inexpensive and robust borosilicate micro-channel substrates for use as Micro-Channel Plates (MCPs). The surfaces of the channels in these glass plates are functionalized to control the conductivity as well as the Secondary Electron Yield (SEY). The extensive SEY data found in literature show significant variation for a given material depending on the apparatus, the measurement procedure, and the sample preparation and handling. We present systematic studies on the effects of film thickness and surface chemical composition on SEY. We have modified an existing ultra-high vacuum apparatus containing X-ray and Ultraviolet Photoelectron Spectrometers (XPS and UPS, respectively) by adding a modified Low Energy Electron Diffraction (LEED) module for SEY measurements. With these tools, we have characterized the secondary electron emissive properties for MgO, Al2O3, and multilayered MgO/TiO2 structures to serve as electron emissive layers in the channels of the MCPs. [Copyright &y& Elsevier]

Abstract: We demonstrate an economical and robust route to fabricate large-area microchannel plate (MCP) detectors which will open new opportunities in larger area MCP-based detector technologies. Using our newly developed bottom-up process flow, we have fabricated large area MCPs (8 x 8). We used Atomic Layer Deposition (ALD), a powerful and precise thin film deposition technique, to tailor the electrical resistance and secondary electron emission (SEE) properties of large area, low cost, borosilicate glass capillary arrays. The self limiting growth mechanism in ALD allows atomic level control over the thickness and composition of resistive and secondary electron emission (SEE) layers that can be deposited conformally on high aspect ratio capillary glass arrays. We have developed several robust and reliable ALD processes for the resistive coatings and SEE layers to give us precise control over the resistance in the target range for MCPs (106-109 Ω) and SEE coefficient (up to 8). The MCPs are tested in stacks of one or two plates and exhibit gains as high as 107 for a pair of MCPs. This approach allows the functionalization of microporous, insulating substrates to produce MCPs with high gain and low noise. These capabilities allow separation of the substrate material properties from the amplification properties. We studied the various MCP parameters such as gain, background counts, and resistance as a function of the ALD process parameters. Here we describe a complete process flow to produce fully functionalized working large area MCPs. [Copyright &y& Elsevier]

Abstract: We report an approach for preparing refractory nanoporous materials using high surface area silica aerogels as templates for the growth of conformal tungsten (W) coatings by atomic layer deposition (ALD). Nanoporous silica aerogel monoliths were prepared with a variety of initial pore sizes and initial densities in the range of 0.3–0.5g/cc using porogen extraction methods. Next, W ALD using Si2H6 and WF6 reactants at 200°C was employed to coat the inner surfaces of the silica aerogels. After coating, scanning electron microscopy revealed a microstructure in which the ALD W completely encapsulated the silica aerogel micro-cells. The porosity of the aerogels was preserved during the first 10 W ALD cycles allowing the density to be controlled by adjusting the number of W ALD cycles to achieve densities as high as 5g/cc. Nitrogen adsorption surface area measurements revealed a gradual decrease in the surface area of the silica aerogels with increasing numbers of W ALD cycles, consistent with a partial filling of the aerogel voids. The high density nanoporous tungsten monoliths survived high temperature vacuum heating (1500°C) making them promising candidates for solid rare-isotope catchers that can be used in the production of short-lived radioactive isotope beams in facilities such as the facility for rare isotope beams (FRIB). [Copyright &y& Elsevier]

Abstract: In an organic photovoltaic (OPV) cell, the buffer layers connecting the active photovoltaic material to the electrodes strongly influence the overall energy conversion efficiency. In this work, we demonstrate that a thin layer (<4nm) of MoO3 formed by atomic layer deposition (ALD) of Mo, followed by oxidation in ozone, performs well as an anode buffer layer in organic photovoltaic cells based on a blend of poly(3-hexylthiophene) and phenyl-C61-butyric acid methyl ester. Compared to the commonly used buffer layer poly(ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), the MoO3 layer causes virtually no degradation in the transmission spectrum. The improvement in optical transmission leads to higher short-circuit current density, and practically the same power conversion efficiency as OPV cells employing PEDOT:PSS. Results from a substantial number of devices indicate that the improvement is statistically significant, demonstrating the reproducibility and reliability of the layer. Moreover, because of the conformal nature of ALD, this approach can be extended to nanostructured systems. [Copyright &y& Elsevier]

A lithium–sulfur (Li–S) battery is one of the post‐lithium‐ion battery chemistry candidates due to the high theoretical capacity of the sulfur cathode (1672 mAh g−1). However, low electronic conductivity of sulfur and severe capacity fading during the charge–discharge process limit the commercial realization of Li–S batteries. The origin of capacity fading is mainly due to the polysulfide shuttling effect, resulting from the dissolution of sulfur in the electrolyte solution. Herein, atomic layer deposition (ALD) (6–8 Å thickness) of alumina is presented as a strategy to suppress capacity degradation on the 2D graphene–sulfur hybrid electrode. Low‐temperature ALD prevents sulfur sublimation from the composite electrode. Despite the insulating property of alumina, atomic layer coating maintains good electrical conductivity, thereby yielding lower charge transfer resistance. Alumina‐coated graphene–sulfur hybrid electrodes (AGS) exhibit a high specific capacity of 960 mAh g−1 at a current density of 50 mA g−1 and retain 519 mAh g−1 after 100 galvanostatic cycles. Superior electrochemical performance is credited to the combination of the high electronic conductivity of multilayered graphene platelets and low charge transfer resistance, resulting from effective polysulfide blocking by the atomic scale Al2O3 coating. [ABSTRACT FROM AUTHOR]

[Display omitted] Atomic layer deposition (ALD) offers unique capabilities to fabricate atomically engineered porous materials with precise pore tuning and multi-functionalization for diverse applications like advanced membrane separations towards sustainable energy-water systems. However, current ALD technique is inhibited on most non-polar polymeric membranes due to lack of accessible nucleation sites. Here, we report a facile method to efficiently promote ALD coating on hydrophobic surface of polymeric membranes via novel protein activation/sensitization. As a proof of concept, TiO 2 ALD-coated membranes activated by bovine serum albumin exhibit remarkable superhydrophilicity, ultralow underwater crude oil adhesion, and robust tolerance to rigorous environments including acid, alkali, saline, and ethanol. Most importantly, excellent cyclable crude oil-in-water emulsion separation performance can be achieved. The mechanism for activation/sensitization is rooted in reactivity for a particular set of amino acids. Furthermore, the universality of protein-sensitized ALD is demonstrated using common egg white, promising numerous potential usages in biomedical engineering, environmental remediation, low-carbon manufacturing, catalysis, and beyond. [ABSTRACT FROM AUTHOR]

[Display omitted] • Donghyeon Kang, Robert E. Warburton, Anil U. Mane, Jeffrey Greeley, Jeffrey W. Elam. • We examined ALD Al 2 O 3 coating growth on LiMn 2 O 4 surfaces using five different precursors. • Density functional theory identified precursor acidity as a key indicator of decomposition mechanisms. • Precursors with greater Lewis acidity increased concentration of surface Mn3+ ions. • Optimal ALD alumina coatings are significantly thinner than previously reported. In this combined theoretical and experimental study, we report the effects of Al precursor selection on the growth chemistry, interfacial structure, and electrochemistry of Al 2 O 3 coatings on spinel LiMn 2 O 4 (LMO) surfaces by atomic layer deposition (ALD). Five Al precursors, exhibiting a range of Lewis acid–base properties, were used to establish trends in the ALD Al 2 O 3 growth chemistry on LMO powders in comparison to redox-inactive planar silicon substrates. We show that the Lewis acid–base properties of the Al precursor ligands can be used to tune both the Mn oxidation states and the Al 2 O 3 coverage on the LMO surface. Density functional theory calculations are used to examine the reaction mechanism of each precursor on LMO surfaces, elucidating a correlation between the Lewis acidity of the ligands and the decomposition thermochemistry. In-depth X-ray photoelectron spectroscopy and in situ Fourier transform infrared spectroscopy measurements support these theoretical predictions and further reveal how different Al precursors modify the atomic and electronic structure near the LMO surface during ALD. While the Mn oxidation state is strongly influenced by the Lewis acidity of the precursor ligand, the surface coverage and thickness of the Al 2 O 3 coating are a more representative descriptor of the electrochemical performance measured in coin cell experiments. We show how the ligand acid–base properties of ALD precursors can be used to rationally tailor atomic layer growth mechanisms, which may enable atomic level control over the structure of functionalized interfaces for various applications related to catalysis, semiconductors, and energy storage. [ABSTRACT FROM AUTHOR]

We present a progress update on plans to establish pilot production and commercialization of Large Area (400 cm 2 ) Picosecond Photodetector (LAPPD ™ ). Steps being taken to commercialize this MCP and LAPPD ™ technology and begin tile pilot production are presented including (1) the manufacture of 203 mm×203 mm borosilicate glass capillary arrays (GCAs), (2) optimization of MCP performance and creation of an ALD coating facility to manufacture MCPs and (3) design, construction and commissioning of UHV tile integration and sealing facility to produce LAPPDs. Taken together these plans provide a “pathway toward commercialization”. [ABSTRACT FROM AUTHOR]

We describe a pin-less design for the high voltage (HV) resistive divider of the all-glass LAPPD TM 8 in.-square thin photodetector module. The divider, which distributes high voltage applied to the photocathode to the two micro-channel plates (MCPs) that constitute the amplification stage, is comprised of the two MCPs and three glass mechanical spacers, each of which is coated with a resistive layer using atomic layer deposition (ALD). The three glass grid spacers and the two MCPs form a continuous resistive path between cathode and anode, with the voltages across the MCPs and the spacers determined by the resistance of each. High voltage is applied on an external tab on the top glass window that connects to the photocathode through the metal seal. The DC ground is supplied by microstrips on the bottom glass plate that form the high-bandwidth anode. The microstrips exit the package through the glass-frit seal of the anode base-plate and the package sidewall. The divider is thus completely internal, with no HV pins penetrating the low-profile flat glass package. Measurements of the performance of the divider are presented for the 8 in.-square MCP and spacer package in a custom test fixture and for an assembled externally pumped LAPPD TM prototype with an aluminum photocathode. [ABSTRACT FROM AUTHOR]

Atomic layer deposition (ALD) was employed to synthesizesupportedPt–Pd bimetallic particles in the 1 to 2 nm range. The metalloading and composition of the supported Pt–Pd nanoparticleswere controlled by varying the deposition temperature and by applyingALD metal oxide coatings to modify the support surface chemistry.High-resolution scanning transmission electron microscopy images showedmonodispersed Pt–Pd nanoparticles on ALD Al2O3- and TiO2-modified SiO2gel. X-rayabsorption spectroscopy revealed that the bimetallic nanoparticleshave a stable Pt-core, Pd-shell nanostructure. Density functionaltheory calculations revealed that the most stable surface configurationfor the Pt–Pd alloys in an H2environment has aPt-core, Pd-shell nanostructure. In comparison to their monometalliccounterparts, the small Pt–Pd bimetallic core–shellnanoparticles exhibited higher activity in propane oxidative dehydrogenationas compared to their physical mixture. [ABSTRACT FROM AUTHOR]

[Display omitted] • Vapor phase grafting is effective for synthesizing selective absorbing materials. • We studied the vapor phase grafting of (3-aminopropyl)triethoxysilane. • We use ALD metal oxide layers as well-defined starting surfaces. • Grafting is monitored in situ by quartz microbalance and infrared spectroscopy. • The underlying metal oxide layer strongly affects the grafting process. Atomic layer deposition (ALD) is a highly versatile surface functionalization technique that can conformally coat both planar and porous substrates. Here we use ALD metal oxide layers to establish a well-defined starting surface for vapor-phase surface organic modification. Vapor-phase (3-aminopropyl)triethoxysilane (APTES) surface silanization of ALD Al 2 O 3 , ZnO and TiO 2 surfaces were studied at 100 °C, 150 °C and 200 °C. In situ quartz crystal microbalance (QCM) and Fourier-transform infrared (FTIR) spectroscopy measurements, and ex situ atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) measurements showed uniform monolayer silane formation through self-limiting APTES reaction. We observed a higher surface density of grafted APTES species following silanization at 100 °C compared to 200 °C, and we attribute this to the temperature-dependent reactivity of the surface hydroxyls and changes in the mode of APTES reaction. The FTIR and XPS measurements revealed that APTES reacts with Al 2 O 3 and ZnO exclusively through metal siloxy bond formation. However, APTES reacts with TiO 2 through both siloxy bond formation and ammonium salt formation via the amine group. [ABSTRACT FROM AUTHOR]