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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]

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]

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]

Atomic layer deposition (ALD) of the well-known Al 2 O 3 on a LiCoO 2 system is compared with that of a newly developed AlW x F y material. ALD coatings (∼1 nm thick) of both materials are shown to be effective in improving cycle life through mitigation of surface-induced capacity losses. However, the behaviors of Al 2 O 3 and AlW x F y are shown to be significantly different when coated directly on cathode particles versus deposition on a composite electrode composed of active materials, carbons, and binders. Electrochemical impedance spectroscopy, galvanostatic intermittent titration techniques, and four-point measurements suggest that electron transport is more limited in LiCoO 2 particles coated with Al 2 O 3 compared with that in particles coated with AlW x F y . The results show that proper design/choice of coating materials (e.g., AlW x F y ) can improve capacity retention without sacrificing electron transport and suggest new avenues for engineering electrode-electrolyte interfaces to enable high-voltage operation of lithium-ion batteries., Competing Interests: The authors declare no competing financial interest.