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Molybdenum disulfide (MoS2) is a popular lamellar material with desirable properties who's form, and function can vary widely, from particles to monolayer/μm thick films and applications in semiconductors to aerospace lubricants and many more. Physical vapor deposition (PVD) is commonly used to produce dense, conformal micron thick MoS2 coatings, but lacks the ability to coat more complex geometries due to line-of-sight constraints and typically exhibit amorphous or nanocrystalline microstructures. Atomic layer deposition (ALD) has also been employed to deposit monolayer to 10's of nanometers thick lamellar solids like MoS2 & WS2 in transistor, sensors or electrocatalyst applications but not commonly for applications as solid lubricants in aerospace like their PVD counterparts. While recent work has shown that ALD MoS2 can exhibit favorable microstructures for solid lubricant applications and allows for non-line of sight deposition on complex geometries, it has not been widely adopted due to high deposition temperatures (>500 °C) that can lead to softening of steel substrates. In this work, we show one of the first applications highlighting the use of ultra-thin (5–10 nm) low temperature (∼250 °C) MoS2 coatings as a promising solid lubricant for macroscale mechanical interfaces. Post-deposition chemical conversion of ALD MoOx to MoS2 by annealing in H2S at temperatures ranging from 200 to 550 °C resulted in highly-ordered basally-oriented surface microstructures. The results from this work suggest that converted-ALD MoS2 coatings can serve as viable solid lubricants for aerospace applications requiring low-temperature processing, including those with complex geometries.

To overcome electronic transport issues of layered titanates in sodium-ion batteries, we have designed and synthesized composites of lepidocrocite titanates with reduced graphene oxide through a solution-based self-assembly approach. The parent lepidocrocite titanate (K0.8[Ti1.73Li0.27]O4) was exfoliated by a soft-chemical approach and mechanical shaking. Exfoliated layered titania sheets (LTO) were then combined with reduced graphene oxide (rGO) layers to assemble into composites through flocculation. Countercations (i.e., Mg2+) were used for the self-assembly of negatively charged titania and rGO nanosheets via flocculation. The carbon content in the composites was tuned from 1 to 17% by changing the ratio of titania and rGO sheets in the mixed colloidal suspensions. Electrodes were processed with as-prepared LTO-rGO composites without any carbon additives and tested in sodium half-cell configurations. Mg+-coagulated LTO-rGO composite electrodes deliver higher capacities than electrodes prepared with coagulated titania sheets and 10% acetylene black in sodium half-cells and display good capacity retention after 50 cycles. Electrochemical impedance spectroscopy results indicate lower charge transfer resistance for LTO-14.5%rGO composites than that of coagulated titania sheets with 10% acetylene black. A power law analysis of cells containing the composites indicate a hybrid mechanism consisting of both surface and diffusional processes. A comparison with a similar system, that of dopamine-derived LTO-C heterostructures, reveal significant differences. While capacities showed a strong dependence on carbon content for the dopamine-derived materials, this was not true for the LTO-rGO composites. Instead, the highest capacity was obtained for the 14.5% rGO sample, with a lower value obtained for the 17% rGO sample. A greater proportion of the redox processes were surface rather than diffusional in nature for the LTO-rGO composites as well.

Lepidocrocite-type titanates that reversibly intercalate sodium ions at low potentials (∼0.6 V vs Na/Na+) are promising anode candidates for sodium-ion batteries. However, large amounts of carbon additives are often used to improve their electrical conductivity and overcome poor cycling performance in the electrode composites. To ameliorate electronic transport issues of lepidocrocite titanate (K0.8Ti1.73Li0.27O4, KTL) in sodium-ion batteries, we have designed and synthesized heterostructures of exfoliated lepidocrocite-type titanium oxide (LTO) nanosheets with alternating carbon layers via a solution-based self-assembly approach. Positively charged dopamine (Dopa) was used as the carbon precursor and intercalated between negatively charged exfoliated titania nanosheets through electrostatic interaction. Dopa-intercalated LTO was then annealed under argon to form conductive carbon layers between titania sheets. The carbon content in the heterostructures was controlled by modifying the self-assembly conditions (i.e., pH, stirring duration, and Dopa-to-LTO ratio). Electrodes were prepared using carbonized heterostructures (LTO-C) without adding more carbon to the composites and tested in sodium half-cell configurations. Higher capacities and improved capacity retention over 250 cycles and lower impedance were observed, as the carbon content of LTO-C heterostructures was increased from 0% (LTO nanosheets) to 30%. These results indicate that the self-assembly approach for 2D heterostructured electrode materials is a promising strategy to overcome electronic transport limitations of layered transition-metal oxides and improve their electrochemical performance for next-generation energy storage applications.

Metal carbonyls are of great importance in chemical vapor deposition (CVD), composite materials fabrication, and other near-net shape technologies. Carbonyl CVD is used for deposition of high-purity metallic and alloy coatings for which vapor pressure data is essential. In this study, we report vapor pressures of solid Ir4(CO)12 and Re2(CO)10 carbonyls measured by using the Knudsen Cell methodology using a torsion effusion thermogravimetric system. The vapor pressure of the Ir4(CO)12 exhibited incongruent vaporization, as the molecular weight (MW) of the effusing species was determined as 128 g/mol as compared to the theoretical MW of 1105 g/mol. It is proposed that the Ir4(CO)12 (s) partially decomposed (∼66%) to Ir4(CO)12(g), Ir(s), and CO(g). The Re2(CO)10 on the other hand, showed congruent behavior with Re2(CO)10(s) vaporizing to Re2(CO)10(g) in the measured temperature range. The raw data for vapor pressures was measured using two sets of Knudsen cells with different orifice sizes, and the equilibrium vapor pressures were calculated using Whitman-Motzfeldt methodology. The equilibrium vapor pressures of these carbonyls, partial pressures of gaseous species in case of decomposition, average molecular weights of the effusing gasses were determined. The vapor pressures and Gibbs energies of vaporization reactions of the two above mentioned carbonyls, as well as comparison of vaporization thermodynamics these two carbonyls with other carbonyls from Group VIB to VIIIB are presented in this paper.

Surface plasmons have found a wide range of applications in plasmonic and nanophotonic devices. The combination of plasmonics with three-dimensional photonic crystals has enormous potential for the efficient localization of light in high surface area photoelectrodes. However, the metals traditionally used for plasmonics are difficult to form into three-dimensional periodic structures and have limited optical penetration depth at operational frequencies, which limits their use in nanofabricated photonic crystal devices. The recent decade has seen an expansion of the plasmonic material portfolio into conducting ceramics, driven by their potential for improved stability, and their conformal growth via atomic layer deposition has been established. In this work, we have created three-dimensional photonic crystals with an ultrathin plasmonic titanium nitride coating that preserves photonic activity. Plasmonic titanium nitride enhances optical fields within the photonic electrode while maintaining sufficient light penetration. Additionally, we show that post-growth annealing can tune the plasmonic resonance of titanium nitride to overlap with the photonic resonance, potentially enabling coupled-phenomena applications for these three-dimensional nanophotonic systems. Through characterization of the tuning knobs of bead size, deposition temperature and cycle count, and annealing conditions, we can create an electrically- and plasmonically-active photonic crystal as-desired for a particular application of choice.

Transition metal dichalcogenides (TMDs) promise to revolutionize optoelectronic applications. While monolayer exfoliation and vapor phase growth produce extremely high quality 2D materials, direct fabrication at wafer scale remains a significant challenge. Here, we present a method that we call ‘lateral conversion’, which enables the synthesis of patterned TMD structures, with control over the thickness down to a few layers, at lithographically predefined locations. In this method, chemical conversion of a metal-oxide film to TMD layers proceeds by diffusion of precursor propagating laterally between silica layers, resulting in structures where delicate chalcogenide films are protected from contamination or oxidation. Lithographically patterned WS2 structures were synthesized by lateral conversion and analyzed in detail by hyperspectral Raman imaging, scanning electron microscopy and transmission electron microscopy. The rate of conversion was investigated as a function of time, temperature, and thickness of the converted film. In addition, the process was extended to grow patterned MoS2, WSe2, MoSe2 structures, and to demonstrate unique WS2/SiO2 multilayer structures. We believe this method will be applicable to a variety of additional chalcogenide materials, and enable their incorporation into novel architectures and devices.

As one of the highest mobility semiconductor materials, carbon nanotubes (CNTs) have been extensively studied for use in field effect transistors (FETs). To fabricate surround-gate FETs- which offer the best switching performance-deposition of conformal, weakly-interacting dielectric layers is necessary. This is challenging due to the chemically inert surface of CNTs and a lack of nucleation sites-especially for defect-free CNTs. As a result, a technique that enables integration of uniform high-k dielectrics, while preserving the CNT's exceptional properties is required. In this work, we show a method that enables conformal atomic layer deposition (ALD) of high-k dielectrics on defect-free CNTs. By depositing a thin Ti metal film, followed by oxidation to TiO2 under ambient conditions, a nucleation layer is formed for subsequent ALD deposition of Al2O3. The technique is easy to implement and is VLSI-compatible. We show that the ALD coatings are uniform, continuous and conformal, and Raman spectroscopy reveals that the technique does not induce defects in the CNT. The resulting bilayer TiO2/Al2O3 thin-film shows an improved dielectric constant of 21.7 and an equivalent oxide thickness of 2.7 nm. The electrical properties of back-gated and top-gated devices fabricated using this method are presented.

Two-dimensional materials with engineered composition and structure will provide designer materials beyond conventional semiconductors. However, the potentials of defect engineering remain largely untapped, because it hinges on a precise understanding of electronic structure and excitonic properties, which are not yet predictable by theory alone. Here, we utilize correlative, nanoscale photoemission spectroscopy to visualize how local introduction of defects modifies electronic and excitonic properties of two-dimensional materials at the nanoscale. As a model system, we study chemical vapor deposition grown monolayer WS2, a prototypical, direct gap, two-dimensional semiconductor. By cross-correlating nanoscale angle-resolved photoemission spectroscopy, core level spectroscopy, and photoluminescence, we unravel how local variations in defect density influence electronic structure, lateral band alignment, and excitonic phenomena in synthetic WS2 monolayers.

Materials for nanophotonic devices ideally combine ease of deposition, very high refractive index, and facile pattern formation through lithographic templating and/or etching. In this work, we present a scalable method for producing high refractive index WS2 layers by chemical conversion of WO3 synthesized via atomic layer deposition (ALD). These conformal nanocrystalline thin films demonstrate a surprisingly high index of refraction (n > 3.9), and structural fidelity compatible with lithographically defined features down to ~10 nm. Although this process yields highly polycrystalline films, the optical constants are in agreement with those reported for single crystal bulk WS2. Subsequently, we demonstrate three photonic structures - first, a two-dimensional hole array made possible by patterning and etching an ALD WO3 thin film before conversion, second, an analogue of the 2D hole array first patterned into fused silica before conformal coating and conversion, and third, a three-dimensional inverse opal photonic crystal made by conformal coating of a self-assembled polystyrene bead template. These results can be trivially extended to other transition metal dichalcogenides, thus opening new opportunities for photonic devices based on high refractive index materials.

In this work, we demonstrate thatcatalyst composition can be usedto direct the crystallographic growth axis of GaN nanowires. By adjustingthe ratio of gold to nickel in a bimetallic catalyst, we achievedselective growth of dense, uniform nanowire arrays along two nonpolardirections. A gold-rich catalyst resulted in single-crystalline nanowiregrowth along the ⟨11̅00⟩ or maxis, whereas a nickel-rich catalyst resulted in nanowire growthalong the ⟨112̅0⟩ or aaxis.The same growth control was demonstrated on two different epitaxialsubstrates. Using proper conditions, many of the nanowires were observedto switch direction midgrowth, resulting in monolithic single-crystalstructures with segments of two distinct orientations. Cathodoluminescencespectra revealed significant differences in the optical propertiesof these nanowire segments, which we attribute to the electronic structuresof their semipolar {112̅2} or {11̅01} sidewalls. [ABSTRACT FROM AUTHOR]

We synthesized Fe3O4nanoparticle/reduced graphene oxide (RGO-Fe3O4) nanocomposites and evaluated their performance as anodes in both half and full coin cells. The nanocomposites were synthesized through a chemical co-precipitation of Fe2橷 Fe3 the presence of graphene oxides within an alkaline solution and a subsequent high-temperature reduction reaction in argon (Ar) environment. The morphology and microstructures of the fabricated RGO-Fe3O4nanocomposites were characterized using various techniques. The results indicated that the Fe3O4nanoparticles had relatively homogeneous dispersions on the RGO sheet surfaces. These as-synthesized RGO-Fe3O4nanocomposites were used as anodes for both half and full lithium-ion cells. Electrochemical measurement results exhibit a high reversible capacity which is about two and a half times higher than that of graphite-based anodes at a 0.05C rate, and an enhanced reversible capacity of about 200 mAh g−1even at a high charge/discharge rate of 10C (9260 mA g−1) in half cells. Most important of all, these fabricated novel nanostructures also show exceptional capacity retention with the assembled RGO-Fe3O4/LiNi1/3Mn1/3Co1/3O2full cell at different C rates. This outstanding electrochemical behavior can be attributed to the unique microstructure, morphology, texture, surface properties of the nanocomposites, and combinative effects from the different chemical composition in the nanocomposites. [ABSTRACT FROM AUTHOR]

Two-dimensional materials with engineered composition and structure will provide designer materials beyond conventional semiconductors. However, the potentials of defect engineering remain largely untapped, because it hinges on a precise understanding of electronic structure and excitonic properties, which are not yet predictable by theory alone. Here, we utilize correlative, nanoscale photoemission spectroscopy to visualize how local introduction of defects modifies electronic and excitonic properties of two-dimensional materials at the nanoscale. As a model system, we study chemical vapor deposition grown monolayer WS 2 , a prototypical, direct gap, two-dimensional semiconductor. By cross-correlating nanoscale angle-resolved photoemission spectroscopy, core level spectroscopy, and photoluminescence, we unravel how local variations in defect density influence electronic structure, lateral band alignment, and excitonic phenomena in synthetic WS 2 monolayers.

Dense and aligned TiO2 nanorod arrays are fabricated using oblique-angle deposition on indium tin oxide (ITO) conducting substrates. The TiO2 nanorods are measured to be 800-1100 nm in length and 45-400 nm in width with an anatase crystal phase. Coverage of the ITO is extremely high with 25 x 10(6) mm(-2) of the TiO2 nanorods. The first use of these dense TiO2 nanorod arrays as working electrodes in photoelectrochemical (PEC) cells used for the generation of hydrogen by water splitting is demonstrated. A number of experimental techniques including UV/Vis absorption spectroscopy, X-ray diffraction, high-resolution scanning electron microscopy, energy-dispersive X-ray spectroscopy, and photoelectrochemistry are used to characterize their structural, optical, and electronic properties. Both UV/Vis and incident-photon-to-current-efficiency measurements show their photoresponse in the visible is limited but with a marked increase around approximately 400 nm. Mott-Schottky measurements give a flat-band potential (V(FB)) of +0.20 V, a carrier density of 4.5 x 10(17) cm(-3), and a space-charge layer of 99 nm. Overall water splitting is observed with an applied overpotential at 1.0 V (versus Ag/AgCl) with a photo-to-hydrogen efficiency of 0.1%. The results suggest that these dense and aligned one-dimensional TiO2 nanostructures are promising for hydrogen generation from water splitting based on PEC cells.