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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.

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.

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.

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.

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.