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Two-dimensional (2D) crystals have renewed opportunities in design and assembly of artificial lattices without the constraints of epitaxy. However, the lack of thickness control in exfoliated van der Waals (vdW) layers prevents realization of repeat units with high fidelity. Recent availability of uniform, wafer-scale samples permits engineering of both electronic and optical dispersions in stacks of disparate 2D layers with multiple repeating units. Here we present optical dispersion engineering in a superlattice structure comprising alternating layers of 2D excitonic chalcogenides and dielectric insulators. By carefully designing the unit cell parameters, we demonstrate greater than 90% narrow band absorption in less than 4 nm of active layer excitonic absorber medium at room temperature, concurrently with enhanced photoluminescence in square-centimetre samples. These superlattices show evidence of strong light–matter coupling and exciton–polariton formation with geometry-tuneable coupling constants. Our results demonstrate proof of concept structures with engineered optical properties and pave the way for a broad class of scalable, designer optical metamaterials from atomically thin layers. Square-centimetre scale, multilayer superlattice structures based on atomically thin two-dimensional chalcogenide monolayers enable the realization of excitonic metamaterials.

X-ray and ultraviolet photoelectron spectroscopy are performed on transition metal dichalcogenides (TMDs) MoS2, MoSe2, and MoTe2 monolayers on Au surfaces, to identify charge transfer processes and...

Tungsten disulfide (WS2) films were grown on c-plane sapphire in a cold-wall gas-source chemical vapor deposition system to ascertain the effect of the chalcogen precursor on the film growth and properties. Tungsten hexacarbonyl (W(CO)6) was used as the tungsten source, and hydrogen sulfide (H2S) and diethyl sulfide (DES-(C2H5)2S) were the chalcogen sources. The film deposition was studied at different temperatures and chalcogen-to-metal ratios to understand the effect of each chalcogen precursor on the film growth rate, thickness, coverage, photoluminescence, and stoichiometry. Larger lateral growth was observed in films grown with H2S than DES. The reduced lateral growth with DES can be attributed to carbon contamination, which also quenches the photoluminescence. Thermodynamic calculations agreed well with the experimental observations, suggesting formation of WS2 with both sulfur precursors and additional formation of carbon when deposition is done using DES.

The effect of substrate (c-plane sapphire versus epitaxial graphene/6H-SiC) on the CVD growth and properties of thin 3R NbS2 films was investigated using niobium (v) pentachloride (NbCl5) and hydrogen disulfide (H2S) as precursors in a hydrogen carrier gas. The growth temperature ranged from 400 °C to 800 °C and the sulfur to niobium ratio (S/Nb) ranged between 640 and 5100 under 100 Torr total pressure. Growth on sapphire resulted in fine grained nanocrystalline NbS2 films under all conditions studied whereas smooth NbS2 films with triangular-shaped domains, on the order of 1–2 μm in size, were obtained on epitaxial graphene under identical conditions. The differences in growth morphology were attributed to enhanced surface diffusion of Nb adatoms on the passivated graphene surface compared to that of c-plane sapphire. This work demonstrates that the substrate choice plays a very crucial role in the deposition of 3R NbS2.

Sulfidation of selected transition metal thin films (Mo, W, Re, Nb, Ta) was combined with thermodynamic calculations to study the synthesis of transition metal dichalcogenides (TMDCs) and understand variations among the metals as well as processing atmosphere. Metal seed layers were prepared by DC magnetron sputtering and sulfidized using sulfur vapor and H2S. Surface chemistry, structure, and morphology of the films were investigated using X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and atomic force microscopy (AFM), respectively. XPS analysis revealed that after treatment with sulfur vapor (p (S2) = 1–10 Torr), Mo, W, and Re films were transformed into MoS2, WS2, and ReS2, respectively. However, Nb and Ta films changed little, and Nb2O5 and Ta2O5 remained the predominant components. Alternatively, conversion of Nb and Ta films to NbS2 and TaS2 was feasible under H2S. Raman spectroscopy also revealed improved crystallinity for Mo, W, and Re sulfidized under H2S. Isobaric and isothermal stability diagrams were calculated to identify feasible processing conditions (sulfur partial pressure and temperatures) for the sulfidation of all of the metals, and our findings were in good agreement with the XPS and Raman results. It was found that for Mo, W, and Re a p (S2) = 10−5 bar is sufficient for the metals to be converted to sulfide phases at 750 °C. On the other hand, due to very high stability of Nb2O5 and Ta2O5, even at very low p (O2), a sulfur partial pressure of 103–104 bar is required to make NbS2 and TaS2, respectively. Nevertheless, thermodynamic calculations confirmed that Nb and Ta could be transformed to NbS2 and TaS2 under 760 Torr H2S. AFM analysis revealed very smooth films for MoS2, WS2, and NbS2 films, but dewetting of TaS2, and ribbons for ReS2. These results provide guidance for designing new processes for synthesizing 2D TMDCs.

Metalorganic chemical vapor deposition (MOCVD) is a promising technique to form large-area, uniform films of monolayer or few-layer transition metal dichalcogenide (TMD) thin films; however, unintentional carbon incorporation is a concern. In this work, we report the presence of a defective graphene layer that forms simultaneously during MOCVD growth of tungsten diselenide (WSe2) on sapphire at high growth temperature and high Se:W ratio when using tungsten hexacarbonyl (W(CO)6) and dimethyl selenide ((CH3)2Se, DMSe) as precursors. The graphene layer alters the surface energy of the substrate reducing the lateral growth and coalescence of WSe2 domains. The use of hydrogen selenide (H2Se) instead of DMSe eliminates the defective graphene layer enabling coalesced monolayer and few-layer WSe2 films.

Bi2Se3 thin films were grown on c-plane sapphire substrates by hybrid physical-chemical vapor deposition (HPCVD) using trimethyl bismuth (TMBi) and Se pellets. A Se-rich environment is created by evaporating Se pellets in the vicinity of the substrate, which is used to suppress the formation of Se vacancies. The effects of pre-cracking temperature and substrate/Se temperature on the growth rate, structural and electrical properties of the Bi2Se3 films were investigated. C-axis oriented films were obtained which show a reduction in the carrier concentration as pre-cracking temperature was increased from 290 °C (1.6×1019 cm−3) to 350 °C (8.4×1018 cm−3). An additional reduction in carrier concentration (7.28×1018 cm−3) was observed on increasing the substrate temperature from 200 to 260 °C.

A detailed thermodynamic analysis of the solid and gas phases of the Mo-S-C-O-H system used for large area chemical vapor deposition (CVD) of MoS2 is presented and compared with experimental results. Given the multivariable nature of the problem, excellent agreement is observed. Deviations, observed from thermodynamic predictions, mainly at low temperatures and high flow rates have been highlighted and discussed. CVD phase diagrams which predict parameter windows in which pure MoS2 can be synthesized have been provided for important gas phase chemistries. Pure H2 as a carrier gas is shown to facilitate the largest contamination free process window. CO presence is shown to significantly reduce the nucleation rate and enable large island sizes but at the cost of carbon contamination. Oxygen leaks are shown to result in sulphur contamination. The absence of H2S during cooling is shown to yield Mo due to the reduction of MoS2 by hydrogen. Oxidation of Mo causes oxide contamination.

Defects have a profound impact on the electronic and physical properties of crystals. For two-dimensional (2D) materials, many intrinsic point defects have been reported, but much remains to be understood about their origin. Using scanning transmission electron microscopy imaging, this study discovers various linear arrays of W-vacancy defects that are explained in the context of the crystal growth of coalesced, monolayer WS2. Atomistic-scale simulations show that vacancy arrays can result from steric hindrance of bulky gas-phase precursors at narrowly separated growth edges, and that increasing the edge separation leads to various intact and defective growth modes, which are driven by competition between the catalytic effects of the sapphire substrate and neighboring growth edge. Therefore, we hypothesize that the arrays result from combined growth modes, which directly result from film coalescence. The connections drawn here will guide future synthetic and processing strategies to harness the engineering potential of defects in 2D monolayers.

Lasing with a narrow linewidth is achieved from large area monolayer tungsten disulfide film synthesized by chemical vapor deposition after integrating onto silicon nitride heterostructure photonic crystal cavities.

Atomically thin transition metal dichalcogenides (TMDs) are of interest for next-generation electronics and optoelectronics. Here, we demonstrate device-ready synthetic tungsten diselenide (WSe2) via metal–organic chemical vapor deposition and provide key insights into the phenomena that control the properties of large-area, epitaxial TMDs. When epitaxy is achieved, the sapphire surface reconstructs, leading to strong 2D/3D (i.e., TMD/substrate) interactions that impact carrier transport. Furthermore, we demonstrate that substrate step edges are a major source of carrier doping and scattering. Even with 2D/3D coupling, transistors utilizing transfer-free epitaxial WSe2/sapphire exhibit ambipolar behavior with excellent on/off ratios (∼107), high current density (1–10 μA·μm–1), and good field-effect transistor mobility (∼30 cm2·V–1·s–1) at room temperature. This work establishes that realization of electronic-grade epitaxial TMDs must consider the impact of the TMD precursors, substrate, and the 2D/3D inte...

A simple microstructural rationale for successful anodization of metallic films into ordered oxide nanostructures has been identified. It applies to three of the most commonly studied systems, Zr, Ti and Al films and can be extended to other such oxides. A dense Zone T or II microstructure, in sputtered films, is the most critical ingredient. While T-substrate > 0.3T(melting) Ching is the simplest route, pressure and plasma heating can also be exploited. Such microstructures are also associated with a unique growth stress signature. (C) 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Recently, single photons have been observed emanating from point defects in two-dimensional (2D) materials including WSe2, WS2, hexagonal-BN, and GaSe, with their energy residing in the direct electronic bandgap. Here, we report single photon emission from a nominal weakly emitting indirect bandgap 2D material through deterministic strain induced localization. A method is demonstrated to create highly spatially localized and spectrally well-separated defect emission sites in the 750–800 nm regime in a continuous epitaxial film of few-layer WSe2 synthesized by a multistep diffusion-mediated gas source chemical vapor deposition technique. To separate the effects of mechanical strain from the substrate or dielectric-environment induced changes in the electronic structure, we created arrays of large isotropically etched ultrasharp silicon dioxide tips with spatial dimensions on the order of 10 μm. We use bending based on the small radius of these tips—on the order of 4 nm—to impart electronic localization effects through morphology alone, as the WSe2 film experiences a uniform SiO2 dielectric environment in the device geometry chosen for this investigation. When the continuous WSe2 film was transferred onto an array of SiO2 tips, an ∼87% yield of localized emission sites on the tips was observed. The outcomes of this report provide fundamental guidelines for the integration of beyond-lab-scale quantum materials into photonic device architectures for all-optical quantum information applications.Recently, single photons have been observed emanating from point defects in two-dimensional (2D) materials including WSe2, WS2, hexagonal-BN, and GaSe, with their energy residing in the direct electronic bandgap. Here, we report single photon emission from a nominal weakly emitting indirect bandgap 2D material through deterministic strain induced localization. A method is demonstrated to create highly spatially localized and spectrally well-separated defect emission sites in the 750–800 nm regime in a continuous epitaxial film of few-layer WSe2 synthesized by a multistep diffusion-mediated gas source chemical vapor deposition technique. To separate the effects of mechanical strain from the substrate or dielectric-environment induced changes in the electronic structure, we created arrays of large isotropically etched ultrasharp silicon dioxide tips with spatial dimensions on the order of 10 μm. We use bending based on the small radius of these tips—on the order of 4 nm—to impart electronic localization eff...

The effect of reactive ion etching using chlorine or fluorine-based plasmas on aluminum-induced crystallization (AIC) of silicon on fused silica glass substrates was investigated with the goal of chemically modifying the substrate surface and thereby influencing the crystallization behavior. Chlorine etching of the glass prior to AIC resulted in six times faster silicon crystallization times and smaller grain sizes than films formed on untreated substrates while fluorine etching resulted in crystallization times double than those on untreated surfaces. The differences in crystallization behavior were attributed to changes in surface chemistry and surface energy of the glass as a result of the plasma treatment as supported by X-ray photoelectron spectroscopy and contact angle measurements. The different surface treatments were then combined with optical lithography to control the location of crystallization on the substrate surface to realize the production of patterned polycrystalline silicon films from i...

Anodized titania, synthesized on oxidized silicon substrate, has been used as oxygen gas sensor. The as-anodized films resulted in a sensitivity of 5756% at 125°C, when exposed to 100% oxygen. The gas-sensing performance of anodized films has been evaluated with post-anodization treatment in de-ionized water and aqueous ammonia solution. The sensitivity increases to 8646% and 16599%, with post-treatment in aqueous ammonia solution and de-ionized water, respectively. This is attributed to increase surface area and activation during the post- anodization treatment. The repeatability of sensor performance has also been evaluated, and it is observed that the de-ionized water treated film is unstable for repeated sensing, possibly due to some structural modifications.