Spatial econometric models become increasingly popular in various subfields of political science. However, the necessity to specify the underlying network of dependencies, denoted by $\boldsymbol{W}$, prior to estimation is a prevalent source of criticism since the true dependence structure is rarely known and theories mostly provide insufficient guidance. The present study investigates the effects of this network uncertainty which is a special case of model uncertainty that arises from uncertainty about the correct specification of $\boldsymbol{W}$. It advocates Bayesian model averaging (BMA) as a superior approach to this problem, located at the intersection of theory and empirics. Conducting Monte Carlo experiments, I demonstrate that, while the effect estimates are robust toward a misspecification in the functional form of $\boldsymbol{W}$, uncertainty in the neighborhood definition can bias the effect estimates derived from spatial autoregressive models. In contrast to alternative techniques, BMA directly addresses network uncertainty, correctly identifies the true network structure in the set of feasible alternatives, and provides unbiased effect estimates. Two replication studies from different subfields of the discipline illustrate the benefits of this approach for applied research.

Selective solar absorbers comprised of plasmonic materials offer great flexibility in design along with a highly promising optical performance. However, the nanopattern generation, typically done with electron beam writing, is a very time-intensive process. In this work, we present a fast, scalable, and flexible method for the fabrication of plasmonic materials by the combination of a deposition mask prepared by nanoimprint lithography and thin film deposition by magnetron sputtering. The fabrication process was first performed on silicon wafer substrates using AFM and SEM measurements to calibrate the deposition time, determine maximal deposition height, and characterize samples. Afterwards, the process was transferred to polished Inconel NiCr-alloy substrates used in high temperature solar absorbers. To investigate the adhesion properties of the nanostructure on the substrate, two different deposition methods were investigated: DC magnetron sputtering and High Power Impulse Magnetron Sputtering (HiPIMS).

The 2D transition metal dichalcogenide (TMDC) tungsten disulfide (WS2) has attracted great interest due to its unique properties and prospects for future (opto)electronics. However, compared to molybdenum disulfide (MoS2), the development of a reproducible and scalable deposition process for 2D WS2 has not advanced very far yet. Here, we report on the systematic investigation of 2D WS2 growth on hydrogen (H2)-desorbed sapphire (0001) substrates using a hydrogen sulfide (H2S)-free metal-organic vapor phase epitaxy (MOVPE) process in a commercial AIXTRON planetary hot-wall reactor in 10 × 2" configuration. Tungsten hexacarbonyl (WCO, 99.9 %) and di-tert-butyl sulfide (DTBS, 99.9999 %) were used as MO sources, nitrogen (N2) was selected as carrier gas for the deposition processes (standard growth time 10 h). In an initial study, the impact of growth temperature on nucleation and growth was investigated and an optimal value of 820 °C was found. The influence of the WCO flow on lateral growth was investigated. The aim was to maximize the edge length of triangular crystals as well as the total surface coverage. Extending gradually the growth time up to 20 h at optimized WCO flow conditions yields fully coalesced WS2 samples without parasitic carbon-related Raman peaks and with only sparse bilayer nucleation. After substrate removal, a fully coalesced WS2 film was implemented into a light-emitting device showing intense red electroluminescence (EL).

It is known that tungsten oxide may be reacted with selenium sources to form WSe2 but literature reports include processing steps that involve high temperatures, reducing atmospheres, and/or oxidative pre-treatments of tungsten oxide. In this work, we report a non-vacuum process for the fabrication of compositionally high quality WSe2 thin films via the selenization of tungsten oxide under milder conditions. Tungsten source materials were various hydrated WO3 and WO2.9 compounds that were prepared using chemical solution techniques. Resulting films were selenized using a two-stage heating profile (250 °C for 15 minutes and 550 °C for 30 minutes) under a static argon atmosphere. Effects of the starting tungsten oxide phase on WSe2 formation after single and double selenization cycles were investigated using Raman spectroscopy and X-ray diffraction (XRD). After two selenization cycles, hydrated WO3 was converted to (002)-oriented WSe2 that exhibits well-resolved peaks for E12g and A1g phonon modes. Only a single selenization cycle was required to convert amorphous WO2.9 to WSe2. All selenizations in this work were achieved in non-reducing atmospheres and at lower temperatures and shorter times than any non-laser-assisted processes reported for WO3-to-WSe2 conversions.

Two-dimensional (2D) materials are very promising with respect to their integration into optoelectronic devices. Monolayer tungsten diselenide (WSe2) is a direct-gap semiconductor with a bandgap of ∼1.6eV, and is therefore a complement to other two-dimensional materials such as graphene, a gapless semimetal, and boron nitride, an insulator. The direct bandgap distinguishes monolayer WSe2 from its bulk and bilayer counterparts, which are both indirect gap materials with smaller bandgaps. This sizable direct bandgap in a two-dimensional layered material enables a host of new optical and electronic devices. In this work, a comprehensive analysis of the effect of optical excitation on the transport properties in few-layer WSe2 is studied. Monolayer WSe2 flakes from natural WSe2 crystals were transferred onto Si/SiO2 (270nm) substrates by mechanical exfoliation. The flakes were observed under an optical microscope. A FET based on mechanically exfoliated WSe2 was fabricated using photolithography with Molybdenum as metal contact and Silicon as back gate and the electronic properties were measured in a wide range of temperatures. The mobility of our device was found to be 0.2 cm /V-S at room temperature. The schottky barrier height was found to decrease from 80 meV to 25 meV as the gate voltage increases.

Evidences show that the composition of β″ formed in age hardening of Al alloys should be the prototype Mg5Si6 with Al and/or Cu addition. In the present work, molecular dynamics simulations are carried out to investigate the influence of the addition of Al and/or Cu to the mechanical properties of the prototype Mg5Si6. Our simulations imply that Mg5Si6 with both Al and Cu addition has relatively poor mechanical performance when compared with other three models. The snapshots of atomic configurations during uniaxial tension test illustrate that only if both Al and Cu dissolve in β″, clusters can form through Al atoms segregating around Cu atoms, thus applying different stress fields on the Al matrix, resulting different mechanical properties in comparison with other three β″ models.

The effect of W addition on microstructure and mechanical properties of Ni3Al (L12) and Ni3V (D022) two-phase intermetallic alloys has been investigated. W was added to the base alloy composition, Ni75Al10V12Nb3 (at. %) in place of either Ni, Al or V. The W-added alloy ingots were heat-treated in vacuum at 1575 K for 5 h. The majority of W-added alloys showed a dual two-phase microstructures while the alloy in which 3 at. % W substituted for Ni exhibited the dual two-phase microstructure containing W solid solution dispersions. Vickers hardness was significantly enhanced by W addition, which is primarily due to solid-solution strengthening.

An excellent candidate for an earth abundant absorber material is WSe2 which can be directly grown as a p-type semiconductor with a band gap near 1.4 eV. In this work we present the structural, optical, and electrical properties of thin film WSe2 grown via the selenization of sputter deposited tungsten films. We will show that highly textured films with an optical band gap in range of 1.4 eV, and absorption coefficients greater than 105/cm across the visible spectrum can be easily achieved. In addition we will present Hall Effect and carrier density measurements as well, where will show densities in the 1017cm-3 range and p-type Hall mobilities greater than 10 cm2/V-s range can be obtained. We employ these results to numerically simulate solar cells based on this material, where we will show efficiencies greater than 20% are possible.

Many theoretical predictions have suggested that the confined length scales and increased interface density of various nanostructured materials may result in desired thermal, mechanical, and radiation properties. An important aspect of this for next generation nuclear reactors is understanding the change in swelling resulting from helium evolution in tungsten alloys, as a function of grain size and grain boundary type. This study investigated this using a new ion irradiation transmission electron microscope (TEM) facility that has been developed at Sandia National Laboratories and is capable of ion implanting helium at energies up to 20 keV. It was demonstrated in this feasibility study that helium could be implanted into an ultrafine grained tungsten TEM sample produced by severe plastic deformation. The size and density of the helium bubbles formed during the experiment appear nearly constant; while the larger voids formed appear to be dependent on the local microstructure. Future work is underway to both optimize the facility, as well as better understand the evolution of ultrafine grained tungsten resulting from both helium implantation and displacement damage.

In our earlier work [1] microstructural evolution in tungsten under self-ion irradiation was investigated as a function of temperature and dose by in-situ 150 keV W+ ion irradiations on the IVEM-Tandem facility at Argonne National Laboratory (ANL). The present work focuses on the thermal stability of this damage. Thin foils of tungsten were irradiated at room temperature (R.T.) to fluences up to 1018 W+m-2 (∼ 1.0 dpa) and were then annealed in-situ for up to 120 min at temperatures between 300 and 800°C.

We found that: (1) loops with Burgers vectors ½ <111> and <100> coexist during annealing; (2) <100> is not a stable loop configuration above 300°C and the fraction of such loops decreased with increasing temperature and/or time; (3) changes in loop populations during annealing were very sensitive to temperature, but less sensitive to time. The majority of changes occurred within 15 min, and were associated with the loss of small (1-2 nm) dislocation loops. The origin of these trends is discussed by considering defect mobility and the energetics of defect configurations predicted by previous DFT calculations [2].

Sharper nanotips are required for application in nanoprobing systems due to a shrinking contact size with each new transistor technology node. We describe a two-step etching process to fabricate W nanotips with controllable tip dimensions. The first process is an optimized AC electrochemical etching in KOH to fabricate nanotips with a radius of curvature (ROC) down to 90 nm. This was followed by a secondary nanotip sharpening process by laser irradiation in KOH. High aspect ratio nanotips with ROC close to 20 nm were obtained. Finally we demonstrate the application of the fabricated nanotips for nanoprobing on advanced technology SRAM devices.

Model alloys have been made of pure W and 1% & 5% W-Ta and W-Re. Indentation hardness and modulus data were obtained by nanoindentation to assess the effect of composition on mechanical properties. Results showed that both the Ta and Re compositions hardened with increasing alloy content, greater in the W-5%Ta composition which showed an increase of 1.03GPa (17%), compared to a 0.43GPa (7%) increase in W-5%Re. The samples also showed very small increases in modulus of ∼ 25GPa (6%) in both W-5%Re and W-5%Ta. The samples were implanted with 3000appm concentration of helium. All samples show a substantial increase in hardness of up to 107% in the case of pure W. An appreciable difference in modulus is also seen in all samples. Initial TEM work has shown no visible He bubbles, suggesting that the mechanical properties changes are due to He-vacancy cluster formation below the resolvable limit.

Chemical Mechanical Planarization (CMP) is widely used to ensure planarity of metal and dielectric surfaces to enable photolithography and hence multilevel metallization in microelectronics manufacturing. The aim of this study is to establish a fundamental understanding on the dynamic growth of nano-scale protective oxide thin films during CMP to enable the selection of proper oxidizer concentrations for slurry formulations. Tungsten was selected as the model metal film to study the formation of these metal oxide films in various oxidizers and Atomic Force Microscope (AFM) was used to measure the surface roughness of the samples conditioned in the oxidizer environment before and after the CMP was conducted. The affect of surface roughness on wettability of the surfaces were also studied through contact angle measurements on the treated tungsten films. Fourier Transform Infrared Spectroscopy with Attenuated Total Reflectance FTIR/ATR technique in combination with the X-Ray Reflectivity (XRR) were utilized to determine the thicknesses of the oxidized nano films on the tungsten surface. The results were evaluated through the material removal responses reported in the literature for the W-CMP in addition to the comparison of the Pilling-Bedworth ratios of the oxidized nano films to determine the ability of the created oxide film as a self-protective oxide.

A series of NiW catalysts supported on SBA-15-type materials modified with Al, Ti or Zr were prepared and tested in simultaneous hydrodesulfurization (HDS) of two model compounds: dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT). Catalysts were prepared by incipient wetness impregnation of SBA-type materials (pure silica SBA-15, Al-SBA-15, Ti-SBA-15 or Zr-SBA-15) using Keggin-type heteropolyacid H4SiW12O40 as active phase precursor and nickel nitrate. Nominal composition of the catalysts was 19 wt.% of WO3 and 3 wt.% of NiO. The supports and catalysts were characterized by SEM-EDX, N2physisorption, small-angle and powder XRD, UV-Vis DRS, TPR and HRTEM. It was shown that a good dispersion of Al, Ti and Zr species on the SBA-15 surface was reached. The characteristic structure of the SBA-15 support was preserved in all supports and NiW catalysts. Addition of metal atoms (Al, Ti, Zr) on the SBA-15 surface prior to catalysts’ preparation improved dispersion of Ni and W oxide species in calcined catalysts. HRTEM characterization of sulfided catalysts showed that the dispersion of NiW active phase was also better on metal-containing SBA-15 supports than on the pure silica one. All NiW catalysts supported on metal-containing SBA-15 materials showed an outstanding catalytic performance in HDS of both model compounds used (DBT and 4,6-DMDBT). A good correlation was found between the dispersion of sulfided NiW active phase and catalytic activity results. The highest HDS activity was obtained with the NiW catalyst supported on Zr-containing SBA-15 molecular sieve, which makes it a promising catalytic system for ultra-deep hydrodesulfurization of diesel fuel.

We have performed density-functional theory (DFT) calculations of phase stability, formation energies of radiation defects in tungsten-based binaries W-Ta and W-V. These alloys are candidate for DEMO divertor applications because of their high melting point and expected improved ductility and fracture toughness in comparison with tungsten. We have identified the lowest energy intermetallic compounds, which should form at low temperatures, and calculated the effective inter-atomic interactions. Using Monte-Carlo calculations, we calculated the temperature of order-disorder phase transformations for these alloys. The predicted temperature of order-disorder phase transformations is relatively low and at high temperature it is found that the short-range order is present for both alloys. Ab-initio calculations also show that vanadium atoms strongly trap self-interstitial atom defects in W-V alloys, whereas Ta atoms in W-Ta alloys have very little effect on either the formation energy or thermally activated mobility of self-interstitial atom defects.

We investigated the resistive switching behavior of WOx films. WOx was obtained from the thermal oxidation of W thin layers. The parameters under investigation were the influence of the temperature (450-500 °C) and time (30-220 s) used to obtain the WOx on the resistive switching characteristics of Si\W\WOx\Metal_electrode ReRAM cells. The metal top electrodes (TE) tested were Pt, Ni, Cu and Au. The elemental composition and microstructure of the samples were characterized by means of elastic recoil detection analysis (ERD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray reflectivity (XRR).

Electrical measurement of the WOx-based memory elements revealed bipolar and unipolar switching and this depended upon the oxidation conditions and TE selected. Indeed, switching events were observed in WOx samples obtained either at 450 °C or 500 °C in time windows of 180-200 s and 30-60 s, respectively. Pt and Au TE promoted bipolar switching while unipolar behavior was observed with Ni TE only; no switching events were observed with Cu TE. Good switching characteristics seems not related to the overall thickness, crystallinity and composition of the oxide, but on the W6+/W5+ ratio present on the WOx surface, surface in contact with the TE material. Interestingly, W6+/W5+ ratio can be tuned through the oxidation conditions, showing a path for optimizing the properties of the WOx-based ReRAM cells.

The early stages of surface oxidation of biaxially textured Ni–W tapes were studied using thermodynamic calculations along with experimental tape oxidation at low P(O2). Tape phase and chemical composition, surface morphology, and roughness were examined using x-ray diffraction (XRD), energy-dispersive x-ray analysis (EDX), secondary ion mass spectroscopy (SIMS), x-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). For a Ni0.95W0.05 alloy tape, the precise position of the tape oxidation line in P(O2)–T coordinates was established. This line includes a break at T ≈ 650 °C that originates from the change of the W oxidation mechanism from internal oxidation to oxidation on a free surface accompanied by segregation of the alloy components in the tape near-surface region. The surface roughness of a polished tape increased drastically during internal oxidation of W; further tape oxidation did not affect the integral roughness parameters, but introduced numerous small (˜;100 nm) features on the tape surface comprising NiO precipitates.

Phase-pure nanostructured WB ceramics are hot pressed at ultrahigh pressures of 1.0 to 3.0 GPa and high temperatures of 700 to 1000 °C (UHPHT) for 60 min. The UHPHT samples are nanograin size from 15 to 40 nm. Our experimental observation shows that ultrahigh pressure could improve densification, and the density of WB samples could reach 99.4% of theoretical. The comparative experiments carried out at ambient pressure and temperatures of 550 to 1100 °C for 60 min indicate that the external pressure was favorable for phase-pure and highly dense WB formation. In addition, the UHPHT samples give a high hardness value of 28.9 ± 0.8 GPa.

Understanding the interaction between atomic hydrogen and solid tungsten is important for the development of fusion reactors in which proposed tungsten walls would be bombarded with high energy particles including hydrogen isotopes. Here, we report results from periodic density-functional theory calculations for three crucial aspects of this interaction: surface-to-subsurface diffusion of H into W, trapping of H at vacancies, and H-enhanced decohesion, with a view to assess the likely extent of hydrogen isotope incorporation into tungsten reactor walls. We find energy barriers of (at least) 2.08 eV and 1.77 eV for H uptake (inward diffusion) into W(001) and W(110) surfaces, respectively, along with very small barriers for the reverse process (outward diffusion). Although H dissolution in defect-free bulk W is predicted to be endothermic, vacancies in bulk W are predicted to exothermically trap multiple H atoms. Furthermore, adsorbed hydrogen is predicted to greatly stabilize W surfaces such that decohesion (fracture) may result from high local H concentrations.

WO3 doped TiO2 nanotube(WO3-doped TNT) thin film was fabricated by anodizing the TiO2 nanotube (TNT) film in an NH4F electrolyte containing WO4- ions. The sample was characterized by Field Emission Scanning Electron Microscopy (FE-SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and UV–Vis diffuse reflectance spectroscopy (DRS). The results show that WO3 was successfully doped into TiO2 nanotubes and the absorption edge of WO3 doped TNT appeared to be red shifted. The photoelectrocatalytic (PEC) activity of WO3 doped TNT electrode was evaluated through the PEC degradation of aqueous Acid Blue 80. The experimental results demonstrated that the PEC degradation rate of WO3 doped TNT is increased by 48% and by 167% over that of non-doped TNT under UVA light irradiation and visible-light irradiation, respectively, at an applied potential of 1.54V. The degradation rates of WO3 doped TNT under photocatalytic (PC), electrochemical (EC), and PEC processes were compared. The results reveal the synergetic effect of PC and EC processes.