Transient porous nickel interlayers for improved silver-based Solid Oxide Fuel Cell brazes
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The interface between polar perovskite LaCrO3 (LCO) and non-polar SrTiO3(001) (STO), grown by molecular beam epitaxy, is examined using a combination of electron microscopy, spectroscopy, and Rutherford backscattering spectrometry. The LCO/STO(001) interface is insulating, a potential counter example for the claim that polar/nonpolar perovskite interfaces should be conductive by virtue of an electronic reconstruction to alleviate the polar discontinuity. The A-site cations of these ABO3 perovskites are found to diffuse across the interface to a greater extent than the B-site cations, based on high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), energy dispersive x-ray spectroscopy (EDS) and electron energy loss spectroscopy (EELS). The B-site cation valences are shown to be partially reduced near the interface by analysis of EELS near-edge structures. The location and direction of these electronic modifications do not intuitively compensate the charge imbalance imposed by uneven cation inter-diffusion, and yet both the film and interface are insulating. These results highlight the importance of both the physical and electronic structure of such complex interfaces in determining their characteristics. Furthermore, the extent of inter-diffusion is shown to increase with increasing LCO film thickness, suggesting a potential mechanism behind the critical thickness for interfacial conductivity in other polar/non-polar oxide systems, and a fundamental limitation on the formation of abrupt interfaces in LCO/STO(001).
Model materials consisting of metal nanoparticles loaded onto oxide supports were synthesized, characterized, and investigated in a number of catalytic chemical reactions. By varying the size, shape, and composition of nanoparticle, as well as the material used to support the nanoparticles, it was found that small changes to the catalyst can have enormous changes to the reaction activity and selectivity. Investigation of these carefully synthesized catalysts via in situ characterization, and reaction studies, leads to a deeper understanding of the molecular level parameters that govern catalysis. Through study of the properties of the nanoparticles it was discovered that nanoparticle size and shape have a dominant role in the chemoselective catalysis of furfural over platinum nanoparticles. When vapor phase furfural and hydrogen gas were passed over Pt nanoparticles ranging in size from 1.5 to 7.1 nm, the catalytic selectivity was found to be dominated by the size of the nanoparticle. Large nanoparticles promoted hydrogenation of furfural to furfuryl alcohol, while smaller nanoparticles favored decarbonylation to furan. The same size specific selectivity was found in the hydrogenative reforming (the transformation of hydrocarbons to branched isomers) of C6 hydrocarbons, in which Pt nanoparticle size controls isomerization selectivity. Methylcyclopentane was found to be extremely size dependent at lower temperatures (553 K). It was found that smaller sized nanoparticles favored isomer formation, while larger sizes catalyzed the aromatization reaction more efficiently. n-hexane was found to be much less dependent on particle size, but still showed an increase in isomerization with small particles over larger sized Pt nanoparticles. The composition of PtxRh1-x bimetallic nanoparticles was also studied. These catalysts were characterized under hexane reforming conditions with Ambient Pressure X-ray Photoelectron Spectroscopy (AP-XPS), in order to find the actual surface atomic composition under real catalytic working conditions. By using AP-XPS and catalytic data in tandem, it was found that an optimum Rh loading occurred when the surface ensemble statistically favored one Rh atom surrounded by Pt atoms. By utilizing different oxide materials for catalytic supports the flow of charge can play a role in the reaction at the surface or interface in a phenomenon known as the strong metal-support interaction (SMSI). When Pt nanoparticles were loaded onto mesoporous supports made of Co3O4, NiO, MnO2, Fe2O3, and CeO2 it was found that their activity for carbon monoxide oxidation was greatly enhanced relative to the support alone or Pt loaded onto inert mesoporous silica. This finding demonstrates that the interface of the metallic Pt nanoparticle and the oxide 2 support is able to produce turnovers that are orders of magnitude higher than the two materials separately. When the same type of experiments were investigated with n-hexane as the reactant and macroporous Al2O3, TiO2, Nb2O5, Ta2O5, and ZrO2 were utilized as supports, it was found that the reaction selectivity was greatly altered depending on the catalytic support material. TiO2, Nb2O5, and Ta2O5 (all of which are strong Lewis acids) were found to be much more selective for isomer production than the standard SiO2 mesoporous silica supported Pt nanoparticle catalyst. Finally, an acidified mesoporous silica material was utilized as the support. This material was synthesized by using AlCl3 to modify the surface of mesoporous silica. This support was found to have no activity for hexane isomerization alone. However, when Pt nanoparticles were supported on the material, the activity and isomer selectivity in hexane reforming was increased several orders of magnitude as compared to the same nanoparticles supported on unmodified mesoporous silica. This dissertation builds on the existing knowledge of known concepts in catalysis science such as structure sensitive reactions, the metal-support interaction, and acid-base chemistry. The results show how small changes in the active sites of a catalyst can create large changes in the catalytic chemistry. This research demonstrates how careful material control, characterization and reaction study can help to elucidate the molecular level components necessary to design efficient catalysts.
The oxidation kinetics of AlN containing 3.5 wt% Y2O3 were studied by thermogravimetric analysis in dry oxygen and 10% H2O/balance oxygen at temperatures between 1000 and 1200 C for times between 48 and 100 h. The oxidation kinetics for AlN in dry oxygen were parabolic and of approximately the same magnitude and temperature dependence as other alumina forming materials. In this case, diffusion of oxygen and/or aluminum through the alumina scale is the rate limiting mechanism. The oxidation kinetics for AlN in wet oxygen were nearly linear and much more rapid than rates observed in dry oxygen. Numerous micropores were observed in the alumina formed on AIN in wet oxygen. These pores provide a fast path for oxygen transport. The linear kinetics observed in this case suggest that the interface reaction rate of AlN with wet oxygen is the oxidation rate limiting step.
Epitaxial interfaces and superlattices comprised of polar and non-polar perovskite oxides have generated a good deal of interest because of the variety of novel properties they possess. In this work, we examine superlattices comprised of SrTiO3 (STO) and LaCrO3 (LCO) layers; we demonstrate that the differing band alignment of the polar LCO layer and the non-polar STO layer produces a ferroelectric phase transition throughout the STO layers of the superlattice. Through x-ray absorption near edge spectroscopy and aberration-corrected scanning transmission electron microscopy we show that the Ti cations are displaced off-center in the TiO6 octahedra along the superlattice growth direction. We also demonstrate that a built-in potential gradient exists within the STO and LCO layers via in situ x-ray photoelectron spectroscopy measurements. Density functional theory models of the system are in excellent agreement with these results, predicting both the ferroelectric octahedral distortion and the built-in electric field. These results represent a new avenue for research in perovskite superlattices, as two non-ferroelectric phases are shown to induce a bulk ferroelectric response due to interfacial phenomena.
Iron plays a vital role in natural processes such as water, mineral, iron, and nutrient cycles. Iron undergoes reduction-oxidation and catalytic reactions to produce various corrosion films depending on its chemical environment. Near ambient pressure X-ray photoelectron spectroscopy, polarized modulated infrared reflection absorption spectroscopy, and Auger electron spectroscopy were used to study the key reactants, from O 2 (g), H 2 O vapor, Na + and Cl – on the initial stages of iron surface corrosion. Here, with increasing the ratio of O 2 and H 2 O, surface hydrocarbons were shown to oxidize into carbonates, while the Cl – was found to migrate into the interface. The effect of each individual reactant was measured separately and water was shown to have a first order rate dependence on the carbonate growth at low pressures, with little dependence for O 2 . Near ambient pressures, both H 2 O and O 2 were found to increase the carbonate growth, which was estimated using the Langmuir isotherm model, yielding Gibbs energies between –9.8 to –8.5 kJ/mol. A mechanism is suggested to explain the oxidation is catalyzed by NaCl on iron surfaces and the adventitious hydrocarbons served as the source for surface carbonation. These findings have implications for understanding other surface catalytic and redox interface chemistry in complex environments.
The growth of lepidocrocite (gamma-FeOOH) has been observed through oxidation of Fe(II) on calcite (CaCO 3 ). Here, we seek to understand the structural relation between lepidocrocite and the calcite substrate and its growth mechanism. The formation of iron oxyhydroxide layers having distinct morphologies was observed during the dissolution of calcite in acidic Fe(II)-rich solutions. A pseudomorphic lepidocrocite shell together with multiple iron oxyhydroxide layers encapsulated within the shell was imaged by optical and transmission X-ray microscopies. The presence of a several-nanometer-thick ordered lepidocrocite film was observed by X-ray reflectivity, with the lepidocrocite (100) plane oriented parallel to the calcite (104) surface. Lath-shaped lepidocrocite aggregates formed during the initial precipitation, which eventually grew into clusters of parallel platy crystals. The formation of a nanometer-thick well-ordered lepidocrocite film on a pristine calcite surface appears critical for the subsequent pseudomorphic overgrowth. Detachment of the lepidocrocite film from the dissolving calcite surface yielded a free-standing pseudomorphic iron oxyhydroxide shell, suggesting weak interactions between the shell and the calcite substrate. This growth mechanism yields the potential of using carbonate minerals as templates for pseudomorphic synthesis of iron oxyhydroxides having well-defined size and morphology.
The surface preparation for depositing Al 2 O 3 for fabricating Au/Ni/Al 2 O 3 /n-GaN (0001) metal oxide semiconductor (MOS) capacitors was optimized as a step toward realization of high performance GaN MOSFETs. The GaN surface treatments studied included cleaning with piranha (H 2 O 2 :H 2 SO 4 = 1:5), (NH 4 )(2)S, and 30% HF etches. By several metrics, the MOS capacitor with the piranha-etched GaN had the best characteristics. It had the lowest capacitance-voltage hysteresis, the smoothest Al 2 O 3 surface as determined by atomic force microscopy (0.2nm surface roughness), the lowest carbon concentration (similar to 0.78%) at the Al 2 O 3 /n-GaN interface (from x-ray photoelectron spectroscopy), and the lowest oxide-trap charge (Q(T) = 1.6 x 10(11) cm(-2) eV(-1)). Its interface trap density (D-it = 3.7 x 10(12) cm(-2) eV(-1)), as measured with photon-assisted capacitance- voltage method, was the lowest from conduction band-edge to midgap. (C) 2015 American Vacuum Society.
Reducing defects at III-V/high-k interfaces is essential for optimizing devices built on these materials. Here, the role of an interfacial AlN process at In{sub 0.53}Ga{sub 0.47}As/ZrO{sub 2} interfaces is investigated by hard x-ray photoelectron spectroscopy (HAXPES) and capacitance/voltage (C-V) measurements. C-V measurements show a significant reduction in the density of interface traps with the interfacial AlN process and a capping TiN layer. To elucidate the specific role of the AlN process, blanket films with various deposition processes are compared. The AlN process alone (without subsequent dielectric deposition) reduces InGaAs oxide levels below the HAXPES detection limit, even though the AlN is ultimately found to be oxidized into AlO{sub x} with only trace N incorporation, yet AlN passivation provides a lower D{sub it} (density of interface traps) when compared with an H{sub 2}O-based Al{sub 2}O{sub 3} deposition. The AlN process does not passivate against re-oxidation of the InGaAs during an O{sub 3} based ZrO{sub 2} deposition process, but it does provide passivation against As-As development during subsequent TiN deposition. The role of chemical defects in the C-V characteristics is also discussed.
High temperature mechanical properties was detected here to study the failure and strengthening mechanism of the coating-substrate (cobalt-based coatings were fabricated on FV520B substrate) integral structure with thermo-mechanical coupling effects. Microstructure, phase composition, element distribution of the coatings was characterized by optical microscopy (OM), scanning electron microscopy (SEM), transmission electron microscope (TEM), electron back scattering diffraction (EBSD), X-ray diffraction (XRD), electron probe microanalysis (EPMA) and energy dispersive X-ray analysis (EDS). Results elucidate that fracture occurs in the coating for Co50 coating-substrate structure from 300 °C to 700 °C, but failure position transfer to substrate from coating at elevated temperatures with the addition of niobium and cerium oxide. Throughout, there is no crack originated from the interface. Fracture mechanism: the dislocation pile-up causes great stress concentration in the grain boundary, which results in the nucleation of the crack, and then the crack extends along the hard brittle Fe-Cr phase until the material fails. HRTEM shows the high density dislocation and the severe lattice distortion was formed during tensile deformation. On the macro level, the fracture tends to occur in the coarse dendrites region.
Evidence of boron diffusion into the MgO barrier of a CoFeB/MgO based magnetic tunnel junction has been identified using analytical scanning transmission electron microscopy (STEM) and X-ray photoelectron spectroscopy. Structures were deposited by DC/RF-magnetron sputtering, where defective, sub-stoichiometric MgO barriers degrading device performance have been previously mitigated against by deposition of thin Mg layers prior to MgO deposition. We show that despite the protection offered by the Mg layer, disorder in the MgO barrier is still evident by STEM analysis and is a consequence of the oxidation of the Co{sub 40}Fe{sub 40}B{sub 20} surface during MgO deposition. Evidence of boron diffusion from CoFeB into the MgO barrier in the as-deposited and annealed structure is also presented, which in the as-deposited case we suggest results from the defective structures at the barrier interfaces. Annealing at 375 Degree-Sign C results in the presence of B in the trigonal coordination of [BO{sub 3}]{sup 3-} in the MgO barrier and partial crystallization of the top electrode (we presume there is also some boron diffusion into the Ta capping layer). The bottom electrode, however, fails to crystallize and much of the boron is retained in this thicker electrode. A higher annealing temperature or lower initial boron content is required to crystallize the bottom electrode.
We report the formation of a quasi-two-dimensional electron gas (2-DEG) at the interface of γ-Al{sub 2}O{sub 3}/TiO{sub 2}-terminated SrTiO{sub 3} (STO) grown by atomic layer deposition (ALD). The ALD growth of Al{sub 2}O{sub 3} on STO(001) single crystal substrates was performed at temperatures in the range of 200–345 °C. Trimethylaluminum and water were used as co-reactants. In situ reflection high energy electron diffraction, ex situ x-ray diffraction, and ex situ cross-sectional transmission electron microscopy were used to determine the crystallinity of the Al{sub 2}O{sub 3} films. As-deposited Al{sub 2}O{sub 3} films grown above 300 °C were crystalline with the γ-Al{sub 2}O{sub 3} phase. In situ x-ray photoelectron spectroscopy was used to characterize the Al{sub 2}O{sub 3}/STO interface, indicating that a Ti{sup 3+} feature in the Ti 2p spectrum of STO was formed after 2–3 ALD cycles of Al{sub 2}O{sub 3} at 345 °C and even after the exposure to trimethylaluminum alone at 300 and 345 °C. The interface quasi-2-DEG is metallic and exhibits mobility values of ∼4 and 3000 cm{sup 2} V{sup −1} s{sup −1} at room temperature and 15 K, respectively. The interfacial conductivity depended on the thickness of the Al{sub 2}O{sub 3} layer. The Ti{sup 3+} signal originated from the near-interfacial region and vanished after annealing in an oxygen environment.
Li8ZrO6 is a pseudolamellar compound with high lithium content. Even though it is intrinsically a poor conductor and does not contain a transition metal with easily variable oxidation states, a new synthetic approach to preparing it in nanocomposite form with intimate contact to a conductive carbon by mechanical delamination enabled galvanostatic cycling of coin half-cells containing Li8ZrO6/C as the cathode and Li-metal as the anode at 221 mAh/g (which corresponds to extracting 2 Li per formula unit) over at least 140 cycles. With a higher capacity limit, a discharge capacity of 331 mAh/g (which corresponds to extracting 3 Li per formula unit) was maintained over 15–20 cycles. Ex-situ and operando X-ray diffraction (XRD) studies of galvanostatically cycled cells showed that at these levels of charge, delithiation follows a reversible, topotactic path with only small distortions around Zr atoms. During this process, crystalline grain sizes decrease continuously, shortening diffusion lengths within grains but increasing the number of grain boundaries and electrode/electrolyte interfaces. Charge storage in Li8ZrO6 appears to involve partial oxidation of oxygen atoms and production of small-polaron holes, as supported by XRD, X-ray photoelectron spectroscopy, and pair-distribution function studies and predicted by quantum mechanical calculations. At higher depths of charge, delithiation results in amorphization of the active electrode material. The charge storage mechanism in Li8ZrO6 is unusual among lithium-ion battery electrode materials and involves a combination of mechanisms that resemble intercalation and conversion reactions. With further refinement, Li8ZrO6/C based materials open up opportunities to develop new cathode materials for lithium-ion batteries that may improve on currently existing capacity barriers.
The effect of CdTe addition on YBa{sub 2}Cu{sub 3}O{sub 7−δ}(CdTe){sub x} (x = 0–0.10) has been studied. XRD patterns showed the presence of impurities including CdTe for x ≥ 0.05 wt%. The resistance versus temperature curves showed metallic behavior for all samples. The onset temperature T{sub c onset} for all samples is between 90 and 92 K. The superconducting transition width, ΔT{sub c} = 4 K for all samples except for x = 0.1 wt% where ΔT{sub c} = 6 K. The superconducting transition determined by AC susceptibility measurement also showed little change in T{sub cχ{sup ′}} (between 89 and 92 K). However, the peak temperature T{sub p} of the imaginary part of the susceptibility χ″, showed a drastic decrease for samples with x > 0.05 wt%. This indicated that the superconducting grains were strongly decoupled for x > 0.05 wt% due to the impurities as observed in the XRD pattern. The intergrain critical current density, J{sub c} at T{sub p} for the x = 0 sample is J{sub c} (82 K) = 17 A cm{sup −2}. These results can be useful in the fabrication of semiconductor/YBCO superconductor hybrid systems.
A tunneling atomic layer deposited (ALD) AlO x layer was inserted in a Si|SiO x |AlO x |MoO x |metal tunnel diode structure to investigate the impact of fixed interface charge on Schottky barrier height. ALD AlO x provides a synthesis-tunable fixed charge and can provide excellent field effect passivation at the SiO x |AlO x interface. A large (>1 × 10 12 q.cm –2 ) negative fixed charge density was expected to decrease Schottky barrier height on p-type silicon and increase Schottky barrier height on n-type silicon by up to 0.4 eV based on an electrostatic model. Fixed charge density and interface trap state density were measured using a thick layer of AlO x in metal oxide semiconductor capacitor structures (MOSCAPs); Schottky barrier height and specific contact resistivity were measured using a tunneling-active layer of AlO x in contacted structures with MoO x . In some samples, HfO x interface layers were inserted between AlO x and silicon to quench the fixed negative charge. The Schottky barrier height was found to vary with processing conditions but did not have a strong correlation with expected fixed charge density. Here, while fixed charge may play a role in determining the Schottky barrier height, other parameters also have significant affect. Further work is needed to minimize contact resistivity and elucidate other factors impacting the Schottky barrier height.
The electronic structures of amorphous indium gallium zinc oxide (a-IGZO) on a SiO{sub 2} layers before and after annealing were observed by constant final state X-ray photoelectron spectroscopy (CFS-XPS) and X-ray adsorption near-edge structure spectroscopy (XANES). From the results of angle-resolved CFS-XPS, the change in the electronic state was clearly observed in the a-IGZO bulk rather than in the a-IGZO/SiO{sub 2} interface. This suggests that the electronic structures of the a-IGZO bulk strongly affected the thin-film transistor characteristics. The results of XANES indicated an increase in the number of tail states upon atmospheric annealing (AT). We consider that the increase in the number of tail states decreased the channel mobility of AT samples.
The development of an efficient photoanode remains the primary materials challenge in the establishment of a scalable technology for solar water splitting. The typical photoanode architecture consists of a semiconductor light absorber coated with a metal oxide that serves a combination of functions, including corrosion protection, electrocatalysis, light trapping, hole transport, and elimination of deleterious recombination sites. To date, such coatings have been mostly limited to simple materials such as TiO 2 and Co-Pi, with extensive experimental and theoretical effort required to provide an understanding of the physics and chemistry of the semiconductor-coating interface. In order to provide a more efficient exploration of metal oxide coatings for a given light absorber, we introduce a high throughput methodology wherein a uniform BiVO 4 thin film is coated with 858 unique metal oxides covering a range of metal oxide loadings and the full Ni–La–Co–Ce oxide quaternary composition space. Photoelectrochemical characterization of each photoanode reveals that approximately one third of the coatings lower the photoanode performance while select combinations of metal oxide composition and loading provide up to a 14-fold increase in the maximum photoelectrochemical power generation for oxygen evolution in pH 13 electrolyte. Particular Ce-rich coatings also exhibit an anti-reflection effect that further amplifies the performance, yielding a 20-fold enhancement in power conversion efficiency compared to bare BiVO 4 . By use of in situ optical spectroscopy and comparisons between the metal oxide coatings and their extrinsic optical and electrocatalytic properties, we present a suite of data-driven discoveries, including composition regions which form optimal interfaces with BiVO 4 and photoanodes that are suitable for integration with a photocathode due to their excellent power conversion and solar transmission efficiencies. The high throughput experimentation and informatics provides a powerful platform for both identifying the pertinent interfaces for further study and discovering high performance photoanodes for incorporation into efficient water splitting devices.
Development of high-performance hydrogen oxidation catalysts with ultralow precious metal loading is critical to the development of next-generation anion-exchange membrane fuel cells. In this work, a novel Ru-rich Pt–RuO 2 heterojunction catalyst was synthesized via a solvothermal process followed by thermal treatment. The Pt–RuO 2 catalyst has ultrafine Pt clusters and a heterojunction interface between Pt and RuO 2 , which facilitates high hydrogen oxidation activity while minimizing adverse adsorption of the phenyl group in the polymer electrolyte. The performance of a membrane electrode assembly employing the Pt–RuO 2 /C reached a peak power density of 0.77 W cm -2 with an anode Pt loading of 25 μg Pt cm -2 , achieving a specific power of 31 W mg Pt -1 under H 2 /O 2 conditions. The combined analysis of electrode performance and cost indicates that Pt–RuO 2 /C is one of the most promising catalysts that is approaching the U.S. DOE 2020 performance and cost targets for transportation applications.