High temperature scanning tunneling microscopy of purely ion conducting yttria stabilized zirconia (YSZ)

Scanning tunneling microscopy (STM) on wide band gap insulators is generally not possible. Here we demonstrate that ionic insulators with high ion mobility, such as yttria stabilized zirconia, are an exception to this rule. The ion conductivity ensures that the sample maintains a defined potential relative to the STM tip and thus a stable tunnel junction. Consequently, ion conductors provide an opportunity for characterizing wide band gap insulators, and thin films and nanostructures supported on them by STM.     

XeCl laser ablation of yttria stabilized zirconia

XeCl laser ablation of yttria stabilized zirconia (YSZ) in air and in vacuum (1.3×10^–4 Pa) is studied by means of etch depth measurements, scanning electron microscopy, and X-ray photoelectron spectroscopy of ablated surfaces. Results on ablation rate, surface morphology, and surface chemical composition are discussed in terms of the influence of ambient atmosphere on the ablation process, rapid melting and solidification of ablated surfaces, and preferential removal of oxygen atoms from the YSZ surface.     

High temperature water electrolysis: The cathodic process at the cermet (Pt+La0.8Sr0.2CrO3)/Zirconia interface

The kinetics of the reduction of steam at the interface of a platinum containing cermet with Yttria Stabilized Zirconia (YSZ) electrolyte at high temperature has been investigated. The presence of an outer porous platinum layer deposited onto the underlying cermet layer results in a remarkable increase of the kinetic parameters of the overall reaction. However, the presence of metallic platinum embedded in the structure of the mixed oxide layer, restricting the section available for the diffusion of the reducible species, results in a worsening of the electrochemical kinetics.A comparison with other previously investigated electrodes has been performed and some hypotheses on the rate determining mechanism have been suggested.     

ESR study of color centers in yttria stabilized zirconia

The ESR of single crystals of yttria stabilized zirconia (YSZ), containing color centers due to reduction in a flowing H₂ atmosphere, has been measured at room temperature. The spin density is about 3 × 10¹⁷ cm^?3 and the strong ESR line displays axial symmetry with principal values g₆ = 1.989, g_⊥ = 1.860.The behaviour of the ESR spectra when the magnetic field is rotated about the 〈1 0 0〉 and 〈1 1 0〉 directions shows that the centers have axial symmetry, the symmetry axis being along the 〈111〉 and equivalent directions. The derivative peak to peak envelope width is g-dependent and varies from 18 Gauss at g = 1.989 to 65 Gauss at g = 1.860. The results are interpretable in terms of an electron trapped at an oxygen vacancy adjacent to an yttrium ion.     

Characterization of laser sealed coatings of yttria partially stabilized zirconia

The present paper reports an experimental investigation based on X-ray diffraction (XRD), energy dispersive spectroscopy (EDS), and wavelength dispersive spectroscopy (WDS) analyses of phases formed after laser sealing of plasma sprayed coatings of 8.5 wt% yttria partially stabilized zirconia (YPSZ). X-ray diffraction and X-ray step-scanning analyses showed that the plasma sprayed and sealed coatings consisted mainly of t′ phase with a very small amount of monoclinic phase (m phase) in the plasma sprayed coatings. It was also found that the small amounts of m and cubic phases (c phase) present in the sealed coatings were dependent on laser processing specific energies (specific energy is equal to laser power/traverse speed x beam diameter). It was also found that rhombohedral (r) phase formed after laser sealing of coatings at higher specific energies. A direct relationship between c/a ratio of transformable tetragonal phase (t phase) produced by thermal treatment of sealed coatings and nontransformable tetragonal phase (t′ phase) and the amount of Yttria was obtained. A new equation was derived, which describes the relationship between Yttria concentration and the c/a ratio of tetragonal phases (t or t′).     

单晶YSZ的Xe+离子辐照效应研究

200keV Xe+离子辐照使单晶YSZ由无色透明变成紫色透明,结果表明,能量为200keV,注量为1×1017cm-22的Xe+离子辐照YSZ单晶产生的损伤高达350dpa,在损伤区产生高密度的缺陷,但仍然没有发生非晶化转变。吸收光谱测试结果表明,产生吸收带的注量阈值大约为1016cm-2。注量为1×1016cm-2和1×1017cm-2的样品,吸收带峰值分别位于522nm和497nm。光吸收带可能与Zr阳离子最近邻的氧空位捕获电子形成的F型色心和Y阳离子近邻的氧离子捕获空穴形成的V型色心有关。     

Kinetic studies of the electrochemical nitrogen reduction and incorporation into yttria stabilized zirconia

The kinetics of the electrochemical reduction of molecular nitrogen at gold micro electrodes on yttria stabilized zirconia (YSZ) solid oxide electrolyte is studied by steady state polarization measurements. From the η / lg i plot for both cathodic and anodic polarization the apparent transfer coefficients α_a and α_c are evaluated. The sum of α_a + α_c exceeds unity and thus a multistep electron transfer process is suggested. The concept of the stoichiometric number is applied to the electrode reaction N₂ + 6e⁻ = 2N³⁻ supposing that the overall process involves at least two intermediate species. On the basis of the evaluation of the experimental results the reaction N₂⁻ + e⁻ ⇌ N₂²⁻ is suggested as the rate determining reaction step for the cathodic nitrogen reduction and nitride formation.     

Anisotropic interface magnetoresistances in Pt(111)/Co n /Pt(111)

It is shown in terms of a fully relativistic spin-polarized ab initio-type approach that in Pt/Co/Pt trilayers two types of anisotropic magnetoresistance (AMR) have to be distinguished: an in-plane and an out-of-plane AMR. The obtained results, namely the magnetic field dependence as well as the thickness dependence of both AMR types are in very good agreement with a very recent experimental study, in which the in-plane as well as the out-of-plane AMR was reported for this system. The difference between the two types of AMR is visualized in terms of layer-resolved resistivities. In particular, it is confirmed that the anisotropic interface magnetoresistance (AIMR) introduced in the recent publication mainly originates in the vicinity of the Co/Pt interfaces.     

Tunable interface anisotropy in a Pt/Co_(1-x)Fe_x/Pt multilayer

Interfacial magnetic anisotropy in a Pt/Co1-xFex /Pt multilayer is tuned by doping iron atoms into the cobalt layer.The perpendicular magnetic anisotropy and out-of-plane coercivity are found to decrease with increasing x.For a specific x,the out-of-plane coercivity acquires a maximal value as a function of the thickness of the CoFe layer.At low temperature,the coercivity is enhanced.Small coercivity but reasonably large perpendicular magnetic anisotropy can be obtained by controlling the x and CoFe layer thickness.     

Characterization of low temperature protonic conductivity in bulk nanocrystalline fully stabilized zirconia

We investigated the conductivity of samples of bulk nanometric cubic yttria stabilized zirconia (YSZ 8%) with a grain size of about 16 nm and a relative density above 98%. In an oxygen atmosphere the material showed a large grain boundary resistivity. However, when exposed to a moist atmosphere at temperatures below 150 °C it showed a high conductivity, several orders of magnitude higher than the corresponding extrapolated ionic conductivity. A fairly high conductivity was measured even at room temperature. The conductivity was strongly dependent on the water partial pressure and showed a distinct isotopic effect, suggesting a protonic conductivity mechanism. This effect was not observed in samples with grain size above 50 nm, suggesting the possibility that nanostructure can induce drastic modification in the conduction mechanism of ceramic electrolytes.     

Electrode reaction at Pt,O2(g)/stabilized zirconia interfaces. Part I: Theoretical consideration of reaction model

This study aims to make clear the reaction kinetics at Pt, O₂(g)/zirconia electrodes in the oxygen partial pressure, P_O2, of ∼ 10⁻⁴ − 1 atm at ∼ 400–∼800°C. By a critical review on the preceding studies, problems were pointed out in the application of the Langmuir adsorption isotherm to the P_O2 dependence of electrode conductance, in the assumption of electric double layer at the electrode interface, and of the inconsistency between the recent reaction model of surface diffusion controlled kinetics and the absolute rate theory. It was shown that the charge transfer kinetics cannot be the rate determining step (RDS) of the electrode reaction. The possible RDS was concluded to be either (i) dissociative adsorption of oxygen molecules on the Pt surface or (ii) surface diffusion of O_ad atoms on the Pt surface to the Pt/zirconia contact. The diffusion of O_ad atoms on the Pt surface was considered to be proportional to θ(1−θ)(∂μ_O/∂x), where θ is the occupancy of O_ad atoms on Pt and μ_O is the oxygen chemical potential on the Pt surface. The rate equation, current-potential relationship, and the electrode conductivity, σ_E, were calculated for the cases the RDS is (i) and (ii), respectively. By comparing the calculated σ_E versus log P_O2 relationship with the reported ones, it was shown that the RDS is (i) for T ≲ 500°C and is (ii) for T ≳ 600°C. In the former case, σ_E is essentially constant irrespective to P_O2, and in the latter case, σ_E maximum appears on the σ_E versus log P_O2 relations.     

Epitaxy of Pt on Au(001): Growth mode,interface state and Pt core-level shifts

The epitaxial growth of Pt deposited on Au(001) has been investigated by means of photoemission. The growth mode is layer-by-layer with an important degree of imperfection. Polar scans of the Pt 4f line intensities reveal qualitatively the degree of non-sequential filling of the different atomic layers. UPS measurements show evidence for an interface state at 1.0 eV below the Fermi energy. Core-level binding energy shifts of Pt atoms have been measured as a function of overlayer thickness.     

The low temperature water formation reaction on Pt(111): A static SIMS and TDS study

The formation of water by the reaction of preadsorbed oxygen with hydrogen on a Pt(111) surface has been characterized, using secondary ion mass spectroscopy, below the desorption temperature of H₂O (180 K). The concentration of chemisorbed water was monitored during the reaction by following the SIMS H₃O⁺ signal. Reaction profiles were measured over a temperature range of 120 to 153 K, and an H₂ pressure range of 10^-9 to 10^-6 Torr. Under all conditions the reaction profiles were characterized by an induction time, a region of rapid reaction, and finally a steady decline in the rate. In the rapid region, an overall activation energy of 2.9 ± 0.3 kcalmol^-1 and a half-order H₂ pressure dependence were observed. At low initial oxygen concentrations the induction time increased and the maximum rate decreased. The reaction was slow in the absence of gas phase hydrogen, even when the surface coverage of hydrogen was relatively high. Water and hydrogen thermal desorption spectra, measured after stopping the reaction by removal of gas phase hydrogen, were complex functions of the H₂ exposure, exhibiting several peaks between 170 and 400 K. However, after an exposure large enough to drive the reaction to completion, only one H₂O peak at 173 K and one H₂ peak at 350 K were observed. The results indicate that only a fraction of the total H(a) on the surface was readily available for reaction during H₂ exposure at T ? 153 K. the remainder either recombined to form H₂ or reacted with O(a) during the thermal desorption ramp. There is good evidence for a surface rearrangement during the induction period. A model is proposed which involves the formation of water clusters that accelerate the rate.     

A competition between (0 0 1) and (0 1 1) alignments in yttria stabilized zirconia thin films fabricated by ion beam assisted deposition

Biaxially textured yttria stabilized zirconia (YSZ) thin films, were deposited on glass substrates by ion beam assisted deposition method with different deposition time. As contrasts, films were also fabricated without assisting ion beam. The orientation properties of the films were characterized by X-ray diffraction. A comparative study shows that there is a competition between (0 0 1) and (0 1 1) alignments during the growth process. Assisting ions make the films (0 0 1)-advantaged and biaxially textured. The competitive growth and the orientation development are explained by selective resputtering and anisotropic damage on growing films induced by assisting ions.     

A temperature programmed desorption study of the reaction of methylacetylene on Pt(111) and Sn/Pt(111) surface alloys

The adsorption and reaction of methylacetylene (H₃CC≡CH) on Pt(111) and the p(2×2) and

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surface alloys were investigated with temperature programmed desorption, Auger electron spectroscopy and low energy electron diffraction. Hydrogenation of methylacetylene to form propylene is the most favored reaction pathway on all three surfaces accounting for ca 20% of the adsorbed monolayer. Addition of Sn to the Pt(111) surface to form these two ordered surface alloys suppresses the decomposition of methylacetylene to surface carbon. The alloy surfaces also greatly increase the amount of reversibly adsorbed methylacetylene, from none on Pt(111) to 60% of the adsorbed layer on the

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surface alloy. Methylacetylene reaction also leads to a small amount of desorption of benzene, along with butane, butene, isobutylene and ethylene. There is some difference in the yield of these other reaction products depending the Sn concentration, with the (2×2)-Sn/Pt(111) surface alloy having the highest selectivity for these. Despite previous experiments showing cyclotrimerization of acetylene to form benzene on the Pt–Sn surface alloys, the analogous reaction of methylacetylene on the alloy surfaces was not observed, that is, cyclotrimerization of methylacetylene to form trimethylbenzene. It is proposed that this and the high yield of propylene is due to facile dehydrogenation of methylacetylene because of the relatively weak H–CH₂CCH bond compared to acetylene. The desorption of several C₄ hydrocarbon products at low (<170 K) temperature indicates that some minor pathway involving C–C bond breaking is possible on these surfaces.     

High coverage states of oxygen adsorbed on Pt(100) and Pt(111) surfaces

Oxygen adsorption on the Pt(100) and Pt(111) surfaces was investigated using X-ray photo-emission and thermal desorption spectroscopies. Low pressure (ca. 10^?5 Pa) oxygen dosing at near ambient crystal temperature resulted in the formation of dissociated adsorbed species at saturation coverages of nominally 0.2–0.25 monolayer on both surfaces. The combination of higher pressure (ca. 10^?3 Pa) and higher surface temperature (570 K) dosing produced a three to five times higher saturation coverage than the low pressure dosing. The effect of dosing condition on the saturation coverage appears to reconcile apparent discrepancies for the Pt(100) surface in the literature. Characterization by XPS of the higher coverage state for oxygen showed that it is in the same chemical state as the oxygen adsorbed at very low coverage. Angle-resolved XPS has shown that in all cases the oxygen appears to reside on the surface with no significant penetration of oxygen into the bulk, as would be characteristic of oxidation. However, some penetration on the surface by oxygen, such as by a place-exchange type restructuring of the first two atomic layers, cannot be entirely ruled out.     

High temperature magnetic behaviour of (GdxY1−x)Fe2 compounds

The thermal variation of reciprocal susceptibility of (Gd_xY_1?x)Fe₂ compounds obeys a Néel type variation. Both the effective and saturation iron moments decrease with the increase of yttrium content. A correlation between the exchange fields acting on iron magnetization and the Fe ordered moment is evidenced. Finally, the magnetic behaviour of iron atoms in these compounds is discussed.     

Charge trapping at Pt/high-k dielectric (Ta2O5) interface

A detailed analysis of the effects of constant low current injection was done, both in accumulation (J=0.001-0.2 mA cm⁻²) and in inversion (J=0.001-0.04 mA/cm²). The samples under investigation were metal-insulator-silicon structures containing high-k dielectric Ta₂O₅ radio frequency sputtered on p-type Si wafers, with Pt metal gate electrodes. The obtained results were compared with the ones obtained for Al gate samples. This experiment confirms the occurrence of charge trapping in the case of high-work-function Pt as metal. The effect has been attributed to emitting of electrons into the Pt conduction band during which creation of empty traps in the dielectric occurs, which then attract electrons injected in the dielectric. In order to examine the reversibility of the process, successive short runs as well as long runs (up to 10000 s) were performed.