High Selective deNO x Electrochemical Cell with Self-Assembled Electro-Catalytic Electrode

A new family of electrochemical cells for decomposition of NO gas in the presence of excess O₂, in which the cathode was covered with mixed oxide layer of NiO and YSZ (electro-catalytic electrode) were designed and investigated. The deNO_x properties were increased by microstructural and compositional control of the electro-catalytic electrode. Nano-size Ni grains were self-assembled at NiO/YSZ interfaces by oxidation-reduction reaction of the NiO during the cell operation. In order to use the reduced Ni for NO decomposition reaction effectively, the authors investigated multilayering of the electro-catalytic electrode. Through this process, the adsorption of coexisting O₂ was prevented and the deNO_x properties of the electrochemical cell were improved.     

Preparation of BaPbO3 Electrode Thin Films by RF Magnetron Sputtering

For electrode materials of Pb(Zr,Ti)O₃ (PZT) thin films in ferroelectric random access memory (FeRAM), various materials have been studied. As new electrode material with which the polarization and fatigue properties are improved, we take notice of barium metaplumbate BaPbO₃ (BPO). Because the BPO contained lead (Pb) and oxygen is conductor that adopted same perovskite structure as PZT. BPO thin films were prepared by rf magnetron sputtering on various substrates. (SiO₂/Si, MgO, Al₂O₃ and Pt-coated substrates), and influence of growth conditions (sputtering gas, rf power, the substrate-heating temperature and post anneals) on crystallization and conductivity were investigated. In case of post anneal after sputtering at room temperature, perovskite single phase was obtained above 400°C. In case of substrate heating while sputtering, without post anneal, perovskite single phase was obtained at 350–500°C on SiO₂/Si substrates (110) preferred orientation BPO films obtained at low temperature, and resistivity of the films decreased at decreasing sputtering temperature. Resistivity of the film at substrate temperature 350°C was 3 × 10^?3 Ω cm. In the case of single crystal substrate, the BPO films were epitaxially grown. Orientation of the films was varied with the sputtering condition. The epitaxial PZT thin films were also grown on the BPO, revealing that PZT(111)[011] //BPO(111)[011] //Pt(100)[011] //MgO(100)[011] and PZT(111)[011] //BPO(111)[011] //Pt(111)[011] //Al₂O₃(001)[100] structures were obtained, and their ferroelectric properties were also evaluated.     

Approximate calculation of triboelectric charge density (σ) of nanoscale contact electrification

We have analytically approximated the triboelectric charge densities generated by triboelectrification reaching equilibrium over time in contact-mode TENG. It is assumed that the surface density of states (SDOS), N_s(E) is constant. The amount of electron transfer at the interface is estimated by calculating the change in vacuum energy level due to the charge density induced in the upper metal electrode and the lower metal electrode within the nanoscale separation range. Numerical results show that N_s(E) and work function difference are dominant compared to dielectric constant (material property) and dielectric thickness (structure parameter).     

Ferroelectric switching and fatigue behavior for PZT/YBCO thin film heterostructures

Abstract

The dielectric and ferroelectric properties for Au/Pb(Zr,Ti)O₃/YBa₂Cu₃O_7?x heterostructures at low temperatures are reported. The fatigue behavior and the ferroelectric switching effect for the structures are also investigated. The PZT/YBCO thin film heterostructures were deposited on MgO(100) substrates by laser ablation. The ferroelectric and dielectric properties and optical response of the oriented PZT films with different thicknesses have been studied over the temperature range from 20 K to 300 K. The dielectric loss of the structure was found to decrease by an order of magnitude when the YBCO bottom electrode became superconducting. A very low fatigue rate of the structure has also been obtained below T _c of YBCO layer.     

Dielectric properties and schottky barriers in silver tantalate-niobate thin film capacitors

Abstract

Submicron thick ferroelectric Ag(Ta,Nb)O₃ films have been pulsed laser deposited on the bulk Pt₈₀lr₂₀ polycrystalline substrates. They are ferroelectric at temperatures below 125 K with the remnant polarization of 0.4 μC/cm² @ 77K and paraelectric at higher temperatures with tanδ@ 100 kHz as low as 0.015. Extensive I-V characterization has been performed in a wide temperature range 77 K to 350 K for vertical Me/Ag(Ta,Nb)O₃/Pt₈₀Ir₂₀ capacitive cells, where the metals Me = Pd, Au, Cr, and Al have been used as a top electrode. The electronic transport in thin Me/Ag(Ta,Nb)O₃/Pt₈₀Ir₂₀ capacitors follows the Schottky emission mechanism with the barrier height for the Pd, Au, Cr, and Al of 0.85, 0.8, 0.74, and 0.69 eV, respectively.     

Thermoelectric properties of Bi and Cu co-doped Ca3Co2O6single crystals

Single crystals of Bi and Cu-doped Ca₃Co₂O₆were synthesized in a molten K₂CO₃flux. Using an obtained single crystal of (Ca_0.985(5)Bi_0.015(5))₃(Co_0.990(3)Cu_0.010(3))₂O₆elongated to the c-axis direction of the crystal structure, the electric resistivity (ρ) and Seebeck coefficient (S) were measured from room temperature to over 1000 K in air. The single crystal showed p-type semiconducting behavior with ρ values of 1.8 Ω cm at 303 K and 0.017 Ω cm at 1000 K. The S values were +254 μ VK^{− 1} at 325 K, +360 μ VK^{− 1} at 420 K, and +214 μ VK^{− 1} at 1000 K. The power factor (S ² ρ ^{− 1}) increased with an increase of temperature and attained 2.70 × 10^{− 4} Wm^{− 1}K^{− 2} at 1000 K.     

Charge storage at the Pt/YSZ interface

The electrochemical behavior of Pt/YSZ electrodes in oxygen containing atmosphere at 450 °C has been investigated by double-step chronoamperometry and programmed linear sweep cyclic voltammetry. The response of the O₂(g),Pt/YSZ system in these experiments could be separated into a time dependent and a steady state contribution, the former being dominated by pseudocapacitive processes. It is proposed that Pt–O type species were stored via different processes at three different locations in the O₂(g),Pt/YSZ system: (1) Build-up of a platinum oxide monolayer at the Pt/YSZ binary interface. (2) Formation of Pt-O species at the triple phase boundary and their spreading-out along the Pt/gas interface. (3) Growth of the platinum oxide layer from the binary Pt/YSZ interface toward the bulk of the platinum electrode.     

Cathodic Polarization Study on Doped Lanthanum Gallate Electrolyte Using Impedance Spectroscopy

The perovskite electrolyte La_{1 – x}Sr_xGa_{1 – y}Mg_yO₃ (LSGM) has received a lot of interest in recent years after it was first reported to have significantly higher oxygen-ion conductivity than conventional YSZ. A very large fraction of the total polarization losses in SOFC is known to occur at the electrode-electrolyte interfaces manifesting itself as the kinetic barrier to charge-transfer reactions. AC complex impedance spectroscopy studies were conducted on symmetrical cells of the type [air, electrode/LSGM electrolyte/electrode, air] to measure the charge-transfer polarization at the cathode-electrolyte interfaces. The electrode materials were slurry-coated on both sides of the LSGM electrolyte support. The cathode materials investigated in this study include La_{1 – x}Sr_xMnO₃(LSM), LSCF (La_{1 – x}Sr_xCo_yFe_{1 – y}O₃) and a two-phase particulate composite consisting of LSM +doped-lanthanum gallate (LSGM). Symmetrical cell studies were also performed on SOFC anode materials. The principal anode material investigated in this study is a porous composite of Ni-gadolinium doped ceria (GDC). It is well known that Ni reacts with the state-of-the-art LSGM anode material. Thus our approach is to use a barrier layer of GDC between the Ni-GDC anode and the LSGM electrolyte. This paper will focus on the influence of microstructure, electrode composition, electrode thickness, interfacial compatibility and electrode processing conditions on cathode and anode polarization.     

Sintering Behavior and Interfacial Analysis of Ni/Cu Electrode with BaTiO<Subscript>3</Subscript> Particulates

The sintering behavior of Ni electrode alloyed with Cu and the interfacial structure between Ni/Cu to BaTiO₃ (BT) have been investigated. The quantitative properties, which include thermal shrinkage, thermal expansion, wetting behaviors of Ni/Cu alloys on BT sheet, and composition distribution were measured by several thermal analysis techniques (TGA/DTA/TMA) and microstructural techniques (SEM/TEM/ HRTEM) with energy-dispersive spectroscopy (EDS). The shrinkage of the Ni/Cu/ BaTiO₃ composite tested in 5%H₂/N₂ atmosphere showed strong influence by the addition of Cu, and retarded slightly due to the addition of the BT particulates. The Cu alloyed with Ni improves the continuity of the electrode and does not trigger mutual reaction between Ni and BT.     

Supression of size effects in ferroelectric films

Abstract

It is widely reported that the dielectric permittivity of ferroelectric films decreases with decreasing film thickness, and understanding and controlling these size effects are very important for charge storage application of these films. By combining phenomenological theory with careful experimental work, we have shown that the form of the boundary condition for the polarization plays a decisive role in the manifestation of size effects in ferroelectric films. We have taken two extreme boundary conditions to prove our point. For the case normal electrodes, it is assumed that the boundary condition for the component of polarization vector at the ferroelectric/electrode interface is P = 0. This case corresponds to the presence of a strong edge field, resulting in “freezing out” of the ferroelectric polarization at the interface and thus exhibiting severe size effects. However, if one utilizes conductive oxide electrodes that are ferroelectric in nature the polarization would not vanish at the ferroelectric/electrode interface and therefore the size effects are largely suppressed. To prove our point and to eliminate grain size, stress, and compositional effects, epitaxial SrTiO₃ thin films with stoichiometric composition on SrTiO₃ single crystal substrates were investigated. In fact, the experimental data also indicates that the use of ferroelectric electrodes indeed suppresses the size effects.     

Surface and morphological investigation of the electrode/electrolyte properties in an all-solid-state battery using a Li<Subscript>2</Subscript>S-P<Subscript>2</Subscript>S<Subscript>5</Subscript> solid electrolyte

All-solid-state lithium-ion batteries represent a promising battery technology thanks to the replacement of the volatile and flammable state-of-the-art liquid electrolyte by a solid electrolyte. Despite the recent progress in the synthesis of sulfide based solid electrolyte with high ionic conductivity, little is known about the interface reactivity of the solid electrolyte with electrode materials. In this study, we synthesized and characterized an amorphous solid electrolyte with the nominal composition (Li₂S)₃(P₂S₅). We assessed the feasibility of using this electrolyte at the laboratory scale, and we discuss the potential challenges that govern its electrochemical performance. Galvanostatic cycling and rate performance measurements were conducted using lithium titanium oxide (Li₄Ti₅O₁₂) as the negative electrode material. The electrochemical measurements were performed using two different counter electrodes, namely Li metal and an InLi_x alloy. The alloy counter electrode suppressed the formation of lithium dendrites, resulting in increased cycling stability and cell safety. Post mortem X-ray photoemission spectroscopy measurements reveal the reactivity of the solid electrolyte Li₃PS₄ with the Li₄Ti₅O₁₂, lithium metal, and InLi_x alloy.     

Pb(Mg1/3Nb2/3)0.97Ti0.03O3 Ferroelectric Thin Films, Deposited by Laser Ablation on TiN Bottom Electrodes

Pb(Mg_1/3Nb_2/3)_0.97Ti_0.03O₃ (PMNT) polycrystalline thin films were deposited on Titanium Nitride electrode at different temperatures by laser ablation, using a wavelength of 248 nm. The morphology of the films was analyzed by scanning electron microscopy (SEM). The nature of the ferroelectric layer-electrode interface is studied by transmission electron microscopy (TEM) as well as the effect of its characteristics in the performance of the multilayer system. The influence of the annealing temperature on the dielectric properties was studied by hysteresis and fatigue measurements.     

Study of Temperature Dependence of Electrode–Glass Ceramic Interface Using Impedance Spectroscopy

The electrical behavior of strontium titanate borosilicate glass ceramics (SrO.TiO₂- 2SiO₂.B₂O₃) with additives K₂O, La₂O₃, CoO and Nb₂O₅ was studied by using Impedance Spectroscopy as a function of temperature and composition. An equivalent circuit model having three parallel RC's connected in series with a capacitor C₄ could represent the data well. By comparing the complex modulus plots with simulated ones and looking at the values of the time constants these RC's were attributed to represent crystalline, glassy and glass-crystal interface regions of the glass- ceramic whereas C₄ represented the glass-ceramic sample and contact electrode interface. When the glass ceramic sample contained only SrTiO₃ crystalline phase and the remaining glassy matrix, the interface capacitance showed an Arrhenius type of nature with an activation energy (0.11 ± 0.04) eV and when the glass- ceramic sample contained number of crystalline phases no clear cut trend appeared. These findings are useful in selecting suitable electrodes for applications as well as in deciding upon experimental techniques for measurement of dielectric constants of materials.     

Crack formation in MLCCs depending on position with and without post-heat treatment

The crack formation behavior and mechanical properties, hardness (H), modulus (E), and fracture toughness (K _IC), at each plane of BaTiO₃ based multilayer ceramic capacitors (MLCCs) have been investigated and estimated using a nanoindentation technique, including effects of the post-heat treatment and the external electrode on the crack formation and mechanical properties. The crack length in each plane, length (x plane) and width (y plane) planes, has been measured for MLCCs with and without the post-heat treatment, as a function of the distance from the internal electrode. H and E values are 11.5–12.0 GPa and 175–190 GPa, respectively, independent of the plane and the post-heat treatment. The crack length in the x plane is smaller than that in the y plane, which is gradually increased as the indentation position is far away from the internal electrode. The external electrode affects the crack formation in regions near to the internal electrode, showing small crack length till 20 μm from the internal electrode. K _IC values in the x plane are larger than those in the y plane. The external electrode affects only the K _IC values in the x plane within the error range, without effect of the post-heat treatment.     

Oriented growth of Bi3.25La0.75Ti3O12 thin films on RuO2/SiO2/Si substrates by using the polymeric precursor method: Structural, microstructural and electrical properties

c-axis oriented Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin films were grown on a RuO₂ top electrode deposited on a (100) SiO₂/Si substrate by the polymeric precursor method. X-ray diffraction and atomic force microscope investigations indicate that the films exhibit a dense, well crystallized microstructure having random orientations with a rather smooth surface morphology. The electrical properties of preferred oriented Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin films deposited on RuO₂ bottom electrode leaded to a large remnant polarization (P _r ) of 17.2 μC/cm² and (V _c ) of 1.8 V, fatigue free characteristics up to 10¹⁰ switching cycles and a current density of 2.2 μA/cm² at 5 V. We found that the polarization loss is insignificant with nine write/read voltages at a waiting time of 10,000 s. Independently of the applied electric field the retained switchable polarization approached a nearly steady-state value after a retention time of 10 s.     

Characteristics of N2/SF6 mixture gas in creeping discharge developing in narrow gap with backside electrode

The flashover voltage with a backside electrode was found to be lower than that without the backside electrode. Under microsecond pulse voltage application, we describe the characteristics of a creeping discharge developed in the narrow gap with the backside electrode. Using a CCD camera and ultrahigh‐speed camera, we observed the corona extension processes. The lowest flashover voltage was found to be obtained at positive polarity with a SF₆ content D = 3%. In the corona extension obtained using an ultrahigh‐speed camera, peculiar differences were observed in the corona extension process. The corona extension increased, and rapid flashover was observed at D = 3%. Using a CCD camera, small coronas were detected from the backside electrode. © 2006 Wiley Periodicals, Inc. Electr Eng Jpn, 158(2): 31–38, 2007; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/eej.20431     

Microwave Dielectric Relaxation in Binary Mixtures of 1,3-Diaminopropane in Dimethylaminoethanol

Abstract

The dielectric dispersion ε′ and dielectric loss ε″ of binary mixture of 1,3-diaminopropane-N,N-dimethylaminoethanol were measured by employing the time domain reflectometry technique over a frequency range 10?MHz to 20?GHz at 288?K, 298?K, 308?K, and 318?K. To evaluate various dielectric parameters, the frequency dependents complex permittivity (ε* (ω) = ε′ – jε″) data viz., dielectric constant (ε₀)_, relaxation time (τ), and permittivity at high frequency (ε_∞) were fitted by the nonlinear least-squares fit method to Debye expression. Temperature dependent ε₀, τ, Kirkwood correlation factor (g^eff), and free energy of activation (ΔG) have been determined and discussed in terms of the effect of -NH₂ and -CH₃ side-group on molecular dynamics and intermolecular hydrogen bonds.     

Effect of substrate surface modification using Ag nano-dots on the improvement of J c and microstructures in YBa2Cu3O7 thin films grown on LaAlO3 (100) by pulsed laser deposition

YBa₂Cu₃O₇ (Y123) thin films were grown by pulsed laser deposition (PLD) on LaAlO₃ (100) substrates whose surfaces were modified by a discontinuously layer of Ag nano-dots. The Y123 films were characterised by atomic force microscope, X-ray diffraction, scanning electron microscope, and DC magnetization measurements. Effect of substrate surface modification using various densities of the Ag nano-dots on the improvements of critical current density J _c and microstructures in the Y123 films has been studied systematically. The results showed that at fixed physical deposition conditions J _c increased with the number of Ag shots, n. Zero field J _c at 77 K increased from 10⁶ to 3.3 × 10⁶ A/cm², and from 1.5 × 10⁷up to 4 × 10⁷A/cm² for 5 K as the number of Ag shots increased from zero to 150. However, a fluctuation of J _c was observed for n < 60 at 77 and 40 K in both low and high fields. Detailed microstructure analysis revealed that ab misalignment was gradually improved as Ag nano-dots density gradually increased and believed to be responsible for the J _c enhancement.     

Fatigue and retention of Pb(Zr0.53Ti0.47)O3 thin film capacitors with Pt and RuO2 electrodes

Abstract

Pb(Zr_0.53Ti_0.47)O₃ (PZT) thin films were deposited on Pt and RuO₂ coated Si and MgO substrates using the sol-gel process. Fatigue and retention tests were performed on these samples. The films grown on RuO₂ electrodes are fatigue-free up to nearly 10¹¹ cycles. Their retention life-time extrapolates to more than 10¹⁰ seconds. The fatigue behavior of films grown on Pt electrodes depends on the PZT film orientation. Highly oriented (001) PZT films maintain 50% of their initial P?r-P?r value after 10¹¹ cycles. The randomly oriented films maintain less than 3% of the initial P?r-P?r value after 10¹¹ cycles. However, the retention life-time of both highly oriented and randomly oriented PZT films grown on Pt electrodes extrapolates to higher than 10¹¹ seconds. It appears that fatigue of films grown on RuO₂ is mainly controlled by the film/electrode interface. On the other hand, fatigue of films grown on Pt appears to depend on both the film/electrode interface as well as on bulk effects.     

Determination of Activation Energies and Electric Dipole Moment of In‐Plane Highly Electrically Conductive Hetero‐C12TCNQ/C20 LB Films Using Thermally Stimulated Current

The activation energies of in‐plane highly electrically conductive 2‐dodecyl‐7,7,8,8‐tetracyanoquinodimethane (C₁₂ TCNQ)/arachidic acid (C₂₀) hetero‐LB films and C₁₂TCNQ homo‐LB films were determined by thermally stimulated current (TSC) measurement. The TSC curves for the upper Al electrode/C₁₂TCNQ/C₂₀/lower Al electrode were nearly of the same shape as those for the upper Al electrode/C₁₂TCNQ/lower Al electrode. The activation energies of the upper Al electrode/C₁₂TCNQ/C₂₀/lower Al electrode and upper Al electrode/C₁₂TCNQ/lower Al electrode were 0.9–1.3 eV at 55–80^°C and 1.6–1.8 eV at 105–120^°C, respectively. The TSC curves for the upper Al electrode/C₁₂TCNQ/C₂₀/lower Al electrode and upper Al electrode/C₁₂TCNQ/lower Al electrode had two peaks at 55–80^°C owing to the depolarization of the electric dipole and two peaks at 105–120^°C owing to the movement of space charges in the C₁₂TCNQ molecule. Copyright © 2008 Institute of Electrical Engineers of Japan. Published by John Wiley & Sons, Inc.