Distinct correlation between CeO2 and YSZ in out-of-plane and in-plane mosaic dispersions of heteroepitaxial CeO2/YSZ/Si(001) films

The structural correlations including the lattice constants and the mosaic dispersions between CeO₂ and yttria-stabilized ZrO₂ (YSZ) in CeO₂/YSZ/Si(001) heteroepitaxial films have been investigated by out-of-plane and in-plane X-ray-diffraction techniques. The distinct linear correlations of the full width at half-maximum (FWHM) of the ω scan between CeO₂ and YSZ have been found in both directions. CeO₂ always has a 0.7° lower FWHM of the ω scan than YSZ in the out-of-plane direction, but has a 2.6° higher FWHM in the in-plane direction. A possible relationship between the out-of-plane and in-plane FWHMs of the ω scans has been demonstrated with a lattice-rotation model. Besides, the lattice constants of CeO₂ are dependent on the FWHMs of the YSZ ω scans: as the FWHM is below 3.5°, CeO₂ has a tetragonal distortion, and as the FWHM is higher than 3.5°, CeO₂ exhibits a cubic structure without distortion. The results are of great interest, both for the fundamental understanding of the film-growth mechanisms and for potential applications. Received: 11 September 2000 / Accepted: 5 June 2001 / Published online: 30 August 2001     

Measurement of mixed conductivity in thin films with microstructured Hebb–Wagner blocking electrodes

Determination of the ionic and electronic contributions to the total conductivity in mixed ionic–electronic conductors (MIEC) is central to understanding their properties, particularly in nanostructured ionic solids. The Hebb–Wagner blocking technique, commonly used to deconvolute ionic and electronic contributions in bulk MIECs, is susceptible to misinterpretation when applied to thin films. In this work, microfabricated electronic blocking electrodes consisting of porous Pt on dense thin yttria-stabilized zirconia (YSZ) films were applied to nanocrystalline CeO₂ thin films. The validity of the blocking structure was expressly considered with respect to alternate current and gas phase reaction pathways, with criteria developed to aid in identifying spurious effects. The ionic partial conductivity in nanocrystalline CeO₂ thin films was confirmed to be pO₂-independent while the electronic partial conductivity was found to be pO₂ dependent with a power dependence of − 0.31 ± 0.02. These results are compared with theoretical predictions of extrinsically-compensated ceria and previous results on bulk nanocrystalline ceria.     

Oxygen vacancy‐induced microstructural changes of annealed CeO2−x nanocrystals

Nanocrystalline ceria (CeO₂) is known for its ionic conductivity and oxygen storage properties, which depend on the presence of oxygen ion vacancies. The vacancies cause several important changes in CeO₂ involving microstrain, electronic structure, magnetic properties, etc. In this article, we focus our attention to the microstructural changes of nanocrystalline CeO_2−x annealed at different temperatures in the range 200–500 °C. Structural and vibrational properties were investigated by X‐ray diffraction and Raman spectroscopy. It was observed that the content of oxygen vacancies changed significantly with increasing annealing temperature, which plays an important role in the observed microstructural changes of the annealed samples. We demonstrate that the observed microstrain changes, because of variable defect content, dominate over the crystallite size effect. This finding is opposite to the conclusions made by several other authors. A new mode, classified as a probable surface mode, was observed in the Raman spectra at ∼480 cm⁻¹, the appearance of which can be explained by the large defective structure and disorder in the ceria lattice. Copyright © 2011 John Wiley & Sons, Ltd.     

Different conduction behaviors of grain boundaries in SiO2-containing 8YSZ and CGO20 electrolytes

Both doped zirconia and ceria have been widely recognized as promising electrolytes in solid oxide fuel cells (SOFC). Total conductivity is an important parameter to evaluate solid electrolytes. It is well know that the contribution to the total conductivity by grain boundaries is especially pronounced for SiO₂-contaminated electrolytes. In this study, we report on the different conduction behaviors of grain boundaries (GB) found in SiO₂-containing (impure) 8YSZ (8 mol% Y₂O₃-doped ZrO₂) and CGO20 (10 mol% Gd₂O₃-doped CeO₂) ceramics. In the grain size range (∼ 0.5–10 μm) studied, the GB conductivity of impure CGO20 ceramics constantly decreases with increasing grain size, in contrast to that observed in impure 8YSZ electrolytes whose GB conductivity increases almost linearly with grain size. It is also found that the variation in GB conductivity versus grain size is different from case to case, depending on the sintering/annealing conditions used to fabricate the ceramics. Two mechanisms were proposed to explain the GB behaviors of the impure 8YSZ and CGO20 ceramics. For doped ceria, the GB phases are supposed to be inert, which do not react with or dissolve into the matrix. Increasing sintering temperature leads to not only grain growth but also change in viscosity and wetting nature of the GB phases. These two factors promote further propagation of the GB phases along the grain boundaries, leading to an increased GB coverage fraction. For doped zirconia, however, the major factor dominating the GB conduction is the further dissolution of SiO₂ into zirconia lattice as a result of increase in sintering temperature or/and time. In addition, we will also evaluate and discuss the validities of the three models that are widely used to analyze the GB conduction in solid electrolytes.     

Characterization of defect type and dislocation density in double oxide heteroepitaxial CeO2/YSZ/Si(001) films

In order to qualitatively and quantitatively analyze the structural defects including the defect types and their concentrations in oxide heteroepitaxial films, a new X-ray rocking-curve width-fitting method was used in the case of doubleCeO₂/YSZ/Si (YSZ=yttria-stabilized ZrO₂) films that were prepared by pulsed laser deposition. Two main defect types, angular rotation and oriented curvature, were found in both CeO₂ and YSZ. Dislocation densities of CeO₂ and YSZ, which were obtained from the angular rotations, are functions of the YSZ thickness. A distinct two-step correlation between dislocation densities of CeO₂ and YSZ was found that as the dislocation density of YSZ is higher than 2.4×10¹¹ cm^-2, the dislocation density of CeO₂ shows a high sensitivity with that of YSZ compared with the low relativity in lower dislocation density (<2.4×10¹¹ cm^-2). In addition, YSZ always has higher dislocation densities and oriented curvatures than CeO₂ in each specimen, which can be attributed to the smaller mosaic domain sizes in YSZ than in CeO₂ as observed by high-resolution transmission electron microscopy. Received: 12 August 2002 / Accepted: 14 August 2002 / Published online: 4 December 2002 RID="*" ID="*"Corresponding author. Fax: +81-3/5734-3369, E-mail: chun_hua_chen@hotmail.com     

Characterization of yttrium-doped ceria with various yttrium concentrations as cathode interlayers of SOFCs

This study focuses on enhancing the efficiency of solid oxide fuel cells (SOFCs) by modulating the thickness of the highly resistive solid solution layer of (Ce,Zr)O₂ formed between the yttria-stabilized zirconia (YSZ) electrolyte and the CeO₂-based interlayer on the cathode side. The effects of the concentration of dopant in CeO₂ on the thickness of the solid solution were analyzed. Yttrium-doped CeO₂ (YDC) interlayers were studied, with dopant concentrations in the range of 5–40 mol%. The results revealed that the thickness of the solid solution decreased with increasing dopant concentration up to 20 mol% and then saturated at higher dopant concentrations. In addition, the electrical conductivities of yttrium-doped ceria (YDC) and the solid solution of YSZ and YDC were measured. YDC with a dopant concentration of 20 mol% exhibited the highest conductivity. The conductivities of the YSZ/YDC solid solution decreased compared to those of YDC and YSZ for each dopant concentration, and the extent of the reductions was approximately the same for all dopant concentrations. These results indicate that a dopant concentration of 20 mol% is optimal to minimize the internal resistance of SOFCs when YDC is used as the interlayer material.     

Correlation between microstructure and degradation in conductivity for cubic Y2O3-doped ZrO2

The application of Yttria-stabilized Zirconia (YSZ) as solid electrolyte in high-temperature solid oxide fuel cells (SOFC) is well established. However, the strong decrease of the ionic conductivity in 8.5 mol% Y₂O₃-doped ZrO₂ at high temperature has not yet been clarified completely. To contribute to the understanding of the degradation process, transmission electron microscopy (TEM) was applied to analyze the microstructure in YSZ electrolyte substrates in as-sintered and aged material. Selected area electron diffraction and conventional TEM imaging were performed to investigate the evolution of different phases and phase transitions in YSZ. Grain boundary charging and the possible formation of a glassy phase at grain boundaries after aging were investigated using transmission electron holography and high-resolution TEM. The ionic conductivity was characterized by dc-conductivity measurements and impedance spectroscopy.     

CeO<Subscript>2</Subscript> and Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> modified Ni-YSZ anode for solid oxide fuel cell

Ni sintering at high temperature (～ 800 °C) operation drastically degrades the performance of Ni-yttria-stabilized zirconia (YSZ) anode in solid oxide fuel cell (SOFC). Mixed ionic and electronic conductive oxides such as CeO₂ and Nb₂O₅ enhance the dispersion of Ni, CeO₂ enhances the redox behavior and promotes charge transfer reactions, and Nb₂O₅ increases the triple phase boundary. In the present work, anode-supported SOFC is fabricated and tested in H₂ fuel at 800 °C. YSZ and lanthanum strontium manganite (LSM)-YSZ are used as the electrolyte and composite cathode with NiO-YSZ, CeO₂-NiO-YSZ, and Nb₂O₅-NiO-YSZ as an anode. The peak power density obtained for the cell with 10% CeO₂–30% NiO-YSZ anode at the 5 and 25 h of operation is 330 and 290 mW cm^?2 which is higher than that for 40% NiO-YSZ anode (275 mW cm^?2 at 5 h). The peak power density obtained for the cell with 10% Nb₂O₅–30% NiO-YSZ anode at the 5 and 25 h of operation is 301 and 285 mW cm^?2 which is higher than that for 40% NiO-YSZ anode (275 mW cm^?2 at 5 h). Physical characterization has been carried to study morphology, elemental analysis, particle size, and phase formation of the fabricated anode before and after cell operation to correlate the cell performance.     

Transitional metal-doped 8 mol% yttria-stabilized zirconia electrolytes

The sintering, grain growth and ionic conductivities (especially the grain-boundary (GB) conductivity), of 8YSZ electrolytes with various silica levels (~ 30 ppm, ~ 500 ppm and ~ 3000 ppm), doped with 1 at% transitional metal oxides (TMOs), have been systematically investigated by means of dilatometer, electron microscopy and impedance analyzer. It is confirmed that small additions of TMOs (i.e., Fe, Mn, Co or Ni) promote the densification and grain growth of both the pure and Si-containing 8YSZ. The effect of TMOs on the ionic conductivities could be negative or positive, relying on the type of TMOs, sintered density and impurity level. For the dense and pure 8YSZ (with ~ 30 ppm SiO₂), the addition of 1 at% TMOs led to a reduction in grain interior (GI) conductivity by ~ 25–33% with little effect on the GB conduction. For the impure 8YSZ (with ~ 500 ppm or 3000 ppm SiO₂), except for FeO_1.5, the other TMOs (i.e., Mn, Co or Ni) are extremely detrimental to the total conductivity by significantly reducing the GB conduction. Moreover, it is also found that the GB conductivity of the impure 8YSZ doped with Co or Ni is less sensitive to sintering temperature. FeO_1.5 showed a scavenging effect on SiO₂ in the impure 8YSZ, which is specially beneficial to the total conductivity of samples with higher silica levels and/or sintered at relatively low temperatures.     

The quantitative measurement of electromigration in CeO2−x

We present an experimental device for the measurement of electromigration in a non stoichiometric oxide which is composed principally of two symmetrical electrolytic cells: CeO_2?x-(ZrO₂, Y₂O₃)-CeO_2?x+? and which permits one to analyse the variation of the oxygen composition at the extremities of a CeO_2?x sample subjected to an electric field.The quantitative measurement of the effective charge and ionic transport numbers are discussed in terms of the reduction or elimination of such undesirable but inherent effects as the exchanges of oxygen between the sample and its neighbourhood and of the heat associated with the electrical current.     

Electrical properties of thin yttria-stabilized zirconia overlayers produced by atomic layer deposition for solid oxide fuel cell applications

Thin films of yttria-stabilized zirconia (YSZ) electrolyte were prepared by atomic layer deposition at 300 °C for solid oxide fuel cell (SOFC) applications. YSZ samples of 300-1000 nm thickness were deposited onto La_0.8Sr_0.2MnO₃ (LSM) cathodes. A microstructural study was performed on these samples and their electrical properties were characterised between 100 and 390 °C by impedance spectroscopy. A remarkable feature is that the as-deposited layers were already crystalline without any annealing treatment. Their resistance decreased when reducing the layer thickness; nevertheless, their conductivity and activation energy were significantly lower than those reported in the literature for bulk YSZ.     

Field enhanced Li ion conduction in nanoferroelectric modified polymer electrolyte systems

Nanocomposite polymer electrolyte (NCPE) films based on polyethylene oxide (PEO) complexed with lithium perchlorate (LiClO₄) and nanosized ferroelectric ceramic fillers such as BaTiO₃, SrTiO3 have been prepared using solution cast technique. The films showed very good mechanical stability when exposed to ambient atmospheres for prolonged periods. Lithium ion transport studies revealed that the conductivity is predominantly ionic. The effect of electric field on ionic conductivity of NCPE films was investigated. One order enhancement in conductivity due to the field was observed at 323 K. NCPE films exhibited conductivity of 3.46?×?10^?5 Scm^?1 at 323 K. NCPE films were characterized using differential scanning calorimetry (DSC) and X-ray diffraction (XRD) technique. The DSC and XRD studies revealed reduced crystallinity which confirmed the higher amorphous phase and hence the improved ionic conductivity.     

Synthesis,structure, and electrochemical properties of epitaxial perovskite La0.8Sr0.2CoO3 film on YSZ substrate

Epitaxial films of the perovskite, La_0.8Sr_0.2CoO₃ (LSC), for SOFCs cathode were deposited on yttria-stabilized zirconia (YSZ) single crystals by pulsed laser deposition method. The films were characterized by thin-film X-ray diffraction measurement, atomic force microscopy (AFM), transmission electron microscope (TEM), and ac impedance spectroscopy. The film orientations depend on the substrate planes. The LSC films on the YSZ (100) and (111) substrates showed the (110) orientation with different twin structures, while those on the YSZ (110) had (100) and (112) orientations. Surface morphology of the films also depends on the substrate orientations. These films showed different electrode properties depending on the orientations. The relationships between the properties, the film orientations, surface morphology, and lattice misfit are discussed.     

Silica-scavenging effect in zirconia electrolytes: assessment of lanthanum silicate formation

Yttria-stabilized zirconia (YSZ)-based composite electrolytes were produced by mixture and firing of the base electrolyte, namely with silica, and silica and lanthanum oxide, to study the impact of presence and formation of new phases on the electrical performance of the composite materials. Combined information obtained from structural, microstructural, and electrical characterization confirmed the formation of an apatite-type solid solution based on La_9.33Si₆O₂₆. The effectiveness of lanthanum oxide addition to remove silica by reaction was demonstrated. However, the conductivity of the composite electrolytes is lower than that of YSZ, probably due to lanthanum zirconate formation in-between the ceramic grains and/or relatively poor transport properties of the formed lanthanum silicate phase. The adopted procedure can be extended to other systems and combinations of properties based on predictable phase interactions.     

Mixed ion effects in Na/Ag-NaZr2(PO4)3

The ionic conductivity against the ionic ratio showed a shallow minimum in Na/Ag-NaZr₂(PO₄)₃ with a three-dimensional diffusion path. The ionic conductivity of the mixed ion system Na/Ag was calculated by means of the path probability method (PPM) using a two-dimensional honeycomb lattice model, resulting from the weak interaction between two different ions.²³Na MAS NMR spectra showed the second-order quadrupole interaction with the electric field gradient. It is concluded that the mixture of two ions in NaZr₂(PO₄)₃ with a three-dimensional diffusion path led to the conductivity minimum due to the ordered distribution of Ag and Na ions. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Spectroscopic studies of interfacial structures of CeO2-TiO2 mixed oxides

We have investigated the geometric and electronic structures of the cerium oxide (CeO₂)-titanium dioxide (TiO₂) mixed oxides with various Ce/TiO₂ weight ratios prepared by the sol-gel method in detail by means of X-ray diffraction (XRD), high-resolution X-ray photoelectron spectroscopy (XPS), Raman spectroscopy excited by 325 and 514.5 nm lasers, and scanning electron microscope (SEM). Existence of cerium effectively inhibits the phase transition of TiO₂ from the anatase phase to the rutile phase. XRD peaks of TiO₂ anatase attenuate continuously with the increasing amount of CeO₂ in the mixed oxide, but the XRD peaks of cubic CeO₂ appear only after the weight ratio of Ce/TiO₂ reaches 0.50. The average crystalline sizes of TiO₂ anatase and cubic CeO₂ in CeO₂-TiO₂ mixed oxides are smaller than those in the corresponding individual TiO₂ anatase and cubic CeO₂. Raman spectroscopy excited by the 514.5 nm laser detects CeO₂ after the weight ratio of Ce/TiO₂ reaches 0.70 whereas Raman spectroscopy excited by the 325 nm laser detects CeO₂ after the weight ratio of Ce/TiO₂ reaches 0.90. XPS results demonstrate that Ti exists in the form of Ti⁴⁺ in the CeO₂-TiO₂ mixed oxide. Ce is completely in the form of Ce³⁺ in the mixed oxides with a 0.05 weight ratio of Ce/TiO₂. With the increasing weight ratio of Ce/TiO₂, Ce⁴⁺ dominates. On basis of these results, we proposed that CeO₂ initially nucleates at the defects (oxygen vacancies) within TiO₂ anatase, forming an interface bridged with oxygen between CeO₂ and TiO₂ anatase. At the interface, Ce species cannot substitute Ti⁴⁺ in the lattice of TiO₂ anatase whereas Ti⁴⁺ can substitute Ce⁴⁺ in the lattice of cubic CeO₂. The decreasing concentration of oxygen vacancies, the Ti-O-Ce interface, and the decreasing average crystalline size of TiO₂ anatase act to inhibit the phase transformation of TiO₂ anatase. With the increasing amounts of CeO₂, the CeO₂ clusters continuously grow and form cubic CeO₂ nanocrystals. Spectroscopic results strongly demonstrate that the surface region of CeO₂-TiO₂ mixed oxide is enriched with TiO₂.     

Characterization of the electrical properties of Y2O3-doped CeO2-rich CeO2–ZrO2 solid solutions

Electrical properties of Y₂O₃-doped CeO₂-rich ZrO₂–CeO₂ system were characterized with a view point of its point-defect structural scheme. Theoretical calculation of partial electronic and ionic conductivity from total conductivity was done to investigate the combined homovalent and aliovalent doping effect on the overall electrolytic property. According to our study, combined homovalent and aliovalent doping can be one of the key solutions to overcome the fatal disadvantage of limited electrolytic stability of doped ceria system by which properly enhances the ionic conductivity and suppresses the electronic conductivity all at once. Feasibility and limitation of Y₂O₃-doped CeO₂-rich ZrO₂–CeO₂ system as a potential alternative electrolyte material for low or intermediate temperature SOFC were discussed.     

Meter-long CeO2/YSZ/Y2O3 buffer layers for YBCO coated conductors using DC reactive sputtering

This paper reports CeO₂/YSZ/Y₂O₃ buffer layers deposited on biaxially textured NiW substrates by DC reactive sputtering in a reel-to-reel system. The effect of partial pressure of water vapor (P_H2O) on surface morphology and orientation of the Y₂O₃ films was examined. The obtained CeO₂/YSZ/Y₂O₃ buffer layers exhibit a highly biaxial texture, with in- and out-of-plane FWHM values respectively in the range of 6.0–7.0° and 4.5–5.5°. Crystallographic consistency of CeO₂/YSZ/Y₂O₃ along meter length is excellent. Atomic force microscope observation (AFM) reveals a smooth, continuous and crack-free surface with a Root-mean-square roughness (RMS) lower than 10 nm.     

Structural investigations of the ionic conductivity in zirconia single crystals by neutron diffraction at high temperatures and simultaneously applied electric field

In situ neutron diffraction studies of CaO and Y₂O₃ stabilized zirconia single crystals were performed at elevated temperatures and simultaneously applied DC electric field, i.e. lasting ionic current. Bragg data from Zr_0.85Ca_0.15O_1.85 (CSZ15) were collected at room temperature without electric field, at 1170 K and 1370 K without and with 3.5 V and 1.8 V, respectively, (field vector Ell[111]), which generated a current of 60 mA in each case. In case of Zr_0.70Y_0.30O_1.85 (YSZ15) the electric field vector was directed along [001]. At 1170 K three data sets were collected: without field, with 1.5 V (I=60 mA), and with 2.5 V (I=120 mA). Atomic displacement parameters (a.d.p.'s) were derived in the frame of a non-Gaussian Debye-Waller factor formalism for the oxygens. Corresponding probability density function (p.d.f.) maps and pseudo potential maps were calculated. Most probable curved diffusion pathways run close to 〈 100 〉, independent of the external field direction, applied voltage and the kind of dopant. With lasting ionic current the potential corresponding to p.d.f. >1% is lowered by about 0.06–0.07 eV.     

Microstructure — Property relationships in nanocrystalline oxide thin films

Results of studies of the preparation, structure and physical properties of nanocrystalline CeO₂, ZrO₂:16%Y (YSZ) and SrCeO₃:5%Yb oxide thin films are presented. A polymeric precursor spin coating technique has been used to obtain dense specimens with stable and uniform microstructure controlled in the grain size range of 1–400 nm. A variety of characterization techniques including X-ray diffraction, impedance spectroscopy, Raman scattering and optical absorption have been used for the evaluation of the microstructure-property relationships. Nanocrystalline specimens are characterized by enhanced electrical conductivity and different stoichiometry compared with microcrystalline materials. A direct comparison has been achieved between the conductivity and quantum confinement effects observed in optical measurements and correlated with a defect model. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.