Stable suspensions of doped ceria nanopowders for electrophoretic deposition of coatings for solid oxide fuel cells

We have studied nonaqueous suspensions of Ce_0.8Sm_0.2O_1.9 (CSO), Ce_0.8Gd_0.2O_1.9 (CGO), and Се_0.8(Sm_0.75Sr_0.2Ba_0.05)_0.2O_2–δ (CSSBO) nanopowders produced by laser evaporation of a target. The nanoparticles were nearly spherical in shape and their average diameter was 9, 7, and 15 nm, respectively. Using ultrasonic processing, we obtained stable nanopowder suspensions in an isopropanol + acetylacetone mixed medium, investigated their particle size composition, evaluated their zeta potential as a function of pH, and obtained potentiometric titration curves. The starting nanopowder suspensions have been shown to be weakly acidic and have a rather high initial zeta potential. During titration of the nanopowder suspensions with 0.17 N KOH in isopropanol, no isoelectric point was observed. The maximum positive values of the zeta potential, favorable for electrophoretic deposition (EPD), were reached in weakly acidic media in the pH range 4–6. Using EPD, we obtained a coating from a stable self-stabilized CSSBO suspension (ζ = +31 mV, pH 4.0), which was then sintered in air at a temperature of 1400°C. Our results demonstrate that the starting nonaqueous suspensions of the CSO, CGO, and CSSBO nanopowders suit well for producing gas-tight, homogeneous solid oxide fuel cell coatings by EPD.     

LaNiO3凝胶薄膜微细图形的制备

采用溶胶-凝胶工艺,以Ni(Ac)_2、La(NO_3)_3为前驱原料,以乙醇和乙二醇甲醚为溶剂,以丙烯酸为稳定剂,乙酰丙酮(AcAc)为化学修饰剂制备了感光性LNO溶胶。通过其溶胶的紫外和红外吸收光谱研究了感光性LNO溶胶的紫外感光机理,并运用溶胶-凝胶直接感光法制备出LNO薄膜的微细图形。     

Effects of bottom electrodes on dielectric properties of epitaxial 2% Mn doped Ba(Zr<Subscript>0.2</Subscript>Ti<Subscript>0.8</Subscript>)O<Subscript>3</Subscript> thin films

2 mol% Mn doped Ba(Zr_0.2Ti_0.8)O₃ (Mn-BZT) thin films were prepared by pulsed laser deposition (PLD) on single crystal oxide substrates LaAlO₃(001) and MgO(001), with conductive oxide bottom electrodes LaNiO₃ and SrRuO₃, respectively. Both the Mn-BZT films and the bottom electrode films could be c-axial oriented with a cube-on-cube arrangement on the corresponding substrates. The dielectric properties measured with parallel plate capacitor configurations of Au/Mn-BZT/LNO and Au/Mn-BZT/SRO revealed that the Mn-BZT film on LNO bottom electrode exhibited comparatively higher dielectric constant, larger dielectric tunability and lower dielectric loss than that on SRO. It could be mainly attributed to the better epitaxial growth characteristics and mismatch stress of Mn-BZT thin film on LNO, as well as less misfit dislocation and the better morphology of LNO bottom electrode.     

Characterization of Sn-doped BST thin films on LaNiO<Subscript>3</Subscript>–coated Si substrate

Sn-doped (Ba,Sr)TiO₃(BSTS) thin films have been deposited on highly (200) oriented LaNiO₃(LNO) thin films by sol-gel method. The atomic force microscope (AFM) images exhibited that the dopant Sn did not decrease the crystalline grain size of BST thin films. The structure of the BST film, determined by X-ray diffraction (XRD), presented the higher intensity (110) and (200) peaks, while the latter was distinctly induced by LNO layer. Evidently, Sn-doped BST thin films on LNO/Si substrate were found to decrease the dielectric constant and the dielectric loss, which is favourable to potentially improve the figures of merits (F _D ) of pyroelectric materials. The BSTS thin films on LNO layer also displayed an excellent leakage current property comparing with the BST thin film on Pt/Ti/SiO₂/Si and LNO/Si substrates.     

Effect of heat-treatment on LaNiO3 film electrode of PZT thin films derived by a sol–gel method

Lanthanum nickel oxide (LaNiO₃ or LNO) conducting thin films that could be used as electrodes for improving fatigue and aging properties of ferroelectric thin films were investigated. In this paper, LNO films were directly spin-coated onto SiO₂/Si(1 0 0) substrates followed by thermal treatment in air and in oxygen. It was found that crack-free dense and uniform films with good crystallinity and medium grains were obtained, preferentially (1 0 0)-oriented LNO thin films could be formed at a lower annealing temperature of 550 °C and that with the increase in thermal annealing temperature the LNO thin film possessed better electrical properties especially at 750 °C. However, the LNO film displayed a structure transformation above 850 °C. A phenomenon was found that the first heat-treatment temperature and time played a key role to determine the crystallite size of LNO films. A subsequent deposition of a sol–gel derived Pb(Zr_0.53Ti_0.47)O₃ (PZT53/47) thin film on the LNO-coated SiO₂/Si(1 0 0) substrates was also found to have a (1 0 0)-oriented texture. Moreover, the Au/PZT/LNO capacitor was found to significantly improve the fatigue and the effects of the LNO electrodes to the fatigue were discussed.     

Effect of heat-treatment on LaNiO3 film electrode of PZT thin films derived by a sol–gel method

Lanthanum nickel oxide (LaNiO₃ or LNO) conducting thin films that could be used as electrodes for improving fatigue and aging properties of ferroelectric thin films were investigated. In this paper, LNO films were directly spin-coated onto SiO₂/Si(1 0 0) substrates followed by thermal treatment in air and in oxygen. It was found that crack-free dense and uniform films with good crystallinity and medium grains were obtained, preferentially (1 0 0)-oriented LNO thin films could be formed at a lower annealing temperature of 550 °C and that with the increase in thermal annealing temperature the LNO thin film possessed better electrical properties especially at 750 °C. However, the LNO film displayed a structure transformation above 850 °C. A phenomenon was found that the first heat-treatment temperature and time played a key role to determine the crystallite size of LNO films. A subsequent deposition of a sol–gel derived Pb(Zr_0.53Ti_0.47)O₃ (PZT53/47) thin film on the LNO-coated SiO₂/Si(1 0 0) substrates was also found to have a (1 0 0)-oriented texture. Moreover, the Au/PZT/LNO capacitor was found to significantly improve the fatigue and the effects of the LNO electrodes to the fatigue were discussed.     

Effect of the electrode structure on the electrical properties of alkoxide derived ferroelectric thin film

Effect of the thermal expansion coefficient of electrode on the electrical properties in lead zirconate titanate (PZT) with morphotropic phase boundary (Pb(Zr_0.53,Ti_0.47)O₃: MPB) composition film was demonstrated in this paper. The lanthanum nickel oxide (LaNiO₃: LNO) and lanthanum strontium cobalt oxide ((La_0.5,Sr_0.5)CoO₃: LSCO) was deposited by chemical solution deposition (CSD) as bottom electrode on Si wafer. Highly (100)-oriented LSCO layers were successfully prepared by CSD on Si wafer using (100)-oriented LNO layers as seeding layer for the crystal orientation control. As a result, (100) and (001) oriented PZT film was also successfully prepared on LSCO/LNO/Si stacking structure. The obtained dielectric and ferroelectric properties changed according to the thermal stress which was influenced by the bottom electrode thickness.     

Effect of the orientation on the ferroelectric-antiferroelectric behavior of sol-gel deposited (Pb,Nb)(Zr,Sn,Ti)O3 thin films

The (Pb,Nb)(Zr,Sn,Ti)O₃ (PNZST) antiferroelectric thin films were prepared on two different substrates by sol-gel methods. Films derived on the LNO/Pt/Ti/SiO₂/Si substrates showed a strong (100) preferred orientation. The dependence of electrical properties derived on the Pt/Ti/SiO₂/Si and LNO/Pt/Ti/SiO₂/Si substrates have been studied, with the emphasis placed on field-induced phase switching from the antiferroectric to the ferroelectric state. The PNZST thin films deposition on two kinds of substrates show different phase transition behavior and associated properties such as antiferroelectric (AFE) to ferrroelectric (FE) switching field E_AFE-FE, FE to AFE switching field E_FE-AFE and the hysteresis ΔE=E_AFE-FE−E_FE-AFE.     

Electrophoretic deposition and photoluminescent properties of Eu-doped BaTiO3 thin film from a suspension of monodispersed nanocrystallites

Monodispersed Eu-doped BaTiO₃ nanocrystallites with a pseudo-cubic perovskite phase were successfully prepared using highly concentrated alkoxide solution under hydrothermal conditions at temperatures <100 °C. The obtained nanoparticles had a very narrow particle size distribution and the average value was about 10 nm. By dispersing a piece of BaTiO₃ bulk gel into mixed solvent of 2-methoxyethonal and acetylacetone, we obtained well-dispersed and stable suspensions of Eu-doped BaTiO₃ nanocrystallites with a high transmittance. Using these suspensions, nanostructured thin films with a low porosity and a smooth surface were synthesized on Pt/Ti/SiO₂/Si substrate by electrophoretic deposition. The obtained Eu-doped BaTiO₃ thin films showed strong, visible room temperature photoluminescence (PL) associated with Eu ions. The PL spectra had typical ones for Eu³⁺ band corresponding to ⁵D_o–⁷F_j electronic transitions with a maximum intensity at 613 nm.     

Electrophoretic deposition and photoluminescent properties of Eu-doped BaTiO3 thin film from a suspension of monodispersed nanocrystallites

Monodispersed Eu-doped BaTiO₃ nanocrystallites with a pseudo-cubic perovskite phase were successfully prepared using highly concentrated alkoxide solution under hydrothermal conditions at temperatures <100 °C. The obtained nanoparticles had a very narrow particle size distribution and the average value was about 10 nm. By dispersing a piece of BaTiO₃ bulk gel into mixed solvent of 2-methoxyethonal and acetylacetone, we obtained well-dispersed and stable suspensions of Eu-doped BaTiO₃ nanocrystallites with a high transmittance. Using these suspensions, nanostructured thin films with a low porosity and a smooth surface were synthesized on Pt/Ti/SiO₂/Si substrate by electrophoretic deposition. The obtained Eu-doped BaTiO₃ thin films showed strong, visible room temperature photoluminescence (PL) associated with Eu ions. The PL spectra had typical ones for Eu³⁺ band corresponding to ⁵D_o–⁷F_j electronic transitions with a maximum intensity at 613 nm.     

Microstructure and electrical properties of Pb(Zr0.52Ti0.48)O3 ferroelectric films on different bottom electrodes

The crystalline quality, dielectric and ferroelectricity of the Pb(Zr_0.52Ti_0.48)O₃ (PZT) films deposited on the LaNiO₃ (LNO), LNO/Pt and Pt bottom electrodes were comparatively analyzed to investigate the possibility for their application. LNO thin films were successfully prepared on Si (100) and Pt(111)/Ti/SiO₂/Si substrates by modified metallorganic decomposition (MOD). The PZT thin films were spin-coated onto the LNO, LNO/Pt and Pt bottom electrodes by sol–gel method. The crystallographic orientation and the microstructure of the resulting LNO films and PZT thin films on the different bottom electrodes were characterized by X-ray diffraction analysis. The dielectric and ferroelectric properties of PZT films on the different bottom electrodes are discussed. The PZT films deposited onto Pt/Ti/SiO₂/Si and LNO/Si substrates show strong (110) and (100) preferred orientation, respectively, while the films deposited onto LNO/Pt/Ti/SiO₂/Si substrates show the peaks of mixed orientations. PZT films on LNO and LNO/Pt bottom electrodes have larger dielectric constant and remnant polarizations compared with those grown on the Pt electrode.     

The effect of LaNiO3 buffer layer thickness on the electric properties of Pb(Zr0.53Ti0.47)O3 thin films deposited on titanium foils

Sol-gel derived Pb(Zr_0.53Ti_0.47)O₃ (PZT) thin films were prepared on LaNiO₃ (LNO) buffered titanium foils. The effect of LNO buffer layer thickness on the electric properties of PZT thin films was investigated. The room temperature dielectric constant of PZT thin films increased with increasing LNO thickness. The remnant polarization of PZT thin films on 150 and 250 nm LNO was about 20 uC/cm². Curie temperatures of PZT thin films were 310, 330 and 340 °C for LNO of 250, 150 and 50 nm respectively. The current-voltage characteristics of PZT thin films were examined for different LNO buffer layer thicknesses, and the space charge limited conduction model was followed in PZT thin films on 50 nm LNO.     

Growth and physico chemical characterization of lanthanum neodymium oxalate single crystals

Single crystals of lanthanum neodymium oxalate (LNO) are grown in sodium meta silicate gels, by the diffusion of a mixture of aqueous solutions of lanthanum nitrate and neodymium nitrate into the test tube having the set gel containing oxalic acid. The bluish pink coloured tabular crystals of LNO having well defined hexagonal basal planes appear either as ‘foggy’ or ‘clear’, the latter at the greater depths inside the gel. The colouration of LNO visually observed is evidenced in UV-visible spectrum, by the revelation of well pronounced characteristic peaks in the visible region (500–900 nm). X-ray diffraction (XRD) of powdered LNO is ordered, meaning crystalline in nature, besides its ‘isostructurality’ with similarly grown lanthanum samarium oxalate crystals. The single crystallinity of LNO is established by its oscillation XRD pattern. Thermogravimetric analysis (TGA) and differential scanning colorimetry (DSC) support that LNO loses water of crystallization around 120°C and CO and CO₂ around 350–450°C, while the infrared absorption (IR) spectrum of LNO establishes the presence of oxalate (C₂O₄)²⁻ ions. Energy dispersive X-ray analysis (EDAX) confirms the presence of La and Nd in the sample. X-ray photoelectron spectroscopic (XPS) studies of LNO establish the presence of La and Nd in their respective oxide states. An empirical structure for LNO has been proposed on the basis of these findings. The ‘smokiness’ in the foggy LNO crystal has been attributed due to the ‘gel inclusion’ during the growth process.     

Electrophoretic coagulation behavior of ferroelectric barium titanate powders in mixed solutions of alcohol and acetylacetone

Although the deposition of BaTiO₃, known as a ferroelectric compound with spontaneous dipole moments, has never occurred in either propanol and acetylacetone, these mixtures were found to enhance the deposition of the powders on a cathode. The present study carried out the systematic investigation of the solution-mixing effect of propanol and acetylacetone on the electrophoretic deposition of BaTiO₃. The optimum mixing ratio for the deposition was 50–70 vol% of propanol, while a depressed migration of BaTiO₃ powders was observed in the mixed solutions. Therefore, it was considered that the enhanced deposition was attributed to the coagulation of the BaTiO₃ powders on the cathode. The deposition characteristics varied with the kind of alcohol used showed that a more highly enhanced deposition was achieved with alcohols having longer side-chains such as octanol. An intertwinement between the side-chains in the alcohols was considered to have an effect on the coagulation of the BaTiO₃ powders.     

Fabrication of epitaxial conductive LaNiO3 films on different substrates by pulsed laser ablation

LaNiO₃ (LNO) thin films were deposited on (1 0 0) MgO, SrTiO₃ (STO) and LaAlO₃ (LAO) crystal substrates by pulsed laser deposition (PLD) under 20 Pa oxygen pressure at different substrate temperatures from 450 to 750 °C. X-ray diffraction (XRD), ex situ reflection high energy electron diffraction (RHEED) and atomic force microscopy (AFM) were employed to characterize the crystal structure of LNO films. LNO films deposited on STO and LAO at a temperature range from 450 to 700 °C exhibit high (0 0 l) orientation. XRD ψ scans and RHEED observations indicate that LNO films could be epitaxially grown on these two substrates with cubic-on-cubic arrangement at a wide temperature range. LNO films deposited at 700 °C on MgO (1 0 0) substrate have the (l l 0) orientation, which was identified to be bicrystalline epitaxial growth. La₂NiO₄ phase appears in LNO films deposited at 750 °C on three substrates. The epitaxial LNO films were tested to be good metallic conductive layers by four-probe method.     

Preparation of La0.5Li0.5TiO3 perovskite thin films by the sol–gel method

Perovskite La_0.5Li_0.5TiO₃ (LLT) thin films, 0.2–1 μm thick, were deposited on non-alkali aluminoborosilicate glass substrates (NA substrates) and glass substrates with ITO (indium tin oxide) coatings (ITO substrates) by the sol–gel method. Alkoxide-based solutions containing titanium alkoxide, lithium alkoxide and lanthanum alkoxide and acetate-based solutions containing titanium alkoxide, lithium acetate and lanthanum acetate, were used as coating solutions. Impurity phases tended to be precipitated on heat treatment in the films derived from the acetate-based solutions. Addition of acetylacetone or partial substitution of lead for lithium in the acetate-based solutions, however, was effective in suppressing the precipitation of impurity phases. Preferred orientation of the LLT (1 1 1/2) plane was observed in the films prepared from the acetate-based solutions when NA substrates were used, whereas the employment of the alkoxide-based solutions or ITO substrates and the partial substitution of lead for lithium, reduced the preferred orientation. The electrical conductivity of the films was much lower than the values reported for the sintered materials. This revised version was published online in November 2006 with corrections to the Cover Date.     

Characterization of ZrO2 and SiC ceramic thin films prepared by electrostatic atomization

ZrO₂ and SiC ceramic thin films and their bilayer have been successfully prepared by a newly developed electrostatic atomization technique. This technique can generate fine spray of ceramic suspensions in a micrometer sized range with a narrow size distribution which is crucial for preparation of uniform thin films of these ceramic materials. Compared to some other thin film deposition techniques, such as Chemical vapour deposition (CVD), physical vapour deposition (PVD) and plasma spray (PS) etc. the thin film deposition process using electrostatic atomization is not only cheap but also controllable. The prepared ZrO₂ and SiC thin films were investigated using scanning electron microscopy (SEM) and energy dispersion analysis (EDA) techniques. These thin films were observed to be homogenous with a particle size less than 10 m. The ZrO₂-SiC bilayer was found to have an abrupt interface, implying that the deposition process is controllable and also that functionally graded ceramic/ceramic materials can be prepared in this way if the thickness of each layer is accurately controlled.     

Cobalt ferrite dispersion in organic solvents for electrophoretic deposition: Influence of suspension parameters on the film microstructure

An electrophoretic deposition (EPD) method was applied for the preparation of CoFe₂O₄ (CFO) films on Al₂O₃/Pt substrates. A coprecipitation process was used to synthesize fine CFO powders with an average particle size of ∼40 nm. Influences of suspension parameters such as solvents, iodine additive, and charged polymer on the suspension stability and film microstructure were investigated in detail. Three suspensions including CFO–acetylacetone, CFO–acetylacetone–0.08 wt% I₂ and CFO–acetylacetone–0.2 wt% polyethylenimine (PEI) were optimized, respectively. It was found that CFO was deposited uniformly and the potential required for the deposition was small for the three optimized suspensions. After sintering at 1250 °C for 2 h, the film from CFO–acetylacetone–0.08 wt% I₂ showed many cracks, which indicates this suspension is not suitable for preparing high quality CFO ceramic films. While the sintered films fabricated from the other two optimized suspensions exhibited dense structures. Based on the electric and magnetic properties of CFO ceramic films, it can be concluded that CFO–acetylacetone–0.2 wt% PEI is the proper suspension to prepare films with better microstructures and properties.     

Probing the Ni(OH)2 Precursor for LiNiO2 at the Atomic Scale: Insights into the Origin of Structural Defect in a Layered Cathode Active Material

In lithium ion batteries (LIBs), the layered cathode materials of composition LiNi_1−x−yCo_xMn_yO₂ are critical for achieving high energy densities. A high nickel content (>80%) provides an attractive balance between high energy density, long lifetime, and low cost. Consequently, Ni-rich layered oxides cathode active materials (CAMs) are in high demand, and the importance of LiNiO₂ (LNO) as limiting case, is hence paramount. However, achieving perfect stoichiometry is a challenge resulting in various structural issues, which successively impact physicochemical properties and result in the capacity fade of LIBs. To better understand defect formation in LNO, the role of the Ni(OH)₂ precursor morphology in the synthesis of LNO requires in-depth investigation. By employing aberration-corrected scanning transmission electron microscopy, electron energy loss spectroscopy, and precession electron diffraction, a direct observation of defects in the Ni(OH)₂ precursor preparedis reported and the ex situ structural evolution from the precursor to the end product is monitored. During synthesis, the layered Ni(OH)₂ structure transforms to partially lithiated (non-layered) NiO and finally to layered LNO. The results suggest that the defects observed in commercially relevant CAMs originate to a large extent from the precursors, hence care must be taken in tuning the co-precipitation parameters to synthesize defect-free Ni-rich layered oxides CAMs.     

Deflection of wafers and cantilevers with Pt/LNO/PZT/LNO/Pt/Ti/SiO2 multilayered structure

The present paper describes a Pt/LNO/PZT/LNO/Pt/Ti/SiO₂ multilayers deposited on 4-inch Si wafers. We have evaluated the variation of the deflection of the Si wafers with deposition of each of the thin films. The deposition of the multilayers has resulted in downward deflection (center is higher than edge) of the Si wafers. The multilayers have been also deposited onto SOI wafers and fabricated into piezoelectric micro cantilevers through MEMS bulk micromachining. The micro cantilevers have shown the upward deflection. We have characterized the ferroelectric and piezoelectric properties of the PZT thin films through electrical tests of the micro cantilevers. The dielectric constant, saturation polarization, remanent polarization and coercive field were measured to be 1050, 31.3 μC/cm², 9.1 μC/cm² and 21 kV/cm, respectively. The transverse piezoelectric constant, d₃₁, was measured to be − 110 pm/V from the DC response of the micro cantilevers.