Effect of microstructure on chemical stability and electrical properties of BaCe<Subscript>0.9</Subscript>Y<Subscript>0.1</Subscript>O<Subscript>3 − <Emphasis Type="Italic">δ</Emphasis></Subscript>

Y-doped barium cerate BaCe_0.9Y_0.1O_3???δ was synthesised by a solid-state reaction method. Materials with different average grain sizes and grain boundary surface areas were obtained. The effect of microstructure on the chemical stability in the CO₂ and H₂O-containing atmosphere and electrical properties was analysed and discussed. To evaluate the chemical stability of BaCe_0.9Y_0.1O_3???δ , the exposure test was performed. Samples were exposed to the carbon dioxide and water vapour-rich atmosphere at 25 °C for 700 h. Thermogravimetry supplied by mass spectrometry was applied to analyse the samples before and after this comprehensive test. The mass loss for samples before and after the test and the amount of BaCO₃ formed during the test were directly treated as the measure of chemical instability of BaCe_0.9Y_0.1O_3???δ in the atmosphere rich in carbon dioxide and water vapour. As it was observed, the BaCe_0.9Y_0.1O_3???δ chemical stability towards CO₂ and H₂O is not affected by the materials’ microstructure. Electrical properties of BaCe_0.9Y_0.1O_3???δ which differs with microstructure were determined using electrochemical impedance spectroscopy (EIS). It was found that the grain interior resistivity and activation energy of grain interior conductivity is microstructure independent. However, the effect on microstructure was seen on the EIS spectra in the range of grain boundary contribution. Therefore, the lowest activation energy and the highest conductivity were observed for a material with the lowest grain boundary surface area.     

The across-plane conductivity and microstructure of SrZr0.95Y0.05O3 − δ thin films

The across-plane electrical conductivity of the proton-conducting SrZr_0.95Y_0.05O_3???δ thin films fabricated by chemical solution deposition on single-crystalline ZrO₂ doped by 10 mol% of Y₂O₃ (YSZ) substrates was investigated using impedance spectroscopy. The average grain size of the films was found to increase considerably with thermal treatment. This change in grain size has a strong effect on the electrical behavior of films. Our results show that the electrochemical performance of the cell is strongly affected by the potential difference at the film/substrate interface. Coarse-grain film microstructure was proved to be preferable for the reduction of both the film resistance and interfacial barrier.     

Pulsed laser deposition of high temperature protonic films

Pulsed laser deposition has been used to fabricate nanostructured BaCe_0.85Y_0.15O_3−δ films. Protonic conduction of the fabricated BaCe_0.85Y_0.15O_3−δ films was compared to the sintered BaCe_0.85Y_0.15O_3−δ. Sintered samples and laser targets were prepared by sintering BaCe_0.85Y_0.15O_3−δ powders derived by solid state synthesis. Films 1 to 8 μm thick were deposited by KrF excimer laser on porous Al₂O₃ substrates. Thin films were fabricated at deposition temperatures of 700 to 950 °C at O₂ pressures up to 200 mTorr using laser pulse energy densities of 1.4–3 J/cm². Fabricated films were characterized by X-ray diffraction, electron microscopy and electrical impedance spectroscopy. Single phase BaCe_0.85Y_0.15O_3−δ films with a columnar growth morphology are observed with preferred crystal growth along the [100] or [001] direction. Results indicate [100] growth dependence upon laser pulse energy. Electrical conductivity of bulk samples produced by solid state sintering and thin film samples were measured over a temperature range of 100 to 900 °C. Electrical conduction behavior was dependent upon film deposition temperature. Maximum conductivity occurs at deposition temperature of 900 °C; the electrical conductivity exceeds the sintered specimen. All other deposited films exhibit a lower electrical conductivity than the sintered specimen. Activation energy for electrical conduction showed dependence upon deposition temperature, it varied from 115 to 54 kJ. Film microstructure was attributed to the difference in electrical conductivity of the BaCe_0.85Y_0.15O_3−δ films.     

Y2O3 stabilized ZrO2 thin films deposited by electron beam evaporation: Structural, morphological characterization and laser induced damage threshold

Four kinds of Y₂O₃ stabilized ZrO₂ (YSZ) thin films with different Y₂O₃ content have been prepared on BK7 substrates by electron-beam evaporation method. Structural properties and surface morphology of thin films were investigated by X-ray diffraction (XRD) spectra and scanning probe microscope. Laser induced damage threshold (LIDT) was determined. It was found that crystalline phase and microstructure of YSZ thin films was dependent on Y₂O₃ molar content. YSZ thin films changed from monoclinic phase to high temperature phase (tetragonal and cubic) with the increase of Y₂O₃ content. The LIDT of stabilized thin film is more than that of unstabilized thin films. The reason is that ZrO₂ material undergoes phase transition during the course of e-beam evaporation resulting in more numbers of defects compared to that of YSZ thin films. These defects act as absorptive center and the original breakdown points.     

Preparation and properties of Y1−xHoxBa2Cu3O7−δ thin films by TFA-MOD method

Y_1?xHo_xBa₂Cu₃O_7?δ (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5) thin films were prepared on LaAlO₃ (0 0 1) substrates by trifluoroacetate metal organic deposition (TFA-MOD) without change of the processing parameters. The highest J_c was attributed to the sample of Y_0.6Ho_0.4Ba₂Cu₃O_7?δ thin film, whose critical current density is about 1.6 times as compared to that of YBa₂Cu₃O_7?δ thin film at 77 K and self field. The flux pinning type was not varied with Ho substitution and can be attributed to δl pinning model, which is attributed to the close ionic radius between the Y³⁺ and Ho³⁺ ions. The improvement of J_c by Ho substitution without change of the processing parameters will provide an effective route to enhance the J_c of YBCO-based thin films using TFA-MOD method.     

The chemical stability and conductivity improvement of protonic conductor BaCe0.8 − x Zr x Y0.2O3 − δ

A series of BaCe_0.8???x Zr _x Y_0.2O_3???δ (BCZYx) (x?=?0, 0.2, 0.4, 0.6, 0.8) powders were prepared by EDTA–citrate complexing sol–gel process in this paper. The electrical conducting behavior, as well as chemical stability, was investigated. X-ray diffraction (XRD) results reveal that all samples are homogenous perovskite phases. Observed from XRD patterns and thermogravimetric curves, the samples with x?≥?0.4 survive in the pure CO₂, while samples with various Zr contents all present structurally stable against steam at 800 °C. The Zr-free sample of BaCe_0.8Y_0.2O_3???δ possesses the maximum bulk conductivity, 4.25?×?10^?2 S/cm, but decomposes into Ba(OH)₂ and Ce_0.8Y_0.2O_3???δ in steam. A negative influence of increasing Zr content on the conductivity of BCZYx can be observed by impedance tests. Considering the effect of temperature on the bulk conductivity, BCZY0.4 is preferred to be applied in SOFC as a protonic conductor, ranging from 1.52?×?10^?4 to 1.51?×?10^?3 S/cm (500–850 °C) with E _a?=?0.859 eV, which is proved to be a good protonic conductor with t _H+?≥?0.9.     

Power-law scaling of proton conductivity in amorphous silicate thin films

Amorphous hafnium silicate, a-Hf_0.1Si_0.9O_x, thin film with thickness of 32, 41, 55, 80, 110, 120, 180 and 320 nm was prepared by multiple spin-cast process and the proton conductivity across the films was measured at intermediate temperatures (100-400 °C) in dry atmosphere. The morphologically- and compositionally-uniform films were prepared on a substrate as confirmed by SEM, RBS and XPS measurements. a-Hf_0.1Si_0.9O_x thin film clearly revealed the H/D isotope effect on ionic conductivity, indicating that protonic conduction is dominant in the measured temperature range. The films did not reveal thickness-dependent proton conductivity in dry air and the σ at given temperatures is almost constant at any thickness. No increment of σ in a-Hf_0.1Si_0.9O_x thin films by reduction of thickness might be related to the absence of the highly-conductive acid network with mesoscopically-sized length because of the relatively low concentration of Brønsted acid sites inside films.     

Thickness-dependent surface morphology of La0.9Sr0.1MnO3 ultrathin films

La_0.9Sr_0.1MnO₃ (LSMO) ultrathin films with various thickness (in the range of 5-50 unit cells) are grown on (0 0 1) substrates of the single-crystal SrTi_0.99Nb_0.01O₃ by laser molecular-beam epitaxy (laser-MBE), and the surface morphology of these films were measured by scanning tunneling microscopy (STM). STM images of LSMO ultrathin film surface reveal that surface morphology becomes more flat with increasing film thickness. This study highlights the important effect of strain caused by the lattice mismatch between substrates and ultrathin films. And the results should be useful to the investigations on growing manganite perovskite materials.     

Structural,thermal and electrical properties of Bi and Y co-doped barium zirconium cerates

Bismuth- and yttrium-co-doped barium cerates were successfully synthesised by solid-state reactions followed by sintering between 1,400 and 1,500 °C for 1 to 6 h allowing densification above 98 % to be obtained. All samples were found to retain their original orthorhombic structure after treatment in either oxidising or reducing atmospheres (dry and wet). Mechanical strength was affected by structure upon reduction due in part to strains and stresses induced by bismuth ionic size variations. Conductivity values as high as 0.055 S/cm were obtained for sample BaCe_0.6Zr_0.1Y_0.1Bi_0.2O_3?δ and of 0.0094 S/cm for the Zr-free compound BaCe_0.7Y_0.2Bi_0.1O_3?δ at 700 °C in air. In all the investigated materials, sample BaCe_0.6Zr_0.1Y_0.1Bi_0.2O_3?δ exhibits the highest conductivity in both air and wet 5 % H₂/Ar with good mechanical strength. BaCe_0.6Zr_0.1Y_0.1Bi_0.2O_3?δ is a promising mixed H⁺/e^? conductor, a potential component of composite anode for solid oxide fuel cells.     

The morphology and optical properties of Cr-doped ZnO films grown using the magnetron co-sputtering method

Undoped ZnO and Zn_0.9Cr_0.1O films were prepared on Al₂O₃ (0 0 0 1) substrates using the magnetron co-sputtering technique. X-ray diffraction scans show that all films exhibit nearly single-phase wurtzite structure with c-axis orientation. Both chromium doping and growth ambient have a significant impact on the lattice constants and nucleation processes in ZnO film. A large quantity of subgrains (10 nm in size) has been observed on Zn_0.9Cr_0.1O film grown under Ar + O₂, while irregular plateau-like grains 40-50 nm in size were observed on Zn_0.9Cr_0.1O film grown under Ar + N₂. The ultraviolet-visible transmittance and optical bandgap of all films were also examined. The photoluminescence spectra of all films exhibit a broad emission located around 400 nm, which is composed of one weak ultraviolet luminescence and another rather intense near-violet one, as determined by Gaussian peak fitting. The near-violet emission centered on 400 nm might originate from the electron transition between the band tail state levels of surface defects and/or lattice imperfection in the ZnO film.     

Effect of bilayer structure and a SrRuO3 buffer layer on ferroelectric properties of BiFeO3 thin films

Effects of the BiFe_0.95Mn_0.05O₃ thickness and a SrRuO₃ (SRO) buffer layer on the microstructure and electrical properties of BiFeO₃/BiFe_0.95Mn_0.05O₃ (BFO/BFMO) bilayered thin films were investigated, where BFO/BFMO bilayered thin films were fabricated on the SRO/Pt/Ti/SiO₂/Si(100) substrate by a radio frequency sputtering. All thin films are of a pure perovskite structure with a mixture of (110) and (111) orientations regardless of the BFMO layer thickness. Dense microstructure is demonstrated in all thin films because of the introduction of BFMO layers. The SRO buffer layer can also further improve the ferroelectric properties of BFO/BFMO bilayered thin films as compared with those of these thin films without a SRO buffer layer. The BFO/BFMO bilayered thin film with a thickness ratio of 220/120 has an enhanced ferroelectric behavior of 2P _r??165.23???C/cm² and 2E _c??518.56?kV/cm, together with a good fatigue endurance. Therefore, it is an effective way to enhance the ferroelectric and fatigue properties of bismuth ferrite thin films by constructing such a bilayered structure and using a SRO buffer layer.     

Surface acoustic wave device properties of (B, Al)N films on 128° Y-X LiNbO3 substrate

A c-axis orientated aluminium nitride (AlN) film on a 128° Y-X lithium niobate (LiNbO₃) surface acoustic wave (SAW) device which exhibit a large electromechanical coupling coefficient (k²) and a high SAW velocity property, is needed for future communication applications. In this study, a c-axis orientated (B, Al)N film (with 2.6 at.% boron) was deposited on a 128° Y-X LiNbO₃ substrate by a co-sputtering system to further boost SAW device properties. The XRD and TEM results show that the (B, Al)N films show highly aligned columns with the c-axis perpendicular to the substrate. The hardness and Young's modulus of (B, Al)N film on 128° Y-X LiNbO₃ substrates are at least 17% and 7% larger than AlN films, respectively. From the SAW device measurement, the operation frequency characteristic of (B, Al)N film on 128° Y-X LiNbO₃ is higher than pure AlN on it. The SAW velocity also increases as (B, Al)N film thickness increases (at fixed IDT wavelength). Furthermore, the k² of (B, Al)N on the IDT/128° Y-X LiNbO₃ SAW device shows a higher value than AlN on it.     

Extraordinary fast oxide ion conductivity in La1.61GeO5−δ thin film consisting of nano-size grain

Thin films of La_1.61GeO_5−δ, a new oxide ionic conductor, were fabricated on dense polycrystalline Al₂O₃ substrates by a pulsed laser deposition (PLD) method and the effect of the film thickness on the oxide ionic conductivity was investigated on the nanoscale. The deposition parameters were optimized to obtain La_1.61GeO_5−δ thin films with stoichiometric composition. Annealing was found necessary to get crystalline La_1.61GeO_5−δ thin films. It was also found that the annealed La_1.61GeO_5−δ film exhibited extraordinarily high oxide ionic conductivity. Due to the nano-size effects, the oxide ion conductivity of La_1.61GeO_5−δ thin films increased with the decreasing thickness as compared to that in bulk La_1.61GeO_5−δ. In particular, the improvement in conductivity of the film at low temperature was significant .The electrical conductivity of the La_1.61GeO_5−δ film with a thickness of 373 nm is as high as 0.05 S cm^− 1 (log(σ/S cm^− 1) = − 1.3) at 573 K.     

Synthesis of Y2O3:(Li,Eu) films using phosphor powders coated with SiO2 nano particles

Y_1.9−xLi_0.1Eu_xO₃ (x=0.02, 0.05, 0.08, and 0.12) films were fabricated by spin-coating method. A colloidal silica suspension with Y_1.9−xLi_0.1Eu_xO₃ phosphor powder was exploited to obtain the highly stable and effective luminescent films onto the glass substrate. After heating as-prepared Y_1.9−xLi_0.1Eu_xO₃ films at 700 °C for 1 h, the phosphor films exhibit a high luminescent brightness as well as a strong adhesiveness on the glass substrate. The emission spectra of spin-coated and pulse-laser deposited Y_1.82Li_0.1Eu_0.08O₃ films were compared. The cathodoluminescence of the phosphor films was carried out at the anode voltage 1 kV.     

Er:YAB nanoparticles and vitreous thin films by the polymeric precursor method

The synthesis of Y_0.9Er_0.1Al₃(BO₃)₄ crystalline powders and vitreous thin films were studied. Precursor solutions were obtained using a modified polymeric precursor method using d-sorbitol as complexant agent. The chemical reactions were described. Y_0.9Er_0.1Al₃(BO₃)₄ composition presents good thermal stability with regard to crystallization. The Y_0.9Er_0.1Al₃(BO₃)₄ crystallized phase can be obtained at 1,150 °C, in agreement with other authors. Crack- and porosity-free films were obtained with very small grain size and low RMS roughness. The films thickness revealed to be linearly dependent on precursor solution viscosity, being the value of 25 mPa s useful to prepare high-quality amorphous multi-layers (up to ∼ 800 nm) at 740 °C during 2 h onto silica substrates by spin coating with a gyrset technology.     

A Ni/YSZ composite containing Ce0.9Ca0.1O2−δ particles as an anode for SOFCs

A composite material (hereafter referred to as NYC) containing Ni, Y₂O₃-stabilized ZrO₂ (YSZ) and Ce_0.9Ca_0.1O_2−δ (CC10) particles was prepared and used as the anode of solid oxide fuel cells (SOFCs). The performance of NYC was better than that of conventional Ni/YSZ anodes in terms of anodic overpotential and interface impedance. The additional CC10 particles improved the anode properties. XRD results suggest that a solid solution of YSZ and CC10 was produced. From impedance measurements, it is concluded that the solid solution exhibits substantial electronic conduction. Ni/YSZ/15 wt% Ce_0.9Ca_0.1O_2−δ anodes exhibited the best properties over the experimental temperature range. A SOFC with an anode of Ni/YSZ/15 wt% Ce_0.9Ca_0.1O_2−δ provided the maximum power density and current density. Addition of CC10 with an average particle size of 0.3 μm was more advantageous than that with an average size of 3 μm.     

Structural and optical properties of La and Gd substituted Bi4 − x M x V2O11 − δ (0.1 ≤ x ≤ 0.3)

Bi_4???x M _x V₂O_11???δ (M?=?La, Gd; 0.1?≤?x?≤?0.3) is synthesised by a solid state reaction method to study the effect of La³⁺ and Gd³⁺ substitution for Bi on the structural and optical properties. The as-prepared samples are characterised by X-ray diffraction, Fourier transform infrared analysis, UV–visible spectroscopy, scanning electron microscopy and energy-dispersive spectroscopy. The refinement results confirmed that even substituted samples exhibit monoclinic structure with space group C2/m. The parameters like band gap energy; Urbach energy has been calculated from the UV–visible spectra. It has been observed that even substitution at the bismuth site by isovalent cations decreases the energy band gap. The lowest observed band gap is 1.86 eV for Bi_3.9La_0.1V₂O_11???δ . The grain size and defects were observed to increase with increasing substitution along with the amount of secondary phase.     

Electrical behavior of BaZr0.1Ti0.9O3 and BaZr0.2Ti0.8O3 thin films

BaZr_0.1Ti_0.9O₃ and BaZr_0.2Ti_0.8O₃ (BZT) thin films were deposited on Pt/Ti/LaAlO₃ (1 0 0) substrates by radio-frequency magnetron sputtering, respectively. The films were further annealed at 800 °C for 30 min in oxygen. X-ray diffraction θ-2θ and Φ-scans showed that BaZr_0.1Ti_0.9O₃ films displayed a highly (h 0 0) preferred orientation and a good cube-on-cube epitaxial growth on the LaAlO₃ (1 0 0) substrate, while there are no obvious preferential orientation in BaZr_0.2Ti_0.8O₃ thin films. The BaZr_0.1Ti_0.9O₃ films possess larger grain size, higher dielectric constant, larger tunability, larger remanent polarization and coercive electric field than that of BaZr_0.2Ti_0.8O₃ films. Whereas, BaZr_0.1Ti_0.9O₃ films have larger dielectric losses and leakage current density. The results suggest that Zr⁴⁺ ion can decrease dielectric constant and restrain non-linearity. Moreover, the enhancement in dielectric properties of BaZr_0.1Ti_0.9O₃ films may be attributed to (1 0 0) preferred orientation.     

Microstructural characterization of La0.4Sr0.6Co0.8Fe0.2O3-δ films deposited by dip coating

The dip-coating method has been successfully used for depositing porous electrodes of La_0.4Sr_0.6Co_0.8Fe_0.2O_3-δ (LSCF) films. Perovskite oxide cobaltites powders have been prepared by an acetic acid-based gel route. Then, cathode films were deposited onto ceramic substrates of the usual electrolyte Cerium Gadolinium Oxide (CGO) by dip coating. The structure and morphology of the powders and films were characterized by X-ray, diffraction (XRD) and scanning electron microscopy (SEM) respectively, to study the correlation between microstructure and deposition parameters. Optimum parameters for obtaining continuous, homogeneous and crack free LSCF films were determined.     

Effect of the substrate crystalline structure on the magnetic, electrical, and crystallographic characteristics of La0.35Nd0.35Sr0.3MnO3 epitaxial films

A study has been made of the electrical resistivity ρ, magnetoresistance Δρ/ρ, and magnetization of La_0.35Nd_0.35Sr_0.3MnO₃ epitaxial films on ZrO₂(Y₂O₃), SrTiO₃, LaAlO₃, and MgO substrates. The first film can exist in four equivalent crystallographic orientations in the sample plane, while the other three have only one orientation. The maxima of ρ and Δρ/ρ of the first film are broadened considerably in the vicinity of the Curie point T _C compared to the three others, the magnitude of ρ itself being larger by 1.5 orders of magnitude, and a large negative magnetoresistance (|Δρ/ρ| ～ 10% in a field of 8.4 kOe) is observed at temperatures 80≤T≤200 K. In all films, the magnetic moment per molecule at 5 K is ～46% smaller than the pure spin value, due to the existence of magnetically disordered regions. The larger value of ρ of the film deposited on ZrO₂(Y₂O₃) is due to the electrical resistance of the boundaries separating regions with different crystallographic orientations, and the magnetoresistance is associated with polarized carriers tunneling through the boundaries coinciding with domain walls. The low-temperature magnetoresistance in fields above technical saturation is caused by the strong p-d exchange coupling within spin-ordered regions.