A review of thin film electrolytes fabricated by physical vapor deposition for solid oxide fuel cells

The ohmic resistance in solid oxide fuel cells (SOFCs) mainly comes from the electrolyte, which can be reduced by developing novel electrolyte materials with higher ionic conductivity and/or fabricating thin-film electrolytes. Among various kinds of thin-film fabrication technology, the physical vapor deposition (PVD) method can reduce the electrolyte thickness to a few micrometers and mitigate the issues associated with high-temperature sintering, which is necessary for wet ceramic methods. This review summarizes recent development progress in thin-film electrolytes fabricated by the PVD method, especially pulsed laser deposition (PLD) and magnetron sputtering. At first, the importance of the substrate surface morphology for the quality of the film is emphasized. After that, the fabrication of thin-film doped-zirconia and doped-ceria electrolytes is presented, then we provide a brief summary of the works on other types of electrolytes prepared by PVD. Finally, we have come to the summary and made perspectives.     

Structural,electrical, and linear/nonlinear optical characteristics of thermally evaporated molybdenum oxide thin films

Homogeneous thin films of Molybdenum oxide (MoO₃) were grown on quartz and glass substrates using the thermal evaporation method. XRD results showed that the MoO₃ powder has a polycrystalline structure with an orthorhombic crystal system whereas the MoO₃ thin films have amorphous nature. SEM images showed that the MoO₃ thin films have a nearly uniform surfaces with worm-like shape grains. The film thickness influences on the linear and nonlinear optical characteristics of MoO₃ thin films that were examined using spectrophotometric measurements and from which, the linear optical constants of the MoO₃ thin films were estimated. The electronic transition type was determined as a direct allowed one. The values of the optical band gap were obtained to be in the range of 3.88–3.72 eV. The dispersion parameters, third-order nonlinear optical susceptibility, and the nonlinear refractive index of the MoO₃ thin films were determined and interpreted in the light of the single oscillator model. The temperature dependence of the DC electrical conductivity and the corresponding conduction mechanism for the MoO₃ films were investigated at temperatures ranging from 303 to 463 K.     

Revealing Nanomechanical Domains and Their Transient Behavior in Mixed-Halide Perovskite Films

Halide perovskites are a versatile class of semiconductors employed for high performance emerging optoelectronic devices, including flexoelectric systems, yet the influence of their ionic nature on their mechanical behavior is still to be understood. Here, a combination of atomic-force, optical, and compositional X-ray microscopy techniques is employed to shed light on the mechanical properties of halide perovskite films at the nanoscale. Mechanical domains within and between morphological grains, enclosed by mechanical boundaries of higher Young's Modulus (YM) than the bulk parent material, are revealed. These mechanical boundaries are associated with the presence of bromide-rich clusters as visualized by nano-X-ray fluorescence mapping. Stiffer regions are specifically selectively modified upon light soaking the sample, resulting in an overall homogenization of the mechanical properties toward the bulk YM. This behavior is attributed to light-induced ion migration processes that homogenize the local chemical distribution, which is accompanied by photobrightening of the photoluminescence within the same region. This work highlights critical links between mechanical, chemical, and optoelectronic characteristics in this family of perovskites, and demonstrates the potential of combinational imaging studies to understand and design halide perovskite films for emerging applications such as photoflexoelectricity.     

Mechanical properties and thermal shock in thin ZrO2–Y2O3–Al2O3 films obtained by the sol-gel method

Thin multilayer coatings of ZrO₂–Y₂O₃–Al₂O₃ were prepared using the sol-gel method and dip-coating technique in order to advance in the study of what influence the incorporation of Al₂O₃ has on films of Y₂O₃-doped ZrO₂, investigating its role in the synthesis of the solutions and in the characteristics and properties of the coatings. After the characterization of the solutions used in the process, the microstructure of the films was studied and their mechanical behaviour and resistance to thermal shock were determined so as to optimize the characteristics and functionality of these coatings. With increased alumina content, 3YSZ-Al₂O₃ (20 mol%), the cubic phase of the zirconia disappeared completely at the sintering temperature used (700 °C), resulting in the tetragonal phase with Al in solution. There was also a decrease in the coatings' hardness and Young's modulus, and an increase in toughness and resistance to thermal shock. These results allow guidelines to be established for the design of multilayer structures that are, tougher, more resistant, and have improved surface properties.     

Mechanical performance of ITO/Ag/ITO multilayer films deposited on glass substrate by RF and DC magnetron sputtering

ITO/Ag/ITO multilayer thin films have been a potential substitute of the conventional single-layer transparent conducting film. Nevertheless, the mechanical stability under preparation and in-service conditions still limits their applications and developments. In this paper, the influences of different structural properties as well as layer structure on both surface morphological properties and mechanical properties of the ITO/Ag/ITO multilayer thin films in comparison with commercial single-layer ITO thin film were systematically investigated. The results demonstrate that, i) the tri-layer composite has large impacts on the preferential orientation, and exhibits the decreased values of surface roughness, net lattice distortion and residual stress; ii) the increased hardness (H) and decreased Young's modulus (E) for full annealed ITO/Ag/ITO multilayer films indicate that it is possible to tailor mechanical properties of the materials by manufacturing multilayer composite; iii) the ITO/Ag/ITO multilayer thin film exhibits remarkable improvements in wear resistance with the increase of annealing temperature, which is mainly attributed to the increased ratios of H/E and H³/E².     

Preparation of transparent BaSO4 nanodispersions by high-gravity reactive precipitation combined with surface modification for transparent X-ray shielding nanocomposite films

BaSO₄ nanoparticles as important functional materials have attracted considerable research interests, due to their X-rays barrier and absorption properties. However, most of BaSO₄ nanoparticles prepared by traditional technology are nanopowders with broad size distribution and poor dispersibility, which may greatly limit their applications. To the best of our knowledge, the synthesis of transparent BaSO₄ nanodispersions was rarely reported. Here, we firstly present a novel and efficient method to prepare transparent and stable BaSO₄ nanodispersions with a relatively small particle size around 10 to 17 nm using a precipitation method in a rotating packed bed (RPB), followed by a modification treatment using stearic acid. Compared with the BaSO₄ prepared in a traditional stirred tank, the product prepared using an RPB has much smaller particle size and narrower size distribution. More importantly, by using RPB, the reaction time can be significantly decreased from 20 min to 18 s. Furthermore, the transparent BaSO₄-polyvinyl butyral nanocomposite films with good X-ray shielding performance can be easily fabricated. We believe that the stable BaSO₄ nanodispersions may have a wide range of applications for transparent composite materials and coatings with X-ray shielding performance for future research.     

Study of Pb-based and Pb-free perovskite solar cells using Cu-doped Ni1-xO thin films as hole transport material

SCAPS solar cell simulation program was applied to model an inverted structure of perovskite solar cells using Cu-doped Ni_1-xO thin films as hole transport layer. The Cu-doped Ni_1-xO film were made by co-sputtering deposition under different deposition conditions. By increasing the amount of the Cu-dopant, the film crystallinity enhanced whereas the bandgap energy decreased. The transmittance of the thin films decreased significantly by increasing the sputtering power of copper. High quality, uniform, compact, and pin-hole free films with low surface roughness were achieved. The structural, chemical, surface morphology, optical, electrical, and electronic properties of the Cu doped Ni_1-xO films were used as input parameters in the simulation of Pb-based (MAPbI_3-xCl_x) and Pb-free (MAGeI₃) perovskite solar cells. Simulation results showed that the performance of both Pb-based and Pb-free perovskite solar cell devices significantly enhanced with Cu-doped Ni_1-xO film. The highest power conversion efficiency (PCE) for the Pb-free perovskite solar cell is 8.9% which is lower than the highest PCE of 17.5% for the Pb-based perovskite solar cell.     

Magnetic field-enhanced photocatalytic nitrogen fixation over defect-rich ferroelectric Bi2WO6

Photocatalytic N₂ fixation is a promising and sustainable manufacturing process of ammonia (NH₃); however, the NH₃ production rate by this method is very low, thus severely restricting further application of this sustainable technology. Therefore, developing an efficient photocatalyst for N₂ fixation under mild conditions is urgently required. Herein, ferroelectric Bi₂WO₆ materials with different surface oxygen defects were prepared, and the concentration of corresponding defects was controlled by adjusting the thermal reduction time. The abundant oxygen defects in Bi₂WO₆ can provide more reactive sites to promote the effective adsorption of N₂, and the photogenerated charge carrier can be efficiently separated benefiting from the internal electric field. These would weaken the N₂ triple bond and reduce the activation energy barrier for the conversion of N₂ to NH₃ under mild conditions. In the absence of sacrificial agents and cocatalysts, the optimized Bi₂WO₆ with oxygen defects shows an indigenous NH₃ yield of 132.175 μmol·g^-1·L^-1·h^-1, which is more than two times higher than that of the original Bi₂WO₆. Surprisingly, the Bi₂WO₆ with oxygen defects produced more than eight times NH₃ (471.13 μmol·g^-1·L^-1·h^-1) than that of the original Bi₂WO₆ when assisted by an external magnetic field, thus providing a new perspective for further enhancing the N₂ fixation performance.     

Dielectric and ferroelectric properties of multilayer BaTiO3/NiFe2O4 thin films prepared by solution deposition technique

In this work different lead-free multilayered structures, composed of perovskite BaTiO₃ and spinel NiFe₂O₄ thin layers, were obtained by solution deposition method. Structural characterization of the sintered thin films confirmed the well-defined layered structure with overall thickness from 160 to 600 nm, crystalline nature of perovskite BaTiO₃ and spinel NiFe₂O₄ phases without secondary phases (after sintering below 900 °C) and grains on nanometer scale. Dielectric properties of the multiferroic multilayer BaTiO₃/NiFe₂O₄ thin films were analyzed in temperature and frequency range from 30 °C to 200 °C and 100 Hz to 1 MHz, respectively. In comparison to the pure BaTiO₃ films, the introduction of ferrite layer reduces dielectric response and increases low frequency permittivity dispersion of the multilayer thin films. The multilayer samples have shown relatively low dielectric loss with stronger contribution of conductivity at higher temperatures, and characteristic broad peak representing “relaxation” of the interface charge accumulation.     

The effects of the modification of the BST-system solid solutions with rare earth elements

The conditions for the preparation of the solid solutions of a binary system of barium-strontium titanates with the substitutions in the A-sublattice with the rare-earth elements (REE), including the solid-phase synthesis, mechanical activation and sintering of dispersed-crystalline products by the conventional ceramic technology, were optimized. The presence (absence) of the impurity phases was established depending on the size effect of the REE. The precision X-ray diffraction analysis revealed the features of the phase formation in the studied solid solutions and showed that the “behavior” of the structural characteristics of the solid solutions with the participation of the REE is determined by the limiting conditions of the isomorphism and anion excess of the media under study. An assumption is made about the nature of the formation of a fine-grained landscape of the modified solid solutions, associated with the multicluster structure of the crystallite structure and the formation of the ballast phases during their synthesis. The dependences of the dielectric properties of the solid-state solution on the external influences – temperature, frequency of an alternating electric field and strength of a constant field – have been established. The possibility of choosing on the basis of the obtained data, promising for practical applications of the compositions is shown.