Growth evolution of CaB6 thin films deposited by DC magnetron sputtering

CaB₆ films were deposited by a DC magnetron sputtering method to explore the growth evolution systematically through changing sputtering time. The crystalline structure was characterized by XRD and GIXRD respectively, which showed that the films were anisotropic with nanocrystalline structure. The grain sizes increased with the deposition time, and a weak (100) texture appeared when the deposition time reached to 120 min. HRTEM was employed to demonstrate the crystalline structure. The surface morphology evolution of CaB₆ films was analyzed by AFM and FESEM. The results showed that the films were initially formed by fine columnar grains. With the deposition time extended, the films exhibited a dense columnar structure with faceted surfaces. The grain size, film thickness and crystallization degree all increased with the sputtering time.     

Comprehensive characterization of CIGS absorber layers grown by one-step sputtering process

We have demonstrated that the use of a one-step sputtering process allowed for the fabrication of copper indium gallium diselenide (CIGS) thin films by RF magnetron sputtering without an additional selenization process. The CIGS thin films deposited at different substrate temperatures were synthesized on soda-lime glass (SLG) substrates using a single quaternary CIGS target. The film composition ratios of ([Cu]/[In]+[Ga]), ([Ga]/[In]+[Ga]), and ([Se]/[Cu]+[In]+[Ga]) were almost consistent with those of the sputtering target. X-ray diffraction (XRD) and Raman results showed that the crystallinity of the CIGS thin films was gradually improved as substrate temperatures increased. Transmission electron microscopy (TEM) showed that the films grown at 600?°C have a columnar structure with the grain size of ~100?nm. In addition, for the CIGS films grown at 600?°C, TEM-EDX analysis revealed that the synchronized fluctuation of the Cu and Se signals was observed in the direction of the film depth, while the In and Ga signals were constant. As a result, the CIGS solar cell made using the film showed a degraded cell efficiency of 2.5%, which might be have been caused by not only Cu-rich and Se-poor compositions but the locally unstable composition in the CIGS films fabricated by one-step sputtering.     

Thin film YSZ coatings on functionally graded freeze cast NiO/YSZ SOFC anode supports

Intermediate temperature (600–800 °C) solid oxide fuel cell (SOFC) technology is often limited by inadequate gas transport in electrodes, and high ion transport resistance electrolytes. In this study, large area filtered arc deposition (LAFAD) and hybrid filtered arc-assisted e-beam physical vapor deposition (FA-EBPVD) technologies, in combination with freeze-tape-casting, were used to fabricate SOFC anode/electrolyte bi-layers with functionally graded porous anode microstructures and thin film electrolytes favorable for both gas transport and low resistance. Traditionally-processed NiO/YSZ in addition to freeze-tape-cast NiO/YSZ anode substrates were fabricated and subsequently coated with thin film (<1–20 μm) YSZ via LAFAD and FA-EBPVD. LAFAD was found to be effective in applying thin (~1 μm) dense YSZ films on porous substrates at ~400 °C. FA-EBPVD produced relatively thick (~10–20 μm) dense YSZ coatings on porous substrates, with columnar morphology and nano-metrical grain size. A ~10 μm FA-EBPVD YSZ coating was observed to bridge NiO/YSZ surface pores of ~10 μm, which typically requires pre-filling prior to conventional thin film coating processes. Coated substrates exhibited negligible curvature, yielding flat anode/electrode bi-layers up to 2.5 cm in diameter. These results are presented with conderations for future SOFC development discussed.     

Yttria-stabilized zirconia thin film electrolyte deposited by EB-PVD on porous anode support for SOFC applications

Electron beam physical vapor deposition (EB-PVD) has been used to deposit thin film (YSZ) electrolytes on NiO-YSZ composite substrates pre-sintered at 1100 °C, followed by further sintering at 1400 °C in order to achieve dense films. Surface morphology of deposited layers has been investigated by AFM and FE-SEM. Increasing the deposition time and YSZ films thickness results in higher roughness and mean particle size of the thin film layer. FE-SEM observations of fresh fractured anodic half cells confirmed dense, crack-free, homogeneous and intensely adhered YSZ electrolyte layers. Sintering behavior of NiO and YSZ grains has been also investigated by the micrographs of cross sections of NiO-YSZ substrates.     

Crystalline structure of YSZ thin films deposited on Si(111) substrate by chemical vapor deposition

Yttria-stabilized zirconia (YSZ) thin films were formed on Si(111) substrate by chemical vapor deposition (CVD) in a temperature range of 650–800 °C using β-diketone metal chelates. The scanning electron microscopy (SEM) and X-ray diffraction (XRD) data evidenced that YSZ thin films have a smooth surface with fine grains and crystalline structure, respectively. The crystalline structure of YSZ films was affected by the deposition temperature. The X-ray photoelectron spectroscopy (XPS) data indicated that the YSZ film grows thick enough to prevent the diffusion of Si.     

Photoactivity enhancement of zinc sulfide ceramics thin films through ultrathin buffering engineering

Zinc-sulfide (ZnS) thin films 200 nm-thick with various crystal features were fabricated using RF sputtering onto patterned sapphire substrates with and without ultrathin homo-ZnS and hetero-zinc oxide (ZnO) ultrathin buffer layers (approximately 45 nm in thickness). Microstructural analyses revealed that the crystalline ZnS thin films with a columnar grain feature were deposited on the various ultrathin buffer layers-coated substrates through RF sputtering. The surface morphology of the ZnS thin films became rough and the crystal defect density of the ZnS thin films increased when the ZnS thin films were grown on the buffer layers. Comparatively, the rugged and island-like ZnO buffer layer engendered the crystal growth of the ZnS thin film with a higher degree of structural disorder than that of the crystal growth on the ZnS buffer layer. An increased crystal defect number together with the highly rugged film surface of the ZnS thin film buffered with ultrathin ZnO layers efficiently enhanced the photoactivity of the 200 nm-thick ZnS thin film in this study.     

Preparation of Nanostructured ZnO Thin Films Using Magnetron Sputtering for the Gas Sensors Applications

ZnO is one of the most promising transparent conducting oxide materials, which widely used in thin film gas sensors. In this research, the dependence of the thermal oxidation time on structural, morphological and gas sensing properties of ZnO thin films is investigated. ZnO nanostructures are synthesized by using DC magnetron sputtering for deposition of pure zinc layers on glass substrates and then thermal oxidation of deposited zinc layers to produce zinc oxide (ZnO) thin films. Obtained results from X-ray diffraction revealed that the degree of crystallinity and the average grain size of the ZnO deposited thin films enhance with increasing the thermal oxidation time. Surface topography and growth behavior of ZnO thin films have important role in optimization of gas sensing properties of these films. In this study, scanning electron microscopy and atomic force microscopy have been used to investigate the effective parameters related to the surface topography of the films. Obtained results from these analyzes revealed that the surface topography of ZnO deposited samples strongly depend on thermal oxidation time. Also the effect of thermal oxidation time on the performance of ZnO gas sensors is investigated. The results indicated that the ethanol gas sensing properties of ZnO samples improve with decreasing the size of grains.     

Lead Zirconate Titanate Thin Films by Aerosol Plasma Deposition: Microstructure Analysis

Lead zirconate titanate (Pb(Zr,Ti)O₃, PZT) thin films were grown on silicon 〈100〉 substrate by aerosol plasma deposition (APD) using solid-state-reacted powder containing donor oxide Nb₂O₅ when keeping the substrate at room temperature and 200°C. Crystalline phases of the deposited films have been analyzed via X-ray diffractometry (XRD), and microstructure via scanning and transmission electron microscopy (SEM and TEM). Cross-sectional TEM revealed that the microstructure comprised several layers including the deposited PZT film and the platinum-electrode-and-titanium-buffered layers on SiO₂–Si substrate. The Pt-electrode layer contained (111)_Pt twinned columnar grains with a slight misorientation and forming low-angle grain boundaries among them. The PZT layer contained randomly oriented grains embedded in an amorphous matrix. Some of the PZT grains, oriented with the zone axis Z = [[Twomacr]11]_PZT parallel to Z = [111]_Pt, were grown epitaxially on the Pt layer by sharing the (111)_PZT plane with the (111)_Pt twinned columnar Pt crystals. However, the existence of such an orientation relationship was confined to several nanosize grains at and near the PZT-Pt interface, and no gross film texture has been developed. An amorphous grain boundary phase, generated by pressure-induced amorphisation (PIA) in the solid state, was identified by high-resolution imaging. Its presence is taken to account for the densification of the PZT thin films via a sintering mechanism involving an amorphous phase on deposition at 25° and 200°C.     

Development of robust YSZ thin-film electrolyte by RF sputtering and anode support design for stable IT-SOFC

Thin-film solid oxide fuel cells (TF-SOFCs) have attracted attention as a strategy for lowering the operating temperature of SOFCs. However, the porous and rough surface of the SOFC support and the shadowing effect have hindered the construction of pinhole-free thin-film electrolytes during sputtering. In this study, we report the deposition of a gas-tight YSZ thin-film electrolyte (approximately 0.8 μm) by RF sputtering on a Ni-YSZ anode support. To utilize a sputtered thin film as an electrolyte, we examined the relationship between the deposition pressure and thin-film properties and determined the optimal deposition conditions. By designing the anode functional layer (AFL) and annealing, a thin-film electrolyte is successfully deposited on the porous Ni-YSZ support without cracks and pinholes. The resulting thin-film electrolyte cell achieves a high open-circuit voltage (OCV) of approximately 1.09 V and a maximum power density of 0.446 W/cm² at 600 °C, which implies high ionic conductivity and gas tightness. Moreover, the single cell exhibited exceptional long-term stability (140 h) despite the extremely thin and vacuum-deposited electrolyte components. This study provides guidelines for the practical application of thin films as electrolytes to lower the operating temperature of SOFCs.     

Chemical solution deposition of pure and Gd-doped ceria thin films: Structural,morphological and optical properties

High quality smooth, uniform and crack-free ceria and gadolinium doped ceria (GDC) thin films were prepared on Si and Si/YSZ substrates by chemical solution deposition. The thermal behavior of Gd-Ce-O precursor was investigated by TG-DSC measurements. The phase purity and structure of deposited films were evaluated using X-ray diffraction (XRD) analysis and Raman spectroscopy. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were employed for the estimation of surface morphological features. Oxidation state of Ce ions in fabricated films was analyzed by X-ray photoelectron spectroscopy (XPS). Optical properties were evaluated by diffuse reflectance UV–vis spectrometry. Thickness of the films can be controlled by applying a certain number of spin coating cycles. A linear relation between the thickness of the films and the number of deposited layers was observed. The single-layer thickness was determined to be approximately 20 nm. The influence of annealing temperature and Gd content on the film structure, morphology and optical properties was studied and discussed. The dependence of an optical band gap as a function of grain size was demonstrated.     

Optimization of DC Reactive Magnetron Sputtering Deposition Process for Efficient YSZ Electrolyte Thin Film SOFC

Yttria‐stabilized zirconia (YSZ, ZrO₂:Y₂O₃) thin films were deposited by reactive DC magnetron sputtering with a high deposition rate from a metallic target of Zr/Y in an argon/oxygen atmosphere. Plasma parameters and composition analysis of the gas phase reveal that the sputtering process in the “compound” mode is reached for a 2.5 sccm oxygen flow rate. Deposition onto silicon in “metal” mode at a flow rate close to the transition, allows obtaining at very high deposition rates (>10 μm h^–1) a compact columnar stoichiometric crystallized YSZ film. When deposited on NiO‐YSZ commercial anode, the obtained coatings show the same properties. In spite of the complexity of the substrate (roughness and porosity), a compact and conformed layer was formed. Annealing treatments in air or hydrogen do not significantly alter the structure of the layers. Electrochemical test at 850 °C with a screen‐printed LSM (LaSrMnO₃) cathode exhibits a satisfying gastightness (OCV = 900 mV) and a maximum power density of 350 mW cm^–2.     

Effects of Individual Layer Thickness on the Microstructure and Optoelectronic Properties of Sol–Gel-Derived Zinc Oxide Thin Films

Zinc oxide (ZnO) thin films were prepared under different conditions on glass substrates using a sol–gel process. The microstructure of ZnO films was investigated by means of diffraction analysis, and plan-view and cross-sectional scanning electron microscopy. It was found that the preparation conditions strongly affected the structure and the optoelectronic properties of the films. A structural evolution in morphology from spherical to columnar growth was observed. The crystallinity of the films was improved and columnar film growth became more dominant as the zinc concentration and the substrate withdrawal speed decreased. The individual layer thickness for layer-by-layer homoepitaxy growth that resulted in columnar grains was <20 nm. The grain columns are grown through the entire film with a nearly unchanged lateral dimension through the full film thickness. The columnar ZnO grains are c -axis oriented perpendicular to the interface and possess a polycrystalline structure. Optical transmittance up to 90% in the visible range and electrical resistivity as low as 6.8 × 10⁻³·Ω·cm were obtained under optimal deposition conditions.     

Microstructure Evolution of Pulsed Laser-Deposited (Ba, Sr)TiO3 Films on MgO for Microwave Applications

To develop low-loss tunable microwave circuits, based on the field dependence of dielectric permittivity, phase pure (Ba_0.5, Sr_0.5)TiO₃ doped with 1% W (BST) thin films 0.3-μm thick were deposited on single crystal MgO wafers by pulsed laser deposition. The BST films were characterized by X-ray θ–2θ scans and pole figure analysis, field emission scanning electron microscopy (FESEM), and cross-sectional transmission electron microscopy (TEM), coupled with selected-area electron diffraction (SAED). Although, the X-ray θ–2θ scan indicated an epitaxial nature of BST with an out-of-plane orientation of (100), the pole figure analysis confirmed the presence (4–6%) of (111)-oriented grains in a matrix of (100) textured grains. The columnar grains exhibited an in-plane (i.e., along the plane perpendicular to the growth direction) grain size that was thickness-dependent. The cross-sectional TEM, coupled with SAED in the thickness direction, corroborated the pole figure analysis. Additionally, from X-ray analysis, it was observed that the textured films were under in-plane tension. The deposited film was characterized at microwave frequencies (1–20 GHz) using interdigitated electrodes deposited on top of the film. The film was characterized by a relatively low dielectric Q of 5–7. A 17% change in the capacitance was observed when applying a 40 V bias. From the observed microstructure, a preliminary understanding of its evolution and its relationship with the microwave dielectric properties is discussed, and some ideas to obtain truly epitaxial BST films are presented.     

Niobium-based catalysts prepared by reactive radio-frequency magnetron sputtering and arc plasma methods as non-noble metal cathode catalysts for polymer electrolyte fuel cells

Two vacuum methods, reactive radio-frequency (RF) magnetron sputtering and arc plasma deposition, were used to prepare niobium-based catalysts for an oxygen reduction reaction (ORR) as non-noble metal cathodes for polymer electrode fuel cells (PEFCs). Thin films with various N and O contents, denoted as NbO_x and Nb-O-N, were prepared on glassy carbon plates by RF magnetron sputtering with controlled partial pressures of oxygen and nitrogen. Electrochemical measurements indicated that the introduction of the nitrogen species into the thin film resulted in improved ORR activity compared to the oxide-only film. Using an arc plasma method, niobium was deposited on highly oriented pyrolytic graphite (HOPG) substrates, and the sub-nanoscale surface morphology of the deposited particles was investigated using scanning tunneling microscopy (STM). To prepare practical cathode catalysts, niobium was deposited on carbon black (CB) powders by arc plasma method. STM and transmission electron microscopy observations of samples on HOPG and CB indicated that the prepared catalysts were highly dispersed at the atomic level. The onset potential of oxygen reduction on Nb-O-N/CB was 0.86 V vs. a reversible hydrogen electrode, and the apparent current density was drastically improved by the introduction of nitrogen.     

在ITO玻璃衬底上制备锆钛酸铅铁电薄膜

利用射频反应性溅射沉积技术在掺的Ｓｎ的Ｉｎ２Ｏ３导电透明膜衬底上制备了钙钛矿型Ｐｂ（Ｚｒ,Ｔｉ）Ｏ３（ＰＺＴ）铁电薄膜。研究了沉积参量与热处理工艺对铁电薄膜结构和性能的影响。运用Ｘ射线衍射、Ｘ射线光电子能谱和扫描电镜等技术,分析了薄膜的晶体结构、表面形貌和表面元素化学状态。测量了不同处理条件下薄膜的铁电性能。结果表明：在掺Ｓｎ的Ｉｎ２Ｏ３导电透明膜衬底上可以得到表面无裂纹,化学计量比符合要求的ＰＺ     

Low temperature growth of gallium nitride

Radio frequency reactive sputtering was used to produce gallium nitride films on glass and silicon substrates at close to room temperature. The films were analysed by transmission electron microscopy and Rutherford backscattering spectroscopy. The films were found to consist of nanocrystalline wurtzite GaN with c-axis-oriented columnar grains growing perpendicular to the substrate. Varying the N₂:Ar sputtering gas ratio was found to have little effect on the grain size. Annealing the films at 400°C was found to increase the E₁(TO) signal observed by Fourier transform IR spectroscopy and to reduce the porosity of the columnar structure.     

铝锰合金表面直流反应磁控溅射制备氧化铟锡薄膜

采用直流反应磁控溅射在AlMn合金表面制备出ITO薄膜.采用扫描电镜、X射线衍射、紫外-可见光测试、磨损试验、盐雾试验、薄膜厚度测量和显微硬度试验等方法对制备的ITO薄膜表面进行检测分析.结果表明:在溅射功率210 W、衬底温度120℃、溅射时间20 min的条件下,AlMn合金表面的ITO薄膜晶粒尺寸细小,与基底结合良好,AlMn合金表面光泽度好,强度、硬度高,并具有一定的耐磨、耐蚀性能.     

Synthesis of nanoporous platinum thin films and application as hydrogen sensor

A nanoporous platinum (np-Pt) thin film based hydrogen sensor was fabricated and studied. The np-Pt thin films were fabricated through a method of chemical dealloying and coarsening starting from a CuPt alloy. The alloy thin films of Cu_xPt_1?x were deposited by sputtering copper and platinum at the same time. The dealloying process completely removed the copper from the film. We demonstrate a method to control the porosity of np-Pt by a method of coarsening. Scanning electron microscopy confirmed the presence of porosity with size ranging from a few nanometers to tens of nanometers. A sensor device with four electrodes was fabricated on the np-Pt thin films using a stainless steel mask and by sputtering copper. The electrical characteristics of the sensor exhibit marked sensitivity or current changes in the presence of hydrogen. The results demonstrate that np-Pt thin films configured as a gas sensor have high sensitivity to hydrogen.     

Microstructure of Molybdenum Disilicide-Silicon Carbide Nanocomposite Thin Films

Composite thin films of molybdenum disilicide-silicon carbide (MoSi₂-SiC) have been deposited via rf magnetron sputtering onto molybdenum substrates. An intermediate layer was deposited in the presence of nitrogen gas and evaluated as a potential diffusion barrier layer. The composite films have been characterized using X-ray diffractometry, scanning electron microscopy, transmission electron microscopy, and Auger electron spectroscopy. The as-deposited films were amorphous but crystallized into nanometer-sized grains after annealing under vacuum at 1000°C for 30 min. There was a significant amount of interdiffusion between the film and substrate, which resulted in the formation of subsilicides such as Mo₅Si₃ and MoSi₃, as well as Mo₂C. The films that were deposited via reactive sputtering in a nitrogen ambient were amorphous in both the as-deposited and annealed conditions. Significantly fewer second phases were detected with the presence of the intermediate layer, which suggests the potential use of the nitrided (MoSi _x N _y C _z ) layer as a high-temperature diffusion barrier layer for the silicon and carbon.