Loss of material from TiSi2 films during annealing in hydrogen

Annealing of co-evaporated TiSi₂ layers on bare and oxidized silicon substrates at high temperatures (above 900 °C) in a hydrogen ambient may lead to loss of silicon from the film. Such a weight loss is caused by the formation of volatile SiO by reaction with trace impurities (of the order of 1 ppm) of oxygen of water vapour in the hydrogen. As well as the weight loss a decrease in the film thickness and an increase in the resistance of TiSi₂ layers on SiO₂/Si is observed. Such effects do not occur in hydrogen at lower temperatures or in an argon ambient. The residual contamination of argon with oxygen and hydrogen vapour leads to a passivation of the annealed samples with SiO₂ but has no measurable effect on the resistance of the TiSi₂ film.     

The influence of films thickness on hydrogenation behavior of titanium thin films

Titanium films of different thicknesses were prepared on sapphire substrates in an UHV chamber, by means of ion beam sputter deposition at room temperature, under Ar-atmosphere at the pressure of 1.5·10 E^?4 mbar. For electrochemical hydrogen loading, the films were covered by a 30-nm thick layer of Pd in order to prevent oxidation and facilitate hydrogen absorption. In situ stress measurements were conducted during step-by-step electrochemical hydrogen charging of the films. XRD measurements using a Phillips X-Pert diffractometer with a Co-Kα radiation were performed before and after hydrogenation in order to investigate the effect of hydrogen loading on the microstructure. The phase boundaries, as well as the stress and strain development during hydrogen absorption, depend strongly on the thickness of the films. The main characteristics of absorption behavior of hydrogen, as well as the thermodynamics and phase boundaries of titanium–hydrogen thin films are discussed in detail with specific emphasis on the influence of films thickness. The obtained results are also compared to literature data on the widely studied titanium–hydrogen bulk system. Shifted phase boundaries and narrowed two-phase field appear in Ti–H film system, which are mainly attributed to the microstructural contribution, as well as to the large stresses in the GPa-range that built up between the films and their substrate.     

Modelling Gas Transmission in Cylindrical Dynamic Accumulation Oxygen Transmission Rate Chambers to Explore Implications of Oxygen Sensor Location Relative to Samples

A model was developed to simulate oxygen accumulation in space and time within cylindrical dynamic accumulation chambers that are used to measure oxygen transmission rate (OTR) of materials. The model is based on Fick's law of diffusion and was validated against actual OTR measurements of polymer film samples. Measured OTR values and thicknesses were inputted into the model and oxygen concentrations outputted by the model. OTRs determined from the output of the model was in close agreement to within 0.3–3% of the measured OTR. Oxygen concentration versus time curves generated from model output oxygen concentrations and experimentally measured oxygen concentrations for three actual films were also in agreement. The model was then used to simulate results from three hypothetical test films at varying chamber lengths in order to evaluate effects of accumulation chamber dimensions relative to films on resulting OTR measurements. A typical design scenario was used, where the oxygen sensor is mounted on the chamber wall opposite the sample film. Results demonstrate that dynamic accumulation OTR instrument designers have considerable flexibility in choosing accumulation chamber dimensions because deviations in OTR are only expected to occur at impractically extreme chamber lengths (>10 m) for the entire envelope of OTRs expected for typical packaging films. Copyright © 2014 John Wiley & Sons, Ltd.     

Influence of substrate properties on the growth of titanium films: Part II

In situ internal stress measurements were used to investigate the influence of the chemical properties of the substrate on the growth of a titanium film deposited under UHV conditions. The substrate films used were titanium films evaporated at different water partial pressures. When the titanium film is evaporated at substrate temperatures of 130 °C and higher the shape of the stress vs thickness curve is interpreted to indicate island growth. Comparing the internal stress curve of titanium on Al₂O₃ and Ti/H₂O substrates it is seen that the initial tensile stress is significantly larger on the Ti/H₂O substrate film. This larger tensile stress is interpreted to originate from a redistribution of oxygen at the substrate interface during the early growth stage of the clean titanium film. A compressive stress contribution at higher thickness of the titanium film is interpreted to be due to hydrogen interdiffusion from the substrate into the titanium film. Annealing of the Ti/H₂O substrate films at 350 °C for 20 min reduces the concentration of the surface oxygen species and the amount of hydrogen incorporated in the films.

Dosing of previously annealed Ti/H₂O substrate films with water affects both the oxygen concentration on the surface of these substrate films and the amount of hydrogen incorporated in the films. Oxygen dosing of these films only increases the concentration of the oxygen species on the substrate surface; thus only the initial tensile stress built up in the titanium film is affected. Dosing the films with hydrogen, on the other hand, only increases the amount of hydrogen incorporated in the substrate film, which by way of interdiffusion into the growing titanium film gives rise to a larger compressive stress at higher film thickness     

负载桑葚花青素的葛根淀粉/壳聚糖复合膜的制备与表征

目的 研究桑葚花青素（Mulberry Anthocyanins, MA）添加量对葛根淀粉/壳聚糖复合膜理化性质及功能活性的影响。方法 以葛根淀粉和壳聚糖为成膜基材，MA为指示剂，采用流延法制备一种新型可食pH指示膜，测定葛根淀粉/壳聚糖复合膜的物理性能、抗氧化性、pH指示等性质，并将指示膜用于猪肉保鲜及新鲜度检测研究。结果 通过对添加不同MA含量的复合膜进行性能测试，发现MA和葛根淀粉之间氢键的形成，极大地改善了复合膜的拉伸强度。MA的加入使得成膜厚度、不透明度、拉伸强度（Tensile Strength,TS）、水蒸气透过率（Water Vapor Permeability,WVP）显著提高，断裂伸长率（Elongation At Break,EAB）显著降低。此外，MA增强了复合膜的抗氧化性和pH敏感性，MA-4的DPPH自由基清除率达到最大值85.24%。将复合膜应用于猪肉新鲜度检测，与对照组相比，负载MA的复合膜可抑制猪肉pH值和TVB-N值，并产生肉眼可辨的颜色变化，其中MA-3的颜色变化最为敏感。结论 加入一定量MA的复合膜能够改善其拉伸强度、不透明度、pH敏感性和抗氧化...     

钯对钛膜吸氢能力的抗污染作用的研究

为寻求一种防止因表面污染而导致钛膜吸氢能力下降的途径，用表面分析方法检测样品表面状态，用质谱仪测量样品吸氧能力，研究了表面状态和吸氢能力的相互关系。采用在钛膜上淀积钯膜（蒸发或溅射）的方法，可使受碳、氧污染的钛膜吸氢能力得以恢复。这种钯／钛复合结构在吸氢能力上对碳、氧污染并不灵敏。对样品的近费米能级处的占有电子态密度（densityofstate，DOS）的测量证明，凡吸氢能力良好的样品，DOS呈峰形结构。具有抗污染能力的钯／钛结构，其DOS因污染而导致的变化很小，而无抗污染能力的钛膜，其峰形结构受污染作用而消失。这种峰形结构能提供氢分子解离吸附过程中所需的电子。     

基体偏压模式对CrN薄膜结构和阻氢性能的影响

为了避免金属材料因为氢扩散而导致的失效,通常在其表面制备氧化物或氮化物等的阻氢薄膜,而薄膜的微观组织、晶体结构等对其阻氢性能的影响显著.本文在不锈钢基体上制备出CrN阻氢薄膜,系统研究了高/低基体偏压调制模式对CrN薄膜结构和阻氢等性能的影响.采用高功率磁控溅射技术在四组基体偏压模式下分别制备了具备一定高温抗氧化性的C...     

All-optical hydrogen-sensing materials based on tailored palladium alloy thin films

Optical reflectance measurements were performed to determine the hydrogen response characteristics of 20-nm-thick Pd-Au (Ag) films. The response characteristics displayed a strong dependence on alpha, mixed alpha/beta, and beta Pd-hydride phases formed in the films. The response time peaks in the alpha --> beta phase transition region (1625 s at 0.4% H(2) for Pd(0.94)Ag(0.06) and 405 s at 1% H(2) for Pd(0.94)Au(0.06)), consistent with critical slowing down phenomena. The alpha --> beta phase transition region was shifted and inhibited by changing the alloy element to Au and increasing its corresponding content to 40 atom %, respectively. Initial hydrogen uptake rate measurements determined that, due to the adsorption of ambient background gases, the rate-limiting step for alpha or beta phase PdH formation is dissociative chemisorption of hydrogen for each palladium alloy film. By tuning the alloy content and composition of the palladium films, the surface properties of the film become more receptive toward the rapid detection of hydrogen and a novel hydrogen-sensing material using Pd alloyed with 40 atom % Au is presented.     

The effect of oxygen and hydrogen contamination on the electrical resistivity of rare earth metal films

The effect of air and hydrogen contamination on the electrical resistivity of Er, Ho, Dy, Tb, Gd and Yb films was studied. The resistivity of the films increases almost discontinuously as soon as air is admitted into the vacuum chamber. After this sudden increase, the change becomes slow and the resistivity attains a constant value for thicker films (> 200 Å). For very thin films (<100 Å) the resistivity increases rapidly after the initial jump and very soon attains a very high value owing to the complete oxidation of the film. When hydrogen is admitted into the system, the resistivity of the films increases as for air contamination, but after a few minutes the resistivity starts to decrease except for Yb films. The increase in the resistivity for Er, Ho, Dy, Tb and Gd films is due to the interstitial solution of hydrogen in these metals (α phase); however, the decrease in ? after the initial increase is due to the formation of high conductivity f.c.c. dihydride. In the case of Yb the resistivity does not decrease because YbH₂ has a higher resistivity than pure Yb. For thin erbium films (about 200 Å) at a hydrogen pressure of several torrs the resistivity rises again after reaching a minimum value. This increase is thought to be due to the interstitial solution of hydrogen in the metallic conductor ErH₂. The investigation supports an earlier suggestion of the authors that the dihydride phase present in rare earth metal films (except Yb and Eu) made in ordinary vacuum may decrease the resistivity of these films below their bulk value.     

Gasochromic switching of reactively sputtered molybdenumoxide films: A correlation between film properties and deposition pressure

Molybdenumoxide (MoO_x) thin films can change their optical properties upon exposure to hydrogen. Since the film properties strongly depend on process parameters we have studied how the films are affected by the total pressure during deposition. Stoichiometric and sub-stoichiometric MoO_x films were prepared by reactive direct current magnetron sputtering in an atmosphere of argon and oxygen. Substoichiometric films were coated with platinum as a catalyst and were colored in diluted hydrogen atmosphere and bleached in air. Optical spectroscopy, X-ray reectometry, spectroscopic ellipsometry and simulations of the measured spectra were used to characterize the films ex situ. In situ switching characteristics as revealed by optical spectroscopy and changes in stress were measured as well. We find that the total pressure during sputter deposition has a strong influence on the optical constants, the film density, and the sputter rate. The mechanical stresses and switching Preprint submitted to Elsevier Science 10 March 2006 cycles during the film coloration and bleaching also strongly depend on the total pressure. The influence of the sputter pressure on film properties is explained by the kinetics during the sputter process.     

X-ray photoelectron spectroscopy and conducting atomic force microscopy investigations on dual ion beam sputtered MgO ultrathin films

Ultrathin films of MgO (~ 6 nm) were deposited on Si(100) using dual ion beam sputtering in different partial pressures of oxygen. These thin films were characterized by X-ray photoelectron spectroscopy (XPS) for chemical state analysis and conducting atomic force microscopy for topography and local conductivity map. No trace of metal Mg was evidenced in these MgO films. The XPS analysis clearly brought out the formation of oxygen interstitials and Mg(OH)₂ primarily due to the presence of residual water vapors in the chamber. An optimum value of oxygen partial pressure of ~ 4.4 × 10^− 2 Pa is identified with regard to homogeneity of film and stoichiometry across the film thickness (O:Mg::0.93-0.97). The local conductivity mapping investigations also established the film homogeneity in respect of electrical resistivity. Non-linear local current-voltage curves revealed typical tunneling characteristics with barrier width of ~ 5.6 nm and barrier height of ~ 0.92 eV.     

钛膜吸氢与释氢特性的研究

在SKL－12型多功能谱仪的预处理室中，采用超高真空镀膜的方法，得到了表面清洁的钛膜。对表面清洁及有一定量氧污染的钛膜进行了吸氢、释氢实验，并用理论模型拟合实验数据。结果表明：表面氧污染使钛膜吸氢能力降低，其原因在于氧原子占据了钛膜表面的吸附位置，使氢解离为原子的几率降低。     

利用氧等离子体预处理增强聚对苯二甲酸乙二醇酯/聚吡咯导电复合薄膜的界面粘附性

首先对聚对苯二甲酸乙二醇酯(PET)薄膜进行氧等离子体预处理,然后通过原位化学氧化聚合法使得吡咯单体在PET薄膜表面沉积聚合,制备了聚对苯二甲酸乙二醇酯/聚吡咯(PET-PPy)复合膜。通过原子力显微镜、X射线光电子能谱仪、ζ电位测试对经不同时长的氧等离子体预处理的PET薄膜进行表征;利用扫描电子显微镜、耐磨性实验和表面电阻测试对PET-PPy复合膜磨损前后的表面形貌和电阻进行分析与表征。结果表明,氧等离子体预处理显著增强了PET-PPy复合膜界面粘附性。氧等离子体预处理使PET薄膜表面粗糙度增大、电负性显著增强。特别地,当预处理时间为120s时,薄膜表面电负性明显增强,此时PET-PPy复合膜磨损后的电阻值变化最小,表明PET薄膜与PPy功能层界面粘附强度得到明显增强。     

Influence of substrate properties on the growth of titanium films: part III

The growth of thin Ti-oxide films (12 nm) on alumina substrate films formed by reactive evaporation of Ti in an oxygen atmosphere was studied by in situ internal stress measurements under ultra high vacuum conditions and transmission electron microscopy. Oxygen pressure and substrate temperatures were the varied parameters of the reactive evaporation. These Ti-oxide-films with different oxygen content (O₂/Ti-films) were then used as substrate films for the deposition of a clean titanium film. The growth stress of the titanium film on the as-deposited O₂/Ti-substrate films is comparable with that previously found for H₂O/Ti-substrates and indicates island growth and the formation of polycrystalline titanium films. Annealing (400°C, 20 min) of the as-deposited – amorphous – O₂/Ti-films gives rise to the formation of crystalline TiO₂. The amount of TiO₂ formed during annealing is strongly dependent on the oxygen content of the O₂/Ti-film. The oxygen content, in return, is dependent on oxygen partial pressure and substrate temperature during O₂/Ti-film deposition. The corresponding changes in the substrate film properties (oxygen content, crystallinity, etc.) are reflected in significant changes in the growth stress of the titanium film. The stress vs. thickness curve of these titanium films appears to indicate a superposition of the growth stress of two different growth modes, i.e. growth of a polycrystalline film with island growth on the as-deposited, amorphous oxide substrate and epitaxial growth of a quasi single crystalline film on the crystalline TiO₂-substrate.     

Crosslinking with ammonium zirconium carbonate improves the formation and properties of spruce galactoglucomannan films

Spruce (Picea abies) O-acetyl-galactoglucomannans (GGMs), low-value by-products from the forestry industry were upgraded to sustainable film-forming materials by crosslinking with ammonium zirconium carbonate (AZC). The purpose of crosslinking was to enhance the film formation, reduce the need of polyol plasticizers, and decrease the sensitivity of the film properties to moisture. Tensile testing showed that AZC-crosslinked GGM can be used to prepare strong and stiff films, with tensile strength up to 52 MPa and Young’s modulus of 4.7 GPa. Dynamic mechanical analysis, performed as a function of relative humidity (RH), showed that AZC-crosslinked GGM films retained their stiffness at higher RH than the reference films without AZC. Water vapor sorption and permeability analyses were done to further study the effect of moisture on the film properties, and those showed that the effect of sorbitol as a plasticizer depended greatly on RH. The oxygen permeability of the AZC-crosslinked GGM films was in the range of 4–11 [cm³ μm/(m² day kPa)]. GGM films could offer a bio-based and biodegradable alternative to existing synthetic oxygen barrier materials, on the condition that they are protected from the effects of moisture, e.g., by hydrophobic laminated layers.     

Studies on the effect of hydrogen doping during deposition of Al:ZnO films using RF magnetron sputtering

Aluminum doped ZnO (ZnO:Al) films were deposited using rf magnetron sputtering in the presence of hydrogen gas in the chamber. A comparative study of the films deposited with and without hydrogen was performed. The XPS studies indicated that the decrease in resistivity of ZnO:Al films with the introduction of hydrogen gas is attributed to the reduced adsorption of oxygen species in the film grain boundaries. The average percentage transmission in the visible region of the films was around 92–95% and band gap was found to be about in the range of 3.15–3.17 eV. The lowest resistivity of 1.8 × 10⁻⁴ Ω cm was achieved for the ZnO:Al film deposited with hydrogen.     

Cat-CVD-prepared oxygen-rich μc-Si:H for wide-bandgap material

Microcrystalline phase-involved oxygen-rich a-Si:H (hydrogenated amorphous silicon) films have been obtained using catalytic chemical vapor deposition (Cat-CVD) process. Pure SiH₄ (silane), H₂ (hydrogen), and O₂ (oxygen) gases were introduced in the chamber by maintaining a pressure of 0.1 Torr. A tungsten catalyzer was fixed at temperatures of 1750 and 1950 °C for film deposition on glass and crystalline silicon substrates at 200 °C. As revealed from X-ray diffraction spectra, the microcrystalline phase appears for oxygen-rich a-Si:H samples deposited at a catalyzer temperature of 1950 °C. However, this microcrystalline phase tends to disappear for further oxygen incorporation. The oxygen content in the deposited films was corroborated by FTIR analysis revealing SiOSi bonds and typical SiH bonding structures. The optical bandgap of the sample increases from 2.0 to 2.7 eV with oxygen gas flow and oxygen incorporation to the deposited films. In the present thin film deposition conditions, no strong tungsten filament degradation was observed after a number of sample preparations.     

表面氧污染影响钛膜吸氢量的机理

表面氧污染的钛膜，其吸氢能力比清洁钛膜降低达数倍之多。在厚度d为40nm，表面氧污染的钛膜表面上，重新蒸镀一层极薄的（约1．2nm）清洁钛膜，吸氢、释氢的测量表明其吸氢能力得到恢复。另外，还对其他四块不同厚度的钛膜，在表面清洁及氧污染的条件下，分别进行了吸氢能力实验。实验结果证实：氧污染降低钛膜吸氢能力的原因是使钛膜上氢分子解离的位置减少，而不是扩散阻挡层的作用。     

Benefits of carbon addition on the hydrogen absorption properties of Mg-based thin films grown by Pulsed Laser Deposition

Mg-Ni thin films were grown using Pulsed Laser Deposition. In situ optical changes from shiny metallic to transparent states were observed for films deposited in vacuum and under an Ar/H₂ gas mixture (93/7%), respectively. Optical changes were also achieved by ex situ hydrogenation under hydrogen gas pressure of 15 bars at 200 °C. However, after ex situ hydrogenation, the optical transmittance of the Mg-based hydrogenated thin films did not exceed 25%. Such limitation was attributed to oxygen contamination, as deduced by High Resolution Transmission Electron Microscopy observations, showing the co-existence of both Mg-based and MgO phases for as-deposited films. A significant decrease in oxygen contamination was successfully achieved with the addition of carbon, leading to the preparation of (Mg-based)-C_x (x < 20%) thin films showing a faster and easier hydrogenation.     

In-situ hydrothermal crystallization Mg(OH)2 films on magnesium alloy AZ91 and their corrosion resistance properties

Mg(OH)₂ films have been fabricated on magnesium alloy AZ91 substrates by an in-situ hydrothermal method. AZ91 alloy substrates act as both the source of Mg²⁺ ion and the support for the Mg(OH)₂ film in synthetic process. The effect of pH value and hydrothermal treatment time on the morphologies and corrosion resisting properties of Mg(OH)₂ film is studied. The obtained Mg(OH)₂ films are uniform and compact. The adhesion between the films and the substrate is strong due to the in-situ growth process, which enhances their potential for practical applications. Potentiodynamic polarization measurements showed that the Mg(OH)₂ films obtained at pH 10, 3 h exhibits the highest increase in corrosion potential at −0.7097 V and lowest i_corr, which suggests that it is the best effective film in improving the corrosion resistance of AZ91in all obtained films.