Recovery characteristics of optical hydrogen sensor using Pd thin film: Behaviour of three-stage hydrogen desorption

The recovery behaviour of optical hydrogen sensor using Pd film has been investigated. The change in reflectance with hydrogen desorption indicated distinctive characteristics with three-stage curve which depended on thickness of the Pd film. Moreover, the distinction became clearer with increasing number of absorption-desorption cycles. These behaviours were related to the change in pressure concentration isotherm.     

表面等离子共振氢敏传感器理论和模拟

提出了一种钯(Pd)膜氢敏感表面等离子共振传感器结构,该传感器以镀在棱镜端面的 Pd作为氢敏感膜。Pd 膜吸氢以后发生化学反应,生成的 PdHx使折射率发生变化,同时,它作为金属膜产生 SPW,当折射率变化时又在金属和介质表面产生表面等离子共振。利用 Fortran 语言程序进行了表面等离子共振氢敏传感器的 Pd 膜厚度和传感器灵敏度数值模拟。氢气浓度的变化引起折射率的变化,数值模拟表明,表面等离子共振氢敏传感器的灵敏度与 Pd 膜厚度有关,当 Pd膜的厚度在 10-30nm 时,氢气浓度在 1%-10%范围内具有较高的灵敏度。这种传感器结构将用于监测氢气作燃料的商用和军用机车的氢气泄漏。     

混凝土植筋锚固极限承载能力分析

混凝土植筋在工程上有广泛的应用,但植筋锚固与常规的钢筋锚固有很大的不同,规范中没有相应的设计计算理论。研究了混凝土植单筋与植群筋在拉拔力作用下的破坏形态与破坏机理,讨论了粘结胶厚度、混凝土强度、锚固深度、多根植筋组合效应等因素对混凝土植筋锚固极限承载能力的影响。分析了锥体-粘结复合破坏形态下的锚固承载能力,并与试验结果进行了比较。结果表明,理论分析与实验结果吻合良好。文中公式可供实际工程参考。     

Depth dependent properties of ITO thin films grown by pulsed DC sputtering

A systematically prepared set of ITO layers for solar cell applications has been analyzed by spectroscopic variable angle ellipsometry in order to trace the dependence of free carriers’ distribution along the film depth as a function of film thickness as well as its change upon annealing. Samples were deposited on silicon substrates with various thicknesses in steps of approximately 10–20 nm. This set was duplicated and these samples were annealed, so that for each thickness an as-deposited and an annealed sample is available. Conventionally measured electrical conductivity and morphological properties (AFM measurements) of the films have been compared with the optical constants’ inhomogeneity, i.e. material properties along the film thickness modelled by variable-angle spectroscopic ellipsometry. The obtained results show that the optical as well as electrical properties of thin ITO films prepared by pulsed DC sputtering are depth dependent. For the deposition conditions used a well-determined reproducible non-uniform distribution of free carriers within the film thickness was determined. In particular it has been found that the majority of free carriers in as-deposited ultra-thin ITO films is concentrated at sample half-depth, while their distribution becomes asymmetric for the thicker films, with a maximum located at approximately 40 nm depth. The distribution of free carriers in annealed samples is qualitatively different from that of as-deposited layers.     

铝酸盐体系下反应时间对ZrH1.8表面阻氢膜层制备的影响

采用微弧氧化技术在NaAlO₂电解液体系下制备ZrH_1.8表面阻氢膜层, 采用场发射扫描电子显微镜(FE-SEM), X射线衍射(XRD), 真空脱氢实验对膜层进行表征, 考察不同反应时间对ZrH_1.8表面阻氢膜层的厚度、形貌、相结构以及阻氢性能的影响规律。研究结果表明：当反应时间在7.5~15 min变化时, 膜层厚度由78.4 μm增大至152.8 μm。膜层由单斜相M-ZrO₂、四方相T-ZrO₂以及立方相C-ZrO₂组成, 反应时间对膜层的相组成并无明显影响。阻氢膜层由致密层和疏松层构成, 膜层外侧为疏松层, 靠近基体一侧为致密层。当反应时间为10 min时, 获得的膜层表面平整, 致密性较好, 厚度适中, 膜层的氢渗透降低因子PRF值为20。     

Influence of hydrogen on the mechanical properties and microstructure of DLC films synthesized by r.f.-PECVD

This paper aims to investigate the influence of hydrogen on the variation of mechanical properties and microstructure of diamond-like carbon (DLC) films synthesized by radio frequency plasma chemical vapor deposition (r.f.-PECVD). The DLC films were deposited on a silicon substrate (p-type). The reactant gases employed in this paper are a mixture of acetylene and hydrogen. The ratio of hydrogen in the gas mixture was successively varied to clarify its influence on the roughness, thickness, microstructure, hardness, modulus, residual stress and wear depth for the DLC films. The results reveal that increasing the concentration of hydrogen decreases thickness and roughness. Meanwhile, increasing the hydrogen concentration causes the decrease of sp³ ratio, hardness as well as modulus. Finally, wear behavior is correlated to the surface morphology and hydrogen concentration for deposition with hydrogen-containing reactant gas.     

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     

Developments in nuclear techniques for hydrogen depth profiling

Hydrogen plays a crucial role in the properties of various materials, devices and in growth of hydrogenated amorphous materials. Therefore, its quantification and determination of concentration at various depths is of immense interest. Among various techniques of hydrogen depth profiling, the nuclear techniques being non-destructive in nature are widely used. Elastic recoil detection analysis (ERDA) with helium ions was first used for hydrogen depth profiling. Later on, the heavy ions were utilised due to certain advantages. It has been shown recently by us that H alongwith other elements in thin film up to Ca can be detected simultaneously with heavy ion ERDA, if the elements being detected are well separated in masses. It also has been shown that even the neighbouring elements such as C, N, O alongwith H can be detected provided a ΔE-E detector telescope is used in ERDA. The time of flight (TOF) with ERDA, nuclear reaction analysis (NRA), neutron TOF are other nuclear techniques such as hydrogen loss during the measurement, which must be taken into account for accurate and reliable results. A scenario of developments in nuclear techniques with suitable examples is given in this brief review.     

Formation mechanism of nano-diamond films from energetic species: From experiment to theory

In this paper, a particular class of nano-diamond films deposited by energetic species is described. Deposition is carried out using the direct-current glow-discharge (DC GD) deposition technique from a methane/hydrogen mixture. In this method, film growth occurs from energetic species being accelerated and incorporated into the film surface. The growth of the nano-diamond film occurs on top of a preferentially oriented graphitic precursor with its basal planes perpendicular to the substrate surface. The nano-diamond films consist of an agglomerate of diamond particles with particle sizes in the 3-5 nm range with amorphous grain boundaries. The hydrogen concentration in the graphitic precursor is only a few percent; however, it increases to ∼15-20 at.% in the nano-diamond film.From a microscopic perspective nano-diamond film and growth from energetic species is explained as a sub-surface process in terms of a four-step cyclic process. The DC GD-deposited nano-diamond films were comprehensively explored by a number of complementary techniques. The hydrogen content and its role in nano-diamond film formation were assessed. The experimental methods used in our studies comprise near-edge X-ray adsorption fine structure (NEXAFS) to prove the short-range coordination of the carbon films and indirectly their phase composition. The surface and grain boundary phase composition were investigated by a combination of electron energy loss spectroscopy (EELS) measured as a function of incident electron energy and hydrogen etching experiments. By transmission electron microscopy (TEM), the micro-structural evolution and their visualization were achieved. The density evolution of the films was determined by X-ray reflectivity (XRR). The hydrogen content and its distribution in the films were studied by secondary ion microscopy spectroscopy (SIMS) and elastic recoil detection (ERD). The hydrogen bonding was investigated by high-resolution electron energy loss spectroscopy (HREELS).Most likely, hydrogen is bonded within the amorphous grain boundaries and saturates the nano-diamond particles. The surface of the films is amorphous in nature.     

Influence of ion bombardment on depth resolution in Auger electron spectroscopy analysis of thin gold films on nickel

Thin film Auger electron analysis of gold films on nickel was performed while simultaneously sputtering with argon ions. The influence of film thickness, electron and ion beam energies, ion beam current density and initial surface roughness on depth resolution was investigated. The intrinsic limitations of depth resolution result from the escape depth of Auger electrons and from atomic mixing due to ion impact. Prolonged ion sputtering leads to the development of microroughness. The influence of this last effect is described by an empirical correlation which shows the width of the transition region to increase with the square root of the product of ion beam energy and film thickness. The original surface roughness also affects depth resolution but, at higher ion beam energies (2 keV) in particular, its influence is somewhat masked by ion-induced microroughness. Optimum resolution (5% of film thickness) in depth profiling is obtained by employing well-polished samples and low ion beam energies.     

Equilibrium depth and spacing of cracks in a tensile residual stressed thin film deposited on a brittle substrate

The depth and spacing of cracks in a tensile residual stressed thin film bonded on a brittle substrate are analyzed thermodynamically using the minimum energy theorem on the basis that the film has the same mechanical properties as the substrate. The results show that the cracks penetrate into the substrate. Simple and approximate relationships between three dimensionless parameters, i.e., the normalized crack depth and spacing, and the cracking resistance number, are derived, which determine the fracture behavior of the film.     

Thermal Diffusivity Measurement for Titanium Thin Films on Copper Substrate by Laser Produced Plasmas

The transport properties of condensed phase materials are, in principle, dependent on the local structure and composition of the specimen. This is particularly evident near the free surface of a solid alloy specimen where the morphology, composition, and thermal diffusivity exhibit significant depth dependence, as demonstrated in an earlier study of the depth-resolved thermal diffusivity of a galvanized steel specimen. A new non-contact method was used, based on time-resolved, spectroscopic measurement of the total mass removed from the specimen surface representatively in elemental composition by a high-power laser pulse. A new study of a titanium thin film of varying thickness deposited on a copper substrate is presented. The titanium thin film is first fabricated in a vacuum and then immediately analyzed for composition and thermophysical properties in situ, both by the method of representative laser-produced plasmas (LPP). Successive ablation layers of the thin film, as exposed by LPP ablation, have revealed the dependence of the thermophysical properties on film thickness as well as on depth. The existence of a characteristic length over which the substrate influences the dynamics of thermal transport in the titanium thin film has also been observed.     

Determination of hydrogen absorption in Pd coated Al thin films

Al films, 80–85 nm in thickness and 10–30 μΩ cm in resistivity, are coated with Pd (8–40 nm). The bilayer is exposed to a hydrogen atmosphere of up to 4.0 kPa. The hydrogen concentration is calculated from the frequency change in a quartz crystal microbalance and the electrical resistance of the Pd film, the Al film and the bilayer is measured as function of hydrogen pressure. Concentration and resistance measurements indicate that the Pd coating enables the Al films to absorb hydrogen from the gas phase.     

Correlation between diamond grain size and hydrogen incorporation in nanocrystalline diamond thin films

Hydrogen-incorporated nanocrystalline diamond thin films have been deposited in microwave plasma enhanced chemical vapour deposition (CVD) system with various hydrogen concentrations in the Ar/CH₄ gas mixture. The bonding environment of carbon atoms was detected by Raman spectroscopy and the hydrogen concentration was determined by elastic recoil detection analysis. Incorporation of H₂ species into Ar-rich plasma was observed to markedly alter the microstructure of diamond films. Raman spectroscopy results showed that part of the hydrogen is bonded to carbon atoms. Raman spectra also indicated the increase of non-diamond phase with the decrease in crystallite size. The study addresses the effects of hydrogen trapping in the samples when hydrogen concentration in the plasma increased during diamond growth and its relation with defective grain boundary region.     

Specific Heat and Superfluid Density of 4He near T λ of a 33.6 nm Film Formed Between Si Wafers

We report measurements of superfluid density and specific heat of a 33.6 nm film near the superfluid transition. The film is formed between two patterned and directly bonded silicon wafers. These measurements were undertaken with the primary purpose of understanding coupling and proximity effects in a situation when the film was in contact with helium in a larger confinement (Perron et al. in Nat. Phys. 6:499, 2010; Perron and Gasparini in Phys. Rev. Lett. 109:035302, 2012). However, these data are also relevant to issues of correlation-length finite-size scaling. This is the thinnest hard-wall confined film for which such scaling has been tested for the specific heat and superfluid density. One expects that at some small thickness such scaling should fail. We compare our results with previous data of helium in a similar confinement but at larger thickness. We find good agreement with scaling in regions where previous data scaled, and confirm the lack of scaling where previously reported. In our analysis we consider a native oxide growth between the etching and bonding steps of cell fabrication and its effect on our scaling analysis.     

直流磁控溅射Ni49.54Mn29.59Ga20.87磁驱动记忆合金薄膜的XPS研究

采用直流磁控溅射技术沉积了Ni49.54Mn29.59Ga20.87磁驱动形状记忆合金薄膜.XRD结果表明,Ni49.54Mn29.59Ga20.87薄膜室温下为5层调制型结构马氏体.X射线光电子能谱(XPS)分析表明,放置于空气中2个月的沉积态薄膜表面吸附少量氧和碳杂质.随Ar 刻蚀深度的增加,表面C杂质易被剥蚀掉,而部分氧杂质以MnO状态存在;Ni、Mn、Ga元素含量由薄膜表面向内层逐渐增加,化学价由正价向零价转变.     

Nanoindentation and deformation properties of nanoscale silicon carbide films on silicon substrate

We propose a model to describe the microhardness of a nanoscale film-substrate system as a function of the depth of indenter penetration. The proposed model has been used to study the deformation characteristics of a nanometer-thick silicon carbide (SiC) grown on a silicon substrate by the method of atomic substitution. The microhardness of as-grown SiC film and a modified silicon layer has been determined. The SiC film thickness has been determined using the nanoindentation technique. The data of nanoindentation are in good agreement with the results of ellipsometric measurements.     

A NEW MACHINE FOR COMBINED VAPOUR DEPOSITION AND ION IMPLANTATION

A low energy ion implanter has been adequately modified in order to perform reactive ion beam enhanced deposition (RIBED) and dynamic recoil ion mixing experiments under controlled conditions in a high vacuum environment (better than 10^-5Pa). The machine consists of a Duoplasmatron ion source, a mass analyzer, a target chamber adaptable for use with various samples, and a 2 crucible electron gun evaporator equipped with film thickness monitor

In this apparatus, independently controlled atom and ion beams of different species able to form the required compounds, impinge sequentially (or simultaneously) on a 4×8 cm²area with a good uniformity (10%). Ion mixing prevails in the first steps of the treatment, resulting in a good relative adhesion between substrate and film; then the RIBED film is grown up to typically 1 um, this thickness being equivalent to a total implanted dose of 1.0×10¹⁹ions/cm²with an excellent depth homogeneity and without sputtering limitations.     

ECR-CVD方法生长a-SiNx:H薄膜的研究

使用微波电子回旋共振等离子体化学气相沉积(ECR-CVD)方法室温生长了非晶氢化的氮化硅薄膜,通过改变前驱气体(SiH4 80%Ar和NH3)的流量比,研究了薄膜的生长速率、等离子体的发射光谱和薄膜的红外特性.结果表明:随着NH3流量的增加,氮化硅薄膜的生长速率呈下降趋势,这主要是由于等离子体中的气相前驱成分之一硅基团浓度的不断下降所导致的;随着NH3流量的增加,薄膜中键合了较多的具有较高电负性的N原子是Si-N和Si-H伸缩振动发生蓝移的主要原因.红外光谱的定量计算表明所制备的氮化硅薄膜具有相对较低的H浓度,约15%左右.文中对氮化硅薄膜的生长机制也进行了讨论.     

Thickness dependence of structure and optoelectronic properties of In2O3:Mo films prepared by spray pyrolysis

The influence of thickness on the structural, morphological and optoelectronic behavior of Mo-doped In₂O₃ films, prepared by spray pyrolysis was investigated. The films had the cubic crystal structure for all the thicknesses investigated although it was found that a change in the preferred orientation and growth mode, from 2D to 3D, has occurred with an increase of film thickness. A small degradation in the optical transmittance has been observed with the increase of film thickness. The variation of electrical resistivity, mobility and charge carrier concentration with film thickness were also studied and the results discussed.