Electrodeposition of CoMoP thin film as diffusion barrier layer for ULSI applications

CoMoP thin films were fabricated by electrodeposition technique from citrate based bath onto Cu sheets for the application as diffusion barriers and metal capping layers in the copper interconnect technology. The study focused on the effect of (NH₄)₆Mo₇O₂₄·4H₂O concentrations in the plating solution on the plating rate and chemical composition of the deposited layer. It was found that the Mo wt.% in the deposited layer increased from 13 to 22 wt.% with increasing (NH₄)₆Mo₇O₂₄·4H₂O concentration. The influence of deposition current density, solution pH and deposition temperature at certain (NH₄)₆Mo₇O₂₄·4H₂O concentration in the plating bath on the plating rate and chemical composition was studied. Polarization behavior of induced co-deposition of CoMoP at various electrolyte pH values was studied using cyclic voltammetry and chronoamperometry to estimate the current efficiency (CE%) of the plating solutions and the optimum pH for the plating process. Scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) techniques have been applied to characterize the morphology and chemical composition of the deposited layer. CoMoP alloys of high P wt.% as-deposited films showed irregular microcracks amorphous structure and of low P wt.% showed amorphous/nanocrystalline structure while, after annealing at 400 °C for 1 h, the films deposited with low and high P wt.% converted into polycrystalline structure. The results of oxidation property showed that, the Co-13.2 wt.% Mo-10.3 wt.% P alloy has highest stability against oxidation and lowest electrical resistance values (100-150 µΩ). The ferromagnetism nature of coated materials has been studied by hysteresis loop measurements. The electrochemical corrosion results were calculated from polarization studies for as-plated and annealed CoMoP coatings in 3.5% NaCl solution.     

pH值对电沉积FeNi／Cu复合丝巨磁阻抗性能的影响

采用脉冲电沉积方法在φ90μm的Cu丝上制备出Fe20＋δNi80-8／Cu复合丝,并测试了巨磁阻抗（GMI）特性。实验表明：电镀液的pH值在1．48～3．1范围内变化,对于复合丝的镀层成分、厚度、表面质量及其巨磁阻抗（GMI）效应具有显著的影响。在pH为1．9～2．5时复合丝表面平整、缺陷少,在pH=2．03时获得了厚度为11μm、成分为Fe20．3Ni79．7的电镀沉积层。采用10mA的激发电流,频率f=29．6kHz时GMI效应达到631．5％,磁场的灵敏度在10kHz时达到560％／Oe,该频率远远低于CoFeSiB非晶丝材的频率。     

Preparation of anodic films on 2024 aluminum alloy in boric acid-containing mixed electrolyte

The anodizing oxidation process on 2024 aluminum alloy was researched in the mixed electrolyte with the composition of 30 g/L boric acid, 2 g/L sulfosalicylic acid and 8 g/L phosphate. The results reveal that the pre-treatment and the composition of the mixed electrolyte have influence on the properties of the films and the anodizing oxidation process. Under the condition of controlled potential, the anodizing oxidation current-time response curve displays “saddle” shape. First, the current density reaches a peak value of 8-20 A/dm^2 and then decreases rapidly, finally maintains at 1-2 A/dm^2. The film prepared in the mixed electrolyte is of porous-type with 20 nm in pore size and 500 μm^-2 in porosity. Compared with the conventional anodic film obtained in sulfuric acid, the pore wall of the porous layer prepared in this work is not continuous, which seems to be deposited by small spherical grains. This porous structure of the anodic film may result from the characteristics of the mixed electrolyte and the special anodizing oxidation process. The surface analysis displays that the anodic film is amorphous and composed of O, Al, C, P, S, Si and no copper element is detected.     

STRUCTURE OF ELECTRODEPOSITED Ni-Mo OR Ni-W ALLOY

研究了电镀条件对电镀Ni-Mo和Ni-W合金结构的影响,发现各个因素中pH值的变化对镀层形成晶态或非晶态起着决定性的作用.这些结构上的变化,仍可用作者在解释Ni-P镀层结构时发展的模型加以解释.     

电火花沉积Invar/非晶复合涂层的组织与性能

采用电火花沉积技术在45Mn2钢基材表面沉积了Invar、Invar/非晶及Invar/非晶/Invar涂层,通过X射线衍射仪(XRD)、扫描电镜(SEM)、摩擦磨损试验仪和电化学工作站等分析了沉积层的组织结构、摩擦磨损和电化学腐蚀性能。结果表明,制备的涂层致密、均匀,与基材呈冶金结合。采用Invar合金打底,获得了约60 μm厚度的无显著裂纹Invar/非晶/Invar涂层。Invar涂层为FCC固溶体结构,Invar/非晶和Invar/非晶/Invar涂层为非晶/固溶体复相结构。Invar、Invar/非晶和Invar/非晶/Invar沉积层的平均硬度分别为176.6、 757.7和772.8 HV0.1,摩擦因数分别为0.44、0.21和0.19。提高沉积层非晶含量可提高硬度,降低摩擦因数,提高耐磨性。沉积层在3.5%NaCl溶液中没有明显的钝化现象,Invar、Invar/非晶及Invar/非晶/Invar涂层的自腐蚀电位分别为-0.74、 -0.54、-0.34和-0.31 V,自腐蚀电流密度分别为7.08、5.15、3.78和3.11 μA·cm^-2。电火花沉积的Invar/非晶/Invar涂层致密、均匀、无裂纹,可极大提高45Mn2钢基体表面的耐磨及耐蚀性能。     

Surface layer pH in electroless nickel plating in hypophosphite solutions

pH values of the layer of solution adjacent to the Ni-P coating being deposited from solutions containing acetate, glycine, fluoride and other additions have been measured using a glass electrode located in the reaction zone. It was found that the pH value at the surface may decrease by three units. It can be seen from data on the pH value at the surface that revision of some kinetic relationships established earlier is required. It is shown that acetate at low concentration levels has only a buffer effect and that ethylenediamine has an additional accelerating effect while glycine, citrate, malonate, lactate and succinate retard the nickel deposition process.     

含硫介质中化学镀Ni-P合金镀层耐蚀性研究

用场发射扫描电子显微镜、X射线光电子能谱仪及X射线衍射仪分析Ni-P合金镀层表面的形貌、组成及结构,用恒电位极化曲线法研究了Ni-P合金镀层在Na2S溶液中的腐蚀行为,通过重量法测试了Ni-P合金镀层在不同温度、不同质量分数Na2S溶液中的腐蚀速率.结果表明:Ni-P合金镀层为非晶态镀层,表面具有胞状结构;在Na2S质量分数一定的条件下,Ni-P合金镀层腐蚀的阳极过程随着温度的升高,钝化区域逐渐变窄.     

Preparation and Characterization of Amorphous Layer on Aluminum Alloy Formed by Plasma Electrolytic Deposition (PED)

PLASMA Electrolytic Deposition(PED)is a relativelynew technology to form ceramic layers on somenon-ferrous metal and their alloys such as aluminum,magnesium and titanium'1'21.By apply high electricalpotential between the work-piece and another counterelectrode in certain electrolysis,the breakdown of thepassive film or the gas envelope surrounding theworkpiece lead to electrical discharge in the interfacebetween the workpiece surface and the electrolysis.Ceramic layers and/or diffusion lay…     

双层辉光等离子渗镀铬的研究

利用双层辉光等离子渗金属技术在低碳钢表面进行了不同温度的渗镀铬处理,对用不同工艺获得的渗铬层的相组成、含铬量、表面硬度进行了测试分析。结果表明,通过控制工艺参数可得到沉积层或扩散层或由沉积层与扩散层组成的渗铬层,表面层均由铁及铁铬固溶体组成,表面含铬量最高可达39.49%;与基体相比,渗铬层表面硬度提高不大,固溶强化效果不明显。     

Novel multilayer structure design of metallic glass film deposited Mg alloy with superior mechanical properties and corrosion resistance

A novel multilayer structure of metallic glass film deposited Mg alloy was designed and fabricated by combining surface mechanical attrition treatment and magnetron sputtering. The multilayer structure consists of amorphous layer and gradient structure sequentially from surface, following with the coarse grains inside. Gradient structure significantly decreases hardness mismatch between the amorphous layer and the matrix of Mg alloy. Wear resistance is increased by 2 orders for this novel multilayer structure with the simultaneous improvement of corrosion resistance.     

热处理对不锈钢表面化学镀Ni-Cr-P合金镀层结构及性能的影响

采用化学镀工艺在不锈钢表面获得了Ni-Cr-P合金镀层。研究了Ni-Cr-P非晶态合金膜随热处理温度升高,其结构以及显微硬度和耐蚀性的变化规律,并对变化的原因进行了分析。结果表明,镀态Ni-Cr-P为非晶态镀层,200℃热处理开始晶化,到400℃时Ni3P晶化比较完全,800℃时Ni3P完全分解,生成含Ni、Cr、Fe的合金膜的Cr2Ni3和FeNi2P相。其显微硬度随热处理温度升高而升高,500～600℃之间显微硬度略有下降,600～700℃又随着热处理温度的升高而略有升高,700℃后显微硬度略有下降;合金膜的耐腐性在热处理温度200～400℃间变化较小,500℃热处理后其耐腐蚀性下降厉害,600～700℃随着热处理温度的升高其耐腐蚀性又略有升高,800℃后由于Ni3P的分解其耐腐蚀性又急剧下降。     

Optical emission spectroscopy as a tool for designing and controlling the deposition of graded TiAlN layers by ECR-assisted reactive RF sputtering

Graded TiAlN layers were deposited by plasma reactive sputtering assisted by electron cyclotron resonance (ECR). For reactive sputtering, dual cathode radio-frequency (RF) magnetron targets, Ti and Al, were used. The deposition process was monitored by optical emission spectroscopy (OES). The OES results indicate that microwave excitation added to RF plasma has contrasting effects on Ti and Al concentration in the gas phase, enhancing titanium and quenching aluminium species reaching the deposited substrate. Thus, by the regulation of the ECR power and the ratio of the nitrogen flow to the nitrogen plus argon flow, the formation of graded layers is allowed. This approach was found to be appropriate for controlling and tailoring the interface between a metallic substrate and a hard coating. The layers were deposited on (100) oriented silicon and M2 steel tools using various combinations of variables, such as power input, bias substrate voltage and gas feed composition. The layers were characterized with regard to structure and composition using X-ray diffractometers and Auger electron spectroscopy. Layers deposited on grounded silicon at a low ECR power (≤100 W) were found to have a (111) oriented crystalline structure; the crystallographic orientation is affected by the bias voltage and substrate composition. Layers deposited at an ECR power >100 W had a random or amorphous structure. The relationship between the OES analyses of the plasma layer and the processing parameters, the structure and the composition of the layers formed are presented and discussed.     

镍含量对激光熔覆镍-铁基涂层结构与性能的影响

采用侧向同步送粉,激光熔覆+重熔的方式在低碳钢表面制备了两种Ni–Fe–Si–B–Nb合金涂层,化学成分分别为(Ni0.5Fe0.5)62Si18B18Nb2(原子数分数x/%)和(Ni0.6Fe0.4)62Si18B18Nb2(x/%)。探讨Ni含量变化对涂层物相组成、显微组织及其性能的影响。试验结果表明,当Ni和Fe的比为1:1时,涂层重熔层物相分析表现为非晶特征的漫散射峰,微观组织由等轴晶+非晶构成,而当Ni和Fe的比为3:2时,涂层重熔层物相分析无漫散射峰形成,微观组织为树枝晶。同时树枝晶组织的显微硬度值较低,这和涂层内部形成的奥氏体较多,而且无Fe2B相和非晶相生成有关。     

Amorphous Ni-Mo-P diffusion barrier deposited by non-isothermal deposition

Ni-Mo-P barrier layers deposited on silicon wafers without Pd activation pretreatment were prepared using the non-isothermal deposition (NITD) method in an acidic electroless bath. The operating conditions for fabricating the Ni-Mo-P barrier layers were presented, and the effect of the pH values on the film composition, electric resistivity and thermal stability have been investigated. The thicknesses of Ni-Mo-P films are around 15-20 nm in acidic bath. Our results indicate increasing amounts of Mo and decreasing amounts of P with increasing pH. The electric resistivity decreased with increasing pH value due to the increase of the Mo content in the Ni-Mo-P film. The amorphous structure was formed at pH 3 and 4, but a quasi-amorphous structure was formed at pH 5. Based on our experimental results, the thermal stability of Ni-Mo-P film prepared at pH 4 remains stable up to 650 °C for 1 h annealing.     

Microstructural feature of crystalline–amorphous transition layer in structurally graded Co–P films produced by an electroless plating process

Abstract

The objective of this study was to clarify the microstructure of crystalline–amorphous transition layers formed in electrolessly deposited Co–P films. Structurally graded Co–P films, including the transition layers, were prepared by controlling the solution pH in electroless plating solutions. TEM analysis indicated that the layers featured a modulated structure comprised of two phases, namely a crystalline phase with low P content and an amorphous phase with high P content.     

化学镀 Cu-Co-P 非晶合金及其催化性能表征

目的优化Cu-Co-P非晶合金的化学镀工艺,研究其对硼氢化钠水解制氢的催化性能。方法以铁片为基体,研究化学镀Cu-Co-P非晶合金的制备工艺,探讨镀液成分对沉积速率、镀液稳定性及镀层质量的影响,并根据研究结果筛选出化学镀Cu-Co-P的优化配方。采用该配方对氧化铝(γ-Al2O3)基体施镀,制备出负载型Cu-Co-P/γ-Al2O3非晶合金催化剂,对其组成、形貌和结构等进行表征。利用硼氢化钠水解制氢实验,评价制备的负载型Cu-Co-P多元合金催化剂的催化性能。结果根据优化配方制备出的负载型非晶合金Cu-Co-P/γ-Al2O3催化剂的比表面积为233 m2/g,相对组成为57.85%Cu+39.69%Co钴+2.46%P(均为质量分数)。45℃条件下,在20 m L含1 g硼氢化钠和1 g氢氧化钠的溶液中,硼氢化钠水解制氢的速率为1295 m L/(g·min)。结论化学镀Cu-Co-P的优化配方组成为:硫酸钴20 g/L,硫酸铜0.7 g/L,次亚磷酸钠40 g/L,柠檬酸钠20 g/L,EDTA-2Na 10 g/L,氟化铵25 g/L。工艺参数为:温度(85±1)℃,p H=9。     

晶化温度对非晶态Cr-Fe-C合金镀层的影响

采用三价铬电镀液,在4Cr10Si2Mo钢工件表面电沉积非晶态Cr-Fe-C合金镀层.通过改变络合剂的含量、电流密度和电镀时间,在阴极上沉积了不同厚度的非晶态Cr-Fe-C层.用扫描电子显微镜和光学显微镜、X射线衍射仪、能谱仪测定、显微硬度计研究了从三价铬镀液中电沉积Cr-Fe-C镀层的工艺以及镀层的形貌、结构与性能.结果表明,利用该工艺获得了厚度为30 μm、27 wt%Fe的非晶态Cr-Fe-C合金镀层.该镀层耐蚀性较好,经600℃×1 h晶化处理后硬度最高可达1 800 HV0.05.     

化学镀Fe—Mo—W—B非晶态合金的晶化

利用化学镀获得非晶态Ｆｅ－Ｍｏ－Ｗ－Ｂ四元合金镀层。用Ｘ射线衍射方法研究了镀层的结构和晶化过程。结果表明;Ｂ含量在９．８ａｔ％－２７．３ａｔ％范围内镀层为非晶态结构,该区域大于Ｆｅ－Ｂ二元合金镀层,但不如Ｆｅ－Ｍｏ－Ｂ三元合金镀层。观察到两步晶化过程：首先析出的晶化相为α－Ｆｅ,Ｆｅ３Ｂ和（Ｍｏ,Ｗ）２Ｂ;然后在较高温度出现Ｆｅ２Ｂ,（Ｍｏ,Ｗ）Ｂ和Ｆｅ（Ｍｏ,Ｗ）的衍射峰。     

Microstructure and mechanical property evaluation of pulsed DC magnetron sputtered Cr–B and Cr–B–N films

CrB₂ and four Cr–B–N films with high Cr/B ratio and various nitrogen contents were deposited by a co-sputtering process using a bipolar asymmetric pulsed DC reactive magnetron sputtering system. The structures and BN bonding nature of the thin films were characterized by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR), respectively. The surface and cross sectional morphologies of the thin films were examined by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The surface roughness of the thin films was explored by atomic force microscopy (AFM). Nanoindentation, microscratch and ball-on-disk wear techniques were used to evaluate the hardness, and tribological properties of the thin films, respectively.The microstructure of the Cr–B–N thin films changed from a coarse columnar structure to a glassy and featureless morphology as the nitrogen content increased from 15.2 at.% to 54.5 at.%, whereas the corresponding structure developed from an amorphous state to a nanocomposite structure consisting of CrN nanograins and amorphous BN phases. It was found that high hardness, good tribological and brittle properties were obtained for the CrB₂ coating. The hardness and elastic modulus of the Cr–B–N thin films decreased with increasing nitrogen content until the nanocomposite structure of nanocrystalline CrN grains and an amorphous BN matrix was formed. However, the hardening effect induced by the nanocomposite structure was limited due to the fact that the small CrN nanograins were surrounded by a thick intergranular soft amorphous BN layer. On the other hand, the fracture toughness and resistance against elastic strain to failure of the Cr–B–N coatings were effectively enhanced by the addition of nitrogen.     

Electroless plating on the surface of kapok fibres: analysis of an effective palladium-free nickel salt activation process

A two-step, palladium-free, nickel salt activation process was tested on kapok fibres (KF). The results showed that the ratio of the concentration of hydrogen ions to the concentration of hydroxide ions ([H⁺]/[OH^?]) in the activation bath needs to be controlled within a range to achieve an optimal outcome. The final amount of deposited active Ni is not only dictated by [NiSO₄·6H₂O] but also dependent on the concentration of the reducing agent, [NaBH₄], whose proper value is complicated by its self-decomposition reaction that can be catalysed by the active Ni and H⁺ ions. The concentration of NiSO₄ employed needs to be capped to attain reasonable mass density and high electrical conductivity as required by light-weight electromagnetic interference shielding materials. An effective activation bath was formulated and experimentally confirmed to successfully initiate and sustain such an electroless plating process and a compact, uniform and amorphous Ni-P layer was formed on the KF surface.