在照相明胶层中金催化的铜无电沉积

利用X射线光电子能谱的原位氩离子束溅射和ESCA技术，研究了无电沉积前后照相明胶中硫元素化学形态的变化，对无电沉积所形成的导电膜进行了深度剖析，探讨了照相明胶层中金催化的铜无电沉积机理．结果表明：在酸性条件下（pH＝3．20），明胶大分子的蛋氨酸亚砜对AU3 仍具有较大的还原能力，明胶大分子的蛋氨酸、蛋氨酸亚砜将Au3 最终还原为胶态金，而蛋氨酸和蛋氨酸亚砜均被氧化为蛋氨酸砜．在无电沉积初期，胶态金作为催化中心引发铜的无电沉积，之后的反应为Cu2 在新生态铜的自催化下的还原沉积．在无电沉积过程的碱性条件下（pH＝12．50），明胶中的部分蛋氨酸砜又被甲醛还原为蛋氨酸．     

Electroless Pd and Ag deposition kinetics of the composite Pd and Pd/Ag membranes synthesized from agitated plating baths

The atomic absorption spectroscopy (AAS) has been successfully utilized for the measurement of the Pd and Ag ion concentrations in the plating baths and to elucidate the effects of temperature, initial metal ion and reducing agent concentrations and agitation on the electroless plating kinetics of Pd and Ag metals. The initial metal ion concentrations for Pd and Ag were varied over a range of 8.2–24.5 mM and 3.1–12.5 mM, respectively. The plating reactions were conducted in a constant temperature electroless plating bath over a temperature range of 20–60 °C and an initial hydrazine concentration range of 1.8–5.4 mM. It was found that the electroless plating of both Pd and Ag were strongly affected by the external mass transfer in the absence of bath agitation. The external mass transfer limitations for both Pd and Ag deposition have been minimized at or above an agitation rate of 400 rpm, resulting in a maximum conversion of the plating reaction at 60 °C and dramatically shortened plating times with the added advantage of uniform deposition morphology. The derivation of the differential rate laws and the estimation of the reaction orders and the activation energies for the electroless Pd and Ag kinetics were conducted via non-linear regression analysis based on the method of initial rates. For a constant-volume batch reactor, the integrated rate law was solved to calculate the conversion and the reactant concentrations as a function of plating time. The model fits were in good agreement with the experimental data. Furthermore, the bath agitation and the plating conditions used in the kinetics study were adopted for the synthesis of 16–20 μm thick composite Pd/Ag membranes (10–12 wt% Ag) and a pure-Pd membrane with a hydrogen selective dense Pd layer as thin as 4.7 μm. While hydrogen permeance of the Pd/Ag membranes A and B at 450 °C were 28 and 32 m³/m²-h-atm^0.5, the H₂ permeance for the 4.7 μm thick pure-Pd membrane at 400 °C was as high as 63 m³/m²-h-atm^0.5_. The long-term permeance testing of all the membranes synthesized from agitated plating baths resulted in a relatively slow leak growth due primarily to the improved morphology obtained via the bath agitation and modified plating conditions.     

照相明胶层中金催化的无电沉积的正电子湮没研究

采用正电子湮没技术(PAT)研究了照相明胶中的自由体积空穴在无电沉积过程中的作用机理。研究结果表明,活化饱和后,照相明胶的自由体积空穴的平均尺寸约减小0.011nm³,相当于一个Au原子的体积的大小,即照相明胶大分子中的每个自由体积空穴平均被填充了一个Au原子,该Au原子作为催化活性核催化铜的沉积,使物理显影生成的影像为紧密铜粒子的堆积形貌,而不是丝状形貌。铜经无电沉积饱和后,照相明胶的自由体积空穴的平均大小约减小了0.020nm³,即照相明胶的自由体积空穴对铜物理显影过程中铜的沉积没有阻碍作用,铜无电沉积近似为各向同性的球状堆积。     

Thermophoretic deposition of palladium aerosol nanoparticles for electroless micropatterning of copper

A method for catalytic activation was introduced by producing palladium aerosol nanoparticles via spark generation and then thermophoretically depositing the particles onto a flexible polyimide substrate through a hole in pattern mask, resulting in a line (24 μm in width) and a square (136 μm × 136 μm) patterns. After annealing, the catalytically activated substrate was placed into a solution for electroless copper deposition. Finally, copper micropatterns of a line (35 μm in width) and a square (165 μm × 165 μm) were formed only on the activated regions of the substrate. Both patterns had the height of 1.6 μm.     

A New Approach on the Active Treatment for Electroless Copper Plating on Glass

A new method is described for the electroless deposition of copper onto glass.Commercially available glass slide was modified with γ-aminopropyltrimethoxysilane to form self-assembled monolayer (SAM) on it .Then it was dipped directly into PdCl2 solution instead of the conventional SnCl2 sensitization followed by PdCl2 activation.Experimental results showed that the Pd^2 ions from PdCl2 solution were coordinated to the amino groups on the glass surface resulting in the formation of N-Pd complex.In an electroless copper bath containin a formaldehyde reducing agent,the N-Pd complexes were reduced to Pd^0 atoms,which then acted as catalysts and initiated the deposition of copper metal.Although the copper deposition rate on SAM-modified glass was slow at the beginning,it reached to that of conventional method in about 5min.     

重氮树脂单层膜上铜的无电沉积

组装于硅片或玻璃片基片上的重氮树脂(DR)单层膜,吸附SnCl₂,Pd催化剂后,通过无电沉积的方法,在这些基片上制备了铜膜.对得到的铜膜进行了SEM,XRD表征.通过选择性无电沉积,成功地制备了铜膜图像.     

乙二胺在化学沉积Ni-B合金中的机理

研究乙二胺稳定剂对化学镀N i-B合金沉积速率和镀液稳定性的影响.实验表明,少量乙二胺可改善镀液的稳定性.镀液的电化学测试发现,乙二胺对体系的阳极过程和阴极过程均有影响,还原剂的氧化电流和合金的还原电流均随乙二胺加入量的增加而减少.红外光谱显示乙二胺附在镍基体表面发生化学吸附,从而抑制了还原剂的氧化,降低N i-B化学沉积速率(稳定了镀液).     

化学镀技术在超大规模集成电路互连线制造过程的应用

总结自大马士革铜工艺建立以来,电化学工作者利用化学镀技术围绕该工艺而开展的一系列相关研究,介绍了应用化学镀沉积镍三元合金防扩散层和化学镀铜种子层的研究以及离子束沉积法(Ion ized C lus-ter Beam,ICB)形成Pd催化层后的化学镀铜技术和超级化学镀铜方法.简要叙述化学镀铜技术在超大规模集成电路中的应用,总结化学镀铜技术的研究进展,并指出了今后的发展方向.     

Novel Electroless Deposition of Cu<Subscript>3</Subscript>Se<Subscript>2</Subscript> Film on Silicon Substrate by a Simple Galvanic Displacement Process

A novel electroless deposition method for depositing highly uniform adhesive thin films of copper selenide (Cu₃Se₂) on silicon substrates from aqueous solutions is described. The deposition is carried out by two coupled galvanic reactions in a single deposition bath containing copper cations, hydrogen fluoride, and selenous acid: the galvanic deposition of copper on silicon and the subsequent galvanic reaction between the deposited copper with selenous acid in the deposition bath. The powder X-ray diffraction and scanning electron microscopy are used to characterize and examine the deposited films.     

卤离子对化学沉积镍的影响

用重量法测定了卤离子对化学沉积镍速度的影响．并借助电化学方法研究了卤离子对镍的化学沉积过程的极化曲线和稳定电位的影响．探讨了卤离子加速和稳定化学沉积镍的机理     

Triangular Ag/Pd nanoplates with sawtooth edges: Displacement synthesis and optical and catalytic properties

Ag/Pd nanoplates with sawtooth edges were prepared via a galvanic displacement reaction in which added Pd(OAc)₂ slowly reacted with Ag nanoplates containing adsorbed hexadecyltrimethylammonium bromide. Control over the optical properties and catalytic activity of the Ag/Pd nanoplates for electroless copper deposition could be achieved by varying the Ag/Pd alloying ratio.     

Self-assembled Pd nanospheres templated with polyvinylpyrrolidone: Electrochemical preparation and their application as novel catalysts in electroless copper deposition

A novel and simple method for the electrochemical preparation of mesoporous self-assembled Pd nanospheres has been developed. The diameters of the self-assembled nanospheres are controlled by varying the concentration ratio of H⁺ to polyvinylpyrrolidone. The results demonstrate for the self-assembly of Pd nanoparticles to form large Pd nanospheres via the regulation of the steric repulsion force of polyvinylpyrrolidone. The regulation is achieved by the addition of H⁺ ions. Further, the prepared Pd nanospheres can be successfully used as catalysts for activating electroless copper deposition. The mesoporous nanospheres were found to show excellent catalytic activity.     

Simultaneous deposition of Ni nanoparticles and wires on a tubular halloysite template: A novel metallized ceramic microstructure

Tubular halloysite can be used as a template to fabricate a novel metallized ceramic microstructure through electroless plating. Reduction of Pd ions by methanol is conducted to initiate Ni plating. There is a simultaneous deposition of Ni nanoparticles on the outer surface and discontinuous wires in the lumen site of the halloysite template obtained. The different deposition could be caused by the different composition distribution of ferric oxide impurity in the wall due to the isomorphic substitution during the formation of halloysite template. Its magnetic property is mainly attributed to the Ni nanoparticles, not the wires. The metallized ceramic microstructure has the potential to be utilized as a novel magnetic material.     

用化学镀法制备Pd/Ag膜时膜厚和组成的控制

 研究了不同 Pd2+含量的镀液在多孔陶瓷载体上的化学沉积规律, 发现当 Pd 沉积层厚度达到约 5 μm 后, 即使镀液中反应物的消耗比例很小, 膜厚增长也明显变缓, 沉积反应主要受膜层表面的催化活性位控制; 当镀液中 Pd2+含量只能沉积形成小于 4 μm 的 Pd 膜时, 在 323 K 化学镀 180 min 后, 镀液中 Pd2+的转化率高于 90%. 与之相似, 当 Ag 镀液中的 Ag+含量等于 0.5~2 μm 的 Ag 膜层所需量时, 在 333 K 化学镀 120 min 后, Ag+的转化率可达 95%. Ag+的高转化率与 Ag 颗粒的择向生长特性有关. 根据 Pd 和 Ag 的化学镀沉积规律, 通过调节镀液中金属离子的含量能够预先设计和精确控制超薄 Pd/Ag 膜的膜厚和组成.     

化学沉积镍-铁-磷合金和它的伏安行为(英文)

在以次亚磷酸钠为还原剂 ,硼酸为缓冲剂和柠檬酸钠为络合剂的碱性介质中 ,研究了镍_铁_磷合金化学沉积条件 (pH值 ,温度及 [Fe2 + ]/([Ni2 + ]+[Fe2 + ])物质的量比 )对沉积速率和镀层组成的影响 ;并由此建立镀液稳定的最佳沉积工艺 .实验表明 ,镀液中硫酸亚铁对沉积镍_铁_磷合金有阻碍作用 (降低了化学沉积速率 ) ,造成镀层中铁含量不高 (小于 2 0 % ) ,使用循环伏安技术研究了镍_铁_磷合金的电沉积机理 .结果发现铁对次亚磷酸钠的氧化不起催化作用 ,提高镀液温度和pH值有增加沉积速率之效     

Electroless Ni–P coated on graphite as catalyst for the electro-oxidation of dextrose in alkali solution

Graphite particles were coated with Ni–P by electroless deposition using a conventional bath consisting of a nickel salt and hypophosphite. After 15 min of electroless deposition, the graphite particles were covered with 10 wt% nickel and 0.7–1.0 wt% phosphorus as analysed by wet chemical method. Surface morphology was studied by scanning electron microscopy (SEM). Electrochemical characterisation for the catalytic activity was done by cyclic voltammetry. Pure Ni powder and electroless Ni–P coated on graphite were used as catalysts for the electro-oxidation of dextrose (1.8 × 10⁻³ to 4.5 × 10⁻³ M) in 0.1 M KOH solution. Comparative studies revealed that electroless Ni–P coated on graphite particles acted as a better catalyst than pure Ni powder for catalytic reaction.     

Effect of additive triblock copolymer PEP-3100 on bottom-up filling in electroless copper plating

Bottom-up copper filling for different sub-micrometer trenches was investigated by electroless deposition technique using a PO-EO-PO triblock copolymer termed PEP-3100 as an additive. It was found that PEP-3100 (molecular weight 3100) had a strong inhibition for the electroless copper deposition. The bottom-up filling behavior of electroless copper bath for different trenches was investigated in a plating bath containing 1.0 mg l⁻¹ PEP-3100. The cross-section SEM observation indicated the trenches with different widths ranging from 100 to 380 nm were all filled completely by electroless copper.     

Macroporous Au materials prepared from colloidal crystals as templates

In this paper, we reported the preparation of macroporous Au materials using organic colloidal crystals as templates and their catalytic activity for electroless copper deposition. The poly(styrene-methyl methacrylate-acrylic acid) (P(St-MMA-AA)) copolymer colloids were deposited in an orderly manner onto the silicon surface, together with the infiltration of the Au nanoparticles into the interspaces of the colloids. The formed hybrid colloidal crystal subsequently was sintered at approximately 550 degrees C to remove the organic components fully to obtain a macroporous Au framework with three-dimensional ordered porous structure. The pore diameter was around 310 nm and almost monodisperse. It was demonstrated that the macroporous Au materials exhibit catalytic activity and can induce electroless copper deposition.     

Ag活化的p型硅(111)表面化学镀Ag膜表面形貌研究

A method of electroless silver deposition on silver activated p-type silicon（111） wafer was proposed. The silver seed layer was deposited firstly on the wafer in the solution of 0.005 mol/L AgNO3 ＋0.06 mol/L HE Then the silver film was electrolessly deposited on the seed layer in the electroless bath of AgNO3＋NH3＋acetic acid＋NH2NH2 （pH 10.2）. The morphology of the seed layer and the silver films prepared under the condition of the different bath composition was compared by atomic force microscopy. The reflectance of the silver films with different thickness was characterized by Fourier transform infrared spectrometry. The experimental results indicate that the seed layer possesses excellent catalytic activity toward electroless silver deposition and rotating of the silicon wafer during the electroless silver deposition could lead to formation of the smoother silver film.     

以次磷酸钠为还原剂化学镀铜的电化学研究

通过电化学方法研究了以次磷酸钠为还原剂, 柠檬酸钠为络合剂的化学镀铜体系. 应用线性扫描伏安法, 检测了温度、pH值、镍离子含量对次磷酸钠阳极氧化和铜离子阴极还原的影响. 结果表明, 升高温度能够加速阳极氧化与阴极还原过程; pH值的提高可促进次磷酸钠氧化, 但抑制铜离子还原; 镍离子的存在不仅对次磷酸钠的氧化有强烈的催化作用, 而且与铜共沉积形成合金. 该合金有催化活性, 使化学镀铜反应得以持续进行.