酸性镀铜研究进展

将至今所使用的酸性镀铜添加剂分成六类进行了归纳叙述;简述近年来的各种物理因素例如脉冲技术、超声波技术、激光技术等在酸性镀铜中的应用现状及其对镀层质量的影响;总结应用阴极极化曲线、交流阻抗、微分电容等测试方法研究添加剂电化学行为和用扫描电镜、X-射线衍射、原子力显微镜等研究镀层结构来探讨酸性镀铜的沉积机理的一般方法。     

电化学方法在无氰碱性镀铜研究中的应用

本文系统分析了电化学方法在焦磷酸盐、HEDP(羟基乙叉二膦酸)、柠檬酸盐、EDTA(乙二胺四乙酸)等无氰碱性镀铜研究中的应用,并指出后续无氰镀铜研究不仅应注重添加剂或第二配体引入对工艺的影响,更要善于借助电化学等有效辅助手段进行分析,以期促进无氰碱性镀铜工艺取得更大的突破。     

氰化镀铜及乙二胺无氰碱性铜镀体系的EIS研究

以乙二胺为络合剂,研究和测量了氰化镀铜体系和乙二胺无氰镀铜体系的电化学交流阻抗(EIS),考察了乙二胺浓度和pH对EIS的影响。研究结果表明,氰化镀铜体系的电荷转移电阻小,铜离子放电速度快,同时存在电化学极化和浓差极化,这可能是氰化镀铜镀层结合力好的原因之一;乙二胺无氰镀铜体系中,当乙二胺浓度为0.45 mol.L-1,pH=9.0时,电荷转移电阻较小,并且EIS图和氰化镀铜体系的相似。     

印制电路板电镀铜添加剂的研究进展

简述了高密度印制板的关键技术——酸性镀铜,列举了目前运用较广的印制电路板酸性镀铜添加剂产品,介绍了酸性镀铜添加剂的常规组成及其电化学行为。通过对运用于印制电路板电镀的酸性镀铜添加剂的研究进展的综述,认为寻求更新的添加剂复配技术以及开发单体性能更为优秀的中间体是满足目前印制电路板酸性镀铜要求的重要途径。     

电化学测试技术在集成电路制程化学机械抛光中的应用现状

简述了包括开路电位法、极化曲线法、恒电位法、电化学阻抗谱在内的常规电化学测试技术的原理。总结了近几年内这几种电化学测试技术在化学机械抛光领域研究中的应用现状,展望了未来的发展方向。     

电镀级焦磷酸钾品质快速评价的电化学方法研究

应用线性扫描伏安法和计时电位法分别测量绘制阴极极化曲线和恒电流电位-时间曲线,研究了铜电极上焦磷酸盐镀铜的电化学行为。结果表明,焦磷酸盐镀液的组成、pH和温度都会影响铜电极电镀过程的阴极极化和恒电流电位。在镀液中,在焦磷酸根与Cu2+质量比为8∶1,Cu2+浓度为0.28～0.39mol/L,镀液pH值为8.8～9.3,镀液温度为45～48℃条件下,有利于得到结晶质量较好的铜镀层。阴极极化越大,恒电流电位越负,对应镀液越容易得到致密的金属镀层,与赫尔槽实验效果一致。阴极极化曲线和恒电流电位-时间曲线可用于电镀级焦磷酸钾品质的快速评价。     

铜包钢线的研制与应用

1　前言铜包钢线已在国外得到广泛的应用 ,而国内只限用于生产镀锡的铜包钢线。我们研制铜包钢线 ,主要是在生产技术、产品性能和用途方面在国内取得较大突破。2　工艺过程总的工艺流程 :来料钢丝镀铜拉丝退火转入下道工序镀铜工艺流程 :钢丝除油清洗除氧化层清洗活化焦磷酸盐预镀铜清洗硫酸盐加厚镀铜清洗成圈3　技术关键铜包钢线主要是研究无氰和高速镀铜的工艺以及与之相匹配的工装问题 (高速 ,动态的线材 )。从电化学的角度来看 ,因钢与铜的电位相差太大 ,较难解决它们间的结合力问题。现时国内外较成熟的工艺是采用氰化镀铜和预镀暗镍…     

HEDP镀铜体系中铜阳极的电化学溶解行为

通过循环伏安、阳极极化曲线等方法研究了羟基乙叉二膦酸(HEDP)镀铜液中铜阳极的电化学行为,分析了不同阳极材料的溶解行为差异及对镀层质量的影响.结果表明,溶液环境的改变会显著影响铜阳极溶解的电化学行为,HEDP体系中加入23CO?可促进铜阳极的溶解及提高Cu还原电势;在HEDP镀铜液中,铜的阳极溶解过程主要包括Cu2O的形成、Cu2+的溶出、浓差极化阻滞溶解、Cu(OH)2和CuCO3的生成及氧气的析出.HEDP镀铜体系中,磷铜阳极反应活性低,表面易钝化;电解铜阳极的溶解过快,易产生"铜粉"Cu2O而影响镀层质量;冷轧紫铜作为阳极最适宜.     

硫酸盐镀铜溶液中铜阳极性能研究

采用电化学联机测试系统对酸性硫酸盐镀铜工艺中含磷质量分数不同的铜阳极的电化学行为进行了阳极极化曲线和循环伏安曲线的对比进行,结果表明在酸性硫酸盐镀铜溶液中低质量分数磷铜阳要要比高质量分数磷铜阳极和纯铜阳极允许使用的阳极电流密度高,产生的Cu^ 离子更少,效果更好。     

钢制长输油气管道硫化氢腐蚀的电化学研究方法

随着我国油气管道事业的快速发展,硫化氢腐蚀已成为油气管道面临的一项主要的腐蚀失效形式。针对钢制油气管道的硫化氢腐蚀阴极、阳极反应机理进行了介绍,同时阐述了腐蚀的环境影响因素及其作用机理。介绍了动电位极化曲线测试、电化学阻抗谱测试和电化学噪声技术等较为成熟的钢制油气管道的硫化氢腐蚀电化学研究方法,并对电化学噪声信号的深入处理和恒电位脉冲技术的应用进行了展望。     

Influence of organic additives on the initial stages of copper electrodeposition on polycrystalline platinum

Effects of two additives, thiourea and saccharin, on copper electrodeposition from acid sulphate solutions were investigated by different electrochemical methods (cyclic voltammetry, chronoamperometry, and electrochemical quartz crystal microbalance) as well as by different observation techniques (scanning electron microscopy and atomic force microscopy). The morphology of copper coating obtained with thiourea leads to a smooth and bright deposit whereas it is only slightly modified by saccharin. The electrochemical reactions of copper electrodeposition were modified by the formation of complexes between thiourea and copper. However, in presence of saccharin, the kinetics and morphology of copper coating remain unchanged. From X-ray photoelectron spectroscopy analysis, thiourea was found to react with copper or copper ions by strong bond formation between the sulphur atoms of thiourea molecule and copper. This is the evidence of the adsorption of thiourea on the coating. Moreover, the thiourea action starts in the initial stages, allowing a homogeneous nuclei size and a large nuclei density. Finally, the nucleation mechanism of electrodeposition appears to be modified according to the additives used.     

Electrodeposition of copper from spent Li-ion batteries by electrochemical quartz crystal microbalance and impedance spectroscopy techniques

Information about the copper electrodeposition mechanism at different pH values was obtained using an electrochemical quartz crystal microbalance (EQCM) technique, as well as potentiodynamic, potentiostatic, and electrochemical impedance spectroscopy (EIS) techniques. In agreement with the measurements obtained from the EQCM and potentiostatic experiments, an intermediate Cu⁺ species and a CuO layer are formed. Simultaneous mechanism of direct reduction of Cu²⁺ and copper oxide (CuO) reduction at pH 2.0 and 4.5 occur. The EIS experiment shows a diffusion-controlled process by the presence of a Warburg element, a CPE related to the irregular metallic copper electrodeposition, and a resistance of the electrodeposit.     

Electrodeposition of palladium on the copper lead frame: Electrode reaction characteristics and the effects of primary additives

This study is mainly concerned with the electrodeposition of palladium on the copper alloy lead frame used for semiconductor assembly process. The role and effect of additives on palladium electrodeposition were studied by using various electrochemical methods. Ortho-formylbenzenesulfonic acid as a primary additive was used in palladium plating on the lead frame in this study. The electrochemical characteristics of electrode reaction were measured by the hanging mercury drop electrode for electrochemical system and the qualities of the plated surface of lead frames were also examined. The additive agent in Pd solution could have been classified as the grain refiner. It acted as the electroactive species, which increased the polarization and decreased the roughness, by adsorption on the electrode in palladium pre-plated process. The reduction of palladium ion was identified to be an irreversible reaction and the diffusion coefficient of palladium ion and the reaction rate constant were obtained from chronopotentiometry experiment.     

超声对铜电化学沉积速度及沉积产物结构的影响

测定了超声作用下铜电化学沉积过程的阴极稳态极化曲线,探讨了超声对沉积铜晶面取向及表面形貌的影响. 结果表明,在实验条件下,超声可以提高铜电化学沉积过程的阴极极限扩散电流密度,超声对铜电化学沉积过程极限扩散电流密度的影响随着反应体系温度的升高而下降,当系统温度从25oC升高到55oC时,有超声与无超声作用下的平均极限扩散电流密度的比值从14.1减低到8.4. 超声还能改变铜电沉积晶面的取向,明显改变电沉积铜的粒径.     

铜铝双金属复合离子液体的电化学行为及电沉积铜机理

铜铝双金属复合离子液体是新型碳四烷基化技术所用的绿色催化剂,电化学处理是回收工业应用过程外排复合离子液体中金属铜的有效途径之一,为此需要深入研究其电化学行为和电沉积铜机理。循环伏安研究发现,铜铝双金属复合离子液体在Pt盘电极、W盘电极和玻碳电极上的还原过程均包括铜的欠电势沉积、Cu(Ⅰ)的还原和铜的超电势沉积,氧化过程均包括Cu→Cu(Ⅰ)、Cu(Ⅰ)→Cu(Ⅱ)。计时安培研究表明,铜的成核方式为三维瞬时成核。长周期实验结果显示Cu(Ⅰ)的浓度随着时间下降的趋势变缓,表明电沉积铜速率逐步下降。电沉积电势对沉积产物的形貌影响较大,-2.60 V下的产物形貌更平整致密。XRD结果表明在-1.20~-2.60 V电势下阴极电沉积只生成金属铜。     

铜铝双金属复合离子液体的电化学行为及电沉积铜机理

铜铝双金属复合离子液体是新型碳四烷基化技术所用的绿色催化剂,电化学处理是回收工业应用过程外排复合离子液体中金属铜的有效途径之一,为此需要深入研究其电化学行为和电沉积铜机理。循环伏安研究发现,铜铝双金属复合离子液体在Pt盘电极、W盘电极和玻碳电极上的还原过程均包括铜的欠电势沉积、Cu(Ⅰ)的还原和铜的超电势沉积,氧化过程均包括Cu→Cu(Ⅰ)、Cu(Ⅰ)→Cu(Ⅱ)。计时安培研究表明,铜的成核方式为三维瞬时成核。长周期实验结果显示Cu(Ⅰ)的浓度随着时间下降的趋势变缓,表明电沉积铜速率逐步下降。电沉积电势对沉积产物的形貌影响较大,-2.60 V下的产物形貌更平整致密。XRD结果表明在-1.20~-2.60 V电势下阴极电沉积只生成金属铜。     

Ordered arrays of copper nanowires enveloped in polyaniline nanotubes

Copper nanowires enveloped in polyaniline (PANI) nanotubes were obtained by ‘second order’ electrodeposition into the pores of anodic porous alumina. The templated synthesis of copper nanowires was performed by both potentiostatic and galvanostatic methods. The morphology of the polyaniline nanotubes, copper nanowires as well as the copper-filled polyaniline nanotubes was investigated by means of scanning electron microscopy. The copper nanowires were protected from corrosion and oxidation by the PANI nanotubes. Energy-dispersive X-ray spectroscopy was performed for the microanalysis of the copper deposition into the polyaniline nanotubes. Cyclic voltammetry was employed to assess the electrochemical properties of the obtained nanostructures as well as the influence of the copper nanowires synthesis method on the properties of filled polyaniline nanotubes.     

Application of the electrochemical quartz crystal microbalance technique to copper sonoelectrochemistry: Part 1. Sulfate-based electrolytes

The applicability of the electrochemical quartz crystal microbalance technique in an ultrasonic field created by an ultrasound probe is demonstrated for the electrodeposition of copper. Cyclic voltammetry and potentiostatic depositions in acidic sulfate-based copper electrolytes were performed at different ultrasonic intensities. The electrochemical quartz crystal microbalance was operated in ultrasonic fields with intensities up to 30 W cm⁻². For cyclic voltammetry, potential resolved and averaged (apparent) current efficiencies were calculated from mass and charge data in function of the amplitude of the ultrasonic horn. Ultrasound slightly affected the current efficiencies during copper deposition in cyclic voltammetry, but did not change the efficiencies during dissolution. During potentiostatic depositions the current efficiency increased from 84% to almost 100% upon application of ultrasound. Morphology of deposits prepared by potentiostatic depositions was analyzed by scanning electron microscopy, and found to be different at high ultrasonic intensities.     

Copper electrodeposition from an acidic plating bath containing accelerating and inhibiting organic additives

Copper electrodeposition on copper from still plating solutions of different compositions was investigated utilising electrochemical impedance spectroscopy (EIS), cyclic voltammetry, and scanning electron microscopy (SEM). An acid copper sulphate plating base solution was employed either with or without sodium chloride in the presence of a single additive, either polyethylene glycol (PEG) or 3-mercapto-2-propanesulphonic acid (MPSA), and their mixture. Thallium underpotential deposition/anodic stripping was employed to determine the adsorption capability of additives on copper. In the absence of chloride ions, MPSA shows a moderate adsorption on copper, whereas PEG is slightly adsorbed. At low cathodic overpotentials, the simultaneous presence of MPSA and chloride ions accelerates copper electrodeposition through the formation of an MPSA-chloride ion complex in the solution, particularly for about 220 μM sodium chloride. The reverse effect occurs in PEG-sodium chloride plating solutions. In this case, from EIS data the formation of a film that interferes with copper electrodeposition can be inferred. At higher cathodic overpotentials, when copper electrodeposition is under mass transport control, the cathode coverage by a PEG-copper chloride-mediated film becomes either partially or completely detached as the concentration of chloride ions at the negatively charged copper surface diminishes. The copper cathode grain topography at the μm scale depends on the cathodic overpotential, plating solution composition and average current density. Available data about the solution constituents and their adsorption on copper make it possible to propose a likely complex mechanism to understand copper electrodeposition from these media, including the accelerating effect of MPSA and the dynamics of PEG-copper chloride complex adsorbate interfering with the surface mobility of depositing copper ad-ions/ad-atoms.     

Galvanostatic studies of the nucleation and growth kinetics of copper in the presence of surfactants

The initial and advanced stage of copper electrodeposition have been studied under galvanostatic conditions. The effect of different surface active compounds on the nucleation and growth kinetics has been examined. Data were obtained for the nucleation and growth parameters characterizing the electrochemical deposition of copper ions.