Electrochemical oxidation of polyethylene glycol in electroplating solution using paraffin composite copper hexacyanoferrate modified (PCCHM) anode

Electrochemical oxidation of polyethylene glycol(PEG) in an acidic(pH 0.18 to 0.42) and high ionic strength electroplating solution was investigated. The electroplating solution is a major source of wastewater in the printing wiring board industry. A paraffin composite copper hexacyanoferrate modified(PCCHM) electrode was used as the anode and a bare graphite electrode was used as the cathode. The changes in PEG and total organic carbon(TOC) concentrations during the course of the reaction were monitored. The efficiency of the PCCHM anode was compared with bare graphite anode and it was found that the former showed significant electrocatalytic property for PEG and TOC removal. Chlorides present in the solution were found to contribute significantly in the overall organic removal process. Short chain organic compounds like acetic acid, oxalic acid, formic acid and ethylene glycol formed during electrolysis were identified by HPLC method. Anode surface area and applied current density were found to influence the electro-oxidation process, in which the former was found to be dominating. Investigations of the kinetics for the present electrochemical reaction suggested that the two stage first-order kinetic model provides a much better representation of the overall mechanism of the process if compared to the generalized kinetic model.

Progress of electroplating and electroless plating on magnesium alloy

The current research processes of electroplating and electroless Ni-P alloy plating on magnesium alloys were reviewed. Theoretically,the reason for difficulties in electroplating and electroless plating on magnesium alloys was given.The zinc immersion, copper immersion,direct electroless Ni-P alloy plating and electroplating and electroless plating on magnesium alloys prepared by chemical conversion coating were presented in detail.Especially,the research development of magnesium alloy AZ91 and AZ31 was discussed briefly.Based on the analysis,the existing problems and future research directions were then given.

Machining characteristics of complex prism pattern on electroplated roll by copper

The BLU (back light unit) is the core component of the LCD for notebook, mobile-phone, navigation, as well as large sized TV, PID (public information display), etc. In order to enhance optical efficiency of LCD, optical films with the uniform prism patterns have been used for BLU by stacking two films up orthogonally. In this case, light interference-phenomenon occurred such as Morie, wet-out, u-turning, etc. It caused several problems such as low brightness, spots and stripes in LCD. Recently, the high-luminance micro complex prism patterns are actively studied to avoid the light interference-phenomenon and enhance the optical efficiency. In this study, the roll master to manufacture complex micro prism pattern film was machined by using the high precision lathe. The machined patterns on the roll master were 50, 45, 40, 35, 30, 25, 20, 15, 10 and 5 μm in the pitch with 25.0, 22.5, 20.0, 17.5, 15.0, 12.5, 10.0, 7.5, 5.0 and 2.5 μm in the peak height, respectively. The roll was 2 000 mm in length and 320 mm in diameter. The electroplated roll by copper and the natural single crystal diamond tool was used for machining the patterns. The cutting force was measured and analyzed for each cutting condition by using the dynamometer. The chips and the surfaces after being machined were analyzed by SEM and microscope.

Electroplating: Applications in the Semiconductor Industry

There is a lot of research that has been done on electroplating of metals depending on the type of application. In this chapter, the importance of this technique to the semiconductor industry is discussed in detail from an experimental as well as a modeling standpoint. In particular, the effect of solution variables i.e. chloride, accelerator, suppressor on copper electrodeposition is discussed. This knowledge is applied to achieve a defect-free, bottom-up metal/copper fill that eventually, is one of the most critical processes in this billion-dollar industry.

On the Role of Boric Acid in the Copper-Tin Alloy Bath

The role of boric acid in the copper tin alloy bath has been investigated by means of the cathodic polarization curves,cyclic voltammograms,rate of alloy electrodeposition and morphological analysis of deposits.The results indicate that the presence of boric acid in weak acidic solution for electrodeposition of Cu Sn alloy raises the overvoltage of hydrogen discharge and lowers the overvoltage of Cu,Sn and Cu Sn alloy deposition on the Pt,and accelerates the rate of depostion.Boric acid was adsorbed on the surface of cathode and inhibited reduction of hydrogen,then the adsorbed boric acid promoted electrodeposition of metals as a catalyzator.However,as the concentration of boric acid is more than 0.50 mol/L,the above effect was weakened due to the complexation reaction between the excessive boric acid and metallic ions.

An Optimization Study on Electrodeposition of Copper from Acid Bath with Supercritical Carbon Dioxide Fluid

Abstract： An optimization study on electrodeposition of copper film from sulfuric acid bath in presence of supercritical carbon dioxide fluid was explored for electronic application. Factors that influence roughness of copper deposit were also discussed. A material property of copper deposition has been considered as a response variable and statistical experimental methods have been used to optimize the process parameters and the response. Effects of various current density, pressure and temperature were investigated to select the optimal operation factors. Scanning electron microscopy and atomic force microscopy were applied to determine average particle sizes and to confirm the characteristic of the metallic film obtained. Box-Behnken design and RSM （response surface methodology） were applied to find the optimal conditions of supercritical electroplating process. Regression model was built by fitting the experimental results with a second-order polynomial and was proved to be statistically significant since the coefficient of determination coefficient （R^2） was 0.9844. The optimal film of deposited can be obtained at current density 0.17 A/dm^2, pressure 186 bar and temperature 31.5 ℃.

多物理场耦合研究HDI板通孔电镀铜

随着终端电子产品不断朝着微型化、多功能、智能化的方向发展,高密度互连(HDI)印制电路板的应用越来越广泛。通孔电镀铜作为HDI板层间互连的关键技术,其镀铜性能一直是电镀铜研究的热点。本文采用多物理场耦合的有限元方法讨论了HDI板在不同镀液体系的通孔电镀铜过程,探讨了添加剂在电极表面的吸附作用及其对镀层的影响,获得了HDI板通孔电镀铜的“蝴蝶”状填充机制。这一结论为HDI板层间互连研究提供了一定的理论指导。

酸性一价铜电镀铜的工艺及能效分析

针对电镀铜过程电力成本高的问题,通过极化曲线、赫尔槽试验、槽压变化以及扫描电镜等手段,分析了酸性一价铜电镀铜的电极过程及能效。通过对阴极的分析表明:优先发生亚铜离子的还原,阴极电流效率高于92%,且随阴极电流密度的增大而提高;当阴极电流密度不高于4.0 A·dm^(-2)时,镀铜层表面状态和微观形貌较为优异。通过对紫铜阳极的分析表明:优先发生铜的氧化,阳极电流效率高于94%,且随阳极电流密度的增大而提高;阳极会发生钝化,导致槽压急剧升高;当采用大阳极小阴极进行电镀时,既可以克服槽压升高的问题又可以保证阴阳极电流效率的匹配。

十六烷基三甲基溴化铵对电镀铜-镍合金耐蚀性的影响

[目的]研究Cu-Ni合金电镀液中添加不同质量浓度的十六烷基三甲基溴化铵(CTAB)对Cu-Ni合金镀层耐蚀性的影响。[方法]通过浸泡腐蚀试验、塔菲尔极化曲线测试和电化学阻抗谱(EIS)考察了Cu-Ni合金镀层的耐蚀性。通过扫描电镜(SEM)、能谱仪(EDS)和X射线衍射仪(XRD)分析了Cu-Ni合金镀层的表面形貌、成分和晶相结构。采用傅里叶变换红外光谱仪(FTIR)分析了CTAB在Cu-Ni合金镀层中的夹杂情况,并通过接触角测量研究了Cu-Ni合金镀层的疏水性。此外,根据阴极极化曲线测试结果,研究了CTAB质量浓度对Cu、Ni及Cu-Ni合金电沉积行为的影响。[结果]随着镀液中CTAB质量浓度增大,Cu-Ni合金镀层的耐蚀性先变好后变差。CTAB质量浓度为80mg/L时所得Cu-Ni合金镀层表面呈花椰菜状的空间立体形貌,镀层中Cu、Ni质量分数分别为50.25%和40.86%,对腐蚀液的接触角达到129.49°,耐蚀性最佳。[结论]镀液中添加适量CTAB能够显著提高Cu-Ni合金镀层的耐蚀性。

反向处理铜箔微纳组织形成机理及其对力学性能的作用机制

目的第五代移动通信技术(5G)时代,高频高速信号传输过程中由于“趋肤效应”引起的信号损耗甚至“失真”越来越严重,为了解决这一问题,提出了一种反向处理铜箔的新技术,然而国内当前应用的高性能反向处理铜箔(RTF)主要依赖进口,要想在短时间内缩小国内外铜箔性能和生产效率的差距,最终实现这类高端铜箔的国产化,必须在明确该类铜箔微纳结构形成机理及其对性能影响的前提下,加快制备工艺的开发和优化。方法采用电镀法在阴极钛辊上沉积了电解生箔,在其光面进行粗化和镀Zn层等后续处理获得反向处理铜箔,同时以国外反向处理铜箔为参照,采用X射线衍射仪、扫描电子显微镜和透射电子显微镜详细分析其微纳组织与结构,采用激光共聚焦显微镜和万能试验机测量其粗糙度和拉伸性能。结果本工作中的RTF具有与国外商业产品相似的微观结构,由小的等轴晶和较大的柱状晶组成,且包含较多的纳米孪晶,孪晶界占比为30.8%,平均宽度为7.9 nm。S面是均匀的米粒状铜颗粒,而M面是较大的圆锥形铜颗粒。S面上的Zn层均匀致密,厚度约为6.5 nm,只有小部分Zn扩散到基底上形成CuZn3相。但从S面到M面,优选取向从(111)Cu逐渐变为(220)Cu,这与参比RTF略有不同。性能方面,参比RTF的Ra和Rz分别为1.22、1.42μm,抗拉强度为335.10 MPa,伸长率为15.5%,本工作中的RTF具有较低的粗糙度,Ra和Rz分别为0.68、1.03μm,其强度也具有明显优势(393.68 MPa),但延展性低于参比样品。通过对比分析,总结了铜箔在初始外延、过渡生长和电沉积条件控制的生长阶段3个阶段的生长特性,给出了影响每个阶段晶粒生长的主要因素,并且详细讨论了晶粒尺寸和纳米孪晶宽度对铜箔拉伸性能的影响。结论对RTF微观结构和性能的深入研究,有助于找到高性能铜箔国产化“瓶颈”的根源,为高性能铜箔在5G通信领域的进一步发展和应用奠定基础。

印制电路板盲孔电镀铜整平剂的合成及其性能

[目的]采用2−甲基咪唑和1,4−丁二醇二缩水甘油醚为原料,合成印制电路板(PCB)盲孔电镀铜整平剂。[方法]使用红外光谱、核磁共振氢谱及凝胶色谱分析了投料温度不同时所得整平剂的结构。通过循环伏安曲线、阴极极化曲线、电化学阻抗谱和计时电位曲线测试,分析了整平剂对铜电沉积的影响,并通过电镀试验验证了它们用于盲孔电镀铜时的整平性能。[结果]投料温度为85℃时所得整平剂ADT-3的整平效果最好,盲孔填充率达94%。[结论]本研究合成整平剂所用原料易得、成本低,合成路线简单,整平效果良好,有望实现工业化生产。

镀镍磷金属片表面处理对电镀铜生长状态影响的研究

对镀镍磷金属片进行了微蚀,化学镀铜,微蚀后化学镀铜这三种表面处理,对比了表面处理方法对镀镍磷金属片表面形貌、电镀铜平整性和可靠性的影响。结果表明,化学镀铜处理能够有效提升镀镍磷金属片表面的平整性,提升导电性,得到平整可靠的电镀铜层。化学镀铜处理方法有效解决了在化学镀镍表面直接电镀铜的平整性和可靠性问题,为提升电镀铜平整性和可靠性提供有效手段。

巯基吡啶异构体对电镀铜填盲孔的影响研究

本文以同分异构体2-巯基吡啶(2-MP)和4-巯基吡啶(4-MP)为研究对象,在对比其作为整平剂填充盲孔性能差异的基础上,阐述其分子构效关系。首先,通过哈林槽镀铜实验研究了2-MP与4-MP的填盲孔性能,结果表明,2-MP的填孔性能更佳,其填孔率可达82%。之后,通过量子化学计算,发现2-MP分子中S原子电子云密度低于4-MP,这说明2-MP更易吸附在铜表面。计时电位法测试结果表明:Cl^(-)可促进2-MP在铜表面的吸附,此外,2-MP与PEG之间的相互作用显著强于4-MP。最后,通过X射线光电子能谱(XPS)检测到了Cu-S键的存在,证明两种整平剂分子在铜表面均发生了化学吸附。然而,由于2-MP分子中的巯基S原子与N原子处于邻位,可以形成S-Cu^(2+)-N配合物,进而与Cl^(-)、PEG形成复杂且致密的抑制层,强烈抑制表面铜沉积,从而提高了其盲孔填孔率。

电镀电流密度对2×0.30HT钢帘线黏合及剥离性能影响

为研究电镀铜过程对钢帘线黏合和剥离性能的影响,以直径1.80 mm钢丝为基础,分别生产不同平均电流密度、槽间电流密度分布及最外层电流密度因素下电镀钢丝,以同机床、同工艺拉拔捻制为2×0.30HT钢帘线,分别考察3因素钢帘线的黏合和剥离性能。结果表明:电镀铜平均电流密度、各阳极架电流密度分布不均以及最外层电流密度在一定范围内变化对钢帘线黏合抽出性能影响较小,但随着电镀平均电流密度增大至17.07 A/dm~2,镀层致密性变差,从而使得钢帘线的剥离性能降低;同时,相比于钢丝最外层电流密度的设置,首节阳极架电流密度过高更容易导致钢帘线的剥离性能不良。

粉煤灰基沸石吸附废液中氨氮化物与铜离子的试验研究

开展了粉煤灰基沸石吸附电镀废液中氮氧化物和铜离子的试验研究。结果表明:粉煤灰基沸石吸附铜离子的适宜条件为:pH值8,溶液中铜离子初始质量浓度200 mg/L,吸附时间0.45 h,温度200℃;粉煤灰基沸石吸附氨氮化物的适宜条件为:粉煤灰基沸石投入量8 g/L,pH值8,吸附时间0.60 h,溶液中氨氮化物初始质量浓度150 mg/L;粉煤灰基沸石吸附铜离子的吸附过程为物理吸附过程,粉煤灰基沸石对氨氮化物的吸附是离子交换和物理吸附共同作用的结果。

预浸对烧结钕铁硼HEDP电镀铜的影响

[目的]烧结钕铁硼(Nd Fe B)的电镀前处理技术还不够成熟,开发适宜的前处理工艺极其重要。[方法]在电镀铜前,先采用以羟基乙叉二膦酸(HEDP)为主配位剂的溶液对NdFeB进行预浸。预浸液组成和工艺条件为:HEDP 20~30 g/L,氢氧化钾20~25 g/L,碳酸钾10~15 g/L,葡萄糖酸钾1~2 g/L,乙酸0.5~1.0 g/L,室温,时间60 s。通过电化学测试对比了Nd Fe B基体有无预浸处理时,铜在其表面的电沉积行为,并通过金相显微镜、扫描电镜、能谱仪和荧光光谱测厚仪,对比了有无预浸处理的Nd FeB基体表面Cu镀层的宏观和微观表面形貌、截面形貌、元素分布及厚度分布均匀性。[结果]Nd Fe B基体预浸后表面被活化,静态电位降低。预浸液能够填满基体表面的孔隙并形成一层水薄膜,在后续电镀铜时保护基体不被腐蚀。预浸处理的Nd Fe B基体表面所得Cu镀层均匀、致密,不易氧化发黑,结合力和耐蚀性较好。[结论]对烧结钕铁硼进行预浸处理,能够保证其在后续电镀铜过程不被腐蚀,提高Cu镀层的综合性能。

HEDP浓度对烧结钕铁硼碱性无氰镀铜的影响

[目的]烧结钕铁硼(NdFeB)磁体在声电磁性器件中的应用日益广泛,但其耐蚀性较差,一般需要进行有效的表面处理以提高其耐腐蚀性能和使用寿命。[方法]采用以羟基乙叉二膦酸(HEDP)为主配位剂的碱性无氰体系对烧结Nd Fe B磁体表面电镀铜。研究了HEDP质量浓度对Cu镀层外观、表面粗糙度、厚度、结合力和耐蚀性的影响。[结果]HEDP的质量浓度为100~150 g/L时所得Cu镀层表面较光亮,厚度约为1.55μm,表面粗糙度较低,结合力和耐蚀性最佳。[结论]适宜的HEDP浓度有利于获得综合性能较好的Cu镀层。

电镀复合铜箔添加剂的研究

[目的]复合铜箔作为锂电负极集流体的新兴关键基础材料,其制备过程中水电镀工艺的镀铜添加剂成为研究重点。[方法]先通过霍尔槽试验和电化学分析筛选硫酸盐体系电镀铜的促进剂、抑制剂和整平剂,然后模拟现场环境进行电镀实验以获得较优的添加剂配方。[结果]较佳的添加剂配方为:聚二硫二丙烷磺酸钠(SPS)2 g/L,改性聚乙二醇100 g/L,整平剂C(硫脲基咪唑啉季铵盐)1 g/L。采用该复合添加剂时,可在超薄有机高分子薄膜两面镀上厚度1~2μm的铜。所得复合铜箔的总厚度约为6μm,具有高抗拉强度(292.39~297.98 MPa)和高断裂伸长率(21.34%~22.68%),外观无异常且不翘曲。[结论]该复合添加剂有望用于制备高抗高延的复合铜箔,具有很好的工业化应用前景。

航空发动机零件环保无氰镀铜工艺

[目的]寻求适用于航空发动机的无氰镀铜工艺,适应绿色环保的发展需求。[方法]从阴极电流效率、深镀能力、均镀能力和沉积速率几个方面对比分析了无氰镀铜溶液和氰化物镀铜溶液的性能,并通过比较镀层外观、结合力、防渗性能和氢脆性,验证了无氰镀铜层的优越性能。[结果]无氰镀铜溶液的上述性能都与氰化物镀铜溶液相当,所得Cu镀层的各项性能均满足航空标准HB/Z 5069–2011的要求。[结论]本研究的无氰镀铜工艺可替代氰化物镀铜工艺,可用于航空发动机零件制造。