铜电化学沉积在微孔金属化中的应用

以分布有微孔的印刷线路板(PCB)作为模板,按照PCB孔金属化工艺路线,研究乙醛酸化学镀铜和柠檬酸盐体系铜电沉积工艺在PCB微孔金属化中的应用.结果表明,乙醛酸化学镀铜和柠檬酸盐体系电沉积铜可以成功地应用于PCB微孔金属化加工工艺中.微孔化学镀铜金属化导电处理后,铜附着于微孔内壁,颗粒细小,但排列疏松且局部区域发生漏镀现象.微孔一经电镀铜加厚,镀层电阻显著下降;孔壁内外的铜沉积速率达到0.8:1.0;铜颗粒具有一定的侧向生长能力,能够完全覆盖化学镀铜时产生的微小漏镀区域;微孔内壁铜镀层连续、结构致密并紧密附着于内壁,大大增强了PCB上下层互连的导电性能.     

化学镀钴和超级化学镀填充的研究进展

随着半导体集成度的不断提高,铜互连线的电阻率迅速提高。当互连线宽度接近7 nm时,铜互连线的电阻率与钴接近。IBM和美国半导体公司（ASE）已经使用金属钴取代铜作为下一代互连线材料。然而,钴种子层的形成和超级电镀钴填充7 nm微孔的技术工艺仍是一个很大的挑战。化学镀是在绝缘体表面形成金属种子层的一种非常简单的方法, 通过超级化学镀填充方式, 直径为几纳米的盲孔可以无空洞和无缝隙的方式完全填充。本文综述了化学镀钴的研究进展,并分析了还原剂种类对化学镀钴沉积速率和镀膜质量的影响。同时, 在长期从事超级化学填充研究的基础上, 作者提出了通过超级化学镀钴技术填充7 nm以及一下微盲孔的钴互连线工艺。     

聚合物材料表面化学镀铜的前处理研究进展

聚合物材料表面金属化在通讯、电子、航空航天领域具有重要应用. 化学镀铜是聚合物材料表面金属化的主要技术之一. 聚合物材料表面的前处理直接影响化学镀铜层的结合力及镀层平整度. 本综述详细介绍非导电聚合物材料的种类、组成以及性能, 并概述其表面化学镀铜前处理的研究进展.     

化学镀铜过程混合电位本质的研究

现场测量了铜基和陶瓷基化学镀铜过程混合电位－时间曲线(Emix－t)，成功地检测到了化学镀诱发过程.考察了添加剂和络合剂的浓度以及pH值对Emix－t曲线的影响，结合阴、阳极极化曲线及双电层理论对各种影响因素进行了讨论.新生铜活化的铜基化学镀铜的诱发过程是一个缓慢激活过程,所对应的Emix－t曲线是一个稍微倾斜的台阶，这不同于钯活化的基体的诱发过程.通过对不同活化工艺的Emix－t曲线的比较，发现较高的活化温度能明显减少活化时间，而且还可加速诱发过程，从而提高化学沉积铜的速度.     

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.     

超级化学镀铜填充微道沟的研究

超级化学铜填充技术不仅可以应用于半导体超大集成电路铜互连线, 而且可以应用于三维封装. 研究了不同浓
度、不同分子量的PEG 对以甲醛为还原剂的化学镀铜溶液中铜的沉积速率的影响. 随着添加剂PEG 浓度和分子量的
增大, 化学铜的沉积速率明显降低. 电化学研究结果表明PEG 通过抑制甲醛的氧化反应降低化学铜的沉积速率, PEG
分子量越大, 对化学铜的抑制作用越强. 利用PEG-6000 对化学铜的抑制作用和在溶液中低的扩散系数, 采用添加
PEG-6000 的化学镀铜溶液, 成功地实现了宽度在0.2 μm 以下微道沟的超级化学填充. 就PEG 的分子量、微道沟的深
径比等因素对超级化学铜填充的影响也做了研究.     

玻璃纤维的表面金属化

采用以甲醛为还原剂、EDTA·Na2和TART·KNa为络合剂的双络合剂体系对玻璃纤维表面进行了化学镀铜.结果表明,在玻璃纤维表面上成功镀覆上一层致密、亮铜色的铜镀层.     

ABS塑料化学镀铜实验

通过研究塑料化学镀铜的时间与铜沉积速率的关系，使学生理解甲醛作为还原剂进行塑料化学镀铜的原理；同时，掌握研究问题的方法和思路，为以后进行课程设计或进行研究性工作奠定基础。     

2,2''''-联吡啶和亚铁氰化钾对乙醛酸化学镀铜的影响

以乙醛酸作还原剂、Na2EDTA为络合剂、2,2'-联吡啶和亚铁氰化钾作为添加剂组成化学镀铜体系,研究了两种添加剂对化学镀铜速率、镀层表面形貌、组成和结构的影响.结果表明:添加适量的2,2'-联吡啶和亚铁氰化钾,不仅提高了镀液的稳定性,而且使沉积速率增加1倍.这两种添加剂的同时使用,使镀层颜色变亮,形貌发生变化.所得镀层是多晶铜,没有发现夹杂Cu20.     

2,2′-联吡啶和亚铁氰化钾对乙醛酸化学镀铜的影响

以乙醛酸作还原剂、Na2EDTA为络合剂、2,2′-联吡啶和亚铁氰化钾作为添加剂组成化学镀铜体系,研究了两种添加剂对化学镀铜速率、镀层表面形貌、组成和结构的影响.结果表明:添加适量的2,2′-联吡啶和亚铁氰化钾,不仅提高了镀液的稳定性,而且使沉积速率增加1倍.这两种添加剂的同时使用,使镀层颜色变亮,形貌发生变化.所得镀层是多晶铜,没有发现夹杂Cu2O.     

Comparison of Bottom-up Filling in Electroless Plating with an Addition of PEG,PPG and EPE

The bottom‐up filling capabilities of electroless copper plating bath with an addition of additives, such as polyethylene glycol (PEG), polypropylene glycol (PPG) and triblock copolymers of PEG and PPG with ethylene oxide terminal blocks termed EPE, were investigated by the cross‐sectional scanning electron microscopy (SEM) observation of sub‐micrometer trenches. Though three additives had inhibition for electroless copper deposition, the suppression degrees of three additives were different. EPE‐2000 had the strongest suppression for electroless copper deposition, and the suppression of PEG‐2000 was the weakest. The bottom‐up filling capability of electroless copper was investigated in a plating bath containing different additives with the concentration of 2.0 mg/L. The cross‐sectional SEM observation indicated the trenches with the width of 280 nm and the depth of 475 nm were all completely filled by the plating bath with an addition of EPE‐2000, but the trenches were not completely filled by the plating bath with an addition of PEG‐2000 or PPG‐2000, and some voids appeared. Linear sweep voltammetry measurement indicated that three additives all inhibited the cathodic reduction reaction and the anodic oxidation reaction, and the inhibition of EPE‐2000 was the strongest among three additives, which agreed with that of the deposition rate of electroless copper. Significant differences in surface roughness of deposited copper film were observed by UV‐visible near‐infrared for different suppressors, and the bright and smooth of deposited copper film were in accordance with the inhibition of three additives.     

3D amino-induced electroless plating: a powerful toolset for localized metallization on polymer substrates

The "3D amino-induced electroless plating" (3D-AIEP) process is an easy and cost-effective way to produce metallic patterns onto flexible polymer substrates with a micrometric resolution and based on the direct printing of the mask with a commercial printer. Its effectiveness is based on the covalent grafting onto substrates of a 3D polymer layer which presents the ability to entrap Pd species. Therefore, this activated Pd-loaded and 3D polymer layer acts both as a seed layer for electroless metal growth and as an interdigital layer for enhanced mechanical properties of the metallic patterns. Consequently, flexible and transparent poly(ethylene terephtalate) (PET) sheets were selectively metalized with nickel or copper patterns. The electrical properties of the obtained metallic patterns were also studied.     

5,5-二甲基乙内酰脲在化学镀铜中的作用

在以酒石酸钾钠和乙二胺四乙酸二钠为双配位剂、 甲醛为还原剂的化学镀铜液中, 研究了5,5-二甲基乙内酰脲(DMH)在化学镀铜中的作用. 化学镀铜实验结果表明, DMH提高了镀液的稳定性; 扫描电子显微镜(SEM)结果表明, DMH使镀层颗粒尺寸减小, 镀层光亮致密; 紫外-可见光谱结果表明, DMH在镀液中与Cu(II)不发生强配位作用; 线性伏安扫描结果表明, DMH在化学镀铜过程中能抑制Cu⁺的产生或促进Cu⁺快速还原, 降低甲醛的氧化速率; X射线衍射(XRD)结果表明, 在含和不含DMH化学镀铜液中, 得到的铜镀层均呈现面心立方混晶结构的特征, 且未出现Cu₂O夹杂衍射峰.     

Regeneration of a Solution for Electroless Copper Plating

The possibility of electrochemical regeneration of a solution for electroless copper plating by membrane electrolysis was studied. The conditions of anodic dissolution of copper in a spent solution for electroless copper plating, under which the concentration of copper ions increases at a rate exceeding by an order of magnitude that of their deposition in the course of electroless copper plating, were examined. A scheme for regeneration of spent solutions for electroless copper plating was suggested.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 4, 2005, pp. 586–590.Original Russian Text Copyright © 2005 by Turaev, Kruglikov.     

Electroless plating of copper on fly ash cenospheres using polyaniline‐Pd activation

The polyaniline of different intrinsic oxidation states, viz., the emeraldine (EM) and the leucoemeraldine (LM) states, were coated on 3‐aminopropyltriethoxy silane modified fly ash cenospheres. Without prior sensitization by SnCl₂ solution, Pd activation by PdCl₂ solution was carried out on EM and LM laden cenospheres, followed by electroless plating of copper (Cu). The topography and composition of the composites were characterized by scanning electron microscopy, X‐ray diffraction, and X‐ray photoelectron spectroscopy, etc. The results indicate that the oxidation state of the LM layer showed a much bigger increase than that of the EM layer in the Pd activation process, while coupled Pd reduction underwent to a more extent on the LM layer. The metallic Pd atoms on the LM and EM layers surface initiated the subsequent electroless plating of Cu, and the coated Cu on LM laden cenospheres had a much more uniform and compact morphology than that on EM laden cenospheres. Copyright © 2012 John Wiley & Sons, Ltd.     

Electroless Deposition of Copper on Poly(tetrafluoroethylene) Films Modified by Plasma-Induced Surface Grafting of Poly(4-vinylpyridine)

Argon plasma-pretreated poly(tetrafluoroethylene) (PTFE) films were solution coated with a thin layer of poly(4-vinyl pyridine) (P4VP). Subsequent exposure of the films to argon plasma resulted in the grafting of P4VP on the PTFE films. Electroless plating of copper could be carried out effectively on the P4VP-grafted PTFE (P4VP-g-PTFE) surface after PdCl₂ activation and in the absence of SnCl₂ sensitization (the Sn-free process). The catalytic processes of the electroless plating of copper in the presence and absence of sensitization by SnCl₂ were also compared. The effect of glow discharge conditions on the P4VP concentration and the adhesion strength of the electrolessly deposited copper was investigated. The T-peel adhesion strength of the electrolessly deposited copper with the graft-modified PTFE film was improved in the absence of SnCl₂ sensitization and could reach about 3 N/cm. PdCl₂ activation and electroless deposition of copper could not be carried out on the pristine or the Ar plasma-treated PTFE surface in the absence of prior sensitization by SnCl₂. X-ray photoelectron spectroscopic (XPS) analysis revealed that the electrolessly deposited copper delaminated from the P4VP-g-PTFE film by cohesive failure inside the PTFE film.