陶瓷电容器化学镀铜的研究

陶瓷电容器化学镀铜的研究袁永明万家义王惠萍（四川大学化学系成都６１００６４）关键词陶瓷电容器以铜代银化学镀中图分类号Ｏ６９陶瓷电容器是最基本的电子元件，目前国内外大都采用涂银（印银）－烧银法制作银电极。这种方法需要消耗大量的贵金属银，设备投资贵、成本...     

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.     

陶瓷表面无敏化活化法微细化学镀铜

本文提出一种新的化学镀铜工艺,与激光微细刻蚀技术相结合可在Al2O3基底上实现无敏化活化化学镀铜,获得光亮致密、分辨率较高(40μm),导电性良好的化学镀层.     

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.     

电位活化现象与金属电沉积初始过程的研究

进行了恒电流电位-时间曲线和循环伏安曲线的测定，显示了铁电极进行氰化物镀铜时，镀层沉积前铁表面的电位活化过程. 对铁电极上焦磷酸盐镀铜的初始过程研究表明，由于铜的析出电位较正，铜是在未活化的电极表面上沉积的，因此镀层的结合强度很差.采用氩离子溅射和X射线光电子能谱相结合的方法，检测焦磷酸盐镀铜层和铁基体界面区含氧量的变化，证明了氧化层的存在. 通过添加辅助络合剂和控制起始电流密度的方法，可以增强无氰电镀时阴极的极化. 当铜的析出电位负于铁基体的活化电位时，可显示出铁表面的电位活化过程，定量测量镀层的结合强度也与氰化物电镀相近.     

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。     

不同化学镀液中p—Si上激光诱导局部沉积铜

在化学镀铜溶液中，ｐ－Ｓｉ片在波长为５１４．５ｎｍ的激光束的照射下，得到了选择性的铜镀层。采用ＡＥＳ、ＳＥＭ、ＲＢＳ和电学技术对比了在３种含不同还原剂的镀液中得到的镀层的形貌、组成、界面扩散及电学性质，探讨了液相激光诱导化学沉积铜的机理。     

Cu-ZSM-5分子筛中铜的超计量交换和铜氧铜桥的形成

用离子选择性电极原位监测离子交换制备Ｃｕ－ＺＳＭ－５的过程，并用ＴＰＤ－ＭＳ研究了样品加热脱水时的变化，发现在ＰＨ值，较高的条件下铜可能多数以Ｃｕ（ＯＨ）＾＋参与交换而使Ｃｕ－ＺＳＭ－５达到所谓的超计量交换，当新鲜样品受热时，Ｃｕ（ＯＨ）＾＋会迁移到另一个Ｃｕ（ＯＨ）＾＋的近邻进行脱水而形成铜氧铜桥，此桥可进一步脱氧而使二价铜还原成一价铜，迁移，脱水形成铜氧铜桥的过程是完全可逆的。     

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。     

乙醛酸化学镀铜的电化学研究

以乙醛酸作还原剂,Na2EDTA.2H2O为络合剂,亚铁氰化钾和2,2'-联吡啶为添加剂组成化学镀铜液体系,应用线性扫描伏安法研究分析了络合剂、添加剂对该镀铜体系电化学性能的影响.结果表明,络合剂Na2EDTA对乙醛酸的氧化和铜的还原有阻碍作用.亚铁氰化钾和过量(20 mg/L)的2,2'-联吡啶对乙醛酸的氧化起较明显的抑制作用.     

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.     

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.     

化学镀镍诱发过程的研究 I:金属催化活性的鉴别和反应机理

Electroless plating is known to be an autocatalytic process. For the reaction to start, the substrate metall should be either catalytic or activated by a suitable catalyst. For example, steel and nickel can be plated directly, but in the case of copper or brass, catalytic metal inducing is need. In this paper, the catalytic activity of different metals and their inducing effects were in vestigated by measuring stationary potentials nd stationary potential-time curves. Experimental results showed: (1) The stationary potential of metal provides a simple parameter to estimate the catalytic activity of metals in electroless nickeling. When 1-hydroxyethylidenediphosphonic acid (HEDP) aelectroless nickeling bath containing NaH2PO2 as reducing agent is used, electrolessnickeling may proceed spontaneously, if the stationary potential of metal is more nagative than -0.60V, no matter whether nickel (autocatalytic active) or other metals(non-autocatalytic active) is used as substrate. (2)When an autocatalytic meta is in contact with the substrate metal in the bath, a sudden decrease of stationary potential is observed. The whole inducing process could be finished within 0.5-2 sec. (3) The stationary potential of electroless nickeling coating in HEDP bath at 80`C is-0.72V, consequently nickel coating itself is a catalytic active metal. Once an electroless nickeling coating is deposited on a substrate metal, electroless nickeling reaction can then proceed continuously. (4) The sufficient conditions of electroless nickeling in HEDP bath containing NaH2PO2 are that the stationary potential of substrate metal must be more nagative than -0.60V and that the temperature of electroless nickeling bath should be higher than 50`C. (5) Inducing mechanism of electroless nickeling can be explained with chemical cell consisting of substrate metal and catalytic metal. Electrons from catalytic metal would suddenly decrease the stationary potential of substrate metal, H+ and Ni2+ complex ion would be reduced on the substrate me     

络合剂和添加剂对化学镀铜影响的电化学研究

以CuSO4·5H2O作主盐,乙二胺四乙酸二钠盐(Na2EDTA)作主络合剂,三乙醇胺(TEA)作辅助络合剂,2,2′＿联吡啶(dipyridine)作添加剂,组成化学镀铜液体系,研究络合剂、添加剂对该镀液电化学极化性能的影响,并结合化学沉积速率考察TEA和2,2′＿联吡啶对镀液性能的影响.     

活化液中稀土离子Ce3+对铜粉化学法镀银的促进作用

通过化学镀活化液中添加微量稀土元素Ce3+,采用电化学在Cu粉表面化学镀银,用电化学法和扫描电子显微镜测试技术分别研究了含稀土活化液的极化曲线、镀银层的表面形貌、银包覆率。结果表明,稀土以适宜比例添加到Pd2+活化液中,能使静止电极电位正移,极化度减小,过电位绝对值增大,活化液中的反应易于进行。适量稀土介入活化液中有助于提高镀银铜粉表面银在铜粉表面的沉积速度和包覆率,逐渐增加稀土含量,使镀层晶粒和组织逐渐细化且致密。 最佳加入值为0.32 g/L