5,5′-二甲基乙内酰脲体系电沉积金(英文)

开发了以5,5′-二甲基乙内酰脲(DMH)为配位剂的无氰电镀金工艺。利用扫描电镜(SEM)和线性扫描伏安曲线对电镀时间和添加剂(由丁炔二醇、糖精和十二烷基硫酸钠组成)对镀金层表面、断面形貌和镀液性能的影响进行了测试,结果表明随着电镀时间的延长镀金层表面形貌几乎没有发生变化,光亮剂的加入增大了阴极极化同时使镀金层结晶变得细致均匀,在由HAuCl4,DMH,K3PO4和KH2PO4组成的基础镀液中金的沉积速度可达0.3μm.min-1,镀液中添加剂的加入没有影响金的沉积速度。利用X射线衍射技术(XRD)和X射线光电子能谱技术(XPS)对镀金层性能进行了测试,结果表明镀金层沿着(111)晶面择优生长并且由纯金组成。利用循化伏安曲线和旋转圆盘电极对Au(Ⅲ)在镀液中的电化学还原机制进行了研究,结果表明当研究电极为玻碳电极(GCE),镀液温度为45℃时,镀液中金的电沉积过程是受扩散控制的不可逆的过程。同时利用循环伏安曲线对镀金液的稳定性进行了分析。     

伏安法快速测定镍、铬、铁和铜镀液中氯离子的浓度

根据氯离子在铂电极上的电化学氧化特性，用DZ-1B型电镀添加剂测定仪测定镍、铬、铁和铜镀液中氯离子的浓度。操作简便．快速，适用于电镀车间的镀液分析。     

电镀液中铜、铁、铅和锌等杂质元素的原子吸收光谱测定

电镀液中常见的有害杂质:铜、铁、铅和锌等的允许含量随镀液种类和杂质元素不同而异。例如,镀镍液中的铜、铁、铅和锌的允许范围在几个至几十个毫克/升内,而镀铬液中的铁的允许范围却在1—几克/升内。1964年Whittington报告用原子吸收加入法测镀镍液中的铜、铁、铅和锌。我们也用过此法。此法比较麻烦。虽然Parker报告把电镀液稀释后直接用原子吸收法测锌、铜、铬,但未报导具体条件。本文除测定镀镍液和镀钻液中低含量铁仍用加入法外,铜、铅、锌及镍、钴镀液中高于50毫克/升铁都用稀释法。实验表明:     

离子色谱法电导检测电镀液中的有机酸、S_2O_3~(2-)和SCN~-

电镀工业中,为了改善镀层性能,通常需要在电镀液中加入适量电镀添加剂,起到稳定镀液、细化结晶、提高分散能力与深镀能力、增加镀层光亮性等作用~([1]).添加剂的含量直接影响着电镀产品的质量,因而能否在生产过程中及时准确地监测其浓度变化是控制电镀过程的至关晕要的环节.常见组分采用化学滴定、高效液相~([2,3])等方法分类测定,相比而言,离子色谱法能同时完成的分析,优势更为明显~([4,5]).本研究建立了一种简单易行的离子色谱方法,同时测定了电镀液中弱保留组分和易极化离子S_2O_3~(2-)和SCN~-,使得电镀槽液的组分变化的监测更为精确且更加实时化.     

钛基二氧化铅平板电极的镀制

得用所镀二氧化铅和氧阴极组装成电解槽，通过测定高氯酸盐生成电流效率及循环伏安、ＳＥＭ、ＳＲＤ等方法，评价所镀钛基二氧化铅平板电极性能，考察了电镀液组成对电极性能的影响，发现必须严格控制镀液中铁离子的含量，增大硝酸的使用量，才能制得用于高氯酸盐电化生产的高性能钛基二氧化铅电极。     

高均匀性的铜柱凸块电镀

随着电子产品的小型化、多功能化和高性能化的发展,促使着2D集成封装向2.5D或3D集成封装发展。铜柱凸块电镀是晶圆级三维封装的关键基础技术之一。本文研究了铜柱凸块的电镀均匀性与添加剂浓度、 镀液对流、 电流密度和电镀设备之间的影响规律。研究结果表明, 添加剂浓度、 镀液对流以及电流密度对单个铜柱凸块的平整度影响较大,而对铜柱凸块高度的均一性影响较小。相反,电镀设备对铜柱凸块的高度均一性的影响较大, 而对铜柱凸块的平整度影响较小。在三种有机添加剂中, 整平剂对铜柱凸块的平整度影响最大, 随着镀液中整平剂浓度的增加,铜柱凸块顶部形状由凸起、变为平整、 再转变为凹陷。电镀液的单向对流会导致所沉积铜柱凸块形貌发生倾斜。 高的电流密度会导致凸顶的铜柱凸块形貌。精密设计的电镀设备可以提高晶圆上电流密度分布的均匀性, 继而大幅提高电镀铜柱凸块的共面性。本文的研究结果可为铜柱凸块的电镀优化提供指导。     

镀液中金属杂质离子对电镀镍层性能的影响

向镍电镀原液中引入2 g/L的Co~(2+),Cr3+,Mn~(2+),Fe~(2+),Cd~(2+),Zn~(2+)等离子,通过电镀得到不同的镀层.X射线衍射(XRD)、X射线光电子能谱(XPS)及扫描电子显微镜(SEM)的结果表明,不同金属离子对镍沉积影响不同,金属杂质离子的存在会使镀层中晶粒尺寸变小,影响镍镀层的均匀性和致密度.通过阴极极化曲线、计时电位和交流阻抗等方法探讨了含有不同金属杂质的镀液在电镀过程中电化学行为的规律性.通过镀液的浓度梯度、耐腐蚀、耐热循环及耐高温等实验获得了不同条件下金属杂质在镀液中所允许的浓度范围.     

玻碳电极阳极溶出法测定高纯铝中PPb级杂质锌

高纯铝中ppm级锌杂质的测定,现都采用酸分解试样后转化成pH约3.5的三氯化铝溶液,而后直接用悬汞电极或铂球镀银沾汞电极阳极溶出伏安法进行测定。在该底液中测定锌,氢离子浓度控制甚严,否则将干扰锌的测定。特别对于高纯铝中ppb级杂质锌的测定,即使底液中微量的氢离子存在,亦使锌波波底平直不易测量,产生严重的干扰。本试验利用玻璃碳电极导电性好、灵敏度高和氢的超电势高等优点,用二硫腙-四氯化碳溶液萃取分离铝基体及试样中共存的干扰杂质元素,同时对锌进行富集,而后在乙酸钠底液中用阳极溶出伏安法进行测定,解决了在一般     

不同分子量PEG的铜电镀液对电化学沉积铜行为的研究

研究了在酸性镀铜溶液中添加不同分子量的PEG对直径为50微米、深径比为1的镀层盲孔填充效果的影响.结果表明,随着PEG分子量的增加,电镀铜溶液的微孔填充力明显提高.电流密度为2 A/dm2,添加剂PEG分子量(u)超过6000时,镀液可以完全填充盲孔,镀层不出现任何空洞和缝隙.这是由于添加剂PEG能明显加强电镀铜镀液阴极极化,抑制了电镀铜的沉积.同时,PEG于镀液中的扩散系数还随其分子量的增加而降低,从而增加了SPS在微孔底部的吸附力,加速了电镀铜在微孔底部的沉积.进一步,增大PEG分子量,沉积铜膜的表面粗糙度、铜膜结晶度和电阻率均有所降低.     

糖精电极测定镍电镀液中糖精含量

糖精是Ni、Pd、Au电镀液中的添加剂,它有利于改进镀件的光亮度、韧性和均一性。一般均需用氯仿萃取分离糖精,后用极谱、紫外分光光度和滴定法测定,一阶导数紫外分光光度法虽可不经分离直接测定,惟仪器复杂。我们研制了PVC膜糖精电极并对电镀液中糖精测定进行了方法研究。实验结果表明,用糖精电极不必分离即可快速测定糖精含量,方法变异系数为3％,结果与常规方法相符。本法设备简单,已在许多电镀厂推广。     

Combined standardless electrochemical method for determination of lead(II), copper(II), and cadmium(II) in aqueous solutions

A combined standardless method (no calibration of the device against standard solutions or use of the method of additives is required) for determination of lead, copper, and cadmium in aqueous solutions is suggested. The method operates on principles of inversion voltammetry and potentiostatic coulometry. It is convenient for automated analysis of technological solutions and wastewater from electroplating and hydrometallurgical shops.     

Voltammetric determination of Cr(III) in plating baths containing Cr(III) salts as the main component

The differential pulse single-sweep voltammetric technique with hanging mercury drop electrode was used for the determination of Cr(III). The determination was carried out in 0.2 mol/l sodium acetate as supporting electrolyte. The reduction peak of Cr(III) was recorded at –1.5 V vs. Ag/AgCl reference electrode. The relative standard deviation was 3% for Cr concentrations in the range of 0.4 mol/l. The determination of impurities (Cd, Cu, Pb and Zn) in fresh and overworked galvanic baths using anodic stripping voltammetry in the differential pulse mode is also described.     

高密度互连印制电路板孔金属化研究和进展

孔金属化互连是印制电路板(PCB)高密度集成的核心制程之一,化学镀铜和电子电镀铜是实现孔金属化的关键技术.本文介绍HDI-PCB的概念和制作流程;综述化学镀铜和电子电镀铜孔金属化互连的研究和进展,包括溶液组成和操作条件的影响,添加剂及其相互作用机理,以及盲孔填充和通孔孔壁加厚机制;展望高密度互连印制电路板电子电镀基础研...     

Benefiting from information-rich multi-frequency AC voltammetry coupled with chemometrics on the example of on-line monitoring of leveler component of electroplating bath

Simultaneous application of multiple sinusoidal waveforms perturbations superimposed onto DC staircase step significantly enriches current response. The measured current is characterized by a matrix of data rather than a conventional voltammetric output in a form of a vector. This increase of the dimensionality of the current response and therefore the wealth of analytical information is achieved without compromising the time of analysis. The natural approach for compression of such data and extraction of relevant information is by utilizing multi-way chemometric decomposition techniques. An electroplating solution presents a very challenging analyte for electroanalysis as its constituents interact synergistically with each other during both the plating process and its simulation during electroanalysis. For some components the mechanism is not entirely understood. Therefore, the only way to benefit from the analytical data is by employing soft modeling. The electrode processes involving additives rely heavily on adsorption and, indirectly, on electron transfer kinetics for which AC voltammetry is an analytical technique capable of delivering informative signals. This paper presents a rigorous universal method for calculating and validating an exemplary multi-way calibration of a leveler component in a copper electroplating bath used in the semiconductor industry. The method presented employs comparatively Parallel Factor Analysis coupled with Inverse Least Squares Regression and multi-linear Partial Least Squares. The calibration training set consists of multi-frequency AC voltammetric data subjected to pretreatments aiming to select informative independent variables and exclude outliers.     

Monitoring metal ion contamination onset in hydrofluoric acid using silicon-diamond and dual silicon sensing electrode assembly.

Potentiometric detection of trace levels of metallic contamination onset in hydrofluoric acid using a silicon-based sensor in conjunction with two non-contaminating reference electrode systems is presented in this paper. In the first case, conductive diamond was used as a non-contaminating reference electrode. Cyclic voltammetry and open-circuit potential experiments demonstrated the feasibility of using a conductive diamond film electrode as a quasi-reference electrode in the HF solution. In the second case, a dual silicon electrode system was used with one of the silicon-based electrodes protected with an anion permeable membrane behaving as the quasi-reference electrode. The dual silicon sensing electrode system possessed an additional operational advantage of being unaffected by the solution acidity. Though both sensing configurations were able to detect the metal ion contamination onsets at the parts-per-trillion to parts-per-billion levels, the dual silicon electrode design showed a greater compatibility for the on-line detection of metallic impurities in HF etching baths commonly used in semiconductor processing.     

A general model of metal underpotential deposition in the presence of thiol-based additives based on an in situ STM study

Bis(3-sulfopropyl)disulfide (SPS) is a common additive in commercial copper electroplating baths. We have studied the influence of SPS on Cu underpotential deposition (UPD) on a Au(111) single crystal surface by means of cyclic voltammetry (CV) and electrochemical scanning tunneling microscopy (EC-STM). By combining our results with the results from the literature we propose a model that describes different stages of Cu UPD in the presence of SPS. Further analysis shows that our model is also applicable to a more general case of UPD of different metals, e.g. Cu and Ag, on a thiol-modified single-crystal surface, where the bond between the substrate and the thiol is adatom mediated. In addition, we have verified our model by in situ observation of the lifting of the Herringbone reconstruction on the Au(111) surface by Cu UPD.     

离子色谱法同时测定电镀液中的S_2O_3~(2-)、SCN~-和有机酸

建立了同时测定镀锌、镀铜、镀金等3种电镀液中添加剂(甲酸、酒石酸、草酸、柠檬酸、 S2O32-和SCN-)的离子色谱分析方法.以IonPac AS19高容量阴离子交换柱分离,KOH流动相梯度淋洗,抑制型电导检测,23 min之内可完成这3种电镀液中6种添加剂的分析.甲酸、酒石酸、草酸、柠檬酸、 S2O32-和SCN-的检测限(25 μL 进样,S/N=3)分别为3.9,9.6,6.9,9.7,12.9,21.2 ng/L,各种待测物均具有较宽的线性范围和较好的线性,相关系数在0.9989～0.9999之间.方法已用于镀锌液、镀铜液、镀金液样品中有机酸、 S2O32-和SCN-的检测,样品加标回收率在93%～107%之间.     

芯片铜互连研究及进展

本文详细介绍芯片制造中铜互连技术,综述酸性硫酸铜电镀工艺要点及常用添加剂作用机理,并概述国内外新型添加剂研究进展. 在此基础上,展望新型铜互连工艺替代酸性硫酸电镀铜工艺的可能性.     

Determination of saccharin in electroplating baths by differential pulse and a.c. polarography

Saccharin can be determined in palladium, gold and nickel electroplating baths by differential pulse polarography or second-harmonic a.c. polarography after extraction with an ethyl acetate/carbon tetrachloride mixture and after masking the noble metal with cyanide. Detection limits lie between 0.025 and 0.005 g l^-1. Bath components such as chloride, nitrate, sulfate, phosphate, glucose, citrate, Fe³⁺, Sn⁴⁺, Cr³⁺, Ni²⁺ and Pb²⁺ do not interfere.     

印制电路中电镀铜技术研究及应用

电镀铜技术是制造印制电路板、封装载板等电子互连器件的核心技术.本文介绍了印制电路中电镀铜技术及其发展概况,主要总结了电子科技大学印制电路与印制电子团队在印制电路电镀铜技术基础研究和产业化应用等方面的工作.首先,以三次电流分布理论为基础,采用多物理场耦合方法构建阴极表面轮廓线随时间变化的镀层生长过程模型.该模型描述了铜沉...