高密度电路板微盲孔电镀铜填充及电化学行为研究

发布时间：2018-03-03 05:11

本文选题：高密度电路板(HDI)　切入点：铜电镀　出处：《沈阳航空航天大学》2017年硕士论文　论文类型：学位论文

【摘要】：随着电子产品朝着小型化、轻型化、功能多样化方向发展,使得印刷电路板(Printed Circuit Board,PCB)的发展产生了革命性变革,高密度互联(High Density Interconnection,HDI)技术的出现很好地满足了这一需求。微盲孔金属化就是高密度互联电路板发展的关键技术所在。为保证电路互联的可靠性,微盲孔需要被电镀铜完全填充,所以微盲孔的填充率以及表面填充厚度就是衡量电镀添加剂性能的关键指标。目前国内印刷电路板电镀药水市场基本被国外公司占领,这也严重制约了我国电路板行业的发展。因此,研究自主知识产权的电路板微盲孔电镀药水具有重大意义。根据HDI电镀填充技术要求:孔填充率大于85%,表面铜厚小于15μm,本工作分别利用健那绿B(JGB)、类藏花红(MST)、碱性黄(BY)三种染料作为整平剂,配制铜电镀药水,研究其微孔填充性能、电化学行为以及在微孔侧壁选择性和竞争性吸附行为,从而揭示其微孔填充机理。研究发现:在PEG-SPS-JGB体系中,能够在较宽的添加剂浓度范围内实现“自底向上”填充,通过优化配比和工艺条件,PEG-SPS-JGB体系在60分钟填充率达到86.8%以上,表面沉铜厚度低于12.8μm;孔口处无“凸起”现象;其无孔洞发生的最大允许电流密度为2A/dm2。相对比,PEG-SPS-MST镀液体系在60分钟填充率可达86%以上,但其表面沉铜厚度仅为1.9μm;当MST浓度大于5ppm时,在孔口处会出现“凸起”现象;对流速度越大,孔填充率越小,表面沉铜厚度越小,晶粒越粗大;与PEG-SPS-JGB体系相比,填孔速率提高了1倍。在EPE-SPS-BY体系中,60分钟填充率可达86.8%以上,表面沉铜厚度为14.3μm;该镀液体系在较窄的添加剂浓度范围内实现自底向上沉积模式;在SPS含量低于1ppm时,有利于形成超等形沉积,随着SPS含量增加,沉积模式转变为等形模式。使用旋转圆盘电极研究各添加剂的电化学行为,利用高、低转速模拟电镀液的对流环境,即100rpm、1000rpm转速分别对应孔底和孔口位置的对流条件。线性扫描伏安曲线(LSV)表明:100rpm时所对应的电流密度高于1000rpm时电流密度,说明在孔底沉积速率高于孔口处,这是“自底向上”沉积模式发生的基本电化学条件。同时发现,Cl-可使Cl--PEG体系的LSV曲线负移,即Cl-能协同PEG的抑制作用;Cl-可使Cl--SPS体系LSV曲线正移,即Cl-能协同SPS的加速作用。三种整平剂JGB、MST、BY与抑制剂PEG或EPE形成复合抑制剂,该复合抑制剂具有较强的对流相关性,即在孔口处或表面抑制能力远远强于孔底处,这是染料型整平剂能够实现超等形沉积和较薄表面沉积厚度的基本原理。在通过先预浸后的计时电位(GM)曲线中发现,相对于PEG-SPS-JGB体系,PEG-SPS-MST体系镀液在高、低转速条件下的电位之差(△η)提高10倍,说明MST在高对流条件下不能钝化SPS的加速作用,这很好解释了孔口处出现“凸起”现象。在EPE-SPS-BY镀液体系中,发现SPS的吸附竞争力弱于BY,但又强于BY-EPE复合体,过量的SPS可减弱BY-EPE抑制剂的吸附,不利于形成超等形沉积模式。
[Abstract]:With the electronic product miniaturization, lightweight, functional diversification, so that the printed circuit board (Printed Circuit, Board, PCB) produced a revolutionary change of the development of high density interconnection (High Density Interconnection, HDI) technology appears very good to meet the demand. The key technology of micro blind hole metallization is high density interconnection circuit board development. In order to ensure the reliability of the circuit interconnection, micro blind hole needs to be completely filled with copper plating, so the microvia filling ratio and surface filling thickness is a measure of the key indicators of performance of electroplating additives. At present, the domestic printed circuit board electroplating solution market by foreign companies occupied, which seriously hampered the development of our in the circuit board industry. Therefore, the circuit board is of great significance to research the independent intellectual property rights. According to HDI microvia electroplating chemical plating filling technical requirements: fill the hole Charge rate is greater than 85%, the surface copper thickness less than 15 m, the use of Janus Green B (JGB), class of Phenosafranine (MST), (BY) three basic yellow dyes as leveling agent, preparation of copper electroplating solution on the micropore filling properties, electrochemical behavior and micropores in the side wall of and the competitive adsorption behavior, so as to reveal the mechanism of micropore filling. It is found that in the PEG-SPS-JGB system, to achieve a "bottom-up" filling additives in a wide concentration range, by optimizing the proportion and process conditions, the PEG-SPS-JGB system of filling rate reached more than 86.8% in 60 minutes, the surface copper thickness less than 12.8 mu m; the orifice without a "bump" phenomenon; the holes the maximum allowable current density of 2A/dm2. compared to PEG-SPS-MST plating solution in 60 minutes filling rate can reach more than 86%, but the surface copper thickness is only 1.9 m; when the MST concentration is higher than 5ppm, in the orifice There will be a "bump" phenomenon; convection velocity increasing, hole filling rate is small, the surface of copper deposition thickness is smaller, the larger the grain size; compared with the system of PEG-SPS-JGB, pore filling rate increased by 1 times. In the EPE-SPS-BY system, 60 minutes filling rate can reach more than 86.8%, the surface of the copper deposition thickness of 14.3 m the plating solution; the additive concentration in a narrow range to achieve the bottom-up sedimentary model; when the content of SPS is lower than 1ppm, is conducive to the formation of super shape deposition, with the increase of SPS content, the sedimentary model into shape model. Using rotating disc electrode studies of the electrochemical behavior of the agent added, using high convection low speed simulation environment, plating 100RPM, 1000rpm speed corresponding convection hole bottom and orifice position. Linear sweep voltammetry (LSV) showed that the current density of 100RPM corresponding to the current density is higher than 1000rpm, indicating that the sediment in the bottom of the hole This is higher than the opening rate, "the basic electrochemical conditions from bottom to top" sedimentary model occurred. At the same time, Cl- can make the LSV curve of Cl--PEG system negative shift, inhibition of Cl- can cooperate with PEG in the Cl- can make the Cl--SPS system; LSV curve is Cl- that can accelerate the shift of collaborative SPS for use. Three kinds of leveling agent JGB, MST, BY and PEG or EPE inhibitor to form a composite inhibitor, the composite inhibitors have a strong correlation in convection, orifice or surface inhibition ability is far stronger than the bottom of the hole, this is the basic principle of dye based leveling agent can realize the thickness of super thin shape deposition and deposition in the surface. By chronopotentiometric pre soaked (GM) curves showed that, compared with PEG-SPS-JGB system, PEG-SPS-MST system solution in the high potential difference, low speed conditions (delta ETA) increased by 10 times, that accelerated the role of MST in high convection conditions cannot be passivated SPS, this Well explain the orifice "bump" phenomenon. In the EPE-SPS-BY plating solution and adsorption competitiveness of SPS is weaker than that of BY, but also strong adsorption on the BY-EPE complex, the overexpression of SPS attenuated BY-EPE inhibitors, is not conducive to the formation of sedimentary model of super shape.

【学位授予单位】：沈阳航空航天大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TN41;TQ153.14

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