添加剂对电解铜箔组织性能的影响及优化
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摘要
近年来铜的电沉积已经受到了广泛研究,因为铜箔在印刷电路板和覆铜板行业中得到很好的应用。而添加剂在铜电沉积过程对铜箔性能的影响中起着很重要的作用,即使是很微量的添加剂也能显著改变沉积层的性能。
本文利用SEM、微机控制万能试验机、高温拉伸机、电子背散射衍射分析技术、应力仪研究了聚二硫二丙烷磺酸钠(SP)、羟乙基纤维素(HEC)、聚乙二醇(PEG)、明胶、稀土铈盐等添加剂单独及共同作用时对铜电沉积的影响。实验表明：SP整平效果较好,能提高铜箔抗拉强度和延伸率,尤其是高温延伸率。加入0.2 mgL左右的SP,铜箔综合性能最好。HEC能促使晶粒面向生长,抑制针孔,但会引起铜箔翘曲。PEG能加大阴极极化,细化晶粒,使晶粒面向生长。能抑制杂质金属的电沉积,防止异常晶粒长大。同时能光滑尖锥状晶粒的峰尖,避免粗糙过度,但PEG过量会降低铜箔高温抗拉强度和延伸率。P-6000效果要好于P-8000。明胶具有细化晶粒和整平的效果,能够保证铜箔具有一定的粗糙度和提高铜箔常温抗拉强度和延伸率,但会降低铜箔高温抗拉强度和延伸率。骨胶的效果要好于胶原蛋白。适量的硫酸铈盐可以细化晶粒,使晶粒均匀致密,并能改善铜箔的力学性能,当铈离子浓度为6 mg/L,晶粒细化效果最好,力学性能最高。
通过正交试验,研究了不同添加剂配方对铜箔亮面晶粒微观结构、力学性能,以及内应力的影响,利用直观图示和数据分析得出了最优的3种添加剂配方,经过试验验证确定了添加剂最佳配比为：明胶、PEG、SP、HEC浓度分别为1.4mg/L、1.5 mg/L、0.35 mg/L、0.6mg/L。制备出的铜箔内应力减少,铜箔缺陷也有所减少,亮面晶粒微观结构：孪晶(界)24.3%,(111)织构22.8%,晶粒平均尺寸250.4nm,毛面晶粒分布较均匀,铜箔力学性能也能提高,其中常温和高温抗拉强度分别是：376.5 MPa、197.1MPa,常温和高温延伸率分别是：5.6%、2.8%。将此配方应用到中试线上,生产出的生箔性能优异,产品质量得到明显改善。
The electrodeposition of Cu has been a subject of recent extensive investigations because of electrodeposition copper foils have been widely used the conductors for printed circuit boards (PCBs). Additives play a major role in controlling the properties of copper foils, even small amounts of certain additives can affect the properties and aspect of the deposit.
The effect of bis-(3-sulfopropyl) disulfide (SP), hydroxyethylcellulose (HEC), polyethylene glycol (PEG), gelatin and cerous sulfate on the copper electrodeposits are investigated by SEM (scanning electron microscope), microcomputer control electronic universal testing machine, high temperature drawing machine, EBSD(electron backscattered diffraction) and stress gauge. The results reveal that SP can decrease the surface roughness and improve the mechanical properties, especially for elongation at room temperature. Copper foil with maximum value comprehensive properties can be obtained with approximately 0.2 mg/L SP content. HEC can promote the growth of grain-oriented and ensure copper foil has certain roughness and improve the mechanical properties at room temperature, but reduce the tensile strength of foil at high temperature. HEC also can inhibit the pinhole, but cause copper foil warp. PEG can increase the depositon over-potential and promote the growth of grain-oriented, resulting in grain refinement and allowing the microscopic roughness of the copper foil to be lower. PEG also has the ability to inhibit the deposition of metal impurities and prevent the growth of abnormal grain. But excess PEG will reduce the tensile strength and elongation of copper foil at high temperature. The leveling and refinement effect of gelatin are well. It can improve the tensile strength and elongation of copper foil at room temperature, but reduce the tensile strength and elongation of copper foil at high temperature. And the effect of bone glue is better than collagen. RE element can obviously improve mechanical properties of the copper foil by refining and uniformly distributing grain size in the foil, where ideal grain size in the copper foil with maximum value mechanical properties can be obtained with approximately 6 mg/L RE content.
The effects of different additive formula on the microstructure of bright side, mechanical properties and internal stress of electrodeposited copper foil are investigated by the orthogonal test and the best 3 additive formulas were gotten by visual diagram and data analysis. The best ratio of formula was proved by experiments:Gelatin、PEG、SP、HEC was 1.4 mg/L、1.5mg/L、0.35mg/L、0.6 mg/L, respectively. The internal stress and defects of copper foil was reduced, microstructure of bright side was:twin of 24.3%, (111) texture of 24.3% and the average grain size of 250.4nm. The grains on rough surface were distributed more uniformly and mechanical properties of copper were improved as well。The tensile strength at room temperature and high temperature were 376.5 MPa and 197.1MPa respectively, elongation at room temperature and high temperature were:5.6% and 2.8%respectively. The best formula is applyed to the pilot line, the performance of the crude foils gets better, and the quality of the products improves obviously.
本文利用SEM、微机控制万能试验机、高温拉伸机、电子背散射衍射分析技术、应力仪研究了聚二硫二丙烷磺酸钠(SP)、羟乙基纤维素(HEC)、聚乙二醇(PEG)、明胶、稀土铈盐等添加剂单独及共同作用时对铜电沉积的影响。实验表明：SP整平效果较好,能提高铜箔抗拉强度和延伸率,尤其是高温延伸率。加入0.2 mgL左右的SP,铜箔综合性能最好。HEC能促使晶粒面向生长,抑制针孔,但会引起铜箔翘曲。PEG能加大阴极极化,细化晶粒,使晶粒面向生长。能抑制杂质金属的电沉积,防止异常晶粒长大。同时能光滑尖锥状晶粒的峰尖,避免粗糙过度,但PEG过量会降低铜箔高温抗拉强度和延伸率。P-6000效果要好于P-8000。明胶具有细化晶粒和整平的效果,能够保证铜箔具有一定的粗糙度和提高铜箔常温抗拉强度和延伸率,但会降低铜箔高温抗拉强度和延伸率。骨胶的效果要好于胶原蛋白。适量的硫酸铈盐可以细化晶粒,使晶粒均匀致密,并能改善铜箔的力学性能,当铈离子浓度为6 mg/L,晶粒细化效果最好,力学性能最高。
通过正交试验,研究了不同添加剂配方对铜箔亮面晶粒微观结构、力学性能,以及内应力的影响,利用直观图示和数据分析得出了最优的3种添加剂配方,经过试验验证确定了添加剂最佳配比为：明胶、PEG、SP、HEC浓度分别为1.4mg/L、1.5 mg/L、0.35 mg/L、0.6mg/L。制备出的铜箔内应力减少,铜箔缺陷也有所减少,亮面晶粒微观结构：孪晶(界)24.3%,(111)织构22.8%,晶粒平均尺寸250.4nm,毛面晶粒分布较均匀,铜箔力学性能也能提高,其中常温和高温抗拉强度分别是：376.5 MPa、197.1MPa,常温和高温延伸率分别是：5.6%、2.8%。将此配方应用到中试线上,生产出的生箔性能优异,产品质量得到明显改善。
The electrodeposition of Cu has been a subject of recent extensive investigations because of electrodeposition copper foils have been widely used the conductors for printed circuit boards (PCBs). Additives play a major role in controlling the properties of copper foils, even small amounts of certain additives can affect the properties and aspect of the deposit.
The effect of bis-(3-sulfopropyl) disulfide (SP), hydroxyethylcellulose (HEC), polyethylene glycol (PEG), gelatin and cerous sulfate on the copper electrodeposits are investigated by SEM (scanning electron microscope), microcomputer control electronic universal testing machine, high temperature drawing machine, EBSD(electron backscattered diffraction) and stress gauge. The results reveal that SP can decrease the surface roughness and improve the mechanical properties, especially for elongation at room temperature. Copper foil with maximum value comprehensive properties can be obtained with approximately 0.2 mg/L SP content. HEC can promote the growth of grain-oriented and ensure copper foil has certain roughness and improve the mechanical properties at room temperature, but reduce the tensile strength of foil at high temperature. HEC also can inhibit the pinhole, but cause copper foil warp. PEG can increase the depositon over-potential and promote the growth of grain-oriented, resulting in grain refinement and allowing the microscopic roughness of the copper foil to be lower. PEG also has the ability to inhibit the deposition of metal impurities and prevent the growth of abnormal grain. But excess PEG will reduce the tensile strength and elongation of copper foil at high temperature. The leveling and refinement effect of gelatin are well. It can improve the tensile strength and elongation of copper foil at room temperature, but reduce the tensile strength and elongation of copper foil at high temperature. And the effect of bone glue is better than collagen. RE element can obviously improve mechanical properties of the copper foil by refining and uniformly distributing grain size in the foil, where ideal grain size in the copper foil with maximum value mechanical properties can be obtained with approximately 6 mg/L RE content.
The effects of different additive formula on the microstructure of bright side, mechanical properties and internal stress of electrodeposited copper foil are investigated by the orthogonal test and the best 3 additive formulas were gotten by visual diagram and data analysis. The best ratio of formula was proved by experiments:Gelatin、PEG、SP、HEC was 1.4 mg/L、1.5mg/L、0.35mg/L、0.6 mg/L, respectively. The internal stress and defects of copper foil was reduced, microstructure of bright side was:twin of 24.3%, (111) texture of 24.3% and the average grain size of 250.4nm. The grains on rough surface were distributed more uniformly and mechanical properties of copper were improved as well。The tensile strength at room temperature and high temperature were 376.5 MPa and 197.1MPa respectively, elongation at room temperature and high temperature were:5.6% and 2.8%respectively. The best formula is applyed to the pilot line, the performance of the crude foils gets better, and the quality of the products improves obviously.
引文
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