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FeNiP化学镀层的制备及其与无铅焊料的润湿性及界面反应性能
周海飞
学位类型博士
导师尚建库 ; 郭敬东
2012
学位授予单位中国科学院金属研究所
学位授予地点北京
学位专业材料学
关键词无铅焊料 凸点下金属化层 Fenip化学镀层 可焊性 界面反应 Lead-free Solder Under Bump Metallization Electroless Fenip Solderability Solder Reactions
摘要新型UBM薄膜材料的研究一直是微电子互连技术研究的关键之一。本论文采用化学镀方法成功制备了可用于UBM的多种FeNiP薄膜材料,并对其润湿性能及界面反应等进行了较为系统的研究。         设计了新的络合体系,通过在镀液中添加EDTA-2Na和DTPA大幅度缩小Fe2+与Ni2+间沉积电位差实现镀层铁含量的提高。在铜、硅基材及wafer表面成功制备出FeNiP化学镀层,镀层中Fe含量0—97at.%粗略可控。研究了EDTA-2Na浓度、镀液温度、镀液中Fe2+/Ni2+摩尔比及各种添加剂对镀层Fe含量和镀层质量的影响规律。         利用座滴法及润湿天平研究了FeNiP镀层与Sn及SnAgCu共晶焊料间的润湿性能。研究发现,镀态下FeNiP化学镀层的润湿角和最大润湿力均普遍优于目前广泛使用的NiP镀层,润湿时间也仅稍长于NiP镀层,而且镀态下FeNiP化学镀层的润湿性能随Fe含量增加呈提高趋势。此外,FeNiP化学镀层较相同Fe含量的FeNi电镀层具有更好的润湿性能,特别是在高温氧化之后,这可能与FeNiP表面的氧化膜更容易被焊剂去除有关。         研究了FeNiP/Sn体系长时间回流后的界面微结构演化。发现界面微结构与镀层中铁含量密切相关:对高Fe含量镀层(55FeNiP与75FeNiP),界面上生成为FeSn2单层结构,而对低Fe含量镀层(25FeNiP),界面则形成FeSn2与Ni3Sn4共存的双层乃至多层结构。FeSn2较Ni3Sn4更负的吉布斯形成自由能是Sn/FeNiP体系回流后界面层由FeSn2支配的主要原因。此外,随着FeNiP化学镀层中铁含量由低到高变化,界面形成的FeSn2相生长速度明显降低,且远低于NiP/Sn体系的Ni3Sn4相。         系统研究了FeNiP化学镀层与Sn及SAC焊料间的固态反应。在与Sn焊料的固态时效中,随FeNiP镀层中铁含量由0--25--55--85at.%渐增,界面层相应由Ni3Sn4单相--Ni3Sn4/FeSn2双相共存--FeSn2单相转变。计算表明,Sn/55FeNiP与Sn/85FeNiP体系中FeSn2界面层的表观激活能分别为46.6kJ/mol与93.8kJ/mol,远大于Sn/NiP体系中Ni3Sn4界面层的27.2kJ/mol,更大的激活能促使了界面层更慢的生长速度。此外,与55FeNi相比,55FeNiP/Sn时效后的界面层生长速度明显更慢。在FeNiP/SAC体系中,界面层由镀层侧的FeSn2层与焊料侧的Cu6Sn5化合物共同构成。随着镀层中铁含量的提高,Cu6Sn5化合物由层状结构渐变为粒状分布而逐渐减少。Sn/xFeNiP及SAC/xFeNiP焊点经固态时效后的界面中均未见明显的富磷层存在。       探讨了Fe电沉积层与FeP化学镀层作为UBM的应用。研究表明:镀态下Fe及FeP层与Sn及SAC焊料的润湿性优于NiP层,而FeP层更为疏松的氧化膜使其在镀态下及180℃时效后均表现出较Fe层更优的润湿性。回流后的Sn/Fe、Sn/FeP、SAC/Fe及SAC/FeP界面上均为极薄的FeSn2层。时效后,Sn/Fe及Sn/FeP体系的界面仍为FeSn2单层结构,而SAC/Fe与SAC/FeP体系中的FeSn2界面层上则有少量Cu6Sn5及Ag3Sn化合物分布。 此外,FeP具有较Fe更慢的界面IMC生长速度,Sn/Fe与Sn/FeP两体系中FeSn2层的表观形成激活能分别为88.1kJ/mol与106.2kJ/mol,远大于Sn/NiP体系中Ni3Sn4界面相的激活能。
其他摘要New under bump metallization (UBM) is required for future microelectronics to minimize reliability concerns with solder interconnects. In the present work, FeNiP thin films as potential UBM were prepared by electroless deposition and their solderability and interfacial reactions with lead-free solders were investigated. New complexing system was designed in order to reduce the difference in the electrode potential between Ni2+ and Fe2+. The iron concentrations of deposited films were improved by complexing with EDTA-2Na and DTPA. FeNiP films were obtained on the surfaces of copper and silicon wafer. The iron content of the electroless deposits was controllable from 0 to 97 at.% by systematically controlling bath temperature, concentration of EDTA-2Na and mole ratio of Fe2+/Ni2+ in the plating bath. The solderability of FeNiP films with Sn and eutectic SnAgCu solders was investigated by the static wetting tests and the wetting balance measurements. Both the final contact angles and the maximum wetting force of as-plated FeNiP films were better than the widely used NiP UBM, although the wetting time was longer in some instances. The as-plated FeNiP platings showed better solderability as the iron content of the film increased. Furthermore, electroless FeNiP had better wetting property than electrodeposite FeNi at the same Fe concentration, especially after annealing at high temperatures. The improved wetting property of electroless FeNiP is believed to be related to a porous oxide layer which was readily removed by the flux. The interfacial microstructures of FeNiP/Sn couples were investigated after reflowing for different times. It was found that the interfacial reactions depended strongly on the Fe percentage in the electroless FeNiP alloys: FeSn2 single layer was observed at the interface in a Fe-rich alloys at 55 and 75 at.%Fe, while both FeSn2 and Ni3Sn4 layers were found at the interface at a low Fe concentration of 25 at.%. The preferential status of FeSn2 phase at the interface was believed to result from the lower Gibbs free energy for FeSn2 formation than that of Ni3Sn4 in the Sn/FeNiP system. Moreover, the growth rate of interfacial intermetallic compounds and the amount of intermetallic whiskers grown on the FeNiP coatings decreased with the increase of Fe percentage. It was much lower than that of Ni3Sn4 phase in NiP/Sn couple. The solid-state interfacial reaction of Sn/xFeNiP and SnAgCu/xFeNiP couples were investigated systemically. During solid-state aging with Sn solder, the interfacial microstructures changed according to Ni3Sn4 single phase--Ni3Sn4 and FeSn2 coexisting--FeSn2 single phase with the increase of Fe content in FeNiP alloys in the direction 0--25--55-85at.%. The activation energy for the growth of FeSn2 phase in Sn/55FeNiP and Sn/85FeNiP couples were 46.6kJ/mol and 93.8kJ/mol, respectively. These are much larger than 27.2kJ/mol of Ni3Sn4 phase in Sn/NiP couple. Higher activation energy means slower growth of IMC. Compared with electrodeposited 55FeNi, IMC growth was obviously slower in 55FeNiP/Sn couple. For xFeNiP/SnAgCu systems, double reaction phases formed at the interface: FeSn2 phase which faced the FeNiP substrate and Cu6Sn5 phase which adhered to SnAgCu solder. The morphology of Cu6Sn5 phase changed from layer to particle and reduced gradually with the Fe contents of FeNiP films increasing from 25 to 85at.%. Both in xFeNiP/Sn and xFeNiP/SnAgCu couples, no P-rich layer was observed at the interfaces after aging process for all the three systems. Application of electrodeposited Fe film and electroless FeP film for UBM on solder joint was discussed. Experimental results showed that wettability of as-plated Fe and FeP with Sn and SnAgCu solders were better than that of electroless NiP. Compared with Fe, FeP showed better wetting property before and after aging at 180℃ because of its looser oxide layer. An extremely thin layer of FeSn2 formed at the interfaces for Sn/Fe, Sn/FeP, SnAgCu/Fe and SnAgCu/FeP couples after reflowing. After aging for Sn/Fe and Sn/FeP couples, the IMC formed at the interfaces was still FeSn2 single layer. A few Cu6Sn5 and Ag3Sn were distributed on the surface of FeSn2 layer when SnAgCu/Fe and SnAgCu/FeP couples were aged. Moreover, IMC growth for FeP UBM was slower than on Fe UBM. The activation energy for the growth of FeSn2 phase in Sn/Fe and Sn/FeP couples were determined to be 88.1kJ/mol and 106.2kJ/mol, respectively, which are much larger than that of Ni3Sn4 in Sn/NiP.
文献类型学位论文
条目标识符http://ir.imr.ac.cn/handle/321006/64482
专题中国科学院金属研究所
推荐引用方式
GB/T 7714
周海飞. FeNiP化学镀层的制备及其与无铅焊料的润湿性及界面反应性能[D]. 北京. 中国科学院金属研究所,2012.
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