CN107680949A - 一种低温纳米锡浆料的制备方法及封装方法 - Google Patents

一种低温纳米锡浆料的制备方法及封装方法 Download PDF

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CN107680949A
CN107680949A CN201710804448.2A CN201710804448A CN107680949A CN 107680949 A CN107680949 A CN 107680949A CN 201710804448 A CN201710804448 A CN 201710804448A CN 107680949 A CN107680949 A CN 107680949A
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祝温泊
胡博
马鑫
李明雨
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Suzhou Han Er Believes Electronic Science And Technology Co Ltd
Shenzhen Graduate School Harbin Institute of Technology
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Shenzhen Graduate School Harbin Institute of Technology
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Abstract

本发明提供了低温纳米锡浆料的制备方法及封装方法，制备方法包括S1制备高活性的纳米锡溶胶；S3制备纳米锡浆料；封装方法包括S1在芯片和基板上对称制备图形化的焊盘或过渡金属化层；S2将制备得到的纳米锡浆料附着在焊盘和过渡金属化层表面，对准堆叠形成封装结构；S3对S2中所述封装结构施加压力并进行低温加热，促使纳米锡浆料烧结实现冶金互连。本发明在低温条件下使用低熔点、低成本、高表面活性的纳米锡浆料进行烧结，完成与基板和芯片之间互连，无需添加贵金属镀层增加润湿和结合强度，简化生产工艺，降低封装结构的复杂性和成本，且烧结后接头具有较好导热率和导电性能，适合应用于电子封装领域中低温及热敏感器件的封装互连。

Description

一种低温纳米锡浆料的制备方法及封装方法
技术领域
本发明涉及电子封装领域，更具体地，涉及一种低温纳米浆料及其封装方法。
背景技术
随着大规模集成电路在军事和民用领域的地位日益提高，小型化、柔性化、多功能化的电子设备在各个行业得到了广泛应用。目前，高性能的电子设备通常都要求将多种芯片或器件同时集成在一个系统中，其中的各种热失配、热敏感材料或器件如多层化芯片、内藏化器件或柔性化基板等，使得系统整体对封装工艺温度越来越敏感。同时，在防雷设备、液晶、LED、通讯和光电子等领域，芯片材料的限制也导致器件的耐受温度较低。因此，多功能、柔性电子器件的应用对低温封装提出了要求。
目前，低温封装一般通过共晶钎料互连或纳米银浆烧结实现。然而，市场上常用的低温钎料合金如Sn-In、Sn-Bi、Sn-Zn等分别存在成本高、易氧化、难润湿、互连可靠性低的缺点，限制了其在低温电子领域的推广应用，而纳米银浆的烧结温度较高（200~250℃）且价格昂贵，缩短了芯片寿命甚至对芯片造成损伤，并大幅提高了制造成本，也无法满足低温电子器件特别是热敏感器件的封装要求。因此，为了完成低温封装，并降低成本、提高可靠性，就需要对低温封装技术进行优化。根据纳米粒子的尺寸效应，根据更低熔点和成本的纳米锡浆料在这方面表现出了巨大的应用前景。
发明内容
要解决的技术问题：本发明的目的是提供一种低温纳米锡浆料制备方法及封装方法，旨在解决现有低温封装工艺成本高、焊接工艺温度高缩短器件寿命的问题。
技术方案：一种低温纳米锡浆料的制备方法，包括以下步骤：
S1：通过酸或有机溶剂对纳米锡进行表面处理，再多次超声清洗、离心，将洗净的纳米锡加入混合有机溶液中进行超声分散，制备高活性的纳米锡溶胶，所述的酸或者有机溶剂为具有挥发性的甲酸、乙醇或丙酮中的一种或者为几种的混合物，所述表面处理方法为电磁搅拌、机械搅拌或者超声清洗；
S2：将表面活性剂、有机载体溶入混合有机溶剂中，得到液体混合物，其中所述的表面活性剂为戊二酸或松香酸中的一种或者为两者的混合物，所述的有机载体为柠檬酸三丁酯、硝化纤维素或聚乙烯醇中的一种或者为几种的混合物；
S3：将步骤S2制得的混合物与步骤S1中所得纳米锡溶胶，超声分散，得到纳米锡浆料。
如上述一种所述的制备方法制备的低温纳米锡浆料的封装方法，包括以下步骤：
S1：在芯片和基板上对称制备图形化的焊盘或过渡金属化层；
S2：将制备得到的纳米锡浆料附着在焊盘和过渡金属化层表面，对准堆叠形成封装结构；
S3：对S3中所述封装结构进行低温加热，并可施加压力，促使纳米锡浆料烧结实现冶金互连。
进一步的，所述的一种低温纳米锡浆料的制备方法，所述步骤S1中纳米锡为激光法制备的纯纳米锡粉末或液相还原法得到的具有邻菲罗啉包覆层的纳米锡颗粒, 平均粒径为20~50 nm。
进一步的，所述的一种低温纳米锡浆料的制备方法，所述步骤S1和S2中的混合有机溶剂为乙二醇、丙三醇或乙醇中的一种或者为几种的混合物，且乙醇的体积百分数小于30%。
进一步的，所述的一种低温纳米锡浆料的制备方法，所述步骤S3中纳米锡浆料中表面活性剂的质量百分数为0.5~1.5%，所述有机载体的质量百分数为5~10%，所述有机溶剂的质量百分数为5~10%，余量为纳米锡。
进一步的，所述的一种低温纳米锡浆料的封装方法，所述步骤S2中纳米锡浆料的附着方法为丝网印刷或喷涂。
进一步的，所述的一种低温纳米锡浆料的封装方法，所述步骤S3中压力在加热前单独施加或与加热同时作用，所述加热方法为热风、红外加热或加热电炉，加热温度为150~200℃，保温时间为10~210分钟，所述可施加的压力为0.1~5MPa。
有益效果：本发明采用低熔点、低成本、高表面活性的纳米锡颗粒制备浆料，具有低温烧结性能，在较低的温度条件下，通过加热促进锡原子与基板和芯片之间的扩散反应即可完成良好的互连，无需添加金、银等贵金属镀层增加润湿和结合强度，简化了生产工艺，降低了封装结构的复杂性和成本，且烧结后所得接头具有较好的导热率和导电性能，适合应用于电子封装领域中低温及热敏感器件的封装互连。
附图说明
图1为红外探测器与基板的低温封装结构；
图2为功率芯片或器件的封装结构；
图3为多层化系统的封装结构。
具体实施方式
实施例1
如图1所示，红外探测器与基板的低温封装中，红外芯片1固定在框架基板2上，Si基封盖3和框架基板2组成密闭腔体保证密封性和真空度，主要工艺步骤包括：
（1）红外芯片1和框架基板2带有信号电路4，Si基封盖3上有通过机械加工制备的凹腔结构，其外表面和内表面非连接区域附着有一层增透膜5，且与框架基板2的连接处对称沉积有图形化的过渡金属化层6。其中，信号电路4为预置的内部铜线及焊盘，过渡金属化层6的材料为铜。
（2）通过乙醇对带有邻菲罗啉包覆层的平均粒径30 nm的纳米锡颗粒进行电磁搅拌和离心清洗，此过程重复三次后，将得到的纳米锡与体积比为2:1的丙三醇和乙醇溶液混合，超声分散获得均匀的纳米锡溶胶。
（3）将松香酸、硝化纤维素和柠檬酸三丁酯的混合物溶入体积比为2:1的丙三醇和乙醇的混合溶液，再与纳米锡溶胶混合，超声分散形成纳米锡浆料7，浆料中松香酸的质量百分比为0.5 %，硝化纤维素和柠檬酸三丁酯的质量比为1:10，总质量百分比为10 %。
（4）通过丝网印刷的方式将纳米锡浆料7沉积在框架基板2和Si基封盖3的焊盘和过渡金属化层6上，并将红外芯片1、框架基板2和Si基封盖3依次对准堆叠形成封装结构。
（5）将封装结构放入真空加热炉，并施加0.1 MPa的压力，在150℃条件下加热2小时，除气除湿并同时完成烧结过程，实现冶金互连。
上述封装过程中，只需一次加热就可同时完成红外芯片1和Si基封盖3与框架基板2的冶金互连，简化了生产工艺，降低了成本，并减小了封装过程对红外芯片1和增透膜5的热影响，延长了器件的工作寿命。
实施例2
如图2所示，在功率芯片或器件的封装中，由于功率密度的提高，芯片或器件必须与热沉或热管互连。其中，芯片8倒装键合在基板9上，并实现信号导出，热沉10为铜、铝所制热沉或热管，与芯片8互连形成导热通路。主要工艺步骤包括：
（1）使用电镀和遮挡层技术在芯片8背面和热沉10的对应位置制备一层纯镍的过渡金属化层6；
（2）对由激光法制得的平均粒径50 nm的纳米锡粉末，采用机械搅拌和体积比为1:40的甲酸酒精溶液进行酸洗，去除表面氧化物，并采用乙醇清洗、离心三次，将得到的纯净纳米锡与乙二醇混合并超声分散后，得到均匀的纳米锡溶胶；
（3）将戊二酸、硝化纤维素和柠檬酸三丁酯的混合物溶入乙二醇中，并与纳米锡溶胶混合进行搅拌和超声分散，得到纳米锡浆料7，最终浆料中戊二酸的质量百分数为1 %，硝化纤维素和柠檬酸三丁酯的质量比为1:40，总质量百分数为5 %；
（4）通过喷涂的方式将纳米锡浆料7涂覆在芯片8背面的过渡金属化层6上，并将芯片8和热沉10对准堆叠形成封装结构；
（5）对封装结构施加5 MPa的压力30s，然后对封装结构进行红外加热，在200℃下保温30分钟，完成冶金互连。
上述封装过程中的工艺温度峰值为200℃，低于常用钎料合金的回流焊接温度，可以避免对基板上前道焊接工序所得接头造成损伤，同时纳米锡的成本较低且导热性能远高于传统的导热胶，降低了封装过程对整体设备和器件的热影响，提高了可靠性。
实施例3
如图3所示，在多层化系统的封装中，各层基板11通过多次焊接或组装集成在一个系统中，其中焊盘12为各基板上的焊盘或铜线。主要工艺步骤包括：
（1）在已完成初步封装的各层基板11上的对称为止制备图形化的铜焊盘；
（2）将带有邻菲罗啉包覆层的平均粒径30 nm的纳米锡颗粒在体积比为3:1的乙二醇和乙醇混合溶液中清洗、离心四次后，与乙二醇和乙醇溶液混合并超声分散，制备均匀的纳米锡溶胶；
（3）将松香酸、聚乙烯醇和柠檬酸三丁酯的混合物溶入体积比为3:1的乙二醇和乙醇的混合溶液，并与纳米锡溶胶混合进行电磁搅拌和超声分散，形成纳米锡浆料7，最终浆料中松香酸的质量百分数为1.5%，聚乙烯醇和柠檬酸三丁酯的质量比为1:3，总质量百分数为8%；
（4）通过丝网印刷的方式将纳米锡浆料7沉积在焊盘12表面，并将各层基板11对准堆叠；
（5）将多层化系统放入150℃的热风炉中加热60分钟，完成基板11间的连接。
实施例3中的纳米锡浆料和封装方法可以有效减小各基板11上的热失配元器件之间的热应力，并在基板11间实现良好的电气和冶金结合，所得烧结接头的电阻率为21.5 µΩ·cm。
本领域的技术人员容易理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (7)

1.一种低温纳米锡浆料的制备方法，其特征在于，包括以下步骤：
S1：通过酸或有机溶剂对纳米锡进行表面处理，再多次超声清洗、离心，将洗净的纳米锡加入混合有机溶液中进行超声分散，制备高活性的纳米锡溶胶，所述的酸或者有机溶剂为具有挥发性的甲酸、乙醇或丙酮中的一种或者为几种的混合物，所述表面处理方法为电磁搅拌、机械搅拌或者超声清洗；
S2：将表面活性剂、有机载体溶入混合有机溶剂中，得到液体混合物，其中所述的表面活性剂为戊二酸或松香酸中的一种或者为两者的混合物，所述的有机载体为柠檬酸三丁酯、硝化纤维素或聚乙烯醇中的一种或者为几种的混合物；
S3：将步骤S2制得的混合物与步骤S1中所得纳米锡溶胶，超声分散，得到纳米锡浆料。
2.如权利要求1所述一种所述的制备方法制备的低温纳米锡浆料的封装方法，其特征在于，包括以下步骤：
S1：在芯片和基板上对称制备图形化的焊盘或过渡金属化层；
S2：将制备得到的纳米锡浆料附着在焊盘和过渡金属化层表面，对准堆叠形成封装结构；
S3：对S3中所述封装结构进行低温加热，并可施加压力，促使纳米锡浆料烧结实现冶金互连。
3.根据权利要求1所述的一种低温纳米锡浆料的制备方法，其特征在于：所述步骤S1中纳米锡为激光法制备的纯纳米锡粉末或液相还原法得到的具有邻菲罗啉包覆层的纳米锡颗粒, 平均粒径为20~50 nm。
4.根据权利要求1所述的一种低温纳米锡浆料的制备方法，其特征在于：所述步骤S1和S2中的混合有机溶剂为乙二醇、丙三醇或乙醇中的一种或者为几种的混合物，且乙醇的体积百分数小于30%。
5.根据权利要求1所述的一种低温纳米锡浆料的制备方法，其特征在于：所述步骤S3中纳米锡浆料中表面活性剂的质量百分数为0.5~1.5%，所述有机载体的质量百分数为5~10%，所述有机溶剂的质量百分数为5~10%，余量为纳米锡。
6.根据权利要求2所述的一种低温纳米锡浆料的封装方法，其特征在于：所述步骤S2中纳米锡浆料的附着方法为丝网印刷或喷涂。
7.根据权利要求2所述的一种低温纳米锡浆料的封装方法，其特征在于：所述步骤S3中压力在加热前单独施加或与加热同时作用，所述加热方法为热风、红外加热或加热电炉，加热温度为150~200℃，保温时间为10~210分钟，所述可施加的压力为0.1~5MPa。
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