CN109243989B - 一种基于石墨烯浆料的硅-硅低温键合的方法 - Google Patents

一种基于石墨烯浆料的硅-硅低温键合的方法 Download PDF

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CN109243989B
CN109243989B CN201811020083.5A CN201811020083A CN109243989B CN 109243989 B CN109243989 B CN 109243989B CN 201811020083 A CN201811020083 A CN 201811020083A CN 109243989 B CN109243989 B CN 109243989B
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杨文华
周成功
周洁
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Hefei Luyang Technology Innovation Group Co.,Ltd.
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Abstract

本发明公开了一种基于石墨烯浆料的硅‑硅低温键合的方法,其是以石墨烯复合油性导电浆料与PVDF粘结剂的混合物作为键合材料,在低温下实现两硅基衬底的键合。本发明的工艺简单、可靠性好,且工艺成本较低,具有高度产业利用的价值。

Description

一种基于石墨烯浆料的硅-硅低温键合的方法
技术领域
本发明属于半导体器件领域,涉及三维封装中的方片键合,特别是涉及一种基于石墨烯浆料的硅-硅低温键合的方法。
背景技术
随着芯片集成度的逐步提高,传统的二维封装技术已经不能满足芯片的高密度集成。在成熟的二维封装基础上逐步向三维封装上发展,已成为芯片封装的新思路。在三维系统封装技术中,键合是实现多层芯片堆叠和垂直互连的关键技术。用于三维封装技术的主要键合方法有:Cu-Cu热压键合、表面活化键合(Surface Activated Bonding,SAB)、自组装单层键合(Self-Assembled Monolayer,SAM)、Ti作钝化层的Cu-Cu键合等。Cu-Cu热压键合具有机械强度高、导电和导热性能好等特点,但是传统的Cu-Cu热压键合温度高(350℃~400℃)、键合压力大,影响封装中敏感元件和结构的性能,增加整个封装体的热应力,降低产品的可靠性。表面活化键合是用高速的离子束物理轰击晶圆表面,使需要键合的晶圆表面的氧化物和污染物得到清除,并激活晶圆表面的化学键,在室温下就能获得较强的键合强度,避免了高温键合对器件的损伤,但工艺复杂且设备成本较高。自组装单层键合是在250℃低温下实现Cu-Cu热压键合,键合强度好,但是关于工艺的部分条件需要继续优化,例如链长选择,研究表明烷烃硫醇的链长越长,防氧化作用越明显,但导致完全去除烷烃硫醇的退火温度也会随着增加,因而自组装单层键合的工艺的部分条件的选择待进一步优化。Ti作钝化层的Cu-Cu键合是在Si衬底上溅射一层300nm的Cu层,然后再在Cu表面溅射一层5-10nm厚Ti层作为钝化层,键合过程中一些铜原子往键合界面进行扩散并形成了新表面,最终,在上下Ti之间形成连续Cu层。
半导体芯片封装所用的导电材料,作为电连接的材料多为金属材料。对用于电互连的金属材料的要求是:电阻率低,能与元件的电极形成良好的低欧姆接触;与二氧化硅层的粘附性要好;便于淀积和光刻加工形成布线等。在金属互连技术中,金属淀积是关键技术,采用的工艺有蒸发、溅射和化学淀积等。因此,以金属材料作为电连接材料,多存在工艺复杂、成本高的问题。
石墨烯具有优异的光学、电学、力学特性,在材料学、微纳加工、能源、生物医学和药物传递等方面具有重要的应用前景,这一迄今导电性能最强的新型材,被认为是一种未来革命性的材料。若以石墨烯作为电连接材料,实现半导体芯片的键合,具有重要的研究意义。
发明内容
为避免上述现有技术所存在的不足之处,本发明提供了一种基于石墨烯浆料的硅-硅低温键合的方法,旨在以石墨烯浆料作为导电材料,低温下实现硅基衬底的键合。
本发明为实现发明目的,采用如下技术方案:
本发明基于石墨烯浆料的硅-硅低温键合的方法,包括如下步骤:
(1)将石墨烯复合油性导电浆料与PVDF粘结剂混合均匀,获得键合材料;
(2)在待键合的两片硅基衬底的待键合表面涂抹所述键合材料;然后以涂有键合材料的待键合面相对,将两硅基衬底对齐放入键合装置的上、下样品台上,形成由第一待键合硅基衬底-第一键合材料层-第二键合材料层-第二待键合硅基衬底组装成的待键合组件;
(3)将所述待键合组件在保护气体中进行低温烧结,使烧结后的键合材料层分别吸附在相应的硅基衬底上;然后再在保护气体中加压,进行低温键合,使第一键合材料层和第二键合材料层中的C原子相互扩散,形成C中间层,并在PVDF粘结剂的协同作用下,实现两片硅基衬底的键合。
作为本发明的一种优选方案:所述石墨烯复合油性导电浆料是将由石墨烯、碳纳米管及导电碳黑按质量比3~5:1~3:1混合而成的导电剂均匀分散在N-甲基吡咯烷酮中获得,所述石墨烯复合油性导电浆料中导电剂的质量浓度为3~10%。
作为本发明的一种优选方案,所述PVDF粘结剂是将PVDF加入到N-甲基吡咯烷酮中,搅拌均匀获得;所述PVDF粘结剂中PVDF的质量浓度为3~7%。
作为本发明的一种优选方案,在所述键合材料中,石墨烯复合油性导电浆料与PVDF粘结剂的体积比为1:0.5~2。
作为本发明的一种优选方案,步骤(2)中,在两片硅基衬底表面涂抹所述键合材料前,先将硅基衬底的待键合表面依次使用丙酮、乙醇和去离子水进行清洗,然后用氮气吹干。
作为本发明的一种优选方案,步骤(3)的具体方法为:将所述待键合组件在N2气氛中,以100~200℃烧结10~30分钟;然后恒温并施加1000~2000N的压力,键合10~30分钟。
作为本发明的一种优选方案,两片硅基衬底相互独立的选自为Si衬底或SiO2衬底;所述硅基衬底还可以包括外围电路和平面存储结构等。所述硅基衬底可以为任意形状和尺寸。
如上所述,本发明的基于石墨烯浆料的硅-硅低温键合的方法,具有以下有益效果:
1、本发明以石墨烯复合油性导电浆料与PVDF粘结剂的混合物作为键合材料,在低温下实现了硅-硅低温键合,键合效果好、工艺简单、可靠性好,且工艺成本较低,具有高度产业利用的价值。
2、本发明采用石墨烯浆料作为电互连材料,导电性较好,与硅的吸附性好,且不需要使用金属淀积技术。
3、本发明的方法在键合之前不需要进行特殊的表面处理,在低温、键合压力小的条件下实现键合,避免了高温键合对敏感元件和结构的性能的影响。
附图说明
图1为本发明的基于石墨烯浆料的硅-硅低温键合的方法流程示意图,图中标号:11为第一待键合硅基衬底;12为第二待键合硅基衬底;21为第一键合材料层;22为第二键合材料层;3为C中间层。
图2为不同烧结温度对键合材料层电阻的影响。
图3为经200℃低温烧结后,吸附在硅片上的键合材料层的SEM图。
图4为实施例1键合温度为200℃下,两硅片的键合界面在不同放大倍数下的SEM图。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂,下面结合实施例对本发明的具体实施方式做详细的说明。以下内容仅仅是对本发明的构思所作的举例和说明,所属本技术领域的技术人员对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代,只要不偏离发明的构思或者超越本权利要求书所定义的范围,均应属于本发明的保护范围。
下述实施例所用键合装置可为市场现有的任意型号、结构的键合装置,也可自行搭建,只需具有上、下对应的样品台以及温度控制系统、压力控制系统,能够实现固定两样品、密封、通气体、升温、加压的基本功能即可。
实施例1
如图1所示,本实施例按如下步骤对两片尺寸为10mm*10mm的Si衬底进行键合:
(1)将石墨烯、碳纳米管及导电碳黑按质量比3:2:1混合均匀,形成导电剂,然后均匀分散在N-甲基吡咯烷酮中,获得导电剂质量浓度为4%的石墨烯复合油性导电浆料。
将PVDF加入到N-甲基吡咯烷酮中,搅拌均匀,获得PVDF质量浓度为5%的PVDF粘结剂。
将石墨烯复合油性导电浆料与PVDF粘结剂按体积比1:1混合均匀,获得键合材料;
(2)将待键合的硅基衬底的待键合表面依次使用丙酮、乙醇和去离子水超声清洗5min,然后用氮气吹干。
在待键合的两片硅基衬底的待键合表面涂抹键合材料;然后以涂有键合材料的待键合面相对,将两硅基衬底对齐放入键合装置的上、下样品台上,形成由第一待键合硅基衬底-第一键合材料层-第二键合材料层-第二待键合硅基衬底组装成的待键合组件;
(3)将待键合组件在N2气氛中,以200℃烧结15分钟,使烧结后的键合材料层分别吸附在相应的硅基衬底上;然后恒温并施加1000N的压力,键合30分钟,使第一键合材料层和第二键合材料层中的C原子相互扩散,形成C中间层,并在PVDF粘结剂的协同作用下,实现两片硅片的键合。
为探索烧结温度对键合材料层电阻的影响,以本实施例相同的硅片进行如下测试:将硅片表面依次使用丙酮、乙醇和去离子水超声清洗5min,然后用氮气吹干。在硅片表面涂抹键合材料(并以只涂石墨烯复合油性导电浆料的硅片作为对比),再在N2气氛中,将硅片以不同温度烧结15分钟,形成键合材料层。图2为不同温度下烧结后,键合材料层的电阻,从图中可以看出键合材料的电阻随着烧结温度的升高而降低。图3为经200℃低温烧结后,吸附在硅片上的键合材料层的SEM图,从图中可以看出形成了一层致密的碳材料导电薄膜。
图4为本实施例键合后两硅片的键合界面在不同放大倍数下的SEM图,从图中可以看出两个硅片通过键合材料(中间层)实现键合,键合的界面没有裂缝小孔。
拉伸测试是测量键合芯片键合强度的一种有效方法,对键合后两硅片施加拉伸力,测得其键合的强度为10MPa~15Mpa,这表明两硅片键合效果较好。
实施例2
本实施例按实施例1相同的方法对SiO2衬底进行键合,键合前在SiO2衬底同样得到了一层致密的碳材料导电薄膜,键合后其键合界面没有裂缝小孔,拉伸测试其键合强度约为10Mpa,这表明,利用所述的键合材料作为中间层也能实现两SiO2衬底的键合。
综上所述,本发明提供了一种基于石墨烯浆料的硅-硅低温键合的方法,该方法在键合前将石墨烯复合油性导电浆料和粘结剂的混合溶液涂抹在硅基衬底上,其中C原子相互扩散并形成稳定的中间层,并在少量粘结剂的作用下最终得到了良好的键合效果。因此,本发明创新的使用石墨烯复合油性导电浆料代替金属材料,大大减少了工艺的复杂性而具有高度产业利用价值。
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)

1.一种基于石墨烯浆料的硅-硅低温键合的方法,其特征在于,包括如下步骤:
(1)将石墨烯复合油性导电浆料与PVDF粘结剂混合均匀,获得键合材料;
(2)在待键合的两片硅基衬底的待键合表面涂抹所述键合材料;然后以涂有键合材料的待键合面相对,将两硅基衬底对齐放入键合装置的上、下样品台上,形成由第一待键合硅基衬底-第一键合材料层-第二键合材料层-第二待键合硅基衬底组装成的待键合组件;
(3)将所述待键合组件在保护气体中进行低温烧结,使烧结后的键合材料层分别吸附在相应的硅基衬底上;然后再在保护气体中加压,进行低温键合,使第一键合材料层和第二键合材料层中的C原子相互扩散,形成C中间层,并在PVDF粘结剂的协同作用下,实现两片硅基衬底的键合。
2.根据权利要求1所述的基于石墨烯浆料的硅-硅低温键合的方法,其特征在于:所述石墨烯复合油性导电浆料是将由石墨烯、碳纳米管及导电碳黑按质量比3~5:1~3:1混合而成的导电剂均匀分散在N-甲基吡咯烷酮中获得,所述石墨烯复合油性导电浆料中导电剂的质量浓度为3~10%。
3.根据权利要求1所述的基于石墨烯浆料的硅-硅低温键合的方法,其特征在于:所述PVDF粘结剂是将PVDF加入到N-甲基吡咯烷酮中,搅拌均匀获得;所述PVDF粘结剂中PVDF的质量浓度为3~7%。
4.根据权利要求1、2或3所述的基于石墨烯浆料的硅-硅低温键合的方法,其特征在于:在所述键合材料中,石墨烯复合油性导电浆料与PVDF粘结剂的体积比为1:0.5~2。
5.根据权利要求1所述的基于石墨烯浆料的硅-硅低温键合的方法,其特征在于:步骤(2)中,在两片硅基衬底表面涂抹所述键合材料前,先将硅基衬底的待键合表面依次使用丙酮、乙醇和去离子水进行清洗,然后用氮气吹干。
6.根据权利要求1所述的基于石墨烯浆料的硅-硅低温键合的方法,其特征在于,步骤(3)的具体方法为:将所述待键合组件在N2气氛中,以100~200℃烧结10~30分钟;然后恒温并施加1000~2000N的压力,键合10~30分钟。
7.根据权利要求1所述的基于石墨烯浆料的硅-硅低温键合的方法,其特征在于:两片硅基衬底相互独立的选自为Si衬底或SiO2衬底。
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