CN1219741A - 应用可开链聚合物浆料的电极改进 - Google Patents

应用可开链聚合物浆料的电极改进 Download PDF

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CN1219741A
CN1219741A CN98123832A CN98123832A CN1219741A CN 1219741 A CN1219741 A CN 1219741A CN 98123832 A CN98123832 A CN 98123832A CN 98123832 A CN98123832 A CN 98123832A CN 1219741 A CN1219741 A CN 1219741A
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slurry
polymer
particle
unzippable
solvent
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CN1093680C (zh
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约翰·米切尔·考特
朱迪斯·玛列·罗尔丹
卡洛斯·朱安·桑普塞蒂
拉维·F·萨拉夫
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International Business Machines Corp
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International Business Machines Corp
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Abstract

提供了一种含有溶剂、可开链聚合物和颗粒,用无氧化物金属层涂覆电极的浆料。电极可以是如C4凸点的互连接。对形成涂层和测试集成电路片的方法也进行了描述。本发明通过在含Pb电极上用Au涂覆以形成适于测试和连接的无氧化物表面,解决了集成电路片上被绝缘氧化物层覆盖的含Pb电极的连接问题。

Description

应用可开链聚合物浆料的电极改进
本发明涉及一种浆料，特别地涉及一种含有可开链聚合物、溶剂和导电颗粒的浆料，用于无氧化物导电颗粒涂覆电极如C4凸点，进行集成电路片和由聚合物/填充剂制成的衬底，如RF4印刷电路板之间的低温联接等。
随着越来越多的晶体管被安装在一片块芯片以增加其功能，每个集成电路芯片上的输入/输出(I/O)焊点数大大增加。每个芯片上I/O焊点数量的增加使传统接合方式如引线键合(WB)和载带自动键合(TAB)变得困难。与周边排列的WB和TAB相反，通常为面排列的芯片倒装式接合(FCA)由于其焊点数少而日益流行。在FCA工艺中，芯片通过如抗掩蔽的金属沉积法用富铅的Pb/Sn合金球形成凸点。芯片的接合是通过其自调整和将芯片置于已用高粘度焊料覆盖以减少氧化物的衬底上实现的。芯片由焊料定位。之后整个组合件被加热到350～400℃的某个温度，在该温度下焊料熔化，形成芯片上的球或凸点与衬底上相应焊点的互连接。
传统的衬底为多层陶瓷(MLC)结构，可承受高达400℃的温度。由于其接点数和低成本，对将相似的C4凸点的集成电路芯片与由聚合物/填充剂复合材料如FR4制成的有机衬底的接合的需求日益增加。在300℃以上的焊料回流温度这类有机衬底将发生降解。这样就需要一种低温焊接材料以实现芯片的C4凸点与相应衬底焊点的接合。
将电极如形成C4凸点的芯片与一有机衬底相接合的一种方法，是先将C4凸点用低温熔化的Pb/Sn共晶焊料覆盖，如由Berger等于1996年9月25日注册，序号US No.08/710992，题目为“低温芯片接合方法”(Y0996073)并转让于本受让人的发明所述。C4凸点上的Pb/Sn焊料覆层可通过抗掩蔽的气相沉积金属元件及后续的焊料回流工艺形成。掩蔽工艺需要有成本昂贵的对准和平版印刷步骤，气相沉积工艺由于高真空制备也成本很高。用酸性焊料在低于250℃的温度下通过Pb/Sn共晶焊料的软熔可完成接合。之后，可用氯-氟-碳(CFC)基的有机溶剂将焊料去除。
根据本发明，所述的浆料包含适用于可开链聚合物的溶剂，可溶于该溶剂形成溶体的可开链聚合物，以及悬浮于该溶体中的颗粒。该颗粒可适用于涂覆所选择材料的表面；该聚合物可占溶体的10wt％或更多。
本发明还提供一种包含衬底和上述浆料层的涂层，该涂层可剩下一层可被加热与衬底材料形成合金的颗粒。
本发明还提供了一种测试具有本公开方法涂覆的C4凸点的集成电路芯片的方法。浆料中的颗粒具有导电性且可粘附于C4表面，在C4凸点与测试探针上导电触点之间形成导电通路。
本发明进一步提出一种涂覆集成电路芯片上C4电极或凸点的方法，包括下列步骤：将上述浆料施于C4电极表面，浆料中的颗粒具有导电性且可粘附于衬底表面，将浆料加热以去除溶剂和可开链聚合物，其中，所述颗粒可与C4中的Pb合金化。
本发明提供一种低成本覆盖C4的方法。
本发明提供一种不需要任何的平版印刷、对准或真空处理步骤的方法。
本发明提供一种在衬底上使用导电胶的、无需任何焊料从而不需清洗步骤的接合工艺。导电胶一般为银或金填充的环氧树脂。
本发明提供一种应用在芯片和衬底之间允许较固态金属焊料连接有更大热失配的导电性有机复合物的接合工艺。
本发明提供一种使芯片倒装于有机衬底的焊点上的接合工艺，其热膨胀系数(TCE)的失配显著大于集成电路片与陶瓷衬底之间的TCE。
本发明提供一种在接合前可通过传统压力接触法测试C4凸点的测试工艺。
通过考虑本发明的以下详述，并在阅读时联系附图，本发明的这些及其它特征、目的及优点可更为明晰，其中：
图1A示出本发明的一个实施方案。
图1B示出采用图1A中实施方案的一个中间步骤。
图1C示出采用图1A的实施方案的最终结果。
图2-4示出在集成电路的C4凸点上形成可开链浆料涂层的步骤序列。
图5是具有图1C层的C4凸点在一个加热循环后的SEM图像。
图6为涂覆工艺之后对C4凸点上涂覆金处的能量分散X射线分析数据图。
图7为图6中C4凸点上未涂覆铅处的能量分散X射线分析数据图。
图8示出与有浆料凸点的衬底与用无氧化物的颗粒涂覆的C4凸点相接合的最终结构。
参照附图1A，示出了衬底10和可开链浆料涂层13。可开链浆料13包含可开链聚合物15和/或溶于溶剂18的其混和物，以及颗粒17如无氧化物金属。无氧化物金属或表面是指其不形成氧化物层使电导率大于1ohm-cm或氧化物层为导电性，其电导率大于1ohm-cm。例如，97wt％Pb和3wt％Sn合金的C4凸点一般有氧化物层，无需C4凸点内焊料的软溶，可产生大于1ohm-cm的接触电阻。可开链聚合物15是一种在定义为开链温度Tunzip的特定温度之上可完全挥发的聚合物。可开链聚合物15的一些例子包括聚甲基丙烯酸甲酯(PMMA)，聚α-甲基苯乙烯(PAMS)，聚碳酸亚丙基脂、聚碳酸亚乙基脂以及吡啶和三氯乙醛产物(polychloral)，所有这些聚合物具有低于400℃的Tunzip。
溶剂18为有机物且可溶解上述聚合物。例如，对PMMA和PAMS来说，N-甲基吡咯烷酮(NMP)是一种良好的溶剂。
颗粒17可由一种或多种金属组成。至少该金属组元中的一种应与Pb或Sn形成合金，其中合金在150℃～400℃温度范围内熔化。例如，颗粒17可以是Au,Sn或Au/Sn合金。颗粒应具有导电性氧化物或是不含氧化物的。颗粒也可由复合材料制成，其内核可为陶瓷或金属，外层为无氧化物金属或导电氧化物。浆料中的颗料可占1-50％的体积比。
浆料13中的溶剂18可在某一所选环境下于Tdry经干燥去除，在衬底10表面剩下聚合物15和颗粒17。之后升温至可开链聚合物的开链温度Tunzip之上，使聚合物降解和挥发。
图1C示出开链之后涂有颗粒17的衬底10的最终结构。Tdry比Tunzip低50℃以上。所选环境可以为空气、N2、真空、成形气氛、Ar、He或其混和物。涂层12可被制作图案或均匀分布于衬底10上。选择性涂层12可通过标准散料工艺如丝网法(Screening)、漏印法(Stenciling)等实现。图1C中所示的颗粒17可以是单层或多层。颗粒17可形成一种互连接的渗流结构或非连续的岛状。
图2-4示出了用可开链浆料13涂覆集成电路的C4凸点的步骤。在一固态衬底22的光滑清洁的表面上，用插入物24隔开可开链浆料。衬底22可以是玻璃、硅或陶瓷。插入物24可含有聚酰亚胺、聚酯或其它有机材料，或金属如钼、镍、不锈钢等。插入物24可具有多个比要涂覆的C4凸点27略大的开孔或通道25。插入物24的厚度小于C4凸点27的厚度。一般C4凸点27的直径为275μm。开孔25的直径可在85～100μm范围内，而插入物24的厚度可为50μm。图2示出用可开链浆料13填充的开孔25。插入物24可通过化学腐蚀、激光烧蚀或其它传统方法处理，以与芯片上的C4凸点图案相匹配。
将可开链浆料13转移到C4凸点27上的其它方法可以是针式传递法、浸渍法、涂刷法等。
然后将衬底22置于其上有很多C4凸点27的芯片或未切割或镶嵌芯片的晶片的上面或下面。填充了可开链浆料13的开孔25与晶片34上相应的凸点27成行排列。成行排列由芯片随插入物24中开孔25的自定位完成。如图3所示，使衬底22靠近芯片或晶片34，从而C4凸起27被压入开孔25并与可开链浆料13相接触。然后，衬底22与芯片34分离或被移开，这样C4凸点27就与开孔25中的可开链浆料13脱离。如图4所示，可开链浆料13的一薄层29在芯片或晶片34从衬底22附近移开时就粘附于C4凸点27上。在此例中，从形状上每个C4的尺寸都精确限定；从组成上，对每个凸点，与可开链浆料13的接触区域在名义上也是一致的。因此，在C4凸点27上形成薄层29的浆料薄膜的厚度和尺寸在名义上也是一样的。薄层29的厚度可在0.1～50μm范围内，厚度波动范围是0.05～25μm。通过升温到Tdry可将该过程重复多次，以增加粘附于C4凸点上的颗粒量。
先将薄层29加热到Tdry干燥，然后升温到Tunzip和C4凸点27中焊料金属的熔融温度之上。颗粒就嵌入熔融的C4中或与焊料金属反应，形成颗粒与C4之间的强的键合。取决于所选择的特定可开链聚合物、金属、合金或其它材料，Tunzip可高于或低于金属、合金或其它材料的熔点Tmelt。当Tunzip大于Tmelt时，可一步加热到Tunzip之上，而当Tunzip小于Tmelt时，则可先加热到高于Tunzip而低于Tmelt，然后再升温到Tmelt之上。
最好在升温到Tmelt或更高温度之前先完全除去可开链聚合物。
加热通常在烘箱或区域加热炉中于氮气或预定气氛下进行。在此热循环中，可开链浆料13开链和挥发，金属填充颗粒17熔化并与相对应的C4凸点27在其上形成一无氧化物导电涂层32。
图5示出了由扫描电镜(SEM)得到的C4凸点27上的导电涂层32的图像。图5中的图像是在成形气氛下360℃保温30分钟的加热循环完成之后得到的。图5中所示的导电涂层32是金的颗粒17的均匀涂层。
图6是对图5所示的C4凸点27上导电涂层32某一位置的能量分散X射线分析图。图6中，纵坐标代表X射线强度，横坐标代表能量，单位为keV。曲线42示出了X射线强度作为能量的函数从0～20keV的变化。峰44表明导电涂层32的上表面为含有微量Pb的Au。曲线44表明在C4凸点27上的导电涂层32中含有高的金覆盖率。
图7是没有导电涂层32的C4凸点27上某一点的能量分散X射线分析图。图7是由图5中所示的C4凸点27所得到的数据作成的。在图7中，纵坐标代表X射线的强度，横坐标代表以keV为单位的能量。曲线46示出了X射线强度作为能量的函数从0～20keV的变化。峰48表明C4凸点27的表面为Pb。
下面描述将芯片50接合到衬底52上的工艺。如上所述，先将要接合的芯片50处理，以在其C4凸点27上形成颗粒17的薄层32。导电粘结浆料54含有一种聚合物粘结剂和加在衬底32的焊点55上的贵金属颗粒。聚合物粘结剂可为热塑性或热固性的聚合物。浆料还可含有一溶剂体系以溶解聚合物粘结剂。在C4凸点27经处理含有金层32后，通过附图8所示的方法将芯片50粘接到衬底52的浆料54或浆料凸点56上。适用于此处的导电浆料的例子可参见1992年2月11日授权的Grube等的US Patent5,086,558和1996年10月21日注册的R.Booth等的USSerial NO.08/734,492，此处把二者引入作为参考文献。通常，若浆料54为环氧树脂基，芯片50通过将组件在150～250℃温度范围0～100psi的压力下加热进行接合。若浆料54为热塑性，温度范围相同，而压力可在10～100psi范围内变化。然后把已接合的芯片50用密封剂填充，形成最后的组件。
下面描述芯片的测试工艺。要测试的芯片的C4凸点将通过上述的工艺涂上涂层32。通过压力的物理接触或上述的热塑性浆料法键合，形成C4凸点与测试探针触点之间的电连接。对这两种方法而言，探针的触点都应不含氧化物。
具有C4凸点的芯片需接合到FR4或其它有机衬底上。这类组件将在计算机、办公室设备、汽车、控制系统，蜂窝电话机等方面获得应用。
尽管在此只描述和说明了在某种结构上形成一金属涂层的工艺，如用金覆盖C4凸点以在集成电路片的C4凸点上形成一无氧化物表面，但对本领域技术人员来说，在不背离后附的权利要求所限定的范围的前提下，很显然可以做出各种改进和变化。

Claims (17)

1．一种浆料，包含：用于可开链聚合物的溶剂，溶于所述溶剂中形成溶液的可开链聚合物和悬浮于所述溶液中的颗粒，所述颗粒适于涂覆所选用材料的表面，所述聚合物占该溶液的10wt％或更多。
2．如权利要求1所述的浆料，其特征在于，所述聚合物在某一预定温度以上完全挥发。
3．如权利要求1所述的浆料，其特征在于，所述聚合物在250℃～450℃范围的某一温度以上完全挥发。
4．如权利要求1所述的浆料，其特征在于，所述聚合物选自聚甲基丙烯酸甲酯(PMMA)、聚α-甲基苯乙烯(PAMS)、聚碳酸亚丙基脂、聚碳酸亚乙基脂以及吡啶和三氯乙醛产物。
5．如权利要求1所述的浆料，其特征在于，所述溶剂是选自酮类、醇类、环状有机化合物和开链有机化合物的一种液体。
6．如权利要求1所述的浆料，其特征在于，所述颗粒选自金属、陶瓷和半导体。
7．一种涂层，包括：衬底和该衬底上的浆料层，该浆料包括：用于可开链聚合物的溶剂，溶于所述溶剂中形成溶液的可开链聚合物和悬浮于所述溶液中的颗粒，所述颗粒适于涂覆所选用材料的表面，所述聚合物占该溶液的10wt％或更多。
8．如权利要求7所述的涂层，其特征在于，所述衬底具有包含预定材料的表面，所述聚合物在某一预定温度以上完全挥发，所述颗粒通过接触粘附于所述预定材料上。
9．如权利要求8所述的涂层，其特征在于，所述溶剂和可开链聚合物通过将它们的温度升高到所述预定温度以上去除。
10．如权利要求8所述的涂层，其特征在于，所述颗粒通过选自合金化、软化、互扩散和互连接(interlocking)的某一种机理与预定材料相粘接。
11．如权利要求7所述的涂层，其特征在于，所述颗粒选自金属、陶瓷和半导体。
12．一种用测试探针测试具有被氧化电极的电子设备的方法，该探针具有与所述电极相对应的触点，该方法包括步骤：
将浆料施于所述电极表面，该浆料包含：用于可开链聚合物的溶剂，溶于所述溶剂中形成溶液的可开链聚合物和悬浮于所述溶液中的颗粒，所述颗粒适于涂覆所述电极的表面，所述聚合物占溶液的10wt％或更多；
所述浆料中的颗粒具有导电性且可粘结于所述电极表面；
将所述浆料加热以去除所述溶剂与可开链聚合物；以及
将所述被涂覆电极与所述探针触点相接触。
13．如权利要求12所述的方法，其特征在于，还包括在所述电极和所述触点之间施加力的步骤。
14．如权利要求12所述的方法，其特征在于，还包括选择一种具有热塑性材料作为其可开链聚合物的浆料的步骤。
15．一种用金属颗粒涂覆半导体芯片上的电极的方法，包括步骤：
将浆料施于所述电极表面，该浆料含有：用于可开链聚合物的溶剂，溶于所述溶剂中形成溶液的可开链聚合物和悬浮于所述溶液中的颗粒，所述颗粒适于涂覆所选用材料的表面，所述聚合物占溶液的10wt％或更多；
所述浆料中的颗粒具有导电性且可粘结于所述衬底表面；以及
将所述浆料加热以去除所述溶剂和可开链聚合物。
16．一种将具有被氧化电极的半导体芯片与衬底上的相应电焊点进行互连接的方法，包括步骤：
将浆料施于所述电极表面，该浆料包含：用于可开链聚合物的溶剂，溶于所述溶剂中形成溶液的可开链聚合物和悬浮于所述溶液中的颗粒，所述颗粒适于涂覆所说电极的表面，所述聚合物占溶液的10wt％或更多；
所述浆料中的颗粒具有导电性且可粘结于所述电极表面；
将所述浆料加热以去除所述溶剂和可开链聚合物；
将含有聚合物粘结剂和贵金属颗粒的导电粘结浆料施于所述衬底的电极上；
将所述电极与相应电触点相接触；以及
通过加热将所述电极与所述相应电触点键合。
17．如权利要求1所述的浆料，其特征在于，所述聚合物具有一低于400℃的Tunzip(开链温度)。
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