CN101573784A - 电极结构体及凸点形成方法 - Google Patents

电极结构体及凸点形成方法 Download PDF

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Publication number
CN101573784A
CN101573784A CNA2007800462189A CN200780046218A CN101573784A CN 101573784 A CN101573784 A CN 101573784A CN A2007800462189 A CNA2007800462189 A CN A2007800462189A CN 200780046218 A CN200780046218 A CN 200780046218A CN 101573784 A CN101573784 A CN 101573784A
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layer
electrode
electrode pattern
electroconductive particle
liquid
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CN101573784B (zh
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谷口泰士
中谷诚一
北江孝史
辛岛靖治
保手浜健一
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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Abstract

装载焊锡凸点的电极结构体(100)包括：由选自Cu、Al、Cr及Ti的电极构成材料形成的电极图案(50)；形成于电极图案(50)上的一部分的Ni层(52)；形成于电极图案(50)上的所述一部分以外的区域的至少一部分的Pd层(54)；以及形成于Ni层(52)和Pd层(54)上的Au层(56)。

Description

电极结构体及凸点形成方法
技术领域
本发明涉及装载焊锡凸点的电极结构体及在该电极结构体上形成凸点的方法。
背景技术
近年来，随着电子设备中使用的半导体集成电路(LSI)的高密度、高集成化，LSI芯片的电极端子的多管脚、窄间距化正在急速发展。在将这些LSI芯片安装于布线基板时，为了减少布线延迟，广泛采用倒装(Flip Chip)。而且在该倒装中，一般是在LSI芯片的电极端子上形成焊锡凸点，通过该焊锡凸点将LSI芯片一齐与形成于布线基板上的电极接合。
以往，作为凸点的形成技术，开发出了镀敷法和丝网印刷法等。镀敷法虽然适合于窄间距，但工序复杂，在生产性方面存在问题，而丝网印刷法虽然生产性优良，但要使用掩模，不适合于窄间距化。
在此过程中，最近开发出数种在LSI芯片或布线基板的电极上选择性地形成焊锡凸点的技术。这些技术不仅适用于微细凸点的形成，而且能够一齐形成焊锡凸点，所以生产性也优良，作为可用于第二代LSI在布线基板上的安装的技术受到瞩目。
其中有一种被称为焊锡膏(solder paste)法的技术(例如参照日本专利特开2000-94179号公报)。该技术如下所述：将由焊锡粉末和熔剂的混合物形成的焊锡膏全面涂布于表面形成有电极的基板上，通过加热基板使焊锡粉末熔化，在浸润性好的电极上选择性地形成焊锡凸点。
此外，被称为超级焊锡(super solder)法的技术(例如参照日本专利特开平1-157796号公报)如下所述：将以有机酸铅盐和金属锡为主要成分的膏状组合物(化学反应析出型焊锡)全面涂布于形成有电极的基板上，通过加热基板引发Pb和Sn置换反应，使Pb/Sn的合金在基板的电极上选择性地析出。
此外，被称为超级捷菲特(super Juffit)法的技术(例如参照日本专利特开平7-74459号公报)如下所述：将表面形成有电极的基板浸在药剂中，仅在电极的表面形成粘着性皮膜，之后使该粘着性皮膜与焊锡粉末接触，使焊锡粉末附着在电极上，然后通过加热基板使熔融焊锡选择性地形成于电极上。
发明的揭示
上述焊锡膏法原本是作为在形成于基板的电极上选择性地预涂焊锡的技术被开发的，为了使其适用于倒装所需的凸点形成，存在如下问题。
焊锡膏法中，通过涂布向基板上供给膏状组合物，所以局部的厚度或浓度会产生偏差，因此，各电极的焊锡析出量不同，难以获得均一的凸点。此外，这些方法中，通过涂布向表面形成有电极的具有凹凸的布线基板上供给膏状组合物，所以也存在难以向作为凸部的电极上稳定地供给足量的焊锡的问题。
此外，超级焊锡法中使用的化学反应析出型焊锡的材料利用了特定的化学反应，所以焊锡组成的选择的自由度低，在Pb游离化的应对方面也留有问题。
另一方面，超级捷菲特法中，焊锡粉末均匀地附着于电极上，所以可获得均一的焊锡凸点，此外，焊锡组成的选择的自由度大，所以易于应对Pb游离化。然而，超级捷菲特法中，在电极表面选择性地形成粘着性皮膜的工序是必需的，该工序中需要进行利用化学反应的特殊的药剂处理，所以工序变得复杂，并且也会导致成本上升，在用于量产工序方面留有问题。
因此，凸点的形成技术中，不仅是镀敷法和丝网印刷法这样的已普及的技术，新开发的技术也存在问题。本发明人认为，不拘泥于已有的凸点的形成技术而是开发新的凸点形成方法，可最终开发出潜力很大的技术，为此反复进行了研究开发。
本发明是鉴于以上问题而完成的发明，其主要目的是提供生产性优良的凸点形成方法。本发明的另一个目的是提供适用于该凸点形成方法的电极结构体。
本发明的电极结构体是装载焊锡凸点的电极结构体，该电极结构体的特征在于，包括：由选自Cu、Al、Cr及Ti的电极构成材料形成的电极图案；形成于所述电极图案上的一部分的Ni层；形成于所述电极图案上的所述一部分以外的区域的至少一部分的Pd层；以及形成于所述Ni层和所述Pd层上的Au层。
在一个优选实施方式中，所述Ni层形成于所述电极图案上的中央部，另一方面，所述Pd层以覆盖所述Ni层的周围的形态形成于所述电极图案上。
此外，本发明的电极结构体是装载焊锡凸点的电极结构体，该电极结构体的特征在于，包括：由选自Cu、Al、Cr及Ti的电极构成材料形成的电极图案；形成于所述电极图案上的至少一部分的Ni层；覆盖所述Ni层的Pd层；以及覆盖所述Pd层的Au层。
在一个优选实施方式中，所述Ni层配置于所述电极图案上的中央部。
此外，本发明的电极结构体是装载焊锡凸点的电极结构体，该电极结构体的特征在于，包括：由选自Cu、Al、Cr及Ti的电极构成材料形成的电极图案；形成于所述电极图案上的Pd层；以及形成于所述Pd层上的Au层。
在一个优选实施方式中，所述电极图案排列在玻璃基板或树脂基板上。
本发明的凸点形成方法的特征在于，在基板的电极图案上形成凸点时，包括：向电极图案上供给含有导电性粒子和发泡剂的流动体的工序(a)；隔着所述流动体在所述基板上配置板状构件的工序(b)；对所述流动体加热，使所述发泡剂产生气泡，并且利用该气泡使所述导电性粒子在所述电极图案上自聚集的工序(c)；以及将所述自聚集好的所述导电性粒子再熔融，使其在形成于所述电极图案上的至少一部分的Ni层上固化的工序(d)。
在一个优选实施方式中，向所述电极图案上赋予在所述再熔融时被所述自聚集好的导电性粒子吸收的金属。
此外，本发明的凸点形成方法的特征在于，在电极结构体上形成凸点时，包括：向电极结构体上供给含有导电性粒子和发泡剂的流动体的工序(a)；隔着所述流动体在所述电极结构体上配置板状构件的工序(b)；对所述流动体加热，使所述发泡剂产生气泡，使所述导电性粒子在所述电极结构体上自聚集的工序(c)；以及将所述自聚集好的所述导电性粒子再熔融，使其在形成于所述电极结构体的电极图案上的至少一部分的Ni层上固化的工序(d)。
在一个优选实施方式中，在所述工序(c)之后还包括除去所述板状构件的工序。
在一个优选实施方式中，所述工序(a)中的所述流动体所含的所述发泡剂由在所述工序(c)中的所述流动体被加热时沸腾的材料构成，或者由通过热分解产生气体的材料构成。
在一个优选实施方式中，在所述工序(c)中，在供给至所述基板上的所述流动体与所述板状构件抵接的状态下实施加热。
在一个优选实施方式中，在所述工序(c)中，在形成于所述基板上的所述电极图案和所述板状构件之间设置有间隙。
在一个优选实施方式中，所述间隙大于所述导电性粒子的粒径。
在一个优选实施方式中，在所述工序(c)中，对所述板状构件施加一定的压力，从而在维持一定的间隙的情况下挤压所述流动体并同时进行加热。
在一个优选实施方式中，在所述工序(c)中，由所述发泡剂产生的气泡从设置于所述板状构件和所述基板之间的间隙的周边部向外部排出。
此外，本发明的凸点形成方法的特征在于，在包括由选自Cu、Al、Cr及Ti的电极构成材料形成的电极图案、形成于所述电极图案上的Pd层、以及形成于所述Pd层上的Au层的权利要求5所述的电极结构体上形成凸点时，包括：向电极结构体上供给含有导电性粒子和发泡剂的流动体的工序(a)；隔着所述流动体在所述电极结构体上配置板状构件的工序(b)；对所述流动体加热，使所述发泡剂产生气泡，并且利用该气泡使所述导电性粒子在所述电极结构体上自聚集的工序(c)；以及将所述自聚集好的所述导电性粒子再熔融，使其在所述电极图案上固化的工序(d)。
在一个优选实施方式中，在所述工序(c)的加热过程中改变所述板状构件和所述基板之间的间隙的大小。
本发明的凸点形成方法中，向布线基板中包括电极在内的区域上供给含有导电性粒子和发泡剂的流动体后，利用流动体在布线基板上配置板状构件，接着对流动体加热，使该流动体中所含的发泡剂产生气泡，并且利用该气泡使导电性粒子在电极上自聚集，然后将自聚集好的导电性粒子再熔融。通过该再熔融，自聚集好的导电性粒子可以吸收金属并使其合金化，结果可提高凸点的高度。此外，通过对流动体加热，使发泡剂产生气泡，可使导电性粒子在电极上自聚集，所以能以良好的生产性形成凸点。除此之外，通过将自聚集好的导电性粒子再熔融，也可将再形成时的凸点的高度平均化(均化)。
本发明的电极结构体中，在由电极构成材料形成的电极图案上的至少一部分形成有Ni层，还形成有覆盖该Ni层的Pd层和覆盖Pd层的Au层，所以自聚集好的导电性粒子可吸收Pd和Au并使其合金化，结果可提高由自聚集好的导电性粒子构成的焊锡凸点的凸点高度。
附图的简单说明
图1是利用树脂的自聚集的凸点形成方法的工序剖视图。
图2是利用树脂的自聚集的凸点形成方法的工序剖视图。
图3是树脂自聚集的机理的说明图。
图4是本实施方式的电极结构体100的剖面模式图。
图5是表示用本实施方式的电极结构体100形成凸点后的状态的图。
图6是表示本发明的实施方式的凸点形成方法的工序剖视图。
图7是不包含Pd层的电极结构体300的结构图和凸点形成后的结构图。
图8是本发明的实施方式的电极结构体100的制造方法的工序剖视图。
图9是本发明的实施方式的电极结构体100的制造方法的工序剖视图。
图10是本发明的另一个实施方式的电极结构体100的制造方法的工序剖视图。
图11是本发明的另一个实施方式的电极结构体200的结构图和凸点形成后的结构图。
图12是本发明的另一个实施方式的电极结构体400的结构图和凸点形成后的结构图。
图13是本发明的另一个实施方式的电极结构体500的结构图和形成凸点的中途过程的结构图以及凸点形成后的结构图。
图14是表示本发明的另一个实施方式的凸点形成方法的工序剖视图。
图15是表示电极的周缘配置的平面图。
图16是表示电极的面阵列配置的平面图。
图17是表示本发明的实施方式的凸点形成装置的结构的剖视图。
实施发明的最佳方式
本申请人对使导电性粒子(例如焊锡粉末)在布线基板或半导体芯片等的电极上自聚集、从而形成凸点的方法，或者使导电性粒子在布线基板或半导体芯片的电极之间自聚集、在电极间形成连接体、从而实施倒装的方法进行了多种研究，提出了以往没有的新的凸点形成方法和倒装方法(日本专利特愿2004-257206号(日本专利特开2006-100775号)、日本专利特愿2004-365684号(日本专利特愿2006-548871号)、日本专利特愿2005-094232号(日本专利特愿2007-510386号))。在本说明书中引用这些专利申请作为参照。
图1(a)～(d)及图2(a)～(d)是表示本申请人在上述专利申请的说明书中揭示的凸点形成方法的基本工序的图。
首先，如图1(a)所示，向具有多个电极32的基板31上供给含有导电性粒子16和发泡剂(未图示)的流动体14。这里，导电性粒子为焊锡粉末。流动体14为树脂。
接着，如图1(b)所示，在流动体14的表面配设平板状的板状构件40。
在此状态下，如果对流动体14加热，则如图1(c)所示，由流动体14中含有的发泡剂产生气泡30。然后，如图1(d)所示，在流动体14中，通过产生的气泡30的成长，其中一部分的气泡30从基板31的外周部被向外挤出。
受到挤压的流动体14如图2(a)所示，在其与基板31的电极32的界面以及其与板状构件40的界面上自聚集成柱状。接着，如果进一步对流动体14加热，则如图2(b)所示，流动体14中含有的焊锡粉末16熔融，自聚集在电极32上的树脂14中含有的焊锡粉末16彼此熔融结合。
电极32对熔融结合后的焊锡粉末16的浸润性好，所以如图2(c)所示，在电极32上形成由熔融的焊锡粉末形成的焊锡凸点19。最后，如图2(d)所示，通过除去流动体14和板状构件40，得到在电极32上形成有焊锡凸点19的基板31。
该方法的特征在于，通过对供给至基板31和板状构件40的间隙的流动体14加热，使发泡剂产生气泡30，利用气泡30的成长将流动体14向气泡外挤压，藉此使流动体14在基板31的电极32和板状构件40之间自聚集。
流动体14在电极32上自聚集的现象可认为是因图3(a)(b)所示的机理而引起的。
图3(a)是表示流动体14因成长的气泡(未图示)而被挤压至基板31的电极32上的状态的图。与电极32相接的流动体14中，其界面上的界面张力(即因树脂的浸润而产生的力)Fs大于因流动体14的粘度η而产生的应力Fη，所以流动体14浸润电极32的整个表面，最终在电极32和板状构件40之间形成以电极32的端部为界的柱状的流动体14。
另外，如图3(b)所示，虽然在电极32上自聚集形成的柱状的流动体14受到因气泡30的成长(或移动)而产生的应力Fb，但因流动体14的粘度η而产生的应力Fη的作用可维持其形状，一旦发生了自聚集，流动体14就不会消失。
在此，自聚集好的流动体14是否能维持一定的形状除了取决于上述界面张力Fs外，也取决于电极32的面积S及电极32和板状构件40之间的间隙的距离L，以及流动体14的粘度η。如果将使流动体14维持一定形状的标准记作T，则可定性地认为T满足如下关系。
T＝K·(S/L)·η·Fs(K为常数)
如上所述，该方法是利用由流动体14的界面张力引起的自聚集来使流动体14自动整合地形成于电极32上的方法，但由于形成于基板31表面的电极32形成凸状，因此可以说该由界面张力引起的自聚集利用了在基板31和板状构件40之间形成的间隙中变得狭窄的电极32上发生的现象。
如果使用本发明人提出的上述方法，则可使分散在树脂中的焊锡粉末高效地在电极上自聚集，可实现均一性良好且生产性好的凸点形成。此外，因为可使分散在流动体14中的焊锡粉末在供给有流动体14的基板上的多个电极上无差别地自聚集，所以上述方法在供给有流动体14的布线基板上的所有电极上一齐形成凸点时特别有用。
本发明人认为，在上述方法中，如果能简便地提高焊锡凸点的高度，则可进一步增大本方法的技术价值，因而对该方法进行了认真研究，从而完成了本发明。
下面，参照附图对本发明的实施方式进行说明。
下面的附图中，为简化说明，对实质上具有相同功能的构成要素用同一参考标号表示。本发明不限定于以下实施方式。
参照图4对本实施方式的凸点形成方法中使用的电极结构体100的结构进行说明。
图4是表示本实施方式的电极结构体100的截面结构的剖面模式图。
电极结构体100是装载焊锡凸点的电极结构体，该电极结构体100排列在基板31上。本实施方式的电极结构体100由电极图案50、形成于电极图案50上的Ni层52和Pd层54、以及形成于Ni层和Pd层上的Au层56构成。
电极图案50形成于基板31上，由电极构成材料(例如Cu、Al、Cr或Ti)构成。电极图案50的构成材料可根据基板31的材质适当地选择合适的材料。图示的例子中，基板31是玻璃基板，此时可选择的电极构成材料例如为Cr或Ti。此外，基板31为树脂基板时，作为电极构成材料，可选择例如Cu或Al。另外，如果要例举本实施方式的电极图案50的厚度，则为10～1000μm。
在电极图案50上的至少一部分形成有Ni层52。本实施方式的Ni层52配置于电极图案50上的中央部。该Ni层52是不易被在加热时熔融的导电性粒子(例如焊锡粉末)溶解(即溶蚀或侵蚀)的金属层。
另外，不仅是Ni层52，Pd层54也形成于电极图案50上。Pd层54形成于形成有Ni层的电极图案50上的部分区域以外的至少一部分。本实施方式的Pd层54配置成覆盖配置于电极图案50的中央部的Ni层52的周围。该Pd层54是易被熔融焊锡溶蚀的金属层。图示的例子中，Ni层52的上表面和Pd层54的上表面被配置成处于同一平面内，如果要例举Ni层52和Pd层54的厚度，则均为10～3000μm。
另外，在Ni层52和Pd层54上形成有Au层56。该Au层56具有在形成焊锡凸点时防止位于下层的Ni层52和Pd层54的氧化的作用。另外，本实施方式的Au层的厚度为10～200μm。
图5是表示用图4所示的电极结构体100通过自聚集法装载焊锡凸点20后的状态的图。焊锡凸点20隔着对熔融焊锡具有比周围更好的浸润性的Ni层52形成于电极图案50上。如该例所示，构成电极结构体100的各金属中，Pd和Au是易被熔融焊锡溶蚀的金属，因此Pd层54和Au层56被熔融焊锡吸收并合金化，藉此，电极图案50上的焊锡凸点20的凸点高度高于图2(d)所示的焊锡凸点19的凸点高度。
本实施方式的电极结构体100中，由电极构成材料形成的电极图案50上的至少一部分形成有Ni层52，还形成有覆盖该Ni层52的Pd层54和覆盖Pd层54的Au层56，因此自聚集好的导电性粒子(例如焊锡粉末)可吸收Pd和Au并使其合金化，结果可提高由自聚集好的导电性粒子(例如焊锡粉末)形成的焊锡凸点的凸点高度。
下面，参照图6(a)～(e)对可提高焊锡凸点20的凸点高度的方面进行更详细的说明。
图6(a)～(e)是表示用本实施方式的电极结构体100通过自聚集法形成焊锡凸点20的基本工序的图。
首先，如图6(a)所示，在基板31中包含电极结构体100的区域上供给含有导电性粒子16和发泡剂(未图示)的流动体14。作为本实施方式中的导电性粒子16，使用焊锡粉末。作为本实施方式中的流动体14，使用环氧树脂。在作为流动体14的环氧树脂中，除作为导电性粒子16的焊锡粉末(本例中为SnAgCu类焊锡粉末)外，还含有防止焊锡粉末氧化的焊锡活性剂(未图示)。本实施方式的焊锡活性剂为熔剂，本例中使用在松香类合成树脂中掺入活性剂而成的焊锡活性剂。
另外，如果要例举本实施方式的流动体14所含的各成分的比例，则为相对于10重量份的环氧树脂、焊锡粉末为30重量份、熔剂为60重量份的比例，但它们的比例可根据形成焊锡凸点的各种条件适当调整。例如，可以是相对于10重量份的环氧树脂、焊锡粉末为40重量份、熔剂为50重量份的比例，也可以是相对于10重量份的环氧树脂、焊锡粉末为60重量份、熔剂为30重量份的比例。
接着，如图6(b)所示，隔着流动体14在基板31上配置板状构件40。板状构件40例如为玻璃基板。此外，不限定于玻璃基板，也可使用陶瓷基板、半导体基板(硅基板等)。作为板状构件40，如果使用透光性基板，则有工序的进展情况和凸点形成的确认变得容易的优点。
另外，板状构件40的表面可以是平坦的面，或者也可以是具有凹凸形状(例如突起面)的面。在板状构件40的表面中与供给流动体14的区域相对的位置上形成有突起面的情况下，可利用与突起面之间的表面张力将流动体14留住，使其在加热时不飞散。此外，也可预先将基板31和板状构件40空开一定的间隙配置，然后向该间隙供给流动体14。基板31和板状构件40的间隙设定为大于导电性粒子16的粒径。
如果在图6(b)所示的状态下对流动体14加热，则由流动体14中含有的发泡剂产生气泡30。本实施方式中，在将板状构件40与流动体14抵接固定的状态下实施加热。在产生的气泡30成长的过程中，流动体14被该气泡30向外挤出。然后，受到挤压的流动体14如图6(c)所示，因界面张力而聚集在板状构件40和电极结构体100之间，与此同时，流动体14中的导电性粒子16聚集在电极结构体100上。然后，通过加热，流动体14中含有的导电性粒子16熔融，结果，导电性粒子16完成最初的自聚集。此时，电极结构体100的Au层56如箭头92所示被熔融的导电性粒子16溶蚀，被熔融的导电性粒子16吸收并在其中扩散。即，本例中，在Ni层52和Pd层54上形成焊锡凸点19，该焊锡凸点19由吸收了Au并将其合金化的导电性粒子16形成。然后，如果除去板状构件40，则如图6(d)所示得到基板31，在该基板31上，隔着Ni层52和Pd层54在电极图案50上形成有焊锡凸点19。
另外，在导电性粒子16自聚集时，Au层56被熔融的导电性粒子16侵蚀，但被Au层56覆盖的Pd层54几乎未被熔融的导电性粒子16溶蚀。这是因为具有作为导电性粒子16的抗氧化剂的功能的焊锡活性剂(例如熔剂)失活。即，由于在导电性粒子16的自聚集处理时间内焊锡活性剂失活，因此在Au层56被侵蚀时，熔融的导电性粒子16被氧化，形成为不熔解异种金属的状态，所以，形成于Au层的更下层的Pd层54不会被熔融的导电性粒子16溶蚀。另外，Pd的扩散系数比Au小，这也是Pd层54不被溶蚀的原因之一。
接着，如果在图6(d)所示的状态(即除去了板状构件40的开放状态)下进一步实施加热，则由在Ni层52和Pd层54上自聚集的导电性粒子16形成的焊锡凸点19再熔融。该导电性粒子16的再熔融在供给新的焊锡活性剂(例如熔剂)的状态下实施。通过该焊锡活性剂的添加，导电性粒子16中的氧化物被除去，因此导电性粒子16再次形成为可熔解异种金属的状态。藉此，在导电性粒子16再熔融时，Pd层54被再熔融的导电性粒子16溶蚀，如箭头94所示被熔融的导电性粒子16吸收并合金化。另外，在再加热时添加的焊锡活性剂可以是与最初添加的焊锡活性剂相同的焊锡活性剂，或者也可以是所含成分不同的焊锡活性剂。添加与最初添加的焊锡活性剂的种类不同的焊锡活性剂的情况下，可适当地选择添加容易溶蚀Pd的构成的焊锡活性剂。
然后，如图6(e)所示，吸收了Pd并将其合金化的熔融的导电性粒子16不是聚集在由Cr形成的电极图案50上，而是聚集在对熔融的导电性粒子16的浸润性比Cr更好的Ni层52上，结果，导电性粒子16完成第二次的自聚集。即，隔着Ni层52在电极图案50上形成了焊锡凸点20，该焊锡凸点20由吸收了Au和Pd并将其合金化的导电性粒子16形成。由于该焊锡凸点20含有Pd，因此其凸点高度比图6(d)所示的在最初的加热时形成的焊锡凸点19的凸点高度更高。另外，该再加热可以在与最初的加热时相同的温度下实施，或者也可以在比最初的加热时更高的温度下实施。
通过该再熔融，自聚集好的导电性粒子16可吸收金属(这里为Au和Pd，特别是Pd)并使其合金化，结果可提高由导电性粒子16形成的焊锡凸点20的高度。除此之外，由于再熔融在除去了板状构件40的开放状态下实施，因此焊锡凸点20为半球体状，所以可进一步提高焊锡凸点20的高度。此外，通过对流动体14加热，使发泡剂产生气泡，可使导电性粒子16在电极上自聚集，所以能够以良好的生产性形成凸点。除此之外，通过将自聚集好的焊锡凸点19再熔融，也可将再形成时的焊锡凸点20的高度平均化(均化)。
可以被熔融的导电性粒子16吸收并合金化的金属不仅限于Pd和Au，也可以是其它金属。例如，作为被熔融的导电性粒子16吸收并合金化的金属，也可使用Ag，即，除Pd层以外，也可使用Ag层来构成电极结构体。或者也可以是如下结构：用含Ag的有机膜等覆盖电极图案50以外的区域，使得熔融的导电性粒子16能从该有机膜吸收Ag。另外，被熔融的导电性粒子16吸收的金属可根据金属在熔融的导电性粒子16中的熔解度和金属在熔融的导电性粒子16中的扩散系数等适当地选择。
另外，即使是上述电极结构体100以外的典型的电极结构(例如图1的电极32所示的由Cu形成的单层结构)，也可获得通过再熔融产生的凸点的均化效果。此时，通过将凸点再熔融，即使无法获得提高凸点高度的效果，也可将凸点的高度平均化。
此外，可利用电极结构体100来提高凸点高度的凸点不限于上述通过自聚集形成的凸点，也可以是利用其它方法形成的凸点。例如，即使是通过转印法形成的凸点，通过用电极结构体100进行再熔融，也可由熔融的导电性粒子16吸收Pd并将其合金化，因此可提高再形成后的凸点的高度。
另外，图6(a)～(e)所示的各结构的尺寸和相对位置关系(例如导电性粒子16的尺寸、基板31和板状构件40的间隙的距离等)是为了容易进行说明而简单地表现的尺寸和相对位置关系，并不表示实际的尺寸等。
图7(a)表示不包含Pd层的情况的电极结构体300的一例。
即，在形成于基板331上的电极图案350上配置有Ni层352，在Ni层352上不隔着Pd层直接形成有Au层356。即使用如上所述不包含Pd层的电极结构体300形成了焊锡凸点，也如图7(b)所示，虽然薄膜状的Au层356被焊锡选择性地吸收，但难以获得进一步提高焊锡凸点320的高度的效果。
下面，对本实施方式的电极结构体100的结构及制造方法进行进一步详述。
首先，参照图8(a)～图9(b)对本实施方式的电极结构体100的制造方法进行说明。
首先，如图8(a)所示，在基板31(本例中为玻璃基板)上层叠构成电极图案50的电极构成材料51(本例中为Cr)，在电极构成材料51上形成规定图案的光致抗蚀层60。图示的例子中的光致抗蚀层60形成于与之后形成的电极图案50相同的位置。接着，通过蚀刻处理除去暴露的电极构成材料51，然后除去光致抗蚀层60，则可得到图8(b)所示的电极图案50。
接着，从图8(b)的状态用非电解镀敷法对整个基板31实施镀Ni处理。通过非电解镀敷法，被还原的Ni在热力学上不稳定的金属表面(这里是电极图案50)上析出，所以可在电极图案50上选择性地层叠Ni层53。
接着，如图8(c)所示，在Ni层53上形成规定图案的光致抗蚀层62，通过蚀刻处理除去不需要的Ni，则可得到图8(d)所示的Ni层52。
接着，从图8(d)的状态用非电解镀敷法对整个基板31实施镀Pd处理，则如图9(a)所示，可在电极图案50上形成Pd层54。此时，由于光致抗蚀层62起到覆盖Ni层52表面的掩模的作用，因此Pd层54以包围中央部的Ni层52的周围的形态层叠在电极图案50上。然后除去光致抗蚀层62。
最后，如图9(b)所示，用非电解镀敷法在Ni层52和Pd层54上选择性地层叠Au层56，则可得到本实施方式的电极结构体100。
另外，图8(b)～(d)所示的在电极图案50上形成Ni层52的工序也可不采用蚀刻处理，而是如图10(a)及图10(b)所示实施。即，如图10(a)所示，在电极图案50上形成规定图案的光致抗蚀层66，以该光致抗蚀层66为掩模，用非电解镀敷法在基板31的整个表面层叠Ni，则可如图10(b)所示形成Ni层52。
此外，在图8及图9所示的例子中，在电极图案50上形成Ni层52，然后形成Pd层54，但形成Ni层52和Pd层54的顺序也可以反过来。即，也可以最先层叠Pd层54，然后层叠Ni层52。
另外，上述例子中，用非电解镀敷法选择性地形成各金属层(Ni层52、Pd层54、Au层56)，但各金属层的形成方法不限定于此，也可利用其它方法形成。例如，也可利用溅射形成Au层56。
上述实施方式中，揭示了被熔融的导电性粒子的焊锡吸收并合金化的Pd层54与装载焊锡凸点20的Ni层52邻接的情况作为一例，但不限定于Pd层54与Ni层52邻接的情况，例如也可以通过其它构件来配置Pd层54和Ni层52。介于Pd层54和Ni层52之间的构件可以是Pd层以外的可被熔融焊锡吸收并合金化的金属层(例如Ag层)，或者也可以是不会被熔融焊锡吸收并合金化的构件。
另外，被熔融焊锡吸收并合金化的Pd层不仅可以与Ni层邻接，也可以形成在Ni层上。例如，图11(a)表示在Ni层上形成有Pd层的电极结构体200的例子。
电极结构体200由电极图案250、形成于电极图案250上的至少一部分的Ni层252、覆盖Ni层252的Pd层254、以及覆盖Pd层254的Au层256构成。
图11(a)的例子中，Ni层252形成于基板231的电极图案250上的所有区域。Pd层254从Ni层252上层叠，以覆盖Ni层252。即，Pd层254也形成于Ni层252的上表面。然后，在Pd层254上配置Au层256，以覆盖Pd层254。
如果用该电极结构体200形成凸点，则如图11(b)所示。
即使是如上所述在Ni层252上配置Pd层254的情况下，Ni层252上的Pd层254也会被熔融焊锡吸收并合金化，所以可在电极图案250上形成凸点高度较高的焊锡凸点220。除此之外，本例中，因为Ni层252形成于电极图案250上的所有区域，所以可以隔着Ni层252在电极图案250的所有区域以较高的高度形成凸点。
由此，通过再加热而熔融的焊锡聚集在对熔融焊锡的浸润性比电极图案更好的Ni层上。换言之，Ni层具有对可形成再熔融后的凸点的区域进行规定的作用。因此，通过适当地改变电极图案上的Ni层的形成区域，也可将可形成凸点的区域设定在合适的位置。
另外，也可以不隔着Ni层在电极图案上直接形成凸点高度较高的凸点。例如，图12(a)表示从图11(a)所示电极结构体200除去Ni层后的电极结构体400的例子。由此，即使不形成Ni层，也可如图12(b)所示，在基板431的电极图案450上直接形成吸收了Au和Pd并将其合金化的凸点高度较高的焊锡凸点420。再熔融后的焊锡之所以聚集在电极图案上，是因为电极图案450对熔融焊锡的浸润性好于周围的区域(本例中为基板31的表面)。这里，最好是隔着Ni层形成凸点，这是因为在凸点的再熔融时可利用界面张力将凸点牢固地紧压在电极图案上。另外，本例中，构成电极图案450的电极构成材料为Cu。
此外，图13(a)表示与上述电极结构体400的结构几乎相同的、将基板531的电极图案550的电极构成材料由Cu换成Ti(或Cr)的例子。即使在上述电极构成材料为Ti(或Cr)的情况下，也可如图13(b)所示，使熔融焊锡在电极图案550上聚集。这里，构成电极图案550的Ti(或Cr)对与Au/Pd合金化的熔融焊锡的浸润性差，因此在电极图案550上聚集的熔融焊锡516的表面积收缩，结果如图13(c)所示，可使所形成的焊锡凸点520在高度方向上进一步成长。
上述凸点的形成方法中，如图6(a)～(e)所示，通过使流动体14在板状构件40和基板31的电极间自聚集，然后在除去板状构件40的状态下将焊锡凸点19再熔融，从而得到凸点高度较高的焊锡凸点20，但凸点的形成方法不限定于此。
例如，如图14(a)～(c)所示，也可以在不使凸点再熔融的情况下通过一次加热工序形成凸点高度较高的焊锡凸点20。
首先，如图14(a)所示，隔着流动体14在基板31上配置板状构件40，接着，如果在该状态下对流动体14加热，则如图14(b)所示，流动体14聚集在板状构件40和电极结构体100之间。此时，流动体14所含的导电性粒子16因加热而熔融，该熔融的导电性粒子16不仅熔解Au层56，也熔解位于Au层56的更下层的Pd层54(参照图中的箭头91及箭头93)。藉此，可使自聚集好的导电性粒子16吸收金属(Au及Pd)并使其合金化，结果如图14(c)所示，可提高所形成的焊锡凸点20的高度。上述结构中，可以不将自聚集好的凸点再熔融，仅实施一次加热工序即可，所以可简便地形成凸点高度较高的凸点。
另外，图14(b)所示的流动体14的加热在使板状构件40上升(向箭头96的方向滑动)、增大板状构件40和基板31之间的距离(间隙)的同时实施。板状构件40的上升例如可通过用可吸附板状构件40的构件将板状构件40提起来实施。除此之外，板状构件40的上升也可通过合适的方法实施。或者，这里揭示了使板状构件40上升、从而改变板状构件40和基板31的间隙的例子，但也可以使基板31侧下降、从而改变板状构件40和基板31的间隙.
通过如上所述在增大板状构件40和基板31的问隙的同时进行加热，可有效地使流动体14聚集在板状构件40和电极之间，除此之外，也可允许吸收并合金化的导电性粒子16在高度方向上成长。还可随着板状构件40的上升利用界面张力沿高度方向拉伸凸点，所以也可藉此使凸点在高度方向上成长。
此外，在上述例中，流动体14中所含的焊锡活性剂的添加量及/或添加成分可适当地调整为合适的量及/或成分，使得焊锡活性剂在流动体的自聚集处理时间内不失活(即Pd层在流动体的自聚集处理时间内确实地被溶蚀)。
另外，本发明人为确认本实施方式的电极结构体(例如图13所示的电极结构体300)的效果，利用将电极结构体配置成6×6的矩阵(面阵列配置)的基板进行了测定图6(d)所示的最初的自聚集后的凸点高度和图6(e)所示的进一步经过再熔融工序后的凸点高度的实验。
结果，再熔融后的凸点高度平均为45μm，与此相对，再熔融前的凸点高度平均为95μm，通过再熔融，可形成具有约2倍的高度的凸点。除此之外，再熔融前后的凸点高度的标准偏差也减小，也可确认均化的效果。
与此相对，用典型的电极结构体(例如图7所示的不包含Pd层的电极结构体200)在相同条件下进行实验，结果再熔融前后的凸点高度基本不变，可以确认，在不包含Pd层的电极结构体中，虽然薄膜状的Au层被选择性地吸收并合金化，但几乎无法获得通过再熔融来提高凸点高度的效果。
另外，本实施方式的工艺中的导电性粒子(例如焊锡粉末)16的最适含量例如可设定如下。
如果假设向基板31上供给的流动体14的体积(VB)中所含的导电性粒子16全部参与基板31的电极图案50上的焊锡凸点20的形成，则焊锡凸点20的总体积(VA)和流动体14的体积(VB)满足如下关系式(1)。
这里，SA表示基板31的电极图案50的总面积(隔着Ni层形成焊锡凸点20时表示Ni层52的总面积)，SB表示基板31的规定区域(具体是表示供给流动体14的区域)的面积。由此，流动体14中所含的导电性粒子16的含量可通过下述式(2)表示。
导电性粒子16的含量＝(SA/SB)·100[体积％]…(2)
由此，可基于下述式(3)来大致设定流动体14中所含的导电性粒子16的最适含量。
导电性粒子16的含量＝(SA/SB)·100±α[体积％]…(3)
另外，上述参数(±α)是用于调整导电性粒子16在基板31的电极图案50上自聚集时的过量或不足的部分的参数，可根据各种条件确定。
基板31的电极图案50的配置可采取各种形态，对于图15、图16所示的典型的电极图案50的配置，如果通过式(3)求出最合适的导电性粒子16的含量，则大致为如下的值。
图15所示的配置(周缘配置)…0.5～5体积％
图16所示的配置(面阵列配置)…15～30体积％
由此，分散在流动体14中的导电性粒子16只要在流动体14中含有0.5～30体积％的比例，就足以在电极图案50上形成所要的焊锡凸点20。
另外，因为导电性粒子16和流动体14的重量比一般约为7左右，所以上述0.5～30体积％的比例大致相当于4～75重量％的比例。
图17表示用于实施本实施方式的凸点形成方法的优选的凸点形成装置70。
凸点形成装置70由用于装载基板31的平台71和与平台71相对配置的板状构件40构成。该形成装置70中，向装载于平台70上的基板31和与平台71相对配置的板状构件40之间供给含有导电性粒子16和发泡剂的流动体14。本实施方式的结构中，板状构件40可装卸。
另外，也可将能供给流动体14的供给机设置于形成装置70。供给流动体14后，通过对该流动体14加热，由流动体14中的发泡剂产生气泡。流动体14的加热可以通过在图17所示的平台71上设置加热器73来实施，也可以将板状构件40与加热器抵接，藉此进行加热。
这里，本实施方式所使用的流动体14、导电性粒子16、焊锡活性剂和发泡剂无特别限定，分别可使用以下材料。
作为流动体14，只要是在从室温到导电性粒子16的熔融温度的范围内具有可流动的程度的粘度的流动体即可，此外也包括粘度会因加热而下降至可流动的粘度的流动体。作为代表性的粒子，除上述的环氧树脂外，可使用酚醛树脂、有机硅树脂、邻苯二甲酸二烯丙酯树脂、呋喃树脂、三聚氰胺树脂等热固性树脂，聚酯弹性体、氟树脂、聚酰亚胺树脂、聚酰胺树脂、芳族聚酰胺树脂等热塑性树脂，或光(紫外线)固化树脂等，或者是将它们组合而成的材料。除树脂外，也可使用高沸点溶剂、油等。
此外，作为导电性粒子16和发泡剂，可从下述的(表1)和(表2)所示的材料中适当组合使用。另外，如果使用熔点高于发泡剂沸点的材料作为导电性粒子16，则可以对流动体14加热，使发泡剂产生气泡，使流动体自聚集后进一步对流动体14加热，使自聚集好的流动体中的导电性粒子16熔融，使导电性粒子16彼此形成金属键。
[表1]
导电性粒子   熔点(固相线)(℃)
  Sn-58Bi   139
  Sn-37Pb   183
  Sn-9Zn   199
  Sn-3.0Ag-0.5Cu   217
  Sn-3.5Ag   221
  Sn-0.7Cu   228
  12Sn-2.0Ag-10Sb-Pb   240
[表2]
  发泡剂   沸点(℃)   发泡剂   沸点(℃)
  己烷   69   二甲胺盐酸盐   171
乙酸乙烯酯 72   二甲亚砜(DMSO) 189
  异丙醇   83   乙二醇   198
水 100   N-甲基-2-吡咯烷酮(NMP) 204
  1，4-二噁烷   101   α-萜品醇   218
  乙酸丁酯   126   丁基卡必醇   231
  丙酸   141   丁基卡必醇乙酸酯   246
此外，发泡剂也可以是由沸点不同的2种以上的材料构成的发泡剂。如果沸点不同，则气泡的产生和成长的时间产生差异，结果，气泡的成长所引起的流动体14的挤出是阶段性地进行的，所以流动体14的自聚集过程均一化，藉此可形成均一性好的导电图案。
另外，作为发泡剂，除上述(表2)例举的材料以外，也可使用在流动体14被加热时通过发泡剂的热分解产生气泡的材料。作为这样的发泡剂，可使用下述(表3)例举的材料。例如在使用含结晶水的化合物(氢氧化铝)的情况下，发泡剂在流动体14被加热时热分解，产生水蒸气，成为气泡。
[表3]
  发泡剂   分解温度(℃)
  硼酸   70～
  偏硼酸铵   120～
  碳酸氢钠   120-150
  4，4-氧化双苯磺酰肼(OBSH) 155-165
  偶氮二酰胺(ADCA)   197-210
  偏硼酸钡   200～
  N，N’-二亚硝基五亚甲基四胺(DPT) 200-250
  氢氧化铝   230
  铝酸钙   230
  片钠铝石   230
此外，作为焊锡活性剂，只要是具有作为导电性粒子16的抗氧化剂的功能的物质即可，流动体14中不仅可含有作为一例举出的松香类熔剂，也可含有各种还原剂。作为代表性的例子，可使用松香酸、己二酸、抗坏血酸、丙烯酸、柠檬酸、苹果酸、聚丙烯酸或将它们组合而成的材料等。
以上通过优选的实施方式对本发明进行了说明，但上述叙述并非限定事项，当然可进行各种改变。
产业上利用的可能性
利用本发明，可提供生产性优良的凸点形成方法，此外也可提供适用于该凸点形成方法的电极结构体。

Claims (18)

1.一种装载焊锡凸点的电极结构体，其特征在于，包括：
由选自Cu、Al、Cr及Ti的电极构成材料形成的电极图案；
形成于所述电极图案上的一部分的Ni层；
形成于所述电极图案上的所述一部分以外的区域的至少一部分的Pd层；以及
形成于所述Ni层和所述Pd层上的Au层。
2.如权利要求1所述的电极结构体，其特征在于，
所述Ni层形成于所述电极图案上的中央部，所述Pd层以覆盖所述Ni层的周围的形态形成于所述电极图案上。
3.一种装载焊锡凸点的电极结构体，其特征在于，包括：
由选自Cu、Al、Cr及Ti的电极构成材料形成的电极图案；
形成于所述电极图案上的至少一部分的Ni层；
覆盖所述Ni层的Pd层；以及
覆盖所述Pd层的Au层。
4.如权利要求3所述的电极结构体，其特征在于，
所述Ni层配置于所述电极图案上的中央部。
5.一种装载焊锡凸点的电极结构体，其特征在于，包括：
由选自Cu、Al、Cr及Ti的电极构成材料形成的电极图案；
形成于所述电极图案上的Pd层；以及
形成于所述Pd层上的Au层。
6.如权利要求1、3、5中任一项所述的电极结构体，其特征在于，
所述电极图案排列在玻璃基板或树脂基板上。
7.一种凸点形成方法，其特征在于，
在基板的电极图案上形成凸点时包括以下工序：
向电极图案上供给含有导电性粒子和发泡剂的流动体的工序(a)；
隔着所述流动体在所述基板上配置板状构件的工序(b)；
对所述流动体加热，使所述发泡剂产生气泡，并且利用该气泡使所述导电性粒子在所述电极图案上自聚集的工序(c)；以及
将进行了所述自聚集之后的所述导电性粒子再熔融，使该导电性粒子在形成于所述电极图案上的至少一部分的Ni层上固化的工序(d)。
8.如权利要求7所述的凸点形成方法，其特征在于，
向所述电极图案上赋予在所述再熔融时被进行了所述自聚集之后的导电性粒子吸收的金属。
9.一种凸点形成方法，其特征在于，
在由选自Cu、Al、Cr及Ti的电极构成材料形成的电极图案和形成于所述电极图案上的至少一部分的Ni层所构成的权利要求1或3所述的电极结构体上形成凸点时，包括以下工序：
向电极结构体上供给含有导电性粒子和发泡剂的流动体的工序(a)；
隔着所述流动体在所述电极结构体上配置板状构件的工序(b)；
对所述流动体加热，使所述发泡剂产生气泡，使所述导电性粒子在所述电极结构体上自聚集的工序(c)；以及
将进行了所述自聚集之后的所述导电性粒子再熔融，使该导电性粒子在形成于所述电极结构体的电极图案上的至少一部分的Ni层上固化的工序(d)。
10.如权利要求7所述的凸点形成方法，其特征在于，
在所述工序(c)之后还包括除去所述板状构件的工序。
11.如权利要求7所述的凸点形成方法，其特征在于，
所述工序(a)中的所述流动体所含的所述发泡剂由在所述工序(c)中的所述流动体被加热时沸腾的材料构成，或者由通过热分解产生气体的材料构成。
12.如权利要求7所述的凸点形成方法，其特征在于，
在所述工序(c)中，在供给至所述基板上的所述流动体与所述板状构件抵接的状态下实施加热。
13.如权利要求7所述的凸点形成方法，其特征在于，
在所述工序(c)中，在形成于所述基板上的所述电极图案和所述板状构件之间设置有间隙。
14.如权利要求13所述的凸点形成方法，其特征在于，
所述间隙大于所述导电性粒子的粒径。
15.如权利要求7所述的凸点形成方法，其特征在于，
在所述工序(c)中，对所述板状构件施加一定的压力，从而在维持一定的间隙的情况下挤压所述流动体并同时进行加热。
16.如权利要求7所述的凸点形成方法，其特征在于，
在所述工序(c)中，由所述发泡剂产生的气泡从设置于所述板状构件和所述基板之间的间隙的周边部向外部排出。
17.一种凸点形成方法，其特征在于，
在包括由选自Cu、Al、Cr及Ti的电极构成材料形成的电极图案、形成于所述电极图案上的Pd层、以及形成于所述Pd层上的Au层的权利要求5所述的电极结构体上形成凸点时，包括以下工序：
向电极结构体上供给含有导电性粒子和发泡剂的流动体的工序(a)；
隔着所述流动体在所述电极结构体上配置板状构件的工序(b)；
对所述流动体加热，使所述发泡剂产生气泡，并且利用该气泡使所述导电性粒子在所述电极结构体上自聚集的工序(c)；以及
将进行了所述自聚集之后的所述导电性粒子再熔融，使该导电性粒子在所述电极图案上固化的工序(d)。
18.如权利要求9或17所述的凸点形成方法，其特征在于，
在所述工序(c)中，在加热工序中改变所述板状构件和所述基板之间的间隙的大小。
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US20100044091A1 (en) 2010-02-25
JP5147723B2 (ja) 2013-02-20

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