CN100536102C - 倒装片安装体和倒装片安装方法及倒装片安装装置 - Google Patents
倒装片安装体和倒装片安装方法及倒装片安装装置 Download PDFInfo
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- CN100536102C CN100536102C CNB2006800105045A CN200680010504A CN100536102C CN 100536102 C CN100536102 C CN 100536102C CN B2006800105045 A CNB2006800105045 A CN B2006800105045A CN 200680010504 A CN200680010504 A CN 200680010504A CN 100536102 C CN100536102 C CN 100536102C
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Abstract
本发明的倒装片安装体,包括:电路基板(213),具有多个连接端子(211);半导体芯片(206),具有与连接端子(211)相对配置的多个电极端子(207);箱形状的多孔片(205),设在半导体芯片(206)的电极端子(207)的形成面的相反侧,在半导体芯片(206)的外周边向电极端子(207)的形成面侧弯折,并抵接在电路基板(213)上;电路基板(213)的连接端子(211)与半导体芯片(206)的电极端子(207)通过焊料层(215)电连接,并且电路基板(213)与半导体芯片(206)由树脂(217)固定。由此,可以提供能够将半导体芯片安装到电路基板上的、生产性及可靠性良好的倒装片安装体和其安装方法及其安装装置。
Description
技术领域
本发明涉及将半导体芯片搭载在电路基板上的倒装片安装方法,特别涉及对于窄节距化的半导体芯片也能够对应的、生产性较高、并且连接的可靠性良好的倒装片安装体和倒装片安装方法及倒装片安装装置。
背景技术
近年来,随着在电子设备中使用的半导体集成电路(以下称作“半导体”)芯片的高密度、高集成化,半导体芯片的电极端子的多引脚、窄节距化迅速发展。在这些半导体芯片向电路基板的安装中,为了减少布线延迟而广泛使用倒装片安装。
此外,在倒装片安装中,一般在半导体芯片的电极端子上形成焊料凸块,将该焊料凸块与形成在电路基板上的连接端子一起接合。
但是,为了将电极端子数超过5000那样的下一代半导体芯片安装到电路基板上,需要形成对应于100μm以下的窄节距的焊料凸块,在目前的焊料凸块形成技术中,难以与其对应。
此外,由于需要形成对应于电极端子数的多个焊料凸块,所以为了实现低成本化,还要求每个芯片的搭载节拍的缩短带来的高生产性。
同样,半导体芯片为了对应于电极端子的增大,电极端子从周边配置变化为区域配置。
此外,因为高密度化、高集成化的要求,预想半导体工艺会从90nm向65nm、45nm发展。结果,布线的微细化进一步发展,所以区域配置的电极端子上的焊料凸块的形成以及半导体芯片的倒装片安装本身变得困难。
因此,希望有能够适用于今后的半导体工艺的发展的薄型、高密度化的倒装片安装方法。
以往,作为焊料凸块的形成技术,开发了镀覆法及丝网印刷法等。但是,镀覆法虽然适合于窄节距,但是有工序变得复杂等生产性问题。此外,丝网印刷虽然生产性良好,但在使用掩模的方面上不适合于窄节距化。
在这样的状况下,最近开发出了一些在半导体芯片或电路基板的电极端子上有选择地形成焊料凸块的技术。这些技术不仅适合于细微的焊料凸块的形成,而且能够将焊料凸块一起形成,所以生产性良好,作为能够适合于下一代半导体芯片向电路基板的安装的技术受到关注。
其中之一,有称作焊料膏法的技术。该技术是将焊料粉与焊剂的混合物的焊料膏整体涂敷在表面形成了电极端子的电路基板上,通过将电路基板加热而使焊料粉熔融、在浸润性较高的电极端子上有选择地形成焊料凸块的技术(例如参照专利文献1)。
此外,有称作超级焊料法的技术。该技术是将以有机酸铅盐和金属锡为主要成分的膏状组成物(化学反应析出型焊料)整体涂敷在形成有电极端子的电路基板上,通过将电路基板加热而产生Pb与Sn的置换反应,使Pb/Sn的合金有选择地析出在基板的电极端子上的技术(例如参照专利文献2)。
此外,在以往的倒装片安装中,在将半导体芯片搭载在形成有焊料凸块的电路基板上后,为了将半导体芯片固定在电路基板上,还需要将称作底部填料的树脂注入到半导体芯片与电路基板之间的工序。由此,还有工序数增加及成品率降低的问题。
所以,作为同时进行半导体芯片与电路基板的相对的电极端子间的电连接、和半导体芯片向电路基板的固定的方法,开发了使用各向异性导电材料的倒装片安装技术。这是一种将含有导电粒子的热固化性树脂供给到电路基板与半导体芯片之间,在将半导体芯片加压的同时将热固化性树脂加热,由此同时实现半导体芯片与电路基板的电极端子间的电连接、和半导体芯片向电路基板的固定的方法(例如参照专利文献3)。
但是,在专利文献1所示那样的焊料膏法及专利文献2所示那样的超级焊料法中,如果单纯地将膏状组成物通过涂敷供给到电路基板上,则会发生局部的厚度及浓度的不均匀,在每个电极端子上焊料析出量不同,所以不能得到高度均匀的焊料凸块。此外,这些方法由于通过涂敷将膏状组成物供给到在表面上形成有电极端子的有凹凸的电路基板上,所以对于作为凸部的电极端子上不能供给充分的焊料量,难以得到在倒装片安装中需要的希望的焊料凸块的高度。
此外,在专利文献3所示那样的倒装片安装方法中,在生产性及可靠性方面有如以下所示的要解决的许多问题。
这些问题是,第1,由于通过经由导电粒子的机械接触来得到电极端子间的电导通,所以难以实现稳定的导通状态。第2,由于根据在半导体芯片与电路基板的电极端子之间存在的导电粒子的量而间隔不一定,所以电气接合是不稳定的。第3,在使热固化性树脂固化的热工艺中,会发生导电粒子飞散而短路带来的成品率的降低。第4,由于半导体芯片与电路基板的接合部为露出的构造,所以会发生湿度等的浸入,电路基板的寿命及可靠性会降低等。
专利文献1:日本特开2000-94179号公报
专利文献2:日本特开平1-157796号公报
专利文献3:日本特开2000-332055号公报
发明内容
本发明是为了解决上述问题而做出的,目的是提供一种倒装片安装体和倒装片安装方法及倒装片安装装置,能够将电极端子数超过5000那样的下一代半导体芯片安装到电路基板上,生产性及可靠性良好。
本发明的倒装片安装体的特征在于,包括:电路基板,具有多个连接端子;半导体芯片,具有与上述连接端子相对配置的多个电极端子;箱形状的多孔片,设在上述半导体芯片的上述电极端子的形成面的相反侧,在上述半导体芯片的外周边向上述电极端子的形成面侧弯折,并抵接在上述电路基板上;上述电路基板的上述连接端子与上述半导体芯片的上述电极端子通过焊料层电连接,并且上述电路基板与上述半导体芯片由树脂固定。
本发明的倒装片安装方法,使具有多个电极端子的半导体芯片与具有多个连接端子的电路基板相对地配置,将上述电路基板的连接端子与上述半导体芯片的电极端子电连接,其特征在于,包括:在将上述半导体芯片粘接在多孔片上后,使周边变形的工序;将以焊料粉和对流添加剂及树脂为主成分的焊料树脂组成物,涂敷在上述电路基板或上述半导体芯片上的工序;将上述多孔片定位配置在上述电路基板上的工序;将上述焊料树脂组成物加热到上述焊料粉熔融的温度,通过上述对流添加剂的沸腾或分解来产生气体的工序;在上述气体对流并通过上述多孔片而飞散之前,使熔融的上述焊料粉在上述树脂组成物中流动,使上述焊料粉自己集合及成长,从而使上述连接端子和上述电极端子电连接的工序。
本发明的另一倒装片安装方法,使具有多个电极端子的半导体芯片与具有多个连接端子的电路基板相对地配置,将上述电路基板的连接端子与上述半导体芯片的电极端子电连接,其特征在于,包括:将多孔片变形为覆盖上述半导体芯片的箱形状的工序;将上述半导体芯片接合在上述多孔片的箱形状的内侧底部上的工序;将以焊料粉和对流添加剂及树脂为主成分的焊料树脂组成物,涂敷在上述电路基板或上述半导体芯片上的工序;将上述多孔片定位配置在上述电路基板上的工序;将上述树脂组成物加热到上述焊料粉熔融的温度,通过上述对流添加剂的沸腾或分解来产生气体的工序;在上述气体对流并通过上述多孔片而飞散之前,使熔融的上述焊料粉在上述树脂组成物中流动,使上述焊料粉自己集合及成长,从而使上述连接端子和上述电极端子电连接的工序。
本发明的又另一倒装片安装方法,使具有多个电极端子的半导体芯片与具有多个连接端子的电路基板相对地配置,将上述电路基板的连接端子与上述半导体芯片的电极端子电连接,其特征在于,包括:将上述半导体芯片粘接在多孔片上的工序;将以焊料粉和对流添加剂及树脂为主成分的焊料树脂组成物,涂敷在上述电路基板或上述半导体芯片上的工序;将上述多孔片定位配置在上述电路基板上的工序;使上述多孔片变形的工序;将上述树脂组成物加热到上述焊料粉熔融的温度,通过上述对流添加剂的沸腾或分解来产生气体的工序;在上述气体对流并通过上述多孔片而飞散之前,使熔融的上述焊料粉在上述树脂组成物中流动,使上述焊料粉自己集合及成长,从而使上述连接端子和上述电极端子电连接的工序。
本发明的再另一倒装片安装方法,使具有多个电极端子的半导体芯片与具有多个连接端子的电路基板相对地配置,将上述电路基板的连接端子与上述半导体芯片的电极端子电连接,其特征在于,包括:将以焊料粉和对流添加剂及树脂为主成分的焊料树脂组成物,涂敷在上述电路基板或上述半导体芯片上的工序;将上述半导体芯片定位配置在上述电路基板上的工序;将粘接剂涂敷在上述半导体芯片上,将多孔片粘接在上述半导体芯片上的工序;使上述多孔片变形的工序;
将上述树脂组成物加热到上述焊料粉熔融的温度,通过上述对流添加剂的沸腾或分解来产生气体的工序;在上述气体对流并通过上述多孔片而飞散之前,使熔融的上述焊料粉在上述树脂组成物中流动,通过使上述熔融焊料粉自己集合及成长,使上述连接端子和上述电极端子电连接的工序。
本发明的倒装片安装装置,将半导体芯片以倒装片方式安装在电路基板上,其特征在于,包括:固定机构,将上述半导体芯片固定在多孔片上;变形机构,使上述多孔片的周边沿着上述半导体芯片的外周变形;涂敷机构,将以焊料粉和对流添加剂及树脂为主成分的焊料树脂组成物,涂敷在上述电路基板或上述半导体芯片上;定位机构,在上述电路基板上保持上述多孔片来定位上述半导体芯片;加热机构,使上述树脂组成物的上述焊料粉熔融。
附图说明
图1A~图1C是表示本发明的一实施例的倒装片安装方法的基本工序机理的剖视图。
图2是本发明的实施方式1的倒装片安装体的剖视图。
图3A~图3E是表示本发明的实施方式1的倒装片安装体与倒装片安装方法的工序剖视图。
图4A~图4D是表示本发明的实施方式2的倒装片安装体与倒装片安装方法的工序剖视图。
图5A~图5D是表示本发明的实施方式3的倒装片安装体与倒装片安装方法的工序剖视图。
图6A~图6D是表示本发明的实施方式4的倒装片安装体与倒装片安装方法的工序剖视图。
具体实施方式
本发明的安装体将电路基板的连接端子与半导体芯片的电极端子用焊料层电连接。该焊料层是焊料粒子集合而形成为焊料接合体的。该焊料层是通过将含有焊料粒子、树脂与对流添加剂的树脂膏加热,使对流添加剂沸腾而在树脂中产生对流,使焊料粒子集合,将连接端子与电极端子之间连结而形成的。即,通过加热,膏中的对流添加剂发生沸腾,伴随着该沸腾,焊料粒子集合。此时,使焊料粒子也熔融,则焊料粒子自己集合到浸润性较高的连接端子和电极端子上,能够形成为焊料层。在半导体芯片的电极端子的形成面的相反侧,设有在半导体芯片的外周边向电极端子的形成面侧弯折、抵接在电路基板上的箱状的多孔片。该多孔片是为了在使焊料粒子在电路基板的连接端子与半导体芯片的电极端子之间集合而形成焊料层时、使气化的对流添加剂散逸到外部、以及保持电路基板的连接端子与半导体芯片的电极间的间隙及位置而使用的。
上述多孔片也可以是覆盖半导体芯片、在其开口周边上具有周端边突出的凸缘的箱形状。
进而,多孔片也可以具有连通至表背侧的空孔。
进而,多孔片也可以是由热塑性树脂、热固化树脂、无纺布、发泡金属构成的可通气的材料。
进而,多孔片的空孔也可以由树脂密封。
进而,多孔片的周边的与电路基板接触的部分也可以由树脂接合或密封。
通过这些结构,能够实现连接等的可靠性及机械强度良好的倒装片安装体。
在本发明方法中,使多孔片变形的工序也可以是伴随着加热的工序。
进而,多孔片也可以在使其周边变形的工序中覆盖半导体芯片而被加工为箱形状,通过箱形状的多孔片的开口周端边接触在电路基板上,将半导体芯片与电路基板以规定的间隔配置。
进而,多孔片也可以覆盖半导体芯片、被加工为在其开口周边上具有周端边突出的凸缘的箱形状。
通过这些方法,将半导体芯片的电极端子与电路基板的连接端子的间隙保持为最合适的距离,所以通过电极端子与连接端子之间的均匀的接合,不易发生断线及高电阻接合等,能够提高成品率。
进而,多孔片也可以具有连通至表背侧的空孔。
进而,多孔片也可以是由热塑性树脂、热固化树脂、无纺布、发泡金属构成的可通气的材料。
进而,也可以是,在树脂组成物中含有的树脂通过电路基板的加热而浸透到多孔片,将多孔片的空孔封闭,通过在电路基板的加热结束后固化,降低或防止透湿性。
进而,也可以通过在树脂组成物中含有的树脂将多孔片周边的与电路基板相接的部分接合或密封。
通过这些方法,能够降低半导体芯片的因湿度及水分等带来的劣化,能够提高可靠性及寿命。此外,由于能够可靠地进行半导体芯片的接合,所以能够实现耐振动性及耐冲击性良好的电路基板。
进而,也可以包围电路基板的连接端子地设置电极。
进而,包围电路基板的连接端子地设置的电极,也可以形成为位于被加工为箱形状的多孔片的内侧,通过电路基板的加热工序而形成虚设凸块。
进而,通过加热工序形成虚设凸块的电极也可以防止涂敷在电路基板的半导体芯片之间的树脂组成物中的焊料粉的通过,并且使树脂能够通过。
通过这些方法,通过形成虚设凸块的电极能够防止涂敷在电路基板与半导体芯片之间的树脂组成物中的焊料粉的飞散或向外部的流出。并且,通过防止与相邻的半导体芯片因飞散的焊料粉造成的接触或短路等,能够实现可靠性及成品率的提高。
此外,由于焊料粉在形成虚设凸块的电极上自己成长,所以限制了焊料粉的通过,另一方面,树脂能够通过。因此,树脂组成物中的树脂适量地从形成虚设凸块的电极流出,浸入到多孔片的外周端与电路基板之间而流出停止。结果,能够通过浸入的树脂将多孔片与电路基板可靠地固接。
此外,本发明的倒装片安装装置是将半导体芯片以倒装片方式安装在电路基板上的倒装片安装装置,具有:固定机构,将半导体芯片固定在多孔片上;变形机构,使多孔片的周边沿着半导体芯片的外周变形;涂敷机构,将以焊料粉和对流添加剂及树脂为主成分的焊料树脂组成物涂敷在电路基板或半导体芯片上;定位机构,保持多孔片地将半导体芯片定位在电路基板上;加热机构,使树脂组成物的焊料粉熔融。通过该装置,能够可靠性良好、低成本、生产性良好地制造倒装片安装体。
另外,在本发明中,所谓的主成分,是指80质量%以上、优选为90质量%以上。
在上述中,焊料粒子的熔点优选为100℃以上300℃以下的范围。
此外,焊料粒子的平均粒子直径优选为1~50μm的范围。
此外,将焊料树脂膏加热的温度优选为焊料的熔点以上。
焊料树脂膏由树脂、焊料粒子和在将上述树脂加热时沸腾的对流添加剂构成,作为树脂,使用热固化性树脂(例如环氧树脂),作为焊料粒子使用无铅焊料粒子。作为对流添加剂,可以使用溶剂(例如有机溶剂),如果举出一例,则可以使用异丁醇(沸点82.4℃)、醋酸丁酯(沸点125~126℃)、二乙二醇一丁醚(二甘醇-丁基醚,沸点201.9℃)、乙二醇(沸点197.6℃)等。对于对流添加剂在树脂中的含有量并没有特别限制,优选地以0.1~20重量%的比例含有在树脂中。
此外,对流添加剂的所谓的“对流”,是指作为运动方式的对流,只要是通过使在树脂中沸腾的对流添加剂运动,对分散到树脂中的焊料粒子赋予运动能量、带来促进焊料粒子的移动的作用的运动,是怎样的方式都可以。另外,对流添加剂除了其自身沸腾而产生对流以外,也可以使用通过树脂的加热而产生气体(H2O、CO2、N2等气体)的对流添加剂,作为这样的例子,可以举出含有结晶水的化合物,通过加热而分解的化合物、或者发泡剂。
焊料粒子可以选择任意的材料来使用。例如,可以举出下面的表1所示的材料。作为一例而举出的表1所示的材料既可以单独使用,也可以适当组合来使用。另外,如果使用焊料粒子的熔点比热固化性树脂的固化温度低的材料,则在使树脂流动而自己集合后,进一步将树脂加热而使其固化,能够进行电连接和树脂的密封的方面是优选的。
[表1]
焊料粒子的组成 | 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 |
焊料粒子的优选的熔点是100~300℃,更优选地如表1所示那样为139~240℃。在熔点不到100℃的情况下,有在耐久性方面产生问题的倾向。如果熔点超过300℃,则树脂的选择变得困难。
焊料粒子的优选的平均粒子直径是1~30μm的范围,更优选为5~20μm的范围。在平均粒子直径不到1μm的情况下,因焊料粒子的表面氧化而熔融变得困难,并且有为了形成电连接体而过多耗费时间的倾向。如果平均粒子直径超过30μm,则难以通过沉降得到电连接体。另外,平均粒子直径可以通过市售的粒度分布计测量。例如,可以使用崛场制作所激光衍射粒度测量器(LA920)、岛津制作所激光衍射粒度测量器(SALD2100)等测量。
接着,对树脂进行说明。作为树脂的代表性的例子,可以使用环氧树脂、酚醛树脂、硅树脂、邻苯二甲酸二烯丙基酯、呋喃树脂、三聚氰胺树脂等热固化性树脂,聚酯弹性体、氟树脂、聚酰亚胺树脂、聚酰胺树脂、芳香族聚酰胺树脂等热塑性树脂,或者光(紫外线)固化树脂等,或者将它们组合后的材料。
焊料粒子与树脂的配合比例优选体积比为导电粒子∶树脂=50~5∶95~50的范围,更优选为导电粒子∶树脂=40~10∶90~60。焊料粒子与树脂优选地在均匀混合后使用。例如使焊料粒子为20体积%、环氧树脂为80体积%,在混匀器中成为均匀混合状态来使用它。另外,也可以在焊料粒子保持为分散的状态下做成膏状,也可以使用形成为片状的树脂。
进而,在本发明的优选例中,作为焊料粒子,可以使用例如无铅而熔点为200~250℃的焊料合金粒子。此外,在树脂是热固化性树脂的情况下,优选地使树脂的固化温度比焊料的熔点高。如果这样,则可以在形成电连接体或形成金属凸块的工序中使树脂固化,能够缩短作业工序。
根据本发明的倒装片安装体及其安装方法,能够进行半导体芯片与电路基板的连接较可靠的安装方法,并且通过对于湿度等的耐候性的提高,能够实现电路基板的长寿命化及可靠性良好的倒装片安装体。进而,能够使电极端子与连接端子间的接合状态变得均匀,所以还能够发挥成品率较高、生产效率也提高的效果。
图1A~图1C是表示本发明的一例的基本工序机理的剖视图。首先,如图1A所示,向形成有多个连接端子11的电路基板10,供给含有焊料粉12、对流添加剂13以及树脂14的树脂组成物15。
接着,如图1B所示,夹着供给到电路基板10与半导体芯片20之间的树脂组成物15,使电路基板10与半导体芯片20抵接。此时,使具有多个电极端子21的半导体芯片20与具有多个连接端子11的电路基板10相对地配置。接着,在此状态下,将电路基板10加热,使树脂组成物15熔融。这里,在电路基板10的加热温度比焊料粉12的熔点高的温度下进行。熔融的焊料粉12在熔融的树脂组成物15中相互结合,如图1C所示,通过自己集合到浸润性较高的连接端子11与电极端子21之间,形成焊料接合体22。
接着,通过使树脂14固化,使半导体芯片20固定在电路基板10上。
该方法的特征是在含有焊料粉12的树脂组成物15中还含有在焊料粉12熔融的温度下沸腾的对流添加剂13这一点。即,在焊料粉12熔融的温度下,在树脂组成物15中含有的对流添加剂13沸腾。并且,通过使沸腾的对流添加剂13在树脂组成物14中对流,促进了在树脂组成物14中浮游的熔融的焊料粉12的移动。结果,均匀地成长的熔融焊料粉自己集合到浸润性较高的电路基板10的连接端子11与半导体芯片20的电极端子21之间,从而在连接端子11与电极端子21之间经由均匀而微细的焊料接合体22电连接。
即,上述方法想要通过在含有焊料粉的树脂组成物中还含有对流添加剂,来附加使熔融的焊料粉强制地移动的手段。另外,对流添加剂可以是通过加热而沸腾或蒸发的溶剂,在工序结束后,在树脂组成物中几乎没有残留。
本发明是立足于与此同样的技术观点,来更可靠地实现可靠性较高的新的倒装片安装方法的技术。并且,通过本发明的实施,能够成品率很高地生产进行了倒装片安装的电路基板。
以下,参照附图详细地说明本发明的实施方式。另外,为了使理解变得容易,而使附图任意地放大表示。
(实施方式1)
图2是本发明的实施方式1的倒装片安装体的剖视图。在图2中,本发明的实施方式1的倒装片安装体200具有如下结构:形成在电路基板213上的多个连接端子211与相对配置的具有多个连接端子207的半导体芯片206,通过焊料层215电连接。并且,在半导体芯片206的连接端子207的形成面的相反侧设置的多孔片205,在半导体芯片206的外周边向连接端子207的形成面侧弯折为箱形状209,覆盖半导体芯片206而形成,箱形状209的端面抵接在电路基板213上。进而,由电路基板213与箱形状的多孔片205形成的空间内,通过对将连接端子211与连接端子207电连接的焊料层215及其周围进行覆盖的树脂217,将半导体芯片206与电路基板213固定,构成倒装片安装体200。
以下,利用图3A~图3E,说明本发明的实施方式1的倒装片安装体与倒装片安装方法。
图3A~图3E是说明本发明的实施方式1的倒装片安装体与倒装片安装方法的概略工序剖视图。
首先,如图3A所示,上模201设有能够经由排气管204和由较小的孔构成的吸气通路203将空气排气而能够进行真空吸附的吸气管202。并且,多孔片205由例如不溶解于溶剂的热固化性树脂或热塑性树脂构成,是在表背侧具有气体能够通过的空孔的材质的部件。例如,可以使用PET(聚对苯二甲酸乙二醇酯)或PTFE(聚四氟乙烯)等具有可通气的微细多孔质的材质。另外,作为多孔片205的材料,除了树脂以外,也可以是无纺布、发泡金属等可通气的材料。
并且,在多孔片205上,粘接有在半导体芯片206的下表面上具有多个连接端子207的半导体芯片206。
接着,如图3B所示,将粘贴有半导体芯片206的多孔片205配置到上模201与下模208之间,通过加压,仅将多孔片205的端部沿着例如半导体芯片206的周边(外周)弯折,变形为箱形状209。此时,如果将上模201与下模208加热到适合于变形的温度(例如在PET的情况下为120℃),则多孔片205的形状的变形能够变得更容易,所以是优选的。
接着,如图3C所示,将下模208取除,在吸引着多孔片205与半导体芯片206的状态下使上模201移动到安装的电路基板213的位置。此时,通过照相机等的图像识别,将形成在电路基板213的表面上的连接端子211与半导体芯片206的连接端子207定位。进而,至少在电路基板213上安装着半导体芯片206的位置上,通过例如分配器等涂敷机构,涂敷含有焊料粉、对流添加剂及树脂的树脂组成物212。此外,在与电路基板213的连接端子211不短路的周围,设有例如形成防止焊料粉的飞散的虚设凸块的电极210。并且,虚设凸块形成用的电极210设在由多孔片205的箱形状209包围的范围内的电路基板213上。
接着,如图3D所示,使半导体芯片206与电路基板213夹着树脂组成物212接触。这里,半导体芯片206的连接端子207与电路基板213的连接端子211,通过多孔片205的箱形状209以规定的间隔相对。另外,规定的间隔是至少半导体芯片的电极端子与电路基板的连接端子不接触的程度、熔融焊料粉能够浸入的程度。
接着,至少从电路基板213侧,通过例如加热器等加热机构,加热到焊料粉熔融的温度,例如220℃~250℃左右。
通过该加热,涂敷在电路基板213上的树脂组成物212中的对流添加剂(未图示)沸腾或蒸发而气化,并且焊料粉(未图示)成为熔融焊料粉。并且,在气体通过被弯折为箱形状209的多孔片205的空孔而从排气管204向外部排出的过程中,通过对流使树脂组成物212中的熔融焊料粉移动。
进而,移动后的熔融焊料粉自己集合到相对配置的浸润性良好的半导体芯片206的连接端子207与电路基板213的连接端子211之间并成长。
如果说明具体的一例,则焊料树脂膏使用将85体积部分的双酚F型环氧树脂(ジヤパネポキシレジン公司制エピコ一ト806,含固化剂)、15体积部分的粒径10~25μm(平均粒子直径17μm)的SnAgCu粉、作为对流添加剂的3重量部分的异丙醇均匀地混合成的膏。将该树脂膏使用分配器注入到电路基板213与半导体芯片206之间,从室温(25℃)升温到250℃,保持30秒钟。然后冷却,如果观察截面,则可以确认图3E的状态。作为多孔片,使用厚度约30μm的PTFE的多孔质膜。
即,如图3E所示,形成将连接端子207与连接端子211电连接的焊料层215,通过将上模201拆下,制作出倒装片安装体250。此外,焊料粉也在虚设凸块形成用的电极210上自己集合而成长,形成虚设凸块214。通过形成该虚设凸块214,没有在焊料层215的形成中使用的熔融焊料粉被捕捉到虚设凸块形成用的电极210上,防止了向外部的流出。
另外,在焊料粉不飞散或即使飞散也不产生问题的情况下,并不一定需要设置虚设凸块形成用的电极210,不设置电极210的结构为图2所示的倒装片安装体200。
另一方面,树脂组成物212中的树脂217,在虚设凸块214的形成过程中有可能向外部露出一些。因此,在气化的对流添加剂几乎都从排气管204排出后,因加热而暂时粘性降低的树脂通过毛细管现象浸透到多孔片205的空孔中,将空孔填埋。由此,浸透到多孔片205内的空孔中的树脂217在固化后将多孔片205的空孔封闭,防止来自外部的湿度等的浸入。
此外,固化后的树脂217将半导体芯片206与电路基板213固定,并且通过从虚设凸块214露出的树脂217,使以箱形状209弯折的多孔片205的周边端部与电路基板213粘接、固定。
根据本发明的实施方式1,电路基板的连接端子与半导体芯片的电极端子的连接可以通过自己集合的焊料层可靠地进行。
此外,电路基板与半导体芯片的间隔能够通过变形为箱形状的多孔片保持为一定且均匀。
此外,由于焊料粉的飞散被围绕半导体芯片的虚设凸块形成用的电极抑制,所以不再有焊料粉向外部的飞散带来的影响。结果,不易发生接触部分或半导体芯片间的短路等,能够实现品质良好的电路基板。
此外,由于多孔片最终成为湿度等难以通过的构造,所以半导体芯片的耐候性提高,还具有能够实现可靠性的提高及长期间的使用的效果。
(实施方式2)
图4A~图4D是说明本发明的实施方式2的倒装片安装体与倒装片安装方法的概略工序图。另外,在图4A~图4D中,对于与图3~E相同的结构要素使用相同的标号而省略说明。
这里,本发明的实施方式2的倒装片安装体300与实施方式1的倒装片安装体250的安装方法不同,其他结构相同。
首先,如图4A所示,预先将电路基板213上的连接端子211与半导体芯片206的连接端子207相对配置。接着,将成为膏状的以焊料粉、对流添加剂及树脂为主成分的树脂组成物212,通过例如分配器等涂敷并夹入在半导体芯片206与电路基板213之间。进而,将多孔片205与半导体芯片206定位而粘接在半导体芯片206上。
接着,如图4B所示,使模具220从上部下降,以使其将半导体芯片206拉入。在此情况下,模具220为了使多孔片205的变形变得容易而优选地进行加热。
接着,如图4C所示,通过模具220使多孔片205沿着半导体芯片206的外周变形为箱形状209。另外,优选地在比半导体芯片206稍大的周边位置进行变形,以便不会发生半导体芯片206的损坏。
接着,经由吸气通路203通过吸气管202的吸引作用,将多孔片205与半导体芯片206拉入到模具220的内部中。由此,多孔片205变形为模具220的形状。接着,通过模具220抵接在电路基板213的表面上,将半导体芯片206与电路基板213的间隔保持为一定。另外,该间隔是至少半导体芯片的电极端子与电路基板的连接端子不接触的程度、熔融焊料粉不能浸入的程度。
进而,在图4C的状态下,通过模具220的加热、或从电路基板213的下表面侧通过例如加热器(未图示)等加热机构,加热到例如焊料粉熔融、对流添加剂沸腾或蒸发而气体216化的温度、例如220℃~250℃。
通过该加热,涂敷在电路基板213上的树脂组成物212中的对流添加剂(未图示)沸腾或蒸发而气体216化,并且焊料粉(未图示)成为熔融焊料粉。接着,在气体216通过被弯折成箱形状209的多孔片205的空孔从排气管204排出到外部的过程中,通过对流使树脂组成物212中的熔融焊料粉移动。
进而,移动的熔融焊料粉自己集合到相对配置的浸润性良好的半导体芯片206的连接端子207与电路基板213的连接端子211之间并成长。
由此,如图4D所示,形成将连接端子207与连接端子211电连接的焊料层215,通过将模具220拆下,制作成倒装片安装体300。217是树脂。
此外,在虚设凸块形成用的电极210上熔融焊料粉也自己集合而成长,形成虚设凸块214。通过形成该虚设凸块214,没有在焊料层215的形成中使用的熔融焊料粉被捕捉到虚设凸块形成用的电极210上,防止了向外部的流出。
另外,虚设凸块形成用的电极210在焊料粉不飞散的情况及即使飞散也不发生问题的情况下,并不一定需要设置。
如以上所述,根据本发明的实施方式2,具有与实施方式1同样的效果,并且不需要下模这一点,能够以简单化的设备进行生产。
此外,在多孔片是热塑性树脂、热固化性树脂或无纺布等的情况下,能够以很低的成本生产性良好地进行倒装片安装。
(实施方式3)
图5A~图5D是说明本发明的实施方式3的倒装片安装体与倒装片安装方法的概略工序图。另外,在图5A~图5D中,对于与图3A~图3E相同的结构要素使用相同的标号而省略说明。
这里,本发明的实施方式3的倒装片安装体400与实施方式1的倒装片安装体250在多孔片205上具有凸缘401这一点、和其安装方法不同,其他结构相同。
首先,如图5A所示,使多孔片205预先通过上模201和下模208变形为具备凸缘401的箱形状。
以下,通过将多孔片205的箱形状的端部弯折来设置凸缘401的例子进行说明,但并不限于此。在此情况下,在箱形状的变形中,由于半导体芯片没有粘接在多孔片205上,所以不需要考虑半导体芯片的可靠性,加压及加热等条件不受限制。因此,特别在多孔片205为发泡金属等受热难以变形的材料的情况下,本发明的实施方式3是有效的。进而,通过使用镍或铁等磁性材料作为发泡金属,还能够得到阻止由安装的半导体芯片的噪音的发生、或防止来自外部的噪音的屏蔽效果。
接着,如图5B所示,将下模208取除,在吸引着多孔片205的状态下,使上模201移动到预先将半导体芯片206的连接端子207和电路基板213的连接端子211相对配置的位置。此时,在半导体芯片206与电路基板213之间,通过例如分配器等涂敷、夹入有成为浆状的以焊料粉、对流添加剂及树脂为主成分的树脂组成物212。
此外,浆状的树脂组成物212优选地稍稍过量地供给,以使其在具有凸缘401的箱形状的多孔片205经由半导体芯片206被压入时稍向外侧扩展。结果,如图5C所示,通过将多孔片205经由半导体芯片206压入,浆状的树脂组成物212充满到具有凸缘401的箱形状的多孔片205的内部中。此外,此时半导体芯片206经由多孔片205的空孔被吸引到多孔片205中。因此,半导体芯片206与电路基板213通过具有凸缘401的多孔片205的箱形状209以规定的间隔相对。另外,规定的间隔是至少半导体芯片的电极端子与电路基板的连接端子不接触的程度、熔融焊料粉能够浸入的程度。
接着,在图5C所示的状态下,通过上模201的加热、或从电路基板213的下表面侧通过例如加热器402等加热机构,加热到例如焊料粉熔融、对流添加剂沸腾或蒸发而气体216化的温度、例如220℃~250℃。
通过该加热,涂敷在电路基板213上的树脂组成物212中的对流添加剂(未图示)沸腾或蒸发而气体216化,并且焊料粉(未图示)成为熔融焊料粉。接着,在气体216通过弯折为具有凸缘401的箱形状的多孔片205的空孔从排气管204排出到外部的过程中,通过对流使树脂组成物212中的熔融焊料粉移动。
进而,移动的熔融焊料粉自己集合到相对配置的浸润性良好的半导体芯片206的连接端子207与电路基板213的连接端子211之间并成长。由此,如图5D所示,形成将连接端子207与连接端子211电连接的焊料层215,通过将上模201拆下,制作成被倒装片安装了的倒装片安装体400。217是树脂。
此外,熔融焊料粉被箱形状的多孔片205的凸缘401捕捉,不能向外部飞散。
进而,在气化的对流添加剂几乎都从排气管204排出后,通过加热而暂时粘性降低的树脂通过毛细管现象浸透到多孔片205的空孔中,将空孔填埋。由此,浸透到多孔片205内的空孔中的树脂在固化后将多孔片205的空孔封闭,防止来自外部的湿度等的浸入。
此外,固化后的树脂组成物中的树脂将半导体芯片206与电路基板213固定,并且树脂的一部分进入到箱形状的多孔片205的凸缘401的部分中,使多孔片205与电路基板213粘接、固定。即,在树脂被冷却而完全固化后,通过树脂的作用,使半导体芯片206与电路基板213、以及成为箱形状的多孔片205相互完全固定。
另外,在图5中,通过与半导体芯片的外周大致相同形状的箱形状的多孔片进行了说明,但并不限于此。例如,也可以与实施方式1同样,是比半导体芯片的外形大的箱形状的多孔片。
此外,在电路基板与多孔片的箱形状的端面的接合强度较大的情况下,不需要特别形成凸缘。
根据本发明的实施方式3,虽然没有使用防止焊料粉的飞散的虚设凸块形成用的电极,但通过形成在箱形状的多孔片的周围的凸缘,能够防止焊料粉及树脂的流出。此外,通过凸缘,使与电路基板的接合面积比没有凸缘的情况取得更大,所以电路基板与多孔片的接合变得牢固,并且对于变形等的可靠性进一步提高。
(实施方式4)
图6A~图6D是说明本发明的实施方式4的倒装片安装体与倒装片安装方法的概略工序图。另外,在图6A~图6D中,对于与图3A~图3E相同的结构要素使用相同的标号而省略说明。
这里,本发明的实施方式4的倒装片安装体500与实施方式3的倒装片安装体400的安装方法不同,其他结构相同。
此外,在本实施方式4中,使多孔片205变形的工序由于与表示实施方式3的工序的图5A相同,所以省略。
首先,如图6A所示,预先将半导体芯片206经由多孔片205的空孔真空吸附到多孔片205的内表面上。
接着,如图6B所示,通过例如分配器等涂敷机构,将膏状的以焊料粉、对流添加剂及树脂为主成分的树脂组成物212涂敷在半导体芯片206的下表面上。当然,树脂组成物212的涂敷也可以在电路基板213上进行。然后,一边将电路基板213的连接端子211与半导体芯片206的连接端子207定位,一边使上模201下降。
接着,如图6C所示,将半导体芯片206与电路基板213配置到多孔片205内。此时,将半导体芯片206的连接端子207与电路基板213的连接端子211定位,以使其以规定的间隔相对。另外,所谓规定的间隔,是至少半导体芯片的电极端子与电路基板的连接端子不接触的程度,是熔融焊料粉能够浸入的程度。
接着,在上述状态下,通过上模201的加热、或从电路基板213的下表面侧通过例如加热器402等加热机构,加热到例如焊料粉熔融、对流添加剂沸腾或蒸发而气体216化的温度、例如220℃~250℃。
通过该加热,涂敷在电路基板213上的树脂组成物212中的对流添加剂(未图示)沸腾或蒸发而气体216化,并且焊料粉(未图示)成为熔融焊料粉。接着,在气体216通过弯折为具有凸缘401的箱形状的多孔片205的空孔从排气管204排出到外部的过程中,通过对流使树脂组成物212中的熔融焊料粉移动。
进而,移动的熔融焊料粉自己集合到相对配置的浸润性良好的半导体芯片206的连接端子207与电路基板213的连接端子211之间并成长。由此,如图6D所示,形成将连接端子207与连接端子211电连接的焊料层215,通过将上模201拆下,制作成被倒装片安装了的倒装片安装体500。217是树脂。
如以上所述,根据本发明的实施方式4,能够得到与各实施方式同等的效果,并且与实施方式3相比较,由于将多孔片205与半导体芯片206一体地输送,所以真空吸附时的空气的漏入较少,能够实现稳定的输送。
以上,通过各实施方式说明了本发明,但这样的记述并不是限定事项,能够进行各种改变。例如,作为含有焊料粉与对流添加剂的树脂,以热固化性树脂为例进行了说明,但是,如果多孔片对光是透过性的树脂,则也可以使用例如在焊料粉的熔融温度以上具有流动性的光固化性树脂、或使用它们的并用型树脂。
此外,在本发明的各实施方式中,半导体芯片以一个的情况为例进行了说明,但实际上能够将多个同时配置在电路基板上、进行各工序的作业。
此外,在本发明的各实施方式中,多孔片的箱形状以直角地弯折的形状进行了说明,但并不限于此。例如也可以是锥形状。由此,能够扩大通过对流添加剂的沸腾等产生的气体通过多孔片的空孔排出的面积,所以能够容易地进行固化温度及时间等的调节。
此外,在本发明的各实施方式中,以从电路基板侧的加热的情况为例进行了说明,但也可以从保持多孔片及半导体芯片的模具侧加热,还可以从两者进行加热。
此外,在本发明的各实施方式中,作为树脂组成物中的树脂,也可以使用以环氧树脂、不饱和聚酯树脂、聚丁二烯、聚酰亚胺树脂、聚酰胺树脂、氰酸盐树脂的任一种为主材的树脂。
进而,在本发明的各实施方式中,作为对流添加剂,可以使用分解型的碳酸氢钠、偏硼酸铵、氢氧化铝、片钠铝石、偏硼酸钡、作为沸腾蒸发型而使用二乙二醇一丁醚、焊剂、异丁醇、二甲苯、异戊醇、醋酸丁酯、四氟乙烯、甲基异丁基甲酮、二甘醇一乙醚乙酸酯、二乙二醇一丁醚、乙二醇等中沸点溶剂或高沸点溶剂。
工业实用性
根据本发明,能够用于使窄节距发展的下一代半导体芯片的倒装片安装中,并且在要求生产性及可靠性良好的倒装片安装的领域中是具有实用性的。
Claims (21)
1、一种倒装片安装体,其特征在于,包括:
电路基板,具有多个连接端子;
半导体芯片,具有与上述连接端子相对配置的多个电极端子;及
箱形状的多孔片,设在上述半导体芯片的上述电极端子的形成面的相反侧,在上述半导体芯片的外周边向上述电极端子的形成面侧弯折,并抵接在上述电路基板上;
上述电路基板的上述连接端子与上述半导体芯片的上述电极端子通过焊料层电连接,并且上述电路基板与上述半导体芯片由树脂固定。
2、如权利要求1所述的倒装片安装体,其特征在于,上述多孔片覆盖上述半导体芯片,被加工为在其开口周边具有周端边突出的凸缘的箱形状。
3、如权利要求1所述的倒装片安装体,其特征在于,上述多孔片具有从表面连通至背面的空孔。
4、如权利要求1所述的倒装片安装体,其特征在于,上述多孔片是从热塑性树脂、热固化树脂、无纺布及发泡金属中选择的可通气的材料。
5、如权利要求3所述的倒装片安装体,其特征在于,上述多孔片的上述空孔由上述树脂密封。
6、如权利要求1所述的倒装片安装体,其特征在于,上述多孔片周边的与上述电路基板连接的部分由上述树脂接合或密封。
7、一种倒装片安装方法,使具有多个电极端子的半导体芯片与具有多个连接端子的电路基板相对地配置,将上述电路基板的连接端子与上述半导体芯片的电极端子电连接,其特征在于,包括:
在将上述半导体芯片粘接在多孔片上后,使周边变形的工序;
将以焊料粉和对流添加剂及树脂为主成分的焊料树脂组成物,涂敷在上述电路基板或上述半导体芯片上的工序;
将上述多孔片定位配置在上述电路基板上的工序;
将上述焊料树脂组成物加热到上述焊料粉熔融的温度,通过上述对流添加剂的沸腾或分解来产生气体的工序;及
在上述气体对流并通过上述多孔片而飞散之前,使熔融的上述焊料粉在上述树脂组成物中流动,使上述焊料粉自己集合及成长,从而使上述连接端子和上述电极端子电连接的工序。
8、如权利要求7所述的倒装片安装方法,其特征在于,使上述多孔片变形的工序是伴随着加热的工序。
9、如权利要求7所述的倒装片安装方法,其特征在于,上述多孔片在使其周边变形的工序中,覆盖上述半导体芯片而被加工为箱形状,通过箱形状的上述多孔片的开口周端边抵接在上述电路基板上,将上述半导体芯片与上述电路基板以规定的间隙配置。
10、如权利要求9所述的倒装片安装方法,其特征在于,上述多孔片覆盖上述半导体芯片,被加工为在其开口周边上具有周端边突出的凸缘的箱形状。
11、如权利要求7所述的倒装片安装方法,其特征在于,上述多孔片具有从表面连通至背面的空孔。
12、如权利要求7所述的倒装片安装方法,其特征在于,上述多孔片是从热塑性树脂、热固化树脂、无纺布及发泡金属中选择的至少一个可通气的材料。
13、如权利要求7所述的倒装片安装方法,其特征在于,在上述树脂组成物中含有的上述树脂通过上述电路基板的加热而浸透到上述多孔片,将上述多孔片的空孔封闭,通过在上述电路基板的加热结束后固化,降低或防止透湿性。
14、如权利要求7所述的倒装片安装方法,其特征在于,通过在上述树脂组成物中含有的上述树脂将上述多孔片周边的与上述电路基板接触的部分接合或密封。
15、如权利要求7所述的倒装片安装方法,其特征在于,包围上述电路基板的上述连接端子地设置电极。
16、如权利要求7所述的倒装片安装方法,其特征在于,包围上述电路基板的上述连接端子地设置的电极,被形成为位于被加工为箱形状的上述多孔片的内侧,通过上述电路基板的加热工序而形成虚设凸块。
17、如权利要求16所述的倒装片安装方法,其特征在于,通过上述加热工序形成虚设凸块的电极,防止涂敷在上述电路基板的上述半导体芯片之间的上述树脂组成物中的上述焊料粉的通过,并且使上述树脂能够通过。
18、一种倒装片安装方法,使具有多个电极端子的半导体芯片与具有多个连接端子的电路基板相对地配置,将上述电路基板的连接端子与上述半导体芯片的电极端子电连接,其特征在于,包括:
将多孔片变形为覆盖上述半导体芯片的箱形状的工序;
将上述半导体芯片接合在上述多孔片的箱形状的内侧底部上的工序;
将以焊料粉和对流添加剂及树脂为主成分的焊料树脂组成物,涂敷在上述电路基板或上述半导体芯片上的工序;
将上述多孔片定位配置在上述电路基板上的工序;
将上述树脂组成物加热到上述焊料粉熔融的温度,通过上述对流添加剂的沸腾或分解来产生气体的工序;及
在上述气体对流并通过上述多孔片而飞散之前,使熔融的上述焊料粉在上述树脂组成物中流动,使上述焊料粉自己集合及成长,从而使上述连接端子和上述电极端子电连接的工序。
19、一种倒装片安装方法,使具有多个电极端子的半导体芯片与具有多个连接端子的电路基板相对地配置,将上述电路基板的连接端子与上述半导体芯片的电极端子电连接,其特征在于,包括:
将上述半导体芯片粘接在多孔片上的工序;
将以焊料粉和对流添加剂及树脂为主成分的焊料树脂组成物,涂敷在上述基板或上述半导体芯片上的工序;
将上述多孔片定位配置在上述电路基板上的工序;
使上述多孔片变形的工序;
将上述树脂组成物加热到上述焊料粉熔融的温度,通过上述对流添加剂的沸腾或分解来产生气体的工序;及
在上述气体对流并通过上述多孔片而飞散之前,使熔融的上述焊料粉在上述树脂组成物中流动,使上述焊料粉自己集合及成长,从而使上述连接端子和上述电极端子电连接的工序。
20、一种倒装片安装方法,使具有多个电极端子的半导体芯片与具有多个连接端子的电路基板相对地配置,将上述电路基板的连接端子与上述半导体芯片的电极端子电连接,其特征在于,包括:
将以焊料粉和对流添加剂及树脂为主成分的焊料树脂组成物,涂敷在上述电路基板或上述半导体芯片上的工序;
将上述半导体芯片定位配置在上述电路基板上的工序;
将粘接剂涂敷在上述半导体芯片上,将多孔片粘接在上述半导体芯片上的工序;
使上述多孔片变形的工序;
将上述树脂组成物加热到上述焊料粉熔融的温度,通过上述对流添加剂的沸腾或分解来产生气体的工序;及
在上述气体对流并通过上述多孔片而飞散之前,使熔融的上述焊料粉在上述树脂组成物中流动,通过使上述熔融焊料粉自己集合及成长,使上述连接端子和上述电极端子电连接的工序。
21、一种倒装片安装装置,将半导体芯片以倒装片方式安装在电路基板上,其特征在于,包括:
固定机构,将上述半导体芯片固定在多孔片上;
变形机构,使上述多孔片的周边沿着上述半导体芯片的外周变形;
涂敷机构,将以焊料粉和对流添加剂及树脂为主成分的焊料树脂组成物,涂敷在上述电路基板或上述半导体芯片上;
定位机构,在上述电路基板上保持上述多孔片来定位上述半导体芯片;及
加热机构,使上述树脂组成物的上述焊料粉熔融。
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JP3698704B2 (ja) | 2003-02-28 | 2005-09-21 | 株式会社加藤建設 | 地盤改良機械 |
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EP1873819A4 (en) * | 2005-04-06 | 2012-07-11 | Panasonic Corp | BALL CONNECTION METHOD AND CONNECTION BALL FORMATION METHOD |
US7745264B2 (en) * | 2007-09-04 | 2010-06-29 | Advanced Micro Devices, Inc. | Semiconductor chip with stratified underfill |
US20090212420A1 (en) * | 2008-02-22 | 2009-08-27 | Harry Hedler | integrated circuit device and method for fabricating same |
-
2006
- 2006-03-14 US US11/909,856 patent/US7732920B2/en not_active Expired - Fee Related
- 2006-03-14 CN CNB2006800105045A patent/CN100536102C/zh not_active Expired - Fee Related
- 2006-03-14 JP JP2007510367A patent/JP4397947B2/ja not_active Expired - Fee Related
- 2006-03-14 WO PCT/JP2006/305004 patent/WO2006103918A1/ja active Application Filing
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2010
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US20090008800A1 (en) | 2009-01-08 |
JP4397947B2 (ja) | 2010-01-13 |
US8071425B2 (en) | 2011-12-06 |
JPWO2006103918A1 (ja) | 2008-09-04 |
US20100203675A1 (en) | 2010-08-12 |
US7732920B2 (en) | 2010-06-08 |
CN101151723A (zh) | 2008-03-26 |
WO2006103918A1 (ja) | 2006-10-05 |
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