CN104425389A - 凸块电极、凸块电极基板以及其制造方法 - Google Patents

凸块电极、凸块电极基板以及其制造方法 Download PDF

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Publication number
CN104425389A
CN104425389A CN201410446263.5A CN201410446263A CN104425389A CN 104425389 A CN104425389 A CN 104425389A CN 201410446263 A CN201410446263 A CN 201410446263A CN 104425389 A CN104425389 A CN 104425389A
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Prior art keywords
solder
core
sec
electrode pad
salient pole
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CN201410446263.5A
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CN104425389B (zh
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服部贵洋
相马大辅
佐藤勇
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Senju Metal Industry Co Ltd
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Senju Metal Industry Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/20—Preliminary treatment of work or areas to be soldered, e.g. in respect of a galvanic coating
    • B23K1/203—Fluxing, i.e. applying flux onto surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/20—Preliminary treatment of work or areas to be soldered, e.g. in respect of a galvanic coating
    • H—ELECTRICITY
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
    • H01L21/4814—Conductive parts
    • H01L21/4846—Leads on or in insulating or insulated substrates, e.g. metallisation
    • H01L21/4853—Connection or disconnection of other leads to or from a metallisation, e.g. pins, wires, bumps
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    • H01L23/49811—Additional leads joined to the metallisation on the insulating substrate, e.g. pins, bumps, wires, flat leads
    • H01L23/49816—Spherical bumps on the substrate for external connection, e.g. ball grid arrays [BGA]
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    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
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    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
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Abstract

本发明涉及凸块电极、凸块电极基板以及其制造方法，研究焊料镀层的熔融工序，以便在电极焊盘上可以将成为凸块电极的核层的Cu球的中心在其水平截面上再现性良好地配置于所包覆的焊料的外壳的中心。具备接合于电极焊盘(12)上、施加焊料(14)到成为核层的Cu球(13)上的凸块电极(30)，在凸块电极(30)涂布助焊剂(16)之后，搭载于电极焊盘(12)上，加热电极焊盘(12)以及Cu核球而将焊料镀层(24)熔融的熔融工序中，将搭载有电极焊盘(12)以及Cu核球的基板(11)的加热率设定为0.01[℃/sec]以上～不足0.3[℃/sec]的范围。

Description

凸块电极、凸块电极基板以及其制造方法
技术领域
本发明涉及使用将焊料镀层包覆于成为核层的芯材的焊料接合体而形成的凸块电极，具有该凸块电极的半导体芯片、印刷线路基板(以下称为凸块电极基板)以及其制造方法。
背景技术
近年来，由于智能手机等小型信息机器的发展，要求搭载于该机器的电子部件急速小型化。电子部件为了基于小型化的要求而应对连接端子的窄小化、电极间的细间距化、安装面积等的缩小化，从平面的树脂的封装体转而应用并列地设置有小球状的电极的球栅阵列(以下称为“BGA”)。BGA为IC芯片的表面安装类型的封装方法，在该封装的周围电极(管脚)不突出，因此具有安装面积小即可的优点。
应用BGA的电子部件中，例如有中央处理器(CPU)等的半导体封装体。半导体封装体中，具有多个电极的半导体芯片用树脂密封。在半导体芯片的电极上形成焊料凸块。该焊料凸块是将焊料成形为球状的焊料球接合于半导体芯片的电极从而形成的。
应用BGA的半导体封装体是接合通过加热而熔融的焊料凸块与印刷基板的导电性连接盘(电极焊盘)从而搭载于印刷基板上的。此外，为了应对进一步高密度安装的要求，考虑半导体封装体在高度方向堆积而成的三维层叠结构。
但是，希望将BGA用于采用三维层叠结构的半导体封装体时，存在由于半导体封装体的自重导致焊料球压塌的问题。焊料球压塌时，存在焊料从连接端子的电极漏出，电极间连接，产生短路的问题。
因此，作为电子部件的电极使用凸块电极。凸块电极是指使用在成为核层的芯材例如Cu球的表面包覆Ni镀层，在其上包覆有焊料镀层的Cu核球而形成的电极。对于使用芯材而形成的凸块电极，电子部件安装到印刷基板时，即便半导体封装体的重量施加于凸块电极，利用在焊料的熔点下不熔融的Cu球也可以支撑半导体封装体。其结果，凸块电极不会因半导体封装体的自重而压塌。
另一方面，至今将电子部件锡焊处理到印刷基板的规定的面的情况下，使用回流焊炉。用回流焊炉形成凸块电极时，使用助焊剂或焊料糊剂来进行。焊料糊剂是混炼粉状的焊料与助焊剂而成的。对于助焊剂、焊料糊剂等，在形成有多个电极焊盘的基板上将金属掩模对准，在金属掩模上滑动操作刮板，使其介由形成于金属掩模的多个开口部涂布到电极焊盘上。助焊剂、焊料糊剂等除了使用金属掩模直接涂布到电极焊盘上的方法以外，也可以采用基于球转印方式、管脚转印方式、分配方式、喷射方式等涂布方法。
助焊剂去除要进行锡焊的金属表面的氧化膜、此外防止在锡焊工序中加热处理时金属表面再次氧化。助焊剂具有减小焊料的表面张力改善润湿的作用。助焊剂是将松脂、触变剂以及活性剂等固体成分用溶剂溶解而成的。
作为此种类型的相关技术，在专利文献1中公开了一种电子部件的制造方法。根据该电子部件的制造方法，将Cu芯焊料球锡焊处理到电极焊盘时，将Cu球体积设为Vc，将焊料镀层的体积设为Vs，将Cu球的直径设为Dc，将电极焊盘的直径设为Dp时，在满足焊料镀层的体积Vs相对于Cu球体积Vc的比为0.05≤Vs/Vc≤0.5、并且电极焊盘的直径Dp相对于成为芯的Cu球的直径Dc的比为0.5≤Dp/Dc≤1.0时，芯存在于中心。
现有技术文献
专利文献
专利文献1：日本特开2006-344624号公报
发明内容
发明要解决的问题
但是，根据以往例子的凸块电极基板以及其制造方法，存在如下的问题。
i.在回流焊炉中将Cu核球锡焊处理到电极焊盘时，产生成为核层的芯材(芯)的Cu球接合于偏离电极焊盘的中心的位置(偏心)的问题。Cu球偏心时，出现焊料极其薄的部分，二次安装中，产生由于金属间化合物(Inter MetallicCompound:以下称为IMC)的露出导致的未接合。此外，存在Cu球脱离电极焊盘而载置于基板上，从而难以确保基板间间隙为一定的问题。
ii.认为若在如专利文献1所示的0.05≤Vs/Vc≤0.5、并且0.5≤Dp/Dc≤1.0的条件下进行锡焊则Cu球的中心配置于焊料外壳的中心。然而，在上述条件下，担心出现焊料量少的情况。因此，担心在回流焊处理后的焊料凸块顶部IMC露出的问题。IMC与焊料的润湿性差，因此存在二次安装时，产生焊料的未接合部位的问题。在上述的条件之外时，Cu球的中心未配置到焊料外壳的中心的概率变高。由此，产生未接合、基板间间隙变得不均匀的问题。
因此，本发明是为了解决这样的问题而作出的，其目的在于，研究焊料镀层的熔融工序，提供可以将在电极焊盘上的成为核层的芯材的中心在其水平方向的切断面上再现性良好地配置在所包覆的焊料的外壳的中心的凸块电极、凸块电极基板以及其制造方法。
用于解决问题的方案
本发明人等认为，对于在凸块电极端子内部成为核层的芯材的中心位置偏移，焊料熔融温度附近的升温速度与形成凸块电极的芯材的偏心具有密切的关系，发现该升温速度在后述的基板加热(回流焊处理)时的芯材偏心控制中发挥效果，从而想到了本发明。在此，芯材偏心控制是指控制升温速度加热基板、减缓来自电极焊盘的助焊剂或焊料糊剂中的助焊剂的爬升、并且减缓向电极焊盘的焊料流落。而且，是指，可以以将电极焊盘上的形成凸块电极的芯材的中心在其水平截面上配置到焊料的外壳的中心的方式来进行的控制。
为了解决上述的问题的技术方案1记载的凸块电极为使用焊料接合体而形成于电极焊盘上的凸块电极，所述焊料接合体是焊料镀层包覆于成为核层的芯材而成的，在将所述焊料接合体搭载于所述电极焊盘上之后，进行加热使所述焊料镀层熔融的工序中，加热率被设定为0.01[℃/sec]以上～不足0.3[℃/sec]的范围。
技术方案2记载的凸块电极基板由设置于规定的基板的电极焊盘和接合于前述电极焊盘的、技术方案1记载的凸块电极构成。
技术方案3记载的凸块电极基板的制造方法包括下述工序：将焊料镀层包覆于成为核层的芯材而成的焊料接合体搭载于规定的基板的电极焊盘上的工序；和加热前述基板而使包覆于前述芯材的焊料镀层熔融的熔融工序，前述焊料镀层的熔融工序中的前述基板的加热率被设定为[0.01℃/sec]以上～不足0.3[℃/sec]的范围。
对于技术方案4记载的凸块电极基板的制造方法，根据技术方案3，搭载于前述电极焊盘上时，使用助焊剂。
发明的效果
根据技术方案1记载的凸块电极以及技术方案2记载的凸块电极基板，具备在使焊料接合体的焊料镀层熔融的工序中将加热率设定为0.01[℃/sec]以上～不足0.3[℃/sec]的范围而进行了处理的芯材。通过该构成，可以提供在电极焊盘上的成为凸块电极的核层的芯材的中心在其水平截面上配置到焊料镀层的外壳的中心的高可靠度的凸块电极基板。
根据技术方案3、4所述的凸块电极基板的制造方法，将焊料镀层的熔融工序中的基板的加热率设定为0.01[℃/sec]以上～不足0.3[℃/sec]的范围时，在加热处理后，可以形成焊料的外壳的中心与芯材的中心共同存在于电极焊盘的中央的凸块电极。
附图说明
图1为表示作为本发明的实施方式的凸块电极基板100的构成例子的截面图。
图2为表示Cu芯偏心量的测定方法，其中图2的(A)以及图2的(B)为在与图1中所示的电极焊盘的接合面平行的水平方向上的前述凸块电极中表示Cu芯偏心量的测定例子的Y-Y箭头方向截面图。
图3的(A)以及图3的(B)为表示凸块电极基板100的形成例子(例1)的截面图。
图4的(A)以及图4的(B)为表示凸块电极基板100的形成例子(例2)的截面图。
图5为表示第1回流焊分布的设定例子的图表。
图6为表示第1回流焊处理例的曲线图。
图7的(A)以及图7的(B)为表示第1回流焊分布中的Cu芯偏心量相对于升温速度的分布例子的图表。
图8为表示第1回流焊分布中的Cu芯偏心量相对于升温速度的出现例子的图表。
图9为表示第2回流焊分布的设定例子的图表。
图10为表示第2回流焊处理例的曲线图。
图11的(A)以及图11的(B)为表示第2回流焊分布中的Cu芯偏心量相对于升温速度的分布例子的图表。
图12为表示第2回流焊分布中的Cu芯偏心量相对于升温速度的出现例子的图表。
附图标记说明
11   基板
12   电极焊盘
13   Cu球(芯材)
14   焊料
15  绝缘膜
16   助焊剂
24   焊料镀层
30   凸块电极
50   Cu核球
100  凸块电极基板
具体实施方式
以下，边参照附图边对于本发明的凸块电极、凸块电极基板以及其制造方法进行说明，首先，对于作为实施方式的凸块电极30以及凸块电极基板100的构成例子进行说明。本例子的情况下，作为芯材选择球状的Cu球，针对包覆该Cu球的Ni镀层、和进而在其上实施了焊料镀层的Cu核球、以及将该Cu核球载置于电极而使用助焊剂的情况。
图1中所示的凸块电极基板100具有基板11、电极焊盘12以及凸块电极30而构成。凸块电极30由Cu球13以及焊料14构成。图中的15为绝缘膜(层)。电极焊盘12具有圆形状，虽未图示但以规定的间距在规定的基板11上具备多个。Cu球13构成成为核层的芯材的一个例子。图中，D为Cu球13的球径，例如为D＝190μm左右。
凸块电极30的成为核层的芯材除Cu球13之外，可以由具有在焊料镀层24熔融的温度下不会熔融的熔点的Cu、Ni、Ag、Bi、Pb、Al、Sn、Fe、Zn、In、Ge、Sb、Co、Mn、Au、Si、Pt、Cr、La、Mo、Nb、Pd、Ti、Zr、Mg的金属单质、金属氧化物、金属混合氧化物、或者合金构成。
此外，芯材可以由具有高于焊料镀层24的熔点的树脂材料、碳材料、或者陶瓷等绝缘体构成。树脂材料、碳材料、陶瓷自身没有通电性，但将金属包覆于芯材，因此即便将以树脂材料、碳材料、陶瓷为核层的核球接合于电极焊盘上的情况下，通过包覆的金属从而也可以在电极间没有问题地通电。芯材中利用绝缘物是以高频率的信号传送时的集肤效应为目的的。
作为芯材的树脂材料中，例如可以列举出将下述单体聚合而得到的树脂：苯乙烯、α-甲基苯乙烯、对甲基苯乙烯、对氯苯乙烯、氯甲基苯乙烯等苯乙烯衍生物；氯乙烯；醋酸乙烯酯、丙酸乙烯酯等乙烯酯类；丙烯腈等不饱和腈类；(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸乙二醇酯、(甲基)丙烯酸三氟乙酯、(甲基)丙烯酸五氟丙酯、(甲基)丙烯酸环己酯等(甲基)丙烯酸酯衍生物等，这些单体可以单独使用、也可以并用2种以上。
芯材为金属时，可以对芯材的表面用Ni、Co等实施镀覆处理。若预先将Ni、Co等镀覆到芯材，则将焊料镀层包覆到芯材时发挥防止芯材的元素向焊料镀层扩散的阻隔的作用。芯材为树脂等绝缘物时，也可以在用Ni、Co等实施镀覆处理之前对芯材实施Cu镀覆处理。若预先实施Cu镀覆，则在凸块电极形成时Cu部分变为通电。针对绝缘物的芯材的镀覆使用化学镀。此外，芯材的粒(球)径的大小优选为1～1000μm。处于该范围时，可以稳定地制造球状的芯材，此外，可以抑制端子间为窄间距时的连接短路。
对于镀覆到芯材的焊料的组成也没有特别限定，焊料的组成元素包含Sn、Ag、Cu、Bi、In、Ni、Sb、Zn、Ge、Ga、Co、Fe、P、Cr、Pb、Fe、Al之中的至少1个以上，使用与芯材相比液相温度低的金属或合金即可。此时，芯材与焊料合金的组成一定不能相同。它们之中，从下落冲击特性的观点出发，焊料镀层覆膜的合金组成优选为Sn-3重量％Ag-0.5重量％Cu合金。
对焊料镀层覆膜的厚度没有特别限制，优选若为100μm(单侧)以下则即足够。通常若为20～50μm即可。该例子中，对于作为芯材使用Cu球13的情况进行说明。在Cu球13的表面实施膜厚2μm左右的Ni镀覆，在其表面实施焊料镀覆。焊料镀层的膜厚为30μm左右。以下，将在Cu球13的表面实施有焊料镀层24的Cu球称为Cu核球50(参照图3的(A))。Cu核球50的整体的球径为265μm左右的大小。
对于该Cu核球50，凸块电极30的形成时，助焊剂16涂布到电极焊盘12之后，搭载于基板11的电极焊盘12上。接着，加热基板11，从常温升温至焊料镀层的液相温度附近，由于助焊剂16的作用，Cu核球50的与助焊剂16接触的部分的表面的氧化膜以及电极焊盘12的表面的氧化膜一同被去除。
紧接着该氧化膜的去除，基板11进一步被升温，成为液相温度以上的将焊料镀层熔融的工序中，源自电极焊盘12的助焊剂16的在Cu核球50的焊料镀层24的表面爬升行进速度变慢，并且，随着在Cu核球50的焊料镀层24的表面助焊剂16爬升、焊料镀层24的表面的氧化膜被去除，氧化膜被去除的部分向电极焊盘12一侧流落，如上所述，由于助焊剂16的在Cu核球50的焊料镀层24的表面爬升行进速度变慢，因此进行加热基板11的温度控制，使得焊料14向电极焊盘12的流落变慢。
以使这样的助焊剂的爬升缓慢，缓慢地去除覆盖焊料的氧化膜，一点一点地使焊料流落的方式，在焊料镀层熔融工序中，进行升温控制的Cu芯偏心控制。Cu芯偏心控制为芯材偏心控制的一个例子。通过该Cu芯偏心控制，从而可以提供Cu芯偏心量极少的凸块电极基板100(参照图2的(A))。
在此，参照图2的(A)以及图2的(B)，对于Cu芯偏心量的测定方法进行说明。该图2的(A)以及图2的(B)为在与图1所示的电极焊盘的接合面平行的水平方向上的前述凸块电极30中表示Cu芯偏心量的测定例子的Y-Y箭头方向截面图。
图2的(A)中，凸块电极30为在Cu球13的表面用均等厚度的焊料14的膜(外壳)包覆的电极。需要说明的是，图中，可见电极焊盘12与焊料14重叠。该凸块电极30中，将成为核层的芯材的截面假定为圆形时，将Cu球13的中心点设为o1、将覆盖Cu球13的焊料14的外壳的中心点设为o2时，通过Cu芯偏心控制可以使其如o1≈o2那样大致相同。以下，将中心点o1、o2间(圆心间)的距离设为x(x＝0时，o1＝o2)。例如距离x通过中心点o1、o2的差的绝对值而得到。
图2的(B)中，凸块电极30’为在Cu球13的表面形成焊料覆膜但Cu球13为偏心的电极。回流焊处理时的Cu球13产生偏心的机理如下所述。首先，从常温升温至焊料镀层24的液相温度附近，利用助焊剂16的作用，电极焊盘12的表面的氧化膜以及Cu核球50的接触助焊剂16的部分的表面的氧化膜一同被去除。
接着，在基板11进一步升温，成为液相温度以上的焊料镀层24的熔融工序中，助焊剂16沿Cu核球50的焊料镀层24的表面向上方爬升。去除焊料镀层24的表面整体的氧化膜时，焊料14向Cu球13的下方流落。此时，根据加热率高的回流焊工艺时，助焊剂16向Cu球13的上方急速爬升，大量的焊料14一次性流落。由此，考虑Cu球13产生偏心。
凸块电极30’中，将Cu球13的中心点o1与焊料14(镀层)的外壳的中心点o2的位置偏移量定义为Cu芯偏心量。实际中，将回流焊处理后的凸块电极30在与基板11平行的水平方向上研磨，露出其截面，测定距离x。
Cu芯偏心控制中，全部凸块电极中，以将圆心间的距离x抑制到10μm以下为目标。为了达成该目标，焊料镀层24的熔融工序中，与以往的方式相比采用缓慢进行的加热工艺。并且，以成为使助焊剂16的爬升缓慢、缓慢地去除覆盖焊料镀层24的氧化膜、焊料14一点一点地流落的熔融工艺的方式进行。通过该熔融工艺，形成Cu球13不易活动的状态(状况)，即便在回流焊处理后，也可以形成在电极焊盘12的中央存在凸块电极30的接合电极。
接着，参照图3以及图4，对于凸块电极基板100的形成例子(例1、例2)进行说明。该例子中，制造凸块电极基板100的情况下，焊料镀层24的熔融工序中，将加热率设定为0.01[℃/sec]～0.3[℃/sec]的范围。
需要说明的是，本文中，焊料镀层24的状态是指在形成凸块电极30时，通过助焊剂16将Cu核球50搭载于电极焊盘12上，通过之后的加热使Cu核球50的焊料镀层24熔融，并且至利用助焊剂16的作用去除表面的氧化膜为止的状态，将去除了表面的氧化膜的状态称为焊料14。因此，在凸块电极形成的过程，从焊料镀层24向焊料14的迁移过程中，存在焊料镀层24与焊料14共存的状态。
将它们作为形成条件，首先，在图3的(A)所示的规定基板11的电极焊盘12上涂布助焊剂16之后，在该电极焊盘12上搭载Cu核球50。电极焊盘12通过在铜箔基板上将圆形状的平面电极(连接盘图案)图案化而得到。Cu核球50使用预先将焊料镀层24实施到Cu球13上的球。本实施例/比较例中，成为核层的芯材使用Cu的纯度为99.95％以上且直径为190μm的Cu球13。
对于焊料镀层24，对成为芯材的Cu球13实施膜厚2μm左右的Ni镀覆，然后将由包含Sn、Ag、Cu、Bi、In、Ni、Sb、Zn、Ge、Ga、Co、Fe、P、Cr、Pb、Fe、Al之中的至少1个以上的、液相温度与芯材相比低的金属或合金构成的焊料14进行镀覆。
本实施例/比较例中，焊料镀层24的组成全部设为Sn-3重量％Ag-0.5重量％Cu。此外，基板11使用树脂基板(开口径：240μm、抗蚀层厚：15μm、表面处理：Cu-OSP)。助焊剂印刷时，将金属掩模对准形成有多个电极焊盘的基板上，在金属掩模上滑动操作刮板，介由形成于金属掩模的多个开口部涂布助焊剂16。
接着，加热基板11，从常温升温至达到焊料的液相温度附近的温度，去除Cu核球50以及电极焊盘12的与助焊剂16接触的表面的氧化膜(第1熔融步骤)。第1熔融步骤的温度条件将从常温达到焊料14的液层温度附近(210℃)的加热温度的加热率(升温速度)设定为例如2.0[℃/sec]。该第1熔融步骤中，通过助焊剂16去除电极焊盘12以及Cu核球50的与助焊剂16接触的仅底面侧的氧化膜。
接着，氧化膜的去除工序之后对基板11进行进一步升温，移送到焊料镀层24的熔融温度(第2熔融步骤)。该第2熔融步骤的温度条件，例如，将加热温度从210℃达到230℃的加热率设定为0.01[℃/sec]以上～不足0.3[℃/sec]的范围。此时，成为焊料镀层24熔融而移送至焊料14的状态，产生Cu核球50的自对准现象与Cu球13沉入至电极焊盘12为止的现象(图3的(B))。自对准现象是指Cu核球50自我调整地移动到电极焊盘12的中央的现象。
此外，此时，Cu核球50的表面仍被氧化膜包覆，焊料镀层24从热容量小的电极焊盘12侧向Cu球13的头顶部开始熔融。在该熔融即将开始之前，Cu球13的底部外壳的焊料镀层24熔融，在其接触部位(基部分)的周围成为焊料14，开始扩展。其结果，Cu球13沉入至电极焊盘12。由于该状态，Cu球13的表面的外壳的焊料镀层24熔融、被氧化膜包覆的内部开始依次迁移至焊料14时，Cu球13脱离焊料镀层24的束缚成为自由的状态。
接着，如图4的(A)所示，助焊剂16去除Cu核球50的焊料镀层24的表面的氧化膜、并且向上方爬升。该例子中，焊料镀层24的熔融温度移送时，如图中的向上的中空箭头那样，以使助焊剂16从电极焊盘12向Cu球13的爬升变慢的方式对基板11加热(氧化膜的去除工序)。
并且，图4的(B)中，焊料镀层24的熔融工序中，如图中的向下的中空箭头那样，以使焊料14从Cu球13向电极焊盘12的流落变慢的方式缓慢地对基板11加热。该第2熔融步骤中，Cu核球50的整体的氧化膜被去除时，焊料14从Cu球13的周围向电极焊盘12的方向流落(Cu芯偏心控制)。
在此，参照图5～图8，关于Cu芯偏心控制，可以列举出第1回流焊分布的设定例子，比较2个实施例1、2与2个比较例1、2，考察Cu芯偏心量变为最少的作为上限的升温速度。该考察中，对于N＝20的样品，测定Cu芯偏心量，根据升温速度与Cu芯偏心量的关系确定最适的上限的升温速度。该例子中，使用高温观察装置(山阳精工株式会社制造的SP-5000 DS)代替回流焊炉。
第1回流焊分布的设定例子中，作为第1熔融步骤，如图5的图表所示，为在30℃(常温)～至210℃的加热温度下，第1熔融步骤中的升温速度为2.0[℃/sec]的情况。第1熔融步骤在实施例1、2以及比较例1、2的任一之中为相同温度条件。
第2熔融步骤为加热温度为210℃～230℃、其实施例1中升温速度为0.1[℃/sec]、实施例2中升温速度为0.2[℃/sec]、比较例1中升温速度为0.3[℃/sec]、比较例2中升温速度为2.0[℃/sec]的情况。
对于第3熔融步骤，将回流焊处理的峰值温度设为245℃时，实施例1、2以及比较例1、2中任一个的加热温度为230℃～245℃、其升温速度为2.0[℃/sec]。需要说明的是，对于降温步骤，实施例1、2以及比较例1、2中任一个的冷却温度为自245℃至180℃，其降温速度为2.0[℃/sec]。为高温观察装置中的氧浓度为100ppm以下，助焊剂16使用WF-6450(千住金属工业株式会社制造)的情况。
图6所示第1回流焊处理例子基于第1回流焊分布，纵轴为高温观察装置中的加热温度[℃]。横轴为基板11的回流焊时间[sec]。图中的实线的粗线为实施例1，为加热温度210℃～230℃下的升温速度为0.1[℃/sec]的情况。虚线的粗线为实施例2，为升温速度为0.2[℃/sec]的情况。点划线的粗线为比较例1，为升温速度为0.3[℃/sec]的情况。双点划线的细线为比较例2，为升温速度为2.0[℃/sec]的情况。
图7的(A)所示的第1回流焊分布中的Cu芯偏心量相对于升温速度的分布例子中，纵轴为加热温度为210℃～230℃时的Cu芯偏心量[μm]。横轴为实施例1、2以及比较例1、2中的升温速度[℃/sec](图中标记为“C/s”)。图中的黑色的菱形为Cu芯偏心量的平均值(Average)。
该例子中，对于N＝20的样品，将回流焊处理后的凸块电极30在与基板11平行的水平方向上研磨，露出其截面，测定其中心点o1、o2间(圆心间)的距离x。实施例1中作为N＝20的样品的平均值，Cu芯偏心量分布在4.4[μm]的附近。实施例2中作为其平均值，Cu芯偏心量分布在6.3[μm]的附近。比较例1中作为其平均值，Cu芯偏心量分布在15.0[μm]的附近。比较例2中作为其平均值，Cu芯偏心量分布在14.8[μm]的附近。
将表示这些关系的表总结于图7的(B)中。如由该表表明的那样，明确为了使Cu芯偏心量降低，若以不足0.3[℃/sec]的升温速度进行加热即可。
图8所示的第1回流焊分布中的Cu芯偏心量相对于升温速度的出现例子中，纵轴为出现个数[％](存在概率)，以百分率表示加热温度为210℃～230℃时的该Cu芯偏心量相对于N＝20出现的个数。横轴为实施例1、2以及比较例1、2中的升温速度[℃/sec]。
图中的左下斜线图案的距离x为0≤x＜5[μm]的范围，右下斜线图案的距离x为5≤x＜10[μm]的范围。横线图案的距离x为10≤x＜15[μm]的范围、格子图案的距离x为15≤x＜20[μm]的范围。梨皮图案的距离x为20≤x＜25[μm]的范围、砖图案的距离x为25≤x＜30[μm]的范围。波纹图案的距离x为30≤x＜35[μm]的范围，斜格子图案的距离x为35≤x＜40[μm]的范围。棋盘图案的距离x为40≤x＜45[μm]的范围。
该例子中，对于N＝20的样品，实施例1(升温速度＝0.1[℃/sec])中N＝20的样品中，其的80％处于0≤x＜5[μm]的范围。包含5≤x＜10[μm]的范围的样品时，占据其的90％。实施例2(升温速度＝0.2[℃/sec])中N＝20的样品中，45％处于0≤x＜5[μm]的范围。包含5≤x＜10[μm]的范围的样品时，占据其的85％。
比较例1(升温速度＝0.3[℃/sec])中N＝20的样品中，35％处于0≤x＜5[μm]的范围，即便包含5≤x＜10[μm]的范围的样品，也为占据其的48％的水平。比较例2(升温速度＝2.0[℃/sec])中N＝20的样品中，20％处于0≤x＜5[μm]的范围，即便包含5≤x＜10[μm]的范围的样品，也为占据其的55％的水平。
如此，明确加热温度210℃～230℃下的Cu芯偏心控制中，凸块电极30中，大体上达到将圆心间的距离x抑制到10μm以下的目的的升温速度的上限若设定为不足0.3[℃/sec]即可。
接着，参照图9～图12，关于Cu芯偏心控制，可以列举出第2回流焊分布的设定例子，比较6个的实施例3～8和1个的比较例3，考察Cu芯偏心量变为最少的下限值的升温速度。该考察中，对于N＝20的样品，测定Cu芯偏心量，根据升温速度与Cu芯偏心量的关系确定最适的下限的升温速度。第2回流焊分布的设定例子中，作为第1熔融步骤，如图9的图表所示，为在30℃(常温)～达到215℃的加热温度下，第1熔融步骤中的升温速度为2.0[℃/sec]的情况。第1熔融步骤在实施例3～8以及比较例3的任一之中为相同温度条件。
第2熔融步骤为加热温度为215℃～228℃、其实施例3中升温速度为0.01[℃/sec]、实施例4中升温速度为0.05[℃/sec]、实施例5中升温速度为0.10[℃/sec]、实施例6中升温速度为0.13[℃/sec]、实施例7中升温速度为0.15[℃/sec]、实施例8中升温速度为0.20[℃/sec]、比较例3中升温速度为2.00[℃/sec]的情况。
对于第3熔融步骤，将回流焊处理的峰值温度设为245℃时，实施例3～8以及比较例3中任一个的加热温度为228℃～245℃、其升温速度为2.0[℃/sec]。需要说明的是，降温步骤与实施例1、2以及比较例1、2同样地操作，实施例3～8以及比较例3中任一个的冷却温度为245℃～180℃且其的降温速度为2.0[℃/sec]。为高温观察装置中的氧浓度为100ppm以下、助焊剂16使用WF-6450的情况。
图10所示的第2回流焊处理例子基于第2的回流焊分布，纵轴为高温观察装置中的加热温度[℃]。横轴为基板11的回流焊时间[sec]。图中的实线的粗线为实施例3、为加热温度215℃～228℃下的升温速度为0.01[℃/sec]的情况，虚线的粗线为实施例4、为升温速度为0.05[℃/sec]的情况。
点划线的粗线为实施例5、为升温速度为0.10[℃/sec]的情况，双点划线的粗线为实施例6、升为温速度为0.13[℃/sec]的情况。实线的细线为实施例7、为升温速度为0.15[℃/sec]的情况，虚线的细线为实施例8、为升温速度为0.20[℃/sec]的情况。点划线的细线为比较例3、为升温速度为2.0[℃/sec]的情况。
本发明的Cu芯偏心控制中，通过在焊料熔融温度的±10[℃]的区域中使升温速度降低，从而抑制Cu芯偏心量。需要说明的是，还明确增加回流焊时间时，担心由于IMC的成长导致接合可靠性降低、或助焊剂16失活、凸块电极的氧化膜增加等，因此使升温速度降低的区域越窄越好。
图11的(A)所示的第2回流焊分布中的Cu芯偏心量相对于升温速度的分布例子中，纵轴为加热温度为215℃～228℃时的Cu芯偏心量[μm]。横轴为实施例3～8以及比较例3中的升温速度[℃/sec]。
该例子中，对于N＝20的样品，将回流焊处理后的凸块电极30在与基板11平行的水平方向上研磨，露出其截面(参照图2的Y-Y箭头方向截面)，测定其中心点o1、o2间(圆心间)的距离x。实施例3中，作为N＝20的样品的平均值，Cu芯偏心量分布于2.5[μm]附近。实施例4中作为其平均值，Cu芯偏心量分布在3.9[μm]的附近。实施例5中作为其平均值，Cu芯偏心量分布在3.6[μm]的附近。
实施例6中作为其平均值，Cu芯偏心量分布于4.0[μm]的附近。实施例7中作为其平均值，Cu芯偏心量分布在6.8[μm]的附近。实施例8中作为其平均值，Cu芯偏心量分布在7.3[μm]的附近。比较例3中作为其平均值，Cu芯偏心量分布在14.8[μm]的附近。将这些关系总结示出于图11的(B)中。如由该表表明的那样，明确为了使Cu芯偏心量降低，若以不足0.3[℃/sec]的升温速度进行加热即可。
图12所示的第2回流焊分布中的Cu芯偏心量相对于升温速度的出现例子中，纵轴为出现个数[％](存在概率)，以百分率表示加热温度为215℃～228℃时的该Cu芯偏心量相对于N＝20出现的个数。横轴为实施例3～8以及比较例3中的升温速度[℃/sec]。
对于图中的左下斜线图案、右下斜线图案、横线图案、格子图案、梨皮图案、砖图案、波纹图案、斜格子图案以及棋盘图案，与第1流分布中的Cu芯偏心量相对于升温速度的出现例子中的图案相同，因此省略其说明。
该例子中，对于N＝20的样品，实施例3(升温速度＝0.01[℃/sec])中，N＝20的样品中、其的90％处于0≤x＜5[μm]的范围。包含5≤x＜10[μm]的范围的样品时，占据其的100％。实施例4(升温速度＝0.05[℃/sec])中，其的70％处于0≤x＜5[μm]的范围。包含5≤x＜10[μm]的范围的样品时，占据其的100％。
实施例5(升温速度＝0.10[℃/sec])中，其的80％处于0≤x＜5[μm]的范围。包含5≤x＜10[μm]的范围的样品时，占据其的100％。实施例6(升温速度＝0.13[℃/sec])中，其的70％处于0≤x＜5[μm]的范围。包含5≤x＜10[μm]的范围的样品时，占据其的100％。
实施例7(升温速度＝0.15[℃/sec])中，其的45％处于0≤x＜5[μm]的范围。包含5≤x＜10[μm]的范围的样品时，占据其的80％。实施例8(升温速度＝0.2[℃/sec])中N＝20的样品中，30％处于0≤x＜5[μm]的范围。包含5≤x＜10[μm]的范围的样品时，占据其的80％。
与之相对，根据比较例3(升温速度＝2.0[℃/sec])，N＝20的样品中，20％处于0≤x＜5[μm]的范围，即便包含5≤x＜10[μm]的范围的样品，也为占据其的55％的水平。
上述的加热温度215℃～228℃下的Cu芯偏心控制中，升温速度为0.13[℃/sec]以下时Cu芯偏心量全部为10μm以下(100％)。认为这是由于，焊料熔融温度附近的升温速度在回流焊处理后的Cu芯偏心控制中发挥效果。由此，明确从没有由于IMC的成长导致接合可靠性的降低的担心、工业上也可以使用的回流焊时间的极限速度的观点出发，凸块电极30中，大体上达到将圆心间的距离x抑制到10μm以下的目的的升温速度的下限值若设为0.01[℃/sec]即可。
如此，根据作为实施方式的凸块电极30以及凸块电极基板100，无论加热温度，若将加热率设定在0.01[℃/sec]以上～不足0.3[℃/sec]的范围，则可以控制Cu球13的偏心。该Cu球13的偏心控制、即以使助焊剂16从电极焊盘12的爬升变慢、并且使焊料14向电极焊盘12的流落变慢的方式对基板11进行加热，具备焊料14熔融而成的Cu球13。
根据该构成，可以提供在电极焊盘12上作为成为核层的芯材的Cu球13的中心在其水平截面配置到焊料14的外壳的中心的高可靠度的凸块电极基板100。
此外，根据作为实施方式的凸块电极基板100的制造方法，电极焊盘12以及Cu球13的氧化膜的去除后的焊料镀层24的熔融工序中，以使助焊剂16从电极焊盘12向Cu球13的爬升变慢、并且使焊料14从Cu球13向电极焊盘12的流落变慢的方式对基板11进行加热。
根据该构成，可以形成助焊剂16的爬升变缓慢、缓慢地去除覆盖焊料镀层24的氧化膜、焊料14一点点地流落的熔融工艺。因此，Cu球13的表面被均等的厚度的焊料14的膜(外壳)包覆，Cu球13成为不易活动的状态(状况)，在加热处理后，可以形成焊料14的外壳的中心与Cu球13的中心共同存在于电极焊盘12的中央的凸块电极30。
该实施方式中，对于芯材为Cu球13的情况进行说明，并不限定于此，芯材即便为Cu、Ni、Ag、Bi、Pb、Al、Sn、Fe、Zn、In、Ge、Sb、Co、Mn、Au、Si、Pt、Cr、La、Mo、Nb、Pd、Ti、Zr、Mg的金属单质、金属氧化物、金属混合氧化物、或者合金的情况下也得到同样的效果。进而，芯材可以由在焊料镀层熔融的温度下非熔融的树脂材料等构成。
此外，无论以往的例子那样的焊料镀层的体积Vs相对于Cu球体积Vc的比为0.05≤Vs/Vc≤0.5、并且电极焊盘12的直径Dp相对于成为芯的Cu球的直径Dc的比为0.5≤Dp/Dc≤1.0的条件，都可以在回流焊处理后，将Cu球13的中心配置于焊料14的外壳的中心。
需要说明的是，本实施例中，对于将助焊剂16涂布到电极焊盘12上的情况进行说明，但不限于此，也可以使用焊料糊剂代替助焊剂16。
产业上的可利用性
本发明极其适合用于可适用于IC芯片的表面安装类型的封装方法即BGA的凸块电极基板以及其锡焊方法。

Claims (4)

1.一种凸块电极，其特征在于，其为使用焊料接合体而形成于电极焊盘上的凸块电极，所述焊料接合体是焊料镀层包覆于成为核层的芯材而成的，
在将所述焊料接合体搭载于所述电极焊盘上之后，进行加热使所述焊料镀层熔融的工序中，加热率被设定为0.01[℃/sec]以上～不足0.3[℃/sec]的范围。
2.一种凸块电极基板，其特征在于，其具备设置于规定的基板的电极焊盘和接合于所述电极焊盘的权利要求1所述的凸块电极。
3.一种凸块电极基板的制造方法，其特征在于，其包括下述工序：
将焊料镀层包覆于成为核层的芯材而成的焊料接合体搭载于规定的基板的电极焊盘上的工序；和
加热所述基板而使包覆于所述芯材的焊料镀层熔融的熔融工序，
所述焊料镀层的熔融工序中的所述基板的加热率被设定为0.01[℃/sec]以上～不足0.3[℃/sec]的范围。
4.根据权利要求3所述的凸块电极基板的制造方法，其特征在于，搭载于所述电极焊盘上时，使用助焊剂。
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