CN1129339A - 导电胶体材料及其应用 - Google Patents

导电胶体材料及其应用 Download PDF

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Publication number
CN1129339A
CN1129339A CN95117360A CN95117360A CN1129339A CN 1129339 A CN1129339 A CN 1129339A CN 95117360 A CN95117360 A CN 95117360A CN 95117360 A CN95117360 A CN 95117360A CN 1129339 A CN1129339 A CN 1129339A
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Prior art keywords
particle
coating
polymeric material
group
colloid
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CN95117360A
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CN1084917C (zh
Inventor
康·K·宋
特里斯塔·O·格雷厄姆
桑普西·普鲁绍茨曼
朱迪思·M·罗丹
雷维·F·萨拉弗
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International Business Machines Corp
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International Business Machines Corp
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    • H01L23/49883—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials the conductive materials containing organic materials or pastes, e.g. for thick films
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Abstract

描述了一种结构和制造方法，该结构是一种聚合物材料及具有导电涂层，如Sn的颗粒，如Cu的组合。施加热量以熔融相邻颗粒的涂层。该聚合物材料是一种热塑材料。该结构放置于两个导电面之间，例如芯片垫片与衬底垫片之间，以便在它们的垫片之间提供电气连接和粘合。

Description

导电胶体材料及其应用
本发明涉及用于在导电部件间形成导电连接的新型连接材料，并涉及用于生产这种导电连接的方法。此外，本发明致力于解决对环境无害的材料和生产过程，它们可作为含铅(Pb)焊接工艺的代用方案。
电子装置中使用的大多数导电体由金属制成，例如铜、铝、金、银、铅/锡(焊剂)、钼和其它金属。在各级电学封装中发挥关键作用的是使用铅/锡合金的焊接工艺，例如倒装连接(或C4)、球网阵列(BGA)中的焊球连接、用于印刷电路板(PCB)的IC封装组合。电子封装中产生的焊点的重要功能既是电气连接又是机械/物理连接。当这些功能中任何一项不起作用时，焊接点即被认为有故障，通常会造成威胁，导致整个电子系统停止工作。
倒装连接是当前高性能封装应用中，例如多芯片模块中，最有效的芯片连接方法，其中含铅(Pb)量多的焊剂凸块将高性能芯片直接连至瓷衬底上。
球网阵列(BGA)封装中的焊球连接是倒装连接方法的延伸，其中使用大焊球的网格阵列将或是单芯片或是多芯片模块连至聚合物PCB。当前使用的焊球具有高锡含量，例如Pb—10％Sn或Pb—20％Sn，以便当用低熔点的Pb—Sn低共熔焊剂将这些模块固定至PCB衬底时，这些焊球可用作非熔性支托。
当将微电子封装组装至印刷电路板上时，具有最低熔点(183℃)的铅锡低共熔焊剂，63％Sn—37％Pb是Pb—Sn合金中应用最广的。在这些应用中，有两种焊接技术用于大批量生产：电镀穿孔(PTH)和表面安装技术(SMT)焊接。这两项技术的基本差别起源于PCB设计及其连线方案的差别。
在PTH焊接中，利用PCB上的电镀穿孔制成焊点。例如，在波峰焊中，熔融的焊剂直接涂在PTH的面积上并由毛细孔力将其进一步吸入，填入I/O管脚与电镀穿孔壁之间的空隙。
在SMT焊接中，微电子包装直接固定至PCB面上。由于SMT在PCB中消除了大部分PTH，同时可以利用PCB的两个面安装元件，所以SMT的一个主要优点是高的封装密度。此外，与传统PTH封装比较，SMT封装具有更细线间距和更小封装尺寸。因此SMT在减小电子封装尺寸及整个系统的体积中发挥了显著作用。
在SMT焊接中，使用网格印刷将焊胶涂到PCB上。焊胶包含细焊粉、熔剂和有机物载体。在回流加热过程中，焊剂颗粒熔融，熔剂活化，溶剂材料蒸发，以及同时熔融的焊剂聚结并合和事实上固体化。相反地，在波峰焊过程中，PCB首先涂上熔剂并将元件安装在它上面。接着它在熔融焊剂的波上方移动。一般将焊点在清洗步骤中处理，去除残留熔剂材料，即完成焊接过程。由于对环境保护的关注，CFC和其它有害清洗剂都取消不用，而由水溶性或不需清洗的熔剂材料所代替。
微电子装置最近的进展要求在电子封装和印刷电路板之间使用非常细的间距连接(几百微米间距的数量级)。当前SMT中使用的焊剂胶体技术，由于其焊接缺陷如架桥或焊球，不能实现这种非常细的间距连接。另一使用Pb—Sn低共熔焊剂的技术限制是它的高回流加热温度，近似215℃。此温度早已高于在大多数聚合物印刷电路板材料中所用环氧树脂的玻璃渡越温度。在此回流加热温度下的热暴露将在焊接后在印刷电路板中产生显著的热应力，特别是在与PCB平面垂直的方向内更显著，因在该方向内没有结构加固。因此组装好的PCB中残留热应力将使电子系统的可靠性降低。
对含铅(Pb)焊剂使用的更严重的关注是环保问题，在其它工业中早已从汽油、油漆和家用铅锡焊剂中取消了铅。
在电子工业中，目前正研制两种不同组的有可能代替含铅焊剂材料的材料；无铅焊剂合金，和导电胶体(ECP)。本发明讨论导电胶体材料的开发与应用。导电胶体(或粘合剂)是由将导电的充填颗粒装在聚合物材料的基体中而制成。图1原理图中所示填以银粒的环氧树脂2是导电胶体中最普通的例子。通常是片状的银粒4利用渗透机理提供导电性，而环氧树脂基体6在部件8与衬底10之间提供粘合连接。该填银环氧树脂材料长时间来已在电子工业用作模片键合材料，其中更多地利用其导热性而不是导电性。然而该材料尚未被用于要求高导电性和细间距连接的场合。此填银环氧树脂材料有数项限制，例如低导电率、在热暴露时接触电阻增加、低接合强度、银纵动、难于再加工、等等。由于该填银环氧树脂材料在所有方向都是导电的，所以它被分类为在导电上是“各向同性的”。
还有一种导电粘合剂(或胶膜)，它只在一个方向提供导电性。这类材料称为“各向异性的”导电粘合剂或胶膜。图2A原理图中所示胶膜12包括位于聚合物粘合材料20内的导电颗粒18。各向异性的导电粘合剂或胶膜12只当压在如图2B所示两块导电垫片间时才具有导电性。这个过程通常需要热和压力。各向异性的导电胶膜主要用于将液晶显示板连接到它的电子印刷电路板上。这些导电颗粒通常是可变形的涂有镍和金的焊球或塑性球。胶合剂或粘合剂材料大多数是热固树脂。
本发明的一个目的是提供一种对环境无害和费用低廉的导电胶体材料。
本发明另一个目的是提供一种其导电率比常规填银环氧树脂的导电率更高的导电胶体材料。
本发明又一个目的是提供一种其接合强度高于常规填银环氧树脂的导电胶体材料。
本发明还有一个目的是提供一种其接点较常规填银环氧树脂更可靠的导电胶体材料，具体说这体现在一定温度/湿度/电压的应用条件下的银纵动。
本发明一个广阔方面是一种由众多颗粒形成的导电材料，每一颗粒具有一层导电涂层，相邻颗粒之间的导电涂层互相熔融，因而形成一个熔融颗粒的网。
本发明的另一个广阔方面是一种包括具有导电材料涂层的颗粒和聚合物材料的胶体。
本发明的又一个广阔方面是一种用于在两个面之间形成导电接点的方法，其中形成一种由具有导电涂层的颗粒和聚合物材料组成的胶体，并将该胶体涂于将被粘接并电气上连接起来的两个面之间进行加热，以便将导电颗粒互相之间熔融，将它们与接触垫片作金相熔接，并使聚合物材料固化。
当结合图1—7详细地描述本发明后，本发明的进一步的目的、特征和优点将很明显，图1—7中：
图1是用于阐述用银片颗粒作为环氧树脂基体中的充填物的导电胶体的原理图。该导电胶体被分类为在导电上是各向同性的(现有技术)。
图2A是用于阐述一种电粘合剂的原理图，当该粘合剂压如图2B所示两个触点或熔接垫片之间时，该粘合剂只在一个方向导电。该导电粘合剂(或胶膜)被分类为各异性的(现有技术)。
图3是根据本发明的胶体的原理图。
图4是用于阐述一种根据本发明的导电胶体材料的原理图，该材料包含充填在热塑聚合树脂基体中的涂有低熔点、无毒金属的颗粒，相邻颗粒之间的金属涂层被熔融以得到相邻颗粒之间和颗粒与使用胶体粘接的接触面之间的金相熔接。
图5是用于阐述使用根据本发明的导电胶体将一个表面安装集成电路封装连至一个电路板的原理剖面图。
图6是用于阐述使用根据本发明的导电胶体将一块集成电路芯片直接固定在高密度印刷电路板上的原理剖面图。
图7是用于阐述一块带有导电胶体结构的多层瓷衬底的原理图，该导电胶体结构与硅衬片上的C4凸块结构位置对应。该多层瓷衬底用作衬片规模老化和芯片测试时的载体。
在一个特定实施例中，我们公开一种新的导电胶体材料，它由涂锡铜粉、聚酰亚胺硅氧烷、溶剂(N甲基吡咯烷或NMP)、羧酸/表面活性剂所组成。熔接操作可在Sn熔点230℃附近完成，可在粒对粒以及粒对衬底垫片界面处完成Sn对Sn或Sn对Au的金相熔接。该熔接过程可以是固态也可是液态反应。决定于胶体配方，聚合物固化过程也可与熔接过程合并。由于采用金相熔接，使用新胶体材料所得接点的导电率要比使用银环氧树脂的接点高。在热暴露和热振荡的情况下，金相熔接能提供新接点的稳定导电率。由于金相熔接和粘接的共同作用，接合强度也较高。决定于应用要求，涂锡粉的颗粒大小、聚合物基体的成分和充填材料的体积比例都可调整。由于本导电胶体主要基于金相熔接，因此为了获得可接受的导电水平而需要的充填材料的临界体积比例比常规银环氧树脂胶体要小得多。
在另一实施例中，我们建议应用从适当功能作用后的可再生资源或生物基材料中制备的聚合树脂，以得到所需热和浓度性能，例如可参照由W.G.Glasser和T.C.Ward所写关于NSF Grant#BCS85—12636的最后报告。木质素(造纸工业的副产品)，纤维素、木或农作物油是用于此目的潜在材料。由于这些材料取自天然的可再生的资源，并在电子组件使用寿命结束时很容易丢弃，因此它们对环保有利。因为使用Cu—Sn粉后就可不再使用含铅(Pb)焊剂，同时最后胶体配方是无毒的并易于丢弃，所以这特别有吸引力。
图3阐述根据本发明的新导电胶体(ECP)材料30，它包括具有导电涂层34的颗粒32和聚合物基体36，该颗粒32用作导电充填材料。颗粒32最好是铜粒。涂层34最好是锡、铟及铋、锑或它们的化合物。聚合物基体最好是热塑材料，尤其是聚酰亚胺硅氧烷。下面将参照最佳实施例描述本发明，但并不限于它。
在铜粉上镀锡的第一步是在淡硫酸中清洗细铜粉。所用铜粉是球状，其直径范围为2至8微米，自NJ的South Plainfield的De-gussa Corporation获得。镀锡是在来自MA的Newfon的Shipley的TINPOSIT LT—34镀锡液中浸泡清洁铜粉而完成。锡的最佳厚度是在5—7微米铜粉上0.3至0.5微米厚。冲洗后镀锡铜粉立即与一种不需清洗熔剂，来自1L的Addison的Qualitek lnter—na-tional，Inc.的FLUX305相混合。这可在该镀锡铜粉加工成导电胶之前防止它氧化。将镀锡铜粉与聚酰亚胺硅氧烷、NMP溶剂、丁酸和乙二醇混合，即配成导电胶。充填粉与聚合物基体的相对数量在重量的30至90％之间变动，这决定于应用的要求。一般说来，用于各向同性导电时，需要高的充填物重量百分比，而低充填物重量百分比则用于各向异性应用场合。为保证成分的均匀扩散，该混合物放在一个三辊剪轧机中加工。调整胶体中充填粉的体积比例可以控制粘度。当充填物重量百分比低时，例如重量的30％时，在将胶体涂布到所需基块上之前，需要一种使溶剂干燥的过程，例如100℃一小时，用于调整胶体粘度。
为了鉴定电气和机械性能，在制做镀锡填铜导电胶的焊接样品时将两片L状铜样片叠在一起。叠装过程是在略高于Sn熔点，例如250℃的温度和25psi的压力下完成的。为比较导电率的值，其它焊接样品也在相似过程中使用商用的银环氧树脂和Sn/Pb低共熔焊剂胶体材料制成。根据本发明的胶体制成的焊接样品显示出最低电阻值；例如，镀锡铜胶为2.6×10-5欧，Sn/Pb焊胶为4，7×10-5欧，和银环氧树脂为7.3×10-5欧，其接触面积相同，约为0.050英寸乘0.050英寸。根据本发明的胶体的电阻甚至比Sn/Pb焊胶的电阻还低。这归功于铜和Sn/Pb焊剂的体积导电率的差别。
接合强度的测量结果表明使用根据本发明的胶体所制成接点的接合强度高于由银环氧树脂胶制成的接点。
由镀锡铜粉和聚酰亚胺硅氧烷树脂制成的ECP能很好用于瓷衬底上的高温焊接点，例如C4和焊球连接(SBC)。但ECP不适用于聚合物印刷电路板，因为如250℃那样的回流加热温度大大地高于如FR—4那样的聚合树脂的玻璃渡越温度。用于此目的的是一种由与聚酰亚胺硅氧烷树脂配用的镀铟铜粉所制成的ECP。镀铟铜粉胶体的回流再热温度是大约180℃，这甚至低于215℃的Pb/sn低共熔焊剂的回流再热温度。参照图4，胶体放置于面40和42之间并加热至回流再热温度，这使颗粒32的导电涂层34与相邻颗粒的导电涂层34互相熔融，从而形成它们之间的熔接64。此外，在接触面42和与这些面邻接的颗粒之间也形成金相熔接46。
考虑到环境方面的问题，也可使用由可再生的或生物基系统制成的另一种聚合树脂，如功能化的木质素、纤维素和桐油或农作物油。这些树脂是生物上可退化的或由非化石燃料资源制成并易于在电子组件使用寿命结束及拆卸后加以回收。
图5是用于描绘使用根据本发明的导电胶体将一块IC封装固定至PCB50上的原理图。该导电胶体如常规焊胶一样，丝网印刷至PCB上的每一个铜焊接垫片52上。一般垫片52具有一层Sn涂层54。胶体56放置于涂Sn58的铅架60与涂Sn54的垫片52之间，该铅架60在电气上将SMT塑料封装62连至PCB50。一般细间距SMT组件使用大约0.025″或更小间距。因此涂锡粉的颗粒大小应在5至10μm范围内。可在120至150℃温度下同时完成连接操作和聚合物固化过程。与焊接过程比较，此低温过程对PCB产生的热变形要小得多。此外，该连接过程不用外加熔剂，因此不需清洗熔剂的步骤。
图6描绘固定在一块高密度电路板52上，例如面叠层电路(SLC)上，的一块IC芯片60，其中根据本发明的导电胶体材料64涂布在与芯片垫片66的基块位置对应的二维阵列上。芯片一侧的连接用金属最好用Cr/Cu/Au，以便在界面处形成Au—Sn熔接。由于聚酰亚胺硅氧烷是一种热塑共聚物，该接点可使用NMP作为溶剂加热到大约200℃以便重新加工。在使用C4焊剂凸块直接固定芯片的情况下，可采用灌封过程以获得焊接点所需热疲劳稳定性。在本应用例中，该聚合物基体用作挠性部分，以便容纳衬底和元件间的热应力差。此外，如果需要，可以用第二种聚合物将胶体垫片间的空间加以灌封，以便进一步加强热疲劳稳定性。
图7显示衬片规模老化C4芯片的应用例。导电胶体材料70涂布于其垫片基块74与硅衬片垫片基块76位置对应的多层瓷衬底72上，在基块76上涂布了将要测试和老化的C4焊堆。MLC衬底提供连接，以便在老化对向芯片供电，及通过管脚网格阵列80提供外部I/O。在老化步骤前，衬底上的导电胶体固化及涂Sn颗粒与衬片上C4熔接在一起。通常在150℃6小时条件下进行老化操作。老化后，衬底与衬片分开，将测试时从C4凸块留下的任何残留焊剂腐蚀掉，或将垫片溶于NMP中，以及重新丝网印刷胶体以形成新垫片，即可重新使用。由于胶体与焊剂之间有限的金相接触面积和压力，芯片C4垫片本身的形状和成分将不会变化。因此人们能在合适的溶剂(例如NMP)中清洗那些好的芯片并如正常过程所做那样将它们组装到衬底上，而不产生任何问题，也不需附加的回流加热步骤。
根据本发明的新导电胶体材料用于对印刷电路板的表面安装封装组件，用于在细间距卡上直接固定芯片，及倒装片的衬片规模老化的一些例子有如下几种配方：
—涂有例如Sn、In、成、Sb和它们的合金那样的低熔点，元素金属薄层的铜粉，与例如不需清洗或水溶性熔剂那样的对环境无害的熔剂相混合。
—涂锡铜粉，与聚酰亚胺硅氧烷、NMP溶剂、及丁酸及乙二醇或不需清洗熔剂相混合。
—涂锡铜粉，与可再生或生物基聚合树脂、合适溶剂、及丁酸及乙二醇或不需清洗熔剂相混合。
—涂铟铜粉，与聚酰亚胺硅氧烷、NMP溶剂、及丁酸及乙二醇或不需清洗熔剂相混合。
—涂铟铜粉，与可再生或生物基聚合树脂、合适溶剂、及丁酸及乙二醇或不需清洗熔剂相混合。
—用于表面安装应用的最佳配方，包括占重量30至90％的涂铟铜粉、聚酰亚胺硅氧烷、NMP溶剂、及丁酸及乙二醇或不需清洗熔剂。
—用于直接固定芯片应用的最佳配方，包括占重量30至90％的涂铟铜粉、聚酰亚胺硅氧烷、NMP溶剂及丁酸及乙二醇或不需清洗熔剂。
—用于老化应用的最佳配方，包括占重量30至90％的涂锡铜粉，聚酰亚胺硅氧烷、NMP溶剂、及丁酸及乙二醇或不需清洗溶剂。
根据本发明的导电胶体在取代加或是减的Cu工艺后可用作常规印刷电路板中的导线、接地板和通路装填。这便于取消处理步骤和化学品，因而减少费用和与印刷电路板制造有关的对环境的影响。
虽然本发明曾结合最佳实施例进行描述，但熟悉技术的人可在不背离本发明的实质和范围的条件下进行很多修正、改变和改善。

Claims (34)

1.一种结构，包括：
众多颗粒；
所述众多颗粒中每一粒具有导电涂层；至少某些所述颗粒通过所述导电涂层与其它所述颗粒相熔融。
2.根据权利要求1的结构，其特征在于所述众多颗粒埋于一种聚合物材料中。
3.根据权利要求1的结构，其特征在于所述结构是一个电气连接装置。
4.根据权利要求1的结构，其特征在于所述导电涂层具有比所述颗粒更低的熔融温度。
5.根据权利要求1的结构，其特征在于进一步包括第一和第二面，在所述第一和所述第二面之间涂布所述结构，以便在所述第一和所述第二面之间提供连接。
6.根据权利要求2的结构，其特征在于所述聚合物材料被固化。
7.根据权利要求1的结构，其特征在于所述颗粒选自Cu、Au、Ag、Al、Pd和Pt所组成的组中的材料所形成。
8.根据权利要求1的结构，其特征在于所述涂层选自Sn、Zn、In、Pb、Bi和Sb所组成的组中。
9.根据权利要求1的结构，其特征在于所述聚合物材料选自聚酰亚胺、硅氧烷、聚酰亚胺硅氧烷、及从木质素、纤维素、桐油和农作物油中提炼出的生物基聚合树脂所组成的组中。
10.根据权利要求2的结构，其特征在于所述聚合物材料是未固化的热塑粘合剂。
11.根据权利要求2的结构，其特征在于所述聚合物材料是固化的热塑粘合剂。
12.根据权利要求5的结构，其特征在于所述聚合物材料提供所述第一和所述第二面的粘合连接。
13.根据权利要求5的结构，其特征在于所述第一导电面是第一电子装置接触处及所述第二导电面是第二电子装置接触处。
14.根据权利要求13的结构，其特征在于所述第一电子装置是半导体芯片及所述第二电子装置是封装衬底。
15.根据权利要求5的结构，其特征在于所述第一和所述第二导电面中的一个是焊剂面。
16.根据权利要求1的结构，其特征在于所述结构是一个电子装置。
17.根据权利要求16的结构，其特征在于所述结构是一个计算装置。
18.一种结构，包括：
中有空间而互相连接的颗粒的网；
所述颗粒中第一粒上具有由可熔材料组成的涂层。
所述网中相邻颗粒通过所述可熔材料粘接在一起。
19.根据权利要求18的结构，其特征在于所述空间包括聚合物材料。
20.一种方法，具有以下步骤：
提供在其上具有导电涂层并埋在聚合物材料中的颗粒的胶体；
在第一和第二导电面之间涂布所述胶体；
将所述胶体加热至足以熔融相邻颗粒上的所述涂层的第一温度，从而形成中有空间而互相连接的颗粒的网；
将所述胶体加热至足以在所述空间内将所述聚合物固化的第二温度。
21.根据权利要求20的方法，其特征在于所述涂层选自Sn、Zn、In、Bi、Pb和Sb所组成的组中。
22.根据权利要求21的方法，其特征在于所述颗粒由选自Cu、Ni、Au、Ag、Al、Pb和Pt所组成的组中的一种材料所形成。
23.根据权利要求20的方法，其特征在于所述聚合物材料选自聚酰亚胺、硅氧烷、聚酰亚胺硅氧烷、由木质素、纤维素、桐油和农作物油中制成的生物基树脂所组成的组中。
24.根据权利要求20的方法，其特征在于所述第一导电面是芯片垫片及所述第二导电面位于衬底上，所述方法进一步包括：
加热并施加电功率以老化所述芯片；
将所述芯片自所述衬底分开。
25.一种结构，包括：
具有选自Sn与In所组成的组中的涂层的铜颗粒；
所述颗粒包含在热塑聚合物母体和溶剂中。
26.根据权利要求1的结构，其特征在于所述颗粒在重量上是所述结构的自大约30％至大约90％。
27.根据权利要求20的结构，其特征在于进一步包括将所述第一面压向所述第二面。
28.根据权利要求20的结构，其特征在于所述第一温度和所述第二温度是自大约150°至大约250℃。
29.根据权利要求24的结构，其特征在于分开的步骤在溶剂中通过加热来完成。
30.一种结构，包括：
具有涂层的铜粉，所述涂层是由一种选自Sn、In、Bi、Sb及其组合所组成的组中的材料与熔剂混合而成。
31.根据权利要求30的结构，其特征在于进一步包括NMP溶剂、丁酸及乙二醇及一种选自聚酰亚胺、硅氧烷、聚酰亚胺硅氧烷和一种生物基聚合树脂所组成的组中的材料。
32.根据权利要求31的结构，其特征在于所述铜粉的重量为所述结构的自大约30％至大约90％。
33.根据权利要求5的结构，其特征在于所述颗粒形成与所述第一和所述第二面的金相熔接。
34.权利要求5的结构，其特征在于所述第一和所述第二面是导电的。
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