CN101313397A - 用于高性能互连的碳纳米管钎料复合材料 - Google Patents

用于高性能互连的碳纳米管钎料复合材料 Download PDF

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CN101313397A
CN101313397A CNA2006800431186A CN200680043118A CN101313397A CN 101313397 A CN101313397 A CN 101313397A CN A2006800431186 A CNA2006800431186 A CN A2006800431186A CN 200680043118 A CN200680043118 A CN 200680043118A CN 101313397 A CN101313397 A CN 101313397A
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solder
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CN101313397B (zh
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D·苏
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Abstract

本发明的实施方案是互连技术。制备碳纳米管(CNT)。形成含有预定体积分数的CNT和钎料的CNT钎料复合浆料。

Description

用于高性能互连的碳纳米管钎料复合材料
技术领域
本发明的实施方案涉及纳米技术领域，并且更具体涉及碳纳米管。
背景技术
碳纳米管(CNT)是纳米技术中的重要组成部分。它们是与富勒烯相关的结构，由石墨烯圆柱体构成。可以使用碳纳米管来获益的应用包括用于未来热包装需求的高导热材料。在硅(Si)管芯和基底之间的互连中使用的钎料具有内在的较低耐电迁移性，主要由于它们的电阻和较低的强度和模量。
典型的钎料具有的关键产品的电迁移值约比铜(Cu)低102倍，其用于在硅管芯中的金属化。对于铜来说，其临界电流密度为约106A/cm2，超过该临界电流密度，电迁移将变得有问题。因此，对于钎料，因为其电迁移值比Cu低102倍，其临界电流密度为约104A/cm2，超过该临界电流密度，电迁移将变得有问题。换句话说，当电流密度达到约104A/cm2时，现有的钎料可能面临严重的电迁移危险。此电流密度现通过已有技术实现。目前，钎料电迁移通过界面反应和/或缺陷(例如空穴或捕获填料)来驱动，不必通过钎料内的内在电迁移。虽然电迁移问题可以通过其他技术实现，但钎料很快面临电迁移危险，因为在电流密度在104A/cm2附近或更高时开始经受强烈的电迁移损失。
附图说明
本发明的实施方案最好参考以下说明和用于阐明本发明实施方案的附图来理解。在附图中：
图1是可实施本发明一个实施方案的系统的示意图。
图2A是根据本发明一个实施方案的封装的示意图。
图2B是用本发明一个实施方案的复合浆料制备的钎料凸点的示意图。
图3是根据本发明的一个实施方案形成复合浆料的过程的流程图。
图4A是根据本发明一个实施方案使用长CNT形成CNT钎料复合浆料的过程的流程图。
图4B是根据本发明一个实施方案使用短CNT形成CNT钎料复合浆料的过程的流程图。
图5是根据本发明一个实施方案以电阻率减小率作为CNT体积分数的函数的示意图。
发明内容
本发明实施方案是互连技术。制备碳纳米管(CNT)。形成含有预定体积分数的CNT和钎料的CNT钎料复合浆料。CNT钎料复合浆料然后可以施用到介于模具和基底之间的互连上。
在以下描述中，列出了许多具体细节。然而，应理解没有这些具体细节也可以实施本发明的实施方案。在其他情况下，公知的电路、结构以及技术没有被列出，以避免妨碍对此描述的理解。
本发明的一个实施方案可以描述为一种方法，其通常作为流程图、流程框图、结构图、或者方块图被描述。虽然流程图可以将操作描述为连续过程，但许多操作可以平行或同时进行。另外，操作的顺序可以重新排列。当结束操作时过程终止。过程可以对应方法、方案、程序、制造或制备方法等。
本发明的实施方案是形成用于高性能互连的复合浆料。该复合浆料可以在任何互连应用中使用，例如封装基底的管芯粘合。复合浆料包括以预定体积分数分散在钎料浆料中的碳纳米管(CNT)。钎料浆料包括钎料粉末和浆料成分的混合物。CNT可以是金属单壁或多壁CNT。
CNT具有在几个方面优于金属材料的热性能和电性能。第一，金属单壁或多壁CNT是沿着管轴独立于管长度的弹道式导体。例如，长度为5-10μm的金属CNT可以具有比铜(Cu)或银(Ag)低几倍的电阻率。第二，CNT具有极强的电流载荷容量，超出109A/cm2也不失效，这归因于他们的强共价连接。实验表明CNT可以显示在250℃下109A/cm2的电流密度下超过300小时不降解。第三，CNT展示了沿着管轴约3000W/Km的非常高的热导率。此热导率远超过最好的金属材料，如铜具有仅约420W/Km的热导率。通过在用于微电子互连的钎料浆料中加入CNT，钎料技术可以超过104A/cm2的电流密度。所得CNT钎料复合浆料提供了许多优点。第一，CNT提供高电子传导路径。第二，经由钎料的电子风减少，这归因于电子传导优先经由CNT，导致在钎料中的电迁移损失降低。第三，CNT增强了钎料基体，导致增强的可靠度。
图1所示为系统100，在该系统100中可实施本发明的一个实施方案。系统100包括晶片制造阶段105，晶片划片阶段120，复合浆料形成阶段125，包封阶段130，测设阶段140，以及板组装阶段150。系统110代表半导体封装过程的制造流程。
晶片制造阶段105制造含有大量管芯的晶片。独立的管芯可以是任何微电子装置，例如微处理器、存储装置，界面电路等。晶片制造阶段105包括用于半导体制造的典型过程，例如晶片表面的制备，二氧化硅(SiO2)的生长，杂质的图案化和随后的植入或扩散以得到希望的电性能，栅介质的生长或沉积、以及绝缘材料的生长或沉积，金属和绝缘材料层的沉积，以及将它蚀刻为希望的图案。典型地金属层由铝或最近更多为铜构成。各金属层通过在绝缘材料中的蚀刻孔(乘坐“通孔”)互连。
晶片制备阶段110制备了包含用于封装和测试的管芯。在此阶段期间，晶片在图案化过程后被分类。进行观察以对晶片缺陷进行检查。然后，晶片可以安装在粘附在晶片背面的背面带上。安装带提供了机械支撑用于在随后阶段处理。
晶片划片阶段120将晶片划片、切割或剪裁成独立的管芯。可以使用高精度剪刀和图像识别设备。可将去离子水分配在晶片上，以便在划片期间洗涤掉任何残留颗粒或污染物。然后晶片通过在高旋转速度下被旋转而干燥。
复合浆料形成阶段125制造或生产在组装中的各互连任务中使用的复合浆料。这些可以包括在包封阶段130中的管芯粘合或在板组装阶段150中的封装粘合。复合浆料具有分散在钎料浆料中的CNT，以便减少电迁移损耗，增强钎料基质，增强可靠性，并且提供高导电路径。
包封阶段130包封管芯和封装基底。管芯可以是均匀的或非均匀的。包封包括使用由复合浆料形成阶段125提供的复合浆料来印刷所述复合浆料，放置管芯，倒装管芯助融和放置、回流、监测、未充满分配和固化等。集成散热器(HIS)可以粘附到管芯和基底组件上。管芯和基底的包封组件成为容易测试的封装。
测试阶段140在各种条件下对封装进行一个或多个测试。测试可以是高加速应力测试(HAST)或偏倚-HAST。封装可以是装有动力的或无动力的。测试阶段140可以是任选的。
板组装阶段150将封装组装为印刷电路板。此阶段将装置封装粘附到板上。此阶段可以包括各种钎焊过程、回流、测试和监测。通过复合浆料形成阶段125提供的复合浆料可以在钎焊过程或回流中使用。组装的板然后安装到系统或装置中的平台内。
图2A所示是封装200，在该封装200中可实施本发明的一个实施方案。封装200代表在图1中所示包封阶段130中完成的封装。其包括基底210和管芯220。
基底210是提供用于管芯220的支撑体和电互连的封装基底210。基底210可以是任何合适的材料，例如硅或任何陶瓷或聚合物基底。基底210具有基底垫212和基底凸点215。基底垫212放置在基底210的顶面上，并且提供用于与管芯220互连的触点。基底凸点215提供钎料凸点以连接到管芯220上。在一些封装技术中，基底凸点215可以是任选的。
管芯220是任何半导体管芯。其可以具有微电子装置，例如微处理器、存储器、接口管芯、集成电路等。管芯220通过大量管芯凸点225粘附到基底210上。管芯凸点225提供与基底210上的基底垫212或基底凸点215的互连。管芯凸点225可以使用任何标准制造或生产技术来制造。管芯220在预钎焊、助熔和回流阶段中粘附到基底210上。基底凸点215(如果使用)和管芯凸点215中至少之一由图1所示的复合浆料形成阶段125所提供的复合浆料来制备。
典型地，钎料凸点、或者基底凸点215或者管芯凸点225可以通过经由干法(例如蒸发)或湿法(例如电镀)逐渐沉积复合浆料来构建。蒸发凸点形成技术典型地用于晶片凸点形成，例如受控塌陷管芯连接(C4)方法。在此方法中，金属掩模(例如钼)对准晶片上的连接垫并被夹住。下凸点技术(UBM)通过蒸发沉积到铝垫上。具有预定体积分数的CNT和钎料浆料的复合浆料然后通过蒸发沉积到UBM表面上。然后将金属掩模除去。所形成的钎料凸点通常回流以熔融钎料。电镀凸点形成技术也用于晶片凸点形成。晶片首先用金属仔晶来金属化。然后暴露所希望的凸点位置用光刻胶来图案化。然后用晶片作为阴极通过电镀浴施加静态电流或脉冲电流。电镀后，剥离光刻胶，并蚀刻掉金属仔晶。复合浆料然后可以使用助熔剂回流以形成钎料凸点。
也可以使用任何其他钎料凸点形成技术。在这些技术中，使用复合浆料代替普通钎料。这些凸点形成技术可以包括液体钎料转移法(例如Meniscus凸点形成、喷流凸点形成)，固体钎料转移法(线凸点形成、球焊接、激光粘附、贴花式钎料转移，粘性点钎料转移、取放式钎料转移、无回流钎料球凸点形成)，以及钎料浆料凸点形成(印刷-脱附-回流，印刷-回流-脱附、分配)不考虑使用使用什么凸点形成技术，都使用复合浆料代替普通钎料以提供增强互连。
图2B所示为通过本发明一个实施方案的复合浆料制备的钎料凸点215/225。钎料凸点215/225是包括钎料浆料230和CNT240的混合物。
钎料浆料230是钎料粉末232和钎料组分235的混合物。钎料粉末232可以是具有适当组成的合适的钎料材料(例如锡-铅(Sn/Pb)或无铅合金)的粉末。典型地，使用共晶合金粉末。浆料成分235可以是任何合适的组分，例如能够除去金属氧化物并促进钎料展开的助熔剂或任何其他化学试剂。
CNT240可以是以预定体积分数分散或镶嵌在钎料浆料203中的金属单壁或多壁CNT。它们可以是长CNT或短CNT，这取决于形成复合浆料的方法。长CNT可具有的长度范围为约10-30μm。短CNT可具有的长度范围为至多约10μm。体积分数可以根据一些希望的电特性来决定。其是CNT重量与整个钎料凸点215/225之间的比例，或者是CNT相对于整个重量的重量百分数。CNT240可以用形成碳化物的元素来涂覆。形成碳化物的元素可以是以下元素中一种：钛(Ti)、铬(Cr)、钒(V)、钨(W)、钼(Mo)和铊(Ta)。
图3所示流程图是根据本发明一个实施方案形成复合浆料的过程300.
开始后，过程300制备碳纳米管(CNT)(框310)。CNT可以是金属单壁或多壁CNT。CNT可以使用任何标准技术来制备、合成、功能化或得到，所述标准技术例如为碳弧法或电弧放电、激光蒸发或烧蚀、以及催化化学汽相沉积(CVP)。接下来，过程300决定是否希望涂覆(框320)。涂覆可以是希望的，从而最小化回流后CNT和钎料之间的任何耐接触性。如果涂覆是不希望的，过程300进行到框340。如果涂覆是希望的，过程300使用以下方法之一用形成碳化物的元素涂覆CNT：电镀、物理汽相沉积(PVD)以及化学汽相沉积(CVD)(框330)。形成碳化物的元素可以是以下元素中的任何一种：钛(Ti)、铬(Cr)、钒(V)、钨(W)、钼(Mo)和铊(Ta)。
然后，过程300形成含有预定体积分数的CNT和钎料的CNT钎料复合浆料(框340)。有至少两种方法来形成CNT-钎料复合浆料，如图4A和4B中所述。体积分数可以根据一些希望的特性来限定(例如30-40％)。接下来，过程300将CNT-钎料复合浆料施用到管芯和基底之间的互连上(框350)。钎料回流后，钎料可以润湿CNT，并且可以形成可靠的CNT-钎料纳米复合互连。然后过程300终止。
图4A所示流程图是根据本发明的一个实施方案使用长CNT形成CNT-钎料复合浆料的过程340。
开始后，过程340将CNT与钎料粉末和浆料成分混合(框410)。优选长度长于10μm的长CNT，以提供最大可能的弹道传导电子路径。根据所希望的体积分数或重量比实施混合。浆料成分可以是任何希望的成分、试剂、添加物，例如溶剂、助熔剂等。然后终止过程340。
图4B所示流程图是根据本发明的一个实施方案使用短CNT形成CNT-钎料复合浆料的过程340。
开始后，过程340使用聚合物金属复合过程形成CNT-钎料复合锭(框430)。典型地，在此过程中优选具有小于10μm长度的短CNT。聚合物-金属复合过程是挤压铸造和粉末混合中一种，随后固结。接下来，过程340使用粉末过程由CNT-钎料复合锭形成CNT-钎料复合粉末(框440)。可以使用任何标准的粉末方法，例如气体雾化法。当使用典型的气体雾化法时，CNT-钎料复合锭可以由加热的坩埚经由熔融进料管流动。然后当其离开孔时遇到高速气流。然后液体在雾化区解体为液滴的集合。在液滴自由降落期间其变成球形，并固化为粉末。在此过程中可以得到极细粉末。然后，过程340使CNT-钎料复合粉末与浆料成分如助熔剂混合以形成CNT-浆料复合浆料(框450)。过程340然后终止。
图5所示为根据本发明一个实施方案的电阻率降低作为CNT体积分数的函数。图5中有两条曲线：曲线520和曲线520。曲线显示CNT-Cu复合物的电阻率降低作为体积分数的函数。垂直轴是电阻率，单位为微欧-cm(μΩ-cm)。水平轴为体积分数、或重量比、或填充分数，以百分数表示(％)。
计算曲线510和520，用于与Cu混合的单壁CNT。曲线510对应定向的CNT。曲线520对应无规的CNT。在0％体积分数或纯Cu时，电阻率约为1.65μΩ-cm。因此，此值的一半是约0.825μΩ-cm。这由直线530显示为50％Cu。曲线510和520与线530的交叉点为点A和B，分别对应约30％和40％的体积分数。因此，介于30-40％的体积分数与纯Cu比可以降低电阻率50％。
电迁移现象是金属质量传输的结果，这归因于传导电子和扩散金属原子之间的动量传输。归因于电迁移的金属原子的通量可以使用在势场中静电模拟和用于扩散的爱因斯坦等式表示如下：
J＝cD(Z*eρj)/kT    (1)
其中J是原子通量，D是用于合适质量传输机理的扩散系数，Z*是代表动量交换的信号和强度的有效价数或有效电荷，ρ是电阻率，j是电流密度。KT是每原子的平均热能。
由等式(1)，电迁移诱导的质量通量直接与(尤其)电阻率、电流密度和扩散系数成正比。因此，较低电阻率降低了电迁移原子通量J，因此降低了钎料中的整个电子-迁移过程。因此，根据曲线510和520，包含CNT和钎料的CNT-钎料复合浆料降低了电阻率，其依次降低了对钎料的整个电迁移损耗。
当已经参考了几个实施方案描述本发明时，本领域技术人员将认识到本发明不限于所描述的实施方案，但是可以在所附权利要求的精神和范围内改变或改进来实施。权利要求书因此应认为是说明性的而非限制性的。

Claims (20)

1.一种方法，其包括：
制备碳纳米管(CNT)：以及
形成具有预定体积分数的CNT和钎料的CNT-钎料复合浆料。
2.权利要求1的方法，其还包括：
使用以下方法之一用形成碳化物的元素涂覆CNT：电镀、物理汽相沉积(PVD)以及化学汽相沉积(CVD)，所述形成碳化物的元素是以下元素之一：钛(Ti)、铬(Cr)、钒(V)、钨(W)、钼(Mo)和铊(Ta)。
3.权利要求1的方法，其还包括：
将CNT-钎料复合浆料涂布到管芯和基底之间的互连上。
4.权利要求1的方法，其中形成CNT-钎料复合浆料包括：
将CNT与钎料粉末和浆料成分混合，所述CNT是长CNT。
5.权利要求1的方法，其中形成CNT-钎料复合浆料包括：
利用聚合物-金属复合法使用短CNT形成CNT-钎料复合锭；
利用粉末法由CNT-钎料复合锭形成CNT-钎料复合粉末；
将CNT-钎料复合粉末与浆料成分混合，形成CNT-钎料复合浆料。
6.权利要求5的方法，其中形成CNT-钎料复合锭包括：
利用聚合物-金属复合法形成CNT-钎料复合锭，所述聚合物-金属复合法是挤压铸造法和粉末混合随之固结法中的一种。
7.权利要求3的方法，其中形成CNT-钎料复合粉末包括：
利用气体雾化由CNT-钎料复合锭形成CNT-钎料复合粉末。
8.一种复合浆料，其包括：
包括钎料粉末和与该钎料粉末混合的浆料成分的钎料浆料；以及
以预定体积分数分散在钎料浆料内的碳纳米管(CNT)。
9.权利要求8的复合浆料，其中CNT包括：
用形成碳化物的元素涂覆的长或短CNT。
10.权利要求9的复合浆料，其中形成碳化物的元素为以下元素之一：钛(Ti)、铬(Cr)、钒(V)、钨(W)、钼(Mo)和铊(Ta)。
11.权利要求8的复合浆料，其中预定体积分数为约30-40％。
12.权利要求8的复合浆料，其中浆料成分是助熔剂。
13.权利要求9的复合浆料，其中长CNT的长度为约10-30μm。
14.权利要求9的复合浆料，其中短CNT的长度为约10μm。
15.一种封装，其包括：
具有管芯凸点的管芯；
具有基底凸点的封装基底，所述基底凸点经由管芯凸点粘附到管芯上，管芯凸点和基底凸点中至少之一由复合浆料形成，该复合浆料包括：
包括钎料粉末和与该钎料粉末混合的浆料成分的钎料浆料，以及
以预定体积分数分散在钎料浆料内的碳纳米管(CNT)。
16.权利要求15的封装，其中CNT包括：
用形成碳化物的元素涂覆的长或短CNT。
17.权利要求16的封装，其中形成碳化物的元素为以下元素之一：钛(Ti)、铬(Cr)、钒(V)、钨(W)、钼(Mo)和铊(Ta)。
18.权利要求15的封装，其中预定体积分数为约30-40％。
19.权利要求15的封装，其中浆料成分是助熔剂。
20.权利要求9的封装，其中长CNT的长度为约5-30μm。
CN2006800431186A 2005-12-20 2006-12-07 用于高性能互连的碳纳米管钎料复合材料 Expired - Fee Related CN101313397B (zh)

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CN101313397B (zh) 2013-02-06
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WO2007120228A3 (en) 2008-03-13
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DE112006003438B4 (de) 2017-03-16
US20070145097A1 (en) 2007-06-28
TWI333688B (en) 2010-11-21
JP2009519136A (ja) 2009-05-14
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US8100314B2 (en) 2012-01-24
US20100126631A1 (en) 2010-05-27

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