CN1275170A - 复合材料及其应用 - Google Patents

复合材料及其应用 Download PDF

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Publication number
CN1275170A
CN1275170A CN98809356A CN98809356A CN1275170A CN 1275170 A CN1275170 A CN 1275170A CN 98809356 A CN98809356 A CN 98809356A CN 98809356 A CN98809356 A CN 98809356A CN 1275170 A CN1275170 A CN 1275170A
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Prior art keywords
heat sink
semiconductor element
composite material
metal
thermal expansion
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CN98809356A
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CN1093565C (zh
Inventor
近藤保夫
金田润也
青野泰久
阿部辉宜
稻垣正寿
斋藤隆一
小池义彦
荒川英夫
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Hitachi Ltd
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Hitachi Ltd
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    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/06—Metallic powder characterised by the shape of the particles
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Abstract

本发明的目的是提供一种具有低的热膨胀率,高的导热率和良好的塑性加工性的复合材料,所述复合材料可应用于半导体器件以及许多其它应用场合。所述复合材料由金属和热膨胀系数比所述金属小的无机粒子构成。其特征在于所述无机粒子分散的方式使95%或者更多的粒子(以横截面上的粒子面积表示)形成具有复杂构形的连接一起的聚集体。所述复合材料含有20—80体积%的铜的氧化物,余下部分是铜。其在室温至300℃的范围内,热膨胀系数为5×10－6—14×10－6/℃,导热率为30—325W/m·k。所述复合材料适于制作半导体器件的散热片和静电吸引器的介电片。

Description

复合材料及其应用
技术领域
本发明涉及具有低的热膨胀率和高的导热率的复合材料和所述复合材料的生产方法，而且还涉及所述复合材料例如在半导体器件中的应用。
背景技术
电力电子学包括涉及对电功率和电能进行转换和控制的功率电子器件，以通断模式工作的功率电子器件的技术，还包括涉及能量转换系统的应用技术。
电功率的转换需要各种具有开关特性的功率半导体。实际使用的这些半导体包括整流二极管(具有一个只在一个方向有电流流动的pn结)，晶闸管，双极晶体管，以及MOSFET(具有多个pn结的组合)。近来开发的半导体包括绝缘栅双极晶体管(IGBF)和响应门信号进行开关的栅控截止晶闸管(GTO)。
这些功率半导体在通电时会发热。随着电量和速度的增加，所述半导体的发热量会更大。为了防止所述半导体由于发热出现劣化和寿命缩短，所述半导体中应安装有防止其自身及相邻部位温度升高的散热体。通常用作散热体的材料是铜，其便宜并且导热率高(393W/m)。不幸的是，铜不适合用于功率半导体器件的散热体，因为铜的热膨胀率高达17×10-6/℃，因而，不能与热膨胀率为4.2×10-6/℃的硅很好地焊在一起。解决该问题的一个方法是采用热膨胀率与硅相近的钼或钨制造散热体，或者在散热体和半导体元件间插入钼或钨。
功率半导体元件与电子半导体元件不同。后者以由在单个半导体芯片上集成形成的电子电路组成的集成电路(IC)为例证。根据其功能，电子半导体元件被分为存储元件，逻辑元件，微处理器等。涉及最近的电子半导体元件的问题是发热，当集成程度和运行速度增加时，发热量增大。更糟的是，为了防止发生失效和劣化，电子半导体元件被一个一个地单独气密封装，以便与大气隔离。广泛采用的封装是陶瓷封装(其中，每个半导体元件均通过芯片焊接固定到陶瓷上)和塑料封装(采用塑料密封)。一个满足高可靠性和高速运行要求的新进展是在单个衬底上安装有多个半导体元件的多片模块(MCM)。
构造塑料封装件时，应使其中的半导体元件的端子通过焊接引线与引线框相连接，并且，整个组件采用塑料密封。为解决不断增加的发热问题所取得的最新进展是其中的引线框起散热作用的封装件或者其中安装有用于散热的散热体的封装件。引线框或者用于散热的散热体通常采用高导热率的铜制造。不幸的是，可以预料会发生故障，原因是铜与硅的热膨胀率差别较大。
相反，构造陶瓷封装件时，半导体元件置于具有印制在其上的布线的陶瓷衬底上，并且，整个组件采用金属或者陶瓷罩密封。陶瓷衬底采用起散热体作用的Cu-Mo或Cu-W复合材料或者可伐合金作里衬。要求能够以低生产成本制造具有低的热膨胀率，高的热传导性和良好的可加工性的陶瓷材料。
MCM包括具有在其上形成薄膜布线的金属或者陶瓷衬底，多个在其上固定的半导体元件(以裸片形式)，容纳上述元件的陶瓷封装和密封罩。如果需要散热，所述封装件可装有散热体或散热翅片。金属衬底采用铜或铝制造。这两种金属的优点是导热率好，但缺点是热膨胀率高，这会导致与半导体元件的匹配性变差。因此，具有高可靠性的MCM的衬底采用硅或氮化铝(AlN)制造。与陶瓷封装件焊接在一起的散热体应采用导热率高而热膨胀率低的材料制造，以便与封装材料实现良好的匹配。
如上所述，所有的半导体器件在运行期间均会发热，而且，如果热量被累积起来，还会出现故障。因此，需要具有良好导热率以便进行散热的散热体。与半导体元件直接或者通过绝缘层间接焊接一起的散热体不仅应具有高的导热率，而且还应具有低的热膨胀率，以便与半导体元件实现良好匹配。
主要的半导体元件以Si或者GaAS为基础，这两种物质的热膨胀系数为分别为2.6×10-6-3.6×10-6/℃和5.7×10-6-6.9×10-6/℃。在热膨胀率上与这两种物质相当的已知材料中包括AlN，SiC，Mo，W和Cu-W。当单独用于散热体时，上述各种物质的传热系数和导热率不能根据要求进行控制。这些物质的可加工性差而且生产成本高。日本专利公开平8-78578提出了一种Cu-Mo烧结合金。日本专利公开平9-181220提出了一种Cu-W-Ni烧结合金。日本专利公开平9-209058提出了一种Cu-SiC烧结合金。日本专利公开平9-15773提出了一种Al-SiC复合材料。这些传统的复合材料中如果各构成物比例发生变化，则其传热系数和导热率可在很大范围内进行调整。然而，上述材料的塑性加工性差，因而难以加工成薄板，而且需要很多的加工步骤。
本发明的一个目的是提供具有低的热膨胀率、高的导热率和良好的塑性加工性的复合材料，提供采用所述复合材制造的半导体器件，提供用于所述半导体器件的散热体，提供一种静电吸引器，以及提供一种用于所述静电吸引器的介电片。
发明公开
本发明的第一个方面在于一种由金属和热膨胀系数比所述金属小的无机粒子构成的复合材料，其特征在于分散所述无机粒子时，应使95％或者更多的粒子(用横截面上的粒子面积的大小表示)形成连接一起的具有复杂构形的聚集体。
本发明的第二个方面在于一种由金属和热膨胀系数比所述金属小的无机粒子构成的复合材料，其特征在于在100μm2的横截面上单独存在的所述无机粒子的个数小于或等于100，余下的粒子以连接一起的具有复杂构形的聚集体形式分布。
本发明的第三个方面在于一种由金属和热膨胀系数比所述金属小的无机粒子构成的复合材料，其特征在于所述无机粒子的维氏硬度小于或等于300。
本发明的第四个方面在于一种由金属和热膨胀系数比所述金属小的无机粒子构成的复合材料，所述复合材料的热膨胀系数在20-105℃的范围内，其增加量，平均为从20℃的值起每W/m·k增加0.025-0.035ppm/℃。
本发明的第五个方面在于一种由金属和热膨胀系数比所述金属小的无机粒子构成的复合材料，其特征在于所述无机粒子以连接一起的聚集体的形式分散分布，所述聚集体沿塑性加工方向呈拉长状。
本发明的第六个方面在于一种由铜和铜的氧化物粒子构成的复合材料，其特征在于分散所述铜的氧化物粒子时，应使95％或者更多的粒子(以横截面积中粒子的面积数表示)形成连接一起的具有复杂构形的聚集体。
本发明的第七个方面在于一种采用所述复合材料制造的用于半导体器件的散热片。
本发明的第八个方面在于一种用于半导体器件的其上具有镍镀层的散热片。
本发明的第九个方面在于一种包括多个绝缘衬底和固定在每个所述绝缘衬底上的多个半导体元件的半导体器件，每个所述绝缘衬底通过形成于所述绝缘衬底的上下表面的导电层直接连接于所述散热片。
本发明的第十个方面在于一种包括具有散热片的绝缘衬底和固定在所述绝缘衬底上的半导体元件的半导体器件，其中，所述散热片是在本发明的第七或者第八方面中定义的散热片。
本发明的第十一个方面在于一种半导体器件，所述半导体器件包括固定在散热片上的半导体元件，与所述散热片相连接的引线框，以及以导电方式将所述引线框与所述半导体元件连接起来的金属布线；所述半导体元件采用塑料密封，其中，所述散热片是在本发明的第七或者第八个方面中定义的散热片。
本发明的第十二个方面在于一种半导体器件，所述半导体器件包括固定在散热片上的半导体元件，与所述散热片相连接的引线框，以及以导电方式将所述引线框与所述半导体元件连结起来的金属布线；所述半导体元件采用塑料密封，所述散热片在与所述半导体元件相连的一侧相对的另一侧是敞开的，其中，所述散热片是在本发明的第七个或者第八个方面中定义的散热片。
本发明的第十三个方面在于一种半导体器件，所述半导体器件包含固定在散热片上的半导体元件，用于与外面的布线相连接的引线，在其中心处存在一敞开空间以安放所述半导体元件的陶瓷多层布线衬底，以及以导电方式将所述半导体元件与衬底的端子相连接的金属布线，所述散热片与所述衬底相互连接，以便使所述半导体元件固定在所述空间处，所述衬底则连接到密封罩上，从而，将所述半导体元件与大气环境隔离开来，其中，所述散热片是在本发明的第七或者第八个方面中定义的散热片。
本发明的第十四个方面在于一种半导体器件，所述半导体器件包含固定在散热片上的半导体元件，用于与外面的布线相连接的端子，在其中心处存在一凹槽以容纳所述半导体元件的陶瓷多层布线衬底，以及以导电方式将所述半导体元件与衬底的端子连接一起的金属布线，所述散热片与所述衬底的凹槽相互连接，以便使所述半导体元件固定于所述凹槽处，所述衬底连接到密封罩上，从而将所述半导体元件与大气环境隔离开，其中，所述散热片是在本发明的第七个或第八个方面中定义的散热片。
本发明的第十五个方面在于一种半导体器件，所述半导体器件包含散热片，通过导热树脂连接到所述散热片上的半导体元件，与陶瓷绝缘衬底相连接的引线框，以及以导电方式将所述半导体元件与引线框连接一起的TAB，所述散热片与所述衬底相互连接，以便使所述半导体元件与大气环境隔离开来，而且，所述半导体元件和所述绝缘衬底被插入两者间的导热的弹性树脂隔离开，其中，所述散热片是在本发明的第七个或第八个方面中定义的散热片。
本发明的第十六个方面在于一种半导体器件，所述半导体器件包含第一个散热片，通过金属与所述散热片相连接的半导体元件，与接地板相连接的第二个散热片，所述第一个散热片固定在该散热片的接地板上，以及以导电方式连接到所述半导体元件的端子的TAB，所述半导体元件采用塑料密封，其中，所述散热片是在本发明的第七个或第八个方面中定义的散热片。
本发明的第十七个方面在于一种用于静电吸引器的介电片，所述介电片由在上述的第一至第六个方面中之任一个方面定义的复合材料制备而成。
本发明的第十八个方面在于一种静电吸引器，所述静电吸引器包含一个电极层和一个与所述电极层焊接一起的介电片，当在所述电极层上施加电压时，所述介电片会产生静电吸引力，以使物体固定到所述介电片的表面上，其中，所述介电片是在本发明的第十七个方面中定义的介电片。
根据本发明的复合材料由金属和无机粒子构成。所述金属包括Au、Ag、Cu和Al，其中，Cu是最理想的，因为它具有高的熔点和高的强度。所述无机粒子应优选是那些较软且烧结后稳定，以及在20-150℃的范围内的平均热膨胀系数等于或小于5.0×10-6/℃，优选等于或小于3.5×10-6/℃，维氏硬度为300或更低的无机粒子。(它们与传统的无机粒子，如SiC和Al2O3不同，这两种物质与基体金属的硬度差别很大)。这种软的无机粒子可使得烧结后具有良好的塑性加工性(热加工或者冷加工)。可轧制性使得在短的加工时间内生产较薄的板材成为可能。所获得的复合材料由于无机粒子分散分布其中而具有高的强度。所述无机粒子的可能的实例包括铜的氧化物，锡的氧化物，铅的氧化物以及镍的氧化物。所述这些实例中，优选铜的氧化物，因其热膨胀系数最小。
本发明的复合材料应该优选采用硬且细小的陶瓷粒子，如SiC和Al2O3进行增强，所述陶瓷粒子的维氏硬度等于或高于1000，平均粒子直径为3μm或更小，其含量为5体积％或更低。
根据本发明的散热片和介电片可以通过烧结，任选的轧制以及塑性加工(例如压制)来获得其最终的形状。
根据本发明的复合材料应优选含有20-80体积％的氧化亚铜(Cu2O)的铜(Cu)合金，其中Cu相和Cu2O相构成所述的分散结构。所述复合材料应优选具有5×10-6-14×10-6/℃的热膨胀系数，以及在室温至300℃的范围内，30-325W/m·k的导热率。
所述铜—氧化亚铜复合材料应优选含有20-80体积％的氧化亚铜(Cu2O)，余者为铜(Cu)。Cu2O相和Cu相应具有取向结构。所述复合材料应优选具有5×10-6-14×10-6/℃的热膨胀系数，以及在室温至300℃的范围内为30-325W/m·k的导热率。取向方向上的导热率应大于与该取向方向相垂直的方向上的导热率的2倍。
根据本发明的复合材料采用下述步骤生产：将铜粉末和氧化亚铜粉末加以混合，对混合后的粉末进行压制，在800-1050℃下烧结所压制的成形体，并且进行冷或者热塑性加工。(铜粉末是所述金属的一个实例，氧化亚铜粉末是所述无机粒子的一个实例。)
根据本发明的铜复合材料由含有不可避免的杂质的氧化铜(CuO)和铜(Cu)的混合粉末制备而成。氧化铜的量为10.8-48.8体积％。其生产过程包括如下步骤：将所述混合粉末压制成形，在800-1050℃下烧结所述的压制成形体，由此使所述压制成形体固化并且通过CuO和Cu间的反应来形成Cu2O，再进行热压或者冷压制(作为塑性加工)以及退火处理。
本发明的铜复合材料由Cu和Cu2O构成，前者的热膨胀系数高达17.6×10-6/℃，导热率高达391W/m·k，而后者的热膨胀系数较低，为2.7×10-6/℃，导热率则为12W/m·k。通过烧结就可将其成形为用于半导体器件的散热片。所获烧结体由Cu和含量为20-80Vol％的Cu2O构成。所述烧结体的热膨胀系数为5×10-6-14×10-6/℃，在室温至300℃的范围内的导热率为30-325W/m·k。Cu2O含量等于或高于20％时，所述复合材料具有散热片所要求的高导热系数。Cu2O含量等于或低于80％时，所述复合材料具有足够的导热率和结构强度。
根据本发明的复合材料基本上通过粉末冶金来获得。所述铜复合材料由Cu粉末和Cu2O粉末或者CuO粉末制备而成。所述这些粉末(作为原材料)按预定的比例进行混合，在模具中冷压所述的混合粉末，以及对所获得的预型件进行烧结。如必要，对所获烧结体再进行热或者冷塑性加工。
原材料粉末的混合通过使用V型混合机，球形磨机，或者通过机械合金化来实现。原材料粉末的粒子尺寸影响压模性能和烧结后Cu2O的分散性。因此，Cu粉末的粒子直径应为100μm或更小，Cu2O和CuO粉末的粒子直径应为10μm或更小，优选为1-2μm。
在400-1000kg/cm2的压力下，对所述混合粉末在模具中进行冷压。所述压力应优选随着Cu2O含量的增加而增大。
在氩气氛中，正常压力下或者采用HIP在压力下进行热压对所述混合粉末的预型件进行烧结。烧结应在800-1050℃下进行约3小时。烧结温度应随着Cu2O含量的增加而升高。烧结温度依据基体金属的种类而改变。基体金属为铜时，如烧结温度为800℃或更低，则所获烧结体将具有低密度。此外，在1050℃或者更高的温度下烧结会发生Cu与Cu2O间的共晶反应，从而导致部分熔化。因此，充分的烧结温度范围为900-1000℃。
根据本发明的铜复合材料由Cu和Cu2O构成，所述复合材料的硬度低。因此，如必要，能够对其进行冷加工或热加工，例如轧制和锻造，在烧结后进行上述加工。加工会导致导热率的各向异性，这对于强度或者某些需要在特定方向进行热传导的应用场合有利。
根据本发明，原材料粉末可以是CuO。将该CuO粉末与Cu粉末混合，并且将所混合的粉末压制成型。烧结所获得的预型件以使Cu氧化。结果，就获得一种由Cu基体和Cu2O分散相构成的烧结体。与Cu共存的CuO在高温下依据下述方程(1)转变成Cu2O(其为热稳定相)。
                                (1)
需要一定长度的时间才能使方程(1)所表示的反应达到平衡。如烧结温度为900℃，则3小时就已足够。
烧结体中的Cu2O粒子应尽可能细小，因为其粒子直径对复合材料的密度，强度和塑性加工性有影响。混合方法对粒子直径的影响很大。混合能量越高，发生凝聚的粉末粒子越少。从而，烧结后可获得细小的Cu2O。
根据本发明，Cu2O相的粒子依据所使用的混合机器可作如下确定。50体积％或更多的粒子的直径等于或小于50μm(如果使用的是V型混合机(混合能量小))，或粒子直径小于或等于50μm(如果使用内装有钢球的球形磨机)，或粒子直径小于或等于10μm(使用机械合金化(混合能量最大)时)，余下部分的粒子直径为50-200μm。当粒子直径为200μm或更大时，所获得的复合材料的孔隙率高，因而，其塑性加工性差。当Cu2O相的含量超过50体积％时，所获得的复合材料的导热率低，且性能不均匀，因而，不足于用来作为半导体器件的散热片。一种优选的结构是一种由Cu相和在其中均匀分布的Cu2O相(50μm或更小)构成的结构。Cu2O粒子的形状极其不规则，并且在烧结前相互连成一体；烧结前它们的粒子直径在高倍下可观察到。Cu2O相应优选为10μm或更小。
附图简述
图1是在本发明的实施例1(试样编号4)中的烧结体(由Cu和55体积％的Cu2O构成)的显微结构的光学显微照片。
图2是在本发明的实施例2中的烧结体(由Cu和55体积％的Cu2O构成)的显微结构的光学显微照片。
图3是在本发明的实施例3中的烧结体(由Cu和40体积％的Cu2O构成)的显微结构的光学显微照片。
图4是本发明的实施例4中的锻造后的材料(由Cu和55体积％的Cu2O构成)的显微结构的光学显微照片，所述显微结构是与锻造时的延伸方向平行的平面的显微结构。
图5是本发明的实施例5(试样编号14)中的烧结体(由Cu和32.2体积％的CuO构成)的显微结构的光学显微照片。
图6示出的热膨胀率与导热率之间的关系。
图7是本发明的实施例6中的IGBT模块的平面视图。
图8是本发明的实施例6中的IGBT模块的剖面图。
图9A-9D是实施例6中的IGBT模块的生产步骤的示意图。
图10示出的是在生产本发明的实施例6中的IGBT模块的每个步骤中的基体弯曲(即翘曲)量。
图11是装备有本发明的实施例6中的IGBT模块的能量转换装置的平面图和剖面图。
图12A和12B示出的是尚未装备有本发明的实施例6中的IGBT模块的能量转换装置的弯曲量。
图13A和13B示出的是已装备有本发明的实施例6中的IGBT模块的能量转换装置的弯曲量。
图14是内置了本发明的实施例7中的散热片的塑料封装件的剖面图。
图15是具有外露的本发明的实施例7中的散热片的塑料封装件的剖面图。
图16是本发明的实施例8中的封装件的剖面图。
图17是具有本发明的实施例8中的散热翅片的陶瓷封装件的剖面图。
图18是本发明的实施例9中的半导体器件的剖面图。
图19是本发明的实施例9中的半导体器件的剖面图。
图20是本发明的实施例10中的MCM的剖面图。
图21是与本发明有关的静电吸引器的剖面图。
实施本发明的最佳模式
实施例1
本实施例中使用的原材料粉末是电解铜粉末(粒子直径为75μm或更小)和Cu2O粉末(粒子直径为1-2μm，纯度为3N)。按照表1所示比例对上述两种粉末进行混合。将所获得的混合物(1400g)在一内装有钢球的干式球形磨机中进行充分混合，时间超过10小时。所获得的混合后的粉末被置于直径为150mm的模具中，并在400-1000kg/cm2的压力下进行冷压，所述压力依据Cu2O含量而定。结果，就获得了直径为150mm，高为17-19mm的预型件。在氩气氛中对所述预型体进行烧结。对所获得的烧结体进行化学分析，结构检验，并进行热膨胀率、导热率和维氏硬度的测定。附带提一下，在900-1000℃下进行烧结3小时，具体温度依据Cu2O含量而定。采用进行TMA分析(热机械分析)的仪器测定室温至300℃范围内的热膨胀率。导热率采用激光烧化法测量。所获结果示于表1中。所获烧结体(试样编号4)具有如图1所示的显微结构。
化学分析结果表明，所获烧结体的组成与混合比例相一致。由表1可明显看出，依据Cu和Cu2O的比例不同，热膨胀率和导热率的变化范围很大。因此，有可能生产出具有散热片所要求的热性能的烧结体。表1
  编号     组成(体积％)     热膨胀系数(×10-6/℃)   导热率(W/m·K)
Cu  Cu2O
 1  20  80      5.5  41
 2  30  70      7.0  63
 3  40  60      8.4  93
 4  45  55      9.3  116
 5  50  50      10.1  138
 6  60  40      10.8  183
 7  70  30      12.9  229
 8  80  20      13.8  280
图1所示的显微照片(×300)显示其显微结构中Cu2O粒子尺寸为50μm或更小，Cu2O相在Cu相中均匀分散。(Cu2O粒子在混合阶段聚集并在烧结阶段稍有长大)。显微照片中，白色部分代表Cu相，黑色部分代表Cu2O相。
由图1可注意到，Cu2O粒子以不规则形状分散，占有横截面积其的99％或更多。
所述Cu相和Cu2O相的硬度(HV)分别为210-230和75-80。所获得的烧结体具有良好的机加工性能(车削和钻削)，能够容易地加工成所要求的形状。
实施例2
所采用的步骤与实施例1相同，只是进行混合时使用的是V型混合机。所获得的烧结体由Cu和55体积％的Cu2O构成。采用与实施例1相同的方法，对所述烧结体的显微结构、热膨胀率和导热率进行了测定。
图2是由Cu和55体积％的Cu2O构成的烧结体的光学显微照片(×300)。由照片可明显看出，显微结构中存在尺寸差别很大的Cu2O粒子。大的Cu2O粒子是在V型混合机中进行混合时发生聚集而形成的。本实施例中的烧结体的热膨胀率和导热率与组成相同的Cu2O相在Cu相中均匀分散的烧结体几乎相当。然而，所测结果因部位不同而异。可注意到，大部分Cu2O粒子象在图1中那样，以不规则形状分散，但它们的聚集程度比图1中大。
实施例3
本实施例中使用的原材料粉末是电解铜粉末(其粒子直径为74μm或更小)和CuO粉末(其粒子直径为1-2μm，纯度为3N)。对上述两种粉末进行混合，以获得由Cu和22.4体积％的CuO的构成的混合物。在内装有钢球(直径8mm)的行星式球磨机(直径120mm)中采用机械合金化法充分混合所获得的混合物(300g)达25小时。将所获得的混合后的粉末置于一直径为80mm的模具中，并且在1000kg/cm2的压力下进行冷压。结果就获得一种预型体。在800℃下，于氩气氛中烧结所述预型体，时间为2小时。采用与实施例1相同的方法对所获得的烧结体进行结构、热膨胀率和导热率检测。对其也采用X射线衍射仪进行了测试。
图3是所述烧结体的显微结构的光学显微照片(×1000)。由图中可明显看出，Cu2O粒子比实施例1和2中的相应粒子更细小，而且，尺寸为10μm或更小的Cu2O粒子是均匀分散的。这种细小的显微结构能够满足改善强度和冷轧性能的要求。可注意到，95％或者更多的Cu2O粒子以如图1中那样的不规则形状分散，但是其中的一些粒子为球状(每100μm2的面积中粒子数约为20个)。
对所述烧结体采用X射线衍射仪进行了测试，以确定其中所含有的氧化物类型。所出现的只是Cu2O的衍射峰。这一结果表明，在烧结过程中，CuO已完全转变成为Cu2O。化学分析的结果显示，正如所期望的那样，所述烧结体由Cu和40体积％的Cu2O构成。
已发现，所述烧结体具有与下面将述及的相同组成的实施例5中烧结体相同的热膨胀率和导热率。
实施例4
本实施例中所用的原材料粉末与实施例1相同。对原材料粉末进行混合，以获得一种由Cu和55体积％Cu2O构成的混合物。在V型混合机中对所获得的混合物(550g)进行充分混合。将所获得的混合后的粉末置于一直径为80mm的模具中，并且在600kg/cm2的压力下进行冷压。结果就获得一个尺寸为80mm×22mm的预型体。在氩气氛中，于975℃下烧结所述预型体，时间为3小时。将所获得的烧结体加热至800℃并且用一台200吨的压锻机对其进行锻造(锻造比为1.8)。锻造后在500℃下进行回火和退火。采用与实施例1相同的方法对所获得的产品的结构、热膨胀率以及导热率进行测定。
已发现，所述锻造产品除出现轻微的边部开裂外，还是令人满意的。本发明的铜复合材料具有较佳的塑性加工性。
图4是所述锻造产品的显微结构的光学显微照片(×300)。可注意到，Cu相和Cu2O相均发生了变形并且沿锻造方向取向分布；然而，并没有缺陷如开裂出现。也注意到，95％或者更多的Cu2O粒子以连接一起的不规则粒子形式分散。所述粒子在塑性加工中发生了伸长。
采用激光烧化法测量了所述烧结体和锻造产品的导热率(表2)。所述烧结体在导热率上并不具有各向异性。然而，所述锻造产品的导热率却表现出各向异性。Cu相和Cu2O相取向分布的L方向上的导热率比与L方向垂直的C方向(锻造方向)上的导热率的2倍还要大。室温至300℃的范围内的热膨胀率几乎没有各向异性；这与实施例1的结果一致。表2
    导热率(W/m·k)
    L方向     C方向
烧结体     111     106
锻造产品     152     67
实施例5
本实施例中所用的原材料粉末是电解铜粉末(其粒子直径为74μm或更小)和CuO粉末(其粒子直径为1-2μm，纯度为3N)。按照表3所示比例对上述两种粉末进行混合。在内装有钢球的干式球形磨机中，对所获得的混合物(1400g)进行充分混合，时间超过10小时。将所获得的混合后的粉末置于一直径为150mm的模具中，并且在400-1000kg/cm2的压力下进行冷压，所述压力的具体值依据CuO含量而定。结果，就获得了预型体，随后，对所述预型体在氩气氛中进行烧结。对所获得的烧结体进行化学分析，结构检测以及热膨胀率和导热率的测定。也采用X射线衍射仪测试了所述烧结体，以便确定其中存在的氧化物类型。顺便提一下，烧结在900-1000℃下进行3小时，具体烧结温度依据CuO含量而定，采用进行TMA分析(热机械分析)的仪器测定了室温至300℃范围内的热膨胀率。导热率采用激光烧化法测量，所获结果如表3所示。表3
  编号      粉末组成(体积％)  烧结体组成(体积％)   热膨胀系数(×10-6/℃)   导热率(W/m·K)
  Cu   CuO  Cu  Cu2O
 11   51.2   48.8  20  80   5.6  55
 12   58.1   41.9  30  70   7.0  80
 13   64.9   35.1  40  60   8.5  105
 14   67.8   32.2  45  55   9.1  129
 15   71.4   28.6  50  50   9.7  149
 16   77.6   22.4  60  40   10.6  185
 17   83.5   16.5  70  30   12.7  228
 18   89.2   10.8  80  20   13.5  282
采用X射线衍射仪检测了所述烧结体，以便确定其中存在的氧化物类型。衍射峰对应的只有Cu2O。这表明，烧结期间，CuO已完全转变成为Cu2O。
样品14的显微结构如图5所示。该光学显微照片(×300)显示，其结构与实施例1中的具有相同组成的样品相一致。Cu2O相由Cu2O(由Cu和CuO的氧化反应形成)和Cu2O(由CuO的分解形成)构成。Cu2O粒子与实施例1中的相应粒子一致。
由表3可明显看出，所述烧结体与由Cu2O粉末制得的烧结体在热膨胀率上差别并不很大。然而，当Cu2O含量超过50体积％时，所述烧结体的导热率较高。这是因为采用CuO粉末制备时，所获烧结体的密度较高。
图6示出的是表示表3中所示的导热率(X)与热膨胀系数(Y)的关系的曲线。所标绘的点位于分别用方程Y＝0.031X+4.65和Y＝0.031X+5.95表示的两条直线之间。20-250℃范围内的热膨胀系数的平均增加值为从20℃的值起每单位W/m·k0.025-0.035ppm/℃。
实施例6
本实施例说明的是本发明的铜复合材料的应用。该应用是作为功率半导体元件之一的IGBT(绝缘栅双极晶体管)的散热片。
图7是展示由24个IGBT元件组成的模块内部的平面视图。图8是一个IGBT的模块的剖视图。采用钎料201将4个IGBT元件101和两个二极管元件102连接到AlN衬底103上。AlN衬底103由两个铜箔薄片202和203与一个AlN板204组成，上述两个铜箔与AlN板采用银钎料(图中未示出)焊接一起。在AlN衬底103上形成有发射极布线区104，集电极布线区105以及栅极布线区106。将IGBT元件101和二极管元件102焊接到集电极布线区105上。每个元件通过金属线107连接到发射极布线区104。此外，在栅极布线区106设置有电阻元件108，IGBT元件101的栅极焊点通过金属导线107与电阻元件108相连。每个均安放有半导体元件的6个AlN衬底103均通过钎料205与散热片109连接一起。具有镀Ni表面的散热片109采用实施例1-5中所述的Cu-Cu2O复合材料制备而成。AlN衬底103通过钎料209与端子206相连。端子206和塑料壳207一起构成基极组块208。塑料壳207采用有机硅橡胶粘结剂210与散热片109粘合一起。从外壳组块208引出的端子与每个AlN衬底在两个发射极端子110，两个发射极定向端子111，两个集电极端子112以及一个栅极端子113处相连接。然后，通过外壳罩211(其具有树脂喷射口)喷射有机硅凝胶212，以便将所述端子完全封盖住。之后，倾倒热固性环氧树脂213，以便将整个表面封盖。从而，就完成了所述模块的制造。散热片109通过8个贯穿8个螺栓孔114的螺栓固定到铝支撑体上。螺栓孔114采用机加工制成。此外，所述外壳207通过另外8个贯穿8个螺栓孔115的螺栓(采用粘结剂210连接)进行连接。
表4示出了通常使用的基体材料与根据本发明的Cu复合材料(含有30体积％Cu2O)的热膨胀率和导热率的比较结果。可注意到，采用Cu-Cu2O基体材料的半导体元件具有比采用通常使用的Cu基体材料的模块更低的热膨胀系数。钎料209将AlN衬底与基体109连接一起使可靠性得以改善。用于改善钎料106在恶劣环境中的可靠性的Mo或Al-SiC基体具有比Cu-Cu2O基体更低的热膨胀系数。然而，其导热率也较小，结果造成模块的热阻较大。根据本发明的具有Cu-Cu2O基体的模块的热疲劳寿命比具有Cu基体的模块的5倍还要长，而且，其热阻相当于具有同样厚度的Mo基体的模块的0.8倍。表4
材料  热膨胀系数(ppm/℃)  导热率(W/m·K) 备注
Cu-Cu2O(30体积％)  13.5  230 本发明
Cu  17  390 现有技术
Mo  5  140
Al-SiC  8  160
上述结果拓宽了模块结构和材料的选择范围，例如，在图7所示的实施例中，Cu-Cu2O基体的导热率比Mo基体高。换言之，该基体的热扩散性能得到改善。因此，在半导体元件运行期间，其端部与中心处的温度差得以减小。半导体元件可以做成传统模块的1.2倍。结果，IGBT的具有30个单元的传统结构现在被一种具有24个单元的IGBT新结构所代替。这样，就能够减小模块的尺寸。此外，现在有可能使用导热率比AlN基体低(低约20％)的氧化铝衬底(作为绝缘衬底)。氧化铝的抗弯强度优于AlN，因此，其可以加工成较大的衬底。氧化铝板的热膨胀系数比AlN板高，而且，其与基体材料间的热膨胀率差别较小。这会使得模块本身的弯曲程度减小。氧化铝衬底可以制造得尺寸较大，而较大的衬底可安装更多的半导体元件。换言之，铝衬底可以使每个衬底中的绝缘面积减小，并且可以使两衬底间的绝缘面积减小。这会导致模块尺寸的减小。
图9A-9D是展示根据本发明的模块的生产步骤的示意图。
(图9A)制备出具有镀镍表面的Cu-Cu2O基体109。该基体在购买时的状态下近乎平直。
(图9B)用钎料205将AlN衬底103焊接到基体109上。AlN衬底安装有采用钎料102与之焊结一起的半导体元件101。当钎料冷却时基体109会弯曲，因为其与由AlN衬底和半导体元件构成的组件的热膨胀率不同。结果，模板的背面会变凹。
(图9C)外壳组块108采用热固性粘结剂进行组装。当粘结剂变冷时，模块的背面会变得几乎平直，因为外壳的热膨胀系数比已进行焊接的组件301高。
(图9D)模块内部用硅胶212和热固性环氧树脂213填充。模块的背面变得凸起，因为所述树脂的热膨胀系数高。
图10中的曲线反映的是每一步骤中背面弯曲的量。正值代表凹下弯曲，负值代表凸起弯曲。具有根据本发明的Cu-Cu2O基体的模块弯曲程度比具有传统的Mo基体的模块小(约为三分之一)。具有Cu基体的模块在加工完成后具有弯曲的凹下背面(凹下量为100μm或更大)，因为其热膨胀率与AlN衬底的差异很大(结果未在图中示出)，所以该模块的背面在步骤(b)会出现弯曲的凹陷。具有根据本发明的Cu-Cu2O基体的模块的弯曲量小；因此，可以将模块做得比以前更大。正如装配过程中弯曲程度较小那样，运行过程中由于温度变化引起的弯曲程度也较小。因此，模块与冷却翅片间的润滑脂不会流动。
图11示出的是本发明的模块应用其中的能量转换装置的实施例，本实施例是一种2电平反相器。功率半导体器件501安装在铝制散热片511上并通过拧紧螺栓512来进行固定，其中，散热润滑脂510被置于所述器件与散热片间。通常，两组模块501对称排列，以便通过一个单一的中间布线503(点B)将二者加以连接。集电极布线502和发射极布线504被施加通过U，V和W相与之相连接的电源电压509。信号线构成于每个IGBT模块501，栅极布线505，发射极辅助布线506以及集电极辅助布线507。负载用508表示。
图12A和12B中的曲线示出的是模块的弯曲量。图13A和13B中的曲线示出的是装配后的模块拧紧前后测得的模块背面上的弯曲量(润滑脂厚度)。图12A和13A代表本发明中的结果，而图12B和13B反映的是现有技术的结果。对于具有已知的传统Al-SiC基体的模块而言，其背面的弯曲(凸起)的量约为100μm。然而，如果模块用润滑脂涂覆，之后再拧紧，则弯曲方向会发生颠倒(由凸起变为凹下)，因为在拧紧时，表面会受到润滑脂的推力作用。结果，在中心处，润滑脂的厚度增加，而且接触电阻也相应增加。相反，对于根据本发明的Cu-Cu2O基体而言，起始弯曲的量为约50μm，而在添加润滑脂以及拧紧之后，模块中心处润滑脂的厚度仍保持为约50μm。这是因为所述基体的刚性非常好。结果，弯曲的量比传统的Al-SiC基体降低一半。另外，模块中润滑脂的厚度也变得均匀。装配时由于润滑脂具有推力作用，具有刚度不及Cu-Cu2O合金基体的Cu基体的模块会发生变形。这一问题通过采用本发明的Cu-Cu2O合金得到解决。
如图所示，本发明的Cu-Cu2O合金基体具有比传统的应用于高可靠性模块的Mo或al-SiC基体材料更低的热阻和接触热阻。因此，该合金允许如图11所示那样，对模块进行密集装配。此外，由于冷却翅片已使散热效果得以改善，因此有可能减少装配所述能量转换装置所要求的面积和体积。润滑脂厚度的降低可使冷却翅片保持平直，而且，这有可能构造具有大尺寸冷却翅片的能量转换装置。另外，有可能免除辅助冷却措施如强制空冷。这又可以导致尺寸的减小和噪音的下降。
实施例7
本实施例中，将实施例1-5中所介绍的本发明的铜复合材料应用于包含如图14和15所示IC的塑料封装件。图14示出的是具有内置散热片的封装件。图15示出的是具有外露的散热片的封装件。
所述散热片由Cu-Cu2O复合材料制备而成，其中，Cu2O含量的变化范围为20-55Vol％。所获得的复合材料在室温至300℃的范围内的热膨胀系数为9×10-6-14×10-6/℃。此热膨胀系数与模压树脂的热膨胀系数接近。所述散热片最终进行机加工以及镀镍处理。
将参照图14对封装件的结构进行解释。所示出的镀镍散热片33由本发明的铜复合材料制成。所示出的引线框31通过绝缘的聚酰亚胺带32与所述散热片33连接一起。所示出的IC34被焊接到散热片33上。所示出的Au线35将IC上的Al电极连接到引线框上。这些组件，除了部分引线框外，均采用主要由环氧树脂、二氧化硅填料及硬化剂构成的模压树脂36密封。如图15所示的具有外露的散热片的封装件与如图14所示的封装件不同，不同之处在于散热片33暴露于模压树脂的外面。
对上面介绍的封装件在散热片与模压树脂间的结合部位进行了弯曲和开裂情况检验。已发现，如果散热片与模压树脂间的热膨胀系数差值为0.5×10-6/℃或者更小，则不会有问题出现。也已发现，如果Cu2O含量为20-35体积％，则所述复合材料具有高的导热率(200W/m·k)。
实施例8
本实施例说明的是一种装配有散热片的IC陶瓷封装件，所述散热片由在实施例1-5中所介绍的本发明的铜复合材料制成。图16和17是所述陶瓷封装件的剖面图。图16中，所示出的是一种采用聚酰亚胺树脂与镀镍的散热片42连接一起的IC41。散热片42被焊接到Al2O3的封装件43上。所述封装件具有铜布线，并且装配有插头44，以便与电路板相连。还示出了一种将IC上的铝电极与所述封装件布线连接一起的铝线45。所述这些组件进行如下密封。由可伐合金制成的焊环通过银钎料与封装件相连。然后，通过使用辊式电极将焊环焊接到由可伐合金制成的罩47上。图17示出的是装有散热翅片48的陶瓷封装件(与图16中所示的封装件相同)。
实施例9
本实施例说明的是一种装配有散热片的封装件，所述散热片由在实施例1-5中介绍的本发明的铜复合材料制成。所述封装件采用TAB(带式自动键合)技术制备而成。图18和19是所述封装件的剖面图。
图18中，可看到采用导热树脂52与镀镍的散热片53结合一起的IC51。所述IC的端子处有Au凸起54形成。Au凸起54与TAB55相连。TAB55通过薄膜布线56与引线框57连接一起。所述IC采用陶瓷衬底59，线框60和密封玻璃61封装，而有机硅橡胶58置于中间。
图19示出了树脂密封的封装件。IC65通过Au-Si合金66与本发明的镀镍散热片67结合一起。所述IC还进一步通过导热树脂68与铜接地板69和本发明的镀镍散热片70相结合。另外，所述IC的端子通过Au制缓冲垫71连接到TAB72上，并且采用树脂73进行密封。引线框57和散热片部分地露在密封树脂的外面。采用环氧树脂基的银膏74将所述TAB固定在所述铜接地板上。
实施例10
本实施例说明的是具有由如图1-5中所示的本发明的铜复合材料制成的散热片的MCM。图20是所述MCM的剖面图。散热片83通过压制由烧结体(已进行轧制或者未经轧制)加工而成。
IC81通过Au线82与形成于本发明的镀镍散热片83上的薄膜布线84相连。所述IC通过Au线还与形成于AlN制的封装件85上的布线相连。所述IC再连接到外部端子86上。所述IC采用焊接而成的罩87密封，Au-Sn预型件88位于所述封装件的W金属化的层之间。
实施例11
本实施例说明的是装备有本发明的复合材料制的介电片的静电吸引器。图21是其剖面图。
如图21所示，静电吸引器用来作为溅射设备中的夹盘，所述溅射设备在真空室95中，减压气氛下，对导体或者半导体制的工件90进行处理。当由直流电源91将电压(约500V)加到静电吸引器的电极94上时，在介电片92和工件90间就会出现静电吸引力。结果，工件90就被吸向介电片的表面。本实施例中，所述介电片由实施例1-5中所述的复合材料制成。
实际溅射时，工件90被固定在静电吸引器上。采用与排气口97相连接的真空泵，对真空室95进行抽真空，直至内部压力降至约1×10-3Pa为止。打开与气体入口96相连接的阀门，使反应气体(氩气等)以约10sccm的流速进入到真空室95中。真空室95中的压力为约2×10-2Pa。
之后，向所述静电吸引器的电极94施加高频功率(13.56MHz下约4KW)，以便在静电吸引器的电极94与另一个电极(未示出)间产生等离子体。所述高频功率的电压为2KV(VDC)和4KV(VPP)。位于所述静电吸引器的电极94和高频功率源93间的匹配盒98被设计用来与真空室进行阻抗匹配，以便使高频功率有效生成等离子体上。
在本溅射设备的实际运行中，工件90的温度可达约450℃。然而，所述静电吸引器的介电片92仍没有变化，无开裂现象(产生外来杂质)出现。这意味所述静电吸引器的工作可靠性得到有效改善。
顺便提一下，当所述静电吸引器应用于任何被设计在减压气氛中对导体或半导体工件(如硅衬底)进行处理的装置时，其都将获得上述相同的效果。所述静电吸引器可用来作为化学气相沉积装置，物理气相沉积装置，研磨装置，蚀刻装置，离子注入装置等的夹盘。
本实施例中的静电吸引器可使介电片的热阻得以改善，而其介电击穿强度并未受到损害。如果根据本发明的静电吸引器用来作为在减压条件下工作的装置的夹盘，则有可能会减少由介电片断裂所引起的外来杂质的出现。
工业实用性
本发明的复合材料具有低的热膨胀率，高的导热率以及良好的塑性加工性。因此，所述复合材料可以通过较少的加工步骤进行大量生产。
本发明的复合材料也具有包含Cu相(导热率极高)和Cu2O相(热膨胀率低)的混合结构；因此，所述复合材料兼有上述两种物质的性能。如果将Cu含量和Cu2O含量加以充分调整，本发明的复合材料将具有低的热膨胀率和高的导热率。本发明的复合材料将用来作为半导体器件的散热片和静电吸引器的介电片。

Claims (18)

1.一种由金属和热膨胀系数比所述金属小的无机粒子构成的复合材料，其特征在于所述无机粒子分散的方式应使95％或者更多的该粒子(用横截面上的粒子面积的大小表示)形成连接一起的具有复杂构形的聚集体。
2.一种由金属和热膨胀系数比所述金属小的无机粒子构成的复合材料，其特征在于在100μm2的横截面上单独存在的所述无机粒子的个数小于或等于100，余下的粒子以连接一起的具有复杂构形的聚集体形式分散。
3.一种由金属和热膨胀系数比所述金属小的无机粒子构成的复合材料，其特征在于所述无机粒子的维氏硬度为300或更小。
4.一种由金属和热膨胀系数比所述金属小的无机粒子构成的复合材料，所述复合材料的热膨胀系数在20-105℃的范围内的平均增加量为从20℃的值起每W/m·k增加0.025-0.035ppm/℃。
5.一种由金属和热膨胀系数比所述金属小的无机粒子构成的复合材料，其特征在于所述无机粒子以连接一起的聚集体形式分散分布，所述聚集体沿塑性加工方向伸展。
6.一种由铜和铜氧化物的粒子构成的复合材料，其特征在于所述铜的氧化物粒子分散的方式应使95％或更多的该粒子(以横截面中粒子的面积数表示)形成连接一起的具有复杂构形的聚集体。
7.由权利要求1-6中之任一项的复合材料制造的半导体器件的散热片。
8.如在权利要求7中所述的半导体器件的散热片，包括其上存在的一个镍镀层。
9.一种半导体器件，其包括多个绝缘衬底和安装在每个所述绝缘衬底上的多个半导体元件，每个所述绝缘衬底通过形成于所述绝缘衬底的上下表面的导电层使所述绝缘衬底直接连接于所述散热片。
10.一种半导体器件，其包括具有散热片的绝缘衬底和安装在所述绝缘衬底上的半导体元件，其中，所述散热片是在权利要求7或8中所述的散热片。
11.一种半导体器件，其包括固定在散热片上的半导体元件，与所述散热片相连接的引线框，以及将所述引线框与所述半导体元件电连接起来的金属布线，所述半导体元件采用塑料密封，其中，所述散热片是在权利要求7或8中所述的散热片。
12.一种半导体器件，其包括固定在散热片上的半导体元件，与所述散热片相连接的引线框，以及将所述引线框与所述半导体元件电连接起来的金属布线，所述半导体元件采用塑料密封，而且，所述散热片在与同所述半导体元件相连接的一侧相对的另一侧是敞开的，其中，所述散热片是在权利要求7或8中所述的散热片。
13.一种半导体器件，其包括固定在散热片上的半导体元件，用于与外面的布线相连接的引线，在其中心处存在一敞开空间以安放所述半导体元件的陶瓷多层布线衬底，以及以导电方式将所述半导体元件与衬底的端子相连接的金属布线，所述散热片与所述衬底相互连接，以便使所述半导体元件固定在所述空间处，并且所述衬底则连接到一个密封罩上，从而将所述半导体元件与大气环境隔离开，其中，所述散热片是在权利要求7或8中所述的散热片。
14.一种半导体器件，其包括安装在散热片上的半导体元件，用于与外面的布线相连接的端子，其中心处存在一凹槽以安放所述半导体元件的陶瓷多层布线衬底，以及以导电方式将所述半导体元件与衬底的端子连接一起的金属布线，所述散热片与所述衬底的凹槽相互连接，以便使所述半导体元件固定于所述凹槽处，并且所述衬底连接到一个密封盖上，从而将所述半导体元件与大气环境隔离开，其中，所述散热片是在权利要求7或8中所述的散热片。
15.一种半导体器件，其包括散热片，通过导热树脂连接到所述散热片上的半导体元件，与陶瓷绝缘衬底相连接的引线框，以及以导电方式将所述半导体元件与引线框连接一起的TAB，所述散热片与所述衬底相互连接，以便将所述半导体元件与大气环境隔离开，并且所述半导体元件和所述绝缘衬底被插入两者间的导热的弹性树脂隔开，其中，所述散热片是在权利要求7或8中所述的散热片。
16.一种半导体器件，其包括第一个散热片，通过金属与所述散热片相连接的半导体元件，与接地板相连接的第二个散热片，所述第一个散热片固定在该散热片的接地板上，以及以导电方式连接所述半导体元件的端子的TAB，所述半导体元件采用塑料密封，其中，所述散热片是在权利要求7或8中所述的散热片。
17.一种由在权利要求1-6中任一项的复合材料制造的用于静电吸引器的介电片。
18.一种静电吸引器，其包括电极层和与所述电极层结合一起的介电片，当在所述电极层上施加电压时，所述介电片会产生静电吸引力，以使物体固定到所述介电片的表面上，其中，所述介电片是在权利要求17中的介电片。
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US6909185B1 (en) 2005-06-21
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