CN101055859A - 半导体器件用管芯贴装组合物、器件贴装法及半导体装置 - Google Patents

半导体器件用管芯贴装组合物、器件贴装法及半导体装置 Download PDF

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CN101055859A
CN101055859A CNA2007100923789A CN200710092378A CN101055859A CN 101055859 A CN101055859 A CN 101055859A CN A2007100923789 A CNA2007100923789 A CN A2007100923789A CN 200710092378 A CN200710092378 A CN 200710092378A CN 101055859 A CN101055859 A CN 101055859A
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composition
die
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metal dust
epoxy resin
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米里埃尔·托马斯
克劳斯·沙克
蒂莫·格尔根
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Umicore AG and Co KG
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Abstract

欧洲议会和委员会的法令2002/95/EC颁布，规定从2006年7月1日起新的电气和电子设备必须不再含铅。因此，已经发展了用于各种电气和电子应用的无铅焊接合金。但是，目前由于缺乏用于高熔化温度型焊料的无铅替代品，所以该法令免除了在高熔化温度型焊料例如用于管芯贴装应用中对铅的替代。本发明提供一种用于将大功率半导体器件贴装到印刷电路板上的无铅的管芯贴装组合物。该管芯贴装组合物包括金属填充的环氧树脂，其中所述金属选择包括铜的粉末并且具有根据XPS的测量在表面层中少于一半铜原子被氧化的类球形颗粒。

Description

半导体器件用管芯贴装组合物、器件贴装法及半导体装置
                     技术领域
本发明提供用于大功率半导体的管芯贴装(die-attachment)的无铅的粘合剂组合物。
                     背景技术
根据欧洲议会和委员会的法令2002/95/EC，从2006年7月1日起投放市场的新的电气和电子设备必须不再含铅和其它有毒物质。该法令已经导致用于各种电气设备的无铅焊接合金的发展。但是该法令仍旧存在部分免除的内容。其中，由于缺乏高熔化温度型焊料的无铅替代品，在这些合金焊料(即，包括85重量％或更多铅的铅基合金)中铅不必被替代。这种免除最近已经被2005年10月21日的委员会决议2005/747/EC证实。
包括超过85重量％铅的铅基焊接合金至今还用于所谓的高温应用中，所谓的高温应用具有超过150℃的平均操作温度以及高达260℃的峰值处理温度。一个重要的实例是用于功率半导体的管芯贴装应用。在这些应用中，当使半导体装置经受热循环处理时，铅基焊接合金提供充分的耐热疲劳性。此外，这些焊料提供用于耗散由功率半导体产生的热量的充分导热性。
根据Philip Adamson在2002年四月/五月的2002JEDEC会议上发表的论文“Lead-free Packaging for discrete Power Semiconductors”，许多小型功率器件的封装(package)已经使用了Ag-填充的环氧树脂形式的无铅管芯贴装。这些Ag-填充的环氧树脂装载有高达70％的银。然而，它们的使用还未扩大到在较大的功率器件封装中的较大的硅尺寸。根据Adamson，Ag-填充的环氧树脂已经对较大的元件例如TO220进行了温度循环测试。这些试验元件经受-40～+125℃的温度循环。这些测试条件遵照2005年5月的JEDEC的标准JESD22-A 104C指定的条件“G”。
JEDEC标准对于Pn/Sn焊接组合物不推荐超过+125℃的测试条件。然而，功率半导体装置的苛刻操作条件需要它们承受JEDEC标准的测试条件“H”指定的测试条件，并且需要经受在-55～+150℃之间的温度循环。
尽管法令2002/95/EC免除了从2006年7月1日在高熔化温度型焊料中用无铅替代品对铅的替代，然而尽可能快地使用用于管芯贴装应用的无铅替代品替代高含铅的焊料对于环境是非常有益的。
Araujo等人在J.Phys.D：Appl Phys.，Vol.9，1976中的第665～675页已经对环氧树脂/金属粉末的组合物进行了从1.7K至300K的导热率测量。WO2004/090942描述了用于装置贴装的导热粘合剂组合物和工艺。该粘合剂组合物包括两种不同类型的金属粉末，一种是高熔点金属的粉末，另一种是低熔点金属的粉末。
                        发明内容
本发明的目的是提供一种用于功率半导体器件的管芯贴装应用的无铅粘合剂组合物，其可靠地经受根据JEDEC测试条件“H”的温度循环至少1000次并且对于最大温度和最小温度具有15分钟的保温时间(soak time)，并且产生类似于目前使用的高含铅焊料的散热作用。
该目的是通过在权利要求中指定的管芯贴装组合物实现的。特别地，根据本发明的管芯贴装组合物包括双组分粘合剂和作为填充剂的金属粉末，其中粘合剂的一种组分是环氧树脂，第二组分是固化剂，以及其中该金属粉末的金属具有超过250W/(m·K)的导热率，并且包括铜，该粉末颗粒具有球形形状。
固化的管芯贴装组合物必须允许与用于贴装大功率半导体装置的传统高铅焊料相似的散热作用。这种高铅焊料合金是例如具有导热率为55W/(m·K)的Pb88Sn10Ag2和具有导热率为44W/(m·K)的Pb92.5Sn5Ag2.5。已经证实固化的管芯贴装组合物满足来自功率半导体器件的有关功耗(power dissipation)的需要以及抗热循环的需要。
固化的管芯贴装组合物的导热率是填充材料导热率、环氧树脂导热率、填充材料的体积百分率和在填充剂和环氧树脂之间的接触热阻的函数。
获得的导热率当然主要受包括铜的填充剂的影响。纯铜的导热率是400W/(m·K)，同时环氧树脂的导热率低至0.3W/(m·K)。为了保证填充剂-环氧树脂组合物的高导热率，填充剂粉末的导热率应该大于250W/(m·K)，优选大于300W/(m·K)，以及最优选大于350W/(m·K)。
填充剂-环氧树脂组合物的导热率还取决于填充剂的体积百分率。以下，术语填充度用于替代填充剂的体积百分率。填充度定义为填充剂与组合物的总重量的重量百分比。根据本发明，金属粉末的粉末颗粒应该具有类球形或球形形状。薄片状粉末显示差的结果，并且此外当在点涂应用中使用管芯贴装组合物时，用片状填充的粘合剂将妨碍注射(springe)。在类球形填充剂颗粒的情况中，对于六角闭合封装获得最大体积百分率，体积百分率为74％。通过使用铜的密度(8.9g/cm3)和环氧树脂(大约1.2g/cm3)的密度，对于作为填充剂的铜粉末该数值换算成95重量％的最大填充度。
铜粉末的平均粒径D50对于填充剂-环氧树脂组合物的耐热疲劳性没有决定性影响。使用具有平均粒径D50在1～50μm之间的填充剂粉末已经获得好的结果。更优选地，粒径在1～30μm之间。
最终，填充剂-环氧树脂组合物的最终导热率取决于在填充剂表面和树脂之间的接触热阻。在填充剂颗粒的表面上的任何杂质层将增加接触热阻。因此，优选使用具有低表面杂质的填充剂粉末。
由于其高的导热率，优选使用包括高的铜百分含量的金属粉末。最优选是使用铜纯度大于99.5重量％以及特别地大于99.9重量％的铜粉末。
在铜粉末的情况中，在粉末颗粒的表面上最有害的杂质是氧化铜(II)。在大约5nm厚的薄表面层中相对于金属铜的氧化铜(II)的比率可以使用XPS(X射线光电子能谱仪)确定。为此目的，获得的XPS光谱通过本领域公知的曲线拟合法分析。已经证实，如果通过XPS分析在表面层中至多50％的原子被氧化成CuO，可以获得关于固化的组合物的导热率和热疲劳的好结果。优选地氧化的铜原子应该不超过30％，更优选地不超过10％。
相对于金属粉末的导热率，固化的环氧树脂的导热率是非常低的。环氧树脂的主要任务是提供与金属填充剂和与半导体装置以及与基板的良好粘性。选自双酚A环氧树脂和双酚F环氧树脂中的环氧树脂已经证明可以提供与铜和镍表面以及与管芯良好粘性。双酚F环氧树脂是最优选的。作为固化剂，可以使用咪唑、丙烯腈以及脂族胺的传统混合物。
包括填充有特定填充剂粉末并且具有厚度在20～80μm之间的粘合层(bond line)的固化的粘合剂的固化的管芯贴装组合物可以承受用于热疲劳的上述测试条件，并且产生与高铅焊料相似的散热作用。
管芯贴装组合物的组分可以使用不同的配方表示：
金属粉末可以是与环氧树脂或与固化剂预混合；在这种情况中，环氧树脂和固化剂可以封装在两个独立的装置中以避免环氧树脂的早期固化，并且仅仅在使用前直接混合在一起。
金属粉末可以与环氧树脂和固化剂的混合物混合；在这种情况中，管芯贴装组合物封装在在一个装置中并且必须在使用前保持在低温下，从而避免环氧树脂的早期固化。
环氧树脂的一部分可以与金属粉末的第一部分预混合，并且金属粉末的第二部分可以与环氧树脂的剩余部分和固化剂的混合物预混合；在这种情况中，管芯贴装组合物再次封装在两个独立装置中以避免环氧树脂的早期固化，并且仅仅在使用前直接混合在一起。
为了使用本发明的管芯贴装组合物将分立的大功率半导体器件贴装到印刷电路板上，将该组合物涂覆到印刷电路板上，半导体器件贴装到所述板上，然后使管芯贴装组合物在80～250℃之间的温度固化，优选地在100～150℃之间的温度固化。
当使用铜作为填充剂材料时，优选通过使用抗氧化材料涂覆铜粉末来避免在储存过程中铜表面的氧化。涂覆材料可以是脂肪酸，优选饱和脂肪酸、聚硅氧烷或磷化物。脂肪酸可以选自油酸、肉豆蔻酸、棕榈酸、十七酸和硬脂酸和花生酸。相对于涂覆铜粉末的总重量，涂覆材料的涂覆量在0.1～1重量％之间。最优选的是具有轻微的亲水性，即具有小的极性基，从而使得水的吸引力最小化的涂覆材料。
表面涂覆的另一功能是提高具有粘合剂的填充剂颗粒的润湿作用，并且由此增加它们的分散性，这对于实现高的填充度是很重要的。
对于标准管芯贴装应用，管芯贴装组合物应该包括相对于所述组合物的总重量为40～90重量％的金属粉末。对于点涂(dispensing)应用，该组合物应该包括在40～70重量％之间，优选在40～60重量％之间的金属以避免点涂喷嘴阻塞。在通过印刷的管芯贴装情况中，粘合剂组合物可以包括相对于该组合物的总重量为40～90重量％的金属粉末。
                        附图说明
以下实施例和附图旨在帮助进一步解释本发明。附图示出了：
图1：用于测量散热作用的试验设备。
图2：填充度为54重量％的填充有各种铜粉末的管芯贴装组合物在固化后散热作用随粘合层厚度的变化。
图3：填充度为80重量％的填充有各种铜粉末的管芯贴装组合物在固化后散热作用随粘合层厚度的变化。
                    具体实施方式
表1列出了多种商业铜粉末与双酚F环氧树脂组合以形成用于温度循环测试和散热作用测量的金属填充的粘合树脂。
所有的铜粉末具有类球形颗粒、纯度大于99.9％以及导热率超过350W/(m·K)。铜粉末Cu1、Cu2、Cu3、Cu4和Cu5满足本发明的要求，鉴于作为比较的原因，选择铜粉末Cu1C和Cu2C以及商业“高导热率填充银的环氧树脂膏剂”(Ag)。两种传统高铅焊锡剂Pb1(Pb88Sn10Ag2)和Pb2(Pb92.5Sn5Ag2.5)作为参考材料。
                                            表1  金属粉末的性质
  材料   Cu1   Cu2   Cu3   Cu4   Cu5   Cu1C   Cu2C
  纯度(未涂覆)   ＞99.9％   ＞99.9％   ＞99.9％   ＞99.9％   ＞99.9％   ＞99.9％   ＞99.9％
  粒径
  D10[μm]   0.5   0.9   1.7   0.3   7.9   0.2   3.1
  D50[μm]   1.5   1.5   3.6   8.3   22.1   0.6   4.5
  D90[μm]   2.5   3.2   6.7   12.3   41.2   0.9   6.7
  颗粒形状   类球形   类球形   类球形   类球形   类球形   类球形   类球形
  颗粒表面的涂覆   0.5重量％脂肪酸   0.5重量％脂肪酸   0.5重量％脂肪酸   0.03重量％聚硅氧烷+磷化物   0.03重量％聚硅氧烷+磷化物   0.05重量％未知物质   0.05重量％未知物质
  表面氧化度   ＜10％   ＜10％   ＜10％   ＜30％   ＜30％   ＞50％   ＞50％
散热作用的测量
为了测量散热作用与粘合层厚度的关系，将一系列硅芯片使用填充有根据表1的不同粉末的双酚F贴装到铜基板上。粘合剂在150℃下固化5分钟。通过使用图1所示的试验设备进行测量。贴装试样，使它们的铜基板(1)贴装到加热至T2＝75℃的提供恒温的铜块(4)上。硅芯片(2)与浸在周围空气(T1＝30℃)的另一铜块(5)接触。使用热电偶(6)和(7)测量夹层结构的铜和硅侧的温度。在这两侧之间的温度差ΔT与由硅芯片(2)、粘合层(3)和铜基板(1)组成的试样的散热作用成比例。
进行两组测量-一组使用填充度为54重量％的管芯贴装组合物通过点涂管芯贴装组合物进行测量，另一组测量使用80重量％的填充度的管芯贴装组合物利用印刷该管芯贴装组合物进行测量。
图2和图3示出了对于不同的粘合层厚度(BLT)在试样中测量的温差。在两图中粗线表示使用商业焊锡膏Pb1和Pb2贴装的参考样品的性能。可以清晰看出使用根据本发明的管芯贴装组合物(Cu1-Cu5)贴装的样品表现出与使用焊料的参考样品相似的导热率。相反，比较样品Ag、Cu1C和Cu2C显示出随着粘合层厚度的增加温差急剧增加，并且因此不能接受。
温度循环/热疲劳
为了进行温度循环测试，使用混合有固化剂的金属填充的树脂将12×12×0.5mm3的硅芯片粘合到尺寸为12×12×1mm3的铜基板上。粘合剂在150℃固化5分钟，并且导致大约50μm的粘合层厚度。为了比较而选择的管芯贴装组合物(Ag、Pb1和Pb2)根据厂商的推荐处理。
试样根据JEDEC标准测试条件“H”(-55～+150℃)使用15分钟的保温时间经受1000次温度循环。
具有金属粉末Cu1至Cu5的管芯贴装组合物在温度循环之后显示没有失效。根据XPS的测量这些粉末在表面层中具有低的CuO含量。相反，使用的具有高表面氧化的铜粉末Cu1C和Cu2C没有能够通过温度循环测试。结果在表2中示出。
表2：在1000次循环之后的热疲劳结果(每一测试5个样品)
  管芯贴装组合物   粘合剂的填充度[重量％]   测试结果
  金属   树脂
  Cu1   双酚F   54   通过
  Cu2   双酚F   54   通过
  Cu4   双酚F   54   通过
  Cu5   双酚F   54   通过
  Cu1C   双酚F   54   失效
  Cu2C   双酚F   54   失效
  Cu1   双酚F   80   通过
  Cu2   双酚F   80   通过
  Cu3   双酚F   80   通过
  Ag   未知   85   失效
  Pb1   焊锡膏   100   通过
  Pb2   焊锡膏   100   通过
通过：没有脱层
失效：芯片被破坏或在贴装处脱层

Claims (15)

1、用于将大功率半导体器件贴装到印刷电路板的管芯贴装组合物的用途，其中所述管芯贴装组合物包括双组分的粘合剂和金属粉末，其中所述粘合剂的一种组分是环氧树脂和第二组分是固化剂，并且其中所述金属粉末的所述金属具有大于250W/(m·K)的导热率并且包括铜，以及所述粉末颗粒具有类球形形状。
2、根据权利要求1的用途，其中所述金属粉末具有在1～50μm之间的平均粒径D50。
3、根据权利要求2的用途，其中所述金属粉末的所述金属是纯度超过99.5重量％的铜。
4、根据权利要求2的用途，其中所述金属粉末的所述金属是纯度超过99.9重量％的铜。
5、根据权利要求3或4的用途，其中根据XPS的测量在表面层中少于一半的铜原子被氧化成CuO。
6、根据权利要求1的用途，其中所述环氧树脂选自双酚A环氧树脂和双酚F环氧树脂。
7、根据权利要求6的用途，其中所述金属粉末与所述环氧树脂或与所述固化剂预混合。
8、根据权利要求7的用途，其中所述金属粉末与所述环氧树脂和所述固化剂预混合。
9、根据权利要求8的用途，其中所述环氧树脂的一部分与所述金属粉末的第一部分预混合，并且所述金属粉末的第二部分与所述固化剂和所述环氧树脂的第二部分的混合物预混合。
10、根据权利要求1的用途，其中所述组合物包括相对于该组合物的总重量为40～90重量％的所述金属粉末。
11、根据权利要求1的用途，其中所述金属粉末在与所述粘合剂的所述组分混合之前，用脂肪酸、聚硅氧烷或磷化物涂覆。
12、根据权利要求1的用途，其中所述管芯贴装组合物通过点涂涂覆，并且所述组合物包括相对于该组合物的总重量为40～70重量％的所述金属粉末。
13、根据权利要求1的用途，其中所述管芯贴装组合物通过印刷涂覆，并且所述组合物包括相对于该组合物的总重量为40～90重量％的所述金属粉末。
14、将分立的大功率半导体器件贴装到印刷电路板上的方法，包括混合如权利要求1至11中任一项所述的管芯贴装组合物的所述成分，并将所述混合物涂覆至所述大功率半导体器件或者所述印刷电路板上，以及将所述半导体器件放置到所述电路板上并且在80～250℃之间的温度下固化所述管芯贴装组合物。
15、包括印刷电路板和在其上贴装的分立的大功率的半导体器件的大功率半导体装置，其中所述大功率半导体器件通过如权利要求1所述的固化的管芯贴装组合物在所述半导体器件和所述印刷电路板之间形成厚度20～80μm的粘合层，从而被贴装到所述印刷电路板上。
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