CN101658083B - 粘合剂组合物用于模片连接大功率半导体的用途 - Google Patents

粘合剂组合物用于模片连接大功率半导体的用途 Download PDF

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CN101658083B
CN101658083B CN200780043947.9A CN200780043947A CN101658083B CN 101658083 B CN101658083 B CN 101658083B CN 200780043947 A CN200780043947 A CN 200780043947A CN 101658083 B CN101658083 B CN 101658083B
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composition
matrix
metal dust
circuit board
printed circuit
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CN101658083A (zh
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M·托马斯
K·沙克
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Heraeus Deutschland GmbH and Co KG
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Abstract

欧洲议会和理事会的指令2002/95/EC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，已开发用于多种电气和电子应用的无铅焊料合金。但目前，高熔点型焊料(例如用于模片连接应用的焊料)中的铅由于缺乏这些合金的无铅替代品而从该指令豁免。本发明提供用于将大功率半导体装置附着至印制电路板的无铅模片连接组合物。所述模片连接组合物包含金属填充的环氧树脂，其中所述金属选自包含铜并具有球形颗粒的粉末，通过XPS测量，表层中的铜原子不到一半被氧化。

Description

粘合剂组合物用于模片连接大功率半导体的用途
本发明提供用于大功率半导体的模片连接(die attachment)的无铅粘合剂组合物。
根据欧洲议会和理事会的指令2002/95/EC，从2006年7月1日起，在市场上销售的新的电气和电子设备必须不再含有铅和其他有害物质。该指令引起了用于多种电气和电子应用的无铅焊料合金的开发。但该指令仍然存在一些例外。其中，高熔点焊料(即含有85重量％或更多铅的铅基合金)中的铅由于缺乏这些合金的无铅替代品而不必代替。该例外最近刚被2005年10月21日的委员会决定(Commission Decision)2005/747/EC确认。
铅基焊料合金含有超过85重量％的铅，且到目前为止对于平均工作温度超过150℃且峰值处理温度不超过260℃的所谓的高温应用仍有需求。一个显著的实例是用于功率半导体的模片连接应用。在这些应用中，当对半导体装置进行热循环时，铅基焊料合金提供足够的耐热疲劳性。此外，这些焊料提供足够的热导率以消散由功率半导体产生的热量。
根据Philip Adamson在2002年4月/5月的2002 JEDEC会议提出的论文“Lead-free Packaging for Discrete Power Semiconductors”，许多小功率组件(packages)已使用Ag填充的环氧树脂的形式的无铅模片连接。这些Ag填充的环氧树脂载有不超过70％的银。然而，它们的使用还未被扩展至较大功率组件中的较大硅尺寸。根据Adamson，已在较大组件(比如TO220)上对Ag填充的环氧化物进行了温度循环试验。这些实验组件在-40和+125℃之间的温度循环。这些试验条件符合2005年5月的JEDEC标准JESD22-A104C指定的条件“G”。
JEDEC标准对Pb/Sn焊接组合物不推荐超过+125℃的试验条件。不过，功率半导体装置的恶劣操作条件要求它们承受JEDEC标准的测试条件“H”指定的试验条件，并要求在-55和+150℃之间的温度循环。
尽管指令2002/95/EC豁免了从2006年7月1日起用无铅替代品替代高熔点型焊料中的铅，但对于模片连接应用尽快用无铅替代品替代高铅含量的焊料对环境将是非常有益的。
本发明的目的在于提供用于功率半导体的模片连接应用的无铅粘合剂组合物，所述功率半导体可靠地承受根据JEDEC测试条件“H”的温度循环至少1000个循环，所述循环中最高和最低温度的保温时间为15分钟，并产生和目前使用的高铅含量焊料相似的热耗散。
这个目的通过在权利要求中指定的模片连接组合物而实现。特别地，根据本发明使用的模片连接组合物包含单组分粘合剂和金属粉末作为填料，其中所述单组分粘合剂是环氧树脂，且其中所述金属粉末的金属的热导率大于250W/(m·K)并包含铜，且所述粉末颗粒具有类似球体的形状。
在本发明的上下文中，术语“单组分粘合剂”指包含粘合剂和潜伏性固化剂的单罐装(one pot)粘合剂组合物，所述潜伏性固化剂可通过提供能量(比如热或紫外辐射)而活化。所述粘合剂可以是环氧树脂，优选为双酚环氧树脂。所述单组分粘合剂的保存期限长且仅在提供外部能量后开始固化。
固化的模片连接组合物必须和常规的用于附着大功率半导体装置的高铅焊料具有相似的热耗散。这些高铅焊料合金是例如热导率为55W/(m·K)的Pb88Sn10Ag2和热导率为44W/(m·K)的Pb92.5Sn5Ag2.5。已发现所述固化的模片连接组合物在从功率半导体功率耗散以及耐温度循环性方面满足需求。
固化的模片连接组合物的热导率是填料材料的热导率、环氧树脂的热导率、填料材料的体积分数、及填料和环氧树脂之间的接触热阻的函数。
得到的热导率当然主要受包含铜的填料的影响。纯铜的热导率是400W/(m·K)，而环氧树脂的热导率低至0.3W/(m·K)。为了保证填料-环氧化物复合物的高热导率，填料粉末的热导率应大于250，优选大于300，最优选大于350W/(m·K)。
填料-环氧化物复合物的热传导率还取决于填料的体积分数。下面，将使用术语填充度代替填料的体积分数。填充度定义为填料相对于复合物的总重量的重量百分数。根据本发明，金属粉末的粉末颗粒应具有类似球体的形状或球状。薄片状粉末得到较差的结果，此外，当在分配应用(dispensingapplications)中使用模片连接组合物时，填充了薄片的粘合剂会堵塞注射器。对于类似球体形状的填料颗粒，六方紧密堆积时得到最大体积分数，体积分数为74％。对于铜粉作为填料，使用铜的密度(8.9g/cm3)和环氧树脂的密度(约1.2g/cm3)来计算，这个值转化为95重量％的最大填充度。
铜粉的平均粒径D50对填料-环氧化物复合物的耐热疲劳性没有决定性的影响。用平均粒径D50在1和50μm之间的填料粉末已获得良好的结果。更优选平均粒径在1和30μm之间，进一步优选平均粒径在1和5μm之间。
最后，填料-环氧化物复合物的得到的热导率取决于填料表面和树脂之间的接触热阻。填料颗粒的表面上的任何杂质层会增大所述接触热阻。因此优选使用具有低表面杂质的填料颗粒。
由于其高热导率，优选使用包含高百分比的铜的金属粉末。最优选铜的纯度大于99.5重量％的铜粉，特别优选大于99.9重量％。
就铜粉而言，粉末颗粒的表面上最有害的杂质是铜(II)氧化物。在约5nm厚度的薄表层中铜(II)氧化物相对于金属铜的比例可通过XPS(X射线光电子光谱学)确定。出于该目的，获得的XPS光谱通过本领域公知的曲线拟合分析。已发现，如果通过XPS分析的表层中至多50％的原子氧化成CuO，可获得固化的组合物的热导率和热疲劳方面良好的结果。优选地，所述被氧化的铜原子应不超过30％，更优选不超过10％。
相对于金属粉末的热传导率，固化的环氧树脂的热传导率非常低。环氧树脂的主要任务在于提供与金属填料和与半导体装置和衬底的良好粘合。已证明，选自双酚A环氧树脂和双酚F环氧树脂的环氧树脂可提供与铜和镍表面以及与芯片的良好粘合。双酚A环氧树脂最为优选。
包含填充了指定的填料粉末的固化的粘合剂且胶层的厚度(bond-linethickness)在20和80μm之间的固化的模片连接组合物可承受对热疲劳的上述试验条件，并产生和高铅焊料相似的热耗散。
为了制备所述模片连接组合物，将金属粉末和环氧树脂充分混合。将所述组合物填塞在一个单元内并可在使用前保持在室温。
为了用所述模片连接组合物将离散的大功率半导体附着至印刷电路板，将所述组合物涂布于所述印刷电路板，将所述半导体置于所述电路板上，然后在80和250℃之间的温度固化所述模片连接组合物，优选在130和180℃之间的温度。
当使用铜作为填料材料，优选通过用防氧化材料涂布铜粉而避免在储存期间铜表面氧化。所述涂布材料可以是脂肪酸，优选为饱和脂肪酸、聚硅氧烷或磷化物。所述脂肪酸可选自油酸、肉豆蔻酸、棕榈酸、十七酸、十八酸和二十酸。所述涂布材料的涂布量相对于被涂布的铜粉的总重量为0.1到1重量％。最优选具有轻微亲水性(即具有很少量极性基团)的涂布材料，从而使对水的引力最小。
对于标准的模片连接应用，所述模片连接组合物应含有相对于组合物总重量的40到90重量％的金属粉末。对于分配应用，所述组合物应含有40和80重量％之间，优选为60和80重量％之间的金属，以避免分配喷嘴的堵塞。对于通过印刷进行的模片连接，所述粘合剂组合物可含有相对于组合物总重量的40和90重量％之间的金属粉末。
下列实施例和附图用于帮助进一步说明本发明。附图显示：
图1：用于测量热耗散的试验设备
图2：用不同填充度的铜粉填充的模片连接组合物固化后，热耗散与胶层厚度的关系。
实施例：
表1列出了包含与双酚A环氧树脂混合的铜粉的模片连接组合物，形成填充度不同的填充金属的粘合剂组合物，用于温度循环试验和热耗散测量。
表1：模片连接组合物的性质
Figure G2007800439479D00041
所述铜颗粒具有类似球体的形状，纯度超过99.9％，热导率超过350W/(m·K)。以Cu1、Cu2、Cu3命名的模片连接组合物符合本发明的要求，为了比较，选择市售的“高热导率银填充的环氧化物膏(High ThermalConductivity Silver Filled Epoxy Paste)”(Ag)。常规的高铅焊膏Pb(Pb88Sn10Ag2)作为参照材料。
热耗散的测量：
为了测量热耗散与胶层厚度的关系，使用表1的组合物将一系列硅模片连接至铜衬底。在150℃下固化胶合层30分钟。通过使用图1显示的试验设备进行测量。将试件和它们的铜衬底(1)置于加热至T2＝75℃的铜块(4)上，提供恒定温度。硅芯片(2)和浸在周围空气(T1＝30℃)中的另一铜块(5)接触。用热电偶(6)和(7)测量所述层状物的铜和硅侧的温度。在所述两侧之间的温差ΔT与由硅芯片(2)、胶层(3)和铜衬底(1)组成的试件的热耗散成正比。
图2显示对不同的胶层厚度(BLT)横穿试件的胶层所测量的温差。用Pb表示的线显示用市售的焊膏Pb附着的参照样品的行为。可以清楚地看到，根据本发明用模片连接组合物Cu1、Cu2和Cu3附着的样品显示与使用软焊的参照样品相似的热导率。相反，比较样品Ag显示温差随着胶层厚度增大而急剧增大，因此不可接受。
温度循环/热疲劳
对于温度循环试验，用所述金属填充的树脂将12×12×0.5mm3的硅芯片和尺寸为12×12×1mm3的铜衬底结合。在150℃下固化所述胶层30分钟，得到约50μm的胶层厚度。对照模片连接组合物(Ag和Pb)根据供应商的推荐而处理。
根据JEDEC标准试验条件“H”(-55到+150℃)对所述试件进行1000次保温时间为15分钟的温度循环。
具有金属粉末Cu1到Cu3的模片连接组合物在温度循环后未显示破坏。与之相反，常规的Ag/环氧化物(Ag)未通过温度循环试验。结果显示于表2中。
表2：1000次循环后的热疲劳结果(每个试验5个样品)
Figure G2007800439479D00061
通过：无分层
未通过：芯片破损或结合处分层

Claims (12)

1.用于将大功率半导体装置附着至印刷电路板的模片连接组合物，其中所述模片连接组合物包含单组分粘合剂和金属粉末，且其中所述单组分粘合剂是环氧树脂，且其中所述金属粉末的金属的热导率大于250W/(m·K)并包含铜，且所述粉末颗粒具有类似球体的形状，其中在所述金属粉末和所述粘合剂的组分混合前，将所述金属粉末用脂肪酸、聚硅氧烷或磷化物涂布。
2.权利要求1的模片连接组合物，其中所述金属粉末的平均粒径D50在1和50μm之间。
3.权利要求2的模片连接组合物，其中所述金属粉末的金属是纯度大于99.5重量％的铜。
4.权利要求2的模片连接组合物，其中所述金属粉末的金属是纯度大于99.9重量％的铜。
5.权利要求3或4的模片连接组合物，其中通过XPS测量，表层中的铜原子不到一半氧化成CuO。
6.权利要求1的模片连接组合物，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.权利要求6的模片连接组合物，其中将所述金属粉末和所述环氧树脂预混合。
8.权利要求1-7中任一项的模片连接组合物用于将大功率半导体装置附着至印刷电路板的用途。
9.权利要求8的用途，其中所述模片连接组合物通过分配而涂布，且相对于所述组合物的总重量，所述组合物含有40到80重量％的金属粉末。
10.权利要求8的用途，其中所述模片连接组合物通过印刷而涂布，且相对于组合物的总重量，所述组合物含有40到90重量％的金属粉末。
11.将离散的大功率半导体附着至印刷电路板的方法，所述方法包括：将模片连接组合物涂至所述功率半导体或所述印刷电路板，将所述半导体置于所述印刷电路板上，并在80和250℃之间的温度固化所述模片连接组合物，其中所述模片连接组合物包含单组分粘合剂和金属粉末，且其中所述单组分粘合剂是环氧树脂，且其中所述金属粉末的金属的热导率大于250W/(m·K)并包含铜，且所述粉末颗粒具有类似球体的形状，其中在所述金属粉末和所述粘合剂的组分混合前，将所述金属粉末用脂肪酸、聚硅氧烷或磷化物涂布。
12.大功率半导体装置，所述装置包含印刷电路板和附着在所述电路板上的离散大功率半导体，其中所述大功率半导体用固化的权利要求1中限定的模片连接组合物附着至所述印刷电路板，在所述半导体和所述印刷电路板之间形成厚度在20和80μm之间的胶层。
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