CN1854231A - 具有改进应力性能的芯片粘合剂 - Google Patents

具有改进应力性能的芯片粘合剂 Download PDF

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Publication number
CN1854231A
CN1854231A CNA2006100723966A CN200610072396A CN1854231A CN 1854231 A CN1854231 A CN 1854231A CN A2006100723966 A CNA2006100723966 A CN A2006100723966A CN 200610072396 A CN200610072396 A CN 200610072396A CN 1854231 A CN1854231 A CN 1854231A
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China
Prior art keywords
epoxy compounds
resin
die attach
calculated
weight
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CNA2006100723966A
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E·蔡
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National Starch and Chemical Investment Holding Corp
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National Starch and Chemical Investment Holding Corp
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Publication of CN1854231A publication Critical patent/CN1854231A/zh
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Abstract

胶粘剂组合物，其含有基本化合物或基本树脂和具有乙烯基官能度的环氧树脂，而不含该环氧树脂的固化剂，该胶粘剂组合物显示了增强的应力性能。该组合物可用于微电子应用中。

Description

具有改进应力性能的芯片粘合剂
                       发明领域
【0001】本发明涉及具有改进应力性能的芯片粘合剂(芯片连接粘合剂(die attach adhesive))，其包括能够通过自由基聚合固化的树脂、自由基固化剂以及具有烯丙基或乙烯基不饱和的环氧化合物或树脂，其中没有环氧化合物的固化剂。
                       发明背景
【0002】出于各种目的，胶粘剂组合物被用于半导体封装体的制造和组装中，例如，集成电路芯片与引线框架或其它衬底的粘结、多芯片叠层组装以及电路封装体或组件与印制线路板的粘结。这些用途的主要要求是快速固化和高的粘结强度，传统上采用环氧树脂实现。然而，环氧树脂可能是脆性的，导致封装体中的高应力，因此，其它树脂已被讦估并应用，以提高柔韧性和其它性能如疏水性。然而，这些备选的树脂并不总是表现出环氧树脂所提供的强粘合力。因此，需要能整合这些性质平衡的芯片粘合剂，以满足用于半导体封装制造的胶粘剂的所有要求。
                    发明概述
【0003】本发明是对美国专利6,750,301中所公开的发明的改进，是一种胶粘剂组合物，其包括(a)能够通过自由基聚合或硅氢化作用(hydrosilation)固化的树脂，(b)含有烯丙基或乙烯基不饱和的环氧化合物，(c)树脂固化剂，和(d)任选地，一种或多种填料，特征在于不含有该环氧树脂的固化剂。如在本说明书和权利要求书中所使用，具有自由基聚合或固化能力的化合物或树脂是含有碳-碳不饱和的化合物或树脂，而能够通过硅氢化作用聚合或固化的化合物或树脂是含有硅烷基团的化合物或树脂。该组合物也可以包含助粘剂或偶联剂。
【0004】本发明人发现，与含有环氧化合物的固化剂的配方相比，去掉环氧化合物的固化剂在应力性能(通过扭曲测量)上产生了意料不到的改进，而仍保持或提高了粘合力。在另一个实施方式中，本发明是半导体封装体，其半导体芯片用本发明胶粘剂与基材粘结。
                    发明详述
【0005】在微电子应用中可用作胶粘剂的自由基固化树脂包括，例如，马来酰亚胺，如可从Ciba Specialty Chemicals获得的马来酰亚胺；聚醚，如可从BASF得到的聚醚；聚酯，如可从Uniqema或Bayer获得的聚酯；聚(丁二烯)，如可从Elf-Atochem获得的聚(丁二烯)；聚氨酯，如可从Bayer或BASF获得的聚氨酯；和丙烯酸酯树脂，如可从Sartomer或UCB Radcure获得的丙烯酸酯树脂。聚醚、聚酯和聚氨酯优选包含末端不饱和，但也可以包含聚合物链内的不饱和。
【0006】硅氧烷和聚硅氧烷，其通过硅氢化作用固化，可以是线型的或环状的聚合物，并且每分子具有至少2个硅烷官能度。示例性的化合物可通过商业途径从Gelest得到。
【0007】技术人员将选择特定的树脂，以得到最终配方中特定的材料性质，例如，流变性质、亲水或疏水性质、韧性、强度或柔韧性。在胶粘剂组合物中，树脂的含量按重量计算在10-80％的范围内。
【0008】环氧化合物可以是具有烯丙基或乙烯基官能度的任何环氧化合物。例子包括2，6-二环氧甘油苯基烯丙醚、二氧化苧烯、缩水甘油乙烯基苄醚或缩水甘油乙烯醚(gylcidyl vinyl ether)。环氧化合物在胶粘剂组合物中的量按重量计算在0.1-30％的范围内。
【0009】示例性的自由基引发剂可以是热引发剂或光引发剂，其在胶粘剂组合物中的含量按重量计算为0.1％到10％，优选为0.1％到3.0％。优选的热引发剂包括过氧化物，例如二-(4-叔丁基环己基)过氧化二碳酸酯、过辛酸丁酯和过氧化二枯基以及偶氮化合物，例如2，2′-偶氮双(2-甲基-丙腈)和2，2′-偶氮双(2-甲基-丁腈)。优选的光引发剂系列是Ciba Specialty Chemicals销售的、商标为Irgacure的光引发剂。在一些配方中，光固化和热固化都可以是期望的，例如，可以通过光辐照开始固化过程，然后在后续处理步骤中可以通过热的应用完成固化。
【0010】一般地，这些组合物将在70℃到250℃的温度范围内固化，并且固化将在10秒到3小时的范围内实现。各配方的时间和温度固化方案随着配方的组成而变化，但本领域的普通技术人员可以对固化方案的参数进行调节，而无需做过多的试验。
【0011】在一些组合物中，可能期望添加有机或无机的填料。合适的导电填料(conductive filler)是碳黑、石墨、金、银、铜、铂、钯、镍、铝、碳化硅、一氮化硼和氧化铝。合适的非导电填料是蛭石、云母、硅灰石、碳酸钙、二氧化钛、沙子、玻璃、熔凝硅石、火成二氧化硅、硫酸钡和卤化乙烯聚合物如四氟乙烯、三氟乙烯、二氟乙烯、氟乙烯、二氯乙烯和氯乙烯的颗粒。当存在时，填料的含量按重量计算为组合物的20％到90％。
【0012】也可以期望加入助粘剂或偶联剂，包括硅烷、硅酸酯、金属丙烯酸盐或甲基丙烯酸盐、钛酸盐和含有螯合配体的化合物，如膦、硫醇和乙酰乙酸盐。当存在时，这些物质的含量按重量计算多达10％，优选地按重量计算为组合物的0.1％到3.0％。
【0013】通过下面的实施例，对本发明做进一步阐述，这些实施例并不意欲对本发明进行限制。
                        实施例
【0014】对于这些实施例而言，半导体芯片与衬底的粘合强度被测量为Kg(公斤)力的芯片剪切强度。用附着在两层BT印制线路板上的3×3mm硅芯片的未封装组件，进行试验。在炉子中固化该未封装组件，炉子温度在30分钟内从室温升至175℃，然后在175℃保持15分钟。之后，将组件分成两组。一组在固化之后(固化后)，直接测试芯片剪切强度。将第二组暴露于模制后烘焙的模拟环境，在175℃烘焙4小时，然后回到室温，测试芯片剪切强度(模制后烘焙)。将固化后(post cure)组和模制后烘焙(post mold bake)组都进一步分成两个亚组，其中第一个亚组在室温下测试芯片剪切强度，而第二个亚组在260℃下测试芯片剪切强度。所有的组件都表现出胶粘剂粘结芯片与衬底失败的内聚模式(cohesive mode)。
【0015】封装体中存在的应力水平用芯片在未封装组件中的扭曲(warpage)表示。较高的扭曲值表明在芯片附着组件中具有较高的应力。对于这些实施例而言，测试了两种类型的组件。在第一种类型中，将12.7×12.7×0.38mm的硅芯片附着在0.2mm厚的镀银的铜引线框架上。在第二种类型中，将7×8×0.076mm的硅芯片附着在0.2mm厚的双马来酰亚胺三嗪(BT)衬底上。在炉子中固化组件，炉子温度在30分钟内从室温升至175℃，然后在175℃保持15分钟。然后将组件回到室温，使用表面糙度测定仪测量芯片的扭曲。
【0016】在下面的实施例中，对含有或不含环氧化合物的固化剂的配方测试了室温下的和热干燥的芯片剪切强度(以kg力量度)，并用上述方案测试了扭曲(以μm量度)，其中环氧化合物具有烯丙基或乙烯基官能度。胶粘剂组合物和性能测试数据列于下面的表格中，表明不含环氧化合物的固化剂的胶粘剂配方具有相当的或更高的芯片剪切强度和较低的扭曲，所述环氧化合物具有烯丙基或乙烯基官能度。因此，数据表明，不含环氧化合物的固化剂的配方出乎意料地改进了胶粘剂的性能，其中所述环氧化合物具有烯丙基或乙烯基不饱和。这些组合物以重量百分比进行描述。
【0017】实施例1
组合物实例1   不含环氧化合物的固化剂   含有环氧化合物的固化剂
  专有的双马来酰亚胺   26.57％   26.51％
  二-(4-叔丁基环己基)过氧化二碳酸酯   0.53   0.53
  二-三羟甲基丙烷四丙烯酸酯   3.99   3.97
  2-丙烯酸苯氧乙酯   7.97   7.95
  聚(丁二烯)   5.31   5.30
  双酚F环氧树脂中40％CTBN   3.99   3.98
  (2，6-二环氧甘油苯基烯丙醚)环氧树脂   6.64   6.63
  2-乙基-4-甲基咪唑-CN   0   0.13
  硅石1   30   30
  硅石2   15   15
  总计   100％   100％
  性能实例1
  芯片扭曲：在室温下固化后，SPCLF 7.7μm 20.7μm
  芯片剪切强度：固化后，室温下固化后，260℃模制后烘焙，室温下模制后烘焙，260℃ 8.31.723.35.3 10.61.624.95.8
【0018】实施例2
组合物实例2   不含环氧化合物的固化剂   含有环氧化合物的固化剂
  专有的双马来酰亚胺   28.65％   28.58％
  二-(4-叔丁基环己基)过氧化二碳酸酯   0.57   0.57
  二-三羟甲基丙烷四丙烯酸酯   4.30   4.29
  2-丙烯酸苯氧乙酯   8.59   8.57
  聚(丁二烯)   5.73   5.71
  (2，6-二环氧甘油苯基烯丙醚)环氧树脂   7.16   7.14
  2-乙基-4-甲基咪唑-CN   0   0.14
  硅石1   30   30
  硅石2   15   15
  总计   100％   100％
  性能实例2
  芯片扭曲：在室温下固化后，SPCLF 12.3μm 26.7μm
  芯片剪切强度：固化后，室温下固化后，260℃模制后烘焙，室温下模制后烘焙，260℃ 11.71.822.43.8 9.11.625.64.0
【0019】实施例3
组合物实例3   不含环氧化合物的固化剂   含有环氧化合物的固化剂
  专有的双马来酰亚胺   43.30％   43.14％
  二-(4-叔丁基环己基)过氧化二碳酸酯   0.89   0.86
  (2，6-二环氧甘油苯基烯丙醚)环氧树脂   10.82   10.78
  2-乙基-4-甲基咪唑-CN   0   0.22
  硅石1   30   30
  硅石2   15   15
  总计   100％   100％
  性能实例3
  芯片扭曲：在室温下固化后，SPCLF固化后，BT 1.03.8 3.28.5
  芯片剪切强度：固化后，室温下固化后，260℃模制后烘焙，室温下模制后烘焙，260℃ 10.02.518.64.1 0.30.27.51.7
【0020】实施例4
组合物实例4   不含环氧化合物的固化剂   含有环氧化合物的固化剂
  专有的双马来酰亚胺   35.03％   34.92％
  二-(4-叔丁基环己基)过氧化二碳酸酯   0.70   0.70
  2-丙烯酸苯氧乙酯   10.51   10.48
  (2，6-二环氧甘油苯基烯丙醚)环氧树脂   8.76   8.73
  2-乙基-4-甲基咪唑-CN   0   0.17
  硅石1   30   30
  硅石2   15   15
  总计   100％   100％
  性能实例4
  芯片扭曲：在室温下
  固化后，SPCLF固化后，BT   1.74.8   2.08.8
  芯片剪切强度：固化后，室温下固化后，260℃模制后烘焙，室温下模制后烘焙，260℃ 7.51.815.12.9 1.20.48.61.7
【0021】实施例5
组合物实例5   不含环氧化合物的固化剂   含有环氧化合物的固化剂
  专有的双马来酰亚胺   35.03   34.92
  二-(4-叔丁基环己基)过氧化二碳酸酯   0.70   0.70
  二-三羟甲基丙烷四丙烯酸酯   10.51   10.48
  (2，6-二环氧甘油苯基烯丙醚)环氧树脂   8.76   8.73
  2-乙基-4-甲基咪唑-CN   0   0.17
  硅石1   30   30
  硅石2   15   15
  总计   100％   100％
  性能实例5
  芯片扭曲：在室温下固化后，SPCLF固化后，BT 3.115.5 6.815.5
  芯片剪切强度：固化后，室温下固化后，260℃模制后烘焙，室温下模制后烘焙，260℃ 11.32.517.74.0 9.01.418.02.8
【0022】实施例6
组合物实例6   不含环氧化合物的固化剂   含有环氧化合物的固化剂
  专有的双马来酰亚胺   14.13％   14.08％
  二-(4-叔丁基环己基)过氧化二碳酸酯   0.28   0.28
  二-三羟甲基丙烷四丙烯酸酯
  2-丙烯酸苯氧乙酯   4.24   4.23
  聚(丁二烯)   2.82   2.82
  (2，6-二环氧甘油苯基烯丙醚)环氧树脂   3.53   3.52
  2-乙基-4-甲基咪唑-CN   0   0.07
  银片   75   75
  总计   100％   100％
  性能实例6
  芯片扭曲：在室温下固化后，SPCLF固化后，BT 15.522.5 19.823.5
  芯片剪切强度：固化后，室温下固化后，260℃模制后烘焙，室温下模制后烘焙，260℃ 9.72.513.14.2 8.73.017.93.8

Claims (4)

1.芯片粘合剂组合物，包括：
(a)树脂，所述树脂能够通过自由基聚合或硅氢化作用固化，其含量按重量计算为10％到80％，
(b)环氧化合物，所述环氧化合物具有乙烯基或烯丙基官能度，其含量按重量计算为0.1％到30％，
(c)树脂(a)的固化剂，其含量按重量计算为0.1％到10％，和
(d)任选地，填料，其含量按重量计算为20％到90％；
其特征在于，不含所述环氧化合物的固化剂。
2.根据权利要求1所述的芯片粘合剂，其中所述树脂选自马来酰亚胺、聚醚、聚酯、聚(丁二烯)、聚氨酯、丙烯酸酯、硅氧烷和聚硅氧烷。
3.根据权利要求1所述的芯片粘合剂，其中所述环氧化合物选自2，6-二环氧甘油苯基烯丙醚、二氧化苧烯、缩水甘油乙烯基苄醚和缩水甘油乙烯醚。
4.根据权利要求1所述的芯片粘合剂，其中所述填料存在并选自碳黑、石墨、金、银、铜、铂、钯、镍、铝、碳化硅、一氮化硼、金刚石、氧化铝、蛭石、云母、硅灰石、碳酸钙、二氧化钛、沙子、玻璃、熔凝硅石、火成二氧化硅、硫酸钡、四氟乙烯、三氟乙烯、二氟乙烯、氟乙烯、二氯乙烯和氯乙烯。
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