CN1427753A - 助熔的底层填料组合物 - Google Patents
助熔的底层填料组合物 Download PDFInfo
- Publication number
- CN1427753A CN1427753A CN01807139A CN01807139A CN1427753A CN 1427753 A CN1427753 A CN 1427753A CN 01807139 A CN01807139 A CN 01807139A CN 01807139 A CN01807139 A CN 01807139A CN 1427753 A CN1427753 A CN 1427753A
- Authority
- CN
- China
- Prior art keywords
- composition
- circuit board
- acid
- semiconductor device
- imidazole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 83
- 239000004065 semiconductor Substances 0.000 claims abstract description 72
- 229910000679 solder Inorganic materials 0.000 claims abstract description 59
- 238000007789 sealing Methods 0.000 claims abstract description 8
- 230000004907 flux Effects 0.000 claims description 98
- -1 anhydride compound Chemical class 0.000 claims description 47
- 239000002253 acid Substances 0.000 claims description 41
- 229920000647 polyepoxide Polymers 0.000 claims description 34
- 239000003822 epoxy resin Substances 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 239000011159 matrix material Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 14
- 150000003839 salts Chemical group 0.000 claims description 14
- 150000002460 imidazoles Chemical class 0.000 claims description 11
- 239000004615 ingredient Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001412 amines Chemical group 0.000 claims description 8
- 150000008064 anhydrides Chemical class 0.000 claims description 6
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 6
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229940015043 glyoxal Drugs 0.000 claims description 5
- 150000004693 imidazolium salts Chemical class 0.000 claims description 5
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
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- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 230000035935 pregnancy Effects 0.000 claims description 3
- NOQONXWBCSGVGF-UHFFFAOYSA-N 1,2,4-triphenylimidazole Chemical class C=1C=CC=CC=1N1C=C(C=2C=CC=CC=2)N=C1C1=CC=CC=C1 NOQONXWBCSGVGF-UHFFFAOYSA-N 0.000 claims description 2
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- KKKDZZRICRFGSD-UHFFFAOYSA-N 1-benzylimidazole Chemical compound C1=CN=CN1CC1=CC=CC=C1 KKKDZZRICRFGSD-UHFFFAOYSA-N 0.000 claims description 2
- SEULWJSKCVACTH-UHFFFAOYSA-N 1-phenylimidazole Chemical compound C1=NC=CN1C1=CC=CC=C1 SEULWJSKCVACTH-UHFFFAOYSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- ICQLQVWXFUWFRI-UHFFFAOYSA-N 2-(2-methylimidazol-1-yl)propanenitrile Chemical compound N#CC(C)N1C=CN=C1C ICQLQVWXFUWFRI-UHFFFAOYSA-N 0.000 claims description 2
- OPHSKKPSEMOQLM-UHFFFAOYSA-N 2-(2-phenylethenyl)-1h-imidazole Chemical class N=1C=CNC=1C=CC1=CC=CC=C1 OPHSKKPSEMOQLM-UHFFFAOYSA-N 0.000 claims description 2
- SLLDUURXGMDOCY-UHFFFAOYSA-N 2-butyl-1h-imidazole Chemical compound CCCCC1=NC=CN1 SLLDUURXGMDOCY-UHFFFAOYSA-N 0.000 claims description 2
- SDQVYUNYDAWYIK-UHFFFAOYSA-N 2-oxobut-3-enal Chemical compound C=CC(=O)C=O SDQVYUNYDAWYIK-UHFFFAOYSA-N 0.000 claims description 2
- RRMINFSIXCUCNS-UHFFFAOYSA-N 2-oxobutanamide Chemical compound CCC(=O)C(N)=O RRMINFSIXCUCNS-UHFFFAOYSA-N 0.000 claims description 2
- UPOLYUOBDJSLRC-UHFFFAOYSA-N 2-undec-1-enyl-1h-imidazole Chemical class CCCCCCCCCC=CC1=NC=CN1 UPOLYUOBDJSLRC-UHFFFAOYSA-N 0.000 claims description 2
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 claims description 2
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 claims description 2
- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 claims description 2
- SZUPZARBRLCVCB-UHFFFAOYSA-N 3-(2-undecylimidazol-1-yl)propanenitrile Chemical compound CCCCCCCCCCCC1=NC=CN1CCC#N SZUPZARBRLCVCB-UHFFFAOYSA-N 0.000 claims description 2
- YGOFNNAZFZYNIX-UHFFFAOYSA-N 3-N-phenylbenzene-1,2,3-triamine Chemical compound NC=1C(=C(C=CC1)NC1=CC=CC=C1)N YGOFNNAZFZYNIX-UHFFFAOYSA-N 0.000 claims description 2
- CJNLEMIVYDYAGD-UHFFFAOYSA-N C(=O)OC=O.C1CCCCC1 Chemical compound C(=O)OC=O.C1CCCCC1 CJNLEMIVYDYAGD-UHFFFAOYSA-N 0.000 claims description 2
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- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical class NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
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- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
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- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- GCWAFWMUTOXMIT-HWKANZROSA-N (e)-heptadec-2-ene Chemical compound CCCCCCCCCCCCCC\C=C\C GCWAFWMUTOXMIT-HWKANZROSA-N 0.000 claims 1
- QVCUKHQDEZNNOC-UHFFFAOYSA-N 1,2-diazabicyclo[2.2.2]octane Chemical compound C1CC2CCN1NC2 QVCUKHQDEZNNOC-UHFFFAOYSA-N 0.000 claims 1
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Abstract
本发明涉及用于助熔金属表面的助熔的底层填料组合物的制备,用于提供电连接和熔封半导体器件[如芯片尺寸或芯片刻度组件(CSP)、球栅阵列接脚(BGA)、焊盘阵列接脚(LGA)、倒装片式组件(FC)等,其中上述各种均具有半导体芯片如大规模集成(LSI)]间的空间或熔封半导体芯片本身和分别与器件或芯片电连接的电路板间的空间。本发明的助熔的底层填料组合物在与所使用的焊剂接近相同的温度下开始固化,从而确定电连接熔体。
Description
发明背景
发明领域
本发明涉及用于助熔金属表面的助熔的底层填料(underfill)组合物,用于提供电连接和熔封半导体器件[如芯片尺寸或芯片刻度组件(CSP)、球栅阵列接脚(BGA)、焊盘阵列接脚(LGA)、倒装片式组件(FC)等,其中上述各种均具有半导体芯片如大规模集成(LSI)]间的空间或熔封半导体芯片本身和分别与器件或芯片电连接的电路板间的空间。本发明的助熔的底层填料组合物在与所使用的焊剂接近相同的温度下开始固化,从而确定电连接熔体。
相关技术的简要说明
这种CSP、BGA和LGA改进电子器件的特征,在此情况下使用所述电子器件,同时它们还充当保护半导体裸片如LSI的作用。一般地,CSP/BGA/LGA组件通过使用焊剂与电路板电连接。一般地,使用焊剂如低共熔锡/铅焊剂(熔点183℃)或铅/铟焊剂(熔点220℃)。
焊剂起提供一种接触焊接点(例如在半导体器件上的金属点)的作用,用于集成电路与基质的连接。开发这种焊剂块的相互连接技术以消除人工电线粘接的费用、不可靠性和低产率。这一技术使产量以及相互连接的密度大大增加,因为它发展到完全占据区域阵列并已克服组装尺寸愈加变小的微电子器件(正如今天我们所了解的)的制造障碍。
然而,当所得CSP/BGA/LGA电路板结构暴露于热循环下时,电路板与CSP/BGA/LGA之间的焊接可靠性常值得怀疑。对于CSP/BGA/LGA组件与电路板之间的空间常用底层填料密封剂填充,从而实现电连接,以便通过紧密匹配半导体器件和基质间热膨胀系数的差别来降低由热循环而引起的应力,从而改进热震动性能并提高结构可靠性。另外,底层填料密封剂常用于缓和可导致电连接失败的振动干扰和物理应力。
典型地,在焊剂的电连接方法中,助熔剂放置在焊剂上,使焊剂在焊剂软熔操作过程中当暴露于所达到的高温时产生安全的电连接,其典型的曲线见图2的曲线B。然后半导体器件沿基质排列和焊剂在如此高温条件下软熔。
过去在焊剂软熔操作过程后,为了防止半导体器件的腐蚀,根据溶剂本性的不同使用有机或含水基溶剂除去来自熔剂中的残渣。然而,半导体器件和基质间窄的空间使得难以除去助熔剂残渣并且耗时,且要求复杂和昂贵的清洁系统。许多半导体清洁制造商优选省略这一步骤,前提是不引入增加的腐蚀。
因此,省略除去助熔剂残渣步骤成为半导体器件制造商的一个重要考虑因素。最近的商业兴趣引起制备环氧基底层填料密封剂的工业努力,所述密封剂能助熔金属并可设计成在焊剂软熔操作过程中固化。
在那方面的努力主要聚焦于在底层填料密封剂中的助熔剂,其中助熔剂可能是上述“不需清洁”的助熔剂。
在一种这样令人困惑的努力下,国际专利申请No.WO98/37134提出了一种倒装片技术用的不流动的底层填料密封剂。该密封剂以环氧树脂和酸酐硬化剂、促进剂、表面活性剂和助熔剂为基础,并使用粘度控制剂如煅制二氧化硅和偶联剂。据报道这种密封剂仅在达到约190-230℃的最大焊接块软熔温度之后,提供最佳的流动和固化反应。
美国专利No.5128746(Pennisi)公开了具有助熔剂的可热固化的粘合剂,用于软熔焊接电子组分和基质。据报道该粘合剂可除去金属化的电子组分上的氧化涂层,和粘合剂当被加热到软熔焊接温度时至少部分固化。粘合剂包括一种热固性树脂、一种助熔剂和一种与热固性树脂反应并当加热受热可固化的粘合剂时固化热固性树脂的固化剂。
直到今天,在商购或已知的环氧基组合物中所使用的环氧固化剂由于固化剂的固化缓慢导致一般地要求在该应用中有后固化加热的步骤以固化组合物,或者环氧基组合物反应性太强,结果过早地形成凝胶,从而导致电连接失败,正如’746专利中描述的组合物的情况。尽管这些情况在一些商业应用中可能不会产生问题,但对要求按计划发生半导体器件在载体基质上的自定位的助熔底层填料应用来说,过早胶凝常引起半导体/器件基质界面的失调。这种失调导致电连接失败,从而使得安装的电子组件无法操作。另外,在环氧基组合物固化缓慢的情况下,许多微电子组装者不愿使用后固化加热步骤,因为这种后固化可通过损坏连接到基质上的一种或多种半导体器件,使温度升高到可危害组装的电子组件作为一个整体的完整性的程度,且还增加加工时间和费用。
对于微电子组装者来说另一可供选择的方法是改变焊剂软熔曲线。这种可供选择的焊剂软熔曲线(所述焊剂软熔曲线由一些材料供应商推广,称为“火山曲线”(参见图2的曲线A))由于温度快速升高使得在短时间内焊剂迅速软熔到焊剂回流温度,而没有任何温度范围的分区或分阶段。结果,半导体组分产生热震动,这也可常危害其完整性。尽管可开发具有助熔能力的底层填料密封剂作为实际的物质来满足该曲线,但认为火山曲线在微电子组分的组装中没有实际应用,因为它与在基质上发生的其它程序不相容。而且,过去销售的具有助熔能力的那些底层填料密封剂与上述分区的熔剂软熔曲线不相容,从而导致产生不能导电的微电子组件。
国际专利申请No.PCT/GB99/01236涉及一种可热固化的粘合剂组合物,其中包括一种可交联的热固性材料和一种具有助熔性能并在没有催化剂作用的材料和/或热存在的情况下显示有限的或不显示热固化活性的化学交联剂。该组合物当加热到介于Sn/Pb60/40合金的液体温度到Sn/Pb3/97合金的液体温度的温度范围并在交联剂作用下在交联材料用的催化剂存在时可热固化。据报道该组合物在没有这种催化剂和介于20-25℃的温度范围的情况下具有储存和反应稳定性。
在Lucus等的标题为“Trends in Controlling Reactivity in EpoxyFormulations”的1986年的商业文献出版物中一般性地公开了反应性和潜在性之间的平衡,以及通过在无水环境(如环氧基基体)中使用胺盐控制反应性(当然包括潜在性)的能力,其中胺盐将分解,从而释放出胺促进剂。胺促进剂的释放是反应速度的测量步骤。
然而,直到今天,认为胺盐不可用于制备组装稳定性器件用的粘合剂组合物,其中粘合剂在胺盐分解的温度范围内固化,这与焊剂熔融的温度范围一致。
过去,二氮杂和三氮杂双环化合物可用于连接粘合剂,如用于促进所使用的主要组分与含氰基丙烯酸酯粘合剂组分的粘接,参见美国专利No.4869722(McDonnell)。
虽然如此,但直到今天,认为以下所详细列出的助熔的底层填料密封剂没有被公开或受到工业上的接受。
因此,提供具有适当固化曲线的助熔的底层填料组合物,以便降低上述的担心是所需的。另外,提供一种可助熔焊剂同时在焊剂软熔操作过程中可发生固化的组合物是所需的。
发明概述
本发明提供一种助熔的底层填料组合物,其中包括一种环氧树脂组分、一种酸性助熔剂组分、一种酸酐组分和一种潜伏固化剂组分。该潜伏固化剂组分包括部分酸性助熔剂与含氮盐组分的配合物。
本发明提供在焊剂软熔操作过程中所达到的温度曲线的规定部分内能固化的一种助熔的底层填料组合物,其中酸性助熔剂被包括在组合物中,从而省去了分离熔剂的步骤。
在组合物的涂覆之前、之后或之中,半导体器件位于载体基质上,和将存在于半导体器件两侧和/或载体基质上的焊剂暴露于在焊剂软熔操作条件的过程中所达到的温度下。在焊剂软熔操作过程中所达到的温度曲线的规定部分期间固化组合物,从而建立并维持电连接,同时将半导体器件囊包在基质上。当固化发生时,酸性助熔剂除去基质表面的氧化物,目前所述氧化物将可能干扰焊剂和底层填料性能。
具有助熔性能的粘合剂可用于软熔焊剂并囊包在表面安装的组件,尤其是倒装片式集成电路,同时提供集成电路的活性表面的环境保护。
本发明的其它益处和优点在阅读“详细说明”部分以及附图之后将更容易地变得显而易见。
附图的简要说明
图1描绘了表明安装结构实施例的横截面视图,其中在本发明的底层填料组合物软熔后使用所述组合物。
图2描绘了典型的焊剂软熔操作的温度(℃)对时间(s)所作的图(“曲线B”)以及用已知的典型的助熔的底层填料材料(如在’746专利中所公开的那些)的典型的焊剂软熔操作的温度(℃)对时间(s)所作的图(“火山曲线”,“曲线A”),其中其温度剧烈升高。
图3A和3B描述了已知的助熔的底层填料材料(如在’746专利中所公开的那些)作为与本发明的助熔的底层填料材料的对比用的以能量补偿模式进行的差示扫描量热曲线,以便测量补偿样品和对照组之间的温差所要求的能量。
发明详述
如上所述,本发明提供了一种助熔的底层填料组合物,其中包括一种环氧树脂组分、一种酸性助熔剂组分、一种酸酐组分和一种潜伏固化剂组分。该潜伏固化剂组分包括部分酸性助熔剂与含氮盐组分的配合物。
典型地,该组合物包括约10-约70wt%的环氧树脂组分(以组合物的总重为基准)、约1-约15wt%的酸性助熔剂组分、约15-约50如约30-约40wt%的酸酐组分和约3-约30wt%的潜伏固化剂组分,所述潜伏固化剂组分中的约0.1-约1.0wt%由含氮盐组分和足以与其形成配合物的酸性助熔剂量组成(以可固化的树脂组分的总重为基准),这当然取决于所选择的潜伏固化剂的类型和种类。
当然,取决于用于具体目的的目标组合物所需特定的物理性能,这些值在一定程度上可以变化。本领域的技术人员在不需过多实验的情况下可实现这种变化,因此认为这些变化包括在本发明的范围内。
本发明的环氧树脂组分可包括任何通用的环氧树脂,如多官能团环氧树脂。一般地,多官能团环氧树脂应当包括约15-约75wt%范围内的用量,如约40-约60wt%,基于环氧树脂组分的总重。在双酚-F型环氧树脂的情况下,其用量理想地应当在约35-约65wt%内,如约40-约50wt%(以环氧树脂组分的总重为基准)。
多官能团环氧树脂的实例包括双酚-A型环氧树脂(如购自日本Nippon Kayaku的RE-310-S或购自Shell Chemical Co.的“EPON”828或“EPON”1002f)、双酚-F型环氧树脂(如购自日本Nippon Kayaku的RE-404-S)、线型酚醛型环氧树脂、甲酚线型酚醛环氧树脂(如购自CibaSpecialty Chemicals,Hawthorne,New York的“ARALDITE”ECN1871)。
其它合适的环氧树脂包括基于芳族胺类和表氯醇的聚环氧化合物,如N,N,N’,N’-四缩水甘油基-4,4’-二氨基二苯基甲烷;N-缩水甘油基-4-氨基苯基缩水甘油基醚和N,N,N’,N’-四缩水甘油基-1,3-亚丙基双-4-氨基苯甲酸酯。
在适于本发明应用的环氧树脂当中还包括酚类化合物的聚缩水甘油基衍生物,如以商品名称“EPON”如“EPON”1031商购于Shell ChemicalCo.的;获自Dow Chemical Co.的“DER”331、“DER”332、“DER”334和“DER”542;以及获自日本Nippon Kayaku的“BREN-S”。其它合适的环氧树脂包括由多元醇等制备的聚环氧化物和线型酚醛树脂的聚缩水甘油基衍生物,后者以商品名称“DEN”如“DEN”431、“DEN”438和“DEN”439商购于Dow Chemical。甲酚类似物也可以商品名称“ARALDITE”,如“ARALDITE”ECN 1235、“ARALDITE”ECN 1273和“ARALDITE”ECN 1299商购于Ciba Specialty Chemicals。认为SU-8是一种获自Interez,Inc.的甲酚线型酚醛环氧树脂。胺、氨基醇的聚缩水甘油基加成物和聚羧酸也可用于本发明,其中商购的树脂包括获自F.I.C.Corporation的“GLYAMINE”135、“GLYAMINE”125和“GLYAMINE”115;获自CibaSpecialty Chemicals的“ARALDITE”MY-720、“ARALDITE”0500和“ARALDITE”0510以及获自Sherwin-Williams Co.的PGA-X和PGA-C。也可使用表氯醇与双酚A的共聚物,如获自Shell Chemical Co.的“EPON”1001和“EPON”1009。
当然不同环氧树脂的组合也可所需地用于本发明。
适用于本发明的合适的酸性助熔剂包括枞酸、己二酸、抗坏血酸、丙烯酸、柠檬酸、2-呋喃酸(furanoic acid)、马来酸、水杨酸、戊二酸、庚二酸、聚丙烯酸和有机酸如苯酚及其衍生物和磺酸如甲苯磺酸。
尤其理想的是DIACID 1550,它是一种商购于Westvaco OleoChemicals的衍生于妥尔油脂肪酸的液体单环的二十一个碳的二羧酸;具体地说,它是5-正己基-2-(羧基正庚基)环己基-3-烯羧酸。
在本发明的组合物中应当包括用量在约1-约15wt%的酸性助熔剂。
适用于本发明的合适的酸酐化合物包括单-和多-酸酐,如六氢苯甲酸酐(HHPA)和甲基六氢苯甲酸酐(MHHPA)(商购于LindauChemicals,Inc.,Columbia,South Carolina,可单独或结合使用它们,其中以商品牌号“LINDRIDE”62C获得所述结合)、5-(2,5-二氧代四氢)-3-甲基-3-环己烯-1,2-二甲酸二酐(以商品牌号B-4400商购于ChriskevCo.,Leewood,Kansas)、甲基桥亚甲基四氢邻苯二甲酸酐、3,3’,4,4’-二苯酮四甲酸二酐(BTDA)、苯均四酸二酐(PMDA)、3,3’,4,4’-二苯基四甲酸二酐(s-BPDA)、2,2’-双-(3,4-羧苯基)六氟丙烷二酐(6FDA)、4,4’-氧联苯二甲酸酐(ODPA)、3,3’,4,4’-二苯基砜四甲酸二酐(DSDA)、乙二醇双(脱水-三苯六甲酸酯)(TMEG-200,TMEG-100)及其结合。
当然,这些酸酐化合物的结合也可所需地用于本发明的组合物。
所需地,酸酐组分应当以介于约15-约50wt%,如约30-约40wt%,所需地约35wt%的用量存在。
潜伏固化剂组分包括一旦引发因素产生(如达到一定的温度)时能催化本发明组合物中的环氧树脂组分聚合的材料。所需地,潜伏固化剂包括含氮化合物的盐和部分酸性助熔剂的配合物。
其中含氮化合物部分的盐通常是胺化合物,其中包括多胺以及二氮杂和三氮杂化合物、酰胺化合物、咪唑化合物及其结合。
其中含氮化合物部分的盐包括二氮杂化合物和三氮杂化合物。
二氮杂或三氮杂化合物的实例包括;
1,4-二氮杂双环[2.2.2]辛烷。
胺化合物的实例包括下述烷基多胺:二亚乙基三胺、三亚乙基四胺、二乙基氨基丙胺、异氟尔酮二胺和亚烷二胺;以及芳族多胺:间-二甲苯二胺、二氨基二苯胺和喹喔啉。
酰胺化合物的实例包括氰基官能化的酰胺如双氰胺。
咪唑化合物可选自咪唑、异咪唑和被取代的咪唑如烷基取代的咪唑(例如2-甲基咪唑、2-乙基-4-甲基咪唑、2,4-二甲基咪唑、丁基咪唑、2-十一碳烯基咪唑、1-乙烯基-2-甲基咪唑、2-正十七基咪唑、2-十一基咪唑、2-十七基咪唑、1-丙基-2-甲基咪唑、1-氰乙基-2-甲基咪唑、1-氰乙基-2-乙基-4-甲基咪唑、1-氰乙基-2-十一基咪唑、1-氰乙基-2-苯基咪唑、1-胍氨基乙基-2-甲基咪唑以及咪唑和三苯六甲酸的加成产物、2-正十七基-4-甲基咪唑等,一般地每个烷基取代基含有高达约17个碳原子和所需地含有高达约6个碳原子),和芳基取代的咪唑[如苯基咪唑、苄基咪唑、2-甲基-4,5-二苯基咪唑、2,3,5-三苯基咪唑、2-苯乙烯基咪唑、1-(十二烷基苄基)-2-甲基咪唑、2-(2-羟基-4-叔丁基苯基)-4,5-二苯基咪唑、2-(2-甲氧基苯基)-4,5-二苯基咪唑、2-(3-羟基苯基)-4,5-二苯基咪唑、2-(对二甲基氨基苯基)-4,5-二苯基咪唑、2-(2-羟基苯基)-4,5-二苯基咪唑、二(4,5-二苯基-2-咪唑)-苯-1,4,2-萘基-4,5-二苯基咪唑、1-苄基-2-甲基咪唑、2-对甲氧基苯乙烯基咪唑等,一般地每个芳基取代基含有高达约10个碳原子和所需地含有高达约8个碳原子]。
商业咪唑化合物的实例是获自Air Products,Allentown,Pennsylvania的商品牌号“CUREZOL”1B2MZ、获自Synthron,Inc.,Morganton,North Carolina的商品牌号“ACTIRON”NXJ-60和获自Borregaard Synthesis,Newburyport,Massachusetts的商品牌号“CURIMID”CN。
当然,这些胺化合物的结合也可所需地用于本发明的组合物。
将含氮化合物(取决于化合物的相对碱度)典型地加入到以弱或强酸形成的盐形式存在的组合物中,从而提供广泛的离子对强度。例如,弱酸如苯酚可与含氮化合物形成盐。其实例为POLYCAT SA-1,它是DBU的苯酚盐且商购于Air Products,Allentown,Pennsylvania。或者强酸如对甲苯磺酸可与含氮化合物形成盐。其实例为POLYCAT SA-102,它是DBU的乙基己酸盐且也商购于Air Products。
与含氮化合物形成盐所使用的酸的pKa值一般应当介于约2.8到约10,其中约4尤其理想,这当然取决于所选择的含氮化合物。这些酸的实例包括乙酸、卤化乙酸和芳族磺酸。
含氮化合物的pKb值一般应当介于约0.5到约9.5,其中约5是理想的,这当然取决于所选择的酸化合物。这些含氮化合物的实例如上所述。当然,应当合适地选择含氮化合物和酸,以便酸和含氮化合物的pKa值和pKb值分别恰当地匹配,形成具有离解可能性的盐,适于在预定的温度如熔剂熔融的温度下从盐和配合物中释放含氮化合物。
在使用中,含氮化合物与酸性助熔剂的盐一起接触形成配合物,从而产生潜伏固化剂组分。如此形成的配合物应当具有解离可能性,适于在环氧基基体中发生解离,其中至少部分在熔剂软熔过程期间所达到的温度范围内发生所述解离。
潜伏固化剂组分可以约0.3到约30wt%的用量存在,基于环氧树脂组分的重量,这当然取决于所选择的潜伏固化剂的类型和种类。
理想地,在本发明组合物中所使用的含氮化合物用量应当在约0.1到约1的范围内,如约0.5,从而形成潜伏固化剂,其具有与配合物中的含氮化合物部分基本相同的量。
添加剂可包括在本发明的组合物中,如反应性共聚单体组分(如反应性稀释剂)、消泡剂(象商购于BYK-Chemie,Wallingford,Connecticut的商品名称为BYK的那些,如BYK-515或BYK-555)、流平剂、染料、颜料和粘合促进剂等。
适用于本发明的合适的反应性稀释剂包括单官能团或一些多官能团的环氧树脂。反应性稀释剂应当具有比环氧树脂组分低的粘度。一般地,反应性稀释剂应当具有小于约250cPs的粘度。最终这种单官能团环氧树脂作为反应性稀释剂而被包括,这种树脂应当使用高达50wt%的用量,基于环氧树脂组分的重量。
单官能团环氧树脂应当具有带约6到约28个碳原子烷基的环氧基,其实例包括C6-26烷基缩水甘油酯、C6-28脂肪酸缩水甘油酯和C6-28烷基苯酚缩水甘油醚。
可商购的单官能团环氧树脂反应性稀释剂包括以商品牌号PEP-6770(新癸酸的缩水甘油酯)、PEP-6740(苯基缩水甘油醚)和PEP-6741(丁基缩水甘油醚)获自Pacific Epoxy Polymers,Richmond,Michigan的那些。
可商购的多官能团环氧树脂反应性稀释剂包括以商品牌号PEP-6752(三羟甲基丙烷三缩水甘油醚)和PEP-6760(二缩水甘油基苯胺)获自Pacific Epoxy Polymers,Richmond,Michigan的那些。
正是消泡剂看起来提供润湿焊剂的有益效果。认为消泡剂降低焊剂的表面张力,这在焊剂的助熔中是重要的。
当消泡剂被使用时,消泡剂可以使用高达约1wt%的用量,基于组合物的总重。
另外可使用粘合促进剂如硅烷、环氧丙氧基丙基三甲氧基硅烷(以商品牌号A-187商购于OSI)、γ-氨基丙基三乙氧基硅烷(以商品牌号A-1100商购于OSI)或三甲氧基甲硅烷基丙基化异氰脲酸酯(以商品名称SILQUEST,如Y-11597商购于OSI)。
当粘合促进剂被使用时,粘合促进剂可至多以约2wt%的用量使用。
本发明的热固性树脂组合物可以是所有成分在一起混合的单组分型,或者可固化组分包括在一部分中而固化剂组分独立地储存在第二部分中且仅在使用前一起混合的双组分型。
在微电子的应用过程中,本发明的助熔的底层填料组合物一般地在存在或不存在光滑步骤的情况下,分散在电路板上,且半导体芯片或半导体器件放置在其上。更具体地说,一般地将本发明的组合物涂敷到具有金属板的电路板上。焊剂排列在涂布的金属板组件上。半导体芯片或半导体器件放置在电路板和软熔的焊剂上并与之相匹配。在软熔步骤过程中,助熔剂促进焊剂与电路板上的金属板的粘接,且固化粘合剂材料,从而机械连接并熔封电路板和半导体芯片或半导体器件之间的孔穴。
设计本发明的组合物在一定时间/温度范围的组合下,在熔剂软熔过程期间所达到的温度曲线的规定部分内固化,这可在熔剂软熔过程期间观察到(参见图2的曲线B)。例如,所设计的本发明组合物的熔剂软熔曲线由数个区段组成,其中经固定的时间段达到或维持某一温度或在固定的时间段内使温度升高。这些区段优选以预热段、保温段和软熔段形式存在。
在预热段中,电路板和半导体组件逐渐加热到保温段的温度。在预热段中的加热梯度可通过在达60秒的时间段内从约30℃到约150℃的温度范围内升高。
在保温段中,使半导体组件达成热平衡,以便可发生半导体组件的热膨胀和可进行温度调节。在保温段中的加热梯度可通过从开始的约60秒到约175秒的时间段内从约150℃到略大于180℃,如约183℃的温度范围内升高。在预热和保温段中,底层填料密封剂所需地保持未凝胶化。
在软熔段,焊剂流动并形成电连接。底层填料密封剂在焊剂流动并形成电连接之后应当胶凝,否则所存在的组分发生移动,从而导致电连接失败。在软熔段中的加热梯度可通过从开始的约175秒到约205-265秒的时间段内从略大于180℃,如约183℃到约220℃±10℃的温度范围内升高。
参见:R.P.Prasad,
Surface Mount Technology:Principles and Practice,第3部分-Manufacturing with Surface Mounting,International Thomson Publishing,New York,578(1997)。在焊剂流动形成电连接之后所需地完全固化底层填料密封剂。
正如所述的,这一序列的定时是重要的,这是因为若底层填料密封剂在焊剂流动之前就开始胶凝,则胶凝的底层填料密封剂将阻碍焊剂的流动和形成电连接的能力。若这一现象发生,则微电子系统可能失败。
作为本发明组合物设计目标而使用的上述分区或分段焊剂软熔曲线广泛用于微电子工业。这一曲线之所以被广泛使用,是因为它避免热震动半导体组件和电路板,若使用火山曲线则所述热震动将可能发生(参见图2的曲线A)。
与以前开发的助熔的底层填料密封剂(如美国专利No.5128746中所公开的那些,所述发明均在焊剂软熔曲线的预热段开始固化(参见图2的曲线B))不同,本发明的组合物在从预热段经保温段的未固化阶段保持其物理性能,且仅在熔剂软熔区段内在所达到的温度下固化。
沿这一曲线固化的益处包括使得发生形成电连接,接着通过固化底层填料密封剂,使用典型的焊剂软熔曲线的能力,而不必调节软熔曲线使之适用于底层填料密封剂的固化曲线的特异性,以及在较低的温度下保温电子组件的能力,而不必一开始就暴露于会损坏其完整性的高温下。
可在固化曲线内通过选择各种组分的类型和比例以实现在25℃的温度下达到介于500-70000cps,如800-3000cps的粘度,以调节本发明的组合物。在此粘度下,也可在约150℃的温度下调节组合物的胶凝时间在固定的时间段(如15秒或1或2分钟)。在此情况下,在约10分钟的时间段后,本发明的组合物应当不显示或基本上不显示粘度的增加。在这一凝胶时间下,该组合物相对快速地渗透到电路板和半导体器件之间的空间(如10-200微米的空间)内,并使得大量组件被填充,而没有观察到组合物中粘度的增加,从而使应用的效果降低。
参考图1显示出半导体器件4和半导体芯片2,其中半导体器件4具有带金属板5和6的电路板1,已使用常规的分配技术用本发明范围内的助熔的底层填料粘合剂组合物3涂布所述半导体器件4。
助熔的底层填料粘合剂组合物可涂敷到载体基质上或涂敷到半导体芯片上。实施其的一种方式是利用国际专利申请No.PCT/FR95/00898中要求并公开的模版。
带有焊剂块7和8的半导体芯片2位于电路板1的上方,以便半导体芯片2中的焊剂块7和8面对电路板1并与金属板5和6大体上排成一行。然后使半导体芯片2与电路板1接触,以便焊剂块7和8以及金属板5和6相连接形成组件。
将如此形成的组件引入到分区的焊剂软熔烘箱中,一旦焊剂到达软熔区则引起预热和保温段之后焊剂流动,从而在半导体芯片2和电路板1之间形成电连接。这使得半导体芯片2中的焊剂块7和8在电路板1上精细地排成一行。
一旦焊剂流动,在没有要求后固化以实现完全固化的情况下底层填料组合物固化。因此,在焊剂软熔区段,半导体器件通过焊剂电连接并通过填充孔穴固定。
一般地可用聚酰亚胺、聚苯并环丁烷或硅氮基材料涂布半导体芯片以钝化环境腐蚀。
电路板1可由陶瓷基质Al2O3、SiN3和莫来石(Al2O3-SiO2);耐热树脂基质或带状物如聚酰亚胺;玻璃增强的环氧;也可用作电路板的ABS和苯酚基质等构成。可使用任何半导体芯片与载体基质的电连接,如通过高熔点焊剂或导电性(或各向异性导电)粘合剂等。为了加速连接,尤其在SBB技术中,可以以电线粘合块的形式形成电极。
证明本发明的热固性树脂组合物的固化反应产物具有优良的粘合力、耐热性和电性能以及可接受的机械性能如抗弯曲龟裂性、抗化学性和耐湿性等,这些性能可用于本发明的应用。
在如上所述地将半导体器件安装到电路板上之后,通过使用本发明的热固性树脂的安装工艺中,相对于半导体器件的特征、半导体器件和电路板之间的连接、其它电性能和密封状态测试所得结构。
参考下述实施例可更容易地理解本发明。
实施例
在这些实施例中,制备本发明的组合物并评价其性能。
实施例1
在这些实施例中,我们由下述组分制备了环氧基粘合剂组合物,其相对用量见表1。
表1
组分 | 样品No./用量(wt%) | ||||||
类型 | 种类 | 1 | 2 | 3 | 4 | 5 | 6 |
环氧 | RE-310-S | 41.5 | 39.7 | 37.8 | 40 | 37.8 | 40 |
EPON1002f | 9.9 | 11.3 | 10.7 | 10 | 10.7 | 10 | |
酸性助熔剂 | DIACID 1550 | 3.5 | 10.3 | 11.9 | 4 | 11.3 | 4 |
水杨酸 | - | - | - | 3 | - | 3 | |
庚二酸 | - | - | - | - | 3.3 | - | |
己二酸 | 3.0 | - | - | - | - | - | |
戊二酸 | - | - | 2.7 | - | - | - | |
酸酐 | LINDRIDE 62C | 34.9 | 37.6 | 35.6 | - | - | - |
B4400 | 6.3 | - | - | - | - | - | |
MHHPA | - | - | - | 41.5 | 35.6 | 42.5 | |
含氮化合物 | DBU | 0.3 | 0.3 | 0.3 | - | 0.3 | - |
POLYCAT SA-1 | - | - | - | 0.5 | - | - | |
2-乙基-4-甲基咪唑 | - | - | - | - | - | 0.5 | |
粘合促进剂 | A-187 | 0.5 | 0.7 | 0.9 | 1.0 | 0.9 | 1.0 |
消泡剂 | BYK-555 | 0.1 | 0.1 | 0.1 | - | 0.1 | - |
BYK-515 | - | - | - | 0.1 | - | 0.1 |
在No.1-3样品中,含氮化合物与酸性助熔剂接触,在其它任何组分加入到混合物之前形成配合物。
通过将EPON 1002f、RE-310-S和选择的酸性助熔剂引入到反应器中制备这些样品。然后在氮气氛围下,在搅拌下加热混合物到约150℃的温度直到获得溶液。然后冷却混合物到约50℃的温度形成A部分环氧预混合物。在一个独立的容器中,在氮气氛围和在约100℃的温度下混合含氮化合物和DIACID 1550,然后冷却到室温形成B部分促进剂预混合物。
然后,向反应器中引入酸酐和A部分环氧预混合物,然后在真空下在约25℃的温度下快速混合该混合物约90分钟,90分钟后,加入粘合促进剂和B部分促进剂预混合物。然后在冷却下真空搅拌该混合物约30分钟,30分钟后释放真空并用氮气清洗混合器。
样品No.1-5在本发明的范围内,然而样品No.6不在本发明的范围内,因为它不包括含氮化合物的盐。相反,样品No.6包括咪唑,但没有酸式盐。
使用样品No.1-3连接并在底部填充10个4×4PB8模头以测试电路板,并使用可与图2的曲线B对比的曲线软熔样品No.1-3。所有这些模头表明具有导电性。使用样品No.4-6连接并在底部填充4个FB250模头以测试电路板,并使用可与图2的曲线B对比的曲线软熔样品No.4-6。所有这4个模头表明样品No.4和5具有导电性,而样品No.6的任何4个模头都没有导电性。
实施例2
重复美国专利No.5128746中的实施例4,证明本发明的益处和优点。
下表2列出了那一个实施例的配方(样品No.7)以及本发明的配方(样品No.8)。
表2
组分 | 样品No./用量(wt%) | ||
类型 | 种类 | 7 | 8 |
环氧 | RE-310-S | 50 | 50 |
酸性助熔剂 | 水杨酸 | 7 | 7 |
酸酐 | MHHPA | 42.5 | 42.5 |
潜伏固化剂 | 2-乙基-4-甲基咪唑 | 0.5 | - |
POLYCAT SA-1 | - | 0.5 |
尽管’746专利的实施例4中的各配方使用EPON828作为环氧树脂和马来酸作为酸性助熔剂,但是作为对比使用RE-310-S作为环氧树脂(这也是双酚A环氧树脂)和水杨酸作为酸性助熔剂。
配方的不同在于潜伏固化剂-对比配方即实施例No.7使用0.5wt%的咪唑,而本发明的配方即实施例No.8使用POLYCAT SA-1(一种DBU-苯酚盐),其用量也为0.5wt%。尽管潜伏固化剂用量是’746专利中所使用的用量的一半,但在所有其它用量相等的情况下,较低用量的潜伏固化剂将延迟固化,这将增强配方的助熔能力。因此,若看出性能上的任何区别,则可预期该区别是一种改进。相反,当使用样品No.7和8连接并在底部填充PB250模头以测试电路板,并使用可与图2的曲线B对比的曲线软熔样品No.7和8时,使用样品No.7连接并底部填充的模头不能显示导电性,而使用样品No.8连接并底部填充的模头显示导电性。
实施例3
在该实施例中,我们比较当使用典型的焊剂软熔曲线(如图2的曲线B所示)固化时,已知的助熔的底层填料材料(如’746专利中所公开的那些)与本发明的助熔的底层填料材料的固化行为。更具体地说,在这些材料(即下表3中所列出的配方)上以能量补偿模式进行差示扫描量热分析,以便测量补偿各材料与对照组之间的温差所要求的能量。这些样品包括无机填料组分以增稠配方。
表3
组分 | 样品No./用量(wt%) | ||
类型 | 种类 | 9 | 10 |
环氧 | RE-310-S | 40 | 40 |
酸性助熔剂 | 水杨酸 | 5.6 | 5.6 |
酸酐 | MHHPA | 34 | 34 |
潜伏固化剂 | 2-乙基-4-甲基咪唑 | 0.4 | - |
POLYCAT SA-1 | - | 0.4 | |
无机填料 | SO-E5 | 19.2 | 19.2 |
AEROSIL R812S | 0.8 | 0.8 |
将样品No.9和10排列在铝制DSC盘内,并根据类似图2的曲线B所描述的焊剂软熔曲线进行加热。参考图3A表明样品No.9在预热段中在约140℃的温度下开始固化。图3A表明样品No.9在保温段已经固化。
相反,参考图3B表明样品No.10仍保持未固化状态(曲线基本上是平的)直到达到软熔区段,在此区段在约160℃下观察到固化的开始点,在约220℃的焊剂软熔温度下固化完全。
上述说明是例举而不是限制本发明的组合物。许多其它实施方案包括在本发明的精神和范围内,而本发明的精神和范围通过权利要求来定义。
Claims (21)
1.一种助熔的底层填料组合物,其中包括:
(a)一种环氧树脂组分;
(b)一种酸性助熔剂组分;
(c)一种酸酐组分;和
(d)一种潜伏固化剂组分;
该潜伏固化剂组分包括部分酸性助熔剂与含氮盐组分的配合物。
2.权利要求1的组合物,其中酸酐化合物可选自六氢苯甲酸酐、甲基六氢苯甲酸酐、5-(2,5-二氧代四氢)-3-甲基-3-环己烯-1,2-二甲酸二酐及其结合。
3.权利要求1的组合物,其中含氮化合物组分选自胺化合物、酰胺化合物、咪唑化合物及其结合。
4.权利要求1的组合物,其中胺化合物选自1,5-二氮杂双环[3.4.0]壬-5-烯、1,8-二氮杂双环[5.4.0]十一碳-7-烯、1,5,7-三氮杂双环[4.4.0]癸-5-烯、奎宁环、1,4-二氮杂双环[2.2.2]辛烷、二亚乙基三胺、三亚乙基四胺、二乙基氨基丙胺、间-二甲苯二胺、二氨基二苯胺、异氟尔酮二胺、亚烷二胺喹喔啉及其结合。
5.权利要求1的组合物,其中酰胺化合物是双氰胺。
6.权利要求1的组合物,其中咪唑化合物选自咪唑、异咪唑、2-甲基咪唑、2-乙基-4-甲基咪唑、2,4-二甲基咪唑、丁基咪唑、2-十七碳烯基-4-甲基咪唑、2-甲基咪唑、2-十一碳烯基咪唑、1-乙烯基-2-甲基咪唑、2-正十七基咪唑、2-十一基咪唑、2-十七基咪唑、2-乙基-4-甲基咪唑、1-丙基-2-甲基咪唑、1-氰乙基-2-甲基咪唑、1-氰乙基-2-乙基-4-甲基咪唑、1-氰乙基-2-十一基咪唑、1-氰乙基-2-苯基咪唑、1-胍氨基乙基-2-甲基咪唑、咪唑和三苯六甲酸的加成产物、2-正十七基-4-甲基咪唑、苯基咪唑、苄基咪唑、2-甲基-4,5-二苯基咪唑、2,3,5-三苯基咪唑、2-苯乙烯基咪唑、1-(十二烷基苄基)-2-甲基咪唑、2-(2-羟基-4-叔丁基苯基)-4,5-二苯基咪唑、2-(2-甲氧基苯基)-4,5-二苯基咪唑、2-(3-羟基苯基)-4,5-二苯基咪唑、2-(对二甲基氨基苯基)-4,5-二苯基咪唑、2-(2-羟基苯基)-4,5-二苯基咪唑、二(4,5-二苯基-2-咪唑)-苯-1,4,2-萘基-4,5-二苯基咪唑、1-苄基-2-甲基咪唑、2-对甲氧基苯乙烯基咪唑及其结合。
7.权利要求1的组合物,其中含氮化合物以与酸形成的盐形式存在。
8.权利要求7的组合物,其中酸是强酸。
9.权利要求7的组合物,其中酸是弱酸。
10.权利要求3的组合物,其中酸的pKa值介于约2.8到约10范围内。
11.权利要求7的组合物,其中含氮化合物的pKb值介于约0.5到约9.5范围内。
12.权利要求7的组合物,其中酸选自乙酸、卤化乙酸、酚、芳族磺酸及其结合。
13.权利要求1的组合物,进一步包括粘合促进剂。
14.权利要求13的组合物,其中粘合促进剂选自环氧丙氧基丙基三甲氧基硅烷、γ-氨基丙基三乙氧基硅烷及其结合。
15.权利要求1的组合物,其中其固化的反应产物能密封半导体器件之间的空间,同时提供半导体芯片和电路板之间或半导体器件和电路板之间的电传导,其中所述半导体器件包括半导体芯片和安装在载体基质上的与所述半导体器件电连接的电路板或者包括半导体器件和与所述半导体芯片电连接的电路板。
16.权利要求11的组合物,能在焊剂软熔操作过程中固化并使得半导体器件和电路板之间或半导体芯片和电路板之间导电。
17.权利要求1的组合物,(a)在暴露于下述时间/温度曲线之后:在约30℃到约150℃下暴露达约60秒,在约150℃到略大于180℃下暴露达约60秒到约约175秒,和(b)在暴露于略大于180℃到约220℃±10℃下约175秒到约205-265秒的时间/温度曲线过程中能固化。
18.由权利要求1的组合物形成的反应产品。
19.一种使用权利要求1的助熔的底层填料组合物助熔电连接并分别熔封半导体器件和电路板或半导体芯片和电路板之间的空间而组装的电子器件,其中包括半导体器件和与所述半导体器件电连接的电路板或者包括半导体芯片和与所述半导体芯片电连接的电路板。
20.权利要求19的电子器件,其中当固化成反应产品时,器件显示导电性。
21.一种通过助熔电连接并熔封半导体器件和与所述半导体器件电连接的电路板或半导体芯片和与所述半导体芯片电连接的电路板之间的孔穴来组装电子器件的方法,其中所述半导体器件包括在载体基质上安装的半导体芯片,该方法包括下述步骤:
(a)将权利要求1的组合物分配到在半导体器件和电路板或半导体芯片和电路板之间的孔穴;和
(b)将如此分配的组合物暴露于适合引起组合物固化成反应产品的条件下,其中当固化成反应产品时,电子器件显示导电性。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US09/755,146 | 2001-01-08 | ||
US09/755,146 US6458472B1 (en) | 2001-01-08 | 2001-01-08 | Fluxing underfill compositions |
Publications (2)
Publication Number | Publication Date |
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CN1427753A true CN1427753A (zh) | 2003-07-02 |
CN1222392C CN1222392C (zh) | 2005-10-12 |
Family
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CNB018071392A Expired - Fee Related CN1222392C (zh) | 2001-01-08 | 2001-12-13 | 助熔的底层填料组合物 |
Country Status (8)
Country | Link |
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US (2) | US6458472B1 (zh) |
EP (1) | EP1339524A1 (zh) |
JP (1) | JP4204865B2 (zh) |
KR (1) | KR100823750B1 (zh) |
CN (1) | CN1222392C (zh) |
CA (1) | CA2401739A1 (zh) |
MX (1) | MX247834B (zh) |
WO (1) | WO2002070191A1 (zh) |
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-
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- 2001-01-08 US US09/755,146 patent/US6458472B1/en not_active Expired - Fee Related
- 2001-12-13 CA CA002401739A patent/CA2401739A1/en not_active Abandoned
- 2001-12-13 CN CNB018071392A patent/CN1222392C/zh not_active Expired - Fee Related
- 2001-12-13 JP JP2002569343A patent/JP4204865B2/ja not_active Expired - Fee Related
- 2001-12-13 MX MXPA03002672 patent/MX247834B/es active IP Right Grant
- 2001-12-13 WO PCT/US2001/047898 patent/WO2002070191A1/en not_active Application Discontinuation
- 2001-12-13 KR KR1020027011746A patent/KR100823750B1/ko not_active IP Right Cessation
- 2001-12-13 EP EP01273400A patent/EP1339524A1/en not_active Withdrawn
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CN102205470A (zh) * | 2010-03-29 | 2011-10-05 | 韩国电子通信研究院 | 填充组合物、包括其的半导体装置及该半导体装置的制法 |
CN102205470B (zh) * | 2010-03-29 | 2014-06-11 | 韩国电子通信研究院 | 填充组合物、包括其的半导体装置及该半导体装置的制法 |
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CN102585166B (zh) * | 2011-01-04 | 2016-06-01 | 山荣化学株式会社 | 活性树脂组合物、表面安装方法以及印刷线路板 |
CN107251163A (zh) * | 2015-08-19 | 2017-10-13 | 积水化学工业株式会社 | 导电材料及连接结构体 |
CN109530957A (zh) * | 2017-09-21 | 2019-03-29 | 丰田自动车株式会社 | 接合材料 |
CN111655421A (zh) * | 2018-01-16 | 2020-09-11 | 千住金属工业株式会社 | 助焊剂和焊膏 |
CN111655421B (zh) * | 2018-01-16 | 2022-07-26 | 千住金属工业株式会社 | 助焊剂和焊膏 |
US11833620B2 (en) | 2018-01-16 | 2023-12-05 | Senju Metal Industry Co., Ltd. | Flux and solder paste |
Also Published As
Publication number | Publication date |
---|---|
MXPA03002672A (es) | 2003-06-24 |
US6458472B1 (en) | 2002-10-01 |
KR100823750B1 (ko) | 2008-04-21 |
MX247834B (es) | 2007-08-06 |
CA2401739A1 (en) | 2002-09-12 |
KR20030028454A (ko) | 2003-04-08 |
CN1222392C (zh) | 2005-10-12 |
US20030124378A1 (en) | 2003-07-03 |
WO2002070191A8 (en) | 2002-12-27 |
JP2004530740A (ja) | 2004-10-07 |
US20020128353A1 (en) | 2002-09-12 |
JP4204865B2 (ja) | 2009-01-07 |
US6706417B2 (en) | 2004-03-16 |
WO2002070191A1 (en) | 2002-09-12 |
EP1339524A1 (en) | 2003-09-03 |
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