CN102108276A - 用于半导体器件的粘合剂组合物和使用此组合物的粘性膜 - Google Patents
用于半导体器件的粘合剂组合物和使用此组合物的粘性膜 Download PDFInfo
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- CN102108276A CN102108276A CN2010106233100A CN201010623310A CN102108276A CN 102108276 A CN102108276 A CN 102108276A CN 2010106233100 A CN2010106233100 A CN 2010106233100A CN 201010623310 A CN201010623310 A CN 201010623310A CN 102108276 A CN102108276 A CN 102108276A
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- coupling agent
- silane coupling
- binder composition
- transition metal
- semiconducter device
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- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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Abstract
一种用于半导体器件的粘合剂组合物,包括弹性体树脂、环氧树脂、可固化酚醛树脂、固化促进剂、硅烷偶联剂和填料。所述硅烷偶联剂包括含环氧基的硅烷偶联剂和含过渡金属清除官能团的硅烷偶联剂。所述粘合剂组合物防止因过渡金属和过渡金属离子迁移引起的半导体芯片可靠性降低,因此在半导体封装期间或之后能最大程度提高半导体器件的运行效率。此外,所述粘合剂组合物为粘性膜提供软化的结构和高抗张强度,因此防止膜被不希望地切割,同时确保粘性膜的高可靠性和硬度。
Description
技术领域
本发明涉及用于半导体器件的粘合剂组合物和使用所述粘合剂组合物的粘性膜。更具体地,本发明涉及一种用于半导体器件的粘合剂组合物,其包括含环氧基的硅烷偶联剂和含过渡金属清除官能团的硅烷偶联剂,以防止因过渡金属和过渡金属离子移动所引起的半导体芯片可靠性降低。此外,本发明涉及使用所述粘合剂组合物的粘性膜。
背景技术
通常,使用银浆料来将半导体器件粘结在一起,或将半导体器件与支撑元件粘结。
为了符合小型化和大容量化的半导体器件发展趋势,用于半导体器件的支撑元件也正在变得更小和更精细。当使用银浆料来将半导体器件粘结在一起,或将半导体器件与支撑元件粘结时,银浆料从半导体器件间的粘结表面中漏出或引起半导体器件的倾斜。结果,Ag浆料引起故障、起泡和在接线时难以控制厚度。最近,将粘性膜广泛用作银浆料的替代品。
用于半导体封装的粘性膜通常与切割膜联合使用。在切割工艺中,切割膜用于固定半导体晶片。切割工艺是将半导体晶片锯切为单个芯片的工艺,且随后进行如扩展、拾取和安装等后续工艺。切割膜可通过以下步骤形成:将UV可固化粘合剂或以一些其它方式固化的粘合剂涂布到基膜如具有氯乙烯或聚烯烃类结构的膜上,并在其上层叠PET类覆盖膜。
用于半导体器件的常规粘性膜贴装到半导体晶片上,且具有上述结构的切割膜堆叠在覆盖膜已从中去除的切割膜上,随后根据锯切工艺锯切。
然而,最近通过简单工艺制备了用于切割芯片模的粘结的半导体粘合剂。在此工艺中,将PET覆盖膜已从中去除的切割膜和粘性膜合并为单个膜,并将半导体晶片贴装到此单个膜上,随后根据切割工艺锯切。然而,与用于切割工艺的常规切割膜不同,此方法需要在拾取工艺中将芯片模和芯片模粘性膜同时分离。此外,当将芯片模贴装膜贴装到半导体晶片的后侧时,在芯片模贴装膜的粗糙面和晶片上电路图案之间会产生间隙或空隙。当暴露于高温环境时,晶片上芯片和芯片模贴装膜间界面中存在的间隙或空隙会膨胀,导致裂纹并引起器件在可靠性测试中失败。因此,对全部半导体封装工艺均需要抑制界面处空隙的形成。
增加粘性膜中可固化组分的含量是抑制空隙形成的一种方法。然而,此方法会导致膜的抗张强度降低,因此在将膜切割为半导体晶片大小的工艺中或在晶片锯切工艺的磨边或修整工艺中引起膜的破裂。此外,对于粘合剂来说,膜的低储能模量提供了高粘合强度,使得膜很可能变形,因此降低拾取成功率。特别地,对于使用大小相同的两个半导体芯片的半导体器件,具有单独粘性膜的半导体芯片被安装在因存在导线而具有不规则性的下层半导体芯片上。此时,对于粘性膜,重要地是要确保其上的半导体芯片绝缘,同时通过覆盖因存在导线引起的不规则性来抑制间隙或空隙形成。
能够满足这些要求的粘性膜通常包括主要由环氧树脂组成的粘合剂组合物。然而,在半导体芯片堆叠工艺期间,环氧树脂相对高的吸收率会导致各种离子杂质渗入粘性膜和半导体芯片间的粘结界面中。
在离子杂质中,过渡金属离子具有高热导率和电导率,因此引起半导体芯片损坏或引起电路故障。因此,需要加入过渡金属清除剂。然而,尚未开发出用于除去过渡金属而不损坏粘性膜性质的改进方法。
发明内容
本发明一个方面提供了用于半导体器件的粘合剂组合物。所述粘合剂组合物包括弹性体树脂、环氧树脂、可固化酚醛树脂、固化促进剂、硅烷偶联剂和填料。所述硅烷偶联剂包括含环氧基的硅烷偶联剂和含过渡金属清除官能团的硅烷偶联剂。
所述过渡金属清除官能团可包括选自由-CN、-COOH、-NCO、-SH和-NH2组成的组中的至少一种。
基于所述硅烷偶联剂的总重量,所述含环氧基的硅烷偶联剂的含量可为15wt%至小于100wt%。
所述硅烷偶联剂可包括30~60wt%的所述含环氧基的硅烷偶联剂和40~70wt%的所述含过渡金属清除官能团的硅烷偶联剂。
所述粘合剂组合物可包括比所述含环氧基的硅烷偶联剂的含量更高的过渡金属清除组分,所述过渡金属清除组分包括含过渡金属清除官能团的硅烷偶联剂。
所述粘合剂组合物可包括2~50wt%的所述弹性体树脂、4~50wt%的所述环氧树脂、3~50wt%的所述可固化酚醛树脂、0.01~10wt%的所述固化促进剂、0.1~10wt%的所述硅烷偶联剂和0.1~50wt%的所述填料。
所述粘合剂组合物可进一步包括过渡金属清除剂。
所述过渡金属清除剂可包括有机化合物,如具有腈基的氰化物和三唑衍生物;和无机离子交换剂,如水滑石类离子清除剂、氧化铋类离子清除剂、氧化锑类离子清除剂、氧化钛类类离子清除剂和磷化锆类离子清除剂。这些化合物可单独使用,或两种或更多种组合使用。
基于所述硅烷偶联剂和所述过渡金属清除剂的总重量,所述过渡金属清除剂和所述含过渡金属清除官能团的硅烷偶联剂的含量可为50wt%至小于100wt%。
所述粘合剂组合物可进一步包括有机溶剂。
所述弹性体树脂可包括含羟基、羧基和环氧基的丙烯酸类聚合物。
所述环氧树脂可包括50wt%或更多的多官能环氧树脂。
所述可固化酚醛树脂可包括50wt%或更多的线型酚醛树脂。
所述固化促进剂可包括膦类、硼类和咪唑类固化促进剂。这些化合物可单独使用,或两种或更多种组合使用。
所述填料可具有球形。所述填料可具有500nm至5μm的平均粒径。
所述粘合剂组合物可具有10kgf/m2或更高的粘合强度,且在30天后显示出小于1%的粘合强度变化。
本发明另一个方面提供了一种使用上述任一粘合剂组合物的用于半导体器件的粘性膜。所述粘性膜可包括小于2%的残留溶剂。
本发明另一方面提供一种包括所述粘性膜的切割芯片模粘结膜。
具体实施方式
现将详细地描述本发明的实施方式。
本发明一方面提供了一种粘合剂组合物,其包括弹性体树脂、环氧树脂、可固化酚醛树脂、固化促进剂、硅烷偶联剂和填料。
在以下说明书中,除非另有说明,所述的每个组分的含量为固体含量。
弹性体树脂
弹性体树脂可为丙烯酸类聚合物树脂。弹性体树脂可为橡胶组分,所述橡胶组分用于形成膜且可包含羟基、羧基或环氧基。
丙烯酸类聚合物树脂可通过(甲基)丙烯酸(C1~C20)烷基酯的共聚制备。具体地,基于丙烯酸类聚合物树脂的总重量,丙烯酸类聚合物树脂可包括50%或更多的(甲基)丙烯酸(C1~C20)烷基酯。(甲基)丙烯酸(C1~C20)烷基酯的实例可包括但不限于(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸-2-乙己酯、丙烯酸异辛酯、甲基丙烯酸硬脂酸酯等。这些化合物可单独使用,或两种或更多种组合使用。
在一个实施方式中,可控制丙烯酸类聚合物树脂的玻璃化转变温度和分子量,或可通过引入适用于聚合的共聚单体将官能团引入丙烯酸类聚合物树脂的侧链中。适用于丙烯酸类聚合物树脂制备的共聚单体可包括丙烯腈、丙烯酸、(甲基)丙烯酸-2-羟基乙酯、苯乙烯单体、(甲基)丙烯酸缩水甘油酯等。这些共聚单体可单独使用,或两种或更多种组合使用。基于丙烯酸类聚合物树脂的总重量,共聚单体的含量可为50wt%或更低,优选30wt%或更低,如0.1~20wt%。
丙烯酸类聚合物树脂可基于它们的环氧当量、玻璃化转变温度和分子量来分类。作为用作环氧当量大于10,000的丙烯酸类聚合物树脂的商品,可使用SG-80H系列产品(Nagase Chemtex)。对于环氧当量为10,000或更低的丙烯酸共聚物树脂,可使用SG-P3系列产品和SG-800H系列产品。在一个实施方式中,丙烯酸类聚合物树脂可具有5,000g/eq.或更低的环氧当量。有利地,丙烯酸类聚合物树脂可具有1,000~4,000g/eq.的环氧当量。
在一个实施方式中,丙烯酸类聚合物树脂可具有1~25mgKOH的羟值,优选5~20mgKOH的羟值。
在另一个实施方式中,丙烯酸类聚合物树脂可具有35~90mgKOH的酸值,优选50~80mgKOH的酸值。
丙烯酸类聚合物树脂可具有0~40℃范围内的玻璃化转变温度(Tg),以防止膜在室温下和在半导体封装的芯片锯切工艺时的磨边或修整中易碎。在一个实施方式中,丙烯酸类聚合物树脂可具有5~40℃范围内的玻璃化转变温度(Tg)。
此外,丙烯酸类聚合物树脂可具有100,000~700,000g/mol的重均分子量。有利地,丙烯酸类聚合物树脂可具有300,000~700,000g/mol的重均分子量。
以粘合剂组合物的总重量计,丙烯酸类聚合物树脂的含量可为2~50wt%(固体含量)。在此范围内时,粘合剂组合物可提供成膜性和可靠性。更有利地,丙烯酸类聚合物树脂的含量可为2~25wt%。在一个实施方式中,丙烯酸类聚合物树脂的含量可为10~20wt%。
环氧树脂
环氧树脂可为具有足够高交联密度以显示出强固化和粘合功能的那些环氧树脂。然而,具有高交联密度的单一可固化环氧系统会提供脆性膜。因此,环氧树脂可通过将液体状环氧树脂或具有最低交联密度的单或双官能团环氧树脂与多官能环氧树脂混合来制备。
具有最低交联密度的环氧树脂可具有100~1500g/eq.,优选150~800g/eq.,更优选150~500g/eq.的环氧当量。在此范围内时,环氧树脂不会引起玻璃化转变温度的降低,同时保证粘性和耐热性。
只要环氧树脂显示出固化和粘合性质,对其具体类型无限制,但考虑到膜的形状,环氧树脂可包括具有至少一个官能团的固体或固体状环氧树脂。
环氧树脂的实例可包括双酚类环氧树脂、邻甲酚醛类环氧树脂(ortho-cresol novolac-based epoxy resins)、多官能环氧树脂、胺类环氧树脂、杂环类环氧树脂、取代的环氧树脂和萘酚类环氧树脂。商购双酚类环氧树脂的具体实例可包括E4275(JAPAN EPOXY RESIN);Epiclon 830-S、EpiclonEXA-830CRP、Epiclon EXA 850-S、Epiclon EXA-835LV等(Dainippon Ink andChemicals,Inc.);Epicoat 807、Epicoat 815、Epicoat 825、Epicoat 827、Epicoat828、Epicoat 834、Epicoat 1001、Epicoat 1004、Epicoat 1007和Epicoat 1009(Yuka Shell Epoxy Co.,Ltd.);DER-330、DER-301和DER-361(Dow ChemicalCo.)和YD-011、YDF-019、YD-128、YDF-170等(Kukdo Chemical Co.,Ltd.)。商购邻甲酚醛类环氧树脂的具体实例可包括:YDCN-500-1P、YDCN-500-4P、YDCN-500-5P、YDCN-500-7P、YDCN-500-80P和YDCN-500-90P(KukdoChemicalCo.,Ltd.);和EOCN-102S、EOCN-103S、EOCN-104S、EOCN-1012、EOCN-1025和EOCN-1027(Nippon Kayaku Co.,Ltd.)。商购多官能环氧树脂的具体实例可包括:Epon 1031S(Yuka Shell Epoxy Co.,Ltd.);Araldite 0163(Ciba Specialty Chemicals);和Detachol EX-611、Detachol EX-614、DetacholEX-614B、Detachol EX-622、Detachol EX-512、Detachol EX-521、DetacholEX-421、Detachol EX-411和Detachol EX-321(NAGA Celsius TemperatureKasei Co.,Ltd.)。商购胺类环氧树脂的具体实例可包括:Epicoat 604(YukaShell Epoxy Co.,Ltd.);YH-434(Tohto Kasei Co.,Ltd.);TETRAD-X和TETRAD-C(Mitsubi shi Gas Chemical Company Inc.);和ELM-120(SumitomoChemicalIndustry Co.,Ltd.)。商购杂环环氧树脂的具体实例可包括PT-810(Ciba Specialty Chemicals)。商购取代的环氧树脂的具体实例可包括ERL-4234、ERL-4299、ERL-4221、ERL-4206等(UCC Co.,Ltd.)。商购萘酚类环氧树脂的具体实例可包括:Epiclon HP-4032、Epiclon HP-4032D、Epiclon HP-4700、Epiclon HP-4701(Dainippon Ink and Chemicals,Inc.)等。这些环氧树脂可单独使用,或两种或更多种组合使用。
在一个实施方式中,环氧树脂可包括50wt%或更多的多官能环氧树脂。当多官能环氧树脂在此范围内时,环氧树脂可具有高交联密度,以提高结构的内部粘结强度并获得良好的可靠性。以环氧树脂的总重量计,多官能环氧树脂的含量可优选为60~90wt%,更优选65~85wt%。
在本发明的实施方式中,基于粘合剂组合物的总重量,环氧树脂的含量可优选为4~50wt%,更优选4~35wt%。在此范围内时,膜可具有优异的可靠性并保持相容性。更有利地,考虑到降低粘性膜在室温下的表面粘性,以降低粘性膜和芯片间的粘合力从而有助于拾取工艺中的拾取,环氧树脂的含量可为35wt%或更低,如4.5~25wt%。在一个实施方式中,粘合剂组合物中环氧树脂的含量可为10~30wt%。
可固化酚醛树脂
酚醛环氧树脂固化剂没有具体限制。可使用任何适合的酚醛环氧树脂固化剂。每分子适合的固化酚醛树脂可具有两个或更多个酚醛羟基。固化酚醛树脂的实例可包括双酚A、双酚F和双酚S树脂、线型酚醛树脂、双酚A酚醛清漆树脂、甲酚醛树脂、新酚(xylok)树脂和联苯树脂,全部这些树脂在吸湿时对电解腐蚀有高抗性。
商购可固化酚醛树脂的具体实例可包括:简单的可固化酚醛树脂,如H-1、H-4、HF-1M、HF-3M、HF-4M和HF-45(Meiwa Kasei Co.,Ltd.);对二甲苯类树脂,如MEH-78004S、MEF-7800SS、MEH-7800S、MEH-7800M、MEH-7800H、MEH-7800HH和MEH-78003H(Meiwa Kasei Co.,Ltd.),以及KPH-F3065(KOLON Chemical Co.,Ltd.);联苯类树脂,如MEH-7851SS、MEH-7851S、MEH-7851M、MEH-7851H、MEH-78513H和MEH-78514H(Meiwa Kasei Co.,Ltd.),以及KPH-F4500(KOLON Chemical Co.,Ltd.);和三苯甲基类树脂,如MEH-7500、MEH-75003S、MEH-7500SS、MEH-7500S、MEH-7500H(Meiwa Kasei Co.,Ltd.)等。这些化合物可单独使用,或两种或更多种组合使用。
在实施中,可固化酚醛树脂可优选具有100~600g/eq.,优选100~300g/eq.的羟基当量。在此范围内时,可保持适合的吸湿性和再流动抗性(reflowresistance),且可不降低玻璃化转变温度,因此提供良好的耐热性。
可固化酚醛树脂可包括50wt%或更多的线型酚醛树脂。在一个实施方式中,可固化酚醛树脂可包括75~100wt%的线型酚醛树脂。如果线型酚醛树脂的加入量为50wt%或更高,固化后的交联密度增加,使得分子间内聚力和内部键合强度增加,因此改进了组合物的粘合力。此外,组合物在外部应力下可显示较低的变形,这有利于保持膜的恒定厚度。
基于粘合剂组合物的总重量,可固化酚醛树脂的含量可优选为3~50wt%,更优选3~30wt%。在一个实施方式中,基于粘合剂组合物的总重量,可固化酚醛树脂的含量可优选为10~35wt%。
固化促进剂
可加入固化促进剂以控制粘合剂组合物的固化速率。适合的固化促进剂可包括膦类、硼类和咪唑类固化促进剂。
膦类固化促进剂的实例可包括但不限于三苯基膦、三邻甲苯基膦、三间甲苯基膦、三对甲苯基膦、三-2,4-二甲苯基膦、三-2,5-二甲苯基膦、三-3,5-二甲苯基膦、三苄基膦、三(对甲氧基苯基)膦、三(对叔丁氧基苯基)膦、二苯基环己基膦、三环己基膦、三丁基膦、三叔丁基膦、三正辛基膦、二苯基膦基苯乙烯、二苯基氯化膦(diphenylphosphinouschloride)、三正辛基氧化膦、二苯基氧膦基氢醌、四丁基氢氧化鏻、四丁基乙酸鏻、苄基三苯基鏻六氟锑酸盐、四苯基鏻四苯基硼酸盐、四苯基鏻四对甲苯基硼酸盐、苄基三苯基鏻四苯基硼酸盐、四苯基鏻四氟硼酸盐、对甲苯基三苯基鏻四对甲苯基硼酸盐、三苯基膦三苯基硼烷、1,2-双(二苯基膦基)乙烷、1,3-双(二苯基膦基)丙烷、1,4-双(二苯基膦基)丁烷、双(二苯基膦基)戊烷等。
硼类固化促进剂的实例可包括但不限于苯基硼酸、4-甲基苯基硼酸、4-甲氧基苯基硼酸、4-三氟甲氧基苯基硼酸、4-叔丁氧基苯基硼酸、3-氟-4-甲氧基苯基硼酸、吡啶-三苯基硼烷、2-乙基-4-甲基咪唑鎓四苯基硼酸盐和1,8-二偶氮二环[5.4.0]十一碳烯-7-四苯基硼酸盐。
咪唑类固化促进剂的实例可包括但不限于2-甲基咪唑、2-十一基咪唑、2-十七基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-苯基咪唑、1,2-二甲基咪唑、1-氰基乙基-2-甲基咪唑、1-氰基乙基-2-乙基-4-甲基咪唑、1-氰基乙基-2-十一基咪唑、1-氰基乙基-2-苯基咪唑、1-氰基乙基-2-十一基咪唑鎓-偏苯三酸盐、1-氰基乙基-2-苯基咪唑鎓-偏苯三酸盐、2,4-二氨基-6-[2′-甲基咪唑基-(1′)]-乙基-s-三嗪、2,4-二氨基-6-[2′-十一基咪唑基-(1′)]-乙基-s-三嗪、2,4-二氨基-6-[2′-乙基-4′甲基咪唑基-(1′)]-乙基-三嗪、2,4-二氨基-6-[2′-甲基咪唑基-(1′)]-乙基-s-三嗪异氰脲酸加合物二水合物、2-苯基咪唑异氰脲酸加合物、2-甲基咪唑异氰脲酸加合物二水合物、2-苯基-4,5-二羟基甲基咪唑、2-苯基-4-甲基-5-羟基甲基咪唑、2,3-二氢-1H-吡咯并[1,2-a]苯并咪唑、4,4′-亚甲基双(2-乙基-5-甲基咪唑)、2-甲基咪唑啉、2-苯基咪唑啉、2,4-二氨基-6-乙烯基-1,3,5-三嗪、2,4-二氨基-6-乙烯基-1,3,5-三嗪异氰脲酸加合物、2,4-二氨基-6-甲基丙烯酰氧基乙基-1,3,5-三嗪异氰脲酸加合物、1-(2-氰基乙基)-2-乙基-4-甲基咪唑、1-氰基乙基-2-甲基咪唑、1-(2-氰基乙基)2-苯基-4,5-二-(氰基乙氧基甲基)咪唑、1-乙酰基-2-苯基肼、2-乙基-4-甲基咪唑啉、2-苄基-4-甲基咪唑啉、2-乙基咪唑啉、2-苯基咪唑、2-苯基-4,5-二羟基甲基咪唑等。
这些固化促进剂可单独使用,或两种或更多种组合使用。
粘合剂组合物中固化促进剂的含量可为0.01~10wt%。更有利地,粘合剂组合物中固化促进剂的含量可为0.01~2wt%。在此范围内时,粘合剂组合物表现出优异的存储稳定性。
硅烷偶联剂和过渡金属清除剂
硅烷偶联剂可包括含环氧基的硅烷偶联剂和含过渡金属清除官能团的硅烷偶联剂。
过渡金属清除官能团通过结合过渡金属离子或通过氧化或还原过渡金属离子可显著降低过渡金属的迁移率。根据本发明,可将能够氧化或还原过渡金属或降低过渡金属迁移率的官能团引入硅烷偶联剂,以提供控制过渡金属并同时保持粘性膜整体功能的功能,以此防止因半导体芯片表面上残留的杂质,即过渡金属或过渡金属离子渗入粘性膜和半导体芯片表面间的界面造成的半导体芯片可靠性降低。
含环氧基的硅烷偶联剂的实例可包括但不限于2-(3,4-环氧环己基)-乙基三甲氧基硅烷、3-缩水甘油醚氧基三甲氧基硅烷、3-缩水甘油醚氧基丙基三甲氧基硅烷、3-缩水甘油醚氧基丙基三乙氧基硅烷等。这些化合物可单独使用,或两种或更多种组合使用。
在一个实施方式中,基于硅烷偶联剂的总重量,含环氧基的硅烷偶联剂的含量可为15wt%至小于100wt%。有利地,含环氧基的硅烷偶联剂的含量可为20~50wt%。例如,含环氧基的硅烷偶联剂的含量可为25~60wt%。
在一个实施方式中,硅烷偶联剂可包括30~60wt%的含环氧基的硅烷偶联剂和40~70wt%的含过渡金属清除官能团的硅烷偶联剂。
过渡金属清除官能团可为选自由-CN、-COOH、-NCO、-SH和-NH2组成的组中的至少一种。例如,可将含氰化物基团的硅烷偶联剂、含巯基的硅烷偶联剂、含酸的硅烷偶联剂、含异氰酸酯的硅烷偶联剂和含胺基的硅烷偶联剂用作过渡金属清除官能团。
含巯基(-SH)的硅烷偶联剂的实例可包括但不限于3-巯基丙基甲基二甲氧基硅烷、3-巯基丙基三乙氧基硅烷和3-巯基丙基三甲氧基硅烷。
含异氰酸酯的硅烷偶联剂的实例可包括但不限于3-异氰酸酯丙基三乙氧基硅烷。
含胺基的硅烷偶联剂的实例可包括但不限于N-2(氨基乙基)-3-氨基丙基甲基二甲氧基硅烷、N-2(氨基乙基)-3-氨基丙基三甲氧基硅烷、N-2(氨基乙基)-3-氨基丙基三乙氧基硅烷、3-氨基丙基三甲氧基硅烷、3-氨基丙基三乙氧基硅烷、3-三乙氧基硅基-N-(1,3-二甲基亚丁基)丙胺和N-苯基-3-氨基丙基三甲氧基硅烷。
含过渡金属清除官能团的硅烷偶联剂可单独使用,或两种或更多种组合使用。例如,有利地可使用含巯基的硅烷偶联剂和含胺基的硅烷偶联剂的组合,和含巯基的硅烷偶联剂和含异氰酸酯基的硅烷偶联剂的组合。
在本发明中,基于粘合剂组合物的总重量,硅烷偶联剂的含量可为0.1~10wt%。在一个实施方式中,硅烷偶联剂的含量可为1~7wt%。
此外,粘合剂组合物可进一步包括过渡金属清除剂,所述过渡金属清除剂包括能控制过渡金属的过渡金属清除官能团,如-CN、-COOH、-NCO、-SH或-NH2。
可将具有腈基的氰化物、丙烯腈、2-氨基-1,1,3-三氰基-1-丙烷、4,4-偶氮双(4-氰基戊酸)、1,1-偶氮双(2,4-二甲基戊腈)、2,2-偶氮双(2-甲基丁腈)、四氰基乙烯、壬二腈、丙二腈二聚体和三唑衍生物(购自Ciba Irgamet Co.,Ltd.)用作具有过渡金属清除官能团的清除剂。此外,根据清除对象,如磷酸、亚磷酸、有机酸阴离子、卤素阴离子、碱金属阳离子和碱土金属阳离子,具有离子清除功能的无机化合物的实例包括水滑石类离子清除剂、氧化铋类离子清除剂、氧化锑类离子清除剂、氧化钛类类离子清除剂和磷化锆类离子清除剂,以用于清除离子杂质。这些化合物可单独使用,或两种或更多种组合使用。有利地,可将氰化物用作过渡金属清除剂。
粘合剂组合物中可选地包括含过渡金属清除官能团的清除剂。在一个实施方式中,当不加入含过渡金属清除官能团的清除剂时,含过渡金属清除官能团的硅烷偶联剂可独自作为过渡金属清除组分。
在另一个实施方式中,可将具有过渡金属清除官能团的清除剂加入到用于半导体器件的粘合剂组合物中。此时,含过渡金属清除官能团的硅烷偶联剂和具有过渡金属清除官能团的清除剂均可作为过渡金属清除组分。
过渡金属清除组分的含量可高于含环氧基的硅烷偶联剂的含量。
在一个实施方式中,相对于硅烷偶联剂和过渡金属清除剂的总重量,含过渡金属清除官能团的硅烷偶联剂和过渡金属清除剂的总重量可为50wt%至小于100wt%,以进一步改进过渡金属清除功能。如果含清除官能团的硅烷偶联剂和过渡金属清除剂的总重量小于50wt%,对过渡金属的反应性会降低。相对于硅烷偶联剂和过渡金属清除剂的总重量,含清除官能团的硅烷偶联剂和过渡金属清除剂的总重量优选为50.5~85wt%,更优选55~75wt%。
填料
可将填料选择性地加入到粘合剂组合物中,以提供触变性质和控制熔体粘度。
根据需要,填料可包括无机或有机填料。无机填料的实例包括但不限于金属组分,如金、银、铜和镍粉;和非金属组分,如氢氧化铝、氢氧化镁、碳酸钙、碳酸镁、硅酸钙、硅酸镁、氧化钙、氧化镁、氧化铝、氮化铝、氧化硅、氮化硼、二氧化钛、玻璃、铁氧体、陶瓷等。有机填料的实例包括但不限于碳、橡胶填料、聚合物类填料等。
对填料的形状和大小无特别限制。在一个实施方式中,可优选将球形氧化硅用作填料。在一个实施方式中,根据需要,填料可为具有疏水表面的球形填料。
球形氧化硅可具有500nm至10μm的粒径。在一个实施方式中,填料可具有500nm至5μm的粒径。在此范围内时,填料不损坏半导体电路。
基于粘合剂组合物的总重量,填料的含量可为0.1~50wt%。在根据一个实施方式将粘性膜用于具有相同大小的芯片模粘性膜的情况下,填料的含量可在10~40wt%的范围内。在此范围内时,膜易于形成并具有良好的抗张强度。
有机溶剂
所述粘合剂组合物可进一步包括有机溶剂。有机溶剂降低粘合剂组合物的粘性,因此有助于粘性膜的制备。然而,残留在粘性膜中的有机溶剂会影响粘性膜的物理性质,因此希望残留有机溶剂的含量保持在2%或更低。
可应用的有机溶剂的实例包括但不限于苯、丙酮、甲乙酮、四氢呋喃、二甲基甲酰胺、环己烷、丙二醇单甲醚乙酸酯和环己酮。这些溶剂可单独使用,或两种或更多种组合使用。例如,有机溶剂可包括高沸点溶剂和低沸点溶剂的混合物。高沸点溶剂的沸点可为约100至约150℃。低沸点溶剂的沸点可为约50至约100℃。例如,低沸点溶剂和高沸点溶剂的比例为约30~100wt%:about 0~70wt%。在此比例范围内,残留有机溶剂的量可调节为约2wt%或更低。
有机溶剂可促进均匀混合物的形成,以减少粘性膜形成时空隙的出现。并且,在粘性膜形成后,残留在膜中的少量有机溶剂使膜变软,因此防止膜被不希望地切割。
粘合剂组合物可具有10kgf/m2或更高的粘合强度,且可在30天后显示出小于1%的粘合强度变化。具体地,粘合剂组合物可具有11~25kgf/m2或更高的粘合强度,且在30天后显示出小于0.5%的粘合强度变化。
本发明另一个方面提供了由粘合剂组合物形成的用于半导体器件的粘性膜。粘性膜可包括小于2%的残留溶剂。
粘性膜可非限制性地在80~120℃下干燥10~60分钟。
通过控制干燥温度或时间,可除去残留在组合物中的低沸点溶剂,且可将高沸点溶剂调节至小于2%。
将粘性膜在120~150℃下固化1~10分钟。
更具体地,可使粘性膜经历(约1至8次)循环固化工艺,所述循环固化工艺可包括在120~130℃下初次固化1~3小时和在130~150℃下二次固化10~60分钟。通过此工艺,可调节残留溶剂的挥发度。
同样地,考虑到各种物理性质和组合物中残留溶剂的种类和含量,可控制因切割工艺期间溶剂挥发性所引起的问题。
在切割工艺中,可仅降低膜中高沸点溶剂的浓度,来消除因挥发性成分引起的空隙出现和减轻芯片模贴装中的气泡膨胀。
更具体地,如果使用沸点小于125℃固化温度的溶剂,在切割工艺期间残留溶剂会引起空隙的形成。此外,如果使用沸点大于200℃的溶剂,在膜形成期间残留溶剂的含量变为2%或更高,因此在EMC模塑工艺或可靠性测试期间引起体积膨胀且降低可靠性。
在以上描述中,对于根据本发明的粘合剂组合物,建议用适合比例和含量的低沸点溶剂和高沸点溶剂。在此比例内时,在界面形成的间隙或空隙的体积膨胀降低,以消除将芯片粘结至界面时空隙的出现,且因导线填充中的间隙或空隙引起的体积膨胀降低,因此提供具有高可靠性的用于半导体器件的粘性膜。此外,在固化前膜的脆性降低,以防止因在锯切或安装工艺中粘性膜碎片引起的膜污染,且有助于膜的处理。
在根据本发明的粘性膜中,残留溶剂的含量小于2wt%。因此,在组合物形成的粘性膜的层中,固体含量为98wt%或更高。如果层中的固体含量小于98wt%,因残留溶剂引起的气泡或吸湿性会引起可靠性的降低。
粘性膜可显示出150~400%的伸长率。
粘性膜可具有25℃下0.1~10MPa的存储弹性模量和80℃下0.01~0.10MPa的存储弹性模量。粘性膜可具有25℃下1,000,000~5,000,000P的熔体粘度和小于0.1Kgf的表面粘性。也就是说,因为膜中存在溶剂,粘性膜在粘度或表面粘性上未改变,使得用于半导体封装工艺所需的性质未受实质影响。具体地,无论是否存在高沸点溶剂,在固化后,粘合剂组合物的存储弹性模量、流动性和表面粘性保持不变。因此,鉴于在室温下存储,粘性膜不受高沸点溶剂的影响。
与由低沸点溶剂形成的膜相比,根据本发明的粘性膜因在125℃至小于175℃温度下挥发率低且挥发量小而具有塑性,因此防止膜的破裂。而且,在半导体封装工艺中,也将空隙产生降低至基板上空隙生成小于5%的程度,因此防止可靠性降低。
本发明的另一方面提供了包括用于半导体器件的粘性膜的切割芯片模粘结膜。根据本发明,切割芯片模粘结膜具有顺序堆叠在基膜上的粘性层和粘性膜,其中粘性膜层由根据本发明实施方式的粘性膜形成。
粘性层可由公知的粘合剂组合物形成,其可包括如基于100重量份的UV可固化丙烯酸酯,100重量份的弹性体树脂、20~150重量份的UV可固化丙烯酸酯和0.1~5重量份的光引发剂。
基膜可为射线可透射的材料。如果使用紫外光活化的可辐射固化的粘合剂,基膜可由选自具有有利透光率的聚合物的材料形成。聚合物的实例可包括但不限于聚烯烃均聚物或共聚物,如聚乙烯、聚丙烯、丙烯乙烯共聚物、乙烯乙基丙烯酸共聚物、乙烯丙烯酸甲酯共聚物、乙烯乙酸乙烯酯共聚物等、聚碳酸酯、聚甲基丙烯酸酯、聚氯乙烯、聚氨酯共聚物等。考虑到抗张强度、伸长率、射线可透射性等,基膜可具有50~200μm的厚度。
从以下实施例中,本发明的优点和特征以及实现它们的方法将变得更明了。然而,本发明不限于所说明的实施例且可以不同方式实施。更确切地,提供公开的实施例,使得本公开全面和完整,且将本发明的范围完全传递给本领域技术人员。本发明的范围由在后的权利要求所限定。
实施例
测试偶联剂和清除剂对过渡金属溶液的反应性
为了确认本发明偶联剂对过渡金属的反应性,将偶联剂与含Cu2+离子的过渡金属溶液混合。具体地,在将过渡金属溶解后,将过渡金属溶液滴入其中具有不同偶联剂的烧杯中,随后测定偶联剂的反应性。结果用O或X总结在表1中。
表1
KBM-303:β-(3,4-环氧基环己基)乙基三甲氧基硅烷
S-810:3-巯基丙基三甲氧基硅烷
KBM-602:N-2(氨基乙基)3-氨基丙基甲基二甲氧基硅烷
“×”:偶联剂不与Cu2+离子反应
“○”:偶联剂与Cu2+离子反应
实施例1至4和比较例1至5
将表2和3所列的组分加入到1L烧杯中并通过高速搅拌器以4000rpm的速度分散20分钟以制备组合物。将每个组合物通过砂磨机处理两次,持续30分钟。随后,将组合物通过50μm囊式过滤器过滤并随后沉积到60μm厚的聚对苯二甲酸乙二醇酯(PET)膜上,使用涂抹器对此膜的表面进行释放涂布(release coating),随后在90~120℃下干燥20分钟,以制备粘性层。实施例和比较例中所用的组分如下。
(1)弹性体树脂:KLS-1045(羟值:13mgKOH/g,酸值:63mgKOH/g,Tg 38℃,重均分子量:690,000,Fujikura Ltd.)
(2)双酚类环氧树脂:YD-011(当量:450(g/eq.),重均分子量:10,000或更低,Kukdo Chemical Co.,Ltd.)
(3)多官能环氧树脂(EP-5100R,Kukdo Chemical Co.,Ltd.)
(4)可固化酚醛树脂:线型酚醛树脂(DL-92,羟基当量:105(g/eq.),重均分子量:1,000或更低,Meiwa Plastic Industries,Ltd.)
(5)固化促进剂:膦类固化促进剂(TPP-K、TPP或TPP-MK,MeiwaPlastic Industries,Ltd.)
(6)环氧硅烷偶联剂(KBM-303,当量:246(g/eq.),Shin-Etsu ChemicalCo.,Ltd.)
(7)巯基硅烷偶联剂(S-810,当量:196(g/eq.),Chisso Corporation)
(8)氨基硅烷偶联剂(KBM-602,当量:206(g/eq.),Shin-Etsu ChemicalCo.,Ltd.)
(9)清除剂(四氰基乙烯,当量:32(g/eq.),Tokyo Kayaku Co.,Ltd.)
(10)填料:球形氧化硅(SC-4500SQ,SC-2500SQ,Admatechs Co.,Ltd.)
表2
表3
[电学可靠性]
将制得的粘性膜粘附到梳型电极上(导体/线宽=100μm/100μm)并在125℃放置1小时,随后在170℃加热2小时并压缩,以制备用于电学可靠性测试的样品。对每个制得的样品通过以下方法进行测试:在130℃和85%RH下施加50V电压,持续100小时,随后使用显微镜观察电极间的间隙。在极端测试条件下测试因导电故障引起的样品腐蚀。未显示出导电故障的样品表示为O,且显示出导电故障的样品表示为X。
[器件的性能]
使用制得的粘性膜封装半导体芯片,并对此芯片进行器件性能测试。检查是否此器件能正常运行,每个器件的性能表示为通过/失败。
[粘合强度]
将涂覆有二氧化物的725μm厚晶片切割为芯片(5×5mm)。将芯片在60℃下用各个制得的粘性膜层叠。切割层叠物以仅留下粘合的部分。通过在100℃下持续1秒施加1.0kgf的力,在热板上将用粘合剂层叠的晶片块压合到涂覆有光敏聚酰亚胺的725μm厚晶片(10×10mm)上,并首先在125℃下固化1小时,并随后在175℃下固化3小时。使样品在85℃和85RH%下吸湿48小时,并在270℃下测定样品的断裂强度。
[吸湿率]
为了测定粘性膜的吸湿率,在60℃下将每个膜层压为14倍,并切割为具有40x40mm大小和2g总重量的样品。将样品首先在125℃下固化1小时,并随后在175℃下固化3小时,并记录样品的重量变化。此外,使样品在85℃和85RH%下吸湿8小时,并记录样品的重量变化。随后,计算固化导致的重量变化与吸湿导致的种类变化的比率,以百分数表示。结果显示在表4中。
[存储稳定性]
在将每个样品在室温下放置30小时后,测定样品在100℃下的熔体粘度和粘合强度,并与初始测量结果比较,以获得粘合强度的变化。结果显示在表4中。
表4
从表4的结果可见,包括过渡金属清除剂和偶联剂的粘性膜因大量与过渡金属离子反应的偶联剂而在电学可靠性和器件性能方面显示出有益的效果,所述过渡金属清除剂和偶联剂具有能够与过渡金属离子反应的特定官能团并同时保持膜形成部分或固化部分。
如表1的实施例所示,这些效果由清除剂和偶联剂对过渡金属的反应性证实,其中每个偶联剂具有特定官能团。然而,对于包含显示出与过渡金属高反应性的过量偶联剂和清除剂的比较例2和5,粘合剂组合物未改进粘合性质。
特别地,如表2和3中可见,在分别使用偶联剂和过渡金属清除剂的情况下,如果用于清除过渡金属离子的原料的当量小于偶联剂和过渡金属清除剂总重量的50%,对过渡金属的反应性降低。
确认当全部这些电学可靠性、器件性能和粘合性质使人满意,而非电学可靠性、器件性能和粘合性质其中之一使人满意后,在半导体封装后芯片的运行效率改进。
从表4中可见,全部实施例1至4显示出小于1%的吸湿率,且未经历以下器件性能故障,所述器件性能故障因与吸湿相关的芯片开裂导致的可靠性降低所引起,或因过渡金属离子迁移率增加导致的电学可靠性降低所引起。因此,可确定,在半导体封装过程的EMC模塑后,通过提供基于抗湿性的高粘合强度和热稳定性,实施例1至4具有能够确保半导体封装高可靠性的基本性质。
相反,在比较例1至5中,缺少包括能影响粘合强度的特定官能团的粘合剂会导致粘合强度和存储稳定性降低。
换句话说,从表4中可见,在粘合剂组合物中使用具有特定官能团的偶联剂提供高粘合强度和良好的再流动抗性,同时确保高电学可靠性和器件性能。
虽然本文已公开了一些实施方式,但本领域技术人员应理解这些实施方式仅以说明的方式提供,且在不背离本发明精神和范围下可进行各种修改、变化和更改。因此,本发明的范围应仅限于所附权利要求和其等价形式。
Claims (20)
1.一种用于半导体器件的粘合剂组合物,包括弹性体树脂、环氧树脂、可固化酚醛树脂、固化促进剂、硅烷偶联剂和填料,其中所述硅烷偶联剂包括含环氧基的硅烷偶联剂和含过渡金属清除官能团的硅烷偶联剂。
2.如权利要求1所述的用于半导体器件的粘合剂组合物,其中所述过渡金属清除官能团包括选自由-CN、-COOH、-NCO、-SH和-NH2组成的组中的至少一种。
3.如权利要求1所述的用于半导体器件的粘合剂组合物,其中基于所述硅烷偶联剂的总重量,所述含环氧基的硅烷偶联剂的含量为15wt%至小于100wt%。
4.如权利要求3所述的用于半导体器件的粘合剂组合物,其中所述硅烷偶联剂包括30~60wt%的所述含环氧基的硅烷偶联剂和40~70wt%的所述含过渡金属清除官能团的硅烷偶联剂。
5.如权利要求3所述的用于半导体器件的粘合剂组合物,其中所述粘合剂组合物具有比所述含环氧基的硅烷偶联剂的含量更高的过渡金属清除组分,所述过渡金属清除组分包括含过渡金属清除官能团的硅烷偶联剂。
6.如权利要求1所述的用于半导体器件的粘合剂组合物,其中所述粘合剂组合物包括2~50wt%的所述弹性体树脂、4~50wt%的所述环氧树脂、3~50wt%的所述可固化酚醛树脂、0.01~10wt%的所述固化促进剂、0.1~10wt%的所述硅烷偶联剂和0.1~50wt%的所述填料。
7.如权利要求1所述的用于半导体器件的粘合剂组合物,进一步包括:过渡金属清除剂。
8.如权利要求7所述的用于半导体器件的粘合剂组合物,其中所述过渡金属清除剂包括以下至少一种:有机化合物,包括氰化物和三唑衍生物;和无机离子交换剂,包括水滑石类离子清除剂、氧化铋类离子清除剂、氧化锑类离子清除剂、氧化钛类类离子清除剂和磷化锆类离子清除剂。
9.如权利要求7所述的用于半导体器件的粘合剂组合物,其中基于所述硅烷偶联剂和所述过渡金属清除剂的总重量,所述过渡金属清除剂和所述含过渡金属清除官能团的硅烷偶联剂的含量为50wt%至小于100wt%。
10.如权利要求1所述的用于半导体器件的粘合剂组合物,进一步包括:有机溶剂。
11.如权利要求1所述的用于半导体器件的粘合剂组合物,其中所述弹性体树脂为含羟基、羧基或环氧基的丙烯酸类聚合物。
12.如权利要求1所述的用于半导体器件的粘合剂组合物,其中所述环氧树脂包括50wt%或更多的多官能环氧树脂。
13.如权利要求1所述的用于半导体器件的粘合剂组合物,其中所述可固化酚醛树脂包括50wt%或更多的线型酚醛树脂。
14.如权利要求1所述的用于半导体器件的粘合剂组合物,其中所述固化促进剂包括选自由膦类固化促进剂、硼类固化促进剂和咪唑类固化促进剂组成的组中的至少一种。
15.如权利要求1所述的用于半导体器件的粘合剂组合物,其中所述填料具有球形且具有500nm至5μm的平均粒径。
16.一种用于半导体器件的粘合剂组合物,具有10kgf/m2或更高的粘合强度,且在30天后显示出粘合强度的变化小于1%。
17.如权利要求16所述的用于半导体器件的粘合剂组合物,包括硅烷偶联剂,所述硅烷偶联剂包括含环氧基的硅烷偶联剂和含过渡金属清除官能团的硅烷偶联剂。
18.一种用于半导体器件的粘性膜,所述粘性膜使用如权利要求1至17中任一项所述的用于半导体器件的粘合剂组合物制备。
19.如权利要求18所述的用于半导体器件的粘性膜,其中所述粘性膜包括小于2%的残留溶剂。
20.一种切割芯片模粘结膜,包括如权利要求18所述的用于半导体器件的粘性膜。
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CN103160220B (zh) * | 2011-12-16 | 2016-03-02 | 第一毛织株式会社 | 用于半导体的粘合剂膜及使用其的半导体装置 |
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US10759971B2 (en) | 2015-04-29 | 2020-09-01 | Lg Chem, Ltd. | Adhesive composition for semiconductor, adhesive film for semiconductor, and dicing die bonding film |
US10865329B2 (en) | 2015-04-29 | 2020-12-15 | Lg Chem, Ltd. | Adhesive film for semiconductor |
CN112513217A (zh) * | 2018-08-03 | 2021-03-16 | 昭和电工材料株式会社 | 胶黏剂组合物、膜状胶黏剂、胶黏剂片及半导体装置的制造方法 |
WO2024066254A1 (zh) * | 2022-09-27 | 2024-04-04 | 武汉市三选科技有限公司 | 低模量垂直堆叠封装用薄膜黏晶胶、其制备方法及应用 |
Also Published As
Publication number | Publication date |
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TW201134903A (en) | 2011-10-16 |
KR101023241B1 (ko) | 2011-03-21 |
US8557896B2 (en) | 2013-10-15 |
TWI476262B (zh) | 2015-03-11 |
US20110160339A1 (en) | 2011-06-30 |
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