CN103160220A - 用于半导体的粘合剂膜及使用其的半导体装置 - Google Patents
用于半导体的粘合剂膜及使用其的半导体装置 Download PDFInfo
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- CN103160220A CN103160220A CN2012105482961A CN201210548296A CN103160220A CN 103160220 A CN103160220 A CN 103160220A CN 2012105482961 A CN2012105482961 A CN 2012105482961A CN 201210548296 A CN201210548296 A CN 201210548296A CN 103160220 A CN103160220 A CN 103160220A
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- binder film
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Classifications
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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Abstract
本文公开了用于半导体的粘合剂膜,所述粘合剂膜同时包含胺类固化剂和酚类固化剂,并呈现优异的与孔隙特性和可靠性相关的性质。所述用于半导体的粘合剂膜呈现固化前的储能模量和80%固化后的储能模量之间的1.5至3.0的高变化比,在芯片贴附时具有挠性以防止孔隙的产生,在EMC模制时利于孔隙的去除以控制贴附界面的孔隙面积,并具有硬度以在固化后提供良好的芯片剪切强度和耐回流,从而确保高可靠性。本文还公开了半导体装置。
Description
技术领域
本申请涉及用于半导体的粘合剂膜,所述粘合剂膜同时包含胺类固化剂和酚类固化剂,并呈现优异的与孔隙特性和可靠性相关的性质。更具体地,本发明涉及用于半导体的粘合剂膜,所述用于半导体的粘合剂膜呈现固化前的储能模量和80%固化后在170℃的储能模量之间的1.5至3.0的高变化比,芯片贴附时具有挠性以防止孔隙的产生,EMC(环氧模制化合物)模制时利于孔隙的去除以控制贴附界面的孔隙面积,并具有硬度以在固化后提供良好的芯片剪切强度和耐回流,从而确保高可靠性。
背景技术
近来,随着半导体二极管的尺寸减小或高容量的增加的趋势,用粘合剂膜互相贴附半导体二极管,或贴附半导体二极管到支持元件上。用于半导体组装的粘合剂膜与切割膜一起使用,以在切割工艺中用于支持半导体晶片。
在半导体晶片的组装中,在切割工艺中,具有切割膜和安装在半导体晶片上的粘合剂膜,所述半导体晶片在切割工艺中被切成单个的芯片,并且在芯片贴附中在高温下堆叠芯片。为支持堆叠的芯片,在125℃至150℃进行预固化预定的时间,并且完成的半导体二极管受到EMC模制。
半导体晶片堆叠其上的电路板由于导线具有不平的表面,因此在芯片贴附中芯片和粘合剂膜之间及半导体芯片之间贴附界面中可产生孔隙。当贴附界面中产生大量孔隙时,存在例如贴附强度劣化、热传导和电传导的劣化、芯片破裂等问题,其可对装置的质量和可靠性有负面影响。
当使用具有高流动性的粘合剂膜以解决这样的问题时,可能会防止在芯片贴附工艺中孔隙的产生。然而在该情况下,芯片剪切强度降低,因而引起可加工性的劣化。另一方面,具有高储能模量的粘合剂膜提供高芯片剪切强度,但是使其不仅在芯片贴附工艺还在EMC模制工艺中难于去除孔隙。
虽然本领域中丙烯酸粘结剂和酚类固化剂通常用作芯片贴附膜(DAF)的组合物(韩国专利公开号10-2009-0103434,韩国专利公开号10-0942356等),苯酚固化***不允许孔隙的易于去除并为固化后的产品提供低模数和芯片剪切强度,因而提供显著低的可靠性。
因此,需要在芯片贴附工艺中呈现优异的芯片剪切强度并且可防止孔隙产生同时在EMC模制时使如果存在的空隙易于去除的粘合剂膜。
发明内容
为解决本领域中由于低的芯片剪切强度和抗冲击性,用于半导体的粘合剂膜的问题,例如在贴附界面中大量孔隙的产生和低可靠性,本发明开发了用于半导体的粘合剂膜,所述用于半导体的粘合剂膜在所述粘合剂膜的制造中使用合适比例的胺类固化剂和酚类固化剂,并呈现优异的与孔隙特性和可靠性相关的性质。
本发明旨在提供一种用于半导体的粘合剂膜,所述用于半导体的粘合剂膜具有在固化前的储能模量和80%固化后在170℃的储能模量之间的1.5至3.0的高变化比。
更具体地,本发明旨在提供一种用于半导体的粘合剂膜,所述用于半导体的粘合剂膜在芯片贴附时呈现挠性以防止孔隙生成,在EMC模制时利于孔隙的去除以控制贴附界面上的孔隙面积,并具有硬度以在固化后提供良好的芯片剪切强度和耐回流,从而确保高可靠性。
本发明的一个方面提供一种用于半导体的粘合剂膜,所述用于半导体的粘合剂膜同时包含胺类固化剂和酚类固化剂,其中,所述粘合剂膜具有在1.5至3.0范围内的80%或更高固化后在170℃的储能模量(b)和固化前在40℃的储能模量(a)的比值(b/a)、5.0×106达因/cm2的固化后储能模量、9kgf或更高的固化后芯片剪切强度和/或在粘合剂膜贴附区域上5%或更小的固化后孔隙面积比。
在一个实施方式中,4次固化循环后在170℃的储能模量(b)和固化前在40℃的储能模量(a)的比值(b/a)为1.5至3.0。此处,每个固化循环由在125℃固化1小时和在150℃固化10分钟组成。
在一个实施方式中,所述胺类固化剂可包含二氨基二苯基砜。
在一个实施方式中,所述酚类固化剂可为双酚A或双酚F。
在一个实施方式中,所述粘合剂膜在125℃固化1小时、在150℃固化10分钟和在175℃固化1小时后,可具有9kgf或更高的芯片剪切强度。
在一个实施方式中,所述粘合剂膜在125℃固化1小时和在150℃固化1小时和在175℃模制60秒,及在175℃模制固化1小时后,在粘合剂膜贴附区域上具有5%或更小的孔隙面积比。
在一个实施方式中,所述粘合剂膜可具有9kgf或更高的固化后芯片剪切强度和5.0×106达因/cm2或更高的在170℃的固化后储能模量。
在一个实施方式中,所述粘合剂膜在粘合剂膜贴附区域上具有5%或更小的模制后孔隙面积比。
本发明的另一个方面提供一种用于半导体的粘合剂膜,所述粘合剂膜包含粘结剂树脂、环氧树脂、填料、胺类固化剂和酚类固化剂,其中,所述胺类固化剂(y)和所述酚类固化剂(x)的摩尔%比(y/x)为0.3至10。
在一个实施方式中,80%固化后在170℃的储能模量(b)和固化前在40℃的储能模量(a)的比(b/a)为1.5至3.0。
在一个实施方式中,所述粘合剂膜可具有9kgf或更高的模制后芯片剪切强度。
在一个实施方式中,基于100重量份的所述粘合剂膜的固含量,所述粘合剂膜可包含40至80重量份的所述粘结剂树脂、1至30重量份的所述环氧树脂、1至30重量份的所述填料、0.1至20重量份的所述胺类固化剂和0.1至20重量份的所述酚类固化剂。
在一个实施方式中,所述粘结剂树脂可为弹性体树脂。
本发明又一个方面提供一种半导体装置,所述半导体装置包含布线基板和半导体芯片,并且通过用于半导体的粘合剂膜连接。
根据本发明的用于半导体的粘合剂膜可抑制在贴附界面中孔隙的产生,并具有高芯片剪切强度和耐回流,因此确保高可靠性。
更具体地,根据本发明的用于半导体的粘合剂膜同时包含胺类固化剂和酚类固化剂,以提供1.5至3.0范围内的固化后储能模量和固化前储能模量的高比值,在芯片贴附时呈现挠性以抑制孔隙的产生,在EMC模制时使如果存在的空隙易于去除,并在固化后具有硬度以提供良好的芯片剪切强度和耐回流,因此确保良好的孔隙特性和高可靠性。
具体实施方式
现将详细说明本发明的实施方式。应理解提供下面实施方式的目的仅为说明的目的,而不应以任何方式解释为限制本发明的范围。
根据本发明,用于半导体的粘合剂膜可包含聚合物树脂、环氧树脂、固化剂、填料和其它添加剂。应理解这些组分的种类和量没有具体地限制,并可如在本领域中所使用的确定。接下来,将说明适合用在本发明的粘合剂膜中的组分的详细的实例。
聚合物树脂
可没有限制地使用在本领域中使用的任何典型的聚合物树脂。适合用在本发明的粘合剂膜中的聚合物树脂的实例可包含聚酰亚胺树脂、聚苯乙烯树脂、聚乙烯树脂、聚酯树脂、聚酰胺树脂、丁二烯橡胶、丙烯酸类橡胶、(甲基)丙烯酸类树脂、聚氨酯树脂、聚苯醚树脂、聚醚酰亚胺树脂、苯氧基树脂、聚碳酸酯树脂、改性的聚苯醚树脂和它们的混合物。这些树脂可单独使用或以两种或更多种的混合物使用。
此外,可使用包含官能单体的聚合物树脂,例如包含官能单体的含环氧基的(甲基)丙烯酸共聚物,例如缩水甘油基丙烯酸脂、缩水甘油基甲基丙烯酸脂等。(甲基)丙烯酸酯共聚物或丙烯醛类橡胶可用作含环氧基的(甲基)丙烯酸共聚物。它们可单独使用,或以其两种或更多种的混合物使用。
所述聚合物树脂可为弹性体树脂。可无限制地使用用在本领域中的任何典型的弹性体树脂。弹性体树脂的实例可包含丙烯腈、丁二烯、苯乙烯、丙烯醛、异戊二烯、乙烯、丙烯、聚氨酯和硅树脂,但不限于此。它们可单独使用,或以其两种或更多种的混合物使用。
所述弹性体树脂优选具有50,000g/mol至5,000,000g/mol,更优选地100,000g/mol至800,000g/mol的重均分子量。
基于100重量份的所述粘合剂膜的固含量,所述聚合物树脂的含量优选为40至80重量份,更优选50至70重量份。在这个范围内,所述粘合剂膜具有良好的孔隙特性和高可靠性。
环氧树脂
可没有限制地使用在本领域中使用的任何典型的环氧树脂。所述环氧树脂可包含液体环氧树脂和固体环氧树脂中的至少一种。
合适的液体环氧树脂的实例可包含双酚A型液体环氧树脂、双酚F型液体环氧树脂、三官能液体环氧树脂或更多官能液体环氧树脂、橡胶改性液体环氧树脂、聚氨酯改性液体环氧树脂、丙烯酸改性液体环氧树脂和光敏性液体环氧树脂。这些液体环氧树脂可单独使用,或以其两种或更多种的混合物使用。
所述液体环氧树脂可具有约100g/eq至约1500g/eq、更优选约150g/eq至约800g/eq、尤其优选约150g/eq至约400g/eq的环氧当量。在这个范围内,可获得在保持高玻璃化转变温度同时具有良好粘合和耐热性的固化产品。
所述液体环氧树脂可具有在100g/mol至1,000g/mol范围内的重均分子量。这个范围的益处在于提供高流动性。
所述固体环氧树脂在室温时可为固体或准固体的至少一种,并具有一种或更多种官能团。合适的固体环氧树脂的实例包含双酚型环氧树脂、苯酚酚醛型环氧树脂、邻甲酚醛型环氧树脂、双酚酚醛环氧树脂、多官能环氧树脂、胺类环氧树脂、杂环环氧树脂、取代的环氧树脂、萘酚类环氧树脂和其衍生物,但不限于此。
可商购的环氧树脂包含如下。双酚型环氧树脂的实例包含YD-017H、YD-020、YD020-L、YD-014、YD-014ER、YD-013K、YD-019K、YD-019、YD-017R、YD-017、YD-012、YD-011H、YD-011S、YD-011、YDF-2004、YDF-2001(Kukdo Chemical有限公司)等。苯酚酚醛型环氧树脂的实例包含EPIKOTE 152和EPIKOTE 154(Yuka ShellEpoxy有限公司);EPPN-201(Nippon Kayaku有限公司);DN-483(Dow Chemical公司);YDPN-641、YDPN-638A80、YDPN-638、YDPN-637、YDPN-644、YDPN-631(Kukdo Chemical有限公司)等。邻甲酚醛型环氧树脂的实例包含YDCN-500-1P、YDCN-500-2P、YDCN-500-4P、YDCN-500-5P、YDCN-500-7P、YDCN-500-8P、YDCN-500-10P、YDCN-500-80P、YDCN-500-80PCA60、YDCN-500-80PBC60、YDCN-500-90P、YDCN-500-90PA75(Kukdo Chemical有限公司);EOCN-102S、EOCN-103S、EOCN-104S、EOCN-1012、EOCN-1025、EOCN-1027(Nippon Kayaku有限公司);YDCN-701、YDCN-702、YDCN-703、YDCN-704(Tohto Kagaku有限公司);Epiclon N-665-EXP(Dainippon Ink and Chemicals股份有限公司)等。双酚酚醛环氧树脂的实例包含KBPN-110、KBPN-120、KBPN-115(Kukdo Chemical有限公司)等。多官能环氧树脂的实例包含Epon 1031S(Yuka Shell Epoxy有限公司);Araldite 0163(Ciba Specialty Chemicals);Detachol EX-611、Detachol EX-614、DetacholEX-25-12614B、Detachol EX-622、Detachol EX-512、Detachol EX-521、Detachol EX-421、Detachol EX-411、Detachol EX-321(NAGA Celsius Temperature Kasei有限公司);EP-5200R、KD-1012、EP-5100R、KD-1011、KDT-4400A70、KDT-4400、YH-434L、YH-434、YH-300(Kukdo Chemical有限公司)等。胺类环氧树脂的实例包含EPIKOTE604(Yuka Shell Epoxy有限公司);YH-434(Tohto Kagakuc有限公司);TETRAD-X和TETRAD-C(Mitsubishi Gas Chemical股份有限公司);ELM-120(Sumitomo ChemicalIndustry有限公司)等。杂环环氧树脂的实例包含PT-810(Ciba Specialty Chemicals)。取代的环氧树脂的实例包含:ERL-4234、ERL-4299、ERL-4221、ERL-4206(UCC有限公司)等。萘酚环氧树脂的实例包含Epiclon HP-4032、Epiclon HP-4032D、EpiclonHP-4700和Epiclon HP-4701(Dainippon Ink and Chemicals股份有限公司)。
基于100重量份的所述粘合剂膜的固含量,所述环氧树脂含量优选为1至30重量份、更优选5至20重量份。在这个范围内,可获得高可靠性和良好的孔隙去除效果。
胺类固化剂
可没有限制地使用在本领域中可使用的任何典型的胺类固化剂。
胺类固化剂的实例可包括3,3'-二氨基联苯胺、4,4'-二氨基二苯甲烷、4,4'-或3,3'-二氨基二苯砜、4,4'-二氨基二苯甲酮、对苯二胺、间苯二胺、间甲苯二胺、4,4'-二氨基二苯醚、3,3'-二氨基二苯甲酮、1,4'-或1,3'-双(4-或3-氨基异丙苯基)苯、1,4'-双(4-或3-氨基苯氧基)苯、2,2'-双[4-(4-或3-氨基苯氧基)苯基]丙烷、双[4-(4-或3-氨基苯氧基)苯基]砜、2,2'-双[4-(4-或3-氨基苯氧基)苯基]六氟砜、2,2'-双[4-(4-或3-氨基苯氧基)苯基]六氟丙烷、4,4'-二氨基-3,3',5,5'-四丁基二苯甲酮、4,4'-二氨基-3,3',5,5'-四乙基二苯甲酮、4,4'-二氨基-3,3',5,5'-四正丙基二苯甲酮、4,4'-二氨基-3,3',5,5'-四异丙基二苯甲酮、4,4'-二氨基-3,3',5,5'-四甲基二苯甲酮、4,4'-二氨基-3,3',5,5'-四正丙基二苯甲烷、4,4'-二氨基-3,3',5,5'-四甲基二苯甲烷、4,4'-二氨基-3,3',5,5'-四异丙基二苯甲烷、4,4'-二氨基-3,3',5,5'-四乙基二苯甲烷、4,4'-二氨基-3,3'-二甲基-5,5'-二乙基二苯甲烷、4,4'-二氨基-3,3'-二甲基-5,5'-二异丙基二苯甲烷、4,4'-二氨基-3,3'-二乙基-5,5'-二乙基二苯甲烷、4,4'-二氨基-3,5-二甲基-3',5'-二乙基二苯甲烷、4,4'-二氨基-3,5-二甲基-3',5'-二异丙基二苯甲烷、4,4'-二氨基-3,5-二乙基-3',5'-二丁基二苯甲烷、4,4'-二氨基-3,5-二异丙基-3',5'-二丁基二苯甲烷、4,4'-二氨基-3,3'-二异丙基-5,5'-二丁基二苯甲烷、4,4'-二氨基-3,3'-二甲基-5,5'-二丁基二苯甲烷、4,4'-二氨基-3,3'-二乙基-5,5'-二丁基二苯甲烷、4,4'-二氨基-3,3'-二甲基二苯甲烷、4,4'-二氨基-3,3'-二乙基二苯甲烷、4,4'-二氨基-3,3'-二正丙基二苯甲烷、4,4'-二氨基-3,3'-二异丙基二苯甲烷、4,4'-二氨基-3,3'-二丁基二苯甲烷、4,4'-二氨基-3,3',5-三甲基二苯甲烷、4,4'-二氨基-3,3',5-三乙基二苯甲烷、4,4'-二氨基-3,3',5-三正丙基二苯甲烷、4,4'-二氨基-3,3',5-三异丙基二苯甲烷、4,4'-二氨基-3,3',5-三丁基二苯甲烷、4,4'-二氨基-3-甲基-3'-乙基二苯甲烷、4,4'-二氨基-3-甲基-3'-异丙基二苯甲烷、4,4'-二氨基-3-甲基-3'-丁基二苯甲烷、4,4'-二氨基-3-异丙基-3'-丁基二苯甲烷、2,2-双(4-氨基-3,5-二甲基苯基)丙烷、2,2-双(4-氨基-3,5-二乙基苯基)丙烷、2,2-双(4-氨基-3,5-二正丙基苯基)丙烷、2,2-双(4-氨基-3,5-二异丙苯基)丙烷、2,2-双(4-氨基-3,5-二丁基苯基)丙烷、4,4'-二氨基-3,3',5,5'-四甲基二苯基苯酰替苯胺、4,4'-二氨基-3,3',5,5'-四乙基二苯基苯酰替苯胺、4,4'-二氨基-3,3',5,5'-四正丙基二苯基苯酰替苯胺、4,4'-二氨基-3,3',5,5'-四异丙基二苯基苯酰替苯胺、4,4'-二氨基-3,3',5,5'-四丁基二苯基苯酰替苯胺、4,4'-二氨基-3,3',5,5'-四甲基二苯砜、4,4'-二氨基-3,3',5,5'-四乙基二苯砜、4,4'-二氨基-3,3',5,5'-四正丙基二苯砜、4,4'-二氨基-3,3',5,5'-四异丙基二苯砜、4,4'-二氨基-3,3',5,5'-四甲基二苯醚、4,4'-二氨基-3,3',5,5'-四乙基二苯醚、4,4'-二氨基-3,3',5,5'-四正丙基二苯醚、4,4'-二氨基-3,3',5,5'-四异丙基二苯醚、4,4'-二氨基-3,3',5,5'-四丁基二苯醚、3,3'-二氨基二苯甲酮、3,4-二氨基二苯甲酮、3,3'-二氨基二苯醚、3,3'-二氨基二苯甲烷、3,4'-二氨基二苯甲烷、2,2'-二氨基-1,2-二苯乙烷或4,4'-二氨基-1,2-二苯乙烷、2,4-二氨基二苯基胺、4,4'-二氨基-八氟联苯、邻联茴香胺等,但不限于此。它们可单独使用,或以其两种或更多种的混合物使用。
作为所述胺类固化剂,优选使用二氨基二苯基砜。
基于100重量份的所述粘合剂膜的固含量,所述胺类固化剂的含量优选为0.1至20重量份,更优选1至10重量份。在这个范围内,模制时有可能防止孔隙的生成,并获得有效的孔隙去除。
酚类固化剂
可没有限制地使用在本领域中可使用的任何典型的酚类固化剂。
酚类固化剂的实例包含双酚型树脂,例如双酚A、双酚F、双酚S等;苯酚酚醛树脂;双酚A型酚醛清漆树脂;和酚醛树脂,例如二甲苯、甲酚酚醛清漆、联苯树脂等,但不限于此。
可商购的酚类固化剂包含下列。苯酚固化剂的实例包含H-1、H-4、HF-1M、HF-3M、HF-4M和HF-45(Meiwa Plastic Industries有限公司);对二甲苯酚类固化剂的实例包含MEH-78004S、MEH-7800SS、MEH-7800S、MEH-7800M、MEH-7800H、MEH-7800HH和MEH-78003H(Meiwa Plastic Industries有限公司)、KPH-F3065(Kolong Industries有限公司);联苯固化剂的实例包含MEH-7851SS、MEH-7851S、MEH7851M、MEH-7851H、MEH-78513H和MEH-78514H(Meiwa Plastic Industries有限公司)和KPH-F4500(Kolong Industries有限公司);和三苯甲基固化剂的实例包含MEH-7500、MEH-75003S、MEH-7500SS、MEH-7500S、MEH-7500H(Meiwa Plastic Industries有限公司)等。它们可单独使用,或以其两种或更多种的混合物使用。
作为酚类固化剂,可使用具有100g/eq至150g/eq环氧当量的双酚A或双酚F。
基于100重量份的所述粘合剂膜的固含量,所述酚类固化剂的含量优选为0.1至20重量份,更优选1至10重量份。当所述酚类固化剂不在这个范围内时,所述粘合剂膜可呈现粘合和固化性质的劣化。当所述酚类固化剂在这个范围内,模制时有可能防止孔隙的生成并在孔隙去除中获得所期望的效果。
所述胺类固化剂(y)与所述酚类固化剂(x)的摩尔%比优选为0.3至10,更优选0.5至10。在这个范围内,可获得所述酚类固化剂对胺类固化剂的有效的酸催化反应,以达到合适的固化反应,并且可提供合适量的所述胺类固化剂,因而允许模制时孔隙的有效去除。
填料
根据本发明的所述粘合剂组合物可包含填料以通过提供触变性质而调节熔融粘度。可无限制地使用本领域中任何典型的填料。作为填料,可根据需要使用无机或有机填料。无机填料的实例包含金属粉末,如金粉末、银粉末、铜粉末和镍粉末;和非金属,如氧化铝、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、二氧化硅、氮化硼、二氧化钛、玻璃、氧化铁和陶瓷等。有机填料的实例包含碳、橡胶、聚合物填料等。虽然对填料的形状和大小无具体的限制,但是填料可为球形填料,并具有约500nm至10μm的平均粒径。
优选地,填料为具有5至20μm的平均粒径的球形二氧化硅填料。
基于100重量份的所述粘合剂膜的固含量,所述填料的含量优选为1至30重量份,更优选5至20重量份。在这个范围内,有可能在防止对被粘物的粘附性的劣化的同时获得填料的充分效果。此外,在这个范围内,可获得高流动性、成膜性和粘附性。
硅烷偶联剂
本发明所述的粘合剂膜可进一步包含硅烷偶联剂,以在组合物的混合过程中通过无机材料例如二氧化硅的表面和有机材料的表面之间的化学偶联提高它们之间的粘附性。
可无限制地使用本领域中使用的任何典型硅烷偶联剂。硅烷偶联剂的实例包含:含环氧基的硅烷偶联剂,如2-(3,4-环氧环己基)-乙基三甲氧基硅烷、3-缩水甘油醚氧基丙基三甲氧基硅烷和3-缩水甘油醚氧基丙基三乙氧基硅烷;含胺基的硅烷偶联剂,如N-2-(氨乙基)-3-氨丙基甲基二甲氧基硅烷、N-2-(氨乙基)-3-氨丙基三甲氧基硅烷、N-2-(氨乙基)-3-氨丙基三乙氧基硅烷、3-氨丙基三甲氧基硅烷、3-氨丙基三乙氧基硅烷、3-三乙氧基甲硅烷基-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;含巯基的硅烷偶联剂,如3-巯丙基甲基二甲氧基硅烷和3-巯丙基三乙氧基硅烷;和含异氰酸基的硅烷偶联剂,如3-异氰酸丙基三乙氧基硅烷。它们可单独使用或以它们两种或更多种的组合使用。
基于100重量份的所述粘合剂膜的固含量,所述硅烷偶联剂的含量优选为0.01至10重量份,更优选0.1至5重量份。在这个范围内,可获得高粘附可靠性,并且可减少气泡的产生。
固化促进剂
适合用在本发明的粘合剂膜的固化促进剂用于减小半导体工艺中所述环氧树脂的固化时间。虽然可使用本领域中使用的任何典型固化促进剂,但是可使用三聚氰胺、咪唑或三苯基膦固化催化剂。可商购的咪唑固化促包含PN-23、PN-40(Ajinomoto FineTechnology股份有限公司)、2P4MZ、2MA-OK、2MAOK-PW、2P4MHZ(ShikokuChemicals公司)、TPP-K、TPP-MK(HOKKO Chemical Industry有限公司)等。它们可单独使用,或以它们两种或更多种的组合使用。
基于100重量份的所述粘合剂膜的固含量,所述固化促进剂的含量优选为0.01至10重量份,更优选0.03至5重量份。在这个范围内,在确保所述环氧树脂充分地反应的同时,获得高耐热性并保持稳定性。
离子吸附剂
所述用于半导体的粘合剂膜可进一步包含离子吸附剂,以在吸收湿气时实现绝缘可靠性的同时吸附离子杂质。可无限制地使用本领域中使用的任何典型离子吸附剂。离子吸附剂的实例包含三嗪硫醇化合物、铬化合物、锑铋化合物、镁铝化合物等,但不限于此。
有机溶剂
根据本发明所述用于半导体的粘合剂膜可进一步包含有机溶剂。所述有机溶剂用于降低粘合剂组合物的粘度,因而利于膜的形成。有机溶剂的实例包含甲苯、二甲苯、丙二醇单甲醚乙酸酯、苯、丙酮、甲乙酮、四氢呋喃、二甲基甲酰胺和环己酮,但不限于此。
不需要特定的仪器或装置用于形成根据本发明的用于半导体的粘合剂膜,可使用本领域中通常使用的任何方法制造所述粘合剂膜。
例如,所述粘合剂膜可用下面的方法制造。在这个方法中,上述的各个组分溶于溶剂中,并用珠磨机充分地揉捏,然后沉积产物到经离型处理的聚对苯二甲酸乙二醇酯(PET)膜上,并于100℃在烘箱中干燥10至30分钟以制备具有合适厚度的粘合剂膜。
所述粘合剂膜优选具有5μm至200μm、更优选10μm至100μm、尤其优选15至60μm的厚度。在这个范围内,在提供经济可行性的同时,通过确保优异的PCB(印刷电路板)填隙能力,防止模制后所述粘合剂膜孔隙特性的劣化。
在一个方面,本发明提供了用于半导体的粘合剂膜,其同时包含胺类固化剂和酚类固化剂,其中,4次固化循环后在170℃的储能模量(b)和固化前在40℃的储能模量(a)的比值(b/a)为1.5至3.0。此处,每个固化循环由在125℃固化1小时和在150℃固化10分钟组成。
此处,固化前在40℃的储能模量(a)是指粘合剂膜在40℃的储能模量值,其可通过在60℃堆叠所述粘合剂膜到400至500μm的厚度,然后在50℃/min的温度上升速度、5%的应变和1rad频率条件下用ARES测量而获得。
此处,固化后储能模量(b)是指粘合剂膜在170℃的储能模量值,其可通过在60℃堆叠所述粘合剂膜到400至500μm的厚度,固化样品超过总共4次循环,其中,每个循环由125℃在烘箱中半固化1小时和150℃在热板上固化10分钟组成,然后,在50℃/min的温度上升速度、5%的应变和1rad频率条件下用ARES测量而获得。
固化前后储能模量的储能模量比(b/a)可为1.5至3.0。在这个范围内,有可能在提供优异的模制后芯片剪切强度和可靠性的同时,防止芯片贴附过程中孔隙的产生,并在EMC模制时利于孔隙的去除。
在一个实施方式中,所述用于半导体的粘合剂膜在125℃固化1小时、在150℃固化10分钟和在175℃固化1小时后具有9kgf或更高的模制后芯片剪切强度。当所述粘合剂膜的芯片剪切强度为9kgf或更高时,所述粘合剂膜具有高强度,并因此可防止由于在热压条件下的膨胀而造成的失败,从而提供高可靠性。
固化后芯片剪切强度通过下面的步骤测量。720μm厚的晶片切成具有5×5mm尺寸的芯片。在60℃同时层压芯片与用于半导体的粘合剂膜,并切割以仅留下粘合部分。然后,将具有5×5mm尺寸的上芯片放在具有10×10mm大小的晶片上,然后在热板上于120℃施加10kgf的力5秒钟。然后,样品于125℃在烘箱中经半固化1小时,在150℃置于热板上10分钟以模拟引线接合条件,并如EMC固化的条件在175℃固化1小时。然后,在250℃用具有100N巴(bar)的Dage 4000在10μm的高度以100mm/s测量所述粘合剂膜的芯片剪切强度
在另一个实施方式中,所述粘合剂膜在125℃固化1小时,在150℃固化1小时,在175℃模制60秒并在175℃模制固化1小时后,在粘合剂膜贴附区域上可具有5%或更小的孔隙面积比。
如果在粘合剂膜在贴附区域上的孔隙面积比超过5%,所述粘合剂膜在粘合强度、热导和电导方面会劣化,并可引起芯片破裂,因而对装置的质量和可靠性提供非期望的影响。因此,所述粘合剂膜在粘合剂膜贴附区域上优选具有5%或更小的孔隙面积比。
所述短评“5%或更小的孔隙面积比”并非意味着孔隙面积比数值上包含0和小于0的负值,而是意味着孔隙面积比具有接近于0的正下限。
为了测量孔隙面积比,所述粘合剂膜与10×10mm的盖玻片在60℃层压在一起,并切割仅留下粘合的部分。然后,所述样品在PCB上在1kgf力的作用下压制1秒,在125℃固化1小时,在150°C固化1小时,并在175℃用EMC(SG-8500B,第一毛织有限公司,韩国)模制60秒。在175℃模制固化1小时后,用研磨机将覆盖盖玻片的模子从样品磨碎,并用低放大率的显微镜观察孔隙。此处,孔隙面积比是指模制后孔隙面积相对于粘合剂膜贴附面积的以百分比为单位的数值((孔隙面积/粘合剂膜贴附面积)×100%))。
在一个实施方式中,所述用于半导体的粘合剂膜在125℃固化1小时、在150℃固化10分钟以及在175℃固化1小时后具有9kgf或更高的芯片剪切强度,和5.0×106达因/cm2或更高的在170℃的固化后储能模量。
当所述粘合剂膜具有5.0×106达因/cm2或更高的在170℃的储能模量时,它可充分地承受在170℃施加到模子上的1吨的压力,以使所述芯片不脱离所述模子,因而消除模制失败。在这种情况下,所述粘合剂膜具有优异的芯片剪切强度和耐回流,因而提供高可靠性。
这里,固化后储能模量是指在170℃的储能模量值;其通过在60℃堆叠所述粘合剂膜到400至500μm的厚度,固化样品超过4次循环的总数,其中每个循环由125℃在烘箱内半固化1小时和150℃在热板上固化10分钟组成,然后在50℃/min的温度上升速度、5%的应变和1rad频率条件下用ARES测量而获得。
在另一个反面,本发明提供了半导体装置,所述半导体装置通过根据本发明的用于半导体的粘合剂膜连接。
所述半导体装置包含布线基板、贴附在所述布线基板的芯片安装表面上的所述用于半导体的粘合剂膜和安装在所述粘合剂膜上的半导体芯片。
可无限制地使用本领域中已知的任何典型的布线基板和半导体芯片。
此外,可无限制地使用本领域中已知的用于制造半导体装置的任何方法。
接下来,参考下面的实施例将更详细地说明本发明,应理解的是以下实施例仅为说明的目的提供,而不限制本发明的范围。
实施例1
同时包含胺类固化剂和酚类固化剂用于半导体的粘合剂膜的制备
基于100重量份的粘合剂膜的固含量,67.7重量份的弹性体树脂(AD-102S,第一毛织工业有限公司)、13.5重量份的环氧树脂(EPPN-502H,日本Chemical有限公司)、7.8重量份的胺类固化剂(DDS,Wako)、1.5重量份的酚类固化剂(BPA,KukdoChemical有限公司)(羟基当量:114g/eq)、0.5重量份的硅烷偶联剂(S-510,Chisso)和9重量份的填料(R-972,Degussa)的混合物溶于作为有机溶剂的环己酮内,用珠磨机充分地搓揉并用涂布器沉积到经离型处理的PET膜上。然后混合物在烘箱中于100℃干燥20分钟,从而制备具有60μm厚度的用于半导体的粘合剂膜。
实施例2
同时包含胺类固化剂和酚类固化剂用于半导体的粘合剂膜的制备
除了基于100重量份的粘合剂膜的固含量,使用12.3重量份的环氧树脂(EPPN-502H,Japan Chemical有限公司)、5.5重量份的胺类固化剂(DDS,Wako)和5.0重量份的酚类固化剂(BPA,Kukdo Chemical有限公司)之外,所述用于半导体的粘合剂膜以与实施例1中相同的方式制备。
实施例3
同时包含胺类固化剂和酚类固化剂的用于半导体的粘合剂膜的制备
除了基于100重量份的粘合剂膜的固含量,使用11.7重量份的环氧树脂(EPPN-502H,Japan Chemical有限公司)、3.9重量份的胺类固化剂(DDS,Wako)和7.2重量份的酚类固化剂(BPA,Kukdo Chemical有限公司)之外,所述用于半导体的粘合剂膜以与实施例1中相同的方式制备。
对比例1
仅包含胺类固化剂作为固化剂的用于半导体的粘合剂膜的制备
除了基于100重量份的粘合剂膜的固含量,使用13.8重量份的环氧树脂(EPPN-502H,Japan Chemical有限公司)和9重量份的胺类固化剂(DDS,Wako),并且未使用酚类固化剂之外,所述用于半导体的粘合剂膜以与实施例1中相同的方式制备。
对比例2
仅包含酚类固化剂作为固化剂的用于半导体的粘合剂膜的制备
除了基于100重量份的粘合剂膜的固含量,使用10.1重量份的环氧树脂(EPPN-502H,Japan Chemical有限公司)和12.7重量份的酚类固化剂(BPA,KukdoChemical有限公司),并且未使用胺类固化剂之外,所述用于半导体的粘合剂膜以与实施例1中相同的方式制备。
对比例3
同时包含胺类固化剂和酚类固化剂的用于半导体的粘合剂膜的制备
除了基于100重量份的粘合剂膜的固含量,使用11.1重量份的环氧树脂(EPPN-502H,Japan Chemical有限公司)、2.5重量份的胺类固化剂(DDS,Wako)和9.2重量份的酚类固化剂(BPA,Kukdo Chemical有限公司)之外,所述用于半导体的粘合剂膜以与实施例1中相同的方式制备。
下表1显示了实施例1至3和对比例1至3中制备的每个粘合剂膜的成分的重量份。
表1
实施例1 | 实施例2 | 实施例3 | 对比例1 | 对比例2 | 对比例3 | |
弹性体树脂 | 67.7 | 67.7 | 67.7 | 67.7 | 67.7 | 67.7 |
环氧树脂 | 13.5 | 12.3 | 11.7 | 13.8 | 10.1 | 11.1 |
胺类固化剂 | 7.8 | 5.5 | 3.9 | 9 | - | 2.5 |
酚类固化剂 | 1.5 | 5 | 7.2 | - | 12.7 | 9.2 |
硅烷偶联剂 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
填料 | 9 | 9 | 9 | 9 | 9 | 9 |
总计(重量份) | 100 | 100 | 100 | 100 | 100 | 100 |
实验例1
固化前储能模量的测量
在60℃层压实施例1至3和对比例1至3中制备的每个粘合剂膜到400至500μm的厚度,然后在50℃/min的温度上升速度、5%的应变和1rad频率条件下用ARES测量在40℃的储能模量。
实验例2
固化后储能模量的测量
在60℃层压实施例1至3和对比例1至3中制备的每个粘合剂膜到450μm的厚度,然后固化超过4次循环的总数,每个循环包含125℃在烘箱中半固化1小时,和150℃在热板上固化10分钟。然后,在50℃/min的温度上升速度、5%的应变和1rad频率条件下用ARES测量在170℃的储能模量。
实验例3
模制后孔隙的观测
实施例1至3和对比例1至3中制备的每个粘合剂膜与10×10mm的盖玻片在60℃层压在一起,用1kgf的力压制到PCB上1秒钟,在125℃固化1小时并在150℃固化1小时,然后在175℃用EMC(SG-8500BC,第一毛织工业有限公司,韩国)模制60秒钟。在175℃模制固化1小时后,用磨光器将样品磨光,然后观察孔隙。用坐标格网尺测量关于粘合剂膜贴附的PCB的面积,5%或更小的孔隙面积比评价为很好的孔隙特性,大于5%且不大于10%的孔隙面积比评价为良好的孔隙特性,大于10%的孔隙面积比评价为差的孔隙特性。
实验例4
固化后芯片剪切强度的测量
切割720μm厚的涂覆二氧化物层的晶片成具有5×5mm尺寸的芯片。所述芯片与实施例1至3和对比例1至3中制备的每个粘合剂膜的在60℃层压在一起,并切割以仅留下粘合部分。具有5×5mm尺寸的上芯片放在具有10×10mm大小的晶片上,然后在热板上于120℃施加10kgf的力5秒钟,以贴附所述芯片到所述粘合剂膜,然后于125℃在烘箱中固化1小时,并于150℃在热板上固化10分钟,或者于125℃在烘箱中固化1小时,150℃在热板上固化10分钟并在175℃固化1小时。然后,在250℃用具有100N巴的Dage 4000以在10μm的高度以100mm/s测量所述芯片剪切强度。
实验例5
耐回流的评价
将实施例1至3和对比例1至3中制备的每个粘合剂膜安装在150μm厚的涂覆二氧化物层并具有10×10mm尺寸的晶片上,然后用1kgf的力在PCB上压制1秒钟,然后在125℃固化1小时并在150℃固化1小时。然后,产物在175℃用EMC(SG-8500BC,第一毛织,韩国)模制60秒,然后在175℃后固化1小时。在后固化后,在85℃,85%RH的恒温恒湿室中使制备的样品吸收水分4小时,然后在260℃的最高温度进行IR回流3次。然后,通过SAT(Sonix quantum 350)的t-scan技术评价样品的剥离。出现剥离的评价为差,没有剥离的评价为良好。
下表2和表3显示了实施例1至3和对比例1至3中制备的粘合剂膜中胺类/酚类固化剂的摩尔%比,以及实验例1至5的测量结果。
表2
表3
比较实施例1至3与对比例1和2可见,同时包含胺类固化剂和酚类固化剂的粘合剂膜呈现固化前和固化后储能模量之间的大的差异。此外,同时包含胺类固化剂和酚类固化剂的粘合剂膜呈现很好的孔隙特性,并具有高固化后的储能模量,因而提供优异的芯片剪切强度和耐回流。
另一方面,比较实施例1至3与对比例1和2可见,当胺类固化剂(y)和酚类固化剂(x)的摩尔%比小于0.3时,固化前后的储能模量间没有有益的变化。此外,当摩尔%比小于0.3时,所述粘合剂膜呈现良好的孔隙特性,但是具有低的固化后储能模量,因此提供不能令人满意的芯片剪切强度和耐回流。
虽然已经结合附图提供了一些实施方式,本领域技术人员明白这些实施方式仅以说明的方式给出,在不背离本发明的精神和范围的情况下可进行各种修改、改变和变化和等同实施方式。本发明的范围应仅由所附权利要求书及其等同方式限定。
Claims (17)
1.一种用于半导体的粘合剂膜,所述粘合剂膜同时包含胺类固化剂和酚类固化剂,所述粘合剂膜具有在1.5至3.0范围内的80%或更多固化后在170℃的储能模量(b)和固化前在40℃的储能模量(a)的比值(b/a)。
2.如权利要求1所述的粘合剂膜,其中,所述胺类固化剂为二氨基二苯基砜。
3.如权利要求1所述的粘合剂膜,其中,所述酚类固化剂为双酚A或双酚F。
4.如权利要求1至3的任一项所述的粘合剂膜,其中,所述粘合剂膜在125℃固化1小时、在150℃固化10分钟和在175℃固化1小时后具有9kgf或更高的模制后芯片剪切强度。
5.如权利要求1至3的任一项所述的粘合剂膜,其中,所述粘合剂膜在125℃固化1小时、在150℃固化10分钟、在175℃模制60秒和在175℃模制固化1小时后,在粘合剂膜贴附区域上具有5%或更小的孔隙面积比。
6.一种用于半导体的粘合剂膜,所述粘合剂膜同时包含胺类固化剂和酚类固化剂,所述粘合剂膜具有在125℃固化1小时和在175℃固化1小时后的9kgf或更高的芯片剪切强度,以及5.0×106达因/cm2或更高的80%固化后在170℃的储能模量。
7.如权利要求6所述的粘合剂膜,其中,所述粘合剂膜在125℃固化1小时、在150℃固化1小时,在175℃模制60秒和在175℃模制固化1小时后,在粘合剂膜贴附区域上具有5%或更小的孔隙面积比。
8.如权利要求6或7所述的粘合剂膜,其中,所述胺类固化剂为二氨基二苯基砜。
9.如权利要求6或7所述的粘合剂膜,其中,所述酚类固化剂为双酚A或双酚F。
10.一种用于半导体的粘合剂膜,所述粘合剂膜包括粘结剂树脂、环氧树脂、填料、胺类固化剂和酚类固化剂,其中,所述胺类固化剂(y)和所述酚类固化剂(x)的摩尔%比(y/x)为0.3至10。
11.如权利要求10所述的粘合剂膜,其中,80%固化后在170℃的储能模量(b)和固化前在40℃的储能模量(a)的比(b/a)为1.5至3.0。
12.如权利要求10所述的粘合剂膜,其中,所述粘合剂膜在125℃固化1小时、在150℃固化10分钟和在175℃固化1小时后具有9kgf或更高的芯片剪切强度。
13.如权利要求10所述的粘合剂膜,其中,基于100重量份的所述粘合剂膜的固含量,所述粘合剂膜包括40至80重量份的所述粘结剂树脂、1至30重量份的所述环氧树脂、1至30重量份的所述填料、0.1至20重量份所述胺类固化剂和0.1至20重量份的所述酚类固化剂。
14.如权利要求10所述的粘合剂膜,其中,所述粘结剂树脂为弹性体树脂。
15.如权利要求10所述的粘合剂膜,其中,所述胺类固化剂为二氨基二苯基砜。
16.如权利要求10至15的任一项所述的粘合剂膜,其中,所述酚类固化剂为双酚A或双酚F。
17.一种半导体装置,所述半导体装置包括布线基板、贴附在所述布线基板的芯片安装表面上的根据权利要求1至16的任一项所述的用于半导体的粘合剂膜,和安装在所述用于半导体的粘合剂膜上的半导体芯片。
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US9169425B2 (en) | 2015-10-27 |
TWI555812B (zh) | 2016-11-01 |
TW201336958A (zh) | 2013-09-16 |
KR101395707B1 (ko) | 2014-05-15 |
CN103160220B (zh) | 2016-03-02 |
US20130154125A1 (en) | 2013-06-20 |
KR20130068889A (ko) | 2013-06-26 |
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