CN111106072A - 半导体封装体和环氧树脂组合物 - Google Patents

半导体封装体和环氧树脂组合物 Download PDF

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Publication number
CN111106072A
CN111106072A CN201910880714.9A CN201910880714A CN111106072A CN 111106072 A CN111106072 A CN 111106072A CN 201910880714 A CN201910880714 A CN 201910880714A CN 111106072 A CN111106072 A CN 111106072A
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epoxy resin
linear polymer
semiconductor package
polyrotaxane
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姜恩实
李政泌
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Samsung Electronics Co Ltd
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Samsung Electronics Co Ltd
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    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
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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
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Abstract

公开了半导体封装体和环氧树脂组合物。用于半导体包封剂的组合物包含环氧树脂、固化剂、填料和聚轮烷，其中所述聚轮烷包含线型聚合物A、端基B和被线型聚合物穿过的环状分子C。环状分子C具有选自由环氧基、氧杂环丁烷基和烷氧基甲硅烷基组成的组中的至少一种官能团，或者具有能够与所述至少一种官能团反应的官能团。

Description

半导体封装体和环氧树脂组合物
相关申请的交叉引用
本申请要求2018年10月29日在韩国知识产权局提交的韩国专利申请号10-2018-0129799的优先权，其公开内容通过引用以其整体并入本文。
技术领域
本发明构思涉及用于半导体包封剂的组合物，其具有高韧性和减少翘曲特性。
背景技术
环氧树脂由于高强度和在粘合强度、热特性、耐化学性、可加工性等方面的出色性质而通常用作半导体包封剂；但是，环氧树脂可能由于高脆性而易于受到外部撞击的影响。特别地，当重复地暴露于大的温差时，如在温度循环测试(TCT)中，环氧树脂可能由于热机械负荷而遭受破裂。为了解决此问题，一般将橡胶添加剂或弹性体加入到环氧树脂中以引起应力松弛。
常规使用的弹性体具有线型结构，所述线型结构具有结合于其末端或侧链的能够与环氧树脂或与固化剂形成交联的官能团或者其他官能团。特别地，当所包含的这类能够与环氧树脂或与固化剂形成交联的官能团不足时，组合物中的弹性体组分可能与树脂组合物分离并且通过与模具形成的间隙渗出到半导体封装体的表面，由此在高温过程如回流过程期间导致外观缺陷。另一方面，当过量地包含这类官能团时，可以与环氧树脂形成足够的交联，由此不会导致渗出到半导体封装体表面的问题；但是，由此形成的固定交联可能降低弹性体的应力松弛效果，并且可能不利地影响后续工序中的层形成和其他材料的润湿。
发明内容
本发明构思的一个方面提供一种用于半导体包封剂的组合物，其通过在固化环氧树脂后允许交联位点自由移动，而能够在不造成外观缺陷的情况下改善韧性和减少翘曲。
根据某些示例实施方案，本公开涉及一种半导体封装体，所述半导体封装体包括：衬底；在所述衬底上的至少一个半导体芯片；和覆盖所述至少一个半导体芯片的半导体包封剂，其中所述半导体包封剂包含：环氧树脂；固化剂；填料；和聚轮烷，其中所述聚轮烷包括线型聚合物A、端基B和被所述线型聚合物A穿过的环状分子C，并且其中所述环状分子C具有选自由环氧基、氧杂环丁烷基和烷氧基甲硅烷基组成的组中的至少一种官能团，或者具有能够与所述至少一种官能团反应的官能团。
根据某些示例实施方案，本公开涉及一种环氧树脂组合物，所述环氧树脂组合物包含：环氧树脂；固化剂；填料；和聚轮烷，其中所述聚轮烷包括线型聚合物A、端基B和被所述线型聚合物A穿过的环状分子C，并且其中所述环状分子C具有选自由环氧基、氧杂环丁烷基和烷氧基甲硅烷基组成的组中的至少一种官能团，或者具有能够与所述至少一种官能团反应的官能团。
根据某些示例实施方案，本公开涉及一种环氧树脂组合物，所述环氧树脂组合物包含：环氧树脂；固化剂；填料；和聚轮烷，其中所述聚轮烷包括线型聚合物A、端基B和被所述线型聚合物A穿过的环状分子C，其中所述线型聚合物A为聚硅氧烷、聚乙二醇、聚丁二烯或其组合，其中所述端基B为选自由以下各项组成的组中的至少一种：金刚烷基、硅倍半氧烷基、苯基、取代或未取代的苄基、环糊精基和硅烷基，并且其中所述环状分子C具有选自由环氧基、氧杂环丁烷基和烷氧基甲硅烷基组成的组中的至少一种官能团，或者具有能够与所述至少一种官能团反应的官能团。
附图说明
通过以下结合附图的详细描述将更清楚地理解本公开的上述和其他方面、特征和优点，在所述附图中：
图1示出了根据本发明构思的一个示例实施方案的聚轮烷的行为以及由聚轮烷形成的交联；
图2示出了根据本发明构思的一个示例实施方案的不同类型的聚轮烷；
图3是示出根据本发明构思的一个示例实施方案和比较例的包封剂的应力-膨胀率的图；
图4是示出根据本发明构思的一个示例实施方案，基于用于包封剂的组合物的杨氏模量和热膨胀系数预测的半导体包封剂的翘曲程度的图；
图5是根据本发明构思的一个示例实施方案，可以结合包封剂使用的半导体封装体的结构的横截面图；以及
图6是根据本发明构思的一个示例实施方案，包括可以结合包封剂使用的半导体封装体的集成电路装置的横截面图。
具体实施方式
在下文中，将参照附图描述本发明构思的示例实施方案。
根据一个示例实施方案，用于半导体包封剂的组合物可以包含环氧树脂、固化剂、填料和交联剂，并且还可以包含用于缩短用于半导体包封剂的组合物的固化时间的固化促进剂，并且甚至还可以包含用于改善半导体包封剂的性质的添加剂。
在根据示例实施方案的用于半导体包封剂的组合物中，可以包含环氧树脂以进行固化和粘合，并且环氧树脂可以是每分子含有至少一个环氧基的化合物，并且可以与结合于作为交联剂使用的聚轮烷的环状分子C的羟基、氨基和酐基反应，以形成交联。
例如，对于环氧树脂来说，可以使用液态环氧树脂、固态环氧树脂或其混合物。
例如，液态环氧树脂可以包括选自由以下各项组成的组中的一种或两种以上的混合物：双酚A液态环氧树脂、双酚F液态环氧树脂、三官能以上的液态环氧树脂、橡胶改性的液态环氧树脂、氨基甲酸酯改性的液态环氧树脂、丙烯酸改性的液态环氧树脂和光敏液态环氧树脂。更优选地，液态环氧树脂可以包括双酚A液态环氧树脂。
对于固态环氧树脂来说，可以使用在室温为固态或接近固态、同时具有一个或多个官能团、并且优选地具有30至100℃的软化点的环氧树脂。例如，固态环氧树脂可以包括选自由以下各项组成的组中的一种或两种以上的混合物：基于双酚的环氧树脂、基于苯酚酚醛清漆的环氧树脂、基于邻甲酚酚醛清漆的环氧树脂、多官能环氧树脂、基于胺的环氧树脂、含杂环的环氧树脂、多环芳烃环氧树脂、取代的环氧树脂、基于萘酚的环氧树脂、基于二环戊二烯的环氧树脂、非酚类环氧树脂及它们的衍生物。
可商购的这类固态环氧类树脂可以包括以下环氧树脂。基于双酚的固态环氧树脂的实例可以包括：YD-017H、D-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(KukdoChemical)等。基于酚类酚醛清漆的树脂的实例可以包括：Epikote 152和Epikote 154(Yuka Shell Epoxy Co.LTD.)；EPPN-201(Nippon Kayaku Co.,LTD.)；DN-483(DowChemical)；以及YDPN-641、YDPN-638A80、YDPN-638、YDPN-637、YDPN-644、YDPN-631(KukdoChemical)等。基于邻甲酚酚醛清漆的树脂的实例可以包括：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(KukdoChemical)等；EOCN-102S、EOCN-103S、EOCN-104S、EOCN-1012、EOCN-1025、EOCN-1027(Nippon Kayaku Co.LTD.)等；YDCN-701、YDCN-702、YDCN-703、YDCN-704(Dokdo ChemicalCo.LTD.)等；以及Epiclon N-665-EXP(Dainippon Ink and Chemicals,Inc.)等。基于双酚的酚醛清漆环氧树脂的实例可以包括KBPN-110、KBPN-120、KBPN-115(Kukdo Chemical)等。多官能环氧树脂的实例可以包括EPPN-501HY、EPPN-502H(Nippon Kayaku Co.LTD.)等；以及KDT-4400、KDMN-1055、KDMN-1065(Kukdo Chemical)等。基于胺的环氧树脂的实例可以包括：Epikote 604(Yuka Shell Epoxy Co.LTD.)等；YH-434(Dokdo Chemical Co.LTD.)等；TETRAD-X,TETRAD-C(Mitsubishi Gas Chemical Company,Inc.)等；以及ELM-120(Sumitomo Chemical Company,Ltd.)等。含杂环的环氧树脂的实例可以包括：异氰尿酸1,3,5-三缩水甘油酯(Ciba Specialty Chemicals Holding Inc.的PT-810)等。多环芳烃环氧树脂的实例可以包括：9,10-蒽二醇-1,4-二氢化物二缩水甘油醚(Mitsubishi GasChemical Company,Inc.的YX-8800)等。取代的环氧树脂的实例可以包括：ERL-4234、ERL-4299、ERL-4221、ERL-4206(UCC Co.,Ltd.)等。基于萘酚的环氧树脂的实例可以包括：Epiclon HP-4032、Epiclon HP-4032D、Epiclon HP-4700、Epiclon HP-4701(DainipponInk and Chemicals,Inc.)等。基于二环戊二烯的环氧树脂的实例可以包括：Epiclon EXA-7200(Dainippon Ink and Chemicals,Inc.)、TACTIX-556(Dow Chemical Company)等。非酚类环氧树脂的实例可以包括：NC-3000、NC-3000H(Nippon Kayaku Co.,Ltd.)等；以及YX-4000、YL-6121(Mitsubishi Gas Chemical Company Inc.)等。这些环氧树脂可以单独使用或两种以上组合使用。
相对于用于包封剂的组合物的总重量，可以包含在1重量％至30重量％范围内、优选在2重量％至15重量％范围内的环氧树脂。在上述范围内可以实现期望的可靠性和力学性能。
在示例实施方案中，固化剂可以包含能够与环氧树脂反应的官能团，并且特别地，可以包含能够与作为交联剂使用的聚轮烷的环状分子C形成交联的官能团。此处使用的固化剂可以是相关领域中已知的任何固化剂。例如，作为固化剂，可以单独地或组合地使用基于聚醚胺的化合物、基于聚酰胺的化合物、基于酰胺胺的化合物、基于亚乙基胺的化合物、基于脂环族胺的化合物、基于芳族胺的化合物、酚醛树脂、基于酐的化合物等。
可商购的这类固化剂可以包括以下固化剂。基于聚醚胺的固化剂的实例可以包括：JEFFAMINE T-403、JEFFAMINE D-230(Huntsman Advanced Materials)等。基于聚酰胺的固化剂和基于酰胺胺的固化剂的实例可以包括：VERSAMIDE 125、GENAMID 490(BASF)等。基于亚乙基胺的固化剂的实例可以包括：二亚乙基三胺(DETA)、三亚乙基四胺(TETA)、四亚乙基五胺(TEPA)、N-氨基乙基哌嗪(AEP)等。基于脂环族胺的固化剂的实例可以包括：双(对氨基环己基)甲烷(PACM)、二氨基环己烷(DACH)等。基于芳族胺的固化剂的实例可以包括：亚甲基二苯胺(MDA)、亚甲基双(邻乙基苯胺)(MBOEA)、间苯二胺(M-PDA)、二氨基苯基砜(DDS)等。
酚醛树脂的实例可以包括：酚类酚醛清漆树脂、烷基苯酚酚醛清漆树脂、双酚A酚醛清漆树脂、二环戊二烯型酚醛树脂、xylok型酚树脂、萜改性的酚醛树脂、甲酚/萘酚树脂、聚乙烯基苯酚、苯酚/萘酚树脂、含α-萘酚骨架的酚醛树脂、含三嗪的甲酚酚醛清漆树脂、多官能树脂等。可商购的酚醛树脂可以包括以下酚醛树脂。酚类酚醛清漆树脂的实例可以包括：HF-4M(Meiwa Plastic Industries,LTD.)等。xylok型酚树脂的实例可以包括：MEH-7800(Meiwa Plastic Industries,LTD.)等。多官能树脂的实例可以包括：MEH-7500、MEH-7600-4H(Meiwa Plastic Industries,LTD.)等。
基于酐的化合物可以包括：四氢邻苯二甲酸酐(THPA)、六氢邻苯二甲酸酐(HHPA)、甲基四氢邻苯二甲酸酐(MeTHPA)、甲基六氢邻苯二甲酸酐(MeHHPA)、甲基降冰片烯二酸酐(nadicmethyl anhydride)(NMA)、水解甲基降冰片烯二酸酐(hydrolyzed methylnadicanhydride)(HNMA)、邻苯二甲酸酐(PA)等。
在示例实施方案中，相对于用于包封剂的组合物的总重量，可以包含在1重量％至30重量％范围内、更优选在2重量％至15重量％范围内的固化剂，并且在上述范围内可以实现期望的可靠性和力学性能。特别地，关于环氧树脂与固化剂的摩尔当量比，环氧树脂的环氧基与固化剂的所有羟基、胺基或酐基的摩尔当量比可以优选的在0.8至1.2的范围内。在上述范围内可以提高组合物的固化程度，由此提高尺寸稳定性。
在示例实施方案中，可以使用固化促进剂以缩短固化时间，由此在进行半导体制造过程的同时使环氧树脂和固化剂完全固化。例如，固化促进剂可以包括选自以下各项的一种或两种以上的混合物：叔胺、胺加成物、基于咪唑的化合物、基于有机膦或鏻盐的化合物、硼化合物、有机金属化合物等。
叔胺的实例可以包括：苄基二甲胺、三乙醇胺、三亚乙基二胺、二乙基氨基乙醇、三(二甲基氨基甲基)苯酚、2-2-(二甲基氨基甲基)苯酚、2,4,6-三(二氨基甲基)苯酚等。胺加成物的实例可以包括：Amicure PN-23、Amicure PN-40、Hardener X-3661S、Hardner X-3670S(Ajinomoto Fine Techno Co.,Inc.)等；以及Novacure HX-3742、Novacure HX-3721(Asahi Kasei Corporation)等。基于咪唑的化合物的实例可以包括诸如2-甲基咪唑、2-十七烷基-1H-咪唑和2-苯基-4-甲基-5-二羟基甲基咪唑的化合物，并且可以包括以下可商购的产品：PN-23、PN-40(Ajinomoto Fine Techno Co.,Inc.)等；以及2P4MZ、2MA-OK、2MAOK-PW、2P4MHZ(Sakook Chemical Co.,Inc.)等。基于有机膦或鏻盐的化合物的实例可以包括诸如四苯基鏻四苯基硼酸盐、四苯基鏻四对甲基苯基硼酸盐和四苯基溴化鏻的化合物，并且可以包括作为可商购的产品的TPP-K、TPP-MK、TPP-PB(Hokko Chemical Industry Co.,Ltd.)等。硼化合物的实例可以包括：三苯基膦四苯基硼酸酯、四苯基硼酸盐、三氟硼烷-正己胺、三氟硼烷单乙胺、四氟硼烷三乙胺、四氟硼烷胺等。有机金属化合物的实例可以包括乙酰丙酮铬、乙酰丙酮锌、乙酰丙酮镍等。
相对于用于包封剂的组合物的总重量，可以包含在0.01重量％至5重量％范围内、更优选在0.1重量％至1.5重量％范围内的固化促进剂。当包含在上述范围内的固化促进剂时，固化促进剂可以防止突然的固化反应，并且可以用于获得期望的流动性以及缩短固化时间，实现高效的包封过程。
当在半导体制造过程期间形成晶片级模制品时，可能由于包封剂的热膨胀系数(CTE)比硅的热膨胀系数高而出现热应力，并且这可能造成半导体封装体中的翘曲并且甚至是裂缝。在示例实施方案中，可以使用填料来降低用于包封剂的组合物的CTE，以缓解在使环氧树脂固化时的收缩，并且改善包封剂的强度。
填料可以具有在0.1至45μm范围内的平均粒度。例如，填料可以包括无机填料，如热解法二氧化硅、晶体二氧化硅和用氧化铝或二氧化硅涂覆的铜，或者可以包括有机填料，如硅粉。填料可以具有选自由羟基、氨基和酐基组成的组中的至少一种官能团。备选地，在使用前，填料可以表面重整以具有环氧基、氧杂环丁烷基或烷氧基甲硅烷基。
填料的官能团，如羟基、氨基或酐基，可以与作为交联剂使用的聚轮烷的环状分子C的环氧基、氧杂环丁烷基或烷氧基甲硅烷基反应以形成交联。另外，如此表面重整以具有环氧基、氧杂环丁烷基或烷氧基甲硅烷基的填料可以与聚轮烷的环状分子C的羟基、氨基或酐基反应以形成交联。
相对于(半导体)包封剂的组合物的总重量，可以包含在68重量％至92重量％范围内的填料。低于68重量％的填料含量可能降低包封剂的强度；可能无法实现低的热膨胀；并且可能使水分容易渗透，这对可靠性特性是不利的。另一方面，超过92重量％的填料含量可能无法实现应力降低，并且可能由于减小的流体特性而降低成型性。
在示例实施方案中，交联剂可以包含滑环(slide-ring)材料，其具有在半导体包封剂内可自由移动的交联。参照图1，当含有滑环材料时，用于包封剂的组合物在使环氧树脂固化后可以形成可自由移动的交联结构，由此分散和缓解由拉伸、弯曲等造成的应力。因此，可以改善基于环氧树脂的半导体包封剂的韧性，所述韧性对半导体封装体的可靠性性能有极重要的影响，此外，可以缓解翘曲，所述翘曲是由热应力造成的晶片级模制品中的问题之一。另外，可以改善在后续过程中与半导体包封剂接触的其他材料的层形成和润湿。
在示例实施方案中，滑环材料可以通过聚轮烷来实现。聚轮烷包括线型聚合物A、端基B和环状分子C。根据线型聚合物A、端基B和环状分子C之间的连接性，或者根据各组分的数量，聚轮烷可以分类为主链型聚轮烷、侧链型聚轮烷、聚[2]轮烷或聚[3]轮烷，其可以在示例实施方案中无限制地使用。
在示例实施方案中，聚轮烷可以包括线型聚合物A、端基B和被所述线型聚合物A穿过的环状分子C。线型聚合物A可以包括侧链，并且环状分子C可以存在于线型聚合物A的主链或侧链上。
参照图2，聚轮烷可以具有以下结构：其中端基B存在于线型聚合物A的两端的结构，或其中端基B存在于线型聚合物A的侧链的一端，侧链的另一端被线型聚合物A的主链封端的结构。备选地，端基B存在于线型聚合物A的一端，线型聚合物A的另一端被另一环状分子C封端。
环状分子C可以不能通过端基B、线型聚合物A的主链或另一环状分子C脱离线型聚合物A，尽管其能够响应于温度变化或外部刺激而沿线型聚合物A的轴转动或滑动。
参照图3，使用具有线型结构的常规交联剂的环氧固化产物具有以下问题：随着交联密度增加，脆性增大(参见例如在图3左上区域中的“线型弹性体”和虚线图线)。然而，通过使用示例实施方案中的聚轮烷，因为环状分子C沿线型聚合物A的轴转动或自由滑动，由此分散应力(参见例如在图3右上区域中的“滑环弹性体”和实线图线)，所以能够改善半导体包封剂的韧性，同时通过控制环状分子C的数量或环状分子C中反应性官能团的数量保持所需的交联密度。另外，参照图4，通过加入聚轮烷并且由此降低半导体包封剂的杨氏模量E，能够缓解半导体包封剂的翘曲，因此防止裂缝形成。
在示例实施方案中，聚轮烷的线型聚合物A可以是具有链结构的聚合物，并且可以是聚硅氧烷、聚乙二醇、聚丁二烯或其组合。线型聚合物A可以包含可与端基B的前体反应的官能团以与端基B键合。此反应性官能团可以适当地选自能够与端基B前体反应，并且优选地不与环状分子C的官能团反应的官能团。
端基B可以与存在于线型聚合物A两端的官能团反应以与线型聚合物A的末端键合，并且可以是任意官能团，只要其具有大到足以防止环状分子C脱离线型聚合物A的结构即可。优选地，端基B可以包括选自由以下各项组成的组中的一种或多种：金刚烷基、硅倍半氧烷基、苯基、取代或未取代的苄基、环糊精基和硅烷基，其中苄基的取代基可以包括选自由以下各项组成的组中的一种或多种：具有1至5个碳原子的烷基、羟基、卤素基团、氰基、磺酰基、羧基、氨基、苯基和酯基。
环状分子C可以具有能够与环氧树脂、固化剂或填料反应形成交联的官能团。优选地，环状分子C可以具有选自由环氧基、氧杂环丁烷基和烷氧基甲硅烷基组成的组中的至少一种官能团，或者可以具有能够与所述至少一种官能团反应的官能团。
在环状分子C的官能团中，选自由环氧基、氧杂环丁烷基和烷氧基甲硅烷基组成的组中的至少一种官能团可以与填料反应以形成交联，所述填料具有选自由羟基、氨基和酐基组成的组中的一种或多种官能团。
另外，能够与环状分子C的选自由环氧基、氧杂环丁烷基和烷氧基甲硅烷基组成的组中的至少一种官能团反应的官能团可以包括选自由羟基、氨基和酐基组成的组中的一种或多种。此外，该官能团可以与填料反应并且与填料形成交联，所述填料表面重整为具有环氧基、氧杂环丁烷基或烷氧基甲硅烷基。
示例实施方案的聚轮烷中的线型聚合物A与环状分子C的摩尔当量比是影响用于半导体包封剂的组合物的应力松弛特性的因素，并且此摩尔当量比基于线型聚合物A的长度和环状分子C的宽度来确定。在示例实施方案中，环状分子C与线型聚合物A的摩尔当量比可以优选为2以上，以使得能够在使环氧树脂固化后形成可自由移动的交联结构。
在示例实施方案中，包含率可以定义为聚轮烷的线型聚合物A中实际包含的环状分子C的数量N’与可以包含的环状分子C的最大数量N的比率。当线型聚合物A中实际包含的环状分子C的数量N’在2以上的范围内时，包含率可以在0.05至0.70的范围内，更优选地，在0.10至0.50的范围内。低于0.05的包含率可能造成环氧树脂固化后交联可移动性和应力分散的不期望的降低；然而，当包含率超过0.70时，环状分子C可能过于致密地设置，由此使环状分子C的可移动性降低。可以通过相关领域中已知的方法适当地控制包含率。
在示例实施方案中，线型聚合物A的分子量可以在1,000至100,000的范围内，优选的，在3,000至40,000的范围内。低于1,000的分子量可能使交联可移动性和耐热性在固化后降低，而超过100,000的分子量可能不期望地降低用于包封剂的组合物的流动性和易处理性。此处的分子量可以是如通过凝胶渗透色谱法测量的相对于标准聚苯乙烯的转换分子量。
在示例实施方案中，相对于用于包封剂的组合物的总重量，可以包含在0.01重量％至7重量％范围内、优选在0.05重量％至5重量％范围内的交联剂。低于0.01重量％的交联剂含量可能无法与环氧树脂、固化剂或填料形成足够的交联，由此减少改善韧性和应力分散的效果，并且可能造成翘曲；然而，超过7重量％的交联剂含量可能降低用于包封剂的组合物的流动特性，这可能导致包封剂制备和封装过程期间的差的产率。
根据预期目的，除了上述环氧树脂、固化促进剂、填料和聚轮烷以外，示例实施方案中的用于包封剂的组合物还可以包含多种在热固性树脂组合物中常用的添加剂。这样的添加剂可以包括软化剂、熔剂、增韧剂、促粘剂、分散剂、着色剂等，其中这样的添加剂的含量可以根据需要调整。
在示例实施方案中，根据用于包封剂的组合物的各组分的性质，半导体包封剂的原始形式可以是液体、粉末形式的固体、颗粒形式的固体或膜形式的固体。
图5是根据示例实施方案的可以结合半导体包封剂使用的半导体封装体的结构的横截面图。参照图5，半导体封装体100可以包括：衬底5；设置在衬底5上的模片连接膜4；设置在衬底5上并且通过模片连接膜4连接至衬底5的芯片3；多个焊球2；连接件6，如接合线，其用于将芯片3和衬底5彼此电连接；和包封剂1，所述包封剂包封芯片3和连接件6，同时保护衬底5以及安装在衬底5上的包括连接件6和芯片3的安装结构。包封剂1可以形成为完全覆盖在衬底5上的芯片3和连接件6。
包封剂1由根据示例实施方案的用于包封剂的组合物得到。通过使用示例实施方案的用于包封剂的组合物，在形成晶片级模制品时可以减小热应力，由此可以缓解半导体包封剂的翘曲。
图6是根据示例实施方案的使用可以结合包封剂使用的半导体封装体的集成电路装置的横截面图。参照图6，集成电路装置200可以包括：包括衬底内部布线212、连接端子214和焊球216的封装衬底210，和在封装衬底210上依次堆叠的多个半导体芯片220，以及连接结构222和232。多个半导体芯片220以及连接结构222和232可以通过连接部250如隆起物(bump)电连接至封装衬底210的连接端子214。
可以在多个半导体芯片220上连接控制芯片230。可以通过包封剂240将多个半导体芯片220的堆叠结构和控制芯片230包封在封装衬底210上。包封剂240可以具有与参照图5描述的包封剂1类似的配置。
包封剂240可以包含根据示例实施方案的用于包封剂的组合物。通过使用根据示例实施方案的用于包封剂的组合物，在形成晶片级模制品时可以减小热应力，由此可以缓解半导体包封剂的翘曲。
同时，示例实施方案涉及环氧树脂组合物。在一些实施方案中，环氧树脂组合物可以含有环氧树脂、固化剂、固化促进剂、填料和交联剂，并且还可以含有改善环氧树脂的性质所需的添加剂。
除了作为半导体包封剂使用以外，根据示例实施方案的环氧树脂组合物还可以用于涉及粘结剂、涂料、层压体、铸造材料和模塑材料等的多种其他领域。
环氧树脂的杨氏模量E可以在7至20GPa的范围内。低于7Gpa的杨氏模量可能使得难以从外部来源获得机械稳定性；然而，超过20GPa的杨氏模量可能造成晶片的过度翘曲，这在过程进行期间造成处理困难性。因此，在上述范围之外的环氧树脂的杨氏模量E可能不是优选的。
在示例实施方案中，环氧树脂的断裂韧性可以在0.3至10MPa·m1/2的范围内。低于0.3MPa·m1/2的断裂韧性可能使得难以从外部来源获得机械稳定性；然而，超过10MPa·m1/2的断裂韧性可能由于可得到组合物的限制而降低可加工性。因此，在上述范围之外的环氧树脂的断裂韧性可能不是优选的。
实施例
1.聚轮烷的制备
合成例
将平均分子量为35,000的二氨基聚乙二醇(二氨基PEG)(7.2g)加入含有溶解于水中的α-环糊精(41g)的溶液，并且将溶液在室温搅拌2天。将通过溶液离心得到的白色沉淀冷冻干燥以从其中蒸发和移除水。将由此制备的白色固体产物(拟轮烷)溶解于无水N,N-二甲基甲酰胺(DMF)(65mL)中。将1-金刚烷甲酸(0.19g)、BOP[(苯并三唑-1-基氧基)-三(二甲基氨基)鏻六氟磷酸盐](0.47g)和DIPEA(N,N-二异丙基乙胺)(0.19mL)溶解于无水DMF(5mL)中，并且将其缓慢地滴到溶解于无水DMF中的白色固体产物上。在搅拌两天后，通过使用二甲基亚砜(DMSO)和水的渗析连同冷冻干燥移除残留的有机溶剂，并且得到作为沉淀的聚轮烷，所述聚轮烷的颜色为乳白色。如通过1H-NMR分析测量的，发现由此合成的聚轮烷具有0.21的包含率，每聚乙二醇分子的轴包含38个α-环糊精分子。
2.用于包封剂的组合物的制备以及包封剂的制备
实施例1
将由化学式1表示的苯酚酚醛清漆树脂和由化学式2表示的多官能树脂以3:1的比率合并以制备环氧树脂，并且将所述苯酚酚醛清漆树脂和所述多官能树脂以5:1的比率合并以制备基于酚树脂的固化剂。接下来，将5重量％的环氧树脂、4重量％的固化剂、90重量％的作为填料的非晶二氧化硅和0.3重量％的着色剂分散并且与1.2重量％的在合成例中合成的聚轮烷辊压混合，以制备用于包封剂的组合物。
[化学式1]
Figure BDA0002205798100000131
[化学式2]
Figure BDA0002205798100000132
通过使用由所述组合物形成的环氧模塑复合物(epoxy mold compound，EMC)，将晶片在135℃模塑600秒，之后在150℃进行后固化2小时以制备半导体包封剂。
比较例1
在与实施例1中的条件相同的条件下制备环氧树脂和固化剂。接下来，将5重量％的环氧树脂、4重量％的固化剂、90重量％的作为填料的非晶二氧化硅和0.3重量％的着色剂分散并且与1.2重量％的硅油(环氧基和聚醚改性的二甲基硅氧烷，Dow Corning,ToraySF 8421EG Fluid)辊压混合，以制备用于包封剂的组合物。
通过使用由此组合物形成的环氧模塑复合物(EMC)，将晶片在135℃模塑600秒，之后在150℃进行后固化2小时以制备半导体包封剂。
比较例2
除了含有0.96重量％的硅油以外，在与比较例1中的条件相同的条件下制备用于包封剂的组合物。通过使用此组合物，制备半导体包封剂。
比较例3
除了含有0.72重量％的硅油以外，在与比较例1中的条件相同的条件下合成用于包封剂的组合物。通过使用此组合物，制备半导体包封剂。
3.外观缺陷测试
检查在实施例1和比较例1至3中制备的半导体包封剂是否存在外观缺陷。将半导体包封剂放置在热板上并加热，如表1中所示，“O”表示存在外观缺陷，而“X”表示不存在外观缺陷。
[表1]在半导体包封剂上是否存在外观缺陷
加热温度 实施例1 比较例1 比较例2 比较例3
140℃ X X X X
160℃ X X X X
180℃ X X X X
200℃ X X X X
220℃ X X X X
240℃ X X X X
260℃ X O O X
280℃ X O O X
300℃ X O O X
4.杨氏模量E的测量
分别在25℃和260℃测量在实施例1和比较例1至3中制备的半导体包封剂的杨氏模量E，结果显示在表2中。
采用等式1计算杨氏模量E，其中Lv、W和H值各自使用测微器测量，并且P/Y值使用TENSILON弯曲强度测试机测量。
Figure BDA0002205798100000141
Lv＝支撑体的跨度
W＝试样的宽度
H＝试样的高度
P/Y＝载荷-挠曲曲线的斜率
[表2]半导体包封剂的杨氏模量
Figure BDA0002205798100000151
5.翘曲的测量
使用Shadow Moiré技术(AKROMETRIX Thermoire AXP)测量的在实施例1和比较例1至3中制备的半导体包封剂的样品的晶片翘曲显示在表3中。
[表3]半导体包封剂的晶片翘曲
Figure BDA0002205798100000152
6.电介质层涂覆测试
在实施例1和比较例1至3中制备的EMC的表面上，通过旋涂形成厚度为5μm的电介质层，并且在320℃进行后固化1.5小时，用裸眼检查其外观。
在实施例1中，电介质层均匀地涂覆在EMC的表面上，因此不造成排斥和反润湿问题，而在比较例1至3中，由于EMC和亲水性的电介质层之间的表面能的差异，润湿性降低，因此观察到排斥和反润湿问题。
根据本发明构思的示例实施方案，通过包含聚轮烷以与环氧树脂形成交联，可以提供能够抑制外观缺陷的形成、改善韧性并且减少翘曲的用于半导体包封剂的组合物。
尽管上文已经示出并且描述了示例实施方案，但是对本领域技术人员显然的是，在不背离如由所附权利要求限定的本发明构思的范围的情况下，可以进行改变和变化。

Claims (20)

1.一种半导体封装体，所述半导体封装体包括：
衬底；
在所述衬底上的至少一个半导体芯片；和
覆盖所述至少一个半导体芯片的半导体包封剂，
其中所述半导体包封剂包含：
环氧树脂；
固化剂；
填料；和
聚轮烷，
其中所述聚轮烷包括线型聚合物A、端基B和被所述线型聚合物A穿过的环状分子C，并且
其中所述环状分子C具有选自由环氧基、氧杂环丁烷基和烷氧基甲硅烷基组成的组中的至少一种官能团，或者具有能够与所述至少一种官能团反应的官能团。
2.权利要求1所述的半导体封装体，其中所述线型聚合物A为聚硅氧烷、聚乙二醇、聚丁二烯或其组合。
3.权利要求1所述的半导体封装体，其中所述端基B为选自由以下各项组成的组中的至少一种：金刚烷基、硅倍半氧烷基、苯基、取代或未取代的苄基、环糊精基和硅烷基。
4.权利要求1所述的半导体封装体，其中所述聚轮烷具有以下结构：其中所述端基B存在于所述线型聚合物A的两端的结构；其中所述端基B存在于所述线型聚合物A的侧链的一端，所述侧链的另一端被所述线型聚合物A的主链封端的结构；或其中所述端基B存在于所述线型聚合物A的一端，所述线型聚合物A的另一端被另一环状分子C封端的结构。
5.权利要求1所述的半导体封装体，其中所述环状分子C存在于所述线型聚合物A的主链或侧链上。
6.权利要求1所述的半导体封装体，其中能够与所述环状分子C的选自由环氧基、氧杂环丁烷基和烷氧基甲硅烷基组成的组中的至少一种官能团反应的官能团为选自由羟基、氨基和酐基组成的组中的至少一种。
7.权利要求1所述的半导体封装体，其中所述至少一种官能团或者所述能够与所述至少一种官能团反应的官能团存在于所述环状分子C的主链、侧链或接枝链上。
8.权利要求1所述的半导体封装体，其中在每个线型聚合物A中包含两个以上环状分子C。
9.权利要求1所述的半导体封装体，其中所述填料具有选自由羟基、氨基和酐基组成的组中的至少一种官能团。
10.权利要求1所述的半导体封装体，其中相对于所述半导体包封剂的总重量，所述半导体包封剂包含1重量％至30重量％的所述环氧树脂、1重量％至30重量％的所述固化剂、68重量％至92重量％的所述填料和0.01重量％至7重量％的所述聚轮烷。
11.权利要求1所述的半导体封装体，其中在所述环氧树脂中存在的环氧基与在所述固化剂中存在的所有羟基、胺基或酐基的摩尔当量比在0.8至1.2的范围内。
12.权利要求1所述的半导体封装体，其中所述半导体包封剂还包含固化促进剂，其中相对于所述半导体包封剂的总重量，所述固化促进剂的含量在0.01重量％至5重量％的范围内。
13.权利要求1所述的半导体封装体，其中所述聚轮烷的包含率在0.05至0.7的范围内。
14.权利要求1所述的半导体封装体，其中所述线型聚合物A的分子量在1,000至100,000的范围内。
15.权利要求1所述的半导体封装体，其中所述聚轮烷为选自由主链型聚轮烷、侧链型聚轮烷、聚[2]轮烷和聚[3]轮烷组成的组中的至少一种。
16.一种环氧树脂组合物，所述环氧树脂组合物包含：
环氧树脂；
固化剂；
填料；和
聚轮烷，
其中所述聚轮烷包括线型聚合物A、端基B和被所述线型聚合物A穿过的环状分子C，并且
其中所述环状分子C具有选自由环氧基、氧杂环丁烷基和烷氧基甲硅烷基组成的组中的至少一种官能团，或者具有能够与所述至少一种官能团反应的官能团。
17.权利要求16所述的环氧树脂组合物，其中相对于所述环氧树脂组合物的总重量，所述环氧树脂组合物包含1重量％至30重量％的所述环氧树脂、1重量％至30重量％的所述固化剂、68重量％至92重量％的所述填料和0.01重量％至7重量％的所述聚轮烷。
18.权利要求16所述的环氧树脂组合物，其中所述环氧树脂组合物的杨氏模量在7至20GPa的范围内。
19.权利要求16所述的环氧树脂组合物，其中所述环氧树脂组合物的断裂韧性在0.3至10MPa·m1/2的范围内。
20.一种环氧树脂组合物，所述环氧树脂组合物包含：
环氧树脂；
固化剂；
填料；和
聚轮烷，
其中所述聚轮烷包括线型聚合物A、端基B和被所述线型聚合物A穿过的环状分子C，
其中所述线型聚合物A为聚硅氧烷、聚乙二醇、聚丁二烯或其组合，
其中所述端基B为选自由以下各项组成的组中的至少一种：金刚烷基、硅倍半氧烷基、苯基、取代或未取代的苄基、环糊精基和硅烷基，并且
其中所述环状分子C具有选自由环氧基、氧杂环丁烷基和烷氧基甲硅烷基组成的组中的至少一种官能团，或者具有能够与所述至少一种官能团反应的官能团。
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