CN105324454A - 用于形成切割膜的粘着层的组合物及切割膜 - Google Patents

用于形成切割膜的粘着层的组合物及切割膜 Download PDF

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Publication number
CN105324454A
CN105324454A CN201480021827.9A CN201480021827A CN105324454A CN 105324454 A CN105324454 A CN 105324454A CN 201480021827 A CN201480021827 A CN 201480021827A CN 105324454 A CN105324454 A CN 105324454A
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China
Prior art keywords
composition
adhesive coating
cutting
formation
cutting film
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CN201480021827.9A
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CN105324454B (zh
Inventor
金荣国
S·R·金
金熹正
曺正镐
李光珠
金丁鹤
南承希
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LG Corp
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LG Chemical Co Ltd
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Priority claimed from PCT/KR2014/012283 external-priority patent/WO2015088282A1/ko
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    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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Abstract

本发明涉及一种用于形成切割膜的粘着层的组合物，其包含：含有一个以上反应性官能团的硅化合物油；粘着粘合剂；和光引发剂，其中含有一个以上反应性官能团的硅化合物油与粘着粘合剂的重量比为0.01％至4.5％；涉及一种包括含有所述组合物的粘着层的切割膜、和包括所述切割膜的切割晶片接合膜、及使用所述切割晶片接合膜的半导体晶圆的切割方法。

Description

用于形成切割膜的粘着层的组合物及切割膜
技术领域
本发明涉及一种用于形成切割膜的粘着层的组合物及切割膜。
背景技术
通常，制备半导体晶片的过程包括在晶圆(wafer)上形成微图案的工艺，并抛光晶圆以满足最终装置规格的封装(packaging)的工艺。
封装工艺包括：晶圆检测过程，检测半导体晶片的缺陷；切割工艺，切割晶圆以便分离为单个的晶片；晶片接合工艺(diebondingprocess)，将分离的晶片附着至引线框架(leadframe)或电路膜(circuitfilm)的安装板；引线接合工艺，使用电连接构件如导线来将装配在半导体晶片上的晶片衬垫(chippad)和引线框架或电路膜的电路图案连接；模塑工艺，使用密封材料来覆盖半导体晶片的外部以保护半导体晶片的内部电路和其他组件；修整工艺，切割连接引线的堤坝杠(dambar)；成型(forming)工艺，将引线弯曲成所需的形状；和成品检测工艺，用于检测完成的封装的缺陷，等。
在切割过程中，利用金刚石砂轮等将晶圆切割成规定厚度。此处，为了固定晶圆，在适当条件下将切割膜层压在晶圆的背面，然后进行所述工艺。并且，为了将所切割的各个晶片附着至电路板而使用晶片接合膜(diebondingfilm)(接合膜)。
同时，切割工艺包括：使用切割刀片来切割半导体晶圆的步骤；将紫外线照射至半导体晶圆的基底膜，并拾取通过半导体晶圆的切割而分离的单个晶片的步骤，但是存在以下问题：因为在拾取过程期间发生膜之间固定，和因膜之间的剥离(peel)强度过大而在拾取期间拾取晶片的成功率被降低或者在拾取过程中产生晶片裂纹的问题。
发明内容
技术目的
本发明提供一种用于形成切割膜的粘着层的组合物，以提供切割晶片接合膜，其可防止在切割过程中发生膜之间固定以增加拾取成功率，并可展现出较高的晶片剪切强度(dieshearstrengh)以防止粘着强度降级而导致的剥离。
本发明还提供一种使用用于形成切割膜的粘着层的上述组合物的切割膜。
本发明还提供一种包含所述切割膜的切割晶片接合膜。
本发明还提供一种使用所述切割膜的半导体晶圆的切割方法。
技术方案
本发明的示例性实施方案提供了一种用于形成切割膜的粘着层的组合物，其包含：含有一个以上反应性官能团的硅化合物油；粘着粘合剂；和光引发剂，其中含有一个以上反应性官能团的硅化合物油与粘着粘合剂的重量比为0.01％至4.5％。
反应性官能团可包括选自羟基、甲醇基(cabinol)、环氧基、氨基、巯基、和羧基中的一种以上官能团。
含有一个以上反应性官能团的硅化合物油包含：选自以下化学式1的硅化合物、以下化学式2的硅化合物、和经聚醚改性的羟基官能聚二甲基硅氧烷中的一种以上硅化合物；和有机溶剂。
[化学式1]
在化学式1中，R1独立地为碳数为1至3的烷基，R2为羟基、碳数为1至10的亚烷基醇、环氧基、氨基、巯基、或羧基，m为0至500的整数，n为1至500的整数。
[化学式2]
在化学式2中，R1独立地为碳数为1至3的烷基；R3和R4的至少一个为碳数为1至3的烷基，另一个为羟基、碳数为1至10的亚烷基醇、环氧基、氨基、巯基或羧基，或者R3和R4独立地为羟基、碳数为1至10的亚烷基醇、环氧基、氨基、巯基或羧基；且p为0至500的整数。
有机溶剂选自醇、醚、乙酸酯、或酮。
在25℃下，所述含有一个以上反应性官能团的硅化合物油的粘度可为10mm2/s至20,000mm2/s。
粘着粘合剂可包含未经取代的或经选自羟基、异氰酸酯基、乙烯基、和(甲基)丙烯酸酯基中的一个以上官能团取代的(甲基)丙烯酸酯聚合物或(甲基)丙烯酸酯共聚物。
粘着粘合剂可包含加入具有键合至(甲基)丙烯酸酯树脂主链的碳-碳双键的丙烯酸酯的嵌入粘着粘合剂。例如，可使用(甲基)丙烯酸系树脂的主链加入有1重量％至45重量％的作为侧链的(甲基)丙烯酸酯官能团的聚合物树脂作为嵌入粘着粘合剂。
粘着粘合剂可包含重均分子量为100,000至1,500,000的聚合物树脂。
光引发剂可包括选自安息香及其烷基醚、苯乙酮、蒽醌、硫代黄嘌呤、二苯甲酮、α-氨基苯乙酮、酰基膦氧化物、和肟酯中的一种以上。
组合物可包含0.01至8重量份、或0.02至5重量份的光引发剂，基于100重量份的粘着粘合剂计。
用于形成切割膜的粘着层的组合物可另外包含固化剂。
固化剂可包含选自异氰酸酯化合物、氮丙啶化合物、环氧化合物、和金属螯合化合物中的一种以上。
用于形成切割膜的粘着层的组合物可包含0.1至30重量份的固化剂，基于100重量份的粘着粘合剂计。
本发明还提供一种切割膜，其包括基底膜、和在所述基底膜的至少一面上形成的粘着层，其中所述粘着层包括用于形成切割膜的粘着层的上述组合物。
基底膜的厚度可为10μm至200μm，且粘着层的厚度可为0.5μm至50μm。
另外，本发明还提供一种切割晶片接合膜，其包括切割膜、和在所述切割膜的至少一面形成的接合层。
此外，本发明提供一种半导体晶圆的切割方法，所述切割方法包括：预处理步骤，通过对包括切割晶片接合膜和层压于切割晶片接合膜的至少一面的晶圆的半导体晶圆进行部分处理，以使其被完全切割或可被切割；在预处理步骤后，对所述半导体晶圆进行扩展的步骤；和向已扩展的半导体晶圆的基底膜照射紫外线，并拾取通过所述半导体晶圆的切割而分离的单个晶片的步骤。
有益效果
本申请提供一种用于形成切割膜的粘着层的组合物，以提供切割晶片接合膜，所述切割晶片接合膜可防止在切割过程中发生膜之间固定以增加拾取成功率并可展现出较高的晶片剪切强度以防止粘着强度降级导致的剥离；一种包含含有所述组合物的粘着层的切割膜；一种包含所述切割膜的切割晶片接合膜；和一种用于对使用了所述切割晶片接合膜的半导体晶圆进行切割的方法。
具体实施方式
下文中，将对根据具体实施方案的切割膜、切割晶片接合膜和半导体晶圆的切割方法进行详细的描述。
根据本发明的一个实施方案，提供一种用于形成切割膜的粘着层的组合物，其包含：含有一个以上反应性官能团的硅化合物油；粘着粘合剂；和光引发剂，其中含有一个以上反应性官能团的硅化合物油与粘着粘合剂的重量比为0.01％至4.5％。
如前所述，存在以下问题：因为在切割工艺中的拾取过程期间膜之间发生固定的问题、和膜之间的剥离强度过大而导致使拾取晶片的成功率可能被降低的问题。
因此，本发明人通过实验证实，如果使用包含由以下组合物形成的粘着层的切割膜，所述组合物包含含有一个以上反应性官能团的硅化合物油，则可防止膜之间固定，并可降低膜之间的剥离强度，以提高晶片拾取的成功率，可展现出较高的晶片剪切强度从而防止因粘着强度降级导致的剥离，并改善半导体制备方法的可靠性，并完成本发明。
包含在含有一个以上反应性官能团的硅化合物油中的、含有一个以上反应性官能团的硅化合物对有机或无机物质具有可释放性(releasability)，并且二甲基硅氧烷结构的烷基充当粘结物(adherend)表面的非极性分子，从而使得硅化合物对极性粘结物具有可释放性和滑动特性。从而，用于形成切割膜的粘着层的组合物可向接合层(晶片接合膜)提供更高的可释放性和滑动特性以促使紫外固化后的剥离。
含有一个以上反应性官能团的硅化合物油与粘着粘合剂的重量比可为0.01％至4.5％，或0.1％至2％。
如果含有一个以上反应性官能团的硅化合物油与粘着粘合剂的重量比过低，则由上述实施方案的用于形成切割膜的粘着层的组合物制备的切割膜的粘着层可具有显著增加的剥离强度，例如显著增加的180度剥离强度和紫外照射之前/之后的粘着力，以及SUS剥离强度。
如果含有一个以上反应性官能团的硅化合物油与粘着粘合剂的重量比过高，则虽然由上述实施方案的用于形成切割膜的粘着层的组合物制备的切割膜的粘着层的剥离强度可能有一定程度的降低，但是可能显著降低粘着层的晶片剪切强度，从而产生因粘着强度的降级而导致的剥离，并从而在半导体制备方法中可能降低可靠性。
同时，在硅化合物油中所包含的硅，可以含有一个以上反应性官能团或可经一个以上反应性官能团取代，且所述反应性官能团的具体实例可包括选自羟基、甲醇基、环氧基、氨基、巯基、和羧基中的一种以上官能团。
含有一个以上反应性官能团的硅化合物油，包含含有一个以上反应性官能团的硅化合物和有机溶剂。
具体而言，含有一个以上反应性官能团的硅化合物油可包含：选自以下化学式1的硅化合物、以下化学式2的硅化合物、和经聚醚改性的羟基官能聚二甲基硅氧烷中的一种以上硅化合物；和有机溶剂。
[化学式1]
在化学式1中，R1独立地为碳数为1至3的烷基，R2为羟基、碳数为1至10的亚烷基醇、环氧基、氨基、巯基或羧基，m为0至500的整数，n为1至500的整数。
[化学式2]
在化学式2中，R1独立地为碳数为1至3的烷基；R3和R4的至少一个为碳数为1至3的烷基，另一个为羟基、碳数为1至10的亚烷基醇、环氧基、氨基、巯基或羧基，或者R3和R4独立地为羟基、碳数为1至10的亚烷基醇、环氧基、氨基、巯基或羧基；且p为0至500的整数。
经聚醚改性的羟基官能聚二甲基硅氧烷的具体实例可包括市售可得的产品如BYK-SILCLEAN3720等，但不限于此。
虽然无特别的限制，但是在含有一个以上官能团的硅化合物油中所包含的有机溶剂的具体实例可为醇、醚、乙酸酯、或酮。
在25℃下，含有一个以上反应性官能团的硅化合物油的粘度(viscosity)为10mm2/s至20,000mm2/s。
同时，可以无特别限制地使用已知的用于形成切割膜的粘着层的聚合物树脂作为粘着粘合剂，例如可以使用经具体的反应性官能团取代的聚合物树脂、或具有含有反应性官能团的主链的聚合物树脂。
具体地，粘着粘合剂可包含未经取代的、或经选自羟基、异氰酸酯基、乙烯基、和(甲基)丙烯酸酯基中的一个以上官能团取代的(甲基)丙烯酸酯聚合物或(甲基)丙烯酸酯共聚物。
粘着粘合剂可为加入具有键合至(甲基)丙烯酸酯树脂主链的碳-碳双键的丙烯酸酯的嵌入粘着粘合剂。例如，可以使用(甲基)丙烯酸系树脂的主链加入有1重量％至45重量％的作为侧链的(甲基)丙烯酸酯官能团的聚合物树脂作为嵌入粘着粘合剂。
粘着粘合剂可包含重均分子量为100,000至1,500,000的聚合物树脂。
具体而言，未经取代的或经选自羟基、异氰酸酯基、乙烯基、和(甲基)丙烯酸酯基中的一个以上官能团取代的(甲基)丙烯酸酯聚合物或(甲基)丙烯酸酯共聚物的重均分子量可为100,000至1,500,000。
如在本说明书中使用的，(甲基)丙烯酸酯意指包含丙烯酸酯和(甲基)丙烯酸酯。
(甲基)丙烯酸酯聚合物或(甲基)丙烯酸酯共聚物的实例可包括(甲基)丙烯酸酯单体和含有可交联官能团的单体的聚合物或共聚物。
在本说明书中，(甲基)丙烯酸酯单体的实例可包含(甲基)丙烯酸烷基酯，且更具体而言，具有C1-20烷基的单体的实例可包含(甲基)丙烯酸戊酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸十二烷基酯或(甲基)丙烯酸癸酯中的一种或其两种或更多种的混合物。随着使用具有更高的烷基数的单体，最终的共聚物的玻璃转变温度降低，从而，可以根据所需要的玻璃转变温度选择适当的单体。
含有可交联的官能团的单体的实例可包含含有羟基的单体、含有羧基的单体、含氮的单体中的一种或其两种以上的混合物。含羟基的化合物的实例可包含(甲基)丙烯酸2-羟乙酯、和(甲基)丙烯酸2-羟丙酯等，含羧基的化合物的实例可包含(甲基)丙烯酸等，含氮单体的实例可包含(甲基)丙烯腈、N-乙烯基吡咯啶酮、和N-乙烯基己内酰胺等，但不限于此。就提高相容性等的其他性能而言，(甲基)丙烯酸酯系树脂可另外包含乙酸乙烯酯、苯乙烯、和含丙烯腈碳-碳双键的低分子量的化合物等。
加入具有键合至(甲基)丙烯酸酯树脂主链的碳-碳双键的丙烯酸酯的嵌入粘着粘合剂的重均分子量可为100,000至1,500,000。
如果在粘着粘合剂中所包含的聚合物树脂的重均分子量过低，则上述实施方案的用于形成切割膜的粘着层的组合物的可涂布性或粘着性可能降级，并且当由组合物形成的粘着层剥离时，残余物可能保留在粘结物中或者粘着层可能会断裂。
如果在粘着粘合剂中所包含的聚合物树脂的重均分子量过高，则上述实施方案的用于形成切割膜的粘着层的组合物的紫外固化可能会发生的不充分，从而由组合物形成的粘着层的剥离强度可能不会充分地降低，从而降低了拾取的成功率。
用于形成切割膜的粘着层的组合物可另外包含紫外可固化化合物。
对紫外可固化化合物的种类没有特别的限制，例如，可以使用重均分子量约为500至300,000的多官能化合物(如，多官能氨基甲酸乙酯丙烯酸酯、多官能丙烯酸酯单体或低聚物等)。根据所需用途，本领域普通技术人员可以容易地选择适当的化合物。
紫外可固化化合物的含量可为5重量份至400重量份、优选10重量份至200重量份，基于100重量份的上述粘着粘合剂计。如果紫外可固化化合物的含量小于5重量份，则固化后的粘着力降低可能不够充分，从而拾取的成功率可能降级；如果紫外可固化化合物大于400重量份，则紫外照射之前的粘着剂的粘着性(cohesiveness)可能不足，或者存在可能不易于实现离型膜剥离等的问题。
在用于形成切割膜的粘着层的组合物中所包含的光引发剂的具体实例没有特别的限制，且可以无特别限制地使用常规已知的光引发剂。例如，可以使用安息香及其烷基醚、苯乙酮、蒽醌、硫代黄嘌呤、二苯甲酮、α-氨基苯乙酮、酰基膦氧化物、和肟酯及其两种以上的混合物作为光引发剂。
可考虑所制备的粘着层的物理特性和特性及所使用的粘着粘合剂的种类和特性等来确定光引发剂的量，例如，用于形成切割膜的粘着层的组合物可含有0.01至5重量份的光引发剂，基于100重量份的粘着粘合剂计。
用于形成切割膜的粘着层的组合物可以还含有固化剂。当将用于形成切割膜的粘着层的组合物涂布在基底膜时，在室温下或在30至50℃的温度下，所述固化剂可以与粘着粘合剂的反应性基团进行反应以形成交联。在固化剂中所包含的具体反应性基团可以保持未反应状态，并在拾取之前通过紫外照射来进一步交联，从而降低粘着层的粘着强度。
固化剂可包含选自异氰酸酯化合物、氮丙啶化合物、环氧化合物、和金属螯合化合物中的一种以上化合物。
可以考虑所制备的粘着层的物理性质和特性以及所使用的粘着粘合剂的种类和特性等来确定固化剂的量，例如，用于形成切割膜的粘着层的组合物可包含0.1至30重量份的固化剂，基于100重量份的粘着粘合剂计。
根据另一实施方案，提供一种包括基底膜、和在基底膜的至少一面上形成的粘着层的切割膜，其中所述粘着层包含上述实施方案的用于形成切割膜的粘着层的组合物。
对基底膜的种类没有特别的限制，例如，可以使用本领域已知的塑料膜或金属箔。例如，基底膜可包含低密度聚乙烯、线型聚乙烯、中密度聚乙烯、高密度聚乙烯、超低密度聚乙烯、聚丙烯无规共聚物、聚丙烯嵌段共聚物、均聚聚丙烯、聚甲基戊烯(polymethylpentene)、乙烯-乙酸乙烯酯共聚物、乙烯-甲基丙烯酸共聚物、乙烯-甲基丙烯酸甲酯共聚物、乙烯-离聚物共聚物、乙烯-乙烯醇共聚物、聚丁烯、苯乙烯共聚物、或其两种以上的混合物。包含两种以上聚合物的混合物的基底膜是指，既包括分别含有上述聚合物的两种或更多种的膜的堆叠结构，也包括含有两种或更多种上述聚合物的单层膜。
对基底膜的厚度没有特别的限制，通常，可使其形成10μm至200μm、优选50μm至180μm的厚度。如果厚度小于10μm，则在切割过程中切割深度(cutbepth)的调节可能不稳定；如果其大于200μm，则在切割过程中可能产生大量毛刺(burr)，或者可能降低伸长率，从而可能不能精确地完成扩展过程。
如果需要，可以对基底膜进行常规的物理或化学处理，如消光处理、电晕放电、底漆处理、和交联处理等。
粘着层的厚度可为0.5μm至50μm，或5μm至30μm。
包含在粘着层中的用于形成切割膜的粘着层的组合物的细节包含上述的所有的内容。
根据本发明的又一实施方案，提供一种包含切割膜和在切割膜的至少一面形成的接合层的切割晶片接合膜。
切割膜的细节包含上述所有内容。
接合层可包含环氧树脂、低弹性高分子量树脂、和用于接合层的固化剂。环氧树脂可含有本领域已知的用于粘着剂的常规环氧树脂，例如，可以使用分子中含有两个或更多个环氧基并且重均分子量为100至5000的环氧树脂。
所述环氧树脂可以通过固化工艺来形成硬的交联结构以展现出优异的粘着特性、耐热性、和机械强度。
更具体地，特别优选使用环氧当量为100至1,000的那些作为环氧树脂。如果环氧树脂的环氧当量小于100，则交联密度可能过高，从而接合膜整体上一般可能展现出硬特性；如果环氧树脂的环氧当量大于1,000，则耐热性可能降级。
环氧树脂的具体实例可包含双官能环氧树脂，如双酚A环氧树脂或双酚F环氧树脂等；或具有3个或更多个官能团的多官能环氧树脂，如甲酚酚醛环氧树脂、苯酚酚醛环氧树脂、四官能环氧树脂、联苯型环氧树脂、三苯酚甲烷型环氧树脂、烷基改性的三苯酚甲烷型环氧树脂、萘型环氧树脂、二环戊二烯型环氧树脂、和二环戊二烯改性的苯酚型环氧树脂等中的一种或其两种以上的混合物，但是不限于此。
优选使用作为环氧树脂的双官能环氧树脂和多官能环氧树脂的混合树脂。
多官能环氧树脂意指具有3个以上官能团的环氧树脂。即，双官能环氧树酯通常具有优异的挠性和高温流动性等，但是具有较差的耐热性和固化速递；相反具有3个或更多个官能团的多官能环氧树脂的固化速度快并且因高交联密度而展现出优异的耐热性，但是具有较差的挠性和流动性。因此，通过将两种树脂适当地混合，在切割过程中可抑制晶片的分散或毛刺的发生，同时控制接合层的弹性和粘性(tack)特征。
低弹性高分子量树脂可在粘着剂中形成软链段(softsegment)以在高温下获得应力松弛。可使用任意的树脂作为高分子量树脂，只要当与环氧树脂共混形成膜时其不引发粉碎、形成交联结构以后可展现出粘弹性、且具有与其他组分的优异的相容性和储存稳定性即可。
对低弹性高分子量树脂的具体种类没有特别的限制，只要其满足上述特性即可，但是可以使用例如聚酰亚胺、聚醚酰亚胺、聚酯酰亚胺、聚酰胺、聚醚砜、聚醚酮、聚烯烃、聚氯乙烯、苯氧基、反应性丙烯腈丁二烯橡胶、和(甲基)丙烯酸酯系树脂等中的一种或其两种以上的混合物。
(甲基)丙烯酸酯系树脂的具体实例可包含丙烯酰基系共聚物，其包含(甲基)丙烯酸及其衍生物，其中(甲基)丙烯酸及其衍生物的实例可包含(甲基)丙烯酸；含有C1-12烷基的(甲基)丙烯酸烷基酯，如(甲基)丙烯酸甲基酯或(甲基)丙烯酸乙基酯等；(甲基)丙烯腈或(甲基)丙烯酰胺；以及其他可共聚的单体。
(甲基)丙烯酸系树脂可包含一种或者两种或更多种官能团，如缩水甘油基、羟基、羧基、和氨基等，其可以通过使单体共聚合而被引入，所述单体如(甲基)丙烯酸缩水甘油酯、(甲基)丙烯酸羟酯、(甲基)丙烯酸羟乙酯、或(甲基)丙烯酸羧基酯等。
对可被引入粘着剂组合物中的固化剂没有特别的限制，只要其可以与环氧树脂和/或低弹性高分子量树脂反应形成交联结构即可。例如，可以使用可与这两种组分反应而形成交联结构的固化剂，且该固化剂分别与粘着剂中的软链段和硬链段形成交联结构以改善耐热性，并且同时，在两个链段的界面处充当两个链段的交联剂以改善半导体封装的可靠性。
虽然没有特别的限制，但是接合层的厚度例如可为1μm至100μm，或3μm至50μm的范围。
根据另一实施方案，提供一种半导体晶圆，其中所述切割晶片接合膜的接合层附着在晶圆一面，所述切割晶片接合膜的基底膜固定在晶圆环框架。
上述半导体晶圆可通过以下过程制备：在0℃至180℃的温度下将切割晶片接合膜的接合部分层压至半导体晶圆的背侧，并将基底膜固定至晶圆环框架。
根据本发明的另一实施方案，提供一种半导体装置，包括布线基板；接合层，其形成在布线基板的晶片装载面，并包括用于半导体的上述接合膜；和半导体晶片，其装载在接合层上。
上述半导体装置可通过以下方法制成。具体地，使用切割设备来将附着有上述切割晶片接合膜的半导体晶圆完全切割而分割为单个晶片。随后，通过照射紫外线或加热等方法将粘着部分固化。通过紫外线或热来固化的粘着剂具有降低了的粘着强度，因此在后续工艺中晶片的拾取变得容易。在本说明书中，如果需要，则实施用于拉伸切割晶片接合膜的扩展工艺，以便扩展晶片之间的距离，并在接合部分和粘着部分的界面处产生错位，从而可以使拾取变得容易。
如果在上述条件下实施晶片的拾取，则半导体晶圆和接合部分从粘着部分剥离，从而可以获得仅附着有接合层的晶片。将所获得的具有接合层的晶片附着至半导体的基板。附着晶片的温度通常为100℃至180℃，附着时间为0.5秒至3秒，且附着压力为0.5kgf/平方厘米至2kgf/平方厘米。
在进行上述工艺之后，进行接合工艺和模塑工艺而得到半导体装置。在本发明中，特别地，通过用于晶片接合的粘着力的强度等的最佳化，可以在不进行晶片接合后的预固化工艺的情况下，在引线接合过程或模塑过程中抑制晶片的剥离、滑移、或倾斜等。
半导体装置的制造方法不限于上述工艺，可包括任意工艺，也可以改变工艺的顺序。例如，可以按照紫外固化→切割→扩展工艺的顺序、或也可以按照切割→扩展→紫外固化工艺的顺序进行该方法。在附着晶片工艺之后，可进一步进行加热或冷却工艺。
同时，根据本发明的另一实施方案，提供一种半导体晶圆的切割方法，所述切割方法包括：预处理步骤，通过对包括上述切割晶片接合膜和层压于所述切割晶片接合膜的至少一面的晶圆的半导体晶圆进行预处理，以使其被完全切割或可被切割；在预处理步骤后对所述半导体晶圆进行扩展的步骤；和向已扩展的半导体晶圆的基底膜照射紫外线，并拾取通过所述半导体晶圆的切割来分离的单个晶片的步骤。
切割晶片接合膜的细节包括上述的所有内容。
除切割方法的步骤的详细内容以外，可以无特别限制地使用通常已知的用于切割半导体晶圆的设备、和切割方法等。
通过使用包含切割膜的切割晶片接合膜，可以在半导体晶圆的切割过程期间使毛刺(burr)的发生最小化，由此防止半导体晶片的污染并改善半导体晶片的可靠性和寿命。
在以下实施例中，将对本发明的具体实施方案进行详细的说明。但是，这些实施例仅是为说明本发明的具体实施方案，且本发明的范围不限于此。
实施例1
基于100重量份的可光固化粘着粘合剂树脂计，将2重量份的异氰酸酯系固化剂(多官能异氰酸酯低聚物)、0.5重量份的硅化合物油X-22-4309(Shin-EtsuCo.Ltd.)、和1重量份的作为光引发剂的DAROCURTPO进行混合，由此制备了紫外可固化粘着剂组合物。使用丙烯酸系树脂(Mw300,000)的主链加入有20重量％的作为侧链的丙烯酸酯官能团的聚合物树脂作为可光固化的粘着粘合剂树脂。
将紫外可固化粘着剂组合物涂布在100μm厚的聚烯烃膜的一面并进行干燥，由此制备了包括10μm厚的粘着层的切割膜。
实施例2
基于100重量份的可光固化粘着粘合剂树脂计，将2重量份的异氰酸酯系固化剂(多官能异氰酸酯低聚物)、0.5重量份的硅化合物油KF-1001(Shin-EtsuCo.Ltd.)、和1重量份的作为光引发剂的DAROCURTPO进行混合，由此制备了紫外可固化粘着剂组合物。使用丙烯酸系树脂(Mw300,000)的主链加入有20重量％的作为侧链的丙烯酸酯官能团的聚合物树脂作为可光固化的粘着粘合剂树脂。
将可紫外固化的粘着剂组合物涂布在100μm厚的聚烯烃膜的一面并进行干燥，由此制备了包括10μm厚的粘着层的切割膜。
实施例3
基于100重量份的可光固化粘着粘合剂树脂计，将2重量份的异氰酸酯系固化剂(多官能异氰酸酯低聚物)、0.5重量份的硅化合物油X-KF-8008(Shin-EtsuCo.Ltd.)、和1重量份的作为光引发剂的DAROCURTPO进行混合，由此制备了紫外可固化粘着剂组合物。使用丙烯酸系树脂(Mw300,000)的主链加入有20重量％的作为侧链的丙烯酸酯官能团的聚合物树脂作为可光固化的粘着粘合剂树脂。
将紫外可固化粘着剂组合物涂布在100μm厚的聚烯烃膜的一面并进行干燥，由此制备了包括10μm厚的粘着层的切割膜。
实施例4
基于100重量份的可光固化粘着粘合剂树脂计，将2重量份的异氰酸酯系固化剂(多官能异氰酸酯低聚物)、0.5重量份的硅化合物油BYK-SILCLEAN、和1重量份的作为光引发剂的DAROCURTPO进行混合，由此制备了紫外可固化粘着剂组合物。使用丙烯酸系树脂(Mw300,000)的主链加入有20重量％的作为侧链的丙烯酸酯官能团的聚合物树脂作为可光固化的粘着粘合剂树脂。
将紫外可固化粘着剂组合物涂布在100μm厚的聚烯烃膜的一面并进行干燥，由此制备了包括10μm厚的粘着层的切割膜。
比较例1
基于100重量份的可光固化粘着粘合剂树脂计，将2重量份的异氰酸酯系固化剂(多官能异氰酸酯低聚物)、和1重量份的作为光引发剂的DAROCURTPO进行混合，由此制备了紫外可固化粘着剂组合物。使用丙烯酸系树脂(Mw300,000)的主链加入有20重量％的作为侧链的丙烯酸酯官能团的聚合物树脂作为可光固化的粘着粘合剂树脂。
将紫外可固化粘着剂组合物涂布在100μm厚的聚烯烃膜的一面并进行干燥，由此制备了包括10μm厚的粘着层的切割膜。
比较例2
基于100重量份的可光固化粘着粘合剂树脂计，将2重量份的异氰酸酯系固化剂(多官能异氰酸酯低聚物)、5重量份的硅化合物油X-22-4039(Shin-EtsuCo.Ltd)、和1重量份的作为光引发剂的DAROCURTPO进行混合，由此制备了紫外可固化粘着剂组合物。使用丙烯酸系树脂(Mw300,000)的主链加入有20重量％的作为侧链的丙烯酸酯官能团的聚合物树脂作为可光固化的粘着粘合剂树脂。
将紫外可固化粘着剂组合物涂布在100μm厚的聚烯烃膜的一面并进行干燥，由此制备了包括10μm厚的粘着层的切割膜。
比较例3
基于100重量份的可光固化粘着粘合剂树脂计，将2重量份的异氰酸酯系固化剂(多官能异氰酸酯低聚物)、5重量份的硅化合物油L-7500(SilvetCo.)、和1重量份的作为光引发剂的DAROCURTPO进行混合，由此制备了紫外可固化粘着剂组合物。
将紫外可固化粘着剂组合物涂布在100μm厚的聚烯烃膜的一面并进行干燥，由此制备了包括10μm厚的粘着层的切割膜。
实验例
如下测量实施例1至4和比较例1至3制备的切割膜的剥离强度、粘着力和拾取成功率，并将结果示于下表1和2中。
1、晶片接合膜/切割膜之间的180度剥离强度的测量(在紫外固化之前/之后)
为了测量切割接合膜与PSA层之间的剥离强度，在室温下将接合膜与切割膜层压，并将其静置1小时，之后制造宽度为25毫米的样品，在300mm/min的速度下测量了180度剥离强度，并另外也测量紫外固化以后的值。每一个样品进行3次以上的测量，并记录平均值。
2、SUS/切割膜之间的90度剥离强度的测量(在紫外固化之前)
制造25mm宽的切割膜，并将其附着至SUS304粘结物。附着后固化1小时，之后在300mm/min的速度下测量90度剥离强度。每一个样品进行3次以上的测量，并记录平均值。
3、粘性测试(在紫外固化之前/之后)
将切割膜放置于板上以使粘着层面朝上，并用直径为1英寸的球型探针(probe)测量粘着力。此处，施加于探针的力为800gf，接触时间为0.01秒，撕掉探针的测量速度为1mm/s，且用于测量的设备为质构分析仪(TextureAnalyzer)。
4、拾取成功率的测量
在70℃下将由实施例和比较例的切割膜所制备的切割晶片接合膜与晶圆一起层压。随后，在以下条件下使用切割设备(由NEON公司制造)进行切割工艺，然后在以下条件下向切割膜一面照射紫外线。随后，用晶片接合机(diebonder)(ShinkawaCo.Ltd.)拾取200个晶片，并测量未拾取的晶片的数目并以百分比形式记录。
[切割条件]
刀片：27HEDD
刀片旋转速度：40,000rpm
速度：30mm/s
晶片尺寸：10mm×10mm
切割深度：70μm
[紫外线照射条件]
灯：金属卤化物型(metalhalidetype)
照明强度：70mW/cm2(用紫外线测量仪测量)
照射量：200mJ/cm2以上(用紫外线测量仪测量)
[拾取条件]
扩展：4mm
针高度：0.15mm
拾取强度：100gf
5、晶片剪切强度
将涂布有二氧化物层的厚度为500μm的晶圆切割成5mm×5mm的尺寸，并在60℃下与切割晶片接合膜层压，随后照射紫外线以去除切割膜，之后进行切割而仅留下晶片大小的接合膜。将5mm×5mm的上部晶片放置于10mm×10mm的下部晶片上，然后在130℃下在热板上用2kgf的力按压2秒，随后在125℃下固化1小时。将以上制造的测试件在175℃下固化2小时，然后在250℃下测量上晶片的晶片剪切强度。
[表1]
[表2]
如表1和表2所示，证实与在比较例1中制备的切割膜相比，在实施例1至4中所制备的切割膜展现出较低的紫外固化之前/之后的180度剥离强度和粘着力、较低的SUS剥离强度、和高的拾取成功率。
此外，证实与在比较例1至3中制备的切割膜相比，在实施例1至4中所制备的切割膜展现出较高的晶片剪切强度，以防止了因粘着强度降低而导致的剥离，从而抑制回焊裂纹(reflowcracks)并提高了半导体制造过程的可靠性。

Claims (17)

1.一种用于形成切割膜的粘着层的组合物，其包含：
含有一个以上反应性官能团的硅化合物油；粘着粘合剂；和光引发剂，其中：
含有一个以上反应性官能团的硅化合物油与粘着粘合剂的重量比为0.01％至4.5％。
2.根据权利要求1所述的用于形成切割膜的粘着层的组合物，其中：
所述反应性官能团包括选自羟基、甲醇基、环氧基、氨基、巯基、和羧基中的一种以上官能团。
3.根据权利要求1所述的用于形成切割膜的粘着层的组合物，其中：
所述含有一个以上反应性官能团的硅化合物油包含：选自以下化学式1的硅化合物、以下化学式2的硅化合物、和经聚醚改性的羟基官能聚二甲基硅氧烷中的一种以上硅化合物；和有机溶剂：
其中，在所述化学式1中，R1独立地为碳数为1至3的烷基，R2为羟基、碳数为1至10的亚烷基醇、环氧基、氨基、巯基或羧基，m为0至500的整数，n为1至500的整数；
其中，在所述化学式2中，R1独立地为碳数为1至3的烷基；R3和R4的至少一个为碳数为1至3的烷基，另一个为羟基、碳数为1至10的亚烷基醇、环氧基、氨基、巯基或羧基，或者R3和R4独立地为羟基、碳数为1至10的亚烷基醇、环氧基、氨基、巯基或羧基；且p为0至500的整数。
4.根据权利要求3所述的用于形成切割膜的粘着层的组合物，其中：
所述有机溶剂选自醇、醚、乙酸酯、或酮。
5.根据权利要求1所述的用于形成切割膜的粘着层的组合物，其中：
在25℃下，含有一个以上反应性官能团的硅化合物油的粘度为10mm2/s至20,000mm2/s。
6.根据权利要求1所述的用于形成切割膜的粘着层的组合物，其中：
所述粘着粘合剂包含未经取代的或经选自羟基、异氰酸酯基、乙烯基、和(甲基)丙烯酸酯基中的一个以上官能团取代的(甲基)丙烯酸酯聚合物或(甲基)丙烯酸酯共聚物。
7.根据权利要求1所述的用于形成切割膜的粘着层的组合物，其中：
所述粘着粘合剂包含加入具有键合至(甲基)丙烯酸酯树脂主链的碳-碳双键的丙烯酸酯的嵌入粘着粘合剂。
8.根据权利要求1所述的用于形成切割膜的粘着层的组合物，其中：
所述粘着粘合剂包含重均分子量为100,000至1,500,000的聚合物树脂。
9.根据权利要求1所述的用于形成切割膜的粘着层的组合物，其中：
所述光引发剂包括选自安息香及其烷基醚、苯乙酮、蒽醌、硫代黄嘌呤、二苯甲酮、α-氨基苯乙酮、酰基膦氧化物、和肟酯中的一种以上。
10.根据权利要求1所述的用于形成切割膜的粘着层的组合物，其中：
所述组合物包含0.01至8重量份的所述光引发剂，基于100重量份的所述粘着粘合剂计。
11.根据权利要求1所述的用于形成切割膜的粘着层的组合物，其还包含固化剂。
12.根据权利要求11的形成切割膜的粘着层的组合物，其中：
所述固化剂包含选自异氰酸酯化合物、氮丙啶化合物、环氧化合物、和金属螯合化合物中的一种以上。
13.根据权利要求11所述的用于形成切割膜的粘着层的组合物，其中：
所述组合物包含0.1至30重量份的所述固化剂，基于100重量份的所述粘着粘合剂计。
14.一种切割膜，其包括基底膜、和在所述基底膜的至少一面上形成的粘着层，其中所述粘着层包含权利要求1的用于形成切割膜的粘着层的组合物。
15.根据权利要求1所述的切割膜，其中：
所述基底膜的厚度为10μm至200μm，且所述粘着层的厚度为0.5μm至50μm。
16.一种切割晶片接合膜，其包括权利要求14所述的切割膜、和在所述切割膜的至少一面形成的接合层。
17.一种半导体晶圆的切割方法，所述方法包括：
预处理步骤，通过对包含权利要求16的切割晶片接合膜和层压于切割晶片接合膜的至少一面的晶圆的半导体晶圆进行部分处理，以使其被完全切割或可被切割；
在预处理步骤之后对所述半导体晶圆进行扩展的步骤；和
向已扩展的半导体晶圆的基底膜照射紫外线，并拾取通过所述半导体晶圆的切割而分离的单个晶片的步骤。
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