CN105143344A - 热固性树脂组合物和半导体装置的制造方法 - Google Patents

热固性树脂组合物和半导体装置的制造方法 Download PDF

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Publication number
CN105143344A
CN105143344A CN201480021494.XA CN201480021494A CN105143344A CN 105143344 A CN105143344 A CN 105143344A CN 201480021494 A CN201480021494 A CN 201480021494A CN 105143344 A CN105143344 A CN 105143344A
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thermosetting resin
compositions
mentioned
semiconductor device
resin
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CN201480021494.XA
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盛田浩介
高本尚英
花园博行
福井章洋
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Nitto Denko Corp
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Nitto Denko Corp
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Publication of CN105143344A publication Critical patent/CN105143344A/zh
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    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
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    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • 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
    • C08G59/62—Alcohols or phenols
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Abstract

提供一种热固性树脂组合物和使用该热固性树脂组合物的半导体装置的制造方法，该热固性树脂组合物通过缓和半导体元件与被粘物的热响应行为的差异，能够确保构件材质的可利用性，并且能够制造连接可靠性高的半导体装置。本发明为包含环氧树脂和羟基当量为200g/eq以上的线型酚醛型酚醛树脂的半导体装置制造用的热固性树脂组合物。上述线型酚醛型酚醛树脂优选包含由下述结构式表示的结构(式中，n为0～12的整数)。

Description

热固性树脂组合物和半导体装置的制造方法
技术领域
本发明涉及热固性树脂组合物和半导体装置的制造方法。
背景技术
近年来，随着电子设备的小型、薄型化，高密度安装的要求急剧增加。因此，半导体封装中，适于高密度安装的表面安装型代替以往的销插入型成为主流。该表面安装型是将导线直接焊接于印刷基板等。作为加热方法，通过红外再流焊、气相再流焊、浸沾软钎焊等，对封装整体加热来进行安装。
在表面安装后，为了确保半导体元件表面的保护、半导体元件与基板之间的连接可靠性，进行向半导体元件与基板之间的空间中填充底填剂材料。作为这样的底填剂材料，考虑配置的容易性、填充程度调节的容易性，使用片状的底填剂材料代替液态材料来填充半导体元件与基板之间的空间的技术(专利文献1)。
一般而言，作为使用片状的底填剂材料的工艺，采用如下步骤，即将片状的底填剂材料贴附于半导体元件后，利用在基板等被粘物上连接安装半导体元件并与半导体元件成为一体的片状的底填剂材料填充基板等被粘物与半导体元件之间的空间。在该工艺中，容易填充被粘物与半导体元件之间的空间。
现有技术文献
专利文献
专利文献1：日本专利第4438973号
发明内容
发明要解决的问题
然而，尽管半导体装置的小型化、薄型化中减薄半导体元件的厚度即可，但随着半导体元件的薄型化的推进，被粘物的热响应行为对半导体元件的影响(翘曲、膨胀等)变大。这是因为，一般而言基板等被粘物的热膨胀系数大于半导体元件的值。半导体元件与被粘物的热响应行为的不同所导致的应力尤其容易集中于将半导体元件和被粘物连接的焊料凸点等连接构件，根据情况有时在接合部产生破裂。与此相对，为了使半导体元件与被粘物之间的热响应性行为匹配，还能够对两者的材质等进行选择，但可选择的材质的范围受到限制。
本发明的目的在于提供一种热固性树脂组合物和使用该热固性树脂组合物的半导体装置的制造方法，该热固性树脂组合物通过缓和半导体元件与被粘物的热响应行为的差异，能够确保构件材质的可利用性，并且能够制造连接可靠性高的半导体装置。
用于解决问题的手段
本申请发明人进行了深入研究，结果发现，通过采用下述构成可以实现上述目的，从而完成了本发明。
本发明是一种半导体装置制造用的热固性树脂组合物，其包含环氧树脂、和羟基当量为200g/eq以上的线型酚醛型酚醛树脂。
该热固性树脂组合物包含环氧树脂以及羟基当量为200g/eq以上的线型酚醛型酚醛树脂(以下也称作“特定酚醛树脂”)，因而可以确保热固化后的固化物(以下也简称为“固化物”)的刚性，并且可以抑制两树脂间的过度交联从而发挥适度的柔软性。由此，可以缓和半导体元件与被粘物的热响应行为的差异，可以得到接合部的破裂被抑制的连接可靠性高的半导体装置。另外，通过使用该热固性树脂组合物，能够缓和半导体元件与被粘物的热响应行为的差异，因而可以对半导体元件、被粘物的材质提供选择的范围。
该热固性树脂组合物适合用于半导体元件密封。
该热固性树脂组合物中，优选上述线型酚醛型酚醛树脂包含由下述结构式表示的结构。
【化1】
(式中，n为0～12的整数。)
通过使用具有上述特定结构的线型酚醛型酚醛树脂，可以以更高水平实现固化物的刚性与柔软性的平衡，可以进一步提高半导体装置的可靠性。
该热固性树脂组合物优选包含平均粒径为10nm以上且1000nm以下的无机填充剂。通过该热固性树脂组合物含有无机填充剂，可以降低固化物的热膨胀率，可以抑制起因于固化物自身的热响应行为的影响，从而可进一步提高半导体装置的可靠性。另外，通过将无机填充剂的平均粒径设成上述范围，由此在该热固性树脂组合物中得到良好的透明性，其结果，容易进行晶片的切割位置、半导体元件在被粘物上的安装位置的对齐。
该热固性树脂组合物在175℃热处理1小时后的热膨胀系数α优选为10ppm/K以上且200ppm/K以下。通过将固化物的热膨胀系数α设成上述范围，可以抑制起因于固化物自身的热响应行为，其结果可进一步提高半导体装置的可靠性。
该热固性树脂组合物在175℃热处理1小时后的储能模量E’优选为100MPa以上且10000MPa以下。由此，固化物得到适度的刚性，可以促进热响应行为的差异的吸收或分散从而进一步提高半导体装置的可靠性。
该热固性树脂组合物优选为片状。由此，可操作性变好，并且在半导体元件与被粘物之间的空间中的配置变得容易，可以提高半导体装置的制造效率。
本发明还包括一种半导体装置的制造方法，其包含：将半导体元件通过该热固性树脂组合物固定于被粘物的固定工序；和使上述热固性树脂组合物固化的固化工序。
通过使用该热固性树脂组合物制造半导体装置，由此可以缓和半导体元件、该热固性树脂组合物的固化物、被粘物这三者间的热响应行为的差异，可以高效率地制造可靠性优异的半导体装置。
附图说明
图1是表示具有本发明的一个实施方式的热固性树脂组合物的密封片的截面示意图。
图2A是表示本发明的一个实施方式的半导体装置的制造工序的一个工序的截面示意图。
图2B是表示本发明的一个实施方式的半导体装置的制造工序的一个工序的截面示意图。
图2C是表示本发明的一个实施方式的半导体装置的制造工序的一个工序的截面示意图。
图2D是表示本发明的一个实施方式的半导体装置的制造工序的一个工序的截面示意图。
图2E是表示本发明的一个实施方式的半导体装置的制造工序的一个工序的截面示意图。
图2F是表示本发明的一个实施方式的半导体装置的制造工序的一个工序的截面示意图。
图3A是表示本发明的另一实施方式的半导体装置的制造工序的一个工序的截面示意图。
图3B是表示本发明的另一实施方式的半导体装置的制造工序的一个工序的截面示意图。
图3C是表示本发明的另一实施方式的半导体装置的制造工序的一个工序的截面示意图。
图3D是表示本发明的另一实施方式的半导体装置的制造工序的一个工序的截面示意图。
具体实施方式
以下，对于本发明的一个实施方式，以片状的热固性树脂组合物与背面磨削用带成为一体的密封片和使用该密封片的半导体装置的制造方法为例进行说明。以下的说明基本上也可以用于只有热固性树脂组合物的情况。
＜密封片＞
如图1所示，密封片10具备背面磨削用带1和层叠在背面磨削用带1上的片状的热固性树脂组合物2。需要说明的是，热固性树脂组合物2可以不像图1所示那样层叠在背面磨削用带1的整面上，只要以足够与半导体晶片3(参照图2A)贴合的尺寸进行设置即可。
[热固性树脂组合物]
本实施方式中的热固性树脂组合物2为片状，可以适合地用作填充被表面安装(例如倒装芯片安装等)的半导体元件与被粘物之间的空间的密封用膜、或者用于将半导体元件固定于被粘物的胶粘膜。
热固性树脂组合物2包含环氧树脂、和羟基当量为200g/eq以上的线型酚醛型酚醛树脂，还可以根据需要包含热固化促进催化剂、焊剂、交联剂、无机填充剂等。
(环氧树脂)
环氧树脂只要是通常用作热固性树脂的环氧树脂就没有特别限定，可以使用例如双酚A型、双酚F型、双酚S型、溴化双酚A型、氢化双酚A型、双酚AF型、联苯型、萘型、芴型、苯酚线型酚醛型、邻甲酚线型酚醛型、三羟苯基甲烷型、四羟苯基乙烷型等二官能环氧树脂或多官能环氧树脂；或者乙内酰脲型；三缩水甘油基异氰脲酸酯型；或者缩水甘油基胺型等环氧树脂。这些可以单独使用或者并用两种以上。这些环氧树脂之中特别优选线型酚醛型环氧树脂、联苯型环氧树脂、三羟苯基甲烷型树脂或四羟苯基乙烷型环氧树脂。这是因于这些环氧树脂富有与作为固化剂的酚醛树脂的反应性且耐热性等优异。
(羟基当量为200g/eq以上的线型酚醛型酚醛树脂)
热固性树脂组合物2中包含的线型酚醛型酚醛树脂作为环氧树脂的固化剂发挥作用，只要其羟基当量为200g/eq以上就没有特别限定。具有这样的羟基当量的线型酚醛型酚醛树脂可以通过将苯酚类与可与该苯酚类进行缩合反应的具有适度分子链长的化合物(例如醛类、双(烷氧基甲基)联苯类等)依据常规方法进行反应而得到。另外，也可适宜地使用市售的羟基当量为200g/eq以上的线型酚醛型酚醛树脂，例如可列举新日铁化学制“SN-495”、明和化成制“MEH-7851H”等。需要说明的是，尽管羟基当量的上限没有特别限定，但若考虑到热固性树脂组合物的固化性、其固化物的刚性等，则优选为250g/eq以下。
其中，优选线型酚醛型酚醛树脂包含由下述结构式表示的结构。
【化2】
(式中，n为0～12的整数。)
通过使用具有上述特定结构的线型酚醛型酚醛树脂，可以以高水平实现固化物的刚性与柔软性的平衡，可以进一步提高半导体装置的可靠性。需要说明的是，上述式中的n只要为0～12的整数即可，优选为0～8的整数。
(其它树脂)
热固性树脂组合物2在上述环氧树脂和特定酚醛树脂以外还可以包含这些以外的热固性树脂、热塑性树脂。
(其它热固性树脂)
作为其它热固性树脂，可列举氨基树脂、不饱和聚酯树脂、聚氨酯树脂、硅树脂或热固性聚酰亚胺树脂等。这些树脂可以单独使用或者并用两种以上。
在上述特定的线型酚醛型酚醛树脂以外，作为酚醛树脂，只要不损害本发明的效果，就可以使用苯酚芳烷基树脂、甲酚线型酚醛树脂、叔丁基苯酚线型酚醛树脂、壬基苯酚线型酚醛树脂等线型酚醛型酚醛树脂、甲阶酚醛型酚醛树脂、聚对羟基苯乙烯等聚羟基苯乙烯等酚醛树脂中的一种或并用两种以上。
上述环氧树脂与上述特定酚醛树脂的配合比例例如优选为以特定酚醛树脂中的羟基相对于上述环氧树脂成分中的每1当量环氧基为0.5～2.0当量的方式配合。更优选为0.8～1.2当量。即这是由于，若两者的配合比例在上述范围以外，则不能进行充分的固化反应，该热固性树脂组合物的固化物的特性容易劣化。
(热塑性树脂)
作为上述热塑性树脂，可列举：天然橡胶、丁基橡胶、异戊二烯橡胶、氯丁橡胶、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸共聚物、乙烯-丙烯酸酯共聚物、聚丁二烯树脂、聚碳酸酯树脂、热塑性聚酰亚胺树脂、6-尼龙、6,6-尼龙等聚酰胺树脂、苯氧基树脂、丙烯酸类树脂、PET或PBT等饱和聚酯树脂、聚酰胺酰亚胺树脂、或氟树脂等。这些热塑性树脂可以单独使用或者并用两种以上。这些热塑性树脂之中，特别优选离子性杂质少、耐热性高且能够确保半导体元件的可靠性的丙烯酸类树脂。
作为上述丙烯酸类树脂，没有特别限定，但可列举以具有碳原子数30以下、尤其碳原子数4～18的直链或支链的烷基的丙烯酸或甲基丙烯酸的酯的一种或两种以上作为成分的聚合物等。作为上述烷基，可列举例如：甲基、乙基、丙基、异丙基、正丁基、叔丁基、异丁基、戊基、异戊基、己基、庚基、环己基、2-乙基己基、辛基、异辛基、壬基、异壬基、癸基、异癸基、十一烷基、月桂基、十三烷基、十四烷基、硬脂基、十八烷基、或十二烷基等。
另外，作为形成上述聚合物的其它单体，没有特别限定，可列举例如：像丙烯腈那样的含氰基单体；丙烯酸、甲基丙烯酸、丙烯酸羧基乙酯、丙烯酸羧基戊酯、衣康酸、马来酸、富马酸或巴豆酸等各种含羧基单体；马来酸酐或衣康酸酐等各种酸酐单体；(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸2-羟基丙酯、(甲基)丙烯酸4-羟基丁酯、(甲基)丙烯酸6-羟基己酯、(甲基)丙烯酸8-羟基辛酯、(甲基)丙烯酸10-羟基癸酯、(甲基)丙烯酸12-羟基月桂酯或丙烯酸(4-羟甲基环己基)甲酯等各种含羟基单体、苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯酰胺-2-甲基丙磺酸、(甲基)丙烯酰胺丙磺酸、(甲基)丙烯酸磺丙酯或(甲基)丙烯酰氧基萘磺酸等各种含磺酸基单体；或者2-羟基乙基丙烯酰基磷酸酯等各种含磷酸基单体。
需要说明的是，在本实施方式中，特别优选使用了环氧树脂、特定酚醛树脂和丙烯酸类树脂的热固性树脂组合物。这些树脂的离子性杂质少、耐热性高，因而能够确保半导体元件的可靠性。对于此时的配合比而言，相对于丙烯酸类树脂成分100重量份，环氧树脂与特定酚醛树脂的混合量为10～200重量份。
(热固化促进催化剂)
作为环氧树脂和特定酚醛树脂的热固化促进催化剂，没有特别限制，可适当从公知的热固化促进催化剂中选用。热固化促进催化剂可以单独使用或组合使用两种以上。作为热固化促进催化剂，可以使用例如胺系固化促进剂、磷系固化促进剂、咪唑系固化促进剂、硼系固化促进剂、磷-硼系固化促进剂等。热固化促进催化剂的添加量相对于环氧树脂与特定酚醛树脂的合计100重量份为0.1～5重量份。
(焊剂)
为了除去焊料凸点表面的氧化膜而使半导体元件容易安装，可以在热固性树脂组合物2中添加焊剂。作为焊剂，没有特别限定，可以使用以往公知的具有焊剂作用的化合物，可列举例如：二苯酚酸、己二酸、乙酰水杨酸、苯甲酸、二苯甲醇酸、壬二酸、苄基苯甲酸、丙二酸、2,2-双(羟甲基)丙酸、水杨酸、邻甲氧基苯甲酸、间羟基苯甲酸、琥珀酸、2,6-二甲氧基甲基对甲酚、苯甲酸酰肼、碳酰肼、丙二酰肼、丁二酰肼、戊二酰肼、水杨酰肼、亚氨基二乙酸二酰肼、衣康酸二酰肼、柠檬酸三酰肼、硫代碳酰肼、二苯甲酮腙、4,4’-氧基双苯磺酰肼和己二酰肼等。焊剂的添加量只要是发挥上述焊剂作用的程度即可，通常相对于热固性树脂组合物中含有的树脂成分100重量份为0.1～20重量份左右。
(交联剂)
在预先使本实施方式的热固性树脂组合物2进行某种程度的交联的情况下，在制作时，可以添加与聚合物的分子链末端的官能团等反应的多官能性化合物作为交联剂。由此，提高高温下的胶粘特性，可以实现耐热性的改善。
作为上述交联剂，尤其更优选为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、对苯二异氰酸酯、1,5-萘二异氰酸酯、多元醇与二异氰酸酯的加成物等多异氰酸酯化合物。作为交联剂的添加量，相对于上述的聚合物100重量份，通常优选设为0.05～7重量份。若交联剂的量多于7重量份，则胶粘力下降，因而不优选。另一方面，若少于0.05重量份，则凝聚力不足，因而不优选。另外，可以根据需要与这样的多异氰酸酯化合物一起含有环氧树脂等其它多官能性化合物。
(无机填充剂)
另外，在热固性树脂组合物2中可以适当配合无机填充剂。无机填充剂的配合能够赋予导电性、提高热传导性、调节储能模量等。
作为上述无机填充剂，可列举例如：二氧化硅、粘土、石膏、碳酸钙、硫酸钡、氧化铝、氧化铍、碳化硅、氮化硅等陶瓷类，铝、铜、银、金、镍、铬、铅、锡、锌、钯、焊料等金属、或者合金类、以及包含碳等的各种无机粉末。这些可以单独使用或并用两种以上。其中，优选使用二氧化硅，尤其优选使用熔融二氧化硅。
无机填充剂的平均粒径没有特别限定，但优选为10nm以上且1000nm以下的范围内、更优选为20nm以上且200nm以下的范围内、进一步优选为30nm以上且100nm以下的范围内。若无机填充剂的平均粒径为10nm，则会导致热固性树脂组合物的挠性下降。另一方面，若上述平均粒径大于1000nm，则导致热固性树脂组合物的透明性下降，并且导致粒径相对于热固性树脂组合物所密封的间隙较大而密封性下降。需要说明的是，在本实施方式中，可以将平均粒径互不相同的无机填充剂彼此组合使用。另外，平均粒径是利用分光光度式的粒度分布计(HORIBA制、装置名；LA-910)求得的值。
上述无机填充剂的配合量相对于有机树脂成分100重量份优选为10～400重量份、更优选为50～250重量份。若无机填充剂的配合量小于10重量份，则有时储能模量下降，使封装的应力可靠性大大受损。另一方面，若超过400重量份，则热固性树脂组合物2的流动性下降，无法充分埋入基板和半导体元件的凹凸而导致产生空隙、裂纹。
(其它添加剂)
需要说明的是，热固性树脂组合物2中，除上述无机填充剂以外，还可以根据需要适当配合其它添加剂。作为其它添加剂，可列举例如阻燃剂、硅烷偶联剂或离子捕获剂等。作为上述阻燃剂，可列举例如三氧化锑、五氧化二锑、溴代环氧树脂等。这些可以单独使用或并用两种以上。作为上述硅烷偶联剂，可列举例如β-(3,4-环氧环己基)乙基三甲氧基硅烷、γ-环氧丙氧基丙基三甲氧基硅烷、γ-环氧丙氧基丙基甲基二乙氧基硅烷等。这些的化合物可以单独使用或并用两种以上。作为上述离子捕获剂，可列举例如水滑石类、氢氧化铋等。这些可以单独使用或并用两种以上。
本实施方式中，热固性树脂组合物2可以根据需要进行着色。热固性树脂组合物2中，作为因着色而呈现的颜色没有特别限制，例如优选黑色、蓝色、红色、绿色等。在着色时，可以适当从颜料、染料等公知的着色剂中选用。
(热固性树脂组合物的物性)
热固化前的热固性树脂组合物的雾度优选为70％以下、更优选为50％以下、进一步优选为30％以下。通过使该热固性树脂组合物的雾度下降来提高透明性，可以更加容易地进行切割或安装时的半导体元件的对齐。各热固性树脂组合物的雾度使用雾度计HM-150(村上色彩技术研究所制)进行测定。测定依据JISK7136进行。
将该热固性树脂组合物在175℃热处理1小时后的固化物的热膨胀系数α没有特别限定，优选为10ppm/K以上且200ppm/K以下、更优选为10ppm/K以上且100ppm/K以下、进一步优选为10ppm/K以上且50ppm/K以下。通过将固化物的热膨胀系数α设成上述范围，可以抑制起因于固化物自身的热响应行为，其结果可进一步提高半导体装置的可靠性。
将该热固性树脂组合物在175℃热处理1小时后的固化物的储能模量E’没有特别限定，优选为100MPa以上且10000MPa以下、更优选为500MPa以上且7000MPa以下、进一步优选为1000MPa以上且5000MPa以下。由此，固化物得到适度的刚性，可以促进热响应行为的差异的吸收或分散从而进一步提高半导体装置的可靠性。
将上述热固性树脂组合物在175℃热固化处理1小时后的玻璃化转变温度(Tg)优选为100～180℃、更优选为130～170℃。通过将热固化后的热固性树脂组合物的玻璃化转变温度设成上述范围，可以抑制热循环可靠性试验的温度范围中的急剧的物性变化，可以期待可靠性的进一步提高。
本实施方式中，热固化前的上述热固性树脂组合物2在100～200℃的最低熔融粘度优选为100Pa·s以上且20000Pa·s以下、更优选为1000Pa·s以上且10000Pa·s以下。通过将最低熔融粘度设成上述范围，可以使连接构件4(参照图2A)容易地进入热固性树脂组合物2中。另外，还可以防止半导体元件5在电连接时产生空隙、以及热固性树脂组合物2从半导体元件5与被粘物6之间的空间溢出(参照图2E)。需要说明的是，最低熔融粘度的测定是使用流变仪(HAAKE公司制、RS-1)，利用平行板法测定出的值。更详细而言，在间隙100μm、旋转板直径20mm、旋转速度10s-1、升温速度10℃/分钟的条件下在60℃～200℃的范围测定熔融粘度，将此时得到的在100℃～200℃的范围内的熔融粘度的最低值作为最低熔融粘度。
另外，热固化前的上述热固性树脂组合物2在23℃的粘度优选为0.01MPa·s以上且100MPa·s以下、更优选为0.1MPa·s以上且10MPa·s以下。通过使热固化前的热固性树脂组合物具有上述范围的粘度，可以提高切割时的半导体晶片3(参照图2C)的保持性、操作时的处理性。需要说明的是，粘度的测定可以依据最低熔融粘度的测定法来进行。
此外，热固化前的上述热固性树脂组合物2在温度23℃、湿度70％的条件下的吸水率优选为1重量％以下、更优选为0.5重量％以下。通过使热固性树脂组合物2具有上述那样的吸水率，从而抑制水分向热固性树脂组合物2中的吸收，可以更有效地抑制半导体元件5在安装时的空隙的产生。需要说明的是，上述吸水率的下限越小越优选，优选实质上为0重量％、更优选为0重量％。
热固性树脂组合物2的厚度(多层的情况下为总厚度)没有特别限定，但若考虑热固性树脂组合物2的强度、半导体元件5与被粘物6之间的空间的填充性，则可以为10μm以上且100μm以下左右。需要说明的是，热固性树脂组合物2的厚度可以考虑半导体元件5与被粘物6之间的间隙、连接构件的高度进行适当设定。
密封片10的热固性树脂组合物2优选通过隔离件来加以保护(未图示)。隔离件具有作为供于实用之前保护热固性树脂组合物2的保护材料的功能。隔离件在向密封片的热固性树脂组合物2上贴附半导体晶片3时被剥离。作为隔离件，可以使用聚对苯二甲酸乙二醇酯(PET)、聚乙烯、聚丙烯、或者利用氟系剥离剂、长链烷基丙烯酸酯系剥离剂等剥离剂进行了表面涂覆后的塑料膜或纸等。
[背面磨削用带]
背面磨削用带1具备基材1a和层叠在基材1a上的粘合剂层1b。需要说明的是，热固性树脂组合物2层叠在粘合剂层1b上。
(基材)
上述基材1a是构成密封片10的强度基础的物质。可列举例如：低密度聚乙烯、直链状聚乙烯、中密度聚乙烯、高密度聚乙烯、超低密度聚乙烯、无规共聚聚丙烯、嵌段共聚聚丙烯、均聚丙烯、聚丁烯、聚甲基戊烯等聚烯烃，乙烯-乙酸乙烯酯共聚物、离聚体树脂、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯(无规、交替)共聚物、乙烯-丁烯共聚物、乙烯-己烯共聚物、聚氨酯、聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯等聚酯，聚碳酸酯、聚酰亚胺、聚醚醚酮、聚酰亚胺、聚醚酰亚胺、聚酰胺、全芳香族聚酰胺、聚苯硫醚、芳酰胺(纸)、玻璃、玻璃纤维布、氟树脂、聚氯乙烯、聚偏氯乙烯、纤维素系树脂、硅树脂、金属(箔)、纸等。粘合剂层1b为紫外线固化型的情况下，基材1a优选为对紫外线具有透过性的基材。
此外，作为基材1a的材料，可列举上述树脂的交联体等聚合物。上述塑料膜可以在未拉伸的状态下使用，也可以根据需要使用实施了单轴或双轴的拉伸处理后的塑料膜。
为了提高与邻接的层的密合性、保持性等，基材1a的表面可以实施惯用的表面处理，例如铬酸处理、臭氧暴露、火焰暴露、高压电击暴露、离子化放射线处理等化学性或物理性的处理、用底涂剂(例如粘合物质)的涂布处理。
上述基材1a可以适当选择使用同种或不同种的基材，根据需要可以将多种基材混合后使用。另外，为了对基材1a赋予抗静电能力，可以在上述的基材1a上设置由金属、合金、它们的氧化物等形成的厚度为30～左右的导电性物质的蒸镀层。基材1a可以为单层或两种以上的多层。
基材1a的厚度可以适当地确定，通常为5μm以上且200μm以下左右，优选为35μm以上且120μm以下。
需要说明的是，基材1a中可以以不损害本发明效果等的范围包含各种添加剂(例如着色剂、填充剂、增塑剂、抗老化剂、抗氧化剂、表面活性剂、阻燃剂等)。
(粘合剂层)
粘合剂层1b的形成中使用的粘合剂只要可控制成在切割时能够借助热固性树脂组合物牢固地保持半导体晶片或半导体芯片、在拾取时能够剥离带有热固性树脂组合物的半导体芯片就没有特别限制。例如，可以使用丙烯酸系粘合剂、橡胶系粘合剂等通常的压敏性胶粘剂。作为上述压敏性胶粘剂，从半导体晶片、玻璃等忌讳污染的电子构件的利用超纯水、醇等有机溶剂的清洁清洗性等方面出发，优选以丙烯酸系聚合物为基础聚合物的丙烯酸系粘合剂。
作为上述丙烯酸系聚合物，可列举将丙烯酸酯用作主要单体成分的聚合物。作为上述丙烯酸酯，可列举例如使用(甲基)丙烯酸烷基酯(例如甲酯、乙酯、丙酯、异丙酯、丁酯、异丁酯、仲丁酯、叔丁酯、戊酯、异戊酯、己酯、庚酯、辛酯、2-乙基己酯、异辛酯、壬酯、癸酯、异癸酯、十一烷酯、十二烷酯、十三烷酯、十四烷酯、十六烷酯、十八烷酯、二十烷酯等烷基的碳原子数为1～30、尤其碳原子数为4～18的直链状或支链状的烷基酯等)和(甲基)丙烯酸环烷基酯(例如环戊酯、环己酯等)中的一种或两种以上作为单体成分的丙烯酸系聚合物等。需要说明的是，(甲基)丙烯酸酯是指丙烯酸酯和/或甲基丙烯酸酯，本发明的(甲基)均为相同的含义。
以凝聚力、耐热性等的改性为目的，上述丙烯酸系聚合物根据需要可以含有与能够同上述(甲基)丙烯酸烷基酯或环烷基酯进行共聚的其它单体成分对应的单元单元。作为这样的单体成分，可以举出例如丙烯酸、甲基丙烯酸、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯、衣康酸、马来酸、富马酸、巴豆酸等含羧基单体；马来酸酐、衣康酸酐等酸酐单体；(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸2-羟基丙酯、(甲基)丙烯酸4-羟基丁酯、(甲基)丙烯酸6-羟基己酯、(甲基)丙烯酸8-羟基辛酯、(甲基)丙烯酸10-羟基癸酯、(甲基)丙烯酸12-羟基月桂酯、(甲基)丙烯酸(4-羟基甲基环己基)甲酯等含羟基单体；苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯酰胺-2-甲基丙磺酸、(甲基)丙烯酰胺丙磺酸、(甲基)丙烯酸磺丙酯、(甲基)丙烯酰氧基萘磺酸等含磺酸基单体；2-羟基乙基丙烯酰磷酸酯等含磷酸基单体；丙烯酰胺、丙烯腈等。这些能够进行共聚的单体成分可以使用一种或两种以上。这些能够进行共聚的单体的使用量优选为全部单体成分的40重量％以下。
此外，为了使上述丙烯酸系聚合物交联，也可以根据需要含有多官能性单体等作为共聚用单体成分。作为这样的多官能性单体，可以举出例如：己二醇二(甲基)丙烯酸酯、(聚)乙二醇二(甲基)丙烯酸酯、(聚)丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、环氧(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯、氨基甲酸酯(甲基)丙烯酸酯等。这些多官能性单体也可以使用一种或两种以上。从粘合特性等方面出发，多官能性单体的使用量优选为全部单体成分的30重量％以下。
上述丙烯酸系聚合物可以通过将单一单体或两种以上的单体混合物加以聚合而得到。聚合也可以以溶液聚合、乳液聚合、本体聚合、悬浮聚合等任意一种方式进行。从防止对清洁的被粘物的污染等方面出发，优选低分子量物质的含量小。从该点出发，丙烯酸系聚合物的数均分子量优选为30万以上、进一步优选为40万～300万左右。
另外，为了提高作为基础聚合物的丙烯酸系聚合物等的数均分子量，在上述粘合剂中还可以适当地采用外部交联剂。作为外部交联方法的具体方法，可列举添加多异氰酸酯化合物、环氧化合物、氮丙啶化合物、三聚氰胺系交联剂等所谓的交联剂使之反应的方法。在使用外部交联剂的情况下，其使用量根据与应交联的基础聚合物的平衡、以及作为粘合剂的使用用途来适当确定。一般而言，相对于上述基础聚合物100重量份，优选为5重量份左右以下、进一步优选配合0.1～5重量份。此外，粘合剂中，根据需要，除了上述成分以外，还可以使用以往公知的各种增粘剂、抗老化剂等添加剂。
粘合剂层1b可以由放射线固化型粘合剂来形成。放射线固化型粘合剂通过紫外线等放射线的照射使交联度增大，能够容易地降低其粘合力，能够容易地进行拾取。作为放射线，可列举X射线、紫外线、电子束、α射线、β射线、中子射线等。
放射线固化型粘合剂可以无特别限制地使用具有碳-碳双键等放射线固化性官能团且显示粘合性的粘合剂。作为放射线固化型粘合剂，可例示出例如在上述丙烯酸系粘合剂、橡胶系粘合剂等一般的压敏性粘合剂中配合了放射线固化性的单体成分、低聚物成分的添加型的放射线固化性粘合剂。
作为所配合的放射线固化性的单体成分，可列举例如：氨基甲酸酯低聚物、氨基甲酸酯(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、四羟甲基甲烷四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇单羟基五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯等。另外，放射线固化性的低聚物成分可列举氨基甲酸酯系、聚醚系、聚酯系、聚碳酸酯系、聚丁二烯系等各种低聚物，适合为其重均分子量为100～30000左右的范围的低聚物。放射线固化性的单体成分、低聚物成分的配合量可以根据上述粘合剂层的种类来适当确定能够降低粘合剂层的粘合力的量。一般而言，相对于构成粘合剂的丙烯酸系聚合物等基础聚合物100重量份，例如为5～500重量份、优选为40～150重量份左右。
另外，作为放射线固化型粘合剂，除了上述说明的添加型的放射线固化性粘合剂以外，可以列举使用了在聚合物侧链或主链中或者主链末端具有碳-碳双键的聚合物作为基础聚合物的内在型的放射线固化性粘合剂。内在型的放射线固化性粘合剂无需含有作为低分子成分的低聚物成分等，或者不含有大量的作为低分子成分的低聚物成分等，因此低聚物成分等不会随着时间在粘合剂中移动，能够形成稳定的层结构的粘合剂层，因此优选。
具有上述碳-碳双键的基础聚合物只要具有碳-碳双键且具有粘合性就可以无特别限制地使用。作为这样的基础聚合物，优选以丙烯酸系聚合物为基础骨架的聚合物。作为丙烯酸系聚合物的基础骨架，可列举上文例示出的丙烯酸系聚合物。
向上述丙烯酸系聚合物中导入碳-碳双键的方法没有特别限制，可以采用各种方法，但碳-碳双键导入聚合物侧链在分子设计中是容易的。例如可列举如下方法：预先将丙烯酸系聚合物与具有官能团的单体共聚后，使具有能够与该官能团反应的官能团以及碳-碳双键的化合物在维持碳-碳双键的放射线固化性的同时进行缩合或加成反应的方法。
作为这些官能团的组合的例子，可列举羧酸基和环氧基、羧酸基和氮丙啶基、羟基和异氰酸酯基等。在这些官能团的组合中，从追踪反应的容易性出发，优选羟基与异氰酸酯基的组合。另外，如果是通过这些官能团的组合能生成上述具有碳-碳双键的丙烯酸系聚合物的组合，则官能团无论处于丙烯酸系聚合物和上述化合物的任意一方均可，上述的优选组合中，优选丙烯酸系聚合物具有羟基、上述化合物具有异氰酸酯基的情况。此时，作为具有碳-碳双键的异氰酸酯化合物，可列举例如甲基丙烯酰基异氰酸酯、2-甲基丙烯酰氧基乙基异氰酸酯、间异丙烯基-α,α-二甲基苄基异氰酸酯等。另外，作为丙烯酸系聚合物，使用将上述例示的含羟基单体、2-羟基乙基乙烯基醚、4-羟基丁基乙烯基醚、二乙二醇单乙烯基醚的醚系化合物等共聚而得到的聚合物。
上述内在型的放射线固化性粘合剂可以单独使用上述具有碳-碳双键的基础聚合物(尤其丙烯酸系聚合物)，但也可以以不使特性恶化的程度配合上述放射线固化性的单体成分、低聚物成分。放射线固化性的低聚物成分等通常相对于基础聚合物100重量份在30重量份的范围内、优选为0～10重量份的范围。
上述放射线固化型粘合剂中，在利用紫外线等进行固化的情况下，优选含有光聚合引发剂。作为光聚合引发剂，可列举例如：4-(2-羟基乙氧基)苯基(2-羟基-2-丙基)酮、α-羟基-α,α′-二甲基苯乙酮、2-甲基-2-羟基苯丙酮、1-羟基环己基苯酮等α-酮系化合物；甲氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基苯乙酮、2-甲基-1-[4-(甲硫基)-苯基]-2-吗啉代丙烷-1等苯乙酮系化合物；苯偶姻乙醚、苯偶姻异丙醚、茴香偶姻甲醚等苯偶姻醚系化合物；联苯酰二甲缩酮等缩酮系化合物；2-萘磺酰氯等芳香族磺酰氯系化合物；1-苯基酮-1,1-丙二酮-2-(O-乙氧基羰基)肟等光活性肟系化合物；二苯甲酮、苯甲酰苯甲酸、3,3′-二甲基-4-甲氧基二苯甲酮等二苯甲酮系化合物；噻吨酮、2-氯噻吨酮、2-甲基噻吨酮、2,4-二甲基噻吨酮、异丙基噻吨酮、2,4-二氯噻吨酮、2,4-二乙基噻吨酮、2,4-二异丙基噻吨酮等噻吨酮系化合物；樟脑醌；卤代酮；酰基氧化膦；酰基磷酸酯等。光聚合引发剂的配合量相对于构成粘合剂的丙烯酸系聚合物等基础聚合物100重量份为例如0.05～20重量份左右。
需要说明的是，在放射线照射时因氧而阻碍固化的情况下，期望利用某些方法从放射线固化型的粘合剂层1b的表面阻隔氧(空气)。可列举例如：以隔离件被覆上述粘合剂层1b的表面的方法；在氮气气氛中进行紫外线等放射线的照射的方法等。
需要说明的是，粘合剂层1b中可以以不损害本发明效果等的范围含有各种添加剂(例如着色剂、增稠剂、增量剂、填充剂、增粘剂、增塑剂、抗老化剂、抗氧化剂、表面活性剂、交联剂等)。
粘合剂层1b的厚度没有特别限定，从防止芯片切割面的缺损和保持热固性树脂组合物2的固定这两者的兼顾性等观点出发，优选为1～50μm左右。优选为2～30μm，更优选为5～25μm。
(密封片的制造方法)
本实施方式涉及的密封片10例如可以通过预先分别制作背面磨削用带1和热固性树脂组合物2，最后将它们贴合来制作。具体来说，可以依据如下所述的步骤来制作。
首先，基材1a可以通过以往公知的制膜方法来制膜。作为该制膜方法，可例示出例如：压延制膜法、有机溶剂中的浇注法、密闭体系中的吹塑挤出法、T模头挤出法、共挤出法、干式层压法等。
接着，制备粘合剂层形成用的粘合剂组合物。粘合剂组合物中配合有在粘合剂层的项中说明的树脂、添加物等。将所制备的粘合剂组合物涂布于基材1a上形成涂布膜后，在规定条件下使该涂布膜干燥(根据需要进行加热使之交联)，形成粘合剂层1b。作为涂布方法没有特别限定，可列举例如：辊涂布、丝网涂布、凹版涂布等。另外，作为干燥条件，例如在干燥温度80～150℃、干燥时间0.5～5分钟的范围内进行。另外，可以在隔离件上涂布粘合剂组合物而形成涂布膜后，在上述干燥条件下使涂布膜干燥而形成粘合剂层1b。之后，将粘合剂层1b与隔离件一起贴合于基材1a上。由此，制作出具备基材1a和粘合剂层1b的背面磨削用带1。
片状的热固性树脂组合物2例如如下所述进行制作。首先，配合作为热固性树脂组合物2的形成材料的环氧树脂和特定酚醛树脂、根据需要的热塑性成分、各种添加剂等，并溶解或分散于适当溶剂(例如甲乙酮、乙酸乙酯等)中，从而制备涂布液。
接着，将所制备的涂布液按照规定厚度涂布于基材隔离件上形成涂布膜后，使该涂布膜在规定条件下干燥，形成片状的热固性树脂组合物。作为涂布方法，没有特别限定，可列举例如辊涂布、丝网涂布、凹版涂布等。另外，作为干燥条件，例如在干燥温度70～160℃、干燥时间1～5分钟的范围内进行。另外，也可以在隔离件上涂布涂布液形成涂布膜后，在上述干燥条件下使涂布膜干燥而形成片状的热固性树脂组合物。之后，使热固性树脂组合物与隔离件一起贴合于基材隔离件上。
接着，分别从背面磨削用带1和热固性树脂组合物2剥离隔离件，按照将热固性树脂组合物和粘合剂层作为贴合面的方式贴合两者。贴合例如可以通过压接进行。这种情况下，层压温度没有特别限定，例如优选为30～50℃、更优选为35～45℃。另外，线压没有特别限定，例如优选为0.98～196N/cm、更优选为9.8～98N/cm。接着，将热固性树脂组合物上的基材隔离件剥离，得到本实施方式涉及的密封片。
＜半导体装置的制造方法＞
接着，对利用上述密封片的半导体装置的制造方法的一个实施方式进行说明。本实施方式的半导体装置的制造方法包含：将半导体元件通过上述热固性树脂组合物固定于被粘物的固定工序、和使上述热固性树脂组合物固化的固化工序。但是，在本实施方式中，上述热固性树脂组合物层叠于背面磨削用带上而形成密封片，另外，在半导体元件的固定时，被粘物和半导体元件被电连接。因此，更详细而言，本实施方式的半导体装置的制造方法包含：贴合工序，将半导体晶片的形成有连接构件的电路面与上述密封片的热固性树脂组合物贴合；磨削工序，对上述半导体晶片的背面进行磨削；晶片固定工序，与上述热固性树脂组合物一起将半导体晶片从背面磨削用带剥离，将该半导体晶片贴附于切割带；切割工序，将上述半导体晶片切割而形成带有上述热固性树脂组合物的半导体元件；以及拾取工序，将带有上述热固性树脂组合物的半导体元件从上述切割带剥离；连接工序，用上述热固性树脂组合物填充上述被粘物与上述半导体元件之间的空间并且通过上述连接构件将上述半导体元件与上述被粘物电连接；以及固化工序，使上述热固性树脂组合物固化。
[贴合工序]
贴合工序中，将半导体晶片3的形成有连接构件4的电路面3a与上述密封片10的热固性树脂组合物2贴合(参照图2A)。
(半导体晶片)
半导体晶片3的电路面3a形成有多个连接构件4(参照图2A)。作为凸点、导电材料等连接构件的材质，没有特别限定，可列举例如：锡-铅系金属材、锡-银系金属材、锡-银-铜系金属材、锡-锌系金属材、锡-锌-铋系金属材等焊料类(合金)、金系金属材、铜系金属材等。连接构件的高度也根据用途确定，一般为15～100μm左右。当然，半导体晶片3中的各个连接构件的高度可以相同或不同。
本实施方式的半导体装置的制造方法中，作为热固性树脂组合物的厚度，优选在半导体晶片表面形成的连接构件的高度X(μm)和上述热固性树脂组合物的厚度Y(μm)满足下述关系。
0.5≤Y/X≤2
通过上述连接构件的高度X(μm)和上述固化膜的厚度Y(μm)满足上述关系，可以充分填充半导体元件与被粘物之间的空间，并且可以防止热固性树脂组合物从该空间过量溢出，可以防止热固性树脂组合物导致的半导体元件的污染等。需要说明的是，各连接构件的高度不同的情况下，以最高的连接构件的高度为基准。
(贴合)
首先，将在密封片10的热固性树脂组合物2上任意设置的隔离件适当地剥离，如图2A所示，使上述半导体晶片3的形成有连接构件4的电路面3a与热固性树脂组合物2相面对，将上述热固性树脂组合物2和上述半导体晶片3贴合(装配(mount))。
贴合的方法没有特别限定，优选利用压接的方法。压接通常边通过压接辊等公知的按压单元负载优选为0.1～1MPa、更优选为0.3～0.7MPa的压力进行按压边进行。此时，可以边加热至40～100℃左右边进行压接。另外，为了提高密合性，还优选在减压下(1～1000Pa)进行压接。
[磨削工序]
磨削工序中，对上述半导体晶片3的电路面3a的相反一侧的面(即背面)3b进行磨削(参照图2B)。作为半导体晶片3的背面磨削中使用的薄型加工机，没有特别限定，可例示出例如磨削机(背磨机)、研磨垫等。另外，可以利用蚀刻等化学方法进行背面磨削。背面磨削进行到直至半导体晶片达到所期望的厚度(例如700～25μm)为止。
[晶片固定工序]
磨削工序后，在贴合有热固性树脂组合物2的状态下将半导体晶片3从背面磨削用带1剥离，将半导体晶片3与切割带11贴合(参照图2C)。此时，半导体晶片3的背面3b和切割带11的粘合剂层11b以面对的方式贴合。因此，在半导体晶片3的电路面3a贴合的热固性树脂组合物2成为露出的状态。需要说明的是，切割带11具有在基材11a上层叠有粘合剂层11b的结构。作为基材11a和粘合剂层11b，可以使用在上述背面磨削用带1的基材1a和粘合剂层1b的项中所示的成分和制法适当进行制作。另外，也可适合地使用市售的切割带。
半导体晶片3从背面磨削用带1剥离时，在粘合剂层1b具有放射线固化性的情况下，通过对粘合剂层1b照射放射线使粘合剂层1b固化，可以容易地进行剥离。放射线的照射量可以考虑所用的放射线的种类、粘合剂层的固化度等进行适当设定。
[切割工序]
切割工序中，基于利用直接光、间接光、红外线等求出的切割位置，如图2D所示那样将半导体晶片3和热固性树脂组合物2切割而形成被切割的带有热固性树脂组合物的半导体元件5。通过利用无机填充剂的平均粒径等来适当调整热固性树脂组合物2的透明性，可以容易地确定切割位置。通过经过切割工序，将半导体晶片3裁切成规定尺寸后而单片化(小片化)，从而制造半导体芯片(半导体元件)5。在此得到的半导体芯片5与裁切成相同形状的热固性树脂组合物2成为一体。切割依据常规方法从半导体晶片3的贴合有热固性树脂组合物2的电路面3a进行。
本工序中，例如可以采用切入直到切割带11的被称为全切割(fullcut)的裁切方式等。作为在本工序中使用的切割装置，没有特别限定，可以使用以往公知的装置。另外，半导体晶片被切割带11以优异的密合性胶粘固定，因而可以抑制芯片残缺和芯片飞溅，并且还可以抑制半导体晶片的破损。需要说明的是，若热固性树脂组合物由包含环氧树脂的树脂组合物形成，则即便通过切割被裁切，也可以抑制或防止在其切割面产生热固性树脂组合物的热固性树脂组合物糊浆的溢出。结果，可以抑制或防止切割面彼此再附着(粘连)，可以更好地进行后述的拾取。
需要说明的是，继切割工序后进行切割带的扩张的情况下，该扩张可以使用以往公知的扩张装置进行。扩张装置具有可通过切割环将切割带压向下方的圆环状的外环、和直径比外环小的支撑切割带的内环。通过该扩张工序，可以在后述的拾取工序防止相邻的半导体芯片彼此接触而破损。
[拾取工序]
为了回收胶粘固定于切割带11的半导体芯片5，如图2E所示，进行带有热固性树脂组合物2的半导体芯片5的拾取，将半导体芯片5与热固性树脂组合物2的层叠体A从切割带11剥离。
作为拾取的方法，没有特别限定，可以采用以往公知的各种方法。可列举例如利用针从切割带的基材侧将各个半导体芯片向上顶，通过拾取装置拾取被上顶的半导体芯片的方法等。需要说明的是，所拾取的半导体芯片5与贴合在电路面3a的热固性树脂组合物2成为一体而构成了层叠体A。
在此，在切割带11的粘合剂层11b为紫外线固化型的情况下，拾取在对该粘合剂层11b照射紫外线后进行。由此，粘合剂层11b对半导体芯片5的粘合力下降，半导体芯片5的剥离变得容易。结果，能够在不损伤半导体芯片5的情况下进行拾取。紫外线照射时的照射强度、照射时间等条件没有特别限定，只要根据需要适当设定即可。另外，作为紫外线照射中使用的光源，可以使用例如低压汞灯、低压高输出灯、中压汞灯、无电极汞灯、氙气闪光灯、准分子灯、紫外LED等。
[安装工序]
安装工序中，利用直接光、间接光、红外线等预先求出半导体元件5的安装位置，根据所求出的安装位置，用热固性树脂组合物2填充被粘物16与半导体元件5之间的空间并且同时借助连接构件4将半导体元件5和被粘物16电连接(参照图2F)。通过利用无机填充剂的平均粒径等适当调整热固性树脂组合物2的透明性，可以容易地确定安装位置。具体来说，依据常规方法以半导体芯片5的电路面3a与被粘物16相面对的形态将层叠体A的半导体芯片5固定于被粘物16。例如，使形成于半导体芯片5的凸点(连接构件)4与粘附在被粘物16的连接垫的接合用的导电材料17(焊料等)接触并进行按压，同时使导电材料熔融，由此能够确保半导体芯片5与被粘物16的电连接，可以将半导体芯片5固定于被粘物16。半导体芯片5的电路面3a贴附有热固性树脂组合物2，因而在半导体芯片5和被粘物16的电连接的同时，半导体芯片5与被粘物16之间的空间被热固性树脂组合物2所填充。
一般而言，作为安装工序中的加热条件，为100～300℃，作为加压条件，为0.5～500N。另外，可以以多个阶段进行安装工序中的热压接处理。例如可以采用在150℃、100N下处理10秒钟后，在300℃、100～200N下处理10秒钟这样的步骤。通过在多个阶段中进行热压接处理，可以高效地除去连接构件与垫间的树脂，得到更好的金属间胶粘。
作为被粘物16，可以使用导线框、电路基板(配线电路基板等)等各种基板、其它半导体元件。作为基板的材质，没有特别限定，可列举陶瓷基板、塑料基板。作为塑料基板，可列举例如环氧基板、双马来酰亚胺三嗪基板、聚酰亚胺基板、玻璃环氧基板等。
需要说明的是，安装工序中，使连接构件和导电材料的一方或双方熔融，从而使半导体芯片5的连接构件形成面3a的凸点4与被粘物16的表面的导电材料17连接，作为该凸点4和导电材料17的熔融时的温度，通常为260℃左右(例如250℃～300℃)。本实施方式的密封片通过利用环氧树脂等形成热固性树脂组合物2，从而可以成为具有也能够耐受该安装工序中的高温的耐热性的密封片。
[热固性树脂组合物固化工序]
进行半导体元件5与被粘物16的电连接后，通过加热使热固性树脂组合物2固化。由此，可以保护半导体元件5的表面，并且可以将半导体元件5与被粘物16之间的空间密封而确保半导体装置的连接可靠性。作为用于热固性树脂组合物的固化的加热温度，没有特别限定，只要为在150～200℃下10～120分钟既可。需要说明的是，热固性树脂组合物由于安装工序中的加热处理而固化的情况下，本工序可以省略。
[后密封工序]
接着，为了保护具有所安装的半导体芯片5的半导体装置20整体，可以进行后密封工序。后密封工序使用密封树脂进行。作为此时的密封条件，没有特别限定，通常通过在175℃进行60秒钟～90秒钟的加热，由此进行密封树脂的热固化，但本发明不限于此，例如可以在165℃～185℃进行几分钟固化。
作为上述密封树脂，只要是具有绝缘性的树脂(绝缘树脂)就没有特别限制，可以从公知的密封树脂等密封材料中适当选用，但更优选为具有弹性的绝缘树脂。作为密封树脂，可列举例如包含环氧树脂的树脂组合物等。作为环氧树脂，可列举上文中例示的环氧树脂等。另外，作为基于包含环氧树脂的树脂组合物的密封树脂，作为树脂成分，在环氧树脂以外也可以包含环氧树脂以外的热固性树脂(酚醛树脂等)、热塑性树脂等。需要说明的是，作为酚醛树脂，也可以以环氧树脂的固化剂的形式来利用，作为这样的酚醛树脂，可列举上文中例示的酚醛树脂等。
[半导体装置]
接着，参照附图对使用该密封片得到的半导体装置进行说明(参照图2F)。本实施方式的半导体装置20中，半导体元件5和被粘物16借助形成在半导体元件5上的凸点(连接构件)4和设置在被粘物16上的导电材料17而被电连接。另外，在半导体元件5与被粘物16之间以填充其空间的方式配置有热固性树脂组合物2。半导体装置20利用采用规定热固性树脂组合物2的上述制造方法而得到，因而半导体元件5的表面保护、半导体元件5与被粘物16之间的空间的填充以及半导体元件5与被粘物16之间的电连接各自达到充分的水平，作为半导体装置20可以发挥高可靠性。
＜第2实施方式＞
在第1实施方式中，使用了在单面形成有电路的半导体晶片，与此相对，在本实施方式中，使用在双面形成有电路的半导体晶片制造半导体装置。另外，由于在本实施方式中使用的半导体晶片具有目标厚度，因此省略磨削工序。因此，作为第2实施方式中的密封片，使用具备切割带和层叠在该切割带上的热固性树脂组合物的密封片。作为第2实施方式中的典型工序，可列举：准备上述密封片的准备工序；将在双面形成有具有连接构件的电路面的半导体晶片与上述密封片的热固性树脂组合物贴合的贴合工序；将上述半导体晶片切割而形成带有上述热固性树脂组合物的半导体元件的切割工序；将带有上述热固性树脂组合物的半导体元件从上述密封片剥离的拾取工序。之后，进行安装工序以后的工序，从而制造半导体装置。
[准备工序]
准备工序中，准备具备切割带41和层叠在该切割带41上的热固性树脂组合物42的密封片(参照图3A)。切割带41具备基材41a和层叠在基材41a上的粘合剂层41b。需要说明的是，热固性树脂组合物42被层叠在粘合剂层41b上。作为这样的切割带41的基材41a和粘合剂层41b以及热固性树脂组合物42，可以使用与第1实施方式同样的基材和粘合剂层以及热固性树脂组合物。
[贴合工序]
贴合工序中，如图3A所示，将在双面形成有具有连接构件44的电路面的半导体晶片43与上述密封片的热固性树脂组合物42贴合。需要说明的是，由于薄型化至规定厚度后的半导体晶片的强度弱，因而为了增强而将半导体晶片通过预固定材料固定于支撑玻璃等支撑体(未图示)。这种情况下，在半导体晶片与热固性树脂组合物的贴合后，还包含与预固定材料一起将支撑体剥离的工序。是否将半导体晶片43的所有电路面与热固性树脂组合物42贴合根据目标半导体装置的结构进行变更。
作为半导体晶片43，在双面形成有具有连接构件44的电路面，并且具有规定厚度，除此以外，与第1实施方式的半导体晶片是同样的。半导体晶片43的双面的连接构件44彼此可以被电连接，也可以不被连接。连接构件44彼此的电连接可列举被称作TSV形式的利用通过导通孔的连接进行的连接等。作为贴合条件，可以适当采用第1实施方式中的贴合条件。
[切割工序]
切割工序中，将上述半导体晶片43和热固性树脂组合物42切割而形成带有上述热固性树脂组合物的半导体元件45(参照图3B)。作为切割条件，可以适当采用第1实施方式中的各条件。需要说明的是，切割是对半导体晶片43的露出的电路面进行的，因而切割位置的检测是容易的。
[拾取工序]
拾取工序中，将带有上述热固性树脂组合物42的半导体元件45从上述切割带41剥离(图3C)。作为拾取条件，可适合地采用第1实施方式中的各条件。
[安装工序]
安装工序中，用热固性树脂组合物42填充被粘物66与半导体元件45之间的空间，并且借助连接构件44将半导体元件45与被粘物66电连接(参照图3D)。安装工序中的条件可以适当地采用第1实施方式中的各条件。由此，可以制造本实施方式的半导体装置60。
此后，可以与第1实施方式同样地根据需要进行热固性树脂组合物固化工序和密封工序。
＜第3实施方式＞
第1实施方式中，使用了作为密封片的构成构件的背面磨削用带，但本实施方式中，未设置该背面磨削用带的粘合剂层而单独使用基材。因此，作为本实施方式的密封片，形成热固性树脂组合物层叠在基材上的状态。本实施方式中，磨削工序是可选进行的，但拾取工序前的紫外线照射由于粘合剂层的省略而不进行。如果除这些方面以外，可以通过经过与第1实施方式同样的工序来制造规定的半导体装置。
实施例
以下，例示性地具体说明该发明的适合的实施例。但是，该实施例中记载的材料、配合量等只要没有特别的限定性记载，则并不意味着将该发明的范围仅限于此。另外，“份”是指重量份。
[实施例1～4和比较例1～4]
(密封片的制作)
将以下的成分以表1所示比例溶于甲乙酮，制备了固体含量浓度为23.6～60.6重量％的胶粘剂组合物的溶液。
弹性体1：以丙烯酸乙酯-甲基丙烯酸甲酯为主要成分的丙烯酸酯系聚合物(商品名“ParachronW-197CM”、根上工业株式会社制)
弹性体2：以丙烯酸丁酯-丙烯腈为主要成分的丙烯酸酯系聚合物(商品名“SG-28GM“、NagaseChemtex株式会社制)
环氧树脂1：商品名“Epicoat828”、JER株式会社制
环氧树脂2：商品名“Epicoat1004”、JER株式会社制
酚醛树脂1：商品名“MEH-7851M”、明和化成株式会社制
酚醛树脂2：商品名“MEH-7851-3H”、明和化成株式会社制
酚醛树脂3：商品名“P-200”、荒川化学株式会社制
酚醛树脂4：商品名“DPP-M”、日本石油化学株式会社制
无机填充剂1：球状二氧化硅(商品名“YC100C-MLC”、株式会社Admatechs制)
无机填充剂2：球状二氧化硅(商品名“SO-25R”、株式会社Admatechs制)
有机酸：邻茴香酸(商品名“オルトアニス酸”、东京化成株式会社制)
固化剂：咪唑催化剂(商品名“2PHZ-PW”、四国化成株式会社制)
在作为剥离衬垫(隔离件)的经硅酮脱模处理的厚度为50μm的由聚对苯二甲酸乙二醇酯膜形成的脱模处理膜上涂布该胶粘剂组合物的溶液后，在130℃干燥2分钟，由此制作了厚度45μm的热固性树脂组合物。
使用手压辊将上述热固性树脂组合物贴合于背磨带(商品名“UB-2154”、日东电工株式会社制)的粘合剂层上，从而制作了密封片。
(热膨胀率α的测定)
对于热膨胀率α，首先将所制作的热固性树脂组合物在175℃热固化处理1小时后，使用热机械测定装置(TAINSTRUMENTS公司制：型号Q-400EM)进行测定。具体来说，将测定试样的尺寸设成长度15mm×宽度5mm×厚度200μm，将测定试样安装于上述装置的膜拉伸测定用夹具后，在-50～300℃的温度范围中在拉伸负荷2g、升温速度10℃/min的条件下放置，根据在20℃～60℃的膨胀率算出热膨胀系数α。结果示于表1中。
(储能模量E’的测定)
对于储能模量的测定而言，将所制作的热固性树脂组合物在175℃热固化处理1小时后，使用固体粘弹性测定装置(RheometricScientific公司制：型号：RSA-III)进行测定。即，将样品尺寸设成长度40mm×宽度10mm×厚度200μm，将测定试样安装于膜拉伸测定用夹具，在频率1Hz、升温速度10℃/min的条件下测定在-50～300℃的温度范围中的拉伸储能模量和损耗模量，读取在25℃的储能模量(E’)而得到。结果示于表1中。
(玻璃化转变温度的测定)
热固性树脂组合物的玻璃化转变温度的测定方法如下所述。首先，将热固性树脂组合物在175℃通过1小时的加热处理使之热固化，之后用切割刀裁切成厚度200μm、长度40mm(测定长度)、宽度10mm的条状，使用固体粘弹性测定装置(RSAIII、RheometricScientific株式会社制)，测定了在-50～300℃的储能模量和损耗模量。测定条件设成频率1Hz、升温速度10℃/min。此外，通过计算tanδ(G”(损耗模量)/G’(储能模量))的值来得到玻璃化转变温度。结果示于表1中。
(半导体装置的制作)
准备在单面形成有凸点的单面带有凸点的硅晶片，在该单面带有凸点的硅晶片的形成有凸点的一侧的面以热固性树脂组合物作为贴合面贴合所制作的密封片。作为单面带有凸点的硅晶片，使用以下的物质。另外，贴合条件如下所述。热固性树脂组合物的厚度Y(＝45μm)相对于连接构件的高度X(＝45μm)的比(Y/X)为1。
＜单面带有凸点的硅晶片＞
硅晶片的直径：8英寸
硅晶片的厚度：0.7mm(700μm)
凸点的高度：45μm
凸点的间距：50μm
凸点的材质：焊料
＜贴合条件＞
贴附装置：商品名“DSA840-WS”、日东精机株式会社制
贴附速度：5mm/min
贴附压力：0.25MPa
贴附时的台面温度：80℃
贴附时的减压度：150Pa
按照上述步骤贴合单面带有凸点的硅晶片和密封片后，在下述条件下对硅晶片的背面进行了磨削。
＜磨削条件＞
磨削装置：商品名“DFG-8560”、DISCO公司制
半导体晶片：从厚度0.7mm(700μm)背面磨削成0.2mm(200μm)
背面磨削后，将硅晶片与热固性树脂组合物一起从背磨带剥离，将硅晶片贴合固定于切割带(DU-300、日东电工株式会社制)的粘合剂层上。此时，硅晶片的背面和粘合剂层被贴合，硅晶片的电路面上贴合的热固性树脂组合物露出。
接着，在下述条件下进行了半导体晶片的切割。切割按照形成7.3m见方的芯片尺寸的方式进行了完全切割。
＜切割条件＞
切割装置：商品名“DFD-6361”DISCO公司制
切割环：“2-8-1”(DISCO公司制)
切割速度：30mm/sec
切割刀片：
Z1；DISCO公司制“203O-SE27HCDD”
Z2；DISCO公司制“203O-SE27HCBB”
切割刀片转速：
Z1；40,000rpm
Z2；45,000rpm
切割方式：阶梯式切割
晶片芯片尺寸：7.3mm见方
接着，以从各密封片的基材侧利用针向上顶的方式，拾取热固性树脂组合物与单面带有凸点的半导体芯片的层叠体。拾取条件如下所述。
＜拾取条件＞
拾取装置：商品名“SPA-300”株式会社新川社制
针根数：9根
针顶起量：500μm(0.5mm)
针顶起速度：20mm/秒
拾取时间：1秒
扩张量：3mm
最后，利用下述的热压接条件，以半导体芯片的凸点形成面与BGA基板相面对的状态将半导体芯片热压接在BGA基板上来进行半导体芯片的安装。由此，得到了在BGA基板安装有半导体芯片的半导体装置。需要说明的是，本工序中，进行继热压接条件1后利用热压接条件2进行热压接的两个阶段的处理。
＜热压接条件1＞
拾取装置：商品名“FCB-3”松下制
加热温度：150℃
负重：98N
保持时间：10秒
＜热压接条件2＞
拾取装置：商品名“FCB-3”松下制
加热温度：260℃
负重：98N
保持时间：10秒
(半导体装置的可靠性的评价)
将实施例和比较例涉及的半导体装置各制作10个样品，将在-55℃～125℃以30分钟循环1次的热循环反复500个循环后，将半导体装置用包埋用环氧树脂包埋。接着，沿与基板垂直方向对半导体装置进行裁切使得焊料接合部露出，对露出的焊料接合部的截面进行了研磨。之后，利用光学显微镜(倍率：1000倍)观察研磨的焊料接合部的截面，焊料接合部未破裂的情况下评价为“○”，即便只有1个样品中焊料接合部发生破裂的情况也评价为“×”。结果示于表1中。
【表1】
由表1可知，在实施例1～4涉及的半导体装置中，焊料接合部的破裂的产生得到了抑制。另一方面，在比较例1～4的半导体装置中，焊料接合部发生了破裂。综上可知，通过使用包含环氧树脂和羟基当量为200g/eq以上的线型酚醛型酚醛树脂的热固性树脂组合物，可以制造焊料接合部的破裂得到抑制的高可靠性的半导体装置。
符号说明
2热固性树脂组合物
3半导体晶片
5半导体芯片(半导体元件)
16被粘物
20半导体装置

Claims (8)

1.一种半导体装置制造用的热固性树脂组合物，其包含：
环氧树脂、和
羟基当量为200g/eq以上的线型酚醛型酚醛树脂。
2.如权利要求1所述的热固性树脂组合物，其用于半导体元件密封。
3.如权利要求1或2所述的热固性树脂组合物，其中，
所述线型酚醛型酚醛树脂包含由下述结构式表示的结构，
式中，n为0～12的整数。
4.如权利要求1～3中任一项所述的热固性树脂组合物，其包含平均粒径为10nm以上且1000nm以下的无机填充剂。
5.如权利要求1～4中任一项所述的热固性树脂组合物，其在175℃热处理1小时后的热膨胀系数α为10ppm/K以上且200ppm/K以下。
6.如权利要求1～5中任一项所述的热固性树脂组合物，其在175℃热处理1小时后的储能模量E’为100MPa以上且10000MPa以下。
7.如权利要求1～6中任一项所述的热固性树脂组合物，其为片状。
8.一种半导体装置的制造方法，其包含：
将半导体元件通过权利要求1～7中任一项所述的热固性树脂组合物固定于被粘物的固定工序；和
使所述热固性树脂组合物固化的固化工序。
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