CN104955912A - 粘接剂组合物、粘接片及半导体装置的制造方法 - Google Patents
粘接剂组合物、粘接片及半导体装置的制造方法 Download PDFInfo
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- CN104955912A CN104955912A CN201480006604.5A CN201480006604A CN104955912A CN 104955912 A CN104955912 A CN 104955912A CN 201480006604 A CN201480006604 A CN 201480006604A CN 104955912 A CN104955912 A CN 104955912A
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- bond layer
- adhesive
- double bond
- reactive double
- wafer
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- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
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- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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Abstract
本发明提供了一种粘接剂组合物、具有该粘接剂组合物所构成的粘接剂层的粘接片以及使用该粘接片的半导体装置的制造方法,所述组合物能够在粘接剂层中将填料均匀的混合,即使在多段封装的制造时对粘接剂层采用一次全部固化工序的情况下,也能够在固化前稳定的进行打线,在固化后显示优异的粘接强度,特别是在半导体装置中能够获得高封装可靠性。本发明的粘接剂组合物包含丙烯酸聚合物(A)、具有反应性双键基的热固性树脂(B)以及在表面上具有反应性双键基的填料(C),该丙烯酸聚合物(A)的重均分子量为50万以上,该热固性树脂(B)由环氧树脂以及热固化剂所构成,该环氧树脂以及该热固化剂中的任一方或者双方具有反应性双键基。
Description
技术领域
本发明涉及一种粘接剂组合物、具有该粘接剂组合物所构成的粘接剂层的粘接片以及使用该粘接片的半导体装置的制造方法,所述粘接剂组合物特别适合使用于将半导体晶片粘接于(晶粒键合(diebonding))有机基板、导线架或其他半导体晶片的步骤。
背景技术
硅、砷化镓等的半导体晶圆以大直径的状态制造,此晶圆被切割分离(dicing)为元件小片(半导体晶片)后,移至作为下一步骤的安装步骤。此时,在半导体晶圆预先贴附于粘接片的状态下施加切割、清洗、干燥、扩展、拾取的各步骤后,移送至下个步骤的键合(bonding)步骤。
在这些步骤中,为了简化拾取步骤以及键合步骤的工序,提出了各种同时兼具有晶圆固定功能与晶粒粘接功能的切割〃晶粒键合用粘接片(专利文献1等)。专利文献1所公开的粘接片,能够进行所谓的晶粒直接键合,并能够省略晶粒粘接用粘接剂的涂布步骤。该粘接剂包含丙烯酸聚合物、含有反应性双键基的环氧树脂及热固化剂,根据需要包含二氧化硅(silica)等填料。
对于近年的半导体装置,所要求的物性变得非常严苛。例如,在电子部件的连接中,进行了将封装全体都暴露于焊料熔点以上的高温中的表面封装法(回流(reflow))。进一步,近年来由于过渡到不含铅的焊料,封装温度上升至260℃左右。因此,封装时的半导体封装内部所发生的应力变得比以往大,产生粘接界面的剥离或封装破裂等不良状况的可能性高。因此,在所述专利文献1中,作为环氧树脂,使用含有反应性双键基的环氧树脂,通过提升丙烯酸聚合物与环氧树脂的相溶性,改善了粘接可靠性。
此外,为了高密度封装,提出了将晶片多段层叠的封装结构。在此封装结构中,不仅需要基板与晶片之间的连接,还需要晶片与晶片之间的连接。多段封装是在晶片上经由粘接剂层使晶片层叠,并于粘接剂层固化后进行打线(wire bonding),进而依次进行晶片的层叠、粘接剂层的固化、打线,以使晶片层叠。
在如上所述的晶片多段层叠的封装结构的半导体装置的制造中,检讨以下步骤。首先,在粘接剂层未固化或半固化的状态下进行层叠或打线,使所有的晶片层叠。然后,利用模封步骤时长时间暴露于高温中,将粘接剂层一次全部进行完全固化。
但是,当采用此制法时,在打线时,粘接剂层为未固化或半固化的状态。因此,打线时会晶片震动、位移,有可能使得导线的位置变为不正确,无法进行打线。为了消除此不良状况,在采用上述制法时,使用即使是未固化状态也比较硬的粘接剂。作为用以使未固化状态的粘接剂层的硬度提高的手段,考虑在粘接剂中添加较多量的填料。
现有技术文献
专利文献
专利文献1:日本专利公开第2008-133330号公报
发明内容
本发明要解决的技术问题
但是,在粘接剂中均匀的混合填料并不见得容易。若粘接剂中的填料的分散性差,填料彼此之间凝集而使外观的粒径变大,成为粘接剂层的厚度的精度降低、与半导体晶圆的贴附性或粘接性降低的原因。特别是如增加填料的添加量,上述的不良状况变得显著。此外,若于粘接剂中添加大量的填料,有可能相对的使固化性成分(环氧树脂等)的添加量降低、且固化后的粘接剂层的可靠性降低。
而且,即使在采用使如上所述的粘接剂层一次全部固化的工艺的情况下,由于打线时需要150℃以上的高温,粘接剂层有可能部分固化。在此种不期望的固化时,由于未进行加压,若粘接剂固化,则仅失去粘接力,导致粘接强度的降低。粘接剂层若部分固化,特别是对于凹凸表面的追随性降低,对于凹凸较大的基板表面或晶粒垫的粘接性显著降低。
因此,本发明的目的为提供一种粘接剂组合物、具有该粘接剂组合物所构成的粘接剂层的粘接片以及使用该粘接片的半导体装置的制造方法,所述组合物能够在粘接剂层中将填料均匀的混合,即使在多段封装的制造时对粘接剂层采用一次全部固化工序的情况下,也能够在固化前稳定的进行打线,在固化后显示优异的粘接强度,特别是在半导体装置中能够获得高封装可靠性。。
解决技术问题的技术手段
为了解决上述问题的本发明包含以下的要旨。
〔1〕一种粘接剂组合物,包含丙烯酸聚合物(A)、具有反应性双键基的热固性树脂(B)以及在表面上具有反应性双键基的填料(C),
该丙烯酸聚合物(A)的重均分子量为50万以上,
该热固性树脂(B)由环氧树脂以及热固化剂所构成,
该环氧树脂以及该热固化剂中的任一方或者双方具有反应性双键基。
〔2〕一种粘接剂组合物,包含丙烯酸聚合物(A)、具有反应性双键基的热固性树脂(B)以及在表面上具有反应性双键基的填料(C),
该填料(C)的平均粒径为0.01~0.2μm的范围,
该热固性树脂(B)由环氧树脂以及热固化剂所构成,
该环氧树脂以及该热固化剂中的任一方或者双方具有反应性双键基。
〔3〕如〔1〕或〔2〕所记载的粘接剂组合物,所述填料(C)为在表面上具有反应性双键基的二氧化硅。
〔4〕如〔1〕~〔3〕中任一项所述的粘接剂组合物,在粘接剂组合物的总重量中,所述丙烯酸聚合物(A)的含有比例为50~90质量%。
〔5〕如〔1〕~〔4〕中任一项所述的粘接剂组合物,所述丙烯酸聚合物(A)具有羟基。
〔6〕一种单层粘接膜,由〔1〕~〔5〕中任一项所述的粘接剂组合物所构成。
〔7〕一种单层粘接膜,由〔2〕所记载的粘接剂组合物所构成,在250℃下固化后的剪切强度为60N/5mm□以上。
〔8〕一种粘接片,将〔1〕~〔5〕中任一项所述的粘接剂组合物所构成的粘接剂层形成于支撑体上而成。
〔9〕一种粘接片,其由将〔2〕所记载的粘接剂组合物所构成的粘接剂层形成于支撑体上而成,在250℃下固化后的粘接剂层的剪切强度为60N/5mm□以上。
〔10〕如〔8〕或〔9〕所记载的粘接片,所述支撑体为树脂膜。
〔11〕如〔8〕或〔9〕所记载的粘接片,所述支撑体为粘着片。
〔12〕一种半导体装置的制造方法,包括下述步骤:将半导体晶圆贴附于上述〔8〕~〔11〕中任一项所述的粘接片的粘接剂层;切割所述半导体晶圆以及粘接剂层以形成半导体晶片;使所述半导体晶片上固定残留粘接剂层而从支撑体剥离;以及将所述半导体晶片经由所述粘接剂层粘接于晶粒垫部上或其他半导体晶片上。
〔13〕一种半导体装置的制造方法,包括下述步骤:在半导体晶圆的表面形成符合单片化半导体晶片的形状的外部轮廓的沟;在半导体晶圆的表面贴附保护片;之后由背面侧进行到达沟为止的薄化处理,以将半导体晶圆单片化为半导体晶片;以及
将所述半导体晶片贴附于上述〔8〕~〔11〕中任一项所述的粘接片的粘接剂层;使所述半导体晶片上固定残留粘接剂层而从支撑体剥离;以及将所述半导体晶片经由所述粘接剂层粘接于晶粒垫部上或其他半导体晶片上。
发明效果
根据本发明的第1发明,通过使用具有规定的重均分子量的丙烯酸聚合物、具有反应性双键基的热固性树脂以及在表面具有反应性双键基的填料,此外,根据本发明的第2发明,通过使用丙烯酸聚合物、具有反应性双键基的热固性树脂、在表面具有反应性双键基以及具有规定的平均粒径的填料,在提升粘接剂组合物中的丙烯酸聚合物、热固性树脂以及填料的相溶性的同时,提升了粘接剂组合物中的填料的分散性。而且,通过反应性双键基彼此的加成聚合,在粘接剂组合物中形成三维网状结构。其结果,能够通过优异的粘接强度将半导体晶片结合于其他的半导体晶片或基板,即使在严苛的环境下,也能够得到显示高封装可靠性的半导体装置。而且,由于未固化或半固化状态的粘接剂层具有一定程度的硬度,对粘接剂层能够稳定的进行打线。
具体实施方式
以下,对本发明的粘接剂组合物、粘接片以及使用该片的半导体装置的制造方法进行更具体的说明。
(粘接剂组合物)
本发明的粘接剂组合物包含丙烯酸聚合物(A)(以下也称为“(A)成分”。对于其他的成分也相同)、热固性树脂(B)、填料(C)作为必须成分,为了改良各种的物性,也可以根据需要含有其他成分。以下对这些各成分具体的进行说明。
(A)丙烯酸聚合物
第1发明的丙烯酸聚合物(A)的重均分子量(Mw)为50万以上,优选为50万~200万,更优选为50万~150万,进一步优选为50万~80万。若丙烯酸聚合物(A)的重均分子量小于50万,则成为粘接剂层的凝集力降低、且使用该粘接剂层所制造的半导体装置的封装可靠性降低的原因。若丙烯酸聚合物(A)的重均分子量过高,则有可能成为对被粘物(半导体晶圆、晶片或基板等)的贴附性降低、且转移不良或空洞等的发生要因。
第2发明的丙烯酸聚合物(A)的重均分子量(Mw)并没有特别限制,但优选为50万以上,更加优选为50万~200万,进一步优选为50万~150万,特别优选为50万~80万。若丙烯酸聚合物(A)的重均分子量未满50万,则粘接剂层的凝集力有可能降低,但在第2发明中,通过使用后述的具有规定的平均粒径的填料,使被粘物与粘接剂层的粘接性升高,其结果是,半导体装置的封装可靠性优异。若丙烯酸聚合物(A)的重均分子量过高,则有可能成为对被粘物的贴附性降低、转移不良或空洞等的发生要因。
此外,丙烯酸聚合物(A)的分子量分布(Mw/Mn、Mn为数均分子量)优选为1~5,更优选为1~3。通过使丙烯酸聚合物(A)的分子量分布在上述范围,本发明所具有的封装可靠性的提升效果变得更高。
此外,丙烯酸聚合物(A)的重均分子量(Mw)、数均分子量(Mn)以及分子量分布(Mw/Mn)的值,是通过凝胶渗透层析(GPC)法,以后述实施例的测定条件进行测定时的值(聚苯乙烯换算值)。
丙烯酸聚合物(A)的玻璃化转变温度(Tg)优选为-20~50℃,更优选为-10~40℃,进一步优选为0~30℃的范围。若丙烯酸聚合物(A)的玻璃化转变温度处于此范围,则封装的可靠性具有升高的倾向。作为丙烯酸聚合物(A)的玻璃化转变温度的调整方法,举出下述的方法。例如,作为提高玻璃化转变温度的方法,可举出当使用后述的烷基的碳原子数为1~18的(甲基)丙烯酸烷基酯作为构成丙烯酸聚合物(A)的单体时,选择烷基的碳原子数小的(甲基)丙烯酸烷基酯的方法,或是使烷基的碳原子数小的(甲基)丙烯酸烷基酯的含有比例增大的方法。
另外,丙烯酸聚合物(A)的玻璃化转变温度为由福克斯(FOX)公式所求得的值。
构成本发明的丙烯酸聚合物(A)的单体,至少包含(甲基)丙烯酸酯单体或其衍生物。
作为(甲基)丙烯酸酯单体或其衍生物,例如可举出烷基的碳原子数为1~18的(甲基)丙烯酸烷基酯、具有环状骨架的(甲基)丙烯酸酯、具有羟基的(甲基)丙烯酸酯、具有环氧丙烷基的(甲基)丙烯酸酯、具有胺基的(甲基)丙烯酸酯、具有羧基的(甲基)丙烯酸酯。
作为烷基的碳原子数为1~18的(甲基)丙烯酸烷基酯,例如可举出(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)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十四烷酯、(甲基)丙烯酸十八烷酯等。
作为具有环状骨架的(甲基)丙烯酸酯,例如可举出(甲基)丙烯酸环烷酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸异冰片酯、二环戊基(甲基)丙烯酸酯、二环戊烯基(甲基)丙烯酸酯、二环戊烯氧乙基(甲基)丙烯酸酯、酰亚胺(甲基)丙烯酸酯等。
作为具有羟基的(甲基)丙烯酸酯,例如可举出(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-2-羟基丁酯等。
作为具有环氧丙基的(甲基)丙烯酸酯,例如可举出(甲基)丙烯酸环氧丙酯。
作为具有胺基的(甲基)丙烯酸酯,例如可举出单乙胺(甲基)丙烯酸酯、二乙胺(甲基)丙烯酸酯等。
作为具有羧基的(甲基)丙烯酸酯,例如可举出2-(甲基)丙烯酰氧基乙基邻苯二甲酸酯、2-(甲基)丙烯酰氧基丙基邻苯二甲酸酯等。
此外,丙烯酸聚合物(A)还可与(甲基)丙烯酸、伊康酸等(甲基)丙烯酸酯以外的具有羧基的单体、乙烯基醇、N-羟甲基(甲基)丙烯酰胺等(甲基)丙烯酸酯以外的具有羟基的单体、(甲基)丙烯酰胺、醋酸乙烯酯、苯乙烯等共聚。
在粘接剂组合物含有后述的交联剂(G)的情况下,丙烯酸聚合物(A)优选具有与交联剂(G)反应的官能基(羟基、胺基、环氧丙基、羧基等),特别是具有羟基的丙烯酸聚合物(A),由于其制造容易,使用交联剂(G)容易导入交联结构,因而优选。此外,具有羟基的丙烯酸聚合物与后述的热固性树脂(B)的相溶性良好。
作为构成丙烯酸聚合物(A)的单体,通过使用具有与交联剂(G)反应的官能基的单体而在丙烯酸聚合物(A)中导入与交联剂(G)反应的官能基时,具有与交联剂(G)反应的官能基的单体在构成丙烯酸聚合物(A)的单体总质量中的比例优选为1~20质量%左右,更优选为3~15质量%。在丙烯酸聚合物(A)中,通过使来自于具有与交联剂(G)反应的官能基的单体的结构单元在上述范围内,与交联剂(G)反应的官能基与交联剂(G)反应而形成三维网状结构,能够提高丙烯酸聚合物(A)的交联密度。其结果,本发明的粘接剂组合物能够形成具有优异的剪切强度的单层粘接膜或粘接剂层。而且,由于粘接剂组合物的吸水性降低,能够得到封装可靠性优异的半导体装置。
在粘接剂组合物的总质量中,优选以50质量%以上的比例包含丙烯酸聚合物(A)。通过以如此的构成,将粘接剂层用于一次全部固化工序时成为优选状态。这是因为即使固化前的粘接剂暴露于高温中时也能保持一定程度的硬度,而能够进行打线。即,若粘接剂组合物中的丙烯酸聚合物(A)的含量较多,则即使在热固化前也能使粘接剂层的储存弹性模量高。因此,即使在粘接剂层为未固化或半固化的状态下,也能够抑制打线时的晶片的震动、位移,稳定的进行打线。由此,在为了确保工艺适宜性而增加丙烯酸聚合物(A)的含量的情况下,热固性树脂(B)的量相对变少。因此,虽然具有固化不足的可能性,但是由于本发明的粘接剂组合物的热固性树脂(B)与填料(C)能够通过反应性双键基结合,故能够克服此固化不足的问题。在粘接剂组合物的总质量中,优选以50~90质量%的比例含有丙烯酸聚合物(A),更优选以50~80质量%的比例含有丙烯酸聚合物(A)。在第1发明中,通过使粘接剂组合物中的重均分子量(Mw)为50万以上的丙烯酸聚合物(A)的比例处于上述范围,本发明的封装可靠性(A)的提升效果变得更为显著。
(B)具有反应性双键基的热固性树脂
热固性树脂(B)由环氧树脂以及热固化剂所构成,在本发明中,在环氧树脂以及热固化剂中任一方或双方具有反应性双键基。作为环氧树脂为具有反应性双键基的环氧树脂(B1)以及不具有反应性双键基的环氧树脂(B1'),作为热固化剂为具有反应性双键基的热固化剂(B2)以及不具有反应性双键基的热固化剂(B2')。本发明的热固性树脂(B)包含作为必须成分的具有反应性双键基的环氧树脂(B1)以及具有反应性双键基的热固化剂(B2)中的任意一方。此外,包含作为必须成分的环氧树脂(B1)以及环氧树脂(B1')中的任意一方,包含作为必须成分的热固化剂(B2)以及热固化剂(B2')中的任意一方。但是,在环氧树脂以及热固化剂双方不具有反应性双键基时除外,即仅由成分(B1')与成分(B2')的组合除外。
由于热固性树脂(B)具有反应性双键基,因此与不具有反应性双键基的热固性树脂相比,与丙烯酸聚合物(A)以及后述的填料(C)的相溶性高。此外,通过使粘接剂组合物中的反应性双键基彼此加成聚合,在粘接剂组合物中形成三维网状结构。因此,本发明的粘接剂组合物与仅包含不具有反应性双键基的热固性树脂作为热固性树脂的粘接剂组合物相比,能够提高半导体装置的可靠性。
反应性双键基为具有聚合性碳-碳双键的官能基,作为具体例可举出乙烯基、烯丙基、(甲基)丙烯酰基、(甲基)丙烯酰氧基((meth)acryloxy group)等,优选可举出丙烯酰基。因此,本发明的反应性双键基并不是不具有聚合性的双键。例如,成分(B)可含有芳香环,但芳香环的不饱和结构并不是本发明的反应性双键基。
作为具有反应性双键基的环氧树脂(B1),为了提升粘接剂的热固化后的强度或耐热性,优选为具有芳香环的树脂。此外,作为此种具有反应性双键基的环氧树脂(B1),例如可举出多官能环氧树脂的环氧基的一部分变换为包含反应性双键基的基团的化合物。此种化合物例如可通过使丙烯酸对环氧基进行加成反应而合成。或者可举出在构成环氧基的芳香环等中使包含反应性双键基的基团直接键结而成的化合物等。
此处,作为具有反应性双键基的环氧树脂(B1),可举出下述式(1)所表示的化合物、下述式(2)所表示的化合物或是使丙烯酸对后述的不具有反应性双键基的环氧树脂(B1')的一部分进行环氧基加成反应所得的化合物等。
[化学式1]
〔R为H-或是CH3-,n为0~10的整数。〕
[化学式2]
〔X为或是R为H-或是CH3-,n为0~10的整数。〕
另外,虽有通过使不具有反应性双键基的环氧树脂(B1')与丙烯酸反应所得的具有反应性双键基的环氧树脂(B1),成为与未反应物或环氧基完全被消耗的化合物的混合物的情况,但是在本发明中,只要是实质的包含上述化合物即可。
作为不具有反应性双键基的环氧树脂(B1'),可使用以往公知的环氧树脂。作为这种环氧树脂,具体而言,可举出多官能类环氧树脂、或联苯化合物、双酚A二环氧丙基醚或其氢化物、甲酚酚醛清漆型环氧树脂、二环戊二烯型环氧树脂、联苯型环氧树脂、双酚A型环氧树脂、双酚F型环氧树脂、伸苯基骨架型环氧树脂等分子中具有2官能以上的环氧化合物。这些物质可单独1种或是组合2种以上使用。
环氧树脂(B1)以及(B1')的数均分子量并没有特别的限制,从粘接剂的固化性或固化后的强度或耐热性的角度考虑,优选为300~30000,更优选为400~10000,特别优选为500~3000。此外,相对于该环氧树脂总量中的环氧基100摩尔,该环氧树脂的总量[(B1)+(B1')]中的反应性双键基的含量期望为0.1~1000摩尔,优选为1~500摩尔,更优选为10~400摩尔。
热固化剂对于环氧树脂(B1)以及(B1')起到固化剂的作用。本发明中,使用具有反应性双键基的热固化剂(B2)以及不具有反应性双键基的热固化剂(B2')中任一方或双方作为热固化剂。在环氧树脂仅由不具有反应性双键基的环氧树脂(B1')构成时,具有反应性双键基的热固化剂(B2)作为必须成分使用。在环氧树脂具有反应性双键基时,使用热固化剂(B2)以及热固化剂(B2')中的任意一方皆可以,也可以使用双方。
具有反应性双键基的热固化剂(B2)为具有聚合性碳-碳双键基的热固化剂。作为反应性双键基,优选举出乙烯基、烯丙基、(甲基)丙烯酰基以及(甲基)丙烯酰氧基等,更加优选包含甲基丙烯酰基。
此外,热固化剂(B2)除了上述的反应性双键基之外,包含可与环氧基反应的官能基。作为可与环氧基反应的官能基,优选可举出苯酚性羟基、醇性羟基、胺基、羧基以及酸酐等,这之中进一步优选列举苯酚性羟基、醇性羟基、胺基,特别优选列举苯酚性羟基。
作为具有反应性双键基的热固化剂(B2),例如可举出苯酚树脂的羟基的一部分以包含反应性双键基的基团取代而成的化合物,或者是在苯酚树脂的芳香环上直接键结包含反应性双键基的基团的化合物等。在此,作为苯酚树脂,可举出下述式(化学式3)所示的酚醛清漆型苯酚树脂、下述式(化学式4)所示的二环戊二烯型苯酚树脂、下述式(化学式5)所示的多官能类苯酚树脂等,特别是优选为酚醛清漆型苯酚树脂。因此,作为具有反应性双键基的热固化剂(B2),优选为将酚醛清漆型苯酚树脂的羟基的一部分以包含反应性双键基的基团取代而成的化合物,或者是在酚醛清漆型苯酚树脂的芳香环上直接键结包含反应性双键基的基团的化合物。
[化学式3]
[化学式4]
[化学式5]
作为具有反应性双键基的热固化剂(B2)的特别优选例,可举出下述化合物,该化合物为如下述式(a)所示的在含有苯酚性羟基的重复单元的一部分中导入反应性双键基的结构,包含如下述式(b)或(c)所示的具有包含反应性双键基的基团的重复单元。特别优选的具有反应性双键基的热固化剂(B2)包含下述式(a)的重复单元与下述式(b)或(c)的重复单元。
[化学式6]
(式中n为0或1。)
[化学式7]
(式中n为0或1,R1为可具有羟基的碳原子数1~5的烃基,X为-O-、-NR2(R2为氢或甲基),或是R1X为单键,A为甲基丙烯酰基)
重复单元(a)所含的苯酚性羟基为可与环氧基反应的官能基,具有作为粘接剂组合物的热固化时与环氧树脂的环氧基反应固化的固化剂的功能。而且,重复单元(b)及(c)所含的反应性双键基,通过使丙烯酸聚合物(A)与热固性树脂(B)的相溶性提升,并且反应性双键基彼此加成聚合,而在粘接剂组合物中形成三维网状结构。依此结果,粘接剂组合物的固化物成为更强韧的性质,由此提升作为粘接剂的可靠性。而且,重复单元(b)及(c)所含的反应性双键基,具有在粘接剂组合物的能量线固化时聚合固化,并使粘接剂层与支撑体的粘接力降低的作用。
该热固化剂(B2)的所述(a)式所示的重复单元的比例为5~95摩尔%,进一步优选为20~90摩尔%,特别优选为40~80摩尔%,所述(b)或(c)式所示的重复单元的比例合计为5~95摩尔%,进一步优选为10~80摩尔%,特别优选为20~60摩尔%。
作为不具有反应性双键基的热固化剂(B2'),可举出1分子中具有2个以上可与环氧基反应的官能基的化合物。作为此官能基可举出苯酚性羟基、醇性羟基、胺基、羧基以及酸酐等。其中优选可举出苯酚性羟基、胺基、酸酐等,进一步优选可举出苯酚性羟基、胺基。
由于含有具有胺基的热固化剂(胺类热固化剂)的粘接剂层的吸湿性高于含有具有苯酚性羟基的热固化剂(苯酚类热固化剂)的粘接剂层,在湿热条件投入后的粘接剂层的粘接性大幅降低,但由于含有苯酚类热固化剂的粘接剂层的耐湿热性高,投入湿热条件后的粘接剂层的粘接性小幅降低。因此,作为热固化剂(B2'),特别优选在分子中具有2个以上的可与环氧基反应的苯酚性羟基的化合物。
作为苯酚类热固化剂的具体例,可举出多官能类苯酚树脂、联苯酚、酚醛清漆型苯酚树脂、二环戊二烯类苯酚树脂、芳烷基苯酚树脂等。
作为胺类热固化剂的具体例,可举出DICY(二氰二胺)。
上述物质可单独1种或是混合使用2种以上。
上述的热固化剂(B2)以及(B2')的数均分子量优选为40~30000,进一步优选为60~10000,特别优选为为80~3000。
相对于100质量份环氧树脂[(B1)以及(B1')],粘接剂组合物的热固化剂[(B2)以及(B2')]的含量优选为0.1~500质量份,更优选为1~200质量份。而且,相对于100质量份丙烯酸聚合物(A),热固化剂[(B2)以及(B2')]的含量优选为5~50质量份,更优选为10~40质量份。通过使粘接剂组合物中的热固化剂的含量或相对于丙烯酸聚合物(A)的热固化剂的含量处于上述范围,使封装的可靠性优异。
在粘接剂组合物的总质量中,热固性树脂(B)(环氧树脂与热固化剂的合计[(B1)+(B1')+(B2)+(B2')])优选以小于50质量%,更优选以1~30质量%,进一步优选以5~25质量%的比例含有。而且,在粘接剂组合物中,相对于100质量份丙烯酸聚合物(A),热固性树脂(B)优选以1质量份以上小于100质量份,更优选以3~60质量份,进一步优选以3~40质量份的范围含有。若热固性树脂(B)的含量过少,则有可能无法得到充分的粘接性,过多则粘接剂层与支撑体的剥离力变高,有可能产生拾取不良。
(C)在表面具有反应性双键基的填料
在表面具有反应性双键基的填料(C),只要在表面具有反应性双键基即没有特别的限定。反应性双键基优选为乙烯基、烯丙基(甲基)丙烯酰基或(甲基)丙烯酰氧基。
上述填料优选为经由具有反应性双键基的化合物进行表面处理的填料。
作为填料(未处理的填料)的材质,可举出二氧化硅(silica)、氧化铝、碳酸钙、硅酸钙、氢氧化镁、氢氧化铝、氧化钛、碳黑、滑石、云母或粘土等。其中优选为二氧化硅。二氧化硅所具有的硅醇基,对于与硅烷偶联剂的结合可发挥有效的作用。
在表面具有反应性双键基的填料,例如是对未处理的填料的表面,通过具有反应性双键基的偶联剂进行表面处理而得到。
上述具有反应性双键基的偶联剂并没有特别的限定。作为该偶联剂,例如适合使用具有乙烯基的偶联剂、具有苯乙烯基的偶联剂、具有(甲基)丙烯酰氧基的偶联剂。上述偶联剂优选为硅烷偶联剂。
作为上述偶联剂的具体例,可举出乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、对苯乙烯基三甲氧基硅烷、3-甲基丙烯酰氧基丙基二甲氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基三乙氧基硅烷、3-甲基丙烯酰氧基丙基甲基二乙氧基硅烷以及3-丙烯酰氧基丙基三甲氧基硅烷等。作为这些市售品,例如可举出KBM-1003、KBE-1003、KBM-1403、KBM-502以及KBM-503、KBE-502、KBE-503、KBM-5103(以上均为信越化学工业社制)。
上述通过偶联剂对上述填料进行表面处理的方法并没有特别的限定。作为此方法,例如可举出在亨舍尔混合机(henschel mixer)或是V型混合机等可高速搅拌的混合机中添加未处理的填料并搅拌,并且将偶联剂直接添加或是将偶联剂溶解、分散于醇水溶液、有机溶剂或是水溶液而添加的干式法。进一步可举出:在未处理的填料的浆料中添加偶联剂的浆料法;将未处理的填料干燥后,以喷涂(spray)赋予偶联剂的喷涂法等的直接处理法,或者是在制备上述组合物时,将未处理的填料与丙烯酸类聚合物混合,于该混合时直接添加的共掺合(Integral Blend)法等。
对100质量份上述未处理的填料进行表面处理的偶联剂的量,优选下限为0.1质量份,优选上限为15质量份。
第1发明的上述填料的平均粒径并没有特别的限定,优选为在0.01~2μm的范围内。上述填料的平均粒径在该优选范围内时,能够不损及与被粘物的贴附性而发挥粘接性。而且,特别是用于将晶片载置于基板或其他的晶片等被粘物时,显著的得到本发明的粘接剂组合物的可靠性提升效果。在第1发明中,填料的平均粒径为超过0.2μm、2μm以下时,具有本发明的单层粘接膜或粘接片的面状态恶化、且与被粘物的贴附性变差的可能性,但通过使用重均分子量为50万以上的丙烯酸聚合物(A),粘接剂组合物的粘度增加,作为其结果,能够防止与被粘物的贴附性降低。若上述平均粒径超过2μm,则具有本发明的单层粘接膜或粘接片的面状态恶化、与晶圆的贴附性变差,且粘接层的面内厚度不均的可能性。另外,上述“平均粒径”是通过使用动态光散射法的粒度分布计(日机装社制,装置名:Nanotrac150)所求取(以下相同)。
第2发明的上述填料的平均粒径在0.01~0.2μm的范围内。上述填料的平均粒径在该范围内时,能够不损及与半导体晶圆的贴附性而发挥粘接性。此外,特别是用于将晶片载置于基板或其他的晶片等被粘物时,显著的得到本发明的粘接剂组合物的可靠性提升效果。若上述平均粒径过大,则具有粘接片的面状态恶化、粘接层的面内厚度不均,且粘接剂组合物的固化物的剪切强度降低之类的不良状况发生的可能性。
在第2发明中,通过使填料的平均粒径处于上述范围,粘接剂组合物的可靠性提升效果变得显著,推测其理由如下。
若填料的粒径大,由埋入填料彼此间的填料以外的成分所形成的结构也大。填料以外的成分比填料的凝集性低。若由填料以外的成分所形成的结构大,则填料以外的成分产生破裂时,具有破裂会扩大为广范围的疑虑。另一方面,若填料细微,则填料以外的成分所形成的结构也细微。依此,即使填料以外的成分产生破裂,混入其细微结构的填料会妨碍破裂的进展。其结果,破裂具有不扩大为广范围的倾向。进而,在本发明中,填料所具有的甲基丙烯酰氧基等反应性双键基能够与填料以外的成分所含的B1成分等的反应性双键基产生键结。若填料细微,则填料与填料以外的成分的接触面积变大。其结果,具有填料与B1成分等的结合增加的倾向。
表面具有反应性双键基的填料(C)与丙烯酸聚合物(A)、热固性树脂(B)的亲和性优异,能够均匀的分散于粘接剂组合物中。
在粘接剂组合物的总质量中,优选以小于50质量%,更优选以1~30质量%,进一步优选以5~25质量%的比例含有上述填料(C)。此外,相对于丙烯酸树脂(A)与热固性树脂(B)的合计100质量份,优选以5质量份以上小于100质量份,更优选以8~60质量份,进一步优选以10~40质量份的范围含有上述填料(C)。若上述填料的量过多,则有可能对晶圆的贴附性或对基板的粘接性变差。若上述填料的量过少,有可能无法充分发挥添加填料的效果。
若在该范围内使粘接剂层含有填料(C),则即使粘接剂层处于未固化或半固化的状态,也能够表现出能耐受打线时的震动程度的弹性模量。因此,打线时晶片不会震动、位移而稳定的进行打线此等本申请发明的效果高。
其他成分
粘接剂组合物除了上述成分之外,可以包含下述成分。
(D)光聚合引发剂
粘接剂组合物优选含有光聚合引发剂。通过含有光聚合引发剂,例如本发明的粘接片作为切割及晶粒键合片使用时,在贴附于晶圆后,通过在切割步骤前照射紫外线,使热固性树脂(B)以及填料(C)所具有的反应性双键基反应,而能够使其预固化。通过进行预固化,在固化前粘接剂层比较软化,因此对于晶圆的贴附性佳,此外在切割时具有适当的硬度而能够防止粘接剂附着于切割刀等其他不良状况。此外,支撑体(树脂膜或粘着片)与粘接剂层的表面的剥离性的控制等成为可能。此外,由于预固化状态比未固化状态的硬度高,提升了打线时的稳定性。
作为光聚合引发剂(D),具体而言可举出二苯基酮、苯乙酮、苯偶姻、苯偶姻甲醚、苯偶姻***、苯偶姻异丙醚、苯偶姻异丁醚、苯偶姻安息香酸、苯偶姻安息香酸甲酯、苯偶姻二甲基缩酮、2,4-二乙基噻吨酮(2,4-diethyl thioxanthone)、α-羟基环己基苯基酮、苄基二苯基硫醚(benzyl diphenyl sulfide)、一硫化四甲基秋兰姆(tetramethyl thiram monosulfide)、偶氮双异丁腈、联苯甲酰、二联苯甲酰、丁二酮、1,2-二苯基甲烷、2-羟基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮、2,4,6-三甲基苯甲酰基二苯基膦氧化物以及β-氯蒽醌等。光聚合引发剂(D)可单独使用1种或组合2种以上使用。
在使用光聚合引发剂(D)的情况下,其添加比例只要是基于所述填料表面的反应性双键基以及热固性树脂所具有的反应性双键基的合计量适当设定即可。虽然并没有限定,但例如相对于热固性树脂(B)以及填料(C)的合计100质量份,光聚合引发剂(D)通常为0.1~10质量份,优选为1~5质量份。若光聚合引发剂(D)的含量低于上述范围,则光聚合不足而有可能无法得到满足的反应,若高于上述范围,则有可能生成未用于光聚合的残留物,粘接剂组合物的固化性变得不充分。
(E)固化促进剂
固化促进剂(E)用于调整粘接剂组合物的固化速度。作为固化促进剂优选可举出三乙烯二胺、苄基二甲胺、三乙醇胺、二甲基胺基乙醇、三(二甲基胺基甲基)苯酚等叔胺类;2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2-苯基-4,5-二羟基甲基咪唑、2-苯基-4-甲基-5-羟基甲基咪唑等咪唑类;三丁基膦、二苯基膦、三苯基膦等的有机膦类;四苯基膦四苯基硼酸酯、三苯基膦四苯基硼酸酯等的四苯基硼酸盐等。这些物质可单独使用1种或组合2种以上使用。
在使用固化促进剂(E)的情况下,相对于100质量份热固性树脂(B)的合计[(B1)+(B1')+(B2)+(B2')],固化促进剂(E)优选为含有0.01~10质量份的量,更优选为含有0.1~1质量份的量。通过以上述范围的量含有固化促进剂(E),即使暴露于高温度高湿度下也具有优异的粘接特性,即使暴露于严苛的回流条件时也能够获得高封装可靠性。若固化促进剂(E)的含量少,则固化不足而无法得到充分的粘接特性,若过剩,则具有高极性的固化促进剂在高温度高湿度下于粘接剂层中向粘接表面侧移动、分凝而导致封装的可靠性降低。
(F)偶联剂
偶联剂(F)具有与无机物反应的官能基以及与有机官能基反应的官能基,也可以为了提升粘接剂层对被粘物的贴附性、粘接性而使用。此外,通过使用偶联剂(F)能够不损及粘接剂层固化所得的固化物的耐热性而提升其耐水性。
作为偶联剂(F),期望使用硅烷偶联剂。
作为这样的硅烷偶联剂,可举出γ-缩水甘油醚氧基丙基三甲氧基硅烷、γ-缩水甘油醚氧基丙基三乙氧基硅烷、γ-缩水甘油醚氧基丙基甲基二乙氧基硅烷、β-(3,4-环氧基环己基)乙基三甲氧基硅烷、γ-(甲基丙烯酰氧基丙基)三甲氧基硅烷、γ-胺基丙基三甲氧基硅烷、N-6-(胺基乙基)-γ-胺基丙基三甲氧基硅烷、N-6-(胺基乙基)-γ-胺基丙基甲基二乙氧基硅烷、N-苯基-γ-胺基丙基三甲氧基硅烷、γ-脲基丙基三乙氧基硅烷、γ-巯基丙基三甲氧基硅烷、γ-巯基丙基甲基二甲氧基硅烷、甲基三甲氧基硅烷、甲基三乙氧基硅烷、乙烯基三甲氧基硅烷等具有2个或3个烷氧基的低分子硅烷偶联剂,四甲氧基硅烷、四乙氧基硅烷等具有4个烷氧基的低分子硅烷偶联剂,双(3-三乙氧基硅基丙基)四硫化氢、乙烯基三乙酰氧基硅烷、咪唑硅烷等。此外,还可举出通过将具有2个或3个上述烷氧基的低分子硅烷偶联剂或具有4个烷氧基的低分子硅烷偶联剂等的烷氧基水解或脱水缩合而得的缩合产物的寡聚物型缩合产物。特别是,在上述低分子硅烷偶联剂中,通过将作为具有2个或3个烷氧基的低分子硅烷偶联剂与具有4个烷氧基的低分子硅烷偶联剂脱水缩合而成的缩合产物的寡聚物,由于烷氧基的反应性高、且具有的充分数量的有机官能基,故而优选,例如可举出作为3-(2,3-乙氧基丙氧基)丙基甲氧基硅氧烷与二甲氧基硅氧烷的共聚物的寡聚物。
这些物质可单独1种或混合2种以上使用。此外,其中优选使用具有可与丙烯酸聚合物(A)、热固性树脂(B)等所具有的官能基反应的基团的化合物。
在使用偶联剂(F)的情况下,相对于丙烯酸树脂(A)与热固性树脂(B)的合计100质量份,偶联剂通常以0.1~20质量份,优选为0.2~10质量份,更优选为0.3~5质量份的比例含有。偶联剂(F)的含量若小于0.1质量份则有可能无法得到上述的效果,超过20质量份则具有成为逸气原因的可能性。
(G)交联剂
为了调节粘接剂层的初期粘接力以及凝集力,可以在粘接剂组合物中添加交联剂(G)。另外,在添加交联剂的情况下,所述丙烯酸聚合物(A)中含有与交联剂反应的官能基。
作为交联剂(G)可举出有机多价异氰酸酯化合物、有机多价亚胺化合物等。
作为上述有机多价异氰酸酯化合物,可举出芳香族多价异氰酸酯化合物、脂肪族多价异氰酸酯化合物、脂环族多价异氰酸酯化合物以及这些有机多价异氰酸酯化合物的三聚物、以及通过这些有机多价异氰酸酯化合物与多元醇化合物反应所得的末端异氰酸酯氨基甲酸酯预聚物等。
作为有机多价异氰酸酯化合物,例如可举出2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、1,3-苯二甲基二异氰酸酯、1,4-苯二甲基二异氰酸酯、二苯甲烷-4,4'-二异氰酸酯、二苯甲烷-2,4'-二异氰酸酯、3-甲基二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷-4,4'-二异氰酸酯、二环己基甲烷-2,4'-二异氰酸酯、甲苯二异氰酸酯的三羟甲基丙烷加成物以及赖氨酸异氰酸酯。
在使用异氰酸酯类交联剂的情况下,作为丙烯酸聚合物(A),优选使用含有羟基的丙烯酸聚合物。若交联剂具有异氰酸酯基,且丙烯酸聚合物(A)具有羟基,则交联剂与丙烯酸聚合物(A)产生反应,能够简便地向粘接剂中导入交联结构。
作为上述有机多价亚胺化合物,可举出N,N'-二苯基甲烷-4,4'-双(1-氮丙啶羧基酰胺)、三羟甲基丙烷-三-β-氮丙啶基丙酸酯、四羟甲基丙烷-三-β-氮丙啶基丙酸酯以及N,N'-甲苯-2,4-双(1-氮丙啶羧基酰胺)三亚乙基三聚氰胺等。
在使用交联剂(G)的情况下,相对于100质量份丙烯酸聚合物(A),交联剂(G)通常以0.01~20质量份,优选以0.1~10质量份,更优选以0.5~5质量份的比例使用。
(H)能量线聚合性化合物
可以在粘接剂组合物中添加能量线聚合性化合物。能量线聚合性化合物(H)包含反应性双键基,受到紫外线、电子线等的能量线照射则聚合固化。作为这样的能量线聚合性化合物(H)的具体例,可举出三羟甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇单羟基五丙烯酸酯、二季戊四醇六丙烯酸酯或1,4-丁二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、寡酯丙烯酸酯、氨基甲酸酯丙烯酸酯类寡聚物、环氧基改性丙烯酸酯、聚醚丙烯酸酯以及亚甲基丁二酸寡聚物等丙烯酸酯类化合物。这样的化合物在分子内至少具有1个具有聚合性的碳-碳双键,通常重均分子量在100~30000、优选在300~10000左右。在使用能量线聚合性化合物(H)时,其添加量并没有特别的限定,相对于粘接剂组合物的固体成分总量100质量份,优选使用1~50质量份左右的比例。
(I)热塑性树脂
粘接剂组合物中可以使用丙烯酸聚合物(A)以外的聚合物。作为这样的聚合物可使用热塑性树脂(I)。热塑性树脂(I)是为了保持固化后粘接剂层的可挠性而添加。作为热塑性树脂(I),重均分子量优选为1000~10万,进一步优选为3000~8万。通过含有热塑性树脂(I),能够使半导体晶片的拾取步骤中的支撑体与粘接剂层的层间剥离容易进行,进而能够使粘接剂层追随基板的凹凸而抑制空洞等的发生。
热塑性树脂(I)的玻璃化转变温度优选为-30~150℃,进一步优选为-20~120℃的范围。若热塑性树脂(I)的玻璃化转变温度过低,有可能使粘接剂层与支撑体的剥离力变大而产生晶片的拾取不良,过高则具有用于固定晶圆的粘接力不充分的疑虑。
作为热塑性树脂(I),可举出聚酯树脂、氨基甲酸酯树脂、苯氧基树脂、聚丁烯、聚丁二烯、聚苯乙烯等。这些物质可单独1种或混合2种以上使用。
在使用热塑性树脂(I)时,相对于丙烯酸树脂(A)与热固性树脂(B)的合计100质量份,其添加量优选为1~300质量份、进一步优选为为2~100质量份的范围。通过使热塑性树脂(I)的含量处于该范围内,能够得到上述的效果。
(J)其他的无机填料
此外,除了所述填料(C)以外,在粘接剂组合物中可以添加无机填料(J)以作为不具有反应性双键基的填料。作为无机填料,可举出二氧化硅、滑石、碳酸钙、钛白、红氧化铁、碳化硅、氮化硼等的粉末,可举出它们的球形化的珠、单结晶纤维以及玻璃纤维等。
(K)通用添加剂
除上述之外,在粘接剂组合物中也可以根据需要添加各种添加剂。作为各种添加剂,可举出塑化剂、抗静电剂、抗氧化剂、颜料、染料、捕获剂(gettering agent)等。
(粘接片)
由含有上述各成分的粘接剂组合物所形成的粘接剂层具有粘接性(例如热粘接性或感压粘接性)与加热固化性。在粘接剂层具有感压粘接剂的情况下,能够以未固化状态按压贴附于被粘物。在粘接剂具有热粘接性的情况下,在按压于被粘物时,能够加热粘接剂层而贴附。本发明的热粘接性虽然在常温不具感压粘接性,但通过热软化而能够粘接于被粘物。
此外,由于在粘接剂层均匀分散有填料,即使半导体晶片接合且进行打线的高温下,粘接剂层的变形也少,而稳定的进行打线。然后经由热固化最终能够提供耐冲击性高的固化物,剪切强度也优异,于严苛的高温度高湿度条件下也能够保持充分的粘接特性。在含有光聚合引发剂(D)时,也具有能量线固化性,能够在完全固化之前通过照射能量线而预固化。通过预固化增加粘接剂层的硬度,提升打线时的稳定性。
虽然粘接片可为由上述粘接剂组合物制膜而成的单层的粘接膜,但优选为上述粘接剂组合物所构成的粘接剂层可剥离的形成于支撑体上而形成的粘接片。特别是,第2发明的由粘接剂组合物所构成的单层粘接膜,在250℃下固化后的剪切强度优选为60N/5mm□以上,更优选为70N/5mm□~150N/5mm□的范围,进一步优选为80N/5mm□~120N/5mm□的范围。此外,具有由第2发明的粘接剂组合物所构成的粘接剂层的粘接片,在250℃下固化后的粘接剂层的剪切强度优选为60N/5mm□以上,更优选为70N/5mm□~150N/5mm□的范围,进一步优选为80N/5mm□~120N/5mm□的范围。
以下,以粘接剂层可剥离的形成于支撑体上而形成的粘接片为例,对其优选形态以及使用形态进行说明。在使用由粘接剂层可剥离的形成于支撑体上而形成的粘接片时,粘接剂层被贴附于晶圆、晶片等被粘物,剥离支撑体以将粘接剂层转移至被粘物。本发明的粘接片的形状,可为带状等所有形状。支撑体可为表面不具有皱褶的树脂膜,也可为在树脂膜上具备粘着剂层的粘着片。
作为用作粘接片的支撑体的树脂膜,例如可使用聚乙烯膜、聚丙烯膜、聚丁烯膜、聚丁二烯膜、聚甲基戊烯膜、聚氯化乙烯膜、氯化乙烯共聚物膜、聚对苯二甲酸乙二酯膜、聚萘二甲酸乙二酯膜、聚对苯二甲酸丁二酯膜、聚氨基甲酸酯膜、乙烯-醋酸乙烯基共聚物膜、离聚物树脂膜、乙烯-(甲基)丙烯酸共聚物膜、乙烯-(甲基)丙烯酸酯共聚物膜、聚苯乙烯膜、聚碳酸酯膜、聚酰亚胺膜、氟树脂膜等透明膜。此外可使用他们的交联膜。进一步,还可以为他们的层叠膜。此外,也可以使用将他们着色的膜、不透明膜等。
本发明的粘接片贴附于各种被粘物,对被粘物施加所需要的加工后,粘接剂层以固定残留于被粘物的状态从支撑体剥离。即,对粘接剂层使用了包括了由支撑体转移至被粘物的步骤的工序。因此,支撑体(树脂膜)的与粘接剂层接触的面的表面张力,优选为40mN/m以下,进一步优选为37mN/m以下,特别优选为35mN/m以下。下限值通常为25mN/m左右。这种表面张力低的树脂膜,能通过适当选择材质而得到,也能够通过在树脂膜表面涂布剥离剂施加剥离处理而得到。
作为树脂膜的剥离处理所使用的剥离剂,使用醇酸类、硅酮类、氟类、不饱和聚酯类、聚烯烃类、石蜡类等,特别是醇酸类、硅酮类、氟类的剥离剂具有耐热性,故而优选。
为了使用上述剥离剂以对树脂膜的表面进行剥离处理,可以将剥离剂直接以无溶剂的状态,或是以溶剂稀释或乳化,通过凹版涂布机、绕线棒涂布机、气刀涂布机、辊涂布机等进行涂布,将涂布有剥离剂的树脂膜供给至常温下或加热下,或者是通过电子线或紫外线固化以形成剥离层即可。此外,可以通过湿层叠或干层叠、热熔融层叠、熔融挤压层叠、共挤压加工等进行膜的层叠,由此调整树脂膜的表面张力。
在使用粘着片作为支撑体的情况下,此粘着片还可以是作为切割片使用的粘着片。切割片在如上所述的树脂膜上具有粘着剂层,在粘着剂层上可剥离地层叠上述粘接剂层。因此,切割片的粘着剂层能够以具有再剥离性的公知粘着剂所构成,通过选择紫外线固化型、加热发泡型、水溶胀型、弱粘性型等的粘着剂,能够使粘接剂层的剥离容易。
此外,粘接片也可以预先将支撑体以及粘接剂层模切为与被粘物(半导体晶圆等)相同的形状。特别是优选支撑体以及粘接剂层所构成的层叠体保持于长尺寸的剥离膜上的形态。
支撑体的厚度通常为10~500μm,优选为15~300μm,特别优选为20~250μm左右。在支撑体为粘着片的情况下,通常由粘着剂所构成的层占支撑体厚度中的1~50μm左右的厚度。此外,粘接剂层的厚度通常为2~500μm,优选为6~300μm,特别优选为10~150μm左右。
粘接片的制造方法并没有特别限定,在支撑体为树脂膜的情况下,也能够以下述方法制造:在树脂膜上涂布干燥粘接剂组合物,以形成粘接剂层。也能够以下述方法制造:将粘接剂层设置于另外的剥离膜上,然后将其转移至上述树脂膜或粘着片。
另外,在粘接片的使用前为了保护粘接剂层,可以在粘接剂层的表面层叠剥离膜。该剥离膜可使用在聚对苯二甲酸乙二酯或聚丙烯膜等的塑料材料上涂布有硅酮树脂等剥离剂的剥离膜。此外,在粘接片的粘接剂层的表面外周部可以另外设置粘着剂层或粘着带,用于固定环状框架等其他夹具。
接着,对于本发明的粘接片的利用方法,以该粘接片适用于半导体装置的制造的情况为例加以说明。
(半导体装置的制造方法)
以下对本发明的半导体装置的制造方法的例子进行详述。
本发明的半导体装置的第1制造方法包括下述步骤:将上述半导体晶圆贴附于粘接片的粘接剂层;切割该半导体晶圆以及粘接剂层以形成半导体晶片;使粘接剂层固定残留于该半导体晶片背面而从支撑体剥离;将该半导体晶片经由粘接剂层粘接于有机基板或导线架的晶粒垫部上或其他半导体晶片上。
在本发明的半导体装置的第1制造方法中,首先,准备在表面上形成电路、背面经过研磨的半导体晶圆。
半导体晶圆可为硅晶圆,或者可为镓〃砷等的化合物半导体晶圆。对晶圆表面的电路形成,可利用包含蚀刻法、剥离法(lift off)等以往通用的方法的各种方法来进行。其次,对半导体晶圆的电路面的相反面(背面)进行研磨。研磨法并没有特别的限定,可以使用研磨器(grinder)等公知手段进行研磨。在背面研磨时,为了保护表面的电路而于电路面贴附称为表面保护片的粘着片。背面研磨是将晶圆的电路面侧(即表面保护片侧)以夹头座(chuck table)等固定,对未形成电路的背面侧以研磨器进行研磨。晶圆的研磨后的厚度并没有特别的限定,通常为20~500μm左右。
然后,将环状框架以及半导体晶圆的背面侧载置于本发明的粘接片的粘接剂层上,轻轻按压以将半导体晶圆固定。在粘接剂层中添加有光聚合引发剂(D)的情况下,从支撑体侧对粘接剂层照射能量线,使热固性树脂(B)以及填料(C)所具有的反应性双键基反应、固化,提升粘接剂层的凝集力,降低粘接剂层与支撑体之间的粘接力。作为照射的能量线,可举出紫外线(UV)或电子线(EB)等,优选使用紫外线。
其后,通过使用切割机(dicing saw)的刀切割法或使用激光的激光切割法等,对上述半导体晶圆进行切割以得到半导体晶片。使用切割机时的切割深度为半导体晶圆的厚度与粘接剂层的厚度的合计再加上切割机的磨耗量的深度,与晶片同尺寸地切割粘接剂层。
另外,能量线的照射可以在半导体晶圆的贴附后、半导体晶片的剥离(拾取)前的任意阶段进行,例如也可以于切割后进行,或者也可于下述扩展步骤之后进行。此外,能量线照射也可以分多次进行。
其次,如根据需要进行粘接片的扩展,则半导体晶片的间隔扩张,半导体晶片的拾取变得更容易进行。此时,粘接剂层与支撑体之间产生滑动,粘接剂层与支撑体之间的粘接力减少,半导体晶片的拾取性提升。如依此进行半导体晶片的拾取,则能够使切割而成的粘接剂层固定残留于半导体晶片的背面而从支撑体剥离。
其次,经由粘接剂层而将半导体晶片载置于作为晶片搭载部的导线架的晶粒垫上或其他的半导体晶片(下段晶片)表面,以将晶片暂时粘接。晶片搭载部也可以在载置半导体晶片前加热,此外,或可以于载置半导体晶片后加热。加热温度通常为80~200℃,优选为100~180℃,加热时间通常为0.1秒~5分钟,优选为0.5秒~3分钟,载置时的压力通常为1kPa~200MPa。
之后,优选在晶片以暂时粘接的状态依次层叠晶片、打线之后,利用封装制造中通常进行的树脂密封中的加热,以将粘接剂层完全固化。通过经过这样的步骤,能够将粘接剂层一次全部固化而提升制造效率。此外,在打线时由于粘接剂层具有一定程度的硬度,因而能够稳定地进行打线。进一步,由于粘接剂层在晶粒键合条件下软化,因此能够充分埋入晶片搭载部的凹凸中,能够防止空洞的发生,封装的可靠性变高。
在本发明的半导体装置的第2制造方法中,首先,在半导体晶圆的表面形成符合单片化半导体晶片的形状的外部轮廓的沟;在半导体晶圆的表面贴附保护片;接着由背面侧进行到达沟为止的薄化处理,由此将半导体晶圆单片化为半导体晶片,以准备通过所谓先切割法所得的多个晶片群。
其次,与第1制造方法相同,将环状框架以及晶片群的背面侧载置于本发明的粘接剂层上,轻轻按压并固定晶片群。之后,仅将粘接剂层切割为晶片尺寸。但并不限定为仅切割粘接剂层的方法,例如可以采用激光切割法。
之后,根据需要进行粘接片的扩展步骤,或使粘接剂层固定残留于半导体晶片而从支撑体剥离,并经由粘接剂层将半导体晶片粘接于晶粒垫部上或其他半导体晶片上的步骤,如同第1制造方法中的说明那样来进行。
本发明的粘接剂组合物以及粘接片,除了如上所述的使用方法之外,也能够使用于半导体化合物、玻璃、陶瓷、金属等的粘接。
实施例
以下通过实施例说明本发明,但是本发明并不限定于这些实施例。另外,在以下的实施例以及比较例中,<丙烯酸聚合物的重均分子量以及分子量分布的测定>、<填料的平均粒径>、<剪切强度测定>以及<封装可靠性评价>以如下方式进行。另外,剪切强度的测定,是以第2发明的实施例(实施例3、4以及比较例3、4)进行。
<丙烯酸聚合物的重均分子量以及分子量分布的测定>
丙烯酸聚合物(A)的重均分子量(Mw)以及分子量分布(Mw/Mn,Mn为数均分子量),以标准聚苯乙烯换算值,以下述的装置以及条件测定。
.装置名:HLC-8220GPC,东曹(株)制
.柱:以TSKgelGMHXL、TSKgelGMHXL以及TSKgel2000HXL的顺序连结的柱
.溶剂:四氢呋喃
.测定温度:40℃
.流速:1ml/分
.检测器:差示折射计
<填料的平均粒径>
填料的平均粒径通过使用动态光散射法的粒度分布计(日机装社制,装置名:Nanotrac150)测定
<剪切强度测定>
(评价试样制作)
在#2000研磨硅晶圆(150mm直径,厚度350μm)的研磨面上,以胶带贴合机(Lintec社制,Adwill RAD2500)进行实施例以及比较例的粘接片的贴附,固定于晶圆切割用环状框架。其次,使用切割装置(株式会社Disco制,DFD651)切割为5mm×5mm的晶片尺寸,得到晶片。切割时的切入量以切入支撑体20μm的方式设定。
作为暂时粘接上述晶片的下段晶片,准备了CMP处理完毕的晶片(尺寸:10mm×10mm,厚度:350μm)。在此下段晶片上,经由粘接剂层以150℃、100gf、1秒钟的条件压接上述所得晶片,暂时固定半导体封装的模封并以175℃、5小时进行粘接剂层的热固化,以制作评价试样。
(评价)
将评价试样置于预设为回流时温度的250℃的热板上,在湿度50%RH的环境条件下,使用接合测试机(dage社制,dage4000)以测定剪切强度。所述接合测试机的设定条件是,头高为50μm、速度为0.2mm/秒。
<封装可靠性评价>
(半导体晶片的制造)
在经干研磨加工的硅晶圆(150mm直径,厚度75μm)的研磨面上,以胶带贴合机(Lintec社制,Adwill RAD2500)进行实施例以及比较例的粘接片的贴附,固定于晶圆切割用环状框架。其次,使用切割装置(株式会社Disco制,DFD651)切割为8mm×8mm的晶片尺寸。切割时的切入量以切入支撑体20μm的方式设定。
(半导体封装的制造)
使用在覆铜箔层叠板(三菱气体化学株式会社制CCL-HL830,铜箔厚度18μm)的铜箔上形成电路图案,且在图案上具有抗镀剂(太阳墨水制PSR-4000AUS303)的基板(株式会社Chino技研制LN001E-001PCB(Au)AUS303)作为基板。将上述所得的粘接片上的晶片与粘接剂层一起从支撑体取出,经由粘接剂层以120℃、250gf、0.5秒钟的条件压着于基板上。
其后,假设为打线时的热在175℃的气氛下施加2小时的热,使用密封装置(Apic Yamada株式会社制MPC-06M TriAl Press)以密封厚度成为400μm的方式,以模封树脂(京瓷化学株式会社制KE-1100AS3)进行密封。其次,以175℃进行6.9MPa的加热加压2分钟,之后,以175℃进行5小时的加热使树脂固化。
之后,将已密封的基板贴附于切割带(Lintec株式会社制,AdwillD-510T)上,使用切割装置(株式会社Disco制,DFD651)切割为8mm×8mm的晶片尺寸,以得到可靠性评价用的半导体封装。
(评价)
将所得的半导体封装放置在85℃、湿度60%RH的条件下168小时、吸湿后,进行3次在预热130℃(严苛条件)下最高温度成为260℃的、加热时间1分钟的红外(IR)回流(回流炉:相模理工制WL-15-20DNX型)。之后,对于基板与晶片的接合部有无浮起及剥离、有无封装破裂发生,以扫描型超声波探伤装置(日立建机Finetec株式会社制Hye-Focus)以及断面研磨机(Refinetec株式会社制,Refine·PolisherHV)切割出断面,并使用数码显微镜(Keyence社制VHX-1000)通过观察断面以进行评价。
将在基板/半导体晶片接合部观察到长度为0.5mm以上的剥离的情况判断为剥离,并对将封装投入27个试验且未发生剥离的个数进行计数。
<粘接剂组合物>
构成粘接剂组合物的各成分如下所示。
(A-1)丙烯酸聚合物:95质量份丙烯酸甲酯以及5质量份丙烯酸-2-羟基乙酯所构成的共聚物(Mw:50万,Mw/Mn:2.9、Tg:9℃,TOYO CHEM社制)
(A-2)丙烯酸聚合物:95质量份丙烯酸甲酯以及5质量份丙烯酸-2-羟基乙酯所构成的共聚物(Mw:46万,Mw/Mn:3.2、Tg:9℃,日本合成化学社制)
(B)热固性树脂:
(B-1)丙烯酰基加成甲酚酚醛清漆型环氧树脂(日本化药株式会社制CNA-147)
(B-2)热固化剂:芳烷基苯酚树脂(三井化学株式会社制MilexXLC-4L)
(C)填料:
(C-1)甲基丙烯酰氧基改性的二氧化硅填料(平均粒径0.05μm,Admatechs社制3-甲基丙烯酰氧基丙基三甲氧基硅烷处理品)
(C-2)甲基丙烯酰氧基改性的二氧化硅填料(平均粒径0.5μm、SO-C2,Admatechs社制3-甲基丙烯酰氧基丙基三甲氧基硅烷处理品)
(C-3)乙烯基改性的二氧化硅填料(平均粒径0.05μm,Admatechs社制乙烯基三甲氧基硅烷处理品)
(C-4)三甲基改性的二氧化硅填料(平均粒径0.07μm、NSS-5N,三甲基硅基处理,TOKUYAMA社制)
(F)硅烷偶联剂(三菱化学株式会社制MKCSilicateMSEP2)
(G)交联剂:芳香族性多价异氰酸酯(日本Polyurethane工业株式会社制CoronateL)
(J)未处理的二氧化硅填料(平均粒径0.4μm、Sunsinol SS-04,TOKUYAMA社制)
(实施例以及比较例)
(粘接剂层)
上述各成分以表1以及表2所记载的量(质量比)调配,得到粘接剂组合物。使用所得的组合物的甲基乙基酮溶液(固体成分浓度20质量%),以干燥后的厚度为20μm的方式,在经硅酮剥离处理的剥离膜(Lintec株式会社制,SP-PET381031)的剥离处理面上涂布粘接剂组合物溶液、干燥(干燥条件:在烘箱中100℃、1分钟),其后贴合于支撑体(聚乙烯膜,厚度100μm,表面张力33mN/m)上,通过将粘接剂层转移至支撑体上以得到粘接片。使用所得的粘接片制作半导体封装,评价其可靠性。此外,对于以表2所记载的量调配得到的粘接剂组合物,按照与上述相同的方式得到粘接片,除了评价可靠性之外,测定固化后的粘接剂层的剪切强度。结果如表1及表2所示。表1及表2中PKG可靠性表示封装可靠性,在上述评价中,以“未发生剥离个数/27(投入试验的封装个数)”表示。
[表1]
[表2]
作为第1发明的实施方案的实施例1以及实施例2的粘接剂组合物中任一粘接剂组合物,相较于比较例1或比较例2的作为第1发明的比较方案的粘接剂组合物,半导体装置的可靠性能够提升,其中比较例1不含有在表面上具有反应性双键基的填料(C),比较例2使用了重均分子量低于50万的丙烯酸聚合物。
根据本发明的第1发明,通过使用具有规定的重均分子量的丙烯酸聚合物(A)、具有反应性双键基的热固性树脂(B)以及在表面上具有反应性双键基的填料(C),在粘接剂层中填料(C)能够均匀混合,此外,能够在粘接剂层中导入三维网状结构。因此,能够以优异的粘接强度将半导体晶片与其他半导体晶片或基板接合,即使于严苛的环境下,也能够得到显示高封装可靠性的半导体装置。此外,由于能够赋予未固化或半固化状态的粘接剂层一定程度的硬度,在多段封装制造时对粘接剂层采用一次全部固化工序的情况下,即使经由长时间的打线,也能够稳定的进行打线。
作为第2发明的实施方案的实施例3以及实施例4的粘接剂组合物所构成的粘接剂层的剪切强度均为60N/5mm□以上。实施例3以及实施例4的粘接剂组合物中的任一粘接剂组合物,相较于比较例3或比较例4的作为第2发明的比较方案的粘接剂组合物,半导体装置的可靠性能够提升,其中比较例3不含有平均粒径的范围为0.01~0.2μm的填料(C),比较例4不含有在表面上具有反应性双键基的填料(C)。
根据本发明的第2发明,通过使用丙烯酸聚合物(A)、具有反应性双键基的热固性树脂(B)以及在表面上具有反应性双键基且具有规定的平均粒径的填料(C),在粘接剂层中填料(C)能够均匀的混合,此外能够在粘接剂层中导入三维网状结构。因此,能够以优异的粘接强度将半导体晶片与其他的半导体晶片或基板接合,即使于严苛的环境下,也能够得到显示高封装可靠性的半导体装置。此外,由于能够赋予未固化或半固化状态的粘接剂层一定程度的硬度,在多段封装的制造时对粘接剂层采用一次全部固化工序的情况下,即使经由长时间的打线,也能够稳定的进行打线。
Claims (13)
1.一种粘接剂组合物,包含丙烯酸聚合物(A)、具有反应性双键基的热固性树脂(B)以及在表面上具有反应性双键基的填料(C),
该丙烯酸聚合物(A)的重均分子量为50万以上,
该热固性树脂(B)由环氧树脂以及热固化剂所构成,
该环氧树脂以及该热固化剂中的任一方或者双方具有反应性双键基。
2.一种粘接剂组合物,包含丙烯酸聚合物(A)、具有反应性双键基的热固性树脂(B)以及在表面上具有反应性双键基的填料(C),
该填料(C)的平均粒径为0.01~0.2μm的范围,
该热固性树脂(B)由环氧树脂以及热固化剂所构成,
该环氧树脂以及该热固化剂中的任一方或者双方具有反应性双键基。
3.如权利要求1或2所述的粘接剂组合物,其中所述填料(C)为表面具有反应性双键基的二氧化硅。
4.如权利要求1~3中任一项所述的粘接剂组合物,其中在粘接剂组合物的总重量中,所述丙烯酸聚合物(A)的含有比例为50~90质量%。
5.如权利要求1~4中任一项所述的粘接剂组合物,其中所述丙烯酸聚合物(A)具有羟基。
6.一种单层粘接膜,由如权利要求1~5中任一项所述的粘接剂组合物所构成。
7.一种单层粘接膜,由如权利要求2所述的粘接剂组合物所构成,在250℃下固化后的剪切强度为60N/5mm□以上。
8.一种粘接片,将如权利要求1~5中任一项所述的粘接剂组合物所构成的粘接剂层形成于支撑体上而形成。
9.一种粘接片,其由将如权利要求2所述的粘接剂组合物所构成的粘接剂层形成于支撑体上而形成,在250℃下固化后的粘接剂层的剪切强度为60N/5mm□以上。
10.如权利要求8或9所述的粘接片,其中所述支撑体为树脂膜。
11.如权利要求8或9所述的粘接片,其中所述支撑体为粘着片。
12.一种半导体装置的制造方法,包括下述步骤:将半导体晶圆贴附于如权利要求8~11中任一项所述的粘接片的粘接剂层,切割所述半导体晶圆以及粘接剂层以形成半导体晶片,使粘接剂层固定残留于所述半导体晶片而从支撑体剥离,以及将所述半导体晶片经由所述粘接剂层粘接于晶粒垫部上或其他半导体晶片上。
13.一种半导体装置的制造方法,包括下述步骤:在半导体晶圆的表面形成符合单片化半导体晶片的形状的外部轮廓的沟,在半导体晶圆的表面贴附保护片,之后由背面侧进行到达沟为止的薄化处理,以将半导体晶圆单片化为半导体晶片;以及
将所述半导体晶片贴附于如权利要求8~11中任一项所述的粘接片的粘接剂层;使粘接剂层固定残留于所述半导体晶片而从支撑体剥离;以及将所述半导体晶片经由所述粘接剂层粘接于晶粒垫部上或其他半导体晶片上。
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CN105358647A (zh) * | 2013-08-02 | 2016-02-24 | 琳得科株式会社 | 粘接剂组合物、粘接片及半导体装置的制造方法 |
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CN115703950A (zh) * | 2021-08-12 | 2023-02-17 | 利诺士尖端材料有限公司 | 晶圆背面研磨用粘结膜 |
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WO2021075901A1 (ko) * | 2019-10-16 | 2021-04-22 | 주식회사 엘지화학 | 경화성 조성물 |
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