CN101884104A - 感光性粘接剂 - Google Patents
感光性粘接剂 Download PDFInfo
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- CN101884104A CN101884104A CN2008801191136A CN200880119113A CN101884104A CN 101884104 A CN101884104 A CN 101884104A CN 2008801191136 A CN2008801191136 A CN 2008801191136A CN 200880119113 A CN200880119113 A CN 200880119113A CN 101884104 A CN101884104 A CN 101884104A
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- photosensitive adhesive
- alkali
- exposure
- resin
- semiconductor chip
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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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
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Abstract
本发明的感光性粘接剂,其是通过曝光及显影来形成图案后对于被粘接物具有粘接性、可以碱显影的感光性粘接剂,用于具有以下工序的半导体装置100的制造方法,所述工序是:通过曝光及显影将设置于半导体芯片20的电路面上的感光性粘接剂1形成图案的工序,和将其他的半导体芯片21与形成图案后的所述感光性粘接剂1直接粘接的工序。
Description
技术领域
本发明涉及感光性粘接剂。
背景技术
在具有层叠有多个半导体芯片的多层构成的半导体装置中,通常使用芯片焊接用的粘接剂将半导体芯片相互粘接。要求该粘接剂具有低应力性、低温下的粘附性、耐湿可靠性及耐焊接回流性这样的各种特性。
在具有多层构成的半导体装置的制造中,通常在设置于下层半导体芯片的电路面的缓冲涂膜和位于其上层的半导体芯片之间配置芯片焊接用的粘接剂,从而将半导体芯片相互粘接。半导体芯片的缓冲涂膜,以形成焊盘露出的开口的形式使用感光性树脂来形成图案。
另一方面,提出了几个兼具感光性和粘接性的感光性粘接剂的方案(参照专利文献1~3)。
专利文献1:日本特开2000-290501号公报
专利文献2:日本特开2001-329233号公报
专利文献3:日本特开平11-24257号公报
发明内容
发明要解决的课题
要求使具有多层构成的半导体装置进一步变薄,但难以通过以往的方法进一步薄型化。另外,半导体芯片的层叠数变多时,也存在工序数变多、制造工艺复杂化这样的问题。进而,如上所述,在具有层叠有多个半导体芯片的多层构成的半导体装置中,半导体芯片间的层构成,由于形成芯片焊接层和缓冲涂层的2层,因此两者的界面粘接性不充分时,或者由两者的热变形的差产生应力时,都存在半导体装置的可靠性降低的问题。
因此,本发明的目的在于,使具有多层构成的半导体装置的进一步薄型化成为可能,同时减少半导体装置制造的工序数。另外,本发明目的还在于提高得到的半导体装置的可靠性。
解决课题的手段
本发明涉及通过曝光及显影来形成图案后具有对于被粘接物的粘接性(再粘接性)、且能够碱显影的感光性粘接剂。本发明的感光性粘接剂,用于具有以下工序的半导体装置的制造方法,所述工序是:通过曝光及显影将设置于半导体芯片的电路面上的该感光性粘接剂形成图案的工序,和将其他的半导体芯片与形成图案后的所述感光性粘接剂直接粘接的工序。形成图案后的上述感光性粘接剂可以是缓冲涂膜。另外,上述缓冲涂膜,不仅具有应力缓和功能,还包含作为半导体电路表面保护膜的功能。
上述本发明的感光性粘接剂,兼具作为芯片焊接用的粘接剂的功能和形成已形成了图案的绝缘树脂膜的功能。通过使用本发明的感光性粘接剂,没有必要设置半导体芯片上的绝缘树脂膜以外的另外的粘接层,因此具有多层构成的半导体装置的进一步薄型化成为可能,同时也能够减少半导体装置制造的工序数。另外,本发明的感光性粘接剂,如上所述,单层即可兼具作为芯片焊接用的粘接剂的功能和作为形成已形成了图案的绝缘树脂膜的感光性树脂的功能,因此没有以往由芯片焊接层和缓冲涂层的2层构成产生的界面。由此,没有由上述界面粘接性的不良而产生的剥离的问题、以及由两者的热变形的差产生应力的问题。因此,可大幅度改善所得到的半导体装置的耐热、耐湿及连接可靠性。
上述本发明的感光性粘接剂,优选含有碱可溶性聚合物、放射线聚合性化合物和光聚合引发剂。由此,特别容易赋予感光性粘接剂在通过曝光及显影来形成图案后对于被粘接物的粘接性。由同样的观点出发,更优选碱可溶性聚合物具有羧基或酚性羟基。
碱可溶性聚合物的玻璃化转变温度优选为150℃以下。由此,能够在更低的温度下将感光性粘接剂设置于半导体晶片或支持构件等被粘接物上。
碱可溶性聚合物优选为聚酰亚胺。聚酰亚胺优选为使四羧酸二酐与二胺反应而得到的,所述二胺包括分别由下述化学式(I-a)、(I-b)、(II-a)、(II-b)及(II-c)表示的芳香族二胺中的至少一种。
[化1]
本发明的感光性粘接剂,优选进一步含有热固化性树脂。
感光性粘接剂可以是薄膜状。
发明的效果
通过本发明,具有多层构成的半导体装置的进一步薄型化成为可能。另外,通过本发明,能够减少半导体装置制造的工序数。进而,通过本发明,能够进一步提高所得到的半导体装置的可靠性。
附图说明
[图1]表示半导体装置的制造方法的一实施方式的剖面图。
[图2]表示半导体装置的制造方法的一实施方式的剖面图。
[图3]表示半导体装置的制造方法的一实施方式的平面图。
[图4]表示半导体装置的制造方法的一实施方式的剖面图。
[图5]表示半导体装置的制造方法的一实施方式的剖面图。
[图6]表示半导体装置的制造方法的一实施方式的剖面图。
[图7]表示半导体装置的制造方法的一实施方式的剖面图。
符号说明
1...薄膜状的感光性粘接剂(粘接薄膜)、2...半导体晶片、5...复合薄膜、7...支持基材、11...开口、20、21...半导体芯片、25...电路面、30...芯片焊接材料、40...切割带、90...切割线、100...半导体装置。
具体实施方式
以下,对于本发明的适合实施方式进行详细说明。但是,本发明并不限定于以下实施方式。
图1、2、3、4、5及6表示半导体装置的制造方法的一实施方式的剖面图或平面图。本实施方式的半导体装置的制造方法,具有以下工序:在半导体晶片2内形成的半导体芯片20的电路面25上设置薄膜状的感光性粘接剂(以下根据情况称为“粘接薄膜”。)1的工序(图1(a)、(b));通过曝光及显影使设置于半导体芯片20的电路面25上的薄膜状的感光性粘接剂1形成图案的工序(图1(c)、图2(a));由与电路面25相反侧的面来研磨半导体晶片2而使半导体晶片2变薄的工序(图2(b));通过切割将半导体晶片2切分成多个半导体芯片20的工序(图2(c)、图4(a));拾取半导体芯片20安装于半导体装置用的板状的支持基材7的工序(图4(b),图5(a));将第二层的半导体芯片21直接粘接于感光性粘接剂1的工序,所述感光性粘接剂1在安装于支持基材7的半导体芯片20的电路面上形成图案(图5(b));以及将各半导体芯片20、21与外部连接端子连接的工序(图6)。
在图1(a)表示的半导体晶片2内,形成通过切割线90区分的多个半导体芯片20。在该半导体芯片20的电路面25侧的面上设置薄膜状的感光性粘接剂1(图1(b))。准备预先成形为薄膜状的感光性粘接剂1,将其粘附于半导体晶片2的方法简便。另外,也可通过以下方法来设置感光性粘接剂1,所述方法是使用旋涂法等将含有感光性粘接剂1的液状的清漆涂布于半导体晶片2并加热干燥的方法。
感光性粘接剂1,其是在通过曝光及显影而形成图案后对于被粘接物具有粘接性,能够碱显影的负型的感光性粘接剂。更详细地说,通过曝光及显影使薄膜状的感光性粘接剂1形成图案而形成的抗蚀剂图案,具有对于半导体芯片及基板等被粘接物的粘接性。例如根据需要将被粘接物一边加热一边压接于抗蚀剂图案,由此能够将抗蚀剂图案与被粘接物粘接。对于具有该功能的感光性接着剂的详细情况如后述。
对层叠于半导体晶片2的感光性粘接剂1,通过在规定的位置形成开口的掩模3照射活性光线(典型的是紫外线)(图1(c))。由此感光性粘接剂1以规定的图案被曝光。
曝光后,通过使用碱显影液的显影除去感光性粘接剂1中没有曝光的部分,以形成开口11的形式感光性粘接剂1形成图案(图2(a))。另外,也可使用正型的感光性粘接剂代替负型,此时薄膜状的感光性粘接剂中曝光的部分通过显影来除去。
图3表示感光性粘接剂1形成图案后的状态的平面图。在开口11处露出半导体芯片20的焊盘。即,形成图案后的感光性粘接剂1为半导体芯片20的缓冲涂膜。矩形状的开口11,在各半导体芯片20上多个并列形成。开口11的形状、配置及数量并不限于如本实施方式的方式,可适宜变形使得焊盘等的规定的部分露出。
形成图案后,研磨半导体晶片2的与感光性粘接剂1相反侧的面,使半导体晶片2变薄至规定的厚度(图2(b))。该研磨,例如,可以将粘接薄膜粘附于感光性粘着剂1上,通过粘着薄膜将半导体晶片2固定于研磨用的夹具来进行。
研磨后,将具有芯片焊接材料30及切割带40并且它们层叠的复合薄膜5粘附在半导体晶片2的与感光性粘接剂1相反侧的面上,该粘附是以使芯片焊接材料30接触连接半导体晶片2的方向进行的。可根据需要加一边加热一边进行粘附。
接着,通过沿着切割线90将半导体晶片2与复合薄膜5一起切断,从而将半导体晶片2切分为多个半导体芯片20(图4(a))。该切割,例如,在通过切割带40将整体固定于框的状态下使用切割刀来进行。
切割后,将半导体芯片20及粘附在其背面的芯片焊接材料30一起拾取(图4(b))。拾取出的半导体芯片20,通过芯片焊接材料30安装于支持基材7(图5(a))。
对于安装于支持基材7的半导体芯片20上的感光性粘接剂1,直接粘接第二层的半导体芯片21(图5(b))。换言之,半导体芯片20和位于其上层的半导体芯片21,通过介于它们之间并形成了图案的感光性粘接剂1(缓冲涂膜)进行粘接。将半导体芯片21粘接于形成图案后的感光性粘接剂1中的开口11不会被堵塞的位置上。另外,在半导体芯片21的电路面上形成已形成图案的感光性粘接剂1(缓冲涂膜)。
半导体芯片21的粘接,例如,通过一边将感光性粘接剂1加热至体现出流动性的温度一边进行热压接的方法来进行。热压接后,根据需要加热感光性粘接剂1进一步进行固化。
其后,半导体芯片20通过连接于其焊盘上的导线80与支持基材7上的外部连接端子进行连接,半导体芯片21通过连接于其焊盘上的导线81与支持基材7上的外部连接端子进行连接。接着,通过密封树脂层60来密封含有多个半导体芯片的层叠体,得到半导体装置100(图6)。
半导体装置的制造方法并不限于以上说明的实施方式,在不脱离本发明宗旨的范围内可进行适宜变更。例如,可适宜变换粘接薄膜的粘附、切割、曝光及显影、以及半导体晶片研磨的各工序的顺序。如图7所示,也可以在通过研磨而使粘附有薄膜状感光性粘接剂1的半导体晶片2变薄后,进行切割。此时,切割后,通过曝光及显影使感光性粘接剂1形成图案,得到与图4(a)同样的层叠体。或者,也可以在通过研磨变薄并将半导体晶片切割后,进行薄膜状感光性粘接剂1的粘附和其曝光及显影。另外,也可层叠3层以上的半导体芯片,此时,至少一组相邻的半导体芯片彼此通过形成图案的感光性粘接剂(下层侧的缓冲涂膜)进行直接粘接。
以下,对于上述实施方式的半导体装置制造方法中使用的感光性粘接剂的适合实施方式进行说明。
本实施方式的感光性粘接剂,是含有碱可溶性聚合物、放射线聚合性化合物和光聚合引发剂的负型感光性树脂。
碱可溶性聚合物只要可溶于碱显影液即可,优选可溶于氢氧化四甲基铵水溶液。例如,只要是具有羧基和/或酚性羟基的聚合物,则多具有针对碱显影液的良好的溶解性。
为了确保曝光后的良好的粘接性,碱可溶性聚合物的玻璃化转变温度(Tg)优选为10~150℃。碱可溶性聚合物的Tg小于10℃时,在曝光后热压接时存在容易产生空隙的倾向。Tg超过150℃时,曝光前的对于被粘接物的粘附温度及曝光后的压接温度变高,存在由于热损伤或热应力等而引起周边构件变形的倾向。另外,上述Tg是使用粘弹性测定装置(流变仪公司(Rheometrics)制)来测定薄膜状感光性粘接剂的粘弹性的温度变化时的tanδ的峰温度。
碱可溶性聚合物的重均分子量优选为5000~150000,更优选为10000~100000,进一步优选为10000~50000。碱可溶性聚合物的重均分子量小于5000时,存在感光性粘接剂的薄膜形成性降低的倾向,超过150000时,存在在碱显影液中的溶解性降低,显影时间变长的倾向。通过使碱可溶性聚合物的重均分子量为5000~150000,还可得到用于确保曝光后再粘接的良好的加热流动性这样的效果。另外,上述的重均分子量是使用高效液相色谱(例如,岛津制作所制“C-R4A”(商品名))来测定的标准聚苯乙烯换算值。
碱可溶性聚合物,可具有乙烯性不饱和基团等放射线聚合性官能团。此时,碱可溶性聚合物作为放射线聚合性化合物发挥功能。作为放射线聚合性化合物,可只使用含有放射线聚合性官能团的碱可溶性聚合物,也可将该碱可溶性聚合物与其之外其他的放射线聚合性化合物组合来使用。
碱可溶性聚合物,优选含有选自聚酰亚胺、聚酰胺酰亚胺、聚酰胺、聚苯并噁唑、丙烯酸类聚合物、苯乙烯-马来酸共聚物、乙烯基化合物-马来酰亚胺化合物共聚物、酚醛清漆树脂及聚降冰片烯树脂的至少一种聚合物。这些物质中,优选聚酰亚胺、聚酰胺酰亚胺、聚酰胺、聚苯并噁唑及丙烯酸类聚合物。
用作为碱可溶性聚合物的聚酰亚胺,由主链中具有酰亚胺骨架的一种或二种以上聚合物构成。聚酰亚胺优选具有羧基和/或酚性羟基。
具有羧基的聚酰亚胺可通过偏苯三酸酐和/或四羧酸二酐与具有羧基及氨基的二胺的反应得到。具有酚性羟基的聚酰亚胺,可通过四羧酸二酐与具有酚性羟基及氨基的二胺的反应得到。通过这些反应,在聚酰亚胺中导入来源于二胺的羧基或酚性羟基。通过适宜调整二胺的种类及其投料比、反应条件等,可将聚酰亚胺的酸值控制在期望的范围。
四羧酸二酐与二胺的反应(缩合反应),可如本领域技术人员能够理解的那样,通过公知方法来进行。例如,在该反应中,首先,在有机溶剂中,以等摩尔或大致等摩尔的比例使四羧酸二酐和二胺在反应温度80℃以下、优选0~60℃下进行加成反应。各成分的添加顺序可任意。随着反应的进行,反应液的粘度慢慢上升,生成作为聚酰亚胺前体的聚酰胺酸。通过将生成的聚酰胺酸加热至50~80℃的温度进行解聚合,可调整其分子量。通过使生成的聚酰胺酸脱水闭环,从而生成聚酰亚胺。脱水闭环,可通过利用加热的热闭环法、或使用脱水剂的化学闭环法进行。
关于四羧酸二酐与二胺的投料比,更具体地说,相对于四羧酸二酐的合计量1.0mol,二胺的合计量优选为0.5~2.0mol,更优选为0.8~1.0mol的范围内。二胺的比例超过2.0mol时,存在生成较多末端为氨基的聚酰亚胺低聚物的倾向,低于0.5mol时,存在生成较多末端为羧酸或酸酐的聚酰亚胺低聚物的倾向。聚酰亚胺低聚物的量变多时,聚酰亚胺的重均分子量降低,容易产生感光性粘接剂组成物的耐热性等各种特性的降低。通过调整上述投料比,可进行调制使得聚酰亚胺的重均分子量为5000~150000的范围内。
作为在聚酰亚胺的合成中使用的二胺,为了使其为在碱显影液中的溶解性特别良好的物质,优选上述的式(I-a)、(I-b)、(II-a)、(II-b)及(II-c)分别表示的芳香族二胺的至少一种。
为了使聚酰亚胺的Tg降低而减少热应力,二胺进一步优选含有下述通式(III)表示的脂肪族醚二胺。式(III)中,Q1、Q2及Q3分别独立地表示碳原子数1~10的亚烷基,n1表示1~80的整数。
[化2]
作为式(III)的脂肪族醚二胺,更具体地可举出下述化学式(IIIa)、(IIIb)或(IIIc)表示的物质。这些物质中,在可以提高曝光前的低温下的粘附性及曝光后的再粘接性方面,优选式(IIIa)的脂肪族醚二胺。
[化3]
作为脂肪族醚二胺的市售品,例如,可举出三井化学(公司)制的ジ工フア一ミン“D-230”、“D-400”、“D-2000”、“D-4000”、“ED-600”、“E D-900”、“ED-2001”、“EDR-148”(以上商品名),巴斯夫(制)的聚醚胺“D-230”“D-400”、“D-2000”(以上商品名)。
进而,为了确保对于曝光后的被粘接物的良好的粘接性,优选使用下述通式(IV)表示的硅氧烷二胺。式(IV)中,R1及R2分别独立地表示可具有碳原子数1~5的亚烷基或取代基的亚苯基,R3、R4、R5及R6分别独立地表示碳原子数1~5的烷基、苯基或苯氧基,n2表示1~5的整数。
[化4]
作为化学式(IV)表示的硅氧烷二胺,例如,式中的n为1时,可举出1,1,3,3-四甲基-1,3-双(4-氨基苯基)二硅氧烷、1,1,3,3-四苯氧基-1,3-双(4-氨基乙基)二硅氧烷、1,1,3,3-四苯基-1,3-双(2-氨基乙基)二硅氧烷、1,1,3,3-四苯基-1,3-双(3-氨基丙基)二硅氧烷、1,1,3,3-四甲基-1,3-双(2-氨基乙基)二硅氧烷、1,1,3,3-四甲基-1,3-双(3-氨基丙基)二硅氧烷、1,1,3,3-四甲基-1,3-双(3-氨基丁基)二硅氧烷、1,3-二甲基-1,3-二甲氧基-1,3-双(4-氨基丁基)二硅氧烷等。n2为2时,可列举1,1,3,3,5,5-六甲基-1,5-双(4-氨基苯基)三硅氧烷、1,1,5,5-四苯基-3,3-二甲基-1,5-双(3-氨基丙基)三硅氧烷、1,1,5,5-四苯基-3,3-二甲氧基-1,5-双(4-氨基丁基)三硅氧烷、1,1,5,5-四苯基-3,3-二甲氧基-1,5-双(5-氨基戊基)三硅氧烷、1,1,5,5-四甲基-3,3-二甲氧基-1,5-双(2-氨基乙基)三硅氧烷、1,1,5,5-四甲基-3,3-二甲氧基-1,5-双(4-氨基丁基)三硅氧烷、1,1,5,5-四甲基-3,3-二甲氧基-1,5-双(5-氨基戊基)三硅氧烷、1,1,3,3,5,5-六甲基-1,5-双(3-氨基丙基)三硅氧烷、1,1,3,3,5,5-六乙基-1,5-双(3-氨基丙基)三硅氧烷、1,1,3,3,5,5-六丙基-1,5-双(3-氨基丙基)三硅氧烷等。
这些二胺,可单独使用一种或组合两种以上使用。例如,优选使式(I a)、(I b)、(II-a)、(II-b)及(II-c)分别表示的芳香族二胺的至少一种为全部二胺的10~50摩尔%,通式(IV)表示的硅氧烷二胺为全部二胺的1~20摩尔%(进一步优选为5~10摩尔%),通式(III)表示的脂肪族醚二胺为全部二胺的10~90摩尔%。通过以上述比例使用式(Ia)或(Ib)表示的芳香族二胺,可确保良好的显影性。硅氧烷二胺小于全部二胺的1摩尔%时,存在对于曝光后的被粘接物的粘接性降低的倾向,超过20摩尔%时,存在在碱显影液中的溶解性降低的倾向。另外,脂肪族醚二胺小于全部二胺的10摩尔%时,聚酰亚胺的Tg变高而存在低温加工性(低温下的粘附性)降低的倾向,超过90摩尔%时,存在曝光后的热压接时由于过流动而容易产生空隙的倾向。
二胺可进一步包括上述以外的二胺。例如,邻苯二胺、间苯二胺、对苯二胺、3,3’-二氨基二苯基醚、3,4’-二氨基二苯基醚、4,4’-二氨基二苯基醚、3,3’-二氨基二苯基甲烷、3,4’-二氨基二苯基甲烷、4,4’-二氨基二苯基醚甲烷、双(4-氨基-3,5-二甲基苯基)甲烷、双(4-氨基-3,5-二异丙基苯基)甲烷、3,3’-二氨基二苯基二氟甲烷、3,4’-二氨基二苯基二氟甲烷、4,4’-二氨基二苯基二氟甲烷、3,3’-二氨基二苯基砜、3,4’-二氨基二苯基砜、4,4’-二氨基二苯基砜、3,3’-二氨基二苯基硫醚、3,4’-二氨基二苯基硫醚、4,4’-二氨基二苯基硫醚、3,3’-二氨基二苯基酮、3,4’-二氨基二苯基酮、4,4’-二氨基二苯基酮、2,2-双(3-氨基苯基)丙烷、2,2’-(3,4’-二氨基二苯基)丙烷、2,2-双(4-氨基苯基)丙烷、2,2-双(3-氨基苯基)六氟丙烷、2,2-双(3,4’-二氨基二苯基)六氟丙烷、2,2-双(4-氨基苯基)六氟丙烷、1,3-双(3-氨基苯氧基)苯、1,4-双(3-氨基苯氧基)苯、1,4-双(4-氨基苯氧基)苯、3,3’-(1,4-亚苯基双(1-甲基亚乙基)双苯胺、3,4’-(1,4-亚苯基双(1-甲基亚乙基)双苯胺、4,4’-(1,4-亚苯基双(1-甲基亚乙基)双苯胺、2,2-双(4-(3-氨基苯氧基)苯基)丙烷、2,2-双(4-(3-氨基苯氧基)苯基)六氟丙烷、2,2-双(4-(4-氨基苯氧基)苯基)六氟丙烷、双(4-(3-氨基苯氧基)苯基)硫醚、双(4-(4-氨基苯氧基)苯基)硫醚、双(4-(3-氨基苯氧基)苯基)砜、双(4-(4-氨基苯氧基)苯基)砜、1,3-双(氨基甲基)环己烷、2,2-双(4-氨基苯氧基苯基)丙烷。
作为合成聚酰亚胺时的原料使用的四羧酸二酐,为了抑制粘接剂的诸特性的降低,优选通过乙酸酐的重结晶进行精制。或者,四羧酸二酐也可通过在比其融点低10~20℃的温度下加热12小时以上进行干燥。四羧酸二酐的纯度可通过示差扫描热量计(DSC)测定的吸热开始温度与吸热峰温度的差来评价,优选将通过重结晶或干燥等精制成为该差在20℃以内、更优选在10℃以内的的四羧酸二酐用于聚酰亚胺的合成。吸热开始温度及吸热峰温度,使用DSC(铂金埃尔默公司制DSC-7型),在样品量:5mg、升温速度:5℃/分钟、测定气氛:氮气的条件下测定。
作为四羧酸二酐,可举出例如,均苯四酸二酐、3,3’,4,4’-联苯四羧酸二酐、2,2’,3,3’-联苯四羧酸二酐、2,2-双(3,4-二羧基苯基)丙烷二酐、2,2-双(2,3-二羧基苯基)丙烷二酐、1,1-双(2,3-二羧基苯基)乙烷二酐、1,1-双(3,4-二羧基苯基)乙烷二酐、双(2,3-二羧基苯基)甲烷二酐、双(3,4-二羧基苯基)甲烷二酐、双(3,4-二羧基苯基)砜二酐、3,4,9,10-苝四羧酸二酐、双(3,4-二羧基苯基)醚二酐、苯-1,2,3,4-四羧酸二酐、3,4,3’,4’-二苯甲酮四羧酸二酐、2,3,2’,3’-二苯甲酮四羧酸二酐、3,3,3’,4’-二苯甲酮四羧酸二酐、1,2,5,6-萘四羧酸二酐、1,4,5,8-萘四羧酸二酐、2,3,6,7-萘四羧酸二酐、1,2,4,5-萘四羧酸二酐、2,6-二氯萘-1,4,5,8-四羧酸二酐、2,7-二氯萘-1,4,5,8-四羧酸二酐、2,3,6,7-四氯萘-1,4,5,8-四羧酸二酐、菲-1,8,9,10-四羧酸二酐、吡嗪-2,3,5,6-四羧酸二酐、噻吩-2,3,5,6-四羧酸二酐、2,3,3’,4’-联苯四羧酸二酐、3,4,3’,4’-联苯四羧酸二酐、2,3,2’,3’-联苯四羧酸二酐、双(3,4-二羧基苯基)二甲基硅烷二酐、双(3,4-二羧基苯基)甲基苯基硅烷二酐、双(3,4-二羧基苯基)二苯基硅烷二酐、1,4-双(3,4-二羧基苯基二甲基硅烷基)苯二酐、1,3-双(3,4-二羧基苯基)-1,1,3,3-四甲基二环己烷二酐、对亚苯基双(偏苯三酸酯酐)、亚乙基四羧酸二酐、1,2,3,4-丁烷四羧酸二酐、十氢萘-1,4,5,8-四羧酸二酐、4,8-二甲基-1,2,3,5,6,7-六氢萘-1,2,5,6-四羧酸二酐、环戊烷-1,2,3,4-四羧酸二酐、吡咯烷-2,3,4,5-四羧酸二酐、1,2,3,4-环丁烷四羧酸二酐、双(外向-二环[2,2,1]庚烷-2,3-二羧酸二酐、二环-[2,2,2]-辛-7-烯-2,3,5,6-四羧酸二酐、2,2-双(3,4-二羧基苯基)丙烷二酐、2,2-双[4-(3,4-二羧基苯基)苯基]丙烷二酐、2,2-双(3,4-二羧基苯基)六氟丙烷二酐、2,2-双[4-(3,4-二羧基苯基)苯基]六氟丙烷二酐、4,4’-双(3,4-二羧基苯氧基)二苯基硫醚二酐、1,4-双(2-羟基六氟异丙基)苯双(偏苯三酸酐)、1,3-双(2-羟基六氟异丙基)苯双(偏苯三酸酐)、5-(2,5-二氧四氢呋喃基)-3-甲基-3-环己烯-1,2-二羧酸二酐及四氢呋喃-2,3,4,5-四羧酸二酐。
特别地为了赋予在溶剂中的良好的溶解性,优选下述化学式(V)或(VI)表示的四羧酸二酐。此时,这些式子表示的四羧酸二酐的比例优选为,相对于全部四羧酸二酐100摩尔%优选为50摩尔%以上。该比例小于50摩尔%时,存在溶解性提高效果降低的倾向。
[化5]
如以上的四羧酸二酐,可单独使用或组合二种以上使用。另外,为了调整对于碱显影液的溶解性及分子量等,根据需要,可并用偏苯三酸酐等单官能酸酐。
放射线聚合性化合物是通过紫外线或电子束等放射线的照射进行聚合的化合物。放射线聚合性化合物,优选具有丙烯酸酯基及甲基丙烯酸酯基这样的乙烯性不饱和基团的化合物。作为放射线聚合性化合物的具体例,可举出丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸-2-乙基己酯、甲基丙烯酸-2-乙基己酯、丙烯酸戊烯酯、丙烯酸四氢糠酯、甲基丙烯酸四氢糠酯、二乙二醇二丙烯酸酯、三乙二醇二丙烯酸酯、四乙二醇二丙烯酸酯、二乙二醇二甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯、四乙二醇二甲基丙烯酸酯、三羟甲基丙烷二丙烯酸酯、三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷二甲基丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、1,4-丁二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、1,4-丁二醇二甲基丙烯酸酯、1,6-己二醇二甲基丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇三甲基丙烯酸酯、季戊四醇四甲基丙烯酸酯、二季戊四醇六丙烯酸酯、二季戊四醇六甲基丙烯酸酯、苯乙烯、二乙烯基苯、4-乙烯基甲苯、4-乙烯基吡啶、N-乙烯基吡咯烷酮、丙烯酸2-羟基乙酯、甲基丙烯酸2-羟基乙酯、1,3-丙烯酰氧基-2-羟基丙烷、1,2-甲基丙烯酰氧基-2-羟基丙烷、亚甲基双丙烯酰胺、N,N-二甲基丙烯酰胺、N-羟甲基丙烯酰胺、三(β-羟乙基)三聚异氰酸酯的三丙烯酸酯、下述通式(10)所示化合物、氨酯丙烯酸酯或氨酯甲基丙烯酸酯、及尿素丙烯酸酯。式(10)中,R3及R4分别独立地表示氢原子或甲基,q及r分别独立地表示1以上的整数。
[化6]
氨酯丙烯酸酯或氨酯甲基丙烯酸酯,例如可通过使二醇类、下述通式(21)表示的异氰酸酯化合物、及下述通式(22)表示的化合物的反应来产生。
[化7]
式(21)中,s表示0或1,R5表示碳原子数1~30的2价或3价的有机基团。式(22)中,R6表示氢原子或甲基,R7表示亚乙基或亚丙基。
尿素甲基丙烯酸酯,例如通过使下述通式(31)表示的二胺和下述通式(32)表示的化合物的反应来产生。
[化8]
H2N-R8-NH2(31)
式(31)中,R8表示碳原子数2~30的2价有机基团。式(32)中,t表示0或1。
除了如上的化合物以外,还可使用侧链上具有乙烯性不饱和基团的放射线聚合性共聚物等,所述共聚物可通过使含有官能团的乙烯基共聚物与具有环氧乙烷环、异氰酸酯基、羟基、羧基等官能团和至少1个乙烯性不饱和基团的化合物加成反应而得到。
这些放射线聚合性化合物可单独使用一种或组合两种以上使用。其中上述通式(10)表示的放射线聚合性化合物可赋予固化后的耐溶剂性,因此优选,氨酯丙烯酸酯及氨酯甲基丙烯酸酯可充分赋予固化后的挠性,因此优选。
放射线聚合性化合物的分子量优选为2000以下。分子量超过2000时,存在感光性粘接剂在碱显影液中的溶解性降低的倾向,另外,粘接薄膜的粘附性降低,存在低温下难以粘附于半导体晶片等被粘接物的倾向。
放射线聚合性化合物的含量,相对于碱可溶性聚合物100质量份优选为5~250质量份,更优选为20~200质量份。放射线聚合性化合物的量超过250质量份时,除了因聚合后的放射线聚合性化合物而使热压接后的粘接性降低以外,还存在翘曲增大的倾向。小于5质量份时,曝光后的耐溶剂性变低,存在难以形成图案的倾向。
另外,为了提高曝光及再粘接后的热固化性,根据需要可使用热自由基发生剂。
为了使图案形成时的敏感度良好,光聚合引发剂优选在300~400nm具有吸收带。作为光聚合引发剂的具体例,可以举出二苯甲酮、N,N’-四甲基-4,4’-二氨基二苯甲酮(米蚩酮)、N,N’-四乙基-4,4’-二氨基二苯甲酮、4-甲氧基-4’-二甲氨基二苯甲酮、2-苄基-2-二甲氨基-1-(4-吗啉代苯基)丁酮-1、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、1-羟基-环己基-苯基酮、2-甲基-1-(4-(甲基硫代)苯基)-2-吗啉代丙酮-1、2,4-二乙硫基呫吨酮、2-乙基蒽醌及菲醌等芳香族酮,苯偶姻甲醚、苯偶姻***及苯偶姻苯醚等苯偶姻醚,甲基苯偶姻、乙基苯偶姻等苯偶姻,偶苯酰二甲基缩酮等偶苯酰衍生物,2-(邻氯苯基)-4,5-二苯基咪唑二聚物、2-(邻氯苯基)-4,5-二(间甲氧苯基)咪唑二聚物、2-(邻氟苯基)-4,5-苯基咪唑二聚物、2-(邻甲氧苯基)-4,5-二苯基咪唑二聚物、2-(对甲氧苯基)-4,5-二苯基咪唑二聚物、2,4-二(对甲氧苯基)-5-苯基咪唑二聚物及2-(2,4-二甲氧苯基)-4,5-二苯基咪唑二聚物等2,4,5-三芳基咪唑二聚物,9-苯基吖啶及1,7-双(9,9-吖啶基)庚烷等吖啶衍生物等,双(2,6-二甲氧基苯甲酰基)-2,4,4-三甲基-戊基膦氧化物及双(2,4,6,-三甲基苯甲酰基)-苯基膦氧化物等二酰基膦氧化物。它们可以单独使用,或者可以组合二种以上使用。
上述光聚合引发剂的使用量,没有特别限制,相对于碱可溶性聚合物100质量份,通常为0.01~30质量份。
感光性粘接剂,优选进一步含有热固化性树脂。本说明书中的热固化性树脂是指能够通过热发生交联反应的反应性化合物。作为这样的化合物,可举出例如,环氧树脂、氰酸酯树脂、双马来酰亚胺树脂、酚醛树脂、尿素树脂、三聚氰胺树脂、醇酸树脂、丙烯酸树脂、不饱和聚酯树脂、邻苯二甲酸二烯丙酯树脂、硅树脂、间苯二酚甲醛树脂、二甲苯树脂、呋喃树脂、聚氨酯树脂、酮树脂、异氰尿酸三烯丙酯树脂、聚异氰酸酯树脂、含有三(2-羟乙基)异氰尿酸酯的树脂、含有三烯丙基偏苯三酸酯的树脂、由环戊二烯合成的热固化性树脂、通过芳香族二氰胺的三聚化生成的热固化性树脂等。其中,从使其在高温下具有优异的粘接力方面出发,优选环氧树脂、氰酸酯树脂及双马来酰亚胺树脂,在操作性及半导体装置组装时的对于热过程的热反应性方面出发,特别优选环氧树脂。这些热固化性树脂可单独或组合二种以上使用。
作为环氧树脂,优选分子内具有至少二个环氧基的化合物。出固化性或固化物特性的方面出发,极优选苯酚的缩水甘油醚型的环氧树脂。作为这样的环氧树脂,可举出例如,双酚A、AD、S型或F的缩水甘油醚、氢化双酚A的缩水甘油醚、双酚A的环氧乙烷加成物的缩水甘油醚、双酚A的环氧丙烷加成物的缩水甘油醚、苯酚酚醛清漆树脂的缩水甘油醚、甲酚酚醛清漆树脂的缩水甘油醚、双酚A酚醛清漆树脂的缩水甘油醚、萘树脂的缩水甘油醚、3官能型或4官能型的缩水甘油醚、二环戊二烯苯酚树脂的缩水甘油醚、二聚酸的缩水甘油酯、3官能型或4官能型的缩水甘油胺、萘树脂的缩水甘油胺。这些树脂可单独或组合二种以上使用。
作为氰酸酯树脂,可举出例如,2,2’-双(4-氰酸酯基苯基)异丙叉、1,1’-双(4-氰酸酯基苯基)乙烷、双(4-氰酸酯基-3,5-二甲基苯基)甲烷、l,3-双[4-氰酸酯基苯基-1-(1-甲基亚乙基)]苯、氰酸酯化苯酚-二环戊二烯加成物、聚邻甲酚氰酸酯(Phenol novolac cyanate ester)、双(4-氰酸酯基苯基)硫醚、双(4-氰酸酯基苯基)醚、间苯二酚二氰酸酯基、1,1,1-三(4-氰酸酯基苯基)乙烷、2-苯基-(4-氰酸酯基苯基)异丙叉。这些树脂可单独或组合二种以上使用。
作为双马来酰亚胺树脂,可举出例如,邻、间、对双马来酰亚胺苯、4-双(对马来酰亚胺枯烯基)苯,1,4-双(间马来酰亚胺枯烯基)苯及下述通式(40)、(41)、(42)或(43)表示的马来酰亚胺化合物。这些树脂可单独或组合二种以上使用。
[化9]
在式(40)中,R40表示-O-、-CH2-、-CF2-、-SO2-、-S-、-CO-、-C(CH3)2-或-C(CF3)2-,四个R41别独立地表示氢原子、低级烷基、低级烷氧基、氟、氯或溴,二个Z1分别独立地表示具有乙烯性不饱和双键的二羧酸残基。
在式(41)中,R42表示-O-、-CH2-、-CF2-、-SO2-、-S-、-CO-、-C(CH3)2-或-C(CF3)2-,4个R43分别独立地表示氢、低级烷基、低级烷氧基、氟、氯或溴,2个Z2分别独立地表示具有乙烯性不饱和双键的二羧酸残基。
在式(42)中,x表示0~4的整数,多个Z3分别独立地表示具有乙烯性不饱和双键的二羧酸残基。
在式(43)中,2个R44分别独立地表示2价的烃基,多个R45分别独立地表示1价的烃基,2个Z4分别独立地表示具有乙烯性不饱和双键的二羧酸残基,y表示1以上的整数。
作为式(40)~(43)的Z1、Z2、Z3及Z4,可举出马来酸残基、柠康酸残基等。
作为式(41)表示的双马来酰亚胺树脂,可举出例如,4,4-双马来酰亚胺二苯基醚、4,4-双马来酰亚胺二苯基甲烷、4,4-双马来酰亚胺-3,3’-二甲基-二苯基甲烷、4,4-双马来酰亚胺二苯基砜、4,4-双马来酰亚胺二苯基硫醚、4,4-双马来酰亚胺二苯基酮、2’-双(4-马来酰亚胺苯基)丙烷、4-双马来酰亚胺二苯基氟甲烷及1,1,1,3,3,3-六氟-2,2-双(4-马来酰亚胺苯基)丙烷。
作为式(42)表示的双马来酰亚胺树脂,可以举出例如,双[4-(4-马来酰亚胺苯氧基)苯基]醚、双[4-(4-马来酰亚胺苯氧基)苯基]甲烷、双[4-(4-马来酰亚胺苯氧基)苯基]氟甲烷、双[4-(4-马来酰亚胺苯氧基)苯基]砜、双[4-(3-马来酰亚胺苯氧基)苯基]砜、双[4-(4-马来酰亚胺苯氧基)苯基]硫醚、双[4-(4-马来酰亚胺苯氧基)苯基]酮、2-双[4-(4-马来酰亚胺苯氧基)苯基]丙烷及1,1,1,3,3,3-六氟-2,2-双[4-(4-马来酰亚胺苯氧基)苯基]丙烷。
使用热固化性树脂时,为了使其固化,可在感光性粘接剂中适当添加固化剂、固化促进剂、催化剂等添加剂。添加催化剂时可根据需要使用助催化剂。
使用环氧树脂时,优选使用环氧树脂的固化剂或固化促进剂,更优选并用它们。作为固化剂,可举出例如酚系化合物、脂肪族胺、脂环族胺、芳香族聚胺、聚酰胺、脂肪族酸酐、脂环族酸酐、芳香族酸酐、双氰胺、有机酸二酰肼、三氟化硼胺络合物、咪唑类、叔胺、分子中具有至少2个酚性羟基的酚系化合物等。这些物质中,从在碱显影液中的溶解性优异的方面出发,优选分子中具有至少2个酚性羟基的苯酚系化合物。
作为上述分子中具有至少2个酚性羟基的苯酚系化合物,可举出例如苯酚酚醛清漆树脂、甲酚酚醛清漆树脂、叔丁基苯酚酚醛清漆树脂、二环戊二烯甲酚酚醛清漆树脂、二环戊二烯苯酚酚醛清漆树脂、亚二甲苯基改性苯酚酚醛清漆树脂、萘酚酚醛清漆树脂、三苯酚酚醛清漆树脂、四苯酚酚醛清漆树脂、双酚A酚醛清漆树脂、聚-对乙烯基苯酚树脂、苯酚芳烷基树脂等。
作为固化促进剂,只要是促进环氧树脂固化的物质就没有特别限制,可举出例如,咪唑类、双氰胺衍生物、二羧酸二酰肼、三苯基膦、四苯基鏻四苯基硼酸盐、2-乙基-4-甲基咪唑-四苯基硼酸盐、1,8-二氮杂双环[5.4.0]十一碳烯-7-四苯基硼酸盐等。
环氧树脂的固化剂的量,优选相对于环氧树脂100质量份为0~200质量份,固化促进剂的量,优选相对于环氧树脂100质量份为0~50质量份。
作为热固化性树脂使用氰酸酯树脂时,优选使用催化剂及根据需要使用助催化剂。作为催化剂,可以举出例如钴、锌、铜等的金属盐或金属络合物等,作为助催化剂,优选烷基酚、双酚化合物、苯酚酚醛清漆等酚系化合物等。
作为热固化性树脂使用双马来酰亚胺树脂时,优选使用自由基聚合剂作为其固化剂。作为自由基聚合剂,可举出例如,乙酰基环己基磺酰过氧化物、异丁酰基过氧化物、苯甲酰基过氧化物、辛酰基过氧化物、乙酰基过氧化物、二枯烯基过氧化物、氢过氧化枯烯、偶氮双异丁腈等。此时,自由基聚合剂的使用量,优选相对于双马来酰亚胺树脂100质量份为0.01~1.0质量份。
为了提高粘接强度等,感光性粘接剂也可适宜含有偶合剂。作为偶合剂,可列举例如硅烷偶合剂、钛系偶合剂等,其中在可以赋予高粘接力的方面,优选硅烷偶合剂。
使用硅烷偶合剂时,其使用量,优选相对于聚酰亚胺100质量份为0~50质量份,更优选为0~20质量份。超过50质量份时存在感光性粘接剂的保存稳定性降低的倾向。
作为硅烷偶合剂,可举出例如,乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三(2-甲氧基乙氧基)硅烷、N-(2-氨基乙基)3-氨基丙基甲基二甲氧基硅烷、N-(2-氨基乙基)3-氨基丙基甲基三甲氧基硅烷、3-氨基丙基三乙氧基硅烷、3-氨基丙基三甲氧基硅烷、3-环氧丙氧基丙基三甲氧基硅烷、3-环氧丙氧基甲基二甲氧基硅烷、2-(3,4-环氧环己基)乙基三甲氧基硅烷、3-异氰酸酯基丙基三乙氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷、3-巯基丙基三甲氧基硅烷、3-脲基丙基三乙氧基硅烷、N-(1,3-二甲基亚丁基)-3-(三乙氧基甲硅烷基)-1-丙胺、N,N’-双[3-(三甲氧基甲硅烷基)丙基]乙二胺、聚氧乙烯丙基三烷氧基硅烷及聚乙氧基二甲基硅氧烷。这些物质可单独或组合二种以上使用。
感光性粘接剂还可含有填料。作为填料,可举出例如,银粉、金粉、铜粉等金属填料,二氧化硅、氧化铝、氮化硼、二氧化钛、玻璃、氧化铁、硼酸铝、陶瓷等非金属无机填料、碳、橡胶系填料等有机填料等。
上述填料可根据期望的功能分别使用。例如,出于对粘接薄膜赋予导电性、触变性的目的而添加金属填料,出于对粘接薄膜赋予低热膨涨性、低吸湿性的目的而添加非金属无机填料,出于对粘接薄膜赋予韧性的目的而添加有机填料。这些金属填料、非金属无机填料及有机填料可单独使用或组合二种以上使用。使用填料时的混合、混炼,可适当组合通常的搅拌机、混砂机、三辊机、球磨机等分散机来进行。
使用填料时,其量优选相对于碱可溶性聚合物100质量份为1000质量份以下,更优选为500质量份以下。下限没有特别制限,通常为1质量份。填料的量超过1000质量份时,存在粘接性降低的倾向。
感光性粘接剂的曝光后的在100℃时的储能模量优选为0.01~10MPa。该储能模量小于0.01MPa时,图案形成后的热压接时对于施加的热及压力的耐性降低,存在图案容易破坏的倾向,超过10MPa时,曝光后的再粘接性降低,图案形成后热压接于被粘接物时,存在为了得到充分的粘接力所要求的温度变高的倾向。
上述储能模量的值,通过测定由曝光后的感光性粘接剂构成的试验片的动态粘弹性来得到。动态粘弹性在升温速度:5℃/分钟、频率:1Hz、测定温度:-50℃~200℃的条件下测定。作为测定装置,例如,可使用流变仪公司(Rheometrics)制粘弹性分析仪“RSA-2”。
用于动粘弹性测定的试验片,典型地如以下那样准备。首先,将PET薄膜及具有在其一面上形成的厚度约40μm的粘接薄膜的粘接薄片切出35mm×10mm的大小,使用高精度平行曝光机(Oak制作所)在曝光量:1000mJ/cm2的条件下由PET薄膜侧照射紫外线。曝光后,剥离PET薄膜得到上述试验片。
感光性粘接剂的、曝光后进一步进行加热固化后的在260℃时的储能模量优选为1MPa以上。该储能模量小于IMPa时,用软钎焊将使用感光性粘接剂得到的半导体装置安装于基板时,存在难以抑制由高温加热引起的剥离或破坏的倾向。
上述储能模量的值,通过测定由曝光后进一步加热固化后的感光性粘接剂构成的试验片的动态粘弹性而得到。动态粘弹性在升温速度:5℃/分钟、频率:1Hz、测定温度:-50℃~300℃的条件下测定。作为测定装置,例如,使用流变仪公司(Rheometrics)制粘弹性分析仪“RSA 2”。
用于上述动态粘弹性测定的试验片,典型地可以如下得到:在与曝光后的用于动态粘弹性测定的试验片的制作说明中所述条件同样的条件下曝光,将曝光后的粘接薄膜进一步在160℃的烘箱中加热3小时进行固化而得到。
曝光后,进一步加热固化后的热重量分析中的感光性粘接剂的重量减少率为5%的温度(以下称为“5%重量减少温度”。)优选为260℃以上。5%重量减少温度低于260℃时,用软钎焊将使用感光性粘接剂得到的半导体装置安装于基板时,用软钎焊将使用感光性粘接剂得到的半导体装置安装于基板时,存在难以抑制由高温的加热引起的剥离或破坏的倾向。另外,由于加热时产生的挥发成分而污染周边材料或构件的可能性变高。
5%重量减少温度是:在升温速度:10℃/分钟、空气流量:80mL/分钟、测定温度:40℃~400℃的条件下进行的热重量分析中,相对于初期重量的重量减少率为5%的温度。用于热重量分析的试料如下制备:在与对于曝光后进一步加热固化后的储能模量的说明中所述的条件同样的条件下进行曝光及加热,将曝光及加热后的粘接薄膜用乳钵粉碎成较细。作为测定装置,例如,使用精工电子纳米科技有限公司制造的示差热热重量同时测定装置“EXSTAR6300”。
以上的诸特性可如下达成:使用聚酰亚胺、放射线聚合性化合物及光聚合引发剂,进而根据需要使用的热固化性树脂及填料来调制感光性粘接剂,通过调整它们的种类及配合比来达成。
薄膜状感光性粘接剂(粘接薄膜),例如,可通过以下方法得到,所述方法是将碱可溶性聚合物、放射线聚合性化合物、光聚合引发剂及根据需要的其他成分在有机溶剂中进行混合,将混合液混炼来调制清漆,在基材上形成该清漆的层,通过加热使清漆层干燥后,根据需要除去基材的方法。
上述混合及混炼,可适当组合通常的搅拌机、混砂机、三辊机、球磨机等分散机来进行。使用热固化性树脂时,在干燥中热固化性树脂不充分反应的温度下,而且溶剂充分挥散的条件下进行干燥。具体地说,通常在60~180℃、通过0.1~90分钟加热来干燥清漆层。
所谓热固化性树脂不充分反应的温度,具体地,是使用DSC(例如,铂金埃尔默社制“DSC-7”型(商品名)),在样品量10mg、升温速度5℃/分钟、测定气氛:空气的条件下测定时的反应热的峰温度以下的温度。
用于清漆调制的有机溶剂,即清漆溶剂,只要可均匀溶解或分散材料的物质,就没有特别制限。可举出例如,二甲基甲酰胺、甲苯、苯、二甲苯、甲基乙基酮、四氢呋喃、乙基溶纤剂、乙基溶纤剂乙酸酯、二噁烷、环己酮、乙酸乙酯、及N-甲基-吡咯烷酮。
清漆层的厚度优选为1~100μm。该厚度小于1μm时,存在固定被粘接物的功能降低的倾向,超过100μm时,存在得到的粘接薄膜1中的残存挥发分变多的倾向。
粘接薄膜的残存挥发分优选为10质量%以下。该残存挥发分超过10质量%时,在为了组装的加热时由溶剂的挥发引起发泡而容易在粘接薄膜内部残存空隙,存在耐湿可靠性容易降低的倾向。另外,加热时产生的挥发成分污染周边材料或构件的可能性变高。该残存挥发成分如下算出:将切断为50mm×50mm尺寸的粘接薄膜的初期质量设为M1,将该粘接薄膜在160℃的烘箱中加热3小时后的质量设为M2时,残存挥发成分(质量%)={(M2-M1)/M1}×100。
用于形成粘接薄膜的基材,只要可耐受上述的干燥条件的物质就没有特别限定。例如,可使用聚酯薄膜、聚丙烯薄膜、聚对苯二甲酸乙二醇酯薄膜、聚酰亚胺薄膜、聚醚酰亚胺薄膜、聚醚萘二酸酯薄膜、甲基戊烯薄膜作为基材。作为基材的薄膜也可以是组合两种以上薄膜而得到的多层薄膜,还可以是表面用硅酮系、二氧化硅系等脱模剂等处理过的物质。
Claims (9)
1.一种感光性粘接剂,其是通过曝光及显影而形成图案后对于被粘接物具有粘接性、且能够碱显影的感光性粘接剂,
用于具有以下工序的半导体装置的制造方法,所述工序是:
通过曝光及显影将设置于半导体芯片的电路面上的该感光性粘接剂形成图案的工序,和
将其他的半导体芯片与形成图案后的所述感光性粘接剂直接粘接的工序。
2.根据权利要求1所述的感光性粘接剂,其中,形成图案后的所述感光性粘接剂为缓冲涂膜。
3.根据权利要求1所述的感光性粘接剂,其含有碱可溶性聚合物、放射线聚合性化合物和光聚合引发剂。
4.根据权利要求3所述的感光性粘接剂,其中,所述碱可溶性聚合物具有羧基或酚性羟基。
5.根据权利要求3所述的感光性粘接剂,其中,所述碱可溶性聚合物的玻璃化转变温度为150℃以下。
6.根据权利要求3所述的感光性粘接剂,其中,所述碱可溶性聚合物为聚酰亚胺。
8.根据权利要求3所述的感光性粘接剂,其进一步含有热固化性树脂。
9.根据权利要求1~8的任一项所述的感光性粘接剂,其为薄膜状。
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