CN112204730A - 半导体装置及其制造中使用的热固化性树脂组合物以及切割-芯片接合一体型带 - Google Patents

半导体装置及其制造中使用的热固化性树脂组合物以及切割-芯片接合一体型带 Download PDF

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CN112204730A
CN112204730A CN201880093364.5A CN201880093364A CN112204730A CN 112204730 A CN112204730 A CN 112204730A CN 201880093364 A CN201880093364 A CN 201880093364A CN 112204730 A CN112204730 A CN 112204730A
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resin composition
thermosetting resin
semiconductor element
parts
mass
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山本和弘
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Resonac Holdings Corp
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Showa Denko KK
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Abstract

本公开的半导体装置具备：基板；配置于基板上的第一半导体元件；将第一半导体元件密封的第一密封层；以及按照将第一密封层的与基板一侧为相反侧的表面覆盖的方式配置、具有比第一半导体元件大的面积的第二半导体元件，第一密封层由热固化性树脂组合物的固化物形成，热固化性树脂组合物的120℃下的熔融粘度为2500～11500Pa·s。

Description

半导体装置及其制造中使用的热固化性树脂组合物以及切 割-芯片接合一体型带
技术领域
本公开涉及半导体装置及其制造中使用的热固化性树脂组合物以及切割-芯片接合一体型带。
背景技术
随着手机等设备的多功能化，将半导体元件多段地层叠而进行了高容量化的堆叠式MCP(Multi Chip Package，多芯片封装体)正在普及。半导体元件的安装中广泛使用膜状粘接剂。作为使用了膜状粘接剂的多段层叠封装体的一例，可举出导线埋入型的封装体。该封装体经由以下工序制造：在基板上对经导线接合的半导体元件压接膜状粘接剂，从而将该半导体元件及导线埋入到膜状粘接剂中。
作为上述堆叠式MCP等半导体装置所要求的重要特性之一，可举出连接可靠性。为了提高连接可靠性，开发了考虑到耐热性、耐湿性及耐回流性等特性的膜状粘接剂。例如专利文献1公开了含有热固化性成分及填充物的厚度为10～250μm的粘接片材。专利文献2公开了包含含环氧树脂和酚醛树脂的混合物及丙烯酸共聚物的粘接剂组合物。
半导体装置的连接可靠性很大程度上取决于是否能够在粘接面上不产生空隙(空孔)的情况下安装半导体元件。因此，下功夫在使用高流动的膜状粘接剂以使得在不产生空隙的情况下能够压接半导体元件，或者使用熔融粘度低的膜状粘接剂以使得能够在半导体元件的密封工序中使所产生的空隙消失等。例如专利文献3公开了低粘度且低粘附强度的粘接片材。
现有技术文献
专利文献
专利文献1：国际公开第2005/103180号公报
专利文献2：日本特开2002-220576号公报
专利文献3：日本特开2009-120830号公报
发明内容
发明要解决的技术问题
上述专利文献1及3的粘接片材由于在压接时将导线埋入，因此以高流动化为目的而含有较多量的环氧树脂。因而，在半导体装置的制造工序中产生的热量的作用下，热固化易于进行。由此，粘接膜发生高弹性化，换而言之，即便在密封时的高温高压条件下、粘接片材也难以变形，在压接时所形成的空隙有时最终不会消失。另一方面，上述专利文献2的粘接剂组合物由于弹性模量低，因此虽然能够在密封工序中使空隙消失，但由于粘度高，压接时的导线的埋入性易于变得不足。
近年来，导线埋入型半导体装置的动作的高速化受到重视。以往在层叠的半导体元件的最上段配置有控制半导体装置动作的控制器芯片。为了实现动作的高速化，开发了在最下段配置有控制器芯片的半导体装置的封装技术。作为这种封装体的一个方式，在对多段地层叠的半导体元件中第二段的半导体元件进行压接时使用较厚的膜状粘接剂、在该膜状粘接剂的内部埋入控制器芯片的封装体受到注目。这种用途中使用的膜状粘接剂需要能够将控制器芯片及连接其与电路图案的导线、以及基板表面的凹凸引起的高度差埋入的高流动性。通过使用专利文献1及3的粘接片材那样的高流动的粘接片材，可以解决该技术问题。
但是，专利文献1及3所记载的粘接片材虽然在固化前表现出高的流动性，但在控制器芯片的埋入时流动的树脂也有时会污染周边的电路。进而，由于埋入后的热固化，粘接片材发生流动，芯片发生位置偏移，或者发生树脂如退潮那样从埋入芯片的端面进入到芯片内侧、树脂从芯片端部消失的被称作“缩痕”的现象(参照图8)。特别是近年来，为了提高埋入性，多在加压条件下进行热固化处理。若如此从外部以具有压力的状态施加热量，则虽然埋入性提高，但树脂变得更易流动，多会发生上述问题。
本公开的目的在于提供具有优异的连接可靠性的半导体装置。另外，本公开的目的在于提供对于制造具有优异的连接可靠性的半导体装置有用的热固化性树脂组合物及具备由其形成的粘接层的切割-芯片接合一体型带。
用于解决技术问题的手段
本发明人们为了开发将控制器芯片埋入至膜状粘接剂的固化物中的方式的封装体，对于膜状粘接剂的树脂的选定及物性的调整反复进行了深入研究。结果，本发明人们发现膜状粘接剂的熔融粘度与埋入时的电路污染及之后热工序中发生的缩痕相关。
本公开的半导体装置具备：基板；配置于基板上的第一半导体元件；按照将基板上的配置有第一半导体元件的区域覆盖的方式配置、将第一半导体元件密封的第一密封层；以及按照将第一密封层的与基板一侧为相反侧的表面覆盖的方式配置、具有比第一半导体元件大的面积的第二半导体元件，第一密封层由热固化性树脂组合物的固化物形成，热固化性树脂组合物的120℃下的熔融粘度为2500～11500Pa·s。
上述半导体装置是将第一半导体元件(例如控制器芯片)埋入至热固化性树脂组合物的固化物中的方式，可以实现动作的高速化。第一密封层通过是120℃下的熔融粘度为2500～11500Pa·s的热固化性树脂组合物的固化物，与基板或第一半导体元件的界面上的空隙足够少，同时还可充分地抑制基板的污染及缩痕问题的发生，因而可以实现基板与第一半导体元件的优异的连接可靠性。
本公开的半导体装置还可以进一步具备：形成于基板表面上的电路图案；以及将第一半导体元件与电路图案电连接的第一导线。本公开的半导体装置还可以进一步具备：将第二半导体元件与电路图案电连接的第二导线；以及将第二半导体元件及第二导线密封的第二密封层。本公开的半导体装置还可以进一步具备层叠于第二半导体元件上的第三半导体元件。
构成上述膜状粘接剂的热固化性树脂组合物优选：包含分子量为10～1000的低分子量成分(例如环氧树脂)和分子量为10万～100万的高分子量成分(例如丙烯酸橡胶)，低分子量成分的含量M1相对于该热固化性树脂组合物所包含的树脂成分的质量100质量份为23～35质量份，高分子量成分的含量M2相对于热固化性树脂组合物所包含的树脂成分的质量100质量份为25～45质量份。通过使用这种组成的热固化性树脂组合物，低分子量成分有助于优异的埋入性，而高分子量成分有助于抑制过剩流动所引起的问题。热固化性树脂组合物优选：相对于该热固化性树脂组合物所包含的树脂成分的质量100质量份，低分子量成分和高分子量成分的合计量(M1+M2)为54～76质量份。
此外，热固化性树脂组合物所包含的树脂成分的分子量(重均分子量)是指利用凝胶渗透色谱法(GPC)进行测定、使用利用标准聚苯乙烯获得的标准曲线进行换算而得到的值。
作为基板使用其表面上具有电路图案者时，本公开的半导体装置还可以进一步具备将第一半导体元件与电路图案电连接的第一导线，还可以进一步具备将第二半导体元件与电路图案电连接的第二导线、以及将第二半导体元件及第二导线密封的第二密封层。
本公开的热固化性树脂组合物是在半导体装置的制造工艺中使用的热固化性树脂组合物，所述半导体制造工艺包含以下工序：经过加热该热固化性树脂组合物的固化处理，形成将导线的至少一部分及半导体元件中的至少一者埋入在固化处理后的热固化性树脂组合物中的状态，热固化性树脂组合物的120℃下的熔融粘度为2500～11500Pa·s。根据上述热固化性树脂组合物，在具有能够埋入半导体元件等的流动性的同时，能够充分地抑制埋入时的周边电路的污染及之后的热工序(热固化性树脂组合物的热固化处理)中的树脂的过剩流动所引起的问题。
本公开的切割-芯片接合一体型带具备粘合层和由上述热固化性树脂组合物形成的粘接层。
发明效果
根据本公开，可提供具有优异的连接可靠性的半导体装置，并且可提供在其制造中使用的热固化性树脂组合物及具备由其形成的粘接层的切割-芯片接合一体型带。该热固化性树脂组合物在具有能够埋入控制器芯片等半导体元件及导线中的至少一者的优异埋入性的同时，可以充分地抑制埋入时的周边电路的污染及之后的热工序中的树脂的过剩流动所引起的问题。
附图说明
图1为示意地表示半导体装置之一例的截面图。
图2为示意地表示由膜状粘接剂和第二半导体元件形成的层叠体之一例的截面图。
图3为示意地表示制造图1所示半导体装置的过程的截面图。
图4为示意地表示制造图1所示半导体装置的过程的截面图。
图5为示意地表示制造图1所示半导体装置的过程的截面图。
图6为示意地表示制造图1所示半导体装置的过程的截面图。
图7(a)～图7(e)为示意地表示制造由膜状粘接剂和第二半导体元件形成的层叠体的过程的截面图。
图8(a)为表示未发生被称作“缩痕”的现象的结构体的截面的照片，图8(b)为表示发生了“缩痕”的结构体(缩痕的深度：140μm)的截面的照片。
图9(a)为示意地表示用于评价有无空孔产生的结构体的截面图，图9(b)为未产生空孔的结构体的照片，图9(c)为产生了空孔的结构体的照片。
具体实施方式
以下一边参照附图一边详细地说明本公开的实施方式。以下的说明中，相同或相当部分带有相同符号，且省略重复的说明。另外，上下左右等位置关系在没有特别限定的情况下是基于附图所示的位置关系。进而，附图的尺寸比例并不限定于图示的比例。此外，本说明书中的“(甲基)丙烯酸”的表述是指“丙烯酸”及与其相对应的“甲基丙烯酸”。
<半导体装置>
图1为示意地表示本实施方式的半导体装置的截面图。该图所示的半导体装置100具备基板10、配置于基板10的表面上的第一半导体元件Wa、将第一半导体元件Wa密封的第一密封层20、配置于第一半导体元件Wa上方的第二半导体元件Wb、以及将第二半导体元件Wb密封的第二密封层40。
基板10在表面上具有电路图案10a、10b。从抑制半导体装置100的翘曲的观点出发，基板10的厚度例如为90～180μm，还可以为90～140μm。此外，基板10可以是有机基板，也可以是引线框等金属基板。
本实施方式中，第一半导体元件Wa是用于驱动半导体装置100的控制器芯片。第一半导体元件Wa介由粘接剂15粘接在电路图案10a上，另外介由第一导线11连接于电路图案10b。俯视下的第一半导体元件Wa的形状例如为矩形(正方形或长方形)。第一半导体元件Wa的一边的长度例如为5mm以下，还可以为2～4mm或1～4mm。第一半导体元件Wa的厚度例如为10～150μm，还可以为20～100μm。
第二半导体元件Wb具有大于第一半导体元件Wa的面积。第二半导体元件Wb按照将第一半导体元件Wa的整体和电路图案10b的一部分覆盖的方式、隔着第一密封层20搭载于基板10上。俯视下的第二半导体元件Wb的形状例如为矩形(正方形或长方形)。第二半导体元件Wb的一边的长度例如为20mm以下，还可以为4～20mm或4～12mm。第二半导体元件Wb的厚度例如为10～170μm，还可以为20～120μm。第二半导体元件Wb在介由第二导线12连接于电路图案10b的同时被密封层25密封。
第一密封层20由膜状粘接剂20P(参照图2)的固化物形成。此外，如图2所示，膜状粘接剂20P与第二半导体元件Wb实质上是相同尺寸。图2所示的层叠体30由膜状粘接剂20P和第二半导体元件Wb形成，也被称作带有粘接剂的半导体芯片。层叠体30如后所述，通过经由切割工序及拾取工序制作而成(参照图7)。
<半导体装置的制造方法>
以下对半导体装置100的制造方法进行说明。首先，制作图3所示的结构体50。即，在基板10的表面上介由粘接剂15配置第一半导体元件Wa。之后，利用第一导线11将第一半导体元件Wa与电路图案10b电连接。
接着，如图3及图4所示，将另外准备好的层叠体30的膜状粘接剂20P向基板10按压。由此，将第一半导体元件Wa及第一导线11埋入至膜状粘接剂20P中。膜状粘接剂20P的厚度根据第一半导体元件Wa的厚度等适当设定即可，例如为20～200μm的范围即可，可以为30～200μm或40～150μm。通过使膜状粘接剂20P的厚度为上述范围，可以充分地确保第一半导体元件Wa与第二半导体元件Wb的间隔(图5中的距离G)。距离G例如优选为50μm以上，还可以为50～75μm或50～80μm。
膜状粘接剂20P向基板10的压接例如优选在80～180℃、0.01～0.50MPa的条件下实施0.5～3.0秒钟。
接着，通过加热使膜状粘接剂20P固化。该固化处理例如优选在60～175℃、0.01～1.0MPa的条件下实施5分钟以上。由此，用膜状粘接剂20P的固化物(第一密封层20)将第一半导体元件Wa密封(参照图6)。膜状粘接剂20P的固化处理从减少空孔的观点出发，还可以在加压气氛下实施。用第二导线12将第二半导体元件Wb与电路图案10b电连接后，利用第二密封层40将第二半导体元件Wb密封，从而完成半导体装置100(参照图1)。
<带有粘接剂的半导体芯片的制作方法>
一边参照图7(a)～图7(e)一边对图2所示的层叠体30(带有粘接剂的半导体芯片)的制作方法之一例进行说明。首先，将切割-芯片接合一体型带8(以下根据情况称作“带8”)配置于规定的装置(未图示)上。带8按顺序具备基材层1、粘合层2和粘接层20A。基材层1例如为聚对苯二甲酸乙二醇酯膜(PET膜)。半导体晶片W例如是厚度为10～100μm的薄型半导体晶片。半导体晶片W可以是单晶硅，也可以是多晶硅、各种陶瓷、镓砷等化合物半导体。
如图7(a)及图7(b)所示，在半导体晶片W的一个面上按照粘接层20A接触的方式粘贴带8。该工序在优选50～100℃、更优选60～80℃的温度条件下实施。温度为50℃以上时，可以使半导体晶片W获得与粘接层20A的良好密合性，为100℃以下时，可抑制在该工序中粘接层20A过度地流动。
如图7(c)所示，对半导体晶片W、粘合层2及粘接层20A进行切割。由此，半导体晶片W被制成单片，变成半导体元件Wb。粘接层20A也被制成单片，变成膜状粘接剂20P。作为切割方法，可举出使用旋转刀或激光的方法。此外，还可以通过在半导体晶片W的切割之前对半导体晶片W进行磨削来进行薄膜化。
接着，当粘合层2例如为UV固化型时，如图7(d)所示，通过对粘合层2照射紫外线来使粘合层2固化，使粘合层2与膜状粘接剂20P之间的粘合力降低。紫外线照射后，如图7(e)所示，一边在常温或冷却条件下通过将基材层1扩展而使半导体元件Wa相互间分离，一边利用针状物42往上顶而使层叠体30的膜状粘接剂20P从粘合层2上剥离，同时利用吸引夹头44对层叠体30进行吸引、拾取。将如此获得的层叠体30供至图3所示的结构体50的制造。
<热固化性树脂组合物>
对构成膜状粘接剂20P的热固化性树脂组合物进行说明。此外，膜状粘接剂20P是将粘接层20A制成单片者，两者由相同的热固化性树脂组合物形成。该热固化性树脂组合物例如是经过半固化(B阶段)状态、通过之后的固化处理可成为完全固化物(C阶段)状态的组合物。
热固化性树脂组合物优选包含以下的成分。
(a)热固化性树脂(以下有时仅称作“(a)成分”)
(b)高分子量成分(以下有时仅称作“(b)成分”)
(c)无机填充物(以下有时仅称作“(c)成分”)
此外，本实施方式中，当(a)热固化性树脂包含环氧树脂时，环氧树脂(以下有时仅称作“(a1)成分”。)相当于“低分子量成分”。此时，(a)热固化性树脂优选包含可成为环氧树脂的固化剂的酚醛树脂(以下有时仅称作“(a2)成分”)。
热固化性树脂组合物还可以进一步包含以下的成分。
(d)偶联剂(以下有时仅称作“(d)成分”)
(e)固化促进剂(以下有时仅称作“(e)成分”)
上述热固化性树脂组合物优选包含分子量为10～1000的低分子量成分((a1)成分)和分子量为10万～100万的高分子量成分((b)成分)这两者。通过将这些成分并用，低分子量成分有助于优异的埋入性、而高分子量成分有助于抑制因过剩的流动所引起的问题。
低分子量成分的含量M1相对于热固化性树脂组合物所包含的树脂成分的质量100质量份，优选为23～35质量份、更优选为25～35质量份。通过低分子量成分的含量M1为23质量份以上，易于实现优异的埋入性，而通过为35质量份以下，可发挥易于实现优异拾取性的效果。此外，低分子量成分的软化点优选为50℃以下，例如可以为10～30℃。
高分子量成分的含量M2相对于热固化性树脂组合物所包含的树脂成分的质量100质量份，优选为25～45质量份、更优选为30～40质量份。通过高分子量成分的含量M2为25质量份以上，易于抑制因过剩的流动引起的问题(基板的污染、缩痕及翘曲等)，而通过为45质量份以下，可发挥易于实现优异埋入性的效果。此外，高分子量成分的软化点优选超过50℃且为100℃以下。
相对于热固化性树脂组合物所包含的树脂成分的质量100质量份，低分子量成分和高分子量成分的合计量(M1+M2)优选为54～76质量份、更优选为55～75质量份。通过该合计量为54质量份以上，具有可充分地发挥并用这些成分的效果的倾向，而通过为76质量份以下，可发挥易于实现优异拾取性的效果。此外，作为热固化性树脂组合物所包含的树脂成分的除低分子量成分及高分子量成分以外的物质，主要可举出分子量为1001～9万9000的热固化性树脂等。
热固化性树脂组合物的120℃下的熔融粘度从连接可靠性的观点出发，为2500～11500Pa·s。通过该熔融粘度为2500Pa·s以上，可以充分地抑制压接处理时等的基板10的污染及缩痕问题的发生。例如，当在第二半导体元件Wb与基板10之间具有不存在热固化性树脂组合物的固化物的区域(缩痕)时，第二密封层40用的密封材料侵入到该区域中，由此容易发生第二半导体元件Wb易于剥离的不良情况。通过热固化性树脂组合物的120℃下的熔融粘度为11500Pa·s以下，可以充分地减少与基板10或第一半导体元件Wa的界面中的空隙。该熔融粘度优选为5000～11000Pa·s、更优选为5000～10000Pa·s、进一步优选为5000～9000Pa·s。此外，熔融粘度是指在一边使用ARES(TA Instruments公司制)对成形为膜状的热固化性树脂组合物赋予5％的变形、一边以5℃/分钟的升温速度使其升温的同时进行测定时的测定值。
热固化性树脂组合物的100℃下的熔融粘度从连接可靠性的观点出发，优选为3500～13500Pa·s。通过该熔融粘度为3500Pa·s以上，可以充分地抑制压接处理时等的基板10的污染及缩痕问题的发生。而通过该熔融粘度为13500Pa·s以下，可以充分地减少与基板10或第一半导体元件Wa的界面中的空隙。该熔融粘度优选为5500～10500Pa·s。为了使热固化性树脂组合物的100℃及120℃下的熔融粘度为上述范围内，适当调整(a)热固化性树脂、(b)高分子量成分及(c)无机填充物的量即可。
图9(a)是具备透明的基板10、其上的第一半导体元件Wa、第一密封层20(膜状粘接剂20P的固化物)、以及其上的第二半导体元件Wb的结构体。图9(b)及图9(c)是从透明的基板10的背面侧(图9(a)中的箭头的方向)拍摄的照片。图9(b)所示的结构体中，膜状粘接剂的埋入性充分，未产生空孔。与此相对，在图9(c)所示的结构体中，膜状粘接剂的埋入性不足，产生了空孔V。
热固化性树脂组合物的固化物(C阶段)的180℃下的储存弹性模量从连接可靠性的观点出发，优选为10MPa以上、更优选为25MPa以上，也可以为50MPa以上或100MPa以上。此外，该储存弹性模量的上限值例如为600MPa，也可以为500MPa。热固化性树脂组合物的固化物的180℃下的储存弹性模量可以以在175℃的温度条件下使膜状粘接剂固化的产物作为试样、使用动态粘弹性装置进行测定。
<(a)热固化性树脂>
(a1)成分只要分子内具有环氧基，则可以没有特别限定地使用。作为(a1)成分，例如可举出双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、苯酚酚醛清漆型环氧树脂、甲酚酚醛清漆型环氧树脂、双酚A酚醛清漆型环氧树脂、双酚F酚醛清漆型环氧树脂、含二环戊二烯骨架的环氧树脂、二苯乙烯型环氧树脂、含三嗪骨架的环氧树脂、含芴骨架的环氧树脂、三苯酚苯酚甲烷型环氧树脂、联苯型环氧树脂、亚二甲苯基型环氧树脂、联苯芳烷基型环氧树脂、萘型环氧树脂、多官能酚类、蒽等多环芳香族类的二缩水甘油基醚化合物等。这些物质可以单独使用1种或者组合使用2种以上。其中，(a1)成分从耐热性的观点出发，可以是甲酚酚醛清漆型环氧树脂、双酚F型环氧树脂、或双酚A型环氧树脂。
(a1)成分的环氧当量可以为90～300g/eq、110～290g/eq或130～280g/eq。(a1)成分的环氧当量为这种范围时，具有在维持膜状粘接剂的块体强度的同时可以确保流动性的倾向。
(a1)成分的含量相对于(a)成分、(b)成分及(c)成分的总质量100质量份，可以为5～50质量份、10～40质量份、或20～30质量份。(a1)成分的含量为5质量份以上时，具有膜状粘接剂的埋入性变得更良好的倾向。(a1)成分的含量为50质量份以下时，具有能够进一步抑制渗出发生的倾向。
(a2)成分只要分子内具有酚性羟基则可没有特别限定地使用。作为(a2)成分，例如可举出在酸性催化剂下使苯酚、甲酚、间苯二酚、邻苯二酚、双酚A、双酚F、苯基苯酚、氨基苯酚等苯酚类及/或α-萘酚、β-萘酚、二羟基萘等萘酚类与甲醛等具有醛基的化合物发生缩合或缩聚所获得的酚醛清漆型酚醛树脂，由烯丙基化双酚A、烯丙基化双酚F、烯丙基化萘二醇、苯酚酚醛清漆、苯酚等苯酚类及/或萘酚类与二甲氧基对二甲苯或双(甲氧基甲基)联苯合成的苯酚芳烷基树脂、萘酚芳烷基树脂等。这些物质可单独使用1种或者组合使用2种以上。其中，(a2)成分从吸湿性及耐热性的观点出发，可以是苯酚芳烷基树脂、萘酚芳烷基树脂、或酚醛清漆型酚醛树脂。
(a2)成分的羟基当量可以是80～250g/eq、90～200g/eq、或100～180g/eq。(a2)成分的羟基当量为这种范围时，具有在确保膜状粘接剂的流动性的同时能够更高地维持粘接力的倾向。
(a2)成分的软化点可以为50～140℃、55～120℃、或60～100℃。
(a2)成分的含量相对于(a)成分、(b)成分及(c)成分的总质量100质量份，可以为5～50质量份、10～40质量份、或20～30质量份。(a2)成分的含量为5质量份以上时，具有获得更良好的固化性的倾向。(a2)成分的含量为50质量份以下时，具有膜状粘接剂的埋入性变得更加良好的倾向。
(a1)成分的环氧当量与(a2)成分的羟基当量之比((a1)成分的环氧当量/(a2)成分的羟基当量)从固化性的观点出发，可以为0.30/0.70～0.70/0.30、0.35/0.65～0.65/0.35、0.40/0.60～0.60/0.40、或0.45/0.55～0.55/0.45。该当量比为0.30/0.70以上时，具有获得更充分的固化性的倾向。该当量比为0.70/0.30以下时，可以防止粘度变得过高，可以获得更充分的流动性。
<(b)高分子量成分>
(b)成分优选玻璃化转变温度(Tg)为50℃以下。
作为(b)成分，例如可举出丙烯酸树脂、聚酯树脂、聚酰胺树脂、聚酰亚胺树脂、有机硅树脂、丁二烯树脂、丙烯腈树脂及它们的改性体等。
(b)成分从流动性的观点出发，可以包含丙烯酸树脂。这里，丙烯酸树脂是指包含来自于(甲基)丙烯酸酯的结构单元的聚合物。丙烯酸树脂优选包含来自于具有环氧基、醇性或酚性羟基、羧基等交联性官能团的(甲基)丙烯酸酯的结构单元作为结构单元的聚合物。另外，丙烯酸树脂还可以是(甲基)丙烯酸酯与丙烯腈的共聚物等丙烯酸橡胶。
丙烯酸树脂的玻璃化转变温度(Tg)可以为-50～50℃或-30～30℃。丙烯酸树脂的Tg为-50℃以上时，具有可以防止粘接剂组合物的柔软性变得过高的倾向。由此，在晶片切割时易于切断膜状粘接剂、可以防止毛刺的发生。丙烯酸树脂的Tg为50℃以下时，具有可以抑制粘接剂组合物的柔软性降低的倾向。由此，在将膜状粘接剂粘贴于晶片时，具有易于将空孔充分地埋入的倾向。另外，还可以防止因晶片的密合性降低所导致的切割时的崩边。这里，玻璃化转变温度(Tg)是指使用DSC(热示差扫描热量计)(例如株式会社Rigaku制“Thermo Plus 2”)测得的值。
丙烯酸树脂的重均分子量(Mw)可以为10万～300万或50万～200万。丙烯酸树脂的Mw为这种范围时，可以适当地控制膜形成性、膜状下的强度、挠性、粘附性等，并且回流性优异、可以提高埋入性。这里，Mw是指利用凝胶渗透色谱法(GPC)进行测定、使用由标准聚苯乙烯获得的标准曲线进行换算而得到的值。
作为丙烯酸树脂的市售品，例如可举出SG-70L、SG-708-6、WS-023EK30、SG-280EK23、HTR-860P-3CSP、HTR-860P-3CSP-3DB(均为Nagasechemtex株式会社制)。
(b)成分的含量相对于(a)成分、(b)成分及(c)成分的总质量100质量份，可以为5～70质量份、10～50质量份、或15～30质量份。(b)成分的含量为5质量份以上时，能够使成形时的流动性的控制及高温下的处理性变得更为良好。(b)成分的含量为70质量份以下时，可以使埋入性变得更为良好。
<(c)无机填充物>
作为(c)成分，例如可举出氢氧化铝、氢氧化镁、碳酸钙、碳酸镁、硅酸钙、硅酸镁、氧化钙、氧化镁、氧化铝、氮化铝、硼酸铝晶须、氮化硼、二氧化硅等。这些物质可以单独使用1种或者组合使用2种以上。其中，(c)成分从与树脂的相容性的观点出发，可以为二氧化硅。
(c)成分的平均粒径从粘接性提高的观点出发，可以为0.005～1μm或0.05～0.5μm。这里，平均粒径是指通过由BET比表面积进行换算所求得的值。
(c)成分的含量相对于(a)成分、(b)成分及(c)成分的总质量100质量份，可以为5～50质量份、15～45质量份、或25～40质量份。(c)成分的含量为5质量份以上时，具有膜状粘接剂的流动性进一步提高的倾向。(c)成分的含量为50质量份以下时，具有膜状粘接剂的切割性变得更为良好的倾向。
<(d)偶联剂>
(d)成分可以是硅烷偶联剂。作为硅烷偶联剂，例如可举出γ-脲基丙基三乙氧基硅烷、γ-巯基丙基三甲氧基硅烷、3-苯基氨基丙基三甲氧基硅烷、3-(2-氨基乙基)氨基丙基三甲氧基硅烷等。这些物质可以单独使用1种或者组合使用2种以上。
(d)成分的含量相对于(a)成分、(b)成分及(c)成分的总质量100质量份，可以为0.01～5质量份。
<(e)固化促进剂>
(e)成分并无特别限定，可以使用通常使用的成分。作为(e)成分，例如可举出咪唑类及其衍生物、有机磷系化合物、仲胺类、叔胺类、季铵盐等。这些物质可以单独使用1种或者组合使用2种以上。其中，从反应性的观点出发，(e)成分可以为咪唑类及其衍生物。
作为咪唑类，例如可举出2-甲基咪唑、1-苄基-2-甲基咪唑、1-氰基乙基-2-苯基咪唑、1-氰基乙基-2-甲基咪唑等。这些物质可以单独使用1种或者组合使用2种以上。
(e)成分的含量相对于(a)成分、(b)成分及(c)成分的总质量100质量份，可以为0.01～1质量份。
[切割-芯片接合一体型带及其制造方法]
对图7(a)所示的切割-芯片接合一体型带8及其制造方法进行说明。带8的制造方法包含以下工序：将含有溶剂的粘接剂组合物的清漆涂布在基材膜(未图示)上的工序；和将所涂布的清漆在50～150℃下加热干燥、从而形成粘接层20A的工序。
粘接剂组合物的清漆例如可以通过将(a)～(c)成分、根据需要的(d)成分及(e)成分在溶剂中混合或混炼来制备。混合或混炼可以使用通常的搅拌机、磨碎机、三联辊、球磨机等分散机，将它们适当地组合进行。
用于制作清漆的溶剂只要能够将上述各成分均匀地溶解、混炼或分散则没有限制，可以使用以往公知的溶剂。作为这种溶剂，例如可举出丙酮、甲乙酮、甲基异丁基酮、环己酮等酮系溶剂，二甲基甲酰胺、二甲基乙酰胺、N甲基吡咯烷酮、甲苯、二甲苯等。从干燥速度快、价格便宜的方面来说，优选使用甲乙酮、环己酮等。
作为基材膜并无特别限定，例如可举出聚酯膜、聚丙烯膜(OPP膜等)、聚对苯二甲酸乙二醇酯膜、聚酰亚胺膜、聚醚酰亚胺膜、聚醚萘二甲酸酯膜、甲基戊烯膜等。
作为将清漆涂布于基材膜的方法，可以使用公知的方法，例如可举出刮刀涂布法、辊涂法、喷涂法、凹版涂布法、棒涂法、帘涂法等。加热干燥的条件只要是所使用的溶剂充分地挥散的条件则无特别限定，例如可以在50～150℃下加热1～30分钟来进行。加热干燥还可以是在50～150℃范围内的温度下阶段性地升温来进行。通过加热干燥使清漆中包含的溶剂挥发，可以获得基材膜与粘接层20A的层叠膜。
通过将如此获得的层叠膜与切割带(基材层1与粘合层2的层叠体)粘贴，可以获得带8。作为基材层1，例如可举出聚四氟乙烯膜、聚对苯二甲酸乙二醇酯膜、聚乙烯膜、聚丙烯膜、聚甲基戊烯膜、聚酰亚胺膜等塑料膜等。另外，基材层1还可以根据需要进行底漆涂布、UV处理、电晕放电处理、研磨处理、刻蚀处理等表面处理。粘合层2可以是UV固化型的，还可以是压敏型的。带8还可以进一步具备覆盖粘合层2的保护膜(未图示)。
以上对本公开的实施方式详细地进行了说明，但本发明并不限定于上述实施方式。例如，在上述实施方式中示例了层叠有2个半导体元件Wa、Wb的方式的封装体，但也可以在第二半导体元件Wb的上方层叠有第三半导体元件，还可以在其上方进一步层叠有一个或多个半导体元件。
实施例
以下举出实施例，对本公开更为具体地进行说明。但本发明并不限定于以下实施例。
(实施例1～6及比较例1、2)
如下地制备包含表1及表2所示成分的清漆(共计6种)。即，在包含作为热固化性树脂的环氧树脂及酚醛树脂和无机填充物的组合物中添加环己酮并进行搅拌。向其中添加作为高分子量成分的丙烯酸橡胶并进行搅拌后，进一步添加偶联剂及固化促进剂，进行搅拌至各成分变得充分均匀，由此获得清漆。
表1及表2所记载的成分如下。
(环氧树脂)
·YDF-8170C(商品名)：东都化成株式会社制、双酚F型环氧树脂、环氧当量为159、常温下为液体、软化点为10～30℃、分子量为100～1000(低分子量成分)
·YDCN-700-10(商品名)：东都化成株式会社制、甲酚酚醛清漆型环氧树脂、环氧当量为210、软化点为75～85℃)、分子量超过1000
(酚醛树脂)
·Milex XLC-LL(商品名)：三井化学株式会社制、酚醛树脂、羟基当量为175、软化点为77℃、分子量超过1000
(丙烯酸橡胶)
·HTR-860P-3CSP：Nagasechemtex株式会社制、重均分子量为80万(高分子量成分)
(无机填充物)
·SC2050-HLG(商品名)：Admatechs株式会社制、二氧化硅填充物分散液、平均粒径为0.50μm
(固化促进剂)
·Curezol 2PZ-CN(商品名)：四国化成工业株式会社制、1-氰基乙基-2-苯基咪唑
利用100目的过滤器对包含上述成分的清漆进行过滤，进行真空脱泡。将真空脱泡后的清漆涂布在实施了脱模处理的聚对苯二甲酸乙二醇酯(PET)膜(厚度为38μm)上。对所涂布的清漆以90℃下5分钟、接着140℃下5分钟的2个阶段进行加热干燥。如此，获得在作为基材膜的PET膜上具备处于B阶段状态的膜状粘接剂(厚度为60μm)的粘接片材。
(膜状粘接剂的熔融粘度的测定)
膜状粘接剂的100℃及120℃下的熔融粘度通过以下方法测定。即，将5张厚度为60μm的膜状粘接剂进行层叠，使厚度达到300μm，将其打孔成10mm×10mm的尺寸，从而获得测定用的试样。在动态粘弹性测定装置ARES(TA Instruments公司制)中安装直径为8mm的圆形铝板夹具，进而在其上安装上述试样。之后，一边在35℃下赋予5％的变形一边以5℃/分钟的升温速度升温至130℃，同时进行测定，记录100℃及120℃时的熔融粘度的值。将结果示于表1及表2中。
(膜状粘接剂的固化物的弹性模量的测定)
测定膜状粘接剂的固化物(在175℃的温度条件下使其固化而得到的)的180℃下的弹性模量。测定中使用动态粘弹性装置(制品名：Rheogel-E4000、株式会社UBM制)，对试样施加拉伸负荷，以频率10Hz、3℃/分钟的升温速度使其升温至300℃，测定180℃下的弹性模量。将结果示于表1及表2中。
Figure BDA0002773712300000171
Figure BDA0002773712300000181
<膜状粘接剂的评价>
对于膜状粘接剂，对以下的项目进行评价。
[埋入性]
利用以下方法评价膜状粘接剂的埋入性。
(由第一半导体元件和膜状粘接剂形成的层叠体的制作)
在半导体晶片(直径：8英寸、厚度：50μm)上粘贴切割-芯片接合一体型膜HR-9004-10(日立化成株式会社制、粘接层的厚度为10μm、粘合层的厚度为110μm)。通过对其进行切割，获得由第一半导体元件(控制器芯片、尺寸：3.0mm×3.0mm)和膜状粘接剂形成的第一层叠体。
(由第二半导体元件和膜状粘接剂形成的层叠体的制作)
制作由实施例及比较例的由各膜状粘接剂(厚度为120μm)和切割用粘合膜形成的切割-芯片接合一体型膜。将其粘贴在半导体晶片(直径：8英寸、厚度：30μm)上。通过对其进行切割，获得由第二半导体元件(尺寸：7.5mm×7.5mm)和膜状粘接剂形成的第二层叠体。
(第一及第二半导体元件的粘接)
准备用于对第一及第二半导体元件进行压接的基板(表面的凹凸：最大为6μm)。介由膜状粘接剂将第一半导体元件在120℃、0.20MPa、2秒钟的条件下压接在该基板上之后，在120℃下加热2小时，由此使膜状粘接剂半固化。
接着，按照将第一半导体元件覆盖的方式，介由评价对象的膜状粘接剂在120℃、0.20MPa、2秒钟的条件下压接第二半导体元件。此时，按照之前压接的第一半导体元件与第二半导体元件的中心位置在俯视下达到一致的方式进行位置对齐。
将如上获得的结构体投入到加压烘箱中，从35℃以3℃/分钟的升温速度升温至140℃，在140℃下加热30分钟。使用超声波图像装置SAT(株式会社Hitachi PowerSolutions制、型号FS200II、探针：25MHz)对加热处理后的结构体进行分析，从而确认埋入性。根据以下的标准进行评价。将结果示于表3及表4中。
A：规定截面中的空孔的面积比例小于5％。
B：规定截面中的空孔的面积比例为5％以上。
[有无封装体污染及缩痕发生]
通过利用显微镜对供至埋入性评价的结构体的上部及侧面进行观察，确认有无污染及有无缩痕发生。对于发生了缩痕的试样，测定缩痕的深度(起点：第二半导体元件的端部)。将结果示于表3及表4中。
[粘接强度的测定]
利用以下方法测定膜状粘接剂的固化物的剪切强度(粘接强度)。首先，在70℃下将实施例及比较例的各膜状粘接剂(厚度为120μm)粘贴在半导体晶片(厚度为400μm)上。通过对其进行切割，获得由半导体元件(尺寸：5mm×5mm)和膜状粘接剂形成的层叠体。另一方面，准备在表面上涂布有阻焊剂油墨(AUS308)的基板。在120℃、0.1MPa、5秒钟的条件下介由膜状粘接剂将半导体元件压接在该表面上。之后，对其在110℃下加热处理1小时后，进一步在170℃下加热3小时，从而使膜状粘接剂固化，由此获得测定用的试样。将该试样在85℃、60RH％条件下放置168小时。之后，将该试样在25℃、50％RH条件下放置30分钟，然后在250℃下测定剪切强度，将其作为粘接强度。剪切强度的测定使用Dage社制的万能Bondtester系列4000。将结果示于表3及表4中。
[耐回流性的评价]
利用下述方法评价膜状粘接剂的耐回流性。首先，制作与供至埋入性评价的结构体相同的结构体。使用模具用密封材料(日立化成株式会社制、商品名：CEL-9750ZHF10)将结构体的第二半导体元件密封，从而获得评价用封装体。此外，树脂密封的条件是175℃/6.7MPa/90秒钟，固化的条件是175℃、5小时。
准备24个上述封装体，将它们暴露在JEDEC所规定的环境下(水平3、30℃、60％RH、192小时)，使它们吸湿。接着，使吸湿后的封装体通过IR回流炉(260℃、最高温度为265℃)3次。根据以下的标准进行评价。将结果示于表3及表4中。
A：封装体的破损、厚度的变化、膜状粘接剂与半导体元件的界面处的剥离等在24个封装体中连1个都未观察到。
B：封装体的破损、厚度的变化、膜状粘接剂与半导体元件的界面处的剥离等在24个封装体中观察到至少1个。
Figure BDA0002773712300000211
Figure BDA0002773712300000221
由表3及表4所示的结果所示确认到：实施例1～5的膜状粘接片材与比较例1～3的膜状粘接片材相比，在利用加压烘箱的处理后埋入性优异，并且可以抑制封装体污染及缩痕的发生。
产业上的可利用性
根据本公开，可以提供具有能够将控制器芯片等半导体元件及导线中的至少一者埋入的流动性、并且能够充分地抑制埋入时的周边电路的污染、之后热工序中的树脂的过剩流动所引起的问题的热固化性树脂组合物、以及使用该热固化性树脂组合物制造的半导体装置及其制造方法。
符号说明
2粘合层、8切割-芯片接合一体型带、10基板、11第一导线、12第二导线、10a，10b电路图案、20第一密封层(膜状粘接剂的固化物)、20A粘接层、20P膜状粘接剂、40第二密封层、100半导体装置、Wa第一半导体元件、Wb第二半导体元件

Claims (10)

1.一种半导体装置，其具备：
基板；
配置于所述基板上的第一半导体元件；
按照将所述基板上的配置有所述第一半导体元件的区域覆盖的方式配置、将所述第一半导体元件密封的第一密封层；以及
按照将所述第一密封层的与所述基板一侧为相反侧的表面覆盖的方式配置、具有比所述第一半导体元件大的面积的第二半导体元件，
所述第一密封层由热固化性树脂组合物的固化物形成，所述热固化性树脂组合物的120℃下的熔融粘度为2500～11500Pa·s。
2.根据权利要求1所述的半导体装置，其中，
所述热固化性树脂组合物包含分子量为10～1000的低分子量成分和分子量为10万～100万的高分子量成分，
所述低分子量成分的含量M1相对于所述热固化性树脂组合物所包含的树脂成分的质量100质量份为23～35质量份，
所述高分子量成分的含量M2相对于所述热固化性树脂组合物所包含的树脂成分的质量100质量份为25～45质量份。
3.根据权利要求2所述的半导体装置，其中，相对于所述热固化性树脂组合物所包含的树脂成分的质量100质量份，所述低分子量成分与所述高分子量成分的合计量为54～76质量份。
4.根据权利要求1～3中任一项所述的半导体装置，其进一步具备：
形成于所述基板的表面上的电路图案；以及
将所述第一半导体元件与所述电路图案电连接的第一导线。
5.根据权利要求4所述的半导体装置，其进一步具备：
将所述第二半导体元件与所述电路图案电连接的第二导线；以及
将所述第二半导体元件及所述第二导线密封的第二密封层。
6.根据权利要求1～5中任一项所述的半导体装置，其进一步具备层叠于所述第二半导体元件上的第三半导体元件。
7.一种热固化性树脂组合物，其为在半导体装置的制造工艺中使用的热固化性树脂组合物，
所述制造工艺包含以下工序：经过加热所述热固化性树脂组合物的固化处理，形成将导线的至少一部分及半导体元件中的至少一者埋入在固化处理后的所述热固化性树脂组合物中的状态，
所述热固化性树脂组合物的120℃下的熔融粘度为2500～11500Pa·s。
8.根据权利要求7所述的热固化性树脂组合物，其包含分子量为10～1000的低分子量成分和分子量为10万～100万的高分子量成分，
所述低分子量成分的含量M1相对于所述热固化性树脂组合物所包含的树脂成分的质量100质量份为23～35质量份，
所述高分子量成分的含量M2相对于所述热固化性树脂组合物所包含的树脂成分的质量100质量份为25～45质量份。
9.根据权利要求8所述的热固化性树脂组合物，其中，相对于该热固化性树脂组合物所包含的树脂成分的质量100质量份，所述低分子量成分与所述高分子量成分的合计量为54～76质量份。
10.一种切割-芯片接合一体型带，其具备粘合层和由权利要求7～9中任一项所述的热固化性树脂组合物形成的粘接层。
CN201880093364.5A 2018-05-15 2018-05-15 半导体装置及其制造中使用的热固化性树脂组合物以及切割-芯片接合一体型带 Pending CN112204730A (zh)

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