CN102047401B - 粘结膜 - Google Patents

粘结膜 Download PDF

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Publication number
CN102047401B
CN102047401B CN2009801202313A CN200980120231A CN102047401B CN 102047401 B CN102047401 B CN 102047401B CN 2009801202313 A CN2009801202313 A CN 2009801202313A CN 200980120231 A CN200980120231 A CN 200980120231A CN 102047401 B CN102047401 B CN 102047401B
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China
Prior art keywords
particle
adhesive film
conductive
filler
average grain
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Expired - Fee Related
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CN2009801202313A
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CN102047401A (zh
Inventor
须贺保博
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Dexerials Corp
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Sony Chemical and Information Device Corp
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Publication of CN102047401A publication Critical patent/CN102047401A/zh
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
    • H05K3/323—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives by applying an anisotropic conductive adhesive layer over an array of pads
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract

在使用含有非导电性填料的粘结膜向布线基板上倒装芯片封装半导体芯片时，即使在不能从两者之间完全排除填料和粘结剂组合物的情况下，也能确保确实的导通的粘结膜包含含有环氧化合物、固化剂和填料的粘结剂组合物。相对于环氧化合物、固化剂和填料的总量，填料的含量为10～70质量％。填料含有平均粒径为0.5～1.0μm的第1非导电性无机颗粒和对平均粒径为0.5～1.0μm的第2非导电性无机颗粒进行无电镀处理而使平均粒径不超过1.5μm而获得的导电性颗粒，填料的10～60质量％为该导电性颗粒。

Description

粘结膜
技术领域
本发明涉及在布线基板上倒装芯片封装(フリツプチツプ実装flip-chip mount)具有凸起的半导体芯片时使用的粘结膜。
背景技术
在布线基板上倒装芯片封装具有凸起的半导体芯片时，需广泛使用将导电性颗粒分散于绝缘性的粘结剂组合物中而成的各向异性导电膜。作为这样的导电性颗粒，使用在树脂核的表面形成有无电镀层的物质以使其在布线基板的连接垫片(接続パツドconnection pad)和半导体芯片的凸起之间压碎。
不过，随着安装布线基板中布线的狭间距化，凸起也向窄面积化发展，故需要减小各向异性导电粘结膜中使用的导电性颗粒的粒径，出现了非常难于制造均一的小粒径树脂颗粒的问题。因此，如下进行：在布线基板和半导体芯片之间夹持非导电性粘结膜(NCF)，使其压碎而将半导体芯片的凸起与布线基板的连接垫片或凸起搭接，通过使非导电性粘结膜固化而使两者连接固定(NCF连接)。
在NCF连接的情况下，为了提升非导电性粘结膜的连接可靠性，有提议为了调整非导电性粘结膜的储藏弹性率、线膨胀系数、熔融粘度等，在非导电性粘结膜中，相对于每100体积份的树脂固体成分掺混1～50体积份的粒径0.005～0.1μm的硅微粒等的非导电性填料(参照专利文献1、0043-0044段)。
专利文献1：日本特开2002-275444号公报
发明内容
发明所要解决的课题
但是，由于使用了掺混了硅微粒等填料的非导电性粘结膜，在布线基板上倒装芯片封装具有凸起的半导体芯片时，会出现不能完全排除布线基板的连接垫片或凸起和半导体芯片的凸起之间的硅微粒和粘结剂组合物的情况，在这样的情况下，会发生布线基板和半导体芯片之间不能取得导通的问题。
本发明的目的在于，通过使用掺混了硅微粒等填料的绝缘性粘结膜的NCF连接，在布线基板上倒装芯片封装具有凸起的半导体芯片时，即使在不能完全排除布线基板的连接垫片或凸起和半导体芯片的凸起之间的非导电性填料和绝缘性粘结剂组合物的情况下，也能确保确实的导通。
解决课题的手段
本发明者们为了改良NCF连接用的非导电性粘结膜，不仅特别规定在粘结剂组合物中应掺混的填料的量，也使用粒径比以往使用的粒径(即，0.005～0.1μm)大得多的填料，但是通过对这种填料的一部分进行无电镀处理，形成粒径(1.5μm以下)比使用以往的树脂核的各向异性导电连接用的导电性颗粒的粒径(约5μm)还要小得多的导电性颗粒，将其在特定的比例下使用，从而发现能达成上述目的，完成了本发明。
即，本发明提供粘结膜，其为包含含有环氧化合物、固化剂和填料的粘结剂组合物，用于在布线基板上倒装芯片封装具有凸起的半导体芯片的粘结膜，其特征在于，
相对于环氧化物、固化剂和填料的总量，填料的含量为10～70质量％，
该填料含有平均粒径为0.5～1.0μm的第1非导电性无机颗粒和对平均粒径为0.5～1.0μm的第2非导电性无机颗粒进行无电镀处理以使平均粒径不超过1.5μm而获得的导电性颗粒，
填料的10～60质量％为该导电性颗粒。
此外，本发明提供经由上述粘结膜而将具有凸起的半导体芯片连接固定在布线基板上的连接结构。
发明效果
本发明的粘结膜特别规定了掺混于粘结剂组合物中的填料量，但将作为填料的特定粒径的非导电性无机颗粒和导电性颗粒以特定比例使用时，即使在不能完全排除在布线基板的连接垫片或凸起和半导体芯片的凸起之间的填料和粘结剂树脂的情况下，也能确保确实的导通。
附图简述
图1为显示了实施例1的粘结膜及比较例4的各向异性导电膜的相对介电常数的测定结果的图。
图2为显示了实施例1的使用粘结膜的情况下的短路的发生和相邻端子间距离之间的关系的图。
图3为显示了比较例4的使用各向异性导电膜的情况下的短路的发生和相邻端子间距离之间的关系的图。
发明的最佳实施方式
本发明是用于布线基板上倒装芯片封装具有凸起的半导体芯片的粘结膜，是使填料分散于粘结剂组合物中膜化而获得的物质。此处，作为布线基板可以使用环氧玻璃钢布线基板、玻璃布线基板、柔性布线基板等的在半导体装置中广泛适用的布线基板，作为半导体芯片可以使用集成电路芯片、发光二级管芯片等的在半导体装置中广泛适用的半导体芯片。此外，粘结剂组合物含有加入作为成膜成分的环氧化合物及固化剂中的填料，显示出热固化性。
填料主要是为了降低粘结膜的线膨胀系数和吸水性而使用的，其含有第1非导电性无机颗粒和对第2非导电性无机颗粒进行无电镀处理而得到的导电性颗粒。作为第1非导电性无机颗粒和第2非导电性无机颗粒，可以使用NCF连接时使用的公知的用于非导电性粘结膜中的填料，可举例优选硅微粒、氧化铝颗粒、二氧化钛颗粒等。其中，从比较廉价地得到硬质的固化物的观点来看，使用硅微粒。需要说明的是，第1非导电性无机颗粒和第2非导电性无机颗粒可以相同，也可以不同。需说明的是，本发明中的填料中，不含有通过对有机树脂核的表面进行无电镀处理来设置金属层而得到的导电性颗粒。
第1及第2非导电性无机颗粒的平均粒径分别为0.5～1.0μm，优选0.5～0.8μm。若不足0.5μm，则进行半导体的封装时，含有的大粒径填料破坏保护半导体电路面的保护膜而引发不良状况，尤其在导电性颗粒的情况下这是发生绝缘性劣化的原因，另一方面，若超过1.0μm则引起绝缘特性的恶化。在此，“平均粒径”为使用激光衍射法测定的值。
此外，第2非导电性无机颗粒，可以通过公知的无电镀处理在表面形成无电镀层，作为赋予了导电性的导电性颗粒使用。因此即使在不能完全排除布线基板的连接垫片或凸起和半导体芯片的凸起之间的填料和粘结剂组合物的情况下，也能确保确实的导通。作为无电镀层，可以使用现有的各向异性导电性颗粒的无电镀层，优选使用例如，包含金、镍、镍/金或焊剂等的无电镀层。但是，使导电性颗粒的平均粒径不超过1.5μm，优选1.1μm以下。这是因为若超过1.5μm则难于确保相邻端子间的绝缘性。
此外，若导电性颗粒的平均粒径比第1该非导电性无机颗粒的平均粒径小得过多，则将半导体的凸起和布线基板的电极之间导通的效力变小，若大得过多则相邻端子间的绝缘性劣化，故优选前者的粒径为后者的1.0～2.0倍，更优选1.0～1.5倍。
填料中的上述导电性颗粒的含有比例为10～60质量％，优选30～50质量％。这是因为若不足10质量％则初期导通性显著降低，若超过60质量％则引起绝缘性显著降低。
在本发明的粘结膜中，相对于相当于粘结剂组合物的全部固体成分的环氧化合物、固化剂和填料的总量，包含第1及第2非导电性无机颗粒的填料的含量为10～70质量％，优选40～60质量％，更优选50～60质量％。这是因为若不足10质量％则连接结构的寿命特性下降，若超过70质量％则膜成形困难。
如前所述，构成本发明的粘结膜的粘结剂组合物包含作为成膜成分的环氧化合物和其固化剂。
作为环氧化合物，可优选列举分子内有2个以上的环氧基的化合物或树脂。其可以为液态，也可以为固态。作为这样的环氧化物化合物，可示例如双酚A型环氧树脂和双酚F型环氧树脂等的双官能环氧树脂、苯酚酚醛型环氧树脂(phenol novolac epoxy resin)和甲酚酚醛型环氧树脂(cresol novolac epoxy resin)等的酚醛型环氧树脂等。此外，也可使用3，4-环氧基环己烯基甲基-3’，4’-环氧基环己烯羧酸酯等的脂环式环氧化合物。
在粘结剂组合物中，可以合用与环氧化合物相容(相溶するcompatible)的苯氧基树脂及丙烯酸树脂。
作为构成本发明的粘结膜的固化剂，可以使用在现有的各向异性导电膜中使用的环氧化合物用固化剂，可列举例如胺类固化剂、咪唑类固化剂、酸酐类固化剂等。固化剂可具有潜在性。
在粘结剂组合物中，根据需要可掺混公知的固化促进剂、偶合剂、金属捕集剂等。
本发明的粘结膜可以依常法制造。可以在环氧化合物中将填料和甲苯、乙酸乙酯等的溶剂共同混合均匀，将得到的混合物涂布于剥离膜上以形成规定的干燥膜厚，干燥，从而制得。
本发明的粘结膜，可优选适用作为在布线基板上倒装芯片封装具有凸起的半导体芯片时使用的粘结膜。故，对于经由本发明的粘结膜将具有凸起的半导体芯片连接固定在布线基板上的连接结构，即使在不能完全排除布线基板的连接垫片或凸起和半导体芯片的凸起之间的粘结剂树脂的情况下，通过此导电性颗粒也能确保确实的导通。此连接结构可以通过将粘结膜暂时贴在布线基板的连接垫片或凸起上，在其上安装具有凸起的半导体芯片，使其凸起面成为布线基板侧地进行载置，并通过加热加压来连接固定而进行制造。
实施例
以下使用实施例对本发明进行具体地说明。
需要说明的是，以下的实施例或比较例中使用的评价用的布线基板是在表面形成有实施了镍/金电镀的厚12μm的铜布线，0.6mm厚×35mm宽×35mm长大小的环氧玻璃钢布线基板。此外，评价用的半导体芯片为设有金球凸点(544针、50μm间距)的0.4mm厚×7.3mm宽×7.3mm长大小的氧化硅芯片。
参考例1(非导电性无机颗粒核的导电性颗粒的制造)
对于平均粒径0.5μm的硅颗粒(球形二氧化硅，Tokuyama社)，使用无电镀镍溶液进行无电镀镍处理。对于通过无电镀镍处理而得到的颗粒，进一步使用无电镀金溶液实施无电镀金处理，从而得到平均粒径0.6μm的导电性颗粒。
参考例2(非导电性无机颗粒核的导电性颗粒的制造)
除了使用粒径1.0μm的硅微粒(球形二氧化硅，Tokuyama社)代替平均粒径0.5μm的硅微粒以外，和参考例1一样地处理得到平均粒径1.1μm的导电性颗粒。
参考例3(非导电性无机颗粒核的导电性颗粒的制造)
除了使用粒径3.5μm的硅微粒(Hipresica，宇部日东化成社)代替平均粒径0.5μm的硅微粒以外，和参考例1一样地处理得到平均粒径3.6μm的导电性颗粒。
比较例1(粘结膜的制造)
将环氧树脂(Epocoat828，Japan Epoxy Resins Co.，Ltd)50份重量和潜在性固化剂(HX3941HP，旭化成化学社)100份重量和平均粒径0.5μm的硅微粒(球形二氧化硅，Tokuyama社)50份重量的混合物溶解、分散于甲苯中以使固体成分为50质量％，形成热固化型粘结组合物，并将此粘结组合物涂布于经剥离处理的50μm厚的聚对苯二甲酸乙二酯(PET)膜(Separator，Tohcello Co.，Ltd)上以使干燥厚为40μm，于80℃下干燥，由此制成热固化型的比较例1的粘结膜。
实施例1
将环氧树脂(Epocoat828，Japan Epoxy Resins Co.，Ltd)50份重量和潜在性固化剂(HX3941HP，旭化成化学社)100份重量和平均粒径0.5μm的硅微粒(球形二氧化硅，Tokuyama社)45份重量和参考例1的导电性颗粒5份质量的混合物，溶解、分散于甲苯中以使固体成分为50质量％，从而形成热固化型粘结组合物，并将此粘结组合物涂布于经剥离处理的50μm厚的PET膜(Separator，Tohcello Co.，Ltd)上以使干燥厚为40μm，于80℃下干燥，由此制成热固化型的实施例1的粘结膜。相对于全部固体成分(环氧树脂、固化剂和填料的总合)，填料的含量为25质量％。
实施例2
除了将平均粒径0.5μm的硅微粒45份质重量改为25份重量，将导电性颗粒改为25份重量以外，和实施例1一样地处理，制成热固化型的实施例2的粘结膜。
比较例2
除了将平均粒径0.5μm的硅微粒45份重量改为5份重量，并将参考例1的导电性颗粒5份重量改为45份重量以外，和实施例1一样地处理，制成热固化型的比较例2的粘结膜。
实施例3
除了将平均粒径0.5μm的硅微粒45份重量改为25份重量，并使用参考例2的导电性颗粒25份重量替代参考例1的导电性颗粒5份重量以外，和实施例1一样地处理，制成热固化型的实施例3的粘结膜。
比较例3
除了使用平均粒径3.5μm的硅颗粒(Hipresica、宇部日东化成社)代替平均粒径0.5μm的硅微粒，使用参考例3的导电性颗粒代替参考例2的导电性颗粒以外，和实施例3一样地处理，制成热固化型的比较例3的粘结膜。
比较例4
不使用平均粒径0.5μm的硅微粒，且使用在有机颗粒核表面实施了无电镀镍/金的平均粒径4.0μm的导电性颗粒(Bright，日本化学社)10份重量来代替参考例1的导电性颗粒5份重量以外，和实施例1一样地处理，制成热固化型的比较例4的各向异性导电膜。
比较例5
除使用在有机颗粒核表面实施了无电镀镍/金的平均粒径4.0μm的导电性颗粒(Bright，日本化学社)来代替参考例1的导电性颗粒以外，和实施例1一样地处理，制成热固化型的比较例5的各向异性导电膜。
实施例4
除将硅微粒45份重量改为75份重量，导电性颗粒5份重量改为75份重量以外，和实施例1一样地处理，制成热固化型的实施例4的各向异性导电膜。在本实施例中，相对于相当于粘结剂组合物的全部固体成分的环氧化合物、固化剂和填料的总量，填料的含量为50质量％。
实施例5
除将硅微粒45份重量改为175份重量，导电性颗粒5份重量改为175份重量以外，和实施例1一样地处理，制成热固化型的实施例5的各向异性导电膜。在本实施例中，相对于相当于粘结剂组合物的全部固体成分的环氧化合物、固化剂和填料的总量，填料的含量为70质量％。
(评价1)
分别将各实施例及比较例的粘结膜及各向异性导电膜暂时贴在评价用的布线基板的电极垫片上，除去剥离膜后，在其上将评价用的半导体芯片从其凸起面上载置，于温度180℃、压力2.5Mpa下对半导体芯片加热加压20秒，从而制成导通电阻测定用的连接结构样品。
对于所得到的连接结构样品，测定初期的导通电阻值(Ω)(顺序链电阻值(デイジ一チエ一ン抵抗值daisy chain resistance)(136电极连接电阻+布线电阻)和绝缘电阻值(Ω)(顺序链布线间绝缘电阻值(Ω)(不足136电极间的最小值108Ω则判断为短路)。随后，将前述样品进行PCT试验(条件：于121℃、饱和水蒸气压的室中放置24小时)作为导通可靠性试验，测定导通电阻值，此外，作为综合评价，未发生断路和短路的情况评价为“良好”，发生至少任一种的场合评价为“不良”。得到的结果如表1所示。
[表1]
从表1可知，使用了硅微粒和对其进行了无电镀处理的导电颗粒的实施例1～5的粘结膜，在评价项目上显示良好的结果。
另一方面，在比较例1的粘结膜的情况下，完全不含有导电性颗粒，故初期的导通电阻测定显示断路。在比较例2的粘结膜的情况下，导电性颗粒的掺混量过多，故相邻电极间发生了短路。在比较例3的粘结膜的情况下，导电性颗粒粒径过大，故每单位体积的导电性颗粒个数变少，出现不能在电极间捕获的情况，在顺序链的电阻测定下发生了断路，另一方面在电极间空间小的情况下发生了短路。
需要说明的是，在不使用硅微粒，使用现有的有机树脂核型的导电性颗粒的比较例4的粘结膜的情况下，初期特性良好，但PCT试验后的导通电阻变为断路，为缺乏导通可靠性的结果。此外，在除有机树脂核型的导电性颗粒之外还使用硅微粒的比较例5的粘结膜的情况下，初期的导通电阻为断路。
(评价2)
对于实施例1的粘结膜及比较例4的各向异性导电膜，以下进行说明而评价相对介电常数和绝缘性。
相对介电常数使用相对介电常数测定装置{LF INPEDANCEANALYZER 4192A，Hewlet Pachard社；使用介电常数测定用电极16451B(电极A，直径38mm)；频率1，2，5，10，20，50，100，200，500，1000，2000，5000(kHz)；电压1V}来测定。结果显示相对介电常数越低，绝缘性越高。得到的结果如图1所示。从图1可知，实施例1的粘结膜比比较例4的各向异性导电膜的绝缘性高。
作为绝缘特性，考察了在ITO垫片中倒装芯片封装半导体芯片(凸起大小：50×150μm，间距：80μm间距)，短路(绝缘电阻值低于108Ω)的发生和相邻端子间距离的关系。得到的结果如图2和图3所示。从这些图中可知，实施例1的粘结膜根本未发生短路，但在比较例4的各向异性导电膜的情况下，短路的发生显著。
产业上的利用可能性
通过本发明的半导体装置的制造方法，使用具有规定厚度的热固化型密封树脂层的密封树脂膜，通过一次的热压焊处理而同时进行向布线基板的半导体芯片的封装和半导体芯片的密封，故布线基板和半导体芯片之间形成的连接部在连接后不再受到加热加压。从而可以实现工序的缩短和产出率的提升。因此，本发明作为半导体装置的制造方法是有用的。

Claims (8)

1.粘结膜，其为包含含有环氧化合物、固化剂和填料的粘结剂组合物，用于在布线基板上倒装芯片封装具有凸起的半导体芯片的粘结膜，其特征在于，
相对于环氧化物、固化剂和填料的总量，填料的含量为10～70质量％，
该填料含有平均粒径为0.5～1.0μm的第1非导电性无机颗粒和对平均粒径为0.5～1.0μm的第2非导电性无机颗粒进行无电镀处理以使平均粒径不超过1.5μm而获得的导电性颗粒，
填料的10～60质量％为该导电性颗粒。
2.权利要求1的粘结膜，其中，第1及第2非导电性无机颗粒为硅微粒、氧化铝颗粒或二氧化钛颗粒。
3.权利要求1或2的粘结膜，其中，所述第1及第2非导电性无机颗粒具有0.5～0.8μm的平均粒径。
4.权利要求1或2的粘结膜，其中，所述导电性颗粒的粒径为1.1μm以下。
5.权利要求1或2的粘结膜，其中，所述导电性颗粒的平均粒径为所述第1非导电性无机颗粒的平均粒径的1.0～2.0倍。
6.权利要求1或2的粘结膜，其中，所述无电镀处理的金属种类为金、镍、镍/金或焊剂。
7.连接结构，其是具有凸起的半导体芯片经由权利要求1～6中任一项的粘结膜在布线基板上连接固定而形成的。
8.权利要求7的连接结构，其将半导体芯片的凸起和布线基板的凸起连接。
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