JP2006120665A - Conductive resin paste composition containing silver and carbon nano tube, and semiconductor device using the same - Google Patents
Conductive resin paste composition containing silver and carbon nano tube, and semiconductor device using the same Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/013—Alloys
- H01L2924/0132—Binary Alloys
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/102—Material of the semiconductor or solid state bodies
- H01L2924/1025—Semiconducting materials
- H01L2924/10251—Elemental semiconductors, i.e. Group IV
- H01L2924/10253—Silicon [Si]
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/11—Device type
- H01L2924/14—Integrated circuits
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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Abstract
Description
本発明は、銀とカーボンナノチューブを含む導電性樹脂ペースト組成物およびこれを用いた半導体装置に関し、より詳しくは、耐マイグレーション性、接着強度、導電性に優れ、ダイボンド用としてＩＣ、ＬＳＩ等の半導体素子をリードフレーム、ガラスエポキシ基板等に接着するのに好適な、銀とカーボンナノチューブを含む導電性樹脂ペースト組成物およびこれを用いた半導体装置に関する。 The present invention relates to a conductive resin paste composition containing silver and carbon nanotubes, and a semiconductor device using the same, and more particularly, has excellent migration resistance, adhesive strength, and conductivity, and is a semiconductor such as an IC or LSI for die bonding. The present invention relates to a conductive resin paste composition containing silver and carbon nanotubes, which is suitable for bonding an element to a lead frame, a glass epoxy substrate, and the like, and a semiconductor device using the same.
従来、半導体装置を製造する際の半導体素子とリードフレーム（支持部材）の接合方法として、金−シリコン共晶体等の無機材料を接着剤として用いる方法や、エポキシ樹脂等の有機材料に銀粉等を分散させてペースト状態とし、これを接着剤として用いる方法などがある。しかしながら、金−シリコン共晶体等を用いる前者の方法では接着剤のコストが高く、３５０℃から４００℃程度の高温での熱処理が必要であり、また接着剤が硬く、熱応力によってチップの破壊が起こるという問題がある。 Conventionally, as a method of joining a semiconductor element and a lead frame (support member) when manufacturing a semiconductor device, a method using an inorganic material such as a gold-silicon eutectic as an adhesive, or silver powder or the like as an organic material such as an epoxy resin There is a method of dispersing and making a paste and using this as an adhesive. However, in the former method using a gold-silicon eutectic, etc., the cost of the adhesive is high, heat treatment at a high temperature of about 350 ° C. to 400 ° C. is necessary, the adhesive is hard, and the chip is broken by thermal stress. There is a problem that happens.
そのため、最近では銀粉を含んだ銀ペーストを用いる後者の方法が主流となっている。しかしながら、この方法にしても、銀が高価であることからペーストも高価なものになるという問題があった。また、銀は高温多湿の雰囲気下で電界が印加されると、マイグレーションと称する銀の電析が生じるという問題もあった。さらに、形状が扁平状等の銀フィラーを用いると、導電性は良好であるが粘度が高くなり、作業性が悪くなるという問題もあった。作業性を改善するためには、希釈剤量を増加させねばならず、そうすると接着強度が低下してしまうという現象が起こる。 Therefore, the latter method using a silver paste containing silver powder has become mainstream recently. However, even this method has a problem that the paste becomes expensive because silver is expensive. In addition, silver has a problem that, when an electric field is applied in a hot and humid atmosphere, silver electrodeposition called migration occurs. Furthermore, when a silver filler having a flat shape or the like is used, there is a problem that the conductivity is good but the viscosity is high and the workability is deteriorated. In order to improve workability, the amount of diluent must be increased, which causes a phenomenon that the adhesive strength is lowered.
これに対して、カーボンナノチューブを用いた導電性ペーストが提案されている（例えば、特許文献１参照）。これは、蛍光表示管にアノード電極形成用として、従来の黒鉛粉末に代わりカーボンナノチューブを用いており、導電性フィラーとして銀粉を用いるペースト組成物ではない。そのため、銀粉を用いることで大きな問題となるマイグレーション性に関しては全く言及されていない。 In contrast, a conductive paste using carbon nanotubes has been proposed (for example, see Patent Document 1). This is not a paste composition in which carbon nanotubes are used in place of conventional graphite powder for forming an anode electrode in a fluorescent display tube, and silver powder is used as a conductive filler. For this reason, no mention is made of the migration which becomes a big problem by using silver powder.
このような状況下、導電性フィラーとして銀粉を含むペースト組成物を用いて半導体素子とリードフレーム（支持部材）を接合する際、耐マイグレーション性に優れ、接着強度、導電性とのバランスも良い組成物の出現が切望されていた。
本発明の目的は、耐マイグレーション性、接着強度、導電性に優れ、ダイボンド用としてＩＣ、ＬＳＩ等の半導体素子をリードフレーム、ガラスエポキシ基板等に接着するのに好適な、銀とカーボンナノチューブを含む導電性樹脂ペースト組成物およびこれを用いた半導体装置を提供することにある。 The object of the present invention includes silver and carbon nanotubes, which are excellent in migration resistance, adhesive strength, and conductivity, and are suitable for bonding semiconductor elements such as IC and LSI to lead frames, glass epoxy substrates and the like for die bonding. An object is to provide a conductive resin paste composition and a semiconductor device using the same.
本発明者らは、かかる従来の課題に鑑み、鋭意研究を行った結果、少なくとも熱硬化性樹脂、および導電性フィラーを含有してなる導電性樹脂ペースト組成物において、銀粉を主成分とする導電性フィラーに、特定量のカーボンナノチューブを配合することにより、高温多湿の雰囲気下で電界が印加されても、マイグレーションと称する銀の電析が生じなくなることを見出して、本発明を完成するに至った。 As a result of intensive studies in view of such conventional problems, the present inventors have found that a conductive resin paste composition containing at least a thermosetting resin and a conductive filler is a conductive material mainly composed of silver powder. By adding a specific amount of carbon nanotubes to the conductive filler, it was found that even when an electric field was applied in a hot and humid atmosphere, silver deposition called migration did not occur, and the present invention was completed. It was.
すなわち、本発明の第１の発明によれば、少なくとも熱硬化性樹脂（Ａ）と導電性フィラー（Ｂ）を含む導電性樹脂ペースト組成物において、導電性フィラー（Ｂ）が、銀粉（Ｂ１）に加えて、耐マイグレーション性を向上させるに十分な量のカーボンナノチューブ（Ｂ２）を含有することを特徴とする導電性樹脂ペースト組成物が提供される。 That is, according to the first invention of the present invention, in the conductive resin paste composition containing at least the thermosetting resin (A) and the conductive filler (B), the conductive filler (B) is silver powder (B1). In addition to the above, a conductive resin paste composition containing a sufficient amount of carbon nanotubes (B2) to improve migration resistance is provided.
また、本発明の第２の発明によれば、第１の発明において、熱硬化性樹脂（Ａ）が、エポキシ樹脂又はフェノール樹脂から選ばれる１種以上の樹脂であることを特徴とする導電性樹脂ペースト組成物が提供される。 According to the second invention of the present invention, in the first invention, the thermosetting resin (A) is one or more resins selected from an epoxy resin and a phenol resin. A resin paste composition is provided.
また、本発明の第３の発明によれば、第１の発明において、熱硬化性樹脂（Ａ）の含有量が、組成物全体に対して５〜８０重量％であることを特徴とする導電性樹脂ペースト組成物が提供される。 According to the third invention of the present invention, in the first invention, the content of the thermosetting resin (A) is 5 to 80% by weight based on the entire composition. An adhesive resin paste composition is provided.
また、本発明の第４の発明によれば、第１の発明において、銀粉（Ｂ１）の含有量が、組成物全体に対して５〜９５重量％であることを特徴とする導電性樹脂ペースト組成物が提供される。 According to a fourth aspect of the present invention, in the first aspect, the conductive resin paste is characterized in that the content of silver powder (B1) is 5 to 95% by weight with respect to the entire composition. A composition is provided.
さらに、本発明の第５の発明によれば、第１の発明において、カーボンナノチューブ（Ｂ２）の含有量が、組成物全体に対して０．０１〜５重量％であることを特徴とする導電性樹脂ペースト組成物が提供される。 Furthermore, according to the fifth invention of the present invention, in the first invention, the content of the carbon nanotube (B2) is 0.01 to 5% by weight with respect to the whole composition. An adhesive resin paste composition is provided.
一方、本発明の第６の発明によれば、第１〜５のいずれかに記載の導電性樹脂ペースト組成物を用いて半導体素子と基板が接着され、ついで封止されてなる半導体装置が提供される。 On the other hand, according to a sixth aspect of the present invention, there is provided a semiconductor device in which a semiconductor element and a substrate are bonded using the conductive resin paste composition according to any one of the first to fifth, and then sealed. Is done.
本発明によれば、耐マイグレーション性、接着強度、導電性に優れるだけでなく、接着強度及び導電性のバランスに優れている導電性樹脂ペースト組成物が提供される。従って、本発明の導電性樹脂ペースト組成物を用いた半導体装置は、高温多湿の雰囲気でも接着強度、導電性が低下せず優れた電気的特性を維持できる。 According to the present invention, there is provided a conductive resin paste composition that not only has excellent migration resistance, adhesive strength, and electrical conductivity, but also has an excellent balance of adhesive strength and electrical conductivity. Therefore, the semiconductor device using the conductive resin paste composition of the present invention can maintain excellent electrical characteristics without deterioration in adhesive strength and conductivity even in a high temperature and high humidity atmosphere.
１．導電性樹脂ペースト組成物
本発明の導電性樹脂ペースト組成物は、熱硬化性樹脂（Ａ）と導電性フィラー（Ｂ）とを含有し、導電性フィラー（Ｂ）の主成分である銀粉（Ｂ１）にカーボンナノチューブ（Ｂ２）を配合したものである。本発明の導電性樹脂ペースト組成物には、ペースト組成物の作製時の作業性、及び使用時の塗布性をより良好するため、必要に応じて希釈剤（Ｃ）を添加することができる。
1. Conductive resin paste composition The conductive resin paste composition of the present invention contains a thermosetting resin (A) and a conductive filler (B), and is a silver powder (B1) that is a main component of the conductive filler (B). ) And carbon nanotubes (B2). Diluent (C) can be added to the conductive resin paste composition of the present invention as necessary in order to improve the workability at the time of preparing the paste composition and the applicability at the time of use.
（Ａ）熱硬化性樹脂
本発明において、熱硬化性樹脂は、バインダー樹脂として機能する成分であり、この熱硬化性樹脂は一般的に市販されているものを用いることができる。例えば、エポキシ樹脂、フェノール樹脂、メラミン樹脂、ポリイミド樹脂、アクリル樹脂、不飽和ポリエステル樹脂、ジアリルフタレート樹脂、およびこれらの各種変性品等が挙げられ、１種もしくは２種以上を混合して用いることができる。
(A) Thermosetting resin In this invention, a thermosetting resin is a component which functions as a binder resin, and what is generally marketed can be used for this thermosetting resin. Examples include epoxy resins, phenol resins, melamine resins, polyimide resins, acrylic resins, unsaturated polyester resins, diallyl phthalate resins, and various modified products thereof. it can.
これらの熱硬化性樹脂の中でも、本発明の効果が充分得られるペースト状の組成物とするためには、２０℃（常温）で液状であることが好ましい。特に、ポットライフや硬化後の種々の特性を得るために、比較的調製が容易なエポキシ樹脂やフェノール樹脂を用いることが好ましい。更には、芳香族基を有するエポキシ樹脂が好ましく用いられる。 Among these thermosetting resins, in order to obtain a paste-like composition that can sufficiently obtain the effects of the present invention, it is preferably liquid at 20 ° C. (normal temperature). In particular, in order to obtain various properties after pot life and curing, it is preferable to use an epoxy resin or a phenol resin that is relatively easy to prepare. Furthermore, an epoxy resin having an aromatic group is preferably used.
例えば、２０℃で液状の熱硬化性樹脂としては、希釈剤を低減できる等の点から、粘度の低いもの、具体的には２０℃で粘度が５０Ｐａ・ｓ以下のものが好ましく、さらには０．１〜１０Ｐａ・ｓのものが好ましい。 For example, the thermosetting resin that is liquid at 20 ° C. is preferably one having a low viscosity, specifically a viscosity of 50 Pa · s or less at 20 ° C. from the viewpoint that the diluent can be reduced. 1 to 10 Pa · s is preferable.
エポキシ樹脂としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、芳香族系のグリシジルアミン型エポキシ樹脂、レゾルシン型エポキシ樹脂などが挙げられる。これらのエポキシ樹脂は、２種以上を適宜組み合わせて用いることもできる。また、上記エポキシ樹脂のうち、粘度が低く、希釈剤量を低減できることから、ビスフェノールＦ型エポキシ樹脂及びビスフェノールＡＤ型エポキシ樹脂が好ましい。なお、ビスフェノールＦ型エポキシ樹脂は、２つのヒドロキシフェニル基を結ぶ基がメチレン基である化合物であり、ビスフェノールＡＤ型エポキシ樹脂は、２つのヒドロキシフェニル基を結ぶ基が１，１−エチレン基である化合物である。また、フェノール樹脂としては、アルカリレゾール型のフェノール樹脂が好ましい。 Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, aromatic glycidylamine type epoxy resin, resorcin type epoxy resin, and the like. Two or more of these epoxy resins can be used in appropriate combination. Of the above epoxy resins, bisphenol F type epoxy resins and bisphenol AD type epoxy resins are preferred because of their low viscosity and the reduced amount of diluent. The bisphenol F type epoxy resin is a compound in which a group connecting two hydroxyphenyl groups is a methylene group, and the bisphenol AD type epoxy resin is a 1,1-ethylene group connecting two hydroxyphenyl groups. A compound. Moreover, as a phenol resin, an alkaline resol type phenol resin is preferable.
熱硬化性樹脂は、樹脂成分（Ａ）と導電性フィラー成分（Ｂ）との総量、すなわち組成物全体に対して５〜８０重量％使用することが好ましく、耐半田リフロー性の点から、１０〜５０重量％使用することがより好ましい。 The thermosetting resin is preferably used in a total amount of the resin component (A) and the conductive filler component (B), that is, 5 to 80% by weight with respect to the entire composition. It is more preferable to use ˜50% by weight.
本発明に用いられる熱硬化性樹脂には、必要に応じて硬化剤を併用することができる。併用できる硬化剤は特に制限はないが、熱硬化性樹脂が例えばエポキシ樹脂であれば、フェノールノボラック樹脂、フェノールアラルキル樹脂、ジシアンジアミド、二塩基酸ジヒドラジドなどを用いることができる。 A curing agent can be used in combination with the thermosetting resin used in the present invention, if necessary. The curing agent that can be used in combination is not particularly limited, but if the thermosetting resin is, for example, an epoxy resin, phenol novolac resin, phenol aralkyl resin, dicyandiamide, dibasic acid dihydrazide, or the like can be used.
（Ｂ）導電性フィラー
本発明において用いられる導電性フィラーの必須成分は、銀粉およびカーボンナノチューブである。
(B) Conductive filler The essential components of the conductive filler used in the present invention are silver powder and carbon nanotubes.
銀粉としては、例えば微細球状銀粉、粗粒球状銀粉、フレーク状銀粉等が挙げられ、これらのいずれか１種もしくは２種以上を組み合せて用いることができる。特に好ましいのは、フレーク状銀粉である。 Examples of the silver powder include fine spherical silver powder, coarse spherical silver powder, and flaky silver powder, and any one or two or more of these can be used in combination. Particularly preferred is flaky silver powder.
微細球状銀粉の球状とは、アスペクト比、すなわち長短度（長径／短径）が１〜２．５のものを指し、特にその長短度が１〜１．２５のものが、より好ましい。ここで、短径とは、前記切断面に現れる粒子について、その粒子の外側に接する二つの平行線の組み合わせが粒子を挟むように選択し、それらの組み合わせのうち最短間隔になる二つの平行線の距離である。一方、長径とは、前記短径を決する平行線に直角方向の二つの平行線であって、粒子外側に接する二つの平行線の組み合わせのうち、最長間隔になる二つの平行線の距離である。これらの四つの線で形成される長方形は、粒子がちょうどその中に納まる大きさとなる。 The spherical shape of the fine spherical silver powder refers to one having an aspect ratio, that is, a length (major axis / minor axis) of 1 to 2.5, and more preferably one having a length of 1 to 1.25. Here, the minor axis is selected such that a combination of two parallel lines in contact with the outside of the particle sandwiches the particle with respect to the particle appearing on the cut surface, and two parallel lines having the shortest distance among these combinations. Is the distance. On the other hand, the major axis is the distance between the two parallel lines that are perpendicular to the parallel line that determines the minor axis and that is the longest interval among the combination of two parallel lines that touch the outside of the particle. . The rectangle formed by these four lines is the size that the particles just fit within.
また、微細球状銀粉の平均粒径は、１０μｍ以下であることが望ましく、これを越えると、十分に緻密な膜が得られない。なお、組成物作製時の混練性を考慮すると、微細球状銀粉の平均粒径は０．１〜５μｍ程度がより好ましい。また、粗粒球状銀粉は必要に応じて使用することができ、その長短度は、上記微細球状銀粉の場合と同様である。 Moreover, it is desirable that the fine spherical silver powder has an average particle size of 10 μm or less, and beyond this, a sufficiently dense film cannot be obtained. In consideration of kneadability at the time of preparing the composition, the average particle size of the fine spherical silver powder is more preferably about 0.1 to 5 μm. The coarse spherical silver powder can be used as necessary, and the length thereof is the same as that of the fine spherical silver powder.
一方、フレーク状銀粉は、長径における平均粒径が０．１〜１０μｍの範囲のものを使用するのが好ましい。その長径における平均粒径が０．１μｍ未満であると、均一な混合が困難となる上、充填率を向上させる効果が少ないため充分な抵抗率が得られない。また１０μｍを越えると、スクリーン印刷等を行う際にスクリーンの目詰まりを生じ易くなるため好ましくない。さらに収縮特性を考慮すると、０．５〜５μｍの範囲のものがより好ましい。また、フレーク状銀粉のアスペクト比（長短度）は１〜５の範囲内、更に好ましくは１〜３．５の範囲内のものを用いるとよい。その厚さは０．０５〜２μｍ、更に好ましくは０．１〜１．２μｍのものを使用するとよい。 On the other hand, it is preferable to use the flaky silver powder having an average particle diameter in the range of 0.1 to 10 μm. If the average particle size of the major axis is less than 0.1 μm, uniform mixing becomes difficult, and a sufficient resistivity cannot be obtained because the effect of improving the filling rate is small. On the other hand, if it exceeds 10 μm, clogging of the screen tends to occur during screen printing or the like, which is not preferable. Further, considering the shrinkage characteristics, those in the range of 0.5 to 5 μm are more preferable. The aspect ratio (long / short) of the flaky silver powder is preferably in the range of 1 to 5, more preferably in the range of 1 to 3.5. The thickness may be 0.05-2 μm, more preferably 0.1-1.2 μm.
上記の微細球状銀粉、粗粒球状銀粉、およびフレーク状銀粉は、必要に応じた混合率で使用できる。混合率としては、銀粉総量の５〜５０重量％を微細球状銀粉が占め、残部を粗粒球状銀粉またはフレーク状銀粉となるようにすることが好ましい。 Said fine spherical silver powder, coarse-grained spherical silver powder, and flaky silver powder can be used with the mixing rate as needed. As the mixing ratio, it is preferable that 5 to 50% by weight of the total amount of silver powder is occupied by fine spherical silver powder, and the remainder is coarse spherical silver powder or flaky silver powder.
また、銀粉の含有量は、組成物全体に対して５〜９５重量％であることが好ましく、１０〜９０重量％がより好ましい。５重量％よりも少ないと充分な低抵抗率を確保できず、また９５重量％よりも多いと組成物の粘度が上昇して実用に耐えられなくなる。 Moreover, it is preferable that content of silver powder is 5-95 weight% with respect to the whole composition, and 10-90 weight% is more preferable. If it is less than 5% by weight, a sufficiently low resistivity cannot be ensured, and if it is more than 95% by weight, the viscosity of the composition increases and it cannot be put into practical use.
また、本発明において、導電性フィラーのもう一方の必須成分であるカーボンナノチューブは、特に限定されず、多層型、単層型、ホーン型のいずれでも使用することができる。 In the present invention, the carbon nanotube which is another essential component of the conductive filler is not particularly limited, and any of a multi-layer type, a single-layer type and a horn type can be used.
これらの製造方法としては、例えば特開２０００−６３１１２号公報、特開２００１−６４００４号公報、特開２００３−２７７０３２号公報、「カーボンナノチューブの基礎」（斎藤弥八、坂東俊治、１９９８年１１月発行、コロナ社」等に開示されており、ここに記載された方法で得ることができる。 As these production methods, for example, JP 2000-63112 A, JP 2001-64004 A, JP 2003-277032 A, “Basics of Carbon Nanotubes” (Yahachi Saito, Shunji Bando, November 1998). It is disclosed in “Issuance, Corona”, etc., and can be obtained by the method described herein.
カーボンナノチューブは、直径０．５〜２００ｎｍであり、長さが０．１〜１００μｍであることが好ましい。また、アスペクト比は、５０〜２００，０００であることが好ましい。この範囲にあることにより、「多湿下に於ける銀イオンの抑制」というメカニズムによって、耐マイグレーション性を改善できるものと考えられる。特に好ましい直径は０．７〜２．０ｎｍであり、長さは０．１〜５０μｍであり、また、アスペクト比は、５０〜７０，０００である。 The carbon nanotubes preferably have a diameter of 0.5 to 200 nm and a length of 0.1 to 100 μm. The aspect ratio is preferably 50 to 200,000. By being in this range, it is considered that the migration resistance can be improved by the mechanism of “suppression of silver ions under high humidity”. A particularly preferable diameter is 0.7 to 2.0 nm, a length is 0.1 to 50 μm, and an aspect ratio is 50 to 70,000.
カーボンナノチューブの含有量は、耐マイグレーション性を向上するのに十分な量でなければならない。具体的には組成物全体に対して０．０１〜５重量％が好ましく、更には０．０５〜２重量％が好ましい。０．０１重量％よりも少ないと、耐マイグレーション性を向上できないだけでなく充分な低抵抗率が得られず、一方、５重量％よりも多いと著しい組成物粘度の上昇を招き本発明の効果を得ることができない。 The content of carbon nanotubes must be sufficient to improve migration resistance. Specifically, it is preferably 0.01 to 5% by weight, more preferably 0.05 to 2% by weight, based on the entire composition. If the amount is less than 0.01% by weight, not only the migration resistance cannot be improved, but also a sufficiently low resistivity cannot be obtained. On the other hand, if the amount exceeds 5% by weight, the viscosity of the composition is significantly increased and the effect of the present invention is achieved. Can't get.
更に、本発明の導電性樹脂ペースト組成物には、必要に応じて硬化促進剤を添加することができる。硬化促進剤としては、有機ボロン塩、三級アミン類及びその塩、イミダゾール類、アセチルアセトン金属塩などが挙げられる。硬化促進剤は単独でもよく、複数種の硬化促進剤を適宜組み合わせて用いてもよい。これらを用いる場合、その量は熱硬化性樹脂に対して０．１〜２０重量％が好ましく、１〜１０重量部がより好ましい。 Furthermore, a curing accelerator can be added to the conductive resin paste composition of the present invention as necessary. Examples of the curing accelerator include organic boron salts, tertiary amines and salts thereof, imidazoles, and acetylacetone metal salts. A hardening accelerator may be individual and may use it in combination of multiple types of hardening accelerator suitably. When using these, the amount is preferably from 0.1 to 20% by weight, more preferably from 1 to 10 parts by weight, based on the thermosetting resin.
（Ｃ）希釈剤
本発明の導電性樹脂ペースト組成物には、必要に応じて希釈剤を添加することができる。
(C) Diluent A diluent can be added to the conductive resin paste composition of the present invention as necessary.
希釈剤としては、ブチルセロソルブ、カルビトール、酢酸ブチルセロソルブ、酢酸カルビトール、エチレングリコールジエチルエーテル、ターピネオールなどの比較的沸点の高い有機溶剤；１分子中に１〜２個のエポキシ基を有する反応性希釈剤が挙げられる。ペースト組成物の作製時の作業性、及び使用時の塗布性をより良好するため、これらは導電性樹脂ペースト組成物中に１重量％以上配合することが好ましく、３〜２０重量％配合することがより好ましい。 Diluents include organic solvents having a relatively high boiling point such as butyl cellosolve, carbitol, butyl cellosolve, carbitol acetate, ethylene glycol diethyl ether, terpineol; reactive diluents having 1 to 2 epoxy groups in one molecule Is mentioned. In order to improve the workability at the time of preparation of the paste composition and the applicability at the time of use, these are preferably blended in an amount of 1% by weight or more in the conductive resin paste composition, and blended in an amount of 3 to 20% by weight. Is more preferable.
更に、本発明の導電性樹脂ペースト組成物には、必要に応じてシランカップリング剤、チタンカップリング剤等の接着性向上剤、ノニオン系界面活性剤、フッ素系界面活性剤等の濡れ性向上剤、シリコーン油等の消泡剤、無機イオン交換体等のイオントラップ剤などの各種添加剤を適宜添加することができる。 Furthermore, the conductive resin paste composition of the present invention has improved wettability such as adhesion improvers such as silane coupling agents and titanium coupling agents, nonionic surfactants, and fluorosurfactants as necessary. Various additives such as an agent, an antifoaming agent such as silicone oil, and an ion trapping agent such as an inorganic ion exchanger can be appropriately added.
２．導電性樹脂ペースト組成物の製造
本発明の導電性樹脂ペースト組成物は、前記の熱硬化性樹脂（Ａ）、及び導電性フィラー（Ｂ）を用い、必要に応じて希釈剤（Ｃ）、及び硬化促進剤ほか各種添加剤を配合して製造される。
2. Production of conductive resin paste composition The conductive resin paste composition of the present invention uses the thermosetting resin (A) and the conductive filler (B), and if necessary, a diluent (C), and Manufactured by blending various accelerators and other additives.
これら成分を、一括又は分割して攪拌機、らいかい機、３本ロール、プラネタリーミキサー等の分散、溶解装置又はこれらを適宜組み合わせた装置に投入する。各成分を混合するには、比較的低温で均一な組成物が得られるまで攪拌すればよい。 These components are batched or divided and charged into a stirrer, a raking machine, a three-roll, a planetary mixer or other dispersing / dissolving apparatus or an apparatus in which these are appropriately combined. In order to mix the components, stirring may be performed until a uniform composition is obtained at a relatively low temperature.
その後、必要に応じて加熱して混合、溶解、解粒混練又は分散して均一なペースト状とすることができる。ただし、硬化剤、硬化促進剤の種類にもよるが、５０℃を超える温度では液状エポキシ樹脂の硬化反応が進行して固化するので注意が必要である。 Thereafter, the mixture can be heated, if necessary, mixed, dissolved, pulverized, kneaded or dispersed to form a uniform paste. However, depending on the type of curing agent and curing accelerator, care must be taken because the curing reaction of the liquid epoxy resin proceeds and solidifies at temperatures exceeding 50 ° C.
３．半導体装置
本発明においては、上記のようにして製造される導電性樹脂ペースト組成物を接着用樹脂ペースト組成物、すなわちダイボンド材として用いることができる。このダイボンド材によって半導体素子と基板とを接着した後、封止することにより本発明の半導体装置が得られる。
3. Semiconductor Device In the present invention, the conductive resin paste composition produced as described above can be used as an adhesive resin paste composition, that is, a die bond material. The semiconductor device of the present invention is obtained by sealing the semiconductor element and the substrate after bonding them with this die bond material.
本発明の導電性樹脂ペースト組成物を用いて、半導体素子をリードフレーム等の基板と接着させるには、まず、基板上に導電性樹脂ペースト組成物をディスペンス法、スクリーン印刷法、スタンピング法などにより塗布する。 In order to adhere a semiconductor element to a substrate such as a lead frame using the conductive resin paste composition of the present invention, first, the conductive resin paste composition is applied on the substrate by a dispensing method, a screen printing method, a stamping method, or the like. Apply.
次いで、半導体素子を圧着し、その後、オーブン、ヒートブロック等の加熱装置を用いて、例えば１００〜３００℃に加熱硬化する。加熱条件は、硬化剤の種類によっても異なるが、オーブン中に１０〜１８０分間放置して導電性樹脂ペースト組成物を硬化させればよい。１００℃未満、或いは１０分間未満では接着剤の硬化が不十分となり、一方、３００℃を超えるか１８０分間を超えると、樹脂成分が分解する恐れが生じるので好ましくない。
さらに、ワイヤボンド工程を経た後、通常の方法、例えば各種封止剤を用いて半導体素子を封止することにより半導体装置を完成することができる。
Next, the semiconductor element is pressure-bonded, and then heated and cured at, for example, 100 to 300 ° C. using a heating device such as an oven or a heat block. Although heating conditions differ also with the kind of hardening | curing agent, what is necessary is just to leave for 10 to 180 minutes in oven, and to cure the conductive resin paste composition. If the temperature is less than 100 ° C. or less than 10 minutes, curing of the adhesive becomes insufficient. On the other hand, if it exceeds 300 ° C. or exceeds 180 minutes, the resin component may be decomposed, which is not preferable.
Further, after the wire bonding step, the semiconductor device can be completed by sealing the semiconductor element using a normal method, for example, various sealing agents.
以下、本発明を実施例及び比較例によってさらに具体的に説明するが、本発明はこれら実施例によって限定されるものではない。
なお、実施例及び比較例で用いた材料は、下記の方法で作製したもの、あるいは入手したものである。
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited by these Examples.
In addition, the material used by the Example and the comparative example was produced by the following method, or was obtained.
（１）導電性樹脂ペースト組成物の材料
Ｂ１ 銀粉
・銀粉１：フレーク状銀粉 （商品名 シルコートＡｇＣ−２０１１、福田金属箔工業社製）、平均粒径１．８μｍ
・銀粉２：フレーク状銀粉 （商品名 シルコートＡｇＣ−２４１１、福田金属箔工業社製）、平均粒径７．７μｍ
Ｂ２ カーボンナノチューブ
・ＳＣＮＴ（単層カーボンナノチューブ、米国カーボンナノテクノロジーズ社製）、直径０．７〜１．５ｎｍ、長さ０．１〜１００μｍ、アスペクト比７０〜１００，０００。
Ａ 熱硬化性樹脂
１）エポキシ樹脂
・樹脂１：ビスフェノールＦ型エポキシ樹脂（商品名：エピコート８０６、ジャパンエポキシレジン株式会社製）、２０℃の粘度３Ｐａ・ｓ
・樹脂２：ビスフェノールＡ型エポキシ樹脂（商品名：エピコート８２５、ジャパンエポキシレジン株式会社製）、２０℃の粘度７Ｐａ・ｓ
２）エポキシ樹脂用硬化剤
・ＤＩＣＹ（ジシアンジアミド、商品名：ＤＩＣＹ７、ジャパンエポキシレジン社製）
３）レゾール型フェノール樹脂
・樹脂３：（商品名：ＰＬ４３４８、群栄化学工業（株））、２０℃の粘度４Ｐａ・ｓ
Ｃ 有機溶媒
・ＢＣＡ（ブチルカルビトールアセテート、沸点２４５℃）
(1) Material of conductive resin paste composition B1 Silver powder Silver powder 1: Flaky silver powder (trade name SILCOAT AgC-2011, manufactured by Fukuda Metal Foil Industry Co., Ltd.), average particle size 1.8 μm
Silver powder 2: flaky silver powder (trade name SILCOAT AgC-2411, manufactured by Fukuda Metal Foil Industry Co., Ltd.), average particle size 7.7 μm
B2 carbon nanotube SCNT (single-walled carbon nanotube, manufactured by US Carbon Nano Technologies), diameter 0.7 to 1.5 nm, length 0.1 to 100 μm, aspect ratio 70 to 100,000.
A Thermosetting resin 1) Epoxy resin Resin 1: Bisphenol F type epoxy resin (trade name: Epicoat 806, manufactured by Japan Epoxy Resin Co., Ltd.), viscosity at 20 ° C. 3 Pa · s
Resin 2: Bisphenol A type epoxy resin (trade name: Epicoat 825, manufactured by Japan Epoxy Resin Co., Ltd.), viscosity at 20 ° C. 7 Pa · s
2) Curing agent for epoxy resin-DICY (dicyandiamide, trade name: DICY7, manufactured by Japan Epoxy Resin Co., Ltd.)
3) Resol type phenol resin Resin 3: (trade name: PL4348, Gunei Chemical Industry Co., Ltd.), viscosity at 20 ° C. 4 Pa · s
C Organic solvent BCA (Butyl carbitol acetate, boiling point 245 ° C)
（２）作製した導電性樹脂ペースト組成物は、以下の通り評価した。
（ｉ）接着強度
導電性樹脂ペースト組成物を銅板上にスクリーン印刷し、この上に２ｍｍ×２ｍｍのＳｉチップ（厚さ０．４ｍｍ）を圧着し、更に２００℃に設定したオーブンに入れ、約６０分加熱した。常温に戻した後、この試料について自動接着力試験装置（Ｄａｇｅ社、マイクロテスター）を用いて、室温における剪断接着強度（ｋｇ／チップ）を測定した。当該接着強度は、数値が大きいほど好ましい。
(2) The produced conductive resin paste composition was evaluated as follows.
(I) Adhesive strength The conductive resin paste composition was screen-printed on a copper plate, a 2 mm × 2 mm Si chip (thickness 0.4 mm) was pressure-bonded thereon, and further placed in an oven set at 200 ° C. Heated for 60 minutes. After returning to normal temperature, the shear adhesive strength (kg / chip) at room temperature was measured for this sample using an automatic adhesive strength test apparatus (Dage, Micro Tester). The adhesive strength is preferably as the numerical value is larger.
（ｉｉ）シート抵抗値
導電性樹脂ペースト組成物をアルミナ基板上に塗布し、更に２００℃で１時間オーブンに入れて加熱した。常温に戻した後、この試料についてデジタルマルチメーター（岩通電子社製 ＶＯＡＣ−７４１１）を用いて、シート抵抗値を測定した。当該シート抵抗値は、数値が小さいほど好ましい。
(Ii) Sheet resistance value The conductive resin paste composition was applied onto an alumina substrate, and further heated in an oven at 200 ° C for 1 hour. After returning to room temperature, the sheet resistance value of this sample was measured using a digital multimeter (VOAC-7411 manufactured by Iwatatsu Electronics Co., Ltd.). The sheet resistance value is more preferable as the numerical value is smaller.
（ｉｉｉ）耐マイグレ−ション性
ウォータードロップ法で耐マイグレーション性を評価した。導電性樹脂ペースト組成物をよく洗浄したアルミナ基板上にスクリーン印刷し、更に２００℃で１時間、オーブン中で加熱した。常温に戻した後、この電極間上に純水で湿らせたろ紙を置き、１０Ｖを印加した。印加中、ろ紙が乾かないように純水を随時ろ紙に滴下し、電極間に１００ｍＡ流れるまでの時間を測定した。この時間が長いほど耐マイグレーション性は良好である。
(Iii) Migration resistance Migration resistance was evaluated by the water drop method. The conductive resin paste composition was screen printed on a well-washed alumina substrate and further heated in an oven at 200 ° C. for 1 hour. After returning to normal temperature, a filter paper moistened with pure water was placed between the electrodes, and 10 V was applied. During the application, pure water was dropped onto the filter paper as needed so that the filter paper did not dry, and the time until 100 mA flowed between the electrodes was measured. The longer this time, the better the migration resistance.
（実施例１〜１２）
銀、カーボンナノチューブ及び熱硬化性樹脂を含む各材料を表１〜２に示す配合割合で計量した後、三本ロールミルで混合混練し、得られた組成物を６６６．６１Ｐａ（５トール（Ｔｏｒｒ））以下で１０分間脱泡処理を行い、本発明の導電性樹脂ペースト組成物を得た。この樹脂ペースト組成物の特性（接着強度、シート抵抗及び耐マイグレーション性）を前記の方法で測定した。結果を表１〜２に示す。
尚、本実施例における銀粉のアスペクト比の具体的測定法を以下に示す。低粘度のエポキシ樹脂（ビューラー社）の主剤（Ｎｏ．１０−８１３０）８ｇと、硬化剤（Ｎｏ．１０−８１３２）２ｇを混合し、ここへ銀粉２ｇを混合して良く分散させ、そのまま３０℃で真空脱泡した後、１０時間３０℃で静置して粒子を沈降させ硬化させた。その後、得られた硬化物を垂直方向に切断し、切断面を電子顕微鏡で１０００倍に拡大して切断面に現れた１５０個の粒子について長径／短径を求め、それらの平均値をもって、アスペクト比とした。
(Examples 1-12)
Each material containing silver, carbon nanotubes, and thermosetting resin was weighed at the blending ratios shown in Tables 1-2, and then mixed and kneaded by a three-roll mill. The resulting composition was 666.61 Pa (5 Torr). ) Defoaming treatment was performed for 10 minutes below to obtain a conductive resin paste composition of the present invention. The properties (adhesive strength, sheet resistance, and migration resistance) of this resin paste composition were measured by the methods described above. The results are shown in Tables 1-2.
In addition, the specific measuring method of the aspect-ratio of the silver powder in a present Example is shown below. 8 g of the main agent (No. 10-8130) of a low-viscosity epoxy resin (Buhler) and 2 g of a curing agent (No. 10-8132) are mixed, and 2 g of silver powder is mixed and well dispersed therein, and is kept at 30 ° C. After vacuum defoaming, the particles were allowed to stand at 30 ° C. for 10 hours to precipitate and harden the particles. Thereafter, the obtained cured product was cut in the vertical direction, the cut surface was magnified 1000 times with an electron microscope, and the major axis / minor axis were obtained for 150 particles appearing on the cut surface. Ratio.
（比較例１〜３）
銀、及び熱硬化性樹脂を配合し、カーボンナノチューブを配合しなかった以外は実施例と同様にして、比較用の導電性樹脂ペースト組成物を得た。この樹脂ペースト組成物の特性（接着強度、シート抵抗及び耐マイグレーション性）を前記の方法で測定した。結果を表３に示す。
(Comparative Examples 1-3)
A comparative conductive resin paste composition was obtained in the same manner as in Example except that silver and a thermosetting resin were blended and no carbon nanotube was blended. The properties (adhesive strength, sheet resistance, and migration resistance) of this resin paste composition were measured by the methods described above. The results are shown in Table 3.
（参考例１、２）
カーボンナノチューブの配合量を変えた以外は実施例と同様にして、導電性樹脂ペースト組成物を得た。この樹脂ペースト組成物の特性（接着強度、シート抵抗及び耐マイグレーション性）を前記の方法で測定した。結果を表３に示す。
(Reference Examples 1 and 2)
Except having changed the compounding quantity of the carbon nanotube, it carried out similarly to the Example, and obtained the conductive resin paste composition. The properties (adhesive strength, sheet resistance, and migration resistance) of this resin paste composition were measured by the methods described above. The results are shown in Table 3.
表１〜３に示した結果から、銀粉およびカーボンナノチューブを含む本発明の導電性樹脂ペースト組成物を用いた場合は、抵抗値や接着強度に問題を与えることなく、耐マイグレーション性が著しく向上することが確認された。これに対して、カーボンナノチューブを含まない比較例の導電性樹脂ペースト組成物を用いた場合は、抵抗値や接着強度に問題を与えることはないものの、耐マイグレーション性が著しく低下することが確認された。 From the results shown in Tables 1 to 3, when the conductive resin paste composition of the present invention containing silver powder and carbon nanotubes is used, the migration resistance is remarkably improved without causing a problem in the resistance value and the adhesive strength. It was confirmed. On the other hand, when the conductive resin paste composition of the comparative example not containing carbon nanotubes was used, it was confirmed that the resistance to migration and the adhesion strength were not adversely affected, but the migration resistance was significantly reduced. It was.
Claims (6)
導電性フィラー（Ｂ）が、銀粉（Ｂ１）に加えて、耐マイグレーション性を向上させるに十分な量のカーボンナノチューブ（Ｂ２）を含有することを特徴とする導電性樹脂ペースト組成物。 In the conductive resin paste composition containing at least the thermosetting resin (A) and the conductive filler (B),
The conductive resin paste composition, wherein the conductive filler (B) contains a sufficient amount of carbon nanotubes (B2) to improve migration resistance in addition to the silver powder (B1).
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