JP2010209266A - Liquid epoxy resin composition for sealing semiconductor, and flip-chip semiconductor device sealed with the same as underfill material - Google Patents
Liquid epoxy resin composition for sealing semiconductor, and flip-chip semiconductor device sealed with the same as underfill material Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—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
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
- H01L2224/161—Disposition
- H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—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
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
- H01L2224/321—Disposition
- H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73201—Location after the connecting process on the same surface
- H01L2224/73203—Bump and layer connectors
- H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
Abstract
Description
本発明は、フリップチップ実装の半導体装置の封止に際し、基板、素子等の間の隙間侵入性と硬化後のチップクラック防止性に優れた半導体封止用液状エポキシ樹脂組成物、及びそれをアンダーフィル材として用いて封止したフリップチップ型半導体装置に関するものである。 The present invention relates to a liquid epoxy resin composition for semiconductor encapsulation, which has excellent penetration into gaps between substrates, elements and the like and prevention of chip cracks after curing when encapsulating a flip-chip mounted semiconductor device, and an undercoat thereof. The present invention relates to a flip chip type semiconductor device that is sealed by using as a filling material.
近年の電気機器の小型化、軽量化、高性能化に伴い、プリント配線板上への電子部品の実装密度向上が要求されてきており、半導体の実装形態はピン挿入タイプからＱＦＰ（Ｑｕａｄ Ｆｌａｔ Ｐａｃｋａｇｅ）、ＳＯＰ（Ｓｍａｌｌ Ｏｕｔｌｉｎｅ Ｐａｃｋａｇｅ）のような表面実装（パッケージＩＣ）、そしてベアチップ実装へと変遷してきている。更に、ベアチップ実装の中でも一番実装密度の向上が見込まれるフリップチップ（Ｆｌｉｐ Ｃｈｉｐ：ＦＣ）実装が注目されている。
ＦＣ実装とは、ＩＣチップの電極に高さ１０〜１００μｍ程度のバンプといわれる半田等で形成される突起を数個から数千個形成し、このバンプを介してＩＣチップの電極と基板の電極を一括接続（ギャングボンディング）させる実装方法で、実装後にアンダーフィル材をＩＣチップと基板の間に流し込んで硬化させることによって完成となる（図２）。
特に、ＦＣ実装技術を使用しながらチップをスタックするＣｏＣ（Ｃｈｉｐ ｏｎ Ｃｈｉｐ）構造を有するＭＣＰ（Ｍｕｌｔｉ−Ｃｈｉｐ Ｐａｃｋａｇｅ）では、一般的に下のチップ周辺上より、信号を伝達するためのリード線が基板に向けて張り出されており、このリード線を固定するパッドがチップ上の周辺に設置されると共に、当該チップは軽薄短小が要求される部位に設置されるため、バンプの高さを１０μｍ程度もの狭間隙に設定する必要があり、この狭間隙にアンダーフィル材を流し込んで硬化させなければならない。
従来、このようなアンダーフィル材としては、エポキシ樹脂、硬化剤及び無機充填材からなる液状エポキシ樹脂組成物が使用されている。また、ＦＣ実装の信頼性を高めるために、このようなアンダーフィル材に、多量（例えば４０質量％以上）の無機充填材配合し、半導体チップ、基板及びバンプ等とこのアンダーフィル材の硬化物の線膨張係数を一致させる試みがなされている。
しかし、従来の無機充填材は、上記ＣｏＣ構造を有する狭間隙に対して、粒子径が大きすぎたり、また、その配合量とアンダーフィル材の流動性やその硬化後の線膨張係数とのバランスが取れていないという問題があった。
即ち、フリップチップ実装の半導体装置の封止に際し、基板、素子等の間の隙間侵入性と硬化後のチップクラック防止性の両方をバランス良く併せ持つ半導体封止用液状エポキシ樹脂組成物が存在していなかった。
なお、本発明に関連する先行技術文献としては、下記のものが挙げられる。
With the recent reduction in size, weight, and performance of electrical devices, it has been required to improve the mounting density of electronic components on a printed wiring board. The semiconductor mounting form is changed from a pin insertion type to a QFP (Quad Flat Package). ), Surface mount (package IC) such as SOP (Small Outline Package), and bare chip mounting. Further, flip chip (FC) mounting, which is expected to have the highest mounting density among bare chip mounting, is attracting attention.
The FC mounting means that several to several thousands of protrusions formed of solder or the like called bumps having a height of about 10 to 100 μm are formed on the electrodes of the IC chip, and the electrodes of the IC chip and the electrodes of the substrate through the bumps. In this mounting method, the underfill material is poured between the IC chip and the substrate and cured after mounting (FIG. 2).
In particular, in an MCP (Multi-Chip Package) having a CoC (Chip on Chip) structure in which chips are stacked while using FC mounting technology, a lead wire for transmitting a signal is generally provided from the lower chip periphery. It is projected toward the substrate, and pads for fixing the lead wires are installed on the periphery of the chip, and the chip is installed in a portion where lightness, thinness and smallness are required, so the bump height is 10 μm. It is necessary to set a narrow gap of a certain degree, and an underfill material must be poured into the narrow gap and cured.
Conventionally, as such an underfill material, a liquid epoxy resin composition comprising an epoxy resin, a curing agent and an inorganic filler has been used. In addition, in order to increase the reliability of FC mounting, a large amount (for example, 40% by mass or more) of an inorganic filler is added to such an underfill material, and a semiconductor chip, a substrate, a bump, and the like, and a cured product of this underfill material Attempts have been made to match the linear expansion coefficients of these.
However, the conventional inorganic filler has a particle size that is too large for the narrow gap having the above CoC structure, and the balance between the blending amount and the fluidity of the underfill material and the linear expansion coefficient after curing. There was a problem that was not removed.
That is, when sealing a flip-chip mounted semiconductor device, there exists a liquid epoxy resin composition for semiconductor sealing that has a good balance of both the gap penetration between substrates and elements and the prevention of chip cracks after curing. There wasn't.
In addition, the following are mentioned as prior art documents relevant to the present invention.
本発明は、上記事情に鑑みなされたもので、フリップチップ実装の半導体装置の封止に際し、基板、素子等の間の隙間侵入性と硬化後のチップクラック防止性に優れた半導体封止用液状エポキシ樹脂組成物、及びそれをアンダーフィル材として用いて封止したフリップチップ型半導体装置を提供することを目的とする。 The present invention has been made in view of the above circumstances. When sealing a flip-chip mounted semiconductor device, the present invention provides a liquid for semiconductor sealing that is excellent in gap penetration between substrates, elements, etc. and chip crack prevention after curing. An object of the present invention is to provide an epoxy resin composition and a flip chip type semiconductor device sealed using the epoxy resin composition as an underfill material.
本発明者は、上記目的を達成するため、鋭意検討を行なった結果、（Ａ）液状エポキシ樹脂、（Ｂ）特定のシリコーン変性フェノール硬化剤：（Ａ）成分中のエポキシ基に対するフェノール性水酸基の比が０．８〜１．１となる量、（Ｃ）平均粒子径が０．１〜１．０μｍである無機充填材：（Ａ）、（Ｂ）及び（Ｃ）成分の合計質量に対して１０〜４０質量％となる量を含有することを特徴とする半導体封止用液状エポキシ樹脂組成物、及び該エポキシ樹脂組成物をアンダーフィル材として用いて封止したフリップチップ型半導体装置が有用であることを見出し、本発明をなすに至った。
つまり、この組成物は、（Ｃ）成分の無機充填材の平均粒子径を適切な範囲にすると共に、その配合量を適切な範囲に抑えることによって、該組成物の流動性を確保し、さらにその硬化後の線膨張係数を低下させるために、（Ｂ）成分の特定のシリコーン変性フェノール硬化剤を用いて低弾性化することによって、フリップチップ実装の半導体装置の封止に際し、基板、素子等の間の隙間侵入性と硬化後のチップクラック防止性の両方をバランス良く併せ持つようにしたものである。
As a result of intensive studies to achieve the above object, the present inventor (A) liquid epoxy resin, (B) specific silicone-modified phenol curing agent: (A) the phenolic hydroxyl group relative to the epoxy group in the component. The amount that the ratio is 0.8 to 1.1, (C) the inorganic filler having an average particle diameter of 0.1 to 1.0 μm: with respect to the total mass of the components (A), (B), and (C) A liquid epoxy resin composition for semiconductor encapsulation characterized by containing an amount of 10 to 40% by mass, and a flip chip semiconductor device encapsulated using the epoxy resin composition as an underfill material are useful As a result, the present invention has been made.
That is, this composition ensures the fluidity of the composition by keeping the average particle diameter of the inorganic filler of the component (C) in an appropriate range and suppressing the blending amount in an appropriate range. In order to reduce the linear expansion coefficient after the curing, by using a specific silicone-modified phenol curing agent of the component (B), the elasticity is lowered, so that a substrate, an element, etc. can be used when sealing a flip-chip mounted semiconductor device. Both the interstitial space penetration property and the chip crack prevention property after curing are combined in a well-balanced manner.
即ち、本発明は、下記半導体封止用液状エポキシ樹脂組成物、及びそれをアンダーフィル材として用いて封止したフリップチップ型半導体装置を提供する。
請求項１：
（Ａ）液状エポキシ樹脂、
（Ｂ）下記式（１）で示されるシリコーン変性フェノール硬化剤：（Ａ）成分中のエポキシ基に対するフェノール性水酸基の比が０．８〜１．１となる量、
（Ｃ）平均粒子径が０．１〜１．０μｍである無機充填材：（Ａ）、（Ｂ）及び（Ｃ）成分の合計質量に対して１０〜４０質量％となる量
を含有することを特徴とする半導体封止用液状エポキシ樹脂組成物。
請求項１記載のエポキシ樹脂組成物をアンダーフィル材として用いて封止したフリップチップ型半導体装置。
That is, this invention provides the following liquid epoxy resin composition for semiconductor sealing, and the flip chip type semiconductor device sealed using it as an underfill material.
Claim 1:
(A) Liquid epoxy resin,
(B) A silicone-modified phenol curing agent represented by the following formula (1): an amount in which the ratio of the phenolic hydroxyl group to the epoxy group in the component (A) is 0.8 to 1.1,
(C) Inorganic filler having an average particle diameter of 0.1 to 1.0 μm: containing an amount of 10 to 40% by mass with respect to the total mass of the components (A), (B) and (C). A liquid epoxy resin composition for semiconductor encapsulation characterized by the above.
A flip chip type semiconductor device sealed using the epoxy resin composition according to
本発明によれば、フリップチップ実装の半導体装置の封止に際し、基板、素子等の間の隙間侵入性と硬化後のチップクラック防止性に優れた半導体封止用液状エポキシ樹脂組成物、及びそれをアンダーフィル材として用いて封止したフリップチップ型半導体装置を提供することができる。 According to the present invention, a liquid epoxy resin composition for encapsulating a semiconductor excellent in gap penetration between a substrate, an element and the like and prevention of chip crack after curing when encapsulating a flip-chip mounted semiconductor device, and the same It is possible to provide a flip-chip type semiconductor device sealed by using as an underfill material.
以下、本発明についてより詳細に説明する。
本発明の液状エポキシ樹脂組成物は、エポキシ樹脂、硬化剤、無機充填材を必須成分として含有している。
（Ａ）液状エポキシ樹脂
エポキシ樹脂としては、一分子あたり２個以上のエポキシ基を持ち、常温で液状のものであればよく、従来から公知のものを全て使用することができる。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ＡＤ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ナフタレン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、脂環式エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂等を挙げることができる。
Hereinafter, the present invention will be described in more detail.
The liquid epoxy resin composition of the present invention contains an epoxy resin, a curing agent, and an inorganic filler as essential components.
(A) Liquid epoxy resin The epoxy resin may be any epoxy resin that has two or more epoxy groups per molecule and is liquid at room temperature, and any conventionally known one can be used. For example, bisphenol A type epoxy resin, bisphenol AD type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, biphenyl type epoxy resin, glycidylamine type epoxy resin, alicyclic epoxy resin, dicyclo A pentadiene type epoxy resin etc. can be mentioned.
特に、耐熱性や耐湿性に優れるビスフェノールＡ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、シクロペンタジエン型エポキシ樹脂が好ましい。この中でも室温（２０〜３０℃）で液状のエポキシ樹脂が好ましい。 In particular, bisphenol A type epoxy resin, bisphenol AD type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, cyclohexane, which are excellent in heat resistance and moisture resistance A pentadiene type epoxy resin is preferred. Among these, a liquid epoxy resin is preferable at room temperature (20 to 30 ° C.).
また、下記構造のエポキシ樹脂も使用することができる。
また、エポキシ樹脂には、その合成過程で使用するエピクロルヒドリン由来の塩素が少量含まれるが、エポキシ樹脂における全塩素含有量は、１５００ｐｐｍ以下、好ましくは１０００ｐｐｍ以下である必要がある。特に、１００℃で５０％エポキシ樹脂濃度における２０時間での抽出水塩素が１０ｐｐｍ以下であることが好ましい。全塩素含有量が１５００ｐｐｍ以上、抽出塩素が１０ｐｐｍ以上では半導体素子の信頼性、特に耐湿性に悪影響を与える。
以上述べたエポキシ樹脂は、１種単独で又は２種以上組み合わせて使用することができる。
The epoxy resin contains a small amount of epichlorohydrin-derived chlorine used in the synthesis process, but the total chlorine content in the epoxy resin needs to be 1500 ppm or less, preferably 1000 ppm or less. In particular, the extracted water chlorine in 20 hours at 100 ° C. and 50% epoxy resin concentration is preferably 10 ppm or less. If the total chlorine content is 1500 ppm or more and the extracted chlorine is 10 ppm or more, the reliability of the semiconductor element, particularly moisture resistance, is adversely affected.
The epoxy resins described above can be used singly or in combination of two or more.
（Ｂ）シリコーン変性フェノール硬化剤
シリコーン変性フェノール硬化剤は、下記式（１）で示されるもので、両末端にＳｉ−Ｈ結合を有する下記式（５）のシリコーンに下記式（４）のジアリル化ビスフェノールを付加反応させて生成される。
このようなシリコーン変性フェノール硬化剤は、上記式（１）のｍの値によって粘度が異なるが、そのようなものを１種単独で又は２種以上を混合して使用することができる。
エポキシ樹脂組成物は、室温における適度な流動性が必要であり、このシリコーン変性フェノール硬化剤は、常温（２０〜３０℃）において液状であるものを使用することが好ましく、常温において固形のものを使用する場合は、常温において液状のものに溶解し、当該硬化剤全体で液状のものとするのが好ましい。
よって、シリコーン鎖長もｍの値が１０を超えると、高粘度化するため、１〜１０の整数と限定される。
Such silicone-modified phenolic curing agents have different viscosities depending on the value of m in the above formula (1), but such ones can be used alone or in admixture of two or more.
The epoxy resin composition needs moderate fluidity at room temperature, and it is preferable to use a silicone-modified phenol curing agent that is liquid at room temperature (20 to 30 ° C.). When used, it is preferable to dissolve in a liquid at room temperature and to make the entire curing agent liquid.
Accordingly, when the value of m exceeds 10, the silicone chain length is limited to an integer of 1 to 10 in order to increase the viscosity.
このような上記式（１）で示される（Ｂ）成分の配合は、（Ａ）成分中のエポキシ基に対する（Ｂ）成分のフェノール性水酸基の比が０．８〜１．１となる量が好ましく、より好ましくは０．８５〜０．９５となる量である。０．８未満であると、弾性率が大きくなり内部応力を吸収できずＳｉのクラック等が発生することがあり、１．１を超えると、未反応ＯＨ基が残存し、樹脂骨格が脆くなるため好ましくない。 The blending of the component (B) represented by the above formula (1) is such that the ratio of the phenolic hydroxyl group of the component (B) to the epoxy group in the component (A) is 0.8 to 1.1. The amount is preferably 0.85 to 0.95. If it is less than 0.8, the elastic modulus becomes large and internal stress cannot be absorbed and cracks of Si may occur. If it exceeds 1.1, unreacted OH groups remain and the resin skeleton becomes brittle. Therefore, it is not preferable.
（Ｃ）無機充填材
無機充填材は、球状シリカを用いる。
この球状シリカの平均粒子径は、遠心沈降法やレーザー回折法等で測定可能であり、０．１〜１．０μｍ、より好ましくは０．３〜０．８μｍにコントロールすることが必要である。平均粒子径が０．１μｍ未満であると無機充填材の表面積が増大し、組成物の流動性が低下し、平均粒子径が１．０μｍを超えると１０μｍ程度の狭間隙のフリップチップ対する侵入性が低下するため好ましくない。
つまり、アンダーフィル材は毛細管現象を利用して半導体装置の狭間隙に注入されるが、狭間隙中の流動性及び無機充填材の沈降を防止するため、無機充填材は、最大粒子径が該狭間隙寸法に対し１／２以下で、且つ平均粒子径は１／１０以下に設計される。この寸法を超えると上述の通り、組成物の流動性を低下させることによるボイドが発生したり、無機充填材沈降により半導体チップ界面付近で充填材の少ない層が形成され、その部分の熱膨張率が大きいことによる信頼性の低下といった問題を生じる。従って、球状シリカの平均粒子径は上記の通り０．１〜１．０μｍ、好ましくは０．３〜０．８μｍであることが好適である。
(C) Inorganic filler As the inorganic filler, spherical silica is used.
The average particle diameter of the spherical silica can be measured by a centrifugal sedimentation method, a laser diffraction method, or the like, and needs to be controlled to 0.1 to 1.0 μm, more preferably 0.3 to 0.8 μm. When the average particle size is less than 0.1 μm, the surface area of the inorganic filler increases and the fluidity of the composition decreases, and when the average particle size exceeds 1.0 μm, the penetration into narrow gap flip chips of about 10 μm. Is unfavorable because of lowering.
In other words, the underfill material is injected into the narrow gap of the semiconductor device using the capillary phenomenon, but in order to prevent fluidity in the narrow gap and settling of the inorganic filler, the inorganic filler has a maximum particle size of It is designed to be ½ or less of the narrow gap size and the average particle size is 1/10 or less. If this dimension is exceeded, voids are generated by reducing the fluidity of the composition as described above, or a layer with less filler is formed near the semiconductor chip interface due to inorganic filler sedimentation, and the coefficient of thermal expansion of that part This causes a problem such as a decrease in reliability due to a large value. Therefore, the average particle diameter of the spherical silica is 0.1 to 1.0 μm, preferably 0.3 to 0.8 μm as described above.
また、無機充填材の含有量は、（Ａ）、（Ｂ）及び（Ｃ）成分の合計質量に対して１０〜４０質量％が好ましく、より好ましくは１５〜３０質量部である。１０質量％未満では、膨張係数が大きくなり、冷熱テストにおいてクラックの発生を誘発させ、４０質量％超過では、粘度が高くなり過ぎ、アンダーフィル材としての流動性が低下するため薄膜侵入性の低下をもたらすため好ましくない。 Moreover, 10-40 mass% is preferable with respect to the total mass of (A), (B) and (C) component, and, as for content of an inorganic filler, More preferably, it is 15-30 mass parts. If it is less than 10% by mass, the expansion coefficient becomes large, and cracks are induced in the cold test, and if it exceeds 40% by mass, the viscosity becomes too high and the fluidity as the underfill material decreases, so that the thin film penetration is reduced. This is not preferable.
無機充填材と上記（Ａ）及び（Ｂ）成分等の樹脂との結合強度を強くするため、無機充填材は、シランカップリング剤、チタネートカップリング剤等のカップリング剤で予め表面処理したものを配合することが好ましい。
このようなカップリング剤としては、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン等のエポキシシラン、Ｎ−β（アミノエチル）−γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ−フェニル−γ−アミノプロピルトリメトキシシラン等のアミノシラン、γ−メルカプトシラン等のメルカプトシランを用いることが好ましい。
ここで、表面処理に用いるカップリング剤の配合量及び表面処理方法については、特に制限されるものではない。
In order to strengthen the bond strength between the inorganic filler and the resin such as the above components (A) and (B), the inorganic filler is previously surface-treated with a coupling agent such as a silane coupling agent or a titanate coupling agent. Is preferably blended.
As such a coupling agent, epoxy silane such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N Use of aminosilanes such as -β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and mercaptosilanes such as γ-mercaptosilane. preferable.
Here, the blending amount of the coupling agent used for the surface treatment and the surface treatment method are not particularly limited.
（Ｄ）その他の添加剤
液状エポキシ樹脂組成物には、（Ａ）及び（Ｂ）成分の硬化反応を促進する硬化促進剤を配合することができる。
硬化促進剤としては、２−メチルイミダゾール、２−エチル−４−メチルイミダゾール、１−シアノエチル−２−メチルイミダゾール、２−フェニル−４，５−ジヒドロキシメチルイミダゾール等のイミダゾール誘導体やトリフェニルフォスフィン等のリン系促進剤をそのまま配合することができるが、組成物の高流動性を維持し、所定の温度で上記硬化反応を促進させることができるよう潜在性を付与させることが好ましく、そのため上記硬化促進剤を（メタ）アクリル系単量体等を用いて重合させたポリマーでマイクロカプセル化したマイクロカプセル型硬化促進剤を配合するのが好ましい。
硬化促進剤の配合量は、（Ａ）及び（Ｂ）成分の合計１００質量部に対して、１〜１０質量部、特に２〜５質量部の範囲で添加することが好適である。添加量が１質量部に満たないと反応性が促進されないことがあり、１０質量部を超えると硬化性に優れるが保存性が低下することがあるため好ましくない。
(D) Other additives The liquid epoxy resin composition may contain a curing accelerator that accelerates the curing reaction of the components (A) and (B).
Examples of the curing accelerator include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, imidazole derivatives such as 2-phenyl-4,5-dihydroxymethylimidazole, and triphenylphosphine. However, it is preferable to impart a latent potential so that the high fluidity of the composition can be maintained and the curing reaction can be promoted at a predetermined temperature. It is preferable to blend a microcapsule type curing accelerator in which the accelerator is microencapsulated with a polymer obtained by polymerizing the accelerator using a (meth) acrylic monomer or the like.
The blending amount of the curing accelerator is preferably added in the range of 1 to 10 parts by mass, particularly 2 to 5 parts by mass with respect to 100 parts by mass in total of the components (A) and (B). If the addition amount is less than 1 part by mass, the reactivity may not be promoted, and if it exceeds 10 parts by mass, the curability is excellent but the storage stability may be deteriorated.
また、液状エポキシ樹脂組成物には、その硬化物の応力を低下させる目的で、シリコーンゴム、シリコーンオイル、液状のポリブタジエンゴム等を配合することができる。 Moreover, silicone rubber, silicone oil, liquid polybutadiene rubber, etc. can be mix | blended with a liquid epoxy resin composition in order to reduce the stress of the hardened | cured material.
更に、液状エポキシ樹脂組成物には、必要に応じて、表面処理剤、接着性向上用のシランカップリング剤、カーボンブラック等の顔料、染料、酸化防止剤等を配合することができる。
例えば、表面処理剤としては、ヘキサメチルジシラザン、テトラエトキシシラン等が挙げられ、その配合によって、無機充填材の表面を疎水化処理し樹脂成分との濡れ性向上に効果を発揮させることができる。
Furthermore, the liquid epoxy resin composition may contain a surface treatment agent, a silane coupling agent for improving adhesion, a pigment such as carbon black, a dye, an antioxidant, and the like, if necessary.
For example, examples of the surface treatment agent include hexamethyldisilazane, tetraethoxysilane, and the like, and by blending the surface treatment agent, the surface of the inorganic filler can be hydrophobized to improve the wettability with the resin component. .
液状エポキシ樹脂組成物の調製
液状エポキシ樹脂組成物の調製は、特に限定されるものではなく、従来から公知の方法を用いることできる。
即ち、上記液状エポキシ樹脂、硬化剤、無機充填材及びその他添加剤を、同時に又は別々に、必要により加熱処理を加えながら、攪拌、溶解、混合又は分散させればよい。
上記攪拌等に用いる装置は、特に限定されないが、攪拌及び加熱装置を備えたライカイ機、３本ロール、ボールミル、プラネタリーミキサー等を用いることができる。これらの装置を適宜組み合わせてもよい。
Preparation of liquid epoxy resin composition The preparation of the liquid epoxy resin composition is not particularly limited, and conventionally known methods can be used.
That is, the liquid epoxy resin, the curing agent, the inorganic filler, and other additives may be stirred, dissolved, mixed, or dispersed simultaneously or separately while heating as necessary.
Although the apparatus used for the said stirring etc. is not specifically limited, A raikai machine provided with stirring and a heating apparatus, 3 rolls, a ball mill, a planetary mixer etc. can be used. You may combine these apparatuses suitably.
このようにして得られる液状エポキシ樹脂組成物は、該組成物の流動性が高く、その硬化後の引張弾性率が低くなる（従来：３０００〜５０００ＭＰａ、本発明：３００〜５００ＭＰａ）ので、フリップチップ実装の半導体装置の封止に際し、基板、素子等の間の隙間侵入性と硬化後のチップクラック防止性の両方をバランス良く併せ持つものである。 The liquid epoxy resin composition thus obtained has a high fluidity and a low tensile elastic modulus after curing (conventional: 3000 to 5000 MPa, the present invention: 300 to 500 MPa). When sealing a mounted semiconductor device, it has both a gap penetration between a substrate and an element and a chip crack prevention after curing in a well-balanced manner.
以下、実施例及び比較例に基づき、本発明を具体的に説明するが、本発明は下記実施例に制限されるものではない。なお、実施例及び比較例中の粘度は２５℃における粘度を示す。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example and a comparative example, this invention is not restrict | limited to the following Example. In addition, the viscosity in an Example and a comparative example shows the viscosity in 25 degreeC.
［実施例１〜２、比較例１〜４］
液状エポキシ樹脂、硬化剤、無機充填材及びその他添加剤を、表１に基づき配合し均一に混練することにより、各種エポキシ樹脂組成物を得た。このようにして得られた各種エポキシ樹脂組成物を用いて各種評価を行った。得られた結果は表１に併記する。
使用した材料及び評価方法を以下に示す。
[Examples 1-2, Comparative Examples 1-4]
Various epoxy resin compositions were obtained by blending a liquid epoxy resin, a curing agent, an inorganic filler and other additives based on Table 1 and kneading them uniformly. Various evaluations were performed using the various epoxy resin compositions thus obtained. The results obtained are also shown in Table 1.
The materials and evaluation methods used are shown below.
［使用した材料］
（Ａ）液状エポキシ樹脂
エポキシ樹脂ａ：ビスフェノール型エポキシ樹脂（東都化成（株）製、ＺＸ−１０５９）
エポキシ樹脂ｂ：ナフタレン型エポキシ樹脂（大日本インキ工業（株）製、ＨＰ−４０３２Ｄ）
エポキシ樹脂ｃ：前述式（２）で示される３官能型エポキシ樹脂（ジャパンエポキシレジン（株）製、エピコート６３０ＬＳＤ）
（Ｂ）硬化剤
硬化剤ａ：シリコーン変性フェノール硬化剤 上記式（１）で、ｍ＝９
硬化剤ｂ：ジアリルビスフェノール（小西化学製：ＤＡＬ−ＢＰＡ）
硬化剤ｃ：メチルテトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸の混合物（新日本理化（株）製、ＭＨ−７００）
硬化剤ｄ：ジエチルジアミノジフェニルメタン（日本化薬（株）製、カヤハードＡ−Ａ）
硬化剤ｃ：ジエチルトルエンジアミン（アルベール・コーポレーション（株）製、ＥＴＨＡＣＵＲＥ１００）
（Ｃ）無機充填材
無機充填材ａ：平均粒子径０．６μｍの球状シリカ（（株）アドマテックス製、ＳＥ２０３０−ＳＥＥ）
無機充填材ｂ：平均粒子径７μｍの球状シリカ（（株）龍森製、ＴＳＳ−ＡＨ）
（Ｄ）その他の添加剤
カップリング剤：γ−グリシドキシプロピルトリメトキシシラン（信越化学工業（株）製、ＫＢＭ４０３）
リン系マイクロカプセル硬化促進剤：日本化薬製、ＥＰＣＡＴ−ＰＳ５
イミダゾール系マイクロカプセル硬化促進剤：旭化成ケミカルズ、ノバキュアＨＸ−３７４１）
[Materials used]
(A) Liquid epoxy resin Epoxy resin a: bisphenol type epoxy resin (ZX-1059, manufactured by Tohto Kasei Co., Ltd.)
Epoxy resin b: Naphthalene type epoxy resin (manufactured by Dainippon Ink and Chemicals, HP-4032D)
Epoxy resin c: Trifunctional epoxy resin represented by the above formula (2) (Japan Epoxy Resin Co., Ltd., Epicoat 630LSD)
(B) Curing agent Curing agent a: Silicone-modified phenol curing agent In the above formula (1), m = 9
Curing agent b: diallyl bisphenol (manufactured by Konishi Chemical: DAL-BPA)
Curing agent c: Mixture of methyltetrahydrophthalic anhydride and hexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., MH-700)
Curing agent d: Diethyldiaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., Kayahard AA)
Curing agent c: diethyltoluenediamine (manufactured by Albert Corporation, ETHACURE100)
(C) Inorganic filler Inorganic filler a: spherical silica having an average particle diameter of 0.6 m (SE2030-SEE, manufactured by Admatechs Co., Ltd.)
Inorganic filler b: spherical silica having an average particle diameter of 7 μm (manufactured by Tatsumori Co., Ltd., TSS-AH)
(D) Other additives Coupling agent: γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403)
Phosphorus microcapsule curing accelerator: Nippon Kayaku, EPCAT-PS5
Imidazole-based microcapsule curing accelerator: Asahi Kasei Chemicals, Novacure HX-3741)
［評価方法］
粘度
粘度は、ブルックフィールド社製コーンプレート測定器にてＮｏ．５１のコーンを用い測定した。
侵入時間
侵入時間は、１５μｍギャップ（幅１０ｍｍ）を形成した二枚重ねのガラス板をホットプレートの上に載せ、１２０℃に加熱し、ガラス端部の隙間から侵入させ、その端部から１０ｍｍに到達するまでの時間を測定した。なお、ガラス板は、予め６００℃で１時間焼成し、アセトンで拭き取ったものを使用した。
引張弾性率
引張弾性率は、各種エポキシ樹脂組成物を表１の硬化条件で硬化させたものをＪＩＳ Ｋ ７１６１に基づき測定した。
チップクラックの有無
下記のように簡易デバイスを作製し、その熱衝撃試験によるチップクラックの有無を評価した。
（ｉ）簡易デバイス１の作製
図１に示すように、寸法２０ｍｍ（ｌ）×２０ｍｍ（ｗ）×０．２ｍｍ（ｔ）のＳｉ板２をその鏡面を上にして、その上に一対の寸法３０ｍｍ（ｌ）×５ｍｍ（ｗ）×７０μｍ（ｔ）の両面テープ（日東製）４を１０ｍｍの間隔で設置し、更にその上に寸法１０ｍｍ（ｌ）×１０ｍｍ（ｗ）×０．２ｍｍ（ｔ）のＳｉ板３をその鏡面を上にして重ね合わせて、７０μｍ（ｈ）×１０ｍｍ（ｗ）の隙間を有する構造体を作製し、これにその隙間端部から上記エポキシ樹脂組成物を１２０℃の条件下で侵入させ、表１の硬化条件下で硬化させることにより簡易デバイス１を作製した。
（ｉｉ）チップクラックの評価
上記（ｉｉ）の簡易デバイス１を、ＪＩＳ Ｃ００２５に基づく、−５５〜１２５℃、５００サイクルの熱衝撃試験を行い、チップに見立てたＳｉ板２，３のクラックについて評価した。
[Evaluation methods]
Viscosity / viscosity was measured using a Brookfield cone plate measuring instrument. Measurements were made using 51 cones.
Intrusion time The intrusion time is reached by placing a two-ply glass plate having a 15 μm gap (width 10 mm) on a hot plate, heating to 120 ° C., allowing the glass edge to enter through the gap between the glass edges, and reaching 10 mm from the edge. The time until was measured. In addition, the glass plate used previously what was baked at 600 degreeC for 1 hour, and wiped off with acetone.
Tensile modulus Tensile modulus was measured by curing various epoxy resin compositions under the curing conditions shown in Table 1 based on JIS K 7161.
Presence / absence of chip cracks Simple devices were prepared as described below, and the presence or absence of chip cracks was evaluated by a thermal shock test.
(I) Fabrication of
(Ii) Evaluation of chip cracks The
１ 簡易デバイス
２、３ Ｓｉ板
４ 両面テープ
５ ＩＣベアチップ
６ アンダーフィル材
７ バンプ
８ プリント基板（ＦＰＣ）
DESCRIPTION OF
Claims (2)
（Ｂ）下記式（１）で示されるシリコーン変性フェノール硬化剤：（Ａ）成分中のエポキシ基に対するフェノール性水酸基の比が０．８〜１．１となる量、
（Ｃ）平均粒子径が０．１〜１．０μｍである無機充填材：（Ａ）、（Ｂ）及び（Ｃ）成分の合計質量に対して１０〜４０質量％となる量
を含有することを特徴とする半導体封止用液状エポキシ樹脂組成物。
(B) A silicone-modified phenol curing agent represented by the following formula (1): an amount in which the ratio of the phenolic hydroxyl group to the epoxy group in the component (A) is 0.8 to 1.1,
(C) Inorganic filler having an average particle diameter of 0.1 to 1.0 μm: containing an amount of 10 to 40% by mass with respect to the total mass of the components (A), (B) and (C). A liquid epoxy resin composition for semiconductor encapsulation characterized by the above.
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| JPH08176409A (en) * | 1994-12-26 | 1996-07-09 | Sumitomo Bakelite Co Ltd | Conductive resin paste |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108250716A (en) * | 2016-12-29 | 2018-07-06 | 广东生益科技股份有限公司 | Polyphenyl ether resin composition and its prepreg, the laminate and printed circuit board of a kind of polysiloxanes-allyl compound modification |
| CN108250443A (en) * | 2016-12-29 | 2018-07-06 | 广东生益科技股份有限公司 | A kind of polysiloxanes-allyl compound fire retardant and its preparation method and application |
| CN108250746A (en) * | 2016-12-29 | 2018-07-06 | 广东生益科技股份有限公司 | Bismaleimide amine composition and its prepreg, the laminate and printed circuit board of a kind of polysiloxanes-allyl compound modification |
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