JP2007235126A - Die bonding resin paste, semiconductor device using resin paste, and their manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To make it possible to easily supply and apply die bonding resin paste by the use of a printing method to a support member that needs to be stuck to a semiconductor device at comparatively low temperature, and to prevent void occurrence and thickness falloff after curing. <P>SOLUTION: This die bonding resin paste contains (A) acrylic acid ester compound or metharylic acid ester compound, (B) at least one or multiple kinds of liquid rubber components chosen from epoxide polybutadiene and carboxy-terminated acrylonitrile butadiene compolymer, (C) radical initiator, (D) non-conductive filler, and (E) spacer filler. And, its viscosity in 25°C is 5 to 1,000 Pa s, thixotropy factor is 1.5 to 8.0, and the variation rate of viscosity (48 hours) with the passage of time at room temperature is no more than ±20%. The semiconductor device using the resin paste and the manufacturing method are also part of the invention. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a resin paste for die bonding used as a bonding material (die bonding material) between a semiconductor element such as IC or LSI and a support member such as a lead frame or an insulating support substrate, a semiconductor device using the resin paste, and It relates to the manufacturing method.

  Conventionally, Au—Si eutectic alloy, solder, silver paste, and the like are known as bonding materials between semiconductor elements such as IC and LSI and support members such as lead frames and insulating support substrates. Further, an adhesive film using a specific polyimide resin previously proposed by the present inventors, an adhesive film for die bonding in which a conductive filler or an inorganic filler is added to a specific polyimide resin, and the like are generally known. (See Patent Documents 1 to 3).

  However, although the Au—Si eutectic alloy has high heat resistance and high moisture resistance, it has a problem that it is easily broken and expensive when applied to a large chip because of its high elastic modulus. Moreover, although solder is cheap, it is inferior in heat resistance, and its elastic modulus is as high as that of an Au—Si eutectic alloy, so that it is difficult to apply it to a large chip. In addition, silver paste is inexpensive, has high moisture resistance, has the lowest elastic modulus, and has heat resistance that can be applied to a thermocompression bonding wire bonder at 350 ° C, so it is still widely used as a die bonding material. However, as the integration of ICs and LSIs increases and the size of the chips increases, it is difficult to spread and apply the silver paste over the entire surface of the chip. Absent.

  On the other hand, the above-mentioned adhesive film for die bonding can form a die bonding layer on a support member relatively easily, and can be suitably used especially for 42 alloy lead frames, and can be bonded at a relatively low temperature. In addition, it has good hot adhesive strength.

  However, in order to efficiently supply and affix this adhesive film to the support member, an affixing device for cutting out (or punching out) and affixing the adhesive film to a chip size in advance is required. Further, the method of punching the adhesive film and pasting a plurality of chips at once tends to waste the adhesive film. Furthermore, since most of the support member has wiring formed therein, the surface to which the adhesive film is applied has many irregularities, and voids are generated when the adhesive film is applied, so that the reliability tends to be lowered.

Therefore, in recent years, for the purpose of reducing manufacturing costs, etc., a method of supplying a die bonding material by a printing method with high mass productivity has been attracting attention. However, depending on the composition of the die bonding material and the curing conditions, the curing is difficult. Since voids were generated later or the designed film thickness could not be maintained, there was a problem that the adhesive strength or the reliability of the package was lowered.
Japanese Patent Application Laid-Open No. 07-228697 Japanese Patent Laid-Open No. 06-145639 Japanese Patent Laid-Open No. 06-264035

  The present invention provides a die that can be easily supplied and applied by a printing method to a support member that requires a semiconductor element to be attached at a relatively low temperature, and can suppress void generation and thickness reduction after post-curing. It is an object of the present invention to provide a bonding resin paste, a semiconductor device using the resin paste, and a manufacturing method thereof.

  The present invention is characterized by the following items <1> to <8>.

  <1> (A) an acrylic ester compound or a methacrylic ester compound, (B) at least one liquid rubber component selected from epoxidized polybutadiene and a carboxy-terminated acrylonitrile butadiene copolymer, (C) a radical initiator, (D) Contains a non-conductive filler and (E) a spacer filler, has a viscosity at 25 ° C. of 5 to 1000 Pa · s, a thixotropy index of 1.5 to 8.0, and a rate of change in viscosity over time at room temperature (48 hours ) Is a resin paste for die bonding, which is ± 20% or less.

  <2> The resin paste for die bonding according to the above <1>, wherein the (E) spacer filler is a cross-linked copolymer resin containing divinylbenzene as a main component.

  <3> The resin paste for die bonding according to the above <1> or <2>, wherein the average particle diameter of the (E) spacer filler is 80 to 100% of the designed thickness of the die bonding layer to be formed.

  <4> Resin for die bonding according to any one of <1> to <3>, wherein silica is contained as the non-conductive filler (D) and the silica is subjected to a hydrophobic surface treatment. paste.

  <5> Resin paste for die bonding as described in said <4> containing the silica whose average particle diameter of a primary particle is 10.0 micrometers or less as said silica.

  <6> A semiconductor device in which a semiconductor element is mounted on a support member using the die bonding resin paste according to any one of <1> to <5>.

  <7> Applying the die bonding resin paste according to any one of the above <1> to <5> to a predetermined position on a support member, forming a die bonding layer, drying the die bonding layer, A method for manufacturing a semiconductor device, comprising: a step of forming a B stage; a step of mounting a semiconductor element on the die bonding layer that has been converted to a B stage; and a step of post-curing the die bonding layer.

  <8> A step of applying the die bonding resin paste according to any one of <1> to <5> above to a predetermined position on a support member to form a die bonding layer, and a semiconductor element on the die bonding layer A method for manufacturing a semiconductor device, comprising a step of mounting and a step of curing the die bonding layer.

  The resin paste for die bonding of the present invention can be easily supplied and applied by a printing method to a substrate on which a semiconductor element needs to be attached at a relatively low temperature, and can suppress generation of voids after curing. . In addition, the die bonding layer formed by applying the resin paste for die bonding of the present invention on the support member can maintain the designed thickness even after curing.

  Moreover, the resin paste for die bonding of the present invention has heat resistance and whitening resistance, is stable at room temperature, is easy to handle, has excellent low-temperature adhesiveness, and is cured without being made into a B-stage. Therefore, the manufacturing process of the semiconductor device can be greatly shortened.

  Furthermore, since the resin paste for die bonding of the present invention has higher adhesion to the support member than the film adhesive, the reliability of the semiconductor device is increased, and for die bonding, an insulating support substrate such as an organic substrate, copper It can also be used for support members such as lead frames and 42 alloy lead frames, and is extremely suitable industrially.

  Hereinafter, the present invention will be described in more detail.

  The resin paste for die bonding of the present invention comprises (A) an acrylic ester compound or a methacrylic ester compound, (B) at least one liquid rubber component selected from epoxidized polybutadiene and a carboxy-terminated acrylonitrile butadiene copolymer, It contains (C) a radical initiator, (D) a non-conductive filler, and (E) a spacer filler.

  The acrylic acid ester compound or methacrylic acid ester compound of the component (A) used in the present invention is a compound having one or more acrylic groups or methacrylic groups in one molecule. For example, the following general formula (I) The compound represented by-(X) can be used.

〔式中、Ｒ^１は水素又はメチル基を表し、Ｒ^２は炭素数１〜１００、好ましくは炭素数１〜３６の２価の脂肪族又は環状構造を持つ脂肪族炭化水素基を表す〕
上記一般式（Ｉ）で示される化合物としては、例えば、メチルアクリレート、エチルアクリレート、プロピルアクリレート、イソプロピルアクリレート、ｎ−ブチルアクリレート、イソブチルアクリレート、ｔ−ブチルアクリレート、アミルアクリレート、イソアミルアクリレート、ヘキシルアクリレート、ヘプチルアクリレート、オクチルアクリレート、２−エチルヘキシルアクリレート、ノニルアクリレート、デシルアクリレート、イソデシルアクリレート、ラウリルアクリレート、トリデシルアクリレート、ヘキサデシルアクリレート、ステアリルアクリレート、イソステアリルアクリレート、シクロヘキシルアクリレート、イソボルニルアクリレート、トリシクロ［５．２．１．０^２，６］デシルアクリレート、２−（トリシクロ）［５．２．１．０^２，６］デカ−３−エン−８又は９−イルオキシエチルアクリレート等のアクリレート化合物、メチルメタクリレート、エチルメタクリレート、プロピルメタクリレート、イソプロピルメタクリレート、ｎ−ブチルメタクリレート、イソブチルメタクリレート、ｔ−ブチルメタクリレート、アミルメタクリレート、イソアミルメタクリレート、ヘキシルメタクリレート、ヘプチルメタクリレート、オクチルメタクリレート、２−エチルヘキシルメタクリレート、ノニルメタクリレート、デシルメタクリレート、イソデシルメタクリレート、ラウリルメタクリレート、トリデシルメタクリレート、ヘキサデシルメタクリレート、ステアリルメタクリレート、イソステアリルメタクリレート、シクロヘキシルメタクリレート、イソボルニルメタクリレート、トリシクロ［５．２．１．０^２．６］デシルメタクリレート、２−（トリシクロ）［５．２．１．０^２．６］デカ−３−エン−８又は９−イルオキシエチルメタクリレート等のメタクリレート化合物が挙げられる。

[Wherein, R ¹ represents hydrogen or a methyl group, and R ² represents a divalent aliphatic group having 1 to 100 carbon atoms, preferably 1 to 36 carbon atoms or an aliphatic hydrocarbon group having a cyclic structure]
Examples of the compound represented by the general formula (I) include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, amyl acrylate, isoamyl acrylate, hexyl acrylate, and heptyl. Acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, isodecyl acrylate, lauryl acrylate, tridecyl acrylate, hexadecyl acrylate, stearyl acrylate, isostearyl acrylate, cyclohexyl acrylate, isobornyl acrylate, tricyclo [5. 2.1.0 ^2,6] decyl acrylate, 2- (tricyclo [5.2.1.0 ^{2, 6]} dec-3-ene -8 or 9-yl acrylate compounds such as oxyethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n- butyl methacrylate, isobutyl methacrylate , T-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, hexadecyl methacrylate, stearyl methacrylate, Isostearyl methacrylate, cyclohexyl methacrylate, Seo isobornyl methacrylate, tricyclo [5.2.1.0 ^2.6] decyl methacrylate, 2- (tricyclo) [5.2.1.0 ^2.6] dec-3-ene -8 or 9-yloxy Examples include methacrylate compounds such as ethyl methacrylate.

〔式中、Ｒ^１及びＲ^２はそれぞれ一般式（Ｉ）におけるものと同じものを表す〕
上記一般式（ＩＩ）で示される化合物としては、例えば、２−ヒドロキシエチルアクリレート、２−ヒドロキシプロピルアクリレート、ダイマージオールモノアクリレート等のアクリレート化合物、２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルメタクリレート、ダイマージオールモノメタクリレート等のメタクリレート化合物等が挙げられる。

[Wherein R ¹ and R ² are the same as those in formula (I)]
Examples of the compound represented by the general formula (II) include acrylate compounds such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and dimer diol monoacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and dimer diol. And methacrylate compounds such as monomethacrylate.

〔式中、Ｒ^１は一般式（Ｉ）におけるものと同じものを表し、Ｒ^３は水素、メチル基又はフェノキシメチル基を表し、Ｒ^４は水素、炭素数１〜６のアルキル基、フェニル基又はベンゾイル基を表し、ｎは１〜５０の整数を表す〕
上記一般式（ＩＩＩ）で示される化合物としては、例えば、ジエチレングリコールアクリレート、ポリエチレングリコールアクリレート、ポリプロピレングリコールアクリレート、２−メトキシエチルアクリレート、２−エトキシエチルアクリレート、２−ブトキシエチルアクリレート、メトキシジエチレングリコールアクリレート、メトキシポリエチレングリコールアクリレート、２−フェノキシエチルアクリレート、フェノキシジエチレングリコールアクリレート、フェノキシポリエチレングリコールアクリレート、２−ベンゾイルオキシエチルアクリレート、２−ヒドロキシ−３−フェノキシプロピルアクリレート等のアクリレート化合物、ジエチレングリコールメタクリレート、ポリエチレングリコールメタクリレート、ポリプロピレングリコールメタクリレート、２−メトキシエチルメタクリレート、２−エトキシエチルメタクリレート、２−ブトキシエチルメタクリレート、メトキシジエチレングリコールメタクリレート、メトキシポリエチレングリコールメタクリレート、２−フェノキシエチルメタクリレート、フェノキシジエチレングリコールメタクリレート、フェノキシポリエチレングリコールメタクリレート、２−ベンゾイルオキシエチルメタクリレート、２−ヒドロキシ−３−フェノキシプロピルメタクリレート等のメタクリレート化合物が挙げられる。

[Wherein R ¹ represents the same as in general formula (I), R ³ represents hydrogen, a methyl group or a phenoxymethyl group, R ⁴ represents hydrogen, an alkyl group having 1 to 6 carbon atoms, and a phenyl group. Or represents a benzoyl group, and n represents an integer of 1 to 50]
Examples of the compound represented by the general formula (III) include diethylene glycol acrylate, polyethylene glycol acrylate, polypropylene glycol acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, methoxydiethylene glycol acrylate, and methoxypolyethylene. Acrylate compounds such as glycol acrylate, 2-phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy polyethylene glycol acrylate, 2-benzoyloxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, diethylene glycol methacrylate, polyethylene glycol methacrylate, polypropylene Glycol methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-butoxyethyl methacrylate, methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, 2-phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, phenoxypolyethylene glycol methacrylate, 2-benzoyloxy And methacrylate compounds such as ethyl methacrylate and 2-hydroxy-3-phenoxypropyl methacrylate.

〔式中、Ｒ^１は一般式（Ｉ）におけるものと同じものを表し、Ｒ^５はフェニル基、ニトリル基、−Ｓｉ（ＯＲ^６）_３（ただし、Ｒ^６は炭素数１〜６のアルキル基を表す）、又は下記式

[Wherein, R ¹ represents the same as in general formula (I), R ⁵ represents a phenyl group, a nitrile group, —Si (OR ⁶ ) ₃ (where R ⁶ is an alkyl group having 1 to ⁶ carbon atoms, Or the following formula

のいずれかの基（ただし、Ｒ^７、Ｒ^８及びＲ^９はそれぞれ独立に水素又は炭素数１〜６のアルキル基を表し、Ｒ^１０は水素又は炭素数１〜６のアルキル基又はフェニル基を表す）を表し、ｍは０、１、２又は３の数を表す〕
上記一般式（ＩＶ）で示される化合物としては、例えば、ベンジルアクリレート、２−シアノエチルアクリレート、γ−アクリロキシプロピルトリメトキシシラン、グリシジルアクリレート、テトラヒドロフルフリルアクリレート、テトラヒドロピラニルアクリレート、ジメチルアミノエチルアクリレート、ジエチルアミノエチルアクリレート、１，２，２，６，６−ペンタメチルピペリジニルアクリレート、２，２，６，６−テトラメチルピペリジニルアクリレート、アクリロキシエチルホスフェート、アクリロキシエチルフェニルアシッドホスフェート、β−アクリロイルオキシエチルハイドロジェンフタレート、β−アクリロイルオキシエチルハイドロジェンサクシネート等のアクリレート化合物、ベンジルメタクリレート、２−シアノエチルメタクリレート、γ−メタクリロキシプロピルトリメトキシシラン、グリシジルメタクリレート、テトラヒドロフルフリルメタクリレート、テトラヒドロピラニルメタクリレート、ジメチルアミノエチルメタクリレート、ジエチルアミノエチルメタクリレート、１，２，２，６，６−ペンタメチルピペリジニルメタクリレート、２，２，６，６−テトラメチルピペリジニルメタクリレート、メタクリロイルオキシエチルホスフェート、メタクリロイルオキシエチルフェニルアシッドホスフェート等のメタクリレート、β−メタクリロイルオキシエチルハイドロジェンフタレート、β−メタクリロイルオキシエチルハイドロジェンサクシネート等のメタクリレート化合物が挙げられる。

(Wherein R ⁷ , R ⁸ and R ⁹ each independently represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and R ¹⁰ represents hydrogen, an alkyl group having 1 to 6 carbon atoms or a phenyl group) M represents a number of 0, 1, 2, or 3]
Examples of the compound represented by the general formula (IV) include benzyl acrylate, 2-cyanoethyl acrylate, γ-acryloxypropyltrimethoxysilane, glycidyl acrylate, tetrahydrofurfuryl acrylate, tetrahydropyranyl acrylate, dimethylaminoethyl acrylate, Diethylaminoethyl acrylate, 1,2,2,6,6-pentamethylpiperidinyl acrylate, 2,2,6,6-tetramethylpiperidinyl acrylate, acryloxyethyl phosphate, acryloxyethyl phenyl acid phosphate, β- Acrylate compounds such as acryloyloxyethyl hydrogen phthalate and β-acryloyloxyethyl hydrogen succinate, benzyl methacrylate, 2-cyano Tyl methacrylate, γ-methacryloxypropyltrimethoxysilane, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, tetrahydropyranyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 1,2,2,6,6-pentamethylpiperidinyl methacrylate , 2,2,6,6-tetramethylpiperidinyl methacrylate, methacrylate such as methacryloyloxyethyl phosphate, methacryloyloxyethyl phenyl acid phosphate, β-methacryloyloxyethyl hydrogen phthalate, β-methacryloyloxyethyl hydrogen succinate, etc. Of the methacrylate compound.

〔式中、Ｒ^１及びＲ^２はそれぞれ一般式（Ｉ）におけるものと同じものを表す〕
上記一般式（Ｖ）で示される化合物としては、例えば、エチレングリコールジアクリレート、１，４−ブタンジオールジアクリレート、１，６−ヘキサンジオールジアクリレート、１，９−ノナンジオールジアクリレート、１，３−ブタンジオールジアクリレート、ネオペンチルグリコールジアクリレート、ダイマージオールジアクリレート、ジメチロールトリシクロデカンジアクリレート等のジアクリレート化合物、エチレングリコールジメタクリレート、１，４−ブタンジオールジメタクリレート、１，６−ヘキサンジオールジメタクリレート、１，９−ノナンジオールジメタクリレート、１，３−ブタンジオールジメタクリレート、ネオペンチルグリコールジメタクリレート、ダイマージオールジメタクリレート、ジメチロールトリシクロデカンジメタクリレート等のジメタクリレート化合物が挙げられる。

[Wherein R ¹ and R ² are the same as those in formula (I)]
Examples of the compound represented by the general formula (V) include ethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,3. -Diacrylate compounds such as butanediol diacrylate, neopentyl glycol diacrylate, dimer diol diacrylate, dimethylol tricyclodecane diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol Dimethacrylate, 1,9-nonanediol dimethacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol dimethacrylate, dimer diol dimethacrylate, dimethylol trisi Rodez dimethacrylate compounds such as Kanji methacrylate.

〔式中、Ｒ^１、Ｒ^３及びｎはそれぞれ一般式（ＩＩＩ）におけるものと同じものを表す〕
上記一般式（ＶＩ）で示される化合物としては、例えば、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、テトラエチレングリコールジアクリレート、ポリエチレングリコールジアクリレート、トリプロピレングリコールジアクリレート、ポリプロピレングリコールジアクリレート等のジアクリレート化合物、ジエチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、テトラエチレングリコールジメタクリレート、ポリエチレングリコールジメタクリレート、トリプロピレングリコールジメタクリレート、ポリプロピレングリコールジメタクリレート等のジメタクリレート化合物が挙げられる。

[Wherein R ¹ , R ³ and n each represent the same as in general formula (III)]
Examples of the compound represented by the general formula (VI) include diacrylates such as diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol diacrylate. Examples thereof include dimethacrylate compounds such as compounds, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, and polypropylene glycol dimethacrylate.

〔式中、Ｒ^１は一般式（Ｉ）におけるものと同じものを表し、Ｒ^１１及びＲ^１２はそれぞれ独立に水素又はメチル基を表す〕
上記一般式（ＶＩＩ）で示される化合物としては、例えば、ビスフェノールＡ、ビスフェノールＦ又はビスフェノールＡＤ１モルとグリシジルアクリレート２モルとの反応物、ビスフェノールＡ、ビスフェノールＦ又はビスフェノールＡＤ１モルとグリシジルメタクリレート２モルとの反応物等が挙げられる。

[Wherein R ¹ represents the same as in general formula (I), and R ¹¹ and R ¹² each independently represent hydrogen or a methyl group]
Examples of the compound represented by the general formula (VII) include a reaction product of 1 mol of bisphenol A, bisphenol F or bisphenol AD and 2 mol of glycidyl acrylate, 1 mol of bisphenol A, bisphenol F or 1 mol of bisphenol AD, and 2 mol of glycidyl methacrylate. Examples include reactants.

〔式中、Ｒ^１、Ｒ^１１及びＲ^１２はそれぞれ一般式（ＶＩＩ）におけるものと同じものを表しＲ^１３及びＲ^１４はそれぞれ独立に水素又はメチル基を表し、ｐ及びｑはそれぞれ独立に１〜２０の整数を表す〕
上記一般式（ＶＩＩＩ）で示される化合物としては、例えば、ビスフェノールＡ、ビスフェノールＦ又はビスフェノールＡＤのポリエチレンオキサイド付加物のジアクリレート、ビスフェノールＡ、ビスフェノールＦ又はビスフェノールＡＤのポリプロピレンオキサイド付加物のジアクリレート、ビスフェノールＡ、ビスフェノールＦ又はビスフェノールＡＤのポリエチレンオキサイド付加物のジメタクリレート、ビスフェノールＡ、ビスフェノールＦ又はビスフェノールＡＤのポリプロピレンオキサイド付加物のジメタクリレート等が挙げられる。

[Wherein R ¹ , R ¹¹ and R ¹² are the same as those in formula (VII), R ¹³ and R ¹⁴ each independently represent hydrogen or a methyl group, and p and q are each independently 1 Represents an integer of ~ 20]
Examples of the compound represented by the above general formula (VIII) include diacrylate of bisphenol A, bisphenol F or polyethylene oxide adduct of bisphenol AD, diacrylate of bisphenol A, bisphenol F or polypropylene oxide adduct of bisphenol AD, bisphenol. A, dimethacrylate of polyethylene oxide adduct of bisphenol F or bisphenol AD, dimethacrylate of polypropylene oxide adduct of bisphenol A, bisphenol F or bisphenol AD, and the like.

〔式中、Ｒ^１は一般式（Ｉ）におけるものと同じものを表し、Ｒ^１５、Ｒ^１６、Ｒ^１７及びＲ^１８はそれぞれ独立に水素又はメチル基を表し、ｘは１〜２０の整数を表す〕
上記一般式（ＩＸ）で示される化合物としては、例えば、ビス（アクリロイルオキシプロピル）ポリジメチルシロキサン、ビス（アクリロイルオキシプロピル）メチルシロキサン−ジメチルシロキサンコポリマー、ビス（メタクリロイルオキシプロピル）ポリジメチルシロキサン、ビス（メタクリロイルオキシプロピル）メチルシロキサン−ジメチルシロキサンコポリマー等が挙げられる。

[Wherein, R ¹ represents the same as in general formula (I), R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent hydrogen or a methyl group, and x represents an integer of 1 to 20] To express〕
Examples of the compound represented by the general formula (IX) include bis (acryloyloxypropyl) polydimethylsiloxane, bis (acryloyloxypropyl) methylsiloxane-dimethylsiloxane copolymer, bis (methacryloyloxypropyl) polydimethylsiloxane, bis ( And methacryloyloxypropyl) methylsiloxane-dimethylsiloxane copolymer.

〔式中、Ｒ^１は一般式（Ｉ）におけるものと同じものを表し、ｒ、ｓ、ｔ及びｕはそれぞれ独立に繰り返し数の平均値を示す０以上の数であり、ｒ＋ｔは０．１以上、好ましくは０．３〜５の範囲であり、またｓ＋ｔは１以上、好ましくは１〜１００の範囲である〕
上記一般式（Ｘ）で示される化合物としては、例えば、無水マレイン酸を付加させたポリブタジエンと分子内に水酸基を持つアクリル酸エステル化合物又はメタクリル酸エステル化合物を反応させて得られる反応物及びその水素添加物があり、例えばＭＭ−１０００−８０、ＭＡＣ−１０００−８０（共に、日本石油化学（株）製、商品名）等が挙げられる。

[Wherein, R ¹ represents the same as in general formula (I), r, s, t and u each independently represent an average number of repetitions of 0 or more, and r + t is 0.1 Or more, preferably in the range of 0.3 to 5, and s + t is 1 or more, preferably in the range of 1 to 100]
Examples of the compound represented by the general formula (X) include a reaction product obtained by reacting a polybutadiene to which maleic anhydride is added and an acrylic ester compound or a methacrylic ester compound having a hydroxyl group in the molecule, and hydrogen thereof. There are additives such as MM-1000-80 and MAC-1000-80 (both manufactured by Nippon Petrochemical Co., Ltd., trade names).

  Moreover, the acrylic acid ester compound or methacrylic acid ester compound of the said (A) component can be used individually or in combination of 2 or more types.

  The epoxidized polybutadiene which is one of the liquid rubber components of the component (B) used in the present invention is not particularly limited, but the epoxy equivalent determined by the perchloric acid method is 1000 (g / eq) or less. It is preferable that it is 50 to 500 (g / eq). The viscosity at room temperature is preferably 1000 Pa · s or less, more preferably 10 to 100 Pa · s. Further, as the epoxidized polybutadiene, one having at least one hydroxyl group in the molecule may be used.

  The carboxy-terminated acrylonitrile butadiene copolymer, which is one of the liquid rubber components, is not particularly limited, but preferably has a viscosity at room temperature of 1000 Pa · s or less, and 50 to 500 Pa · s. It is more preferable that As what is marketed as a carboxy terminal acrylonitrile butadiene copolymer, Hycer CTB-2009x162, CTBN-1300x31, CTBN-1300x8, CTBN-1300x13, CTBNX-1300x9 (any (Ube Industries, Ltd.) and trade name).

  Moreover, the said epoxidized polybutadiene and the said carboxy terminal acrylonitrile butadiene copolymer can be used individually or in combination, respectively.

  Moreover, it is preferable to use 10-100 weight part with respect to 100 weight part of said (A) component, and, as for the compounding quantity of the said (B) component, it is more preferable to use 30-80 weight part. If the blending amount is less than 10 parts by weight, the chip warp reduction effect tends to be inferior, and if it exceeds 100 parts by weight, the viscosity increases, and the workability of the resin paste tends to decrease.

  The radical initiator of the component (C) used in the present invention is not particularly limited, but is preferably a peroxide from the viewpoint of suppressing the generation of voids, and the curability of the resin paste and From the viewpoint of viscosity stability, it is preferable that the decomposition temperature of the peroxide in the rapid heating test is 70 to 170 ° C. Specific examples of the radical initiator include, for example, 1,1,3,3-tetramethylperoxy 2-ethylhexanoate, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis ( t-butylperoxy) cyclododecane, di-t-butylperoxyisophthalate, t-butylperbenzoate, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t -Butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne, cumene hydroperoxide and the like.

  Moreover, 0.1-10 weight part is preferable with respect to 100 weight part of total amounts of the said (A) component, and, as for the compounding quantity of the said (C) radical initiator, 0.5-5 weight part is especially preferable. If the blending ratio is less than 0.1 parts by weight, the curability tends to decrease, and if it exceeds 10 parts by weight, the volatile matter increases, and voids called voids tend to occur in the cured product. is there.

  There is no restriction | limiting in particular as a nonelectroconductive filler of the said (D) component used for this invention, Various things can be used, For example, a silica, an alumina, a titania, glass, iron oxide, a ceramic etc. are mentioned. . These nonconductive fillers impart low thermal expansion, low moisture absorption, and thixotropic properties to the resin paste of the present invention. The (D) non-conductive filler preferably contains silica, and more preferably contains silica subjected to a hydrophobic surface treatment. By using such silica, the hygroscopicity of the resin paste of the present invention can be reduced, and the rate of change in viscosity with time at room temperature can be effectively suppressed. The hydrophobic surface treatment is not particularly limited, and can be performed, for example, by imparting (binding) an alkyl group such as a methyl group or a trimethylsilyl group to the silica surface.

  When silica is contained in the nonconductive filler (D), the average particle size of the primary particles of the silica is preferably 10.0 μm or less, and more preferably 1.0 μm or less. When the average particle diameter of the primary particles of silica used exceeds 10.0 μm, it tends to be difficult to impart sufficient thixotropy to the resin paste of the present invention.

Moreover, in order to improve the electrical reliability of a semiconductor device, you may add an inorganic ion exchanger as said (D) nonelectroconductive filler. Examples of the inorganic ion exchanger include ions extracted into an aqueous solution when the cured resin paste of the present invention is extracted in hot water, such as Na ⁺ , K ⁺ , Cl ⁻ , F ⁻ , RCOO ⁻ , Br ^−. Those having an ion trapping action such as are effective. More specifically, naturally occurring zeolites, natural minerals such as zeolites, acid clay, dolomite, hydrotalcites, artificially synthesized synthetic zeolites and the like can be mentioned.

  The amount of the (D) non-conductive filler is usually 1 to 100 parts by weight, preferably 2 to 50 parts by weight, with respect to 100 parts by weight of the total amount of the resin paste of the present invention. If it is less than 1 part by weight, it tends to be difficult to impart sufficient thixotropic properties (thixotropic index: 1.5 or more) to the resin paste of the present invention. Further, when the amount exceeds 100 parts by weight, the adhesiveness tends to decrease, and furthermore, the elastic modulus of the cured product increases, and as a result, the stress relaxation capability of the die bonding material decreases and the mounting reliability of the semiconductor device decreases. Tend to.

  The spacer filler of the component (E) used in the present invention not only gives the resin paste of the present invention low thermal expansion, low moisture absorption, and thixotropy, but also applies the resin paste of the present invention on a support member. This is for maintaining the thickness of the die-bonding layer formed in this way almost as designed even after curing (spacer effect). Examples of the (E) spacer filler include a cross-linked copolymer resin filler mainly composed of divinylbenzene, other resin fillers, silica, alumina, titania, glass, iron oxide, ceramics, etc. A resin filler capable of reducing chip attack by the filler is sometimes preferable, and a filler having a small variation in particle size is preferable. Among these, it is particularly preferable to use a crosslinked copolymer resin filler mainly composed of divinylbenzene.

  The average particle size of the (E) spacer filler may be a non-conductive filler having a particle size larger than that used as the component (D) in consideration of the design thickness of the die bonding layer. Although not limited, it is preferably 80-100% of the designed thickness. That is, when forming a die bonding layer having a designed thickness of 100 μm, the average particle diameter of the (E) spacer filler is preferably 80 to 100 μm, and thus the thickness of the die bonding layer after curing is 80 to 100 μm. It becomes possible to hold in the range. When a die bonding layer having a design thickness of 100 μm is formed by a printing method, a printing plate having a thickness of about 110 μm is usually used.

  The amount of the (E) spacer filler is usually 0.3 to 5 parts by weight, preferably 0.5 to 2 parts by weight with respect to 100 parts by weight of the total amount of the resin paste of the present invention. If it is less than 0.3 part by weight, it tends to be difficult to give a spacer effect to the resin paste of the present invention. On the other hand, when the amount exceeds 5 parts by weight, the viscosity of the resin paste tends to be lowered and workability tends to be lowered, and further, the adhesiveness is lowered and the mounting reliability of the semiconductor device tends to be lowered.

  In addition to the above-described components, the resin paste of the present invention includes a toughness-improving material such as acrylonitrile-butadiene rubber, styrene-butadiene rubber, urethane acrylate, a hygroscopic agent such as calcium oxide and magnesium oxide, silane coupling, as necessary. Adhesives such as adhesives, titanium coupling agents, acid anhydrides, nonionic surfactants, wetting improvers such as fluorosurfactants, antifoaming agents such as silicone oil, solvents, etc. may be added as appropriate. it can.

  Production of the resin paste of the present invention comprises (A) an acrylic ester compound or a methacrylic ester compound, (B) at least one liquid rubber component selected from epoxidized polybutadiene and a carboxy-terminated acrylonitrile butadiene copolymer, ( C) radical initiator, (D) non-conductive filler, and (E) spacer filler, together with various additives that are added as necessary, in a lump or divided into a stirrer, a raking machine, three rolls, A dispersion / dissolution apparatus such as a planetary mixer is appropriately combined and heated as necessary to mix, dissolve, pulverize and knead or disperse. The above components are preferably dispersed so as to be uniform.

Moreover, it is preferable that the thixotropy index | exponent of the resin paste of this invention is 1.5-8.0. If the thixotropy index of the resin paste is less than 1.5, sagging or the like occurs in the paste supplied and applied by the printing method, resulting in a poor printed shape. On the other hand, if the thixotropy index exceeds 8.0, “chips”, blurring, etc. are likely to occur in the paste supplied and applied by the printing method. Incidentally, thixotropic index is an E-type rotational viscometer, 25 ° C., and viscosity measured at a rotation speed 0.5 min ^-1, the ratio [thixotropy index of the viscosity measured at a rotation speed 5min ^-1 = ( Viscosity at 0.5 rpm) / (viscosity at 5 rpm)].

Further, the viscosity (25 ° C.) of the resin paste of the present invention is suitably adjusted depending on the type of printing method, and is preferably in the range of 5 to 1000 Pa · s from the viewpoint of printing workability. For example, when a mesh or the like is stretched at the mask opening as in a screen mesh plate or the like, it is preferable to adjust to a range of 5 to 200 Pa · s in consideration of the detachability of the mesh portion. Is preferably adjusted to a range of 20 to 500 Pa · s. In addition, let the said viscosity be a value when it measures by 25 degreeC and rotation speed 0.5min < ^-1 > using an E-type rotational viscometer.

  Further, the rate of change in viscosity when the resin paste of the present invention is allowed to stand at room temperature for 48 hours is preferably ± 20% or less. When the viscosity change rate exceeds ± 20%, the pot life is very short and the usability is poor.

  The semiconductor device of the present invention is not particularly limited as long as the semiconductor element is mounted on the support member using the resin paste of the present invention, and the manufacturing process may be according to known methods and conditions. The supply and application of the resin paste onto the support member are preferably performed by a printing method. Specifically, for example, the resin paste of the present invention is supplied and applied to a predetermined position on the support member by a printing method, and after forming a die bonding layer by drying and semi-curing (B-stage), A semiconductor element (chip) such as an IC or LSI can be heated and pressed on the die bonding layer under suitable conditions, and then the resin paste layer can be post-cured. Note that this post-curing of the resin paste layer may be performed together with the post-curing step of the sealing material when there is no problem in the mounting assembly process. In addition, after supplying and applying the resin paste of the present invention on the support substrate, if there is no effect on the package reliability, the semiconductor element is heated and pressed without being semi-cured (B-stage). Also good.

  The support member is not particularly limited. For example, a lead frame such as a 42 alloy lead frame or a copper lead frame, a plastic film such as a polyimide resin, an epoxy resin or a polyimide resin, a polyimide resin on a substrate such as a glass nonwoven fabric, Examples thereof include a material impregnated and cured with a resin composition containing an epoxy resin, a polyimide resin, or the like (prepreg), or a ceramic support member such as alumina.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these descriptions.

(Examples 1 to 3, Comparative Examples 2 and 3)
Each material was put in a rake machine in the mixing ratio shown in Table 1 and kneaded, and then defoamed and kneaded for 1 hour at 5 Torr or less to obtain a resin paste for die bonding.

(Comparative Example 1)
Prepare 35 parts by weight of a carbitol acetate solution (the thermosetting resin has a solid content of about 40% by weight) containing 14 parts by weight of epoxy resin (YDCN-702) and 10 parts by weight of phenol resin (H-1) in advance. Each material was put in a rake machine at the ratio shown in Table 1 and kneaded, and then defoamed and kneaded for 1 hour at 5 Torr or less to obtain a resin paste for die bonding.

  The properties (viscosity, thixotropy index, viscosity after 2 days of standing at room temperature, die shear strength during heating, void area, paste thickness after curing) of the resin paste for die bonding obtained in each example and comparative example were examined by the following methods. . The results are shown in Table 1.

(1) Viscosity: An EHD viscometer (manufactured by Tokyo Keiki Co., Ltd.) was used to measure the viscosity (Pa · s) at 25 ° C. and a rotation speed of 0.5 min ⁻¹ using a 3 ° cone.

(2) thixotropic index: in EHD viscometer (Tokyo Keiki Co., Ltd.), 25 ° C. using a 3 ° cone viscosity at rpm 0.5 min ^-1 and the rotational speed 5min ^-1 a (Pa · s) measured, and a thixotropy index the ratio of (a viscosity at rpm 0.5 min ^-1) / (viscosity at rpm 5min ^-1).

(3) Die shear strength during heating: A resin paste is printed on a 42 alloy lead frame, and a 5 mm × 5 mm silicon chip (thickness 0.4 mm) is pressed onto the resin paste for 1 second under a load of 50 g. It was. Thereafter, it was cured in an oven at 180 ° C. for 1 hour. This was measured for shear strength (N / chip) at 250 ° C. using an automatic adhesive strength tester (manufactured by Daisy).

(4) Void area (occupancy ratio): A resin paste is printed on a 42 alloy lead frame, and an 8 mm × 10 mm silicon chip (thickness 0.4 mm) is pressed onto the resin paste with a load of 50 g for 1 second. I let you. After that. This was observed using a scanning ultrasonic microscope to determine the occupied area of voids contained in the cured resin paste.

(5) Paste thickness after curing: In order to form a die bonding layer having a design thickness of 100 μm, a resin paste is printed using a printing plate having a thickness of 110 μm to form a resin paste layer, and this is performed in an oven at 180 ° C. for 1 hour. After curing, the thickness of the layer was determined.

なお、表１における各種成分の略号は下記の意味である。

In addition, the symbol of various components in Table 1 has the following meaning.

R-712: Nippon Kayaku Co., Ltd., Bisphenol F polyethylene glycol diacrylate
SR-349: Sartomer, ethoxylated bisphenol A diacrylate
AMP-20GY: Shin-Nakamura Chemical Co., Ltd., phenoxydiethylene glycol acrylate
FA-512M: Hitachi Chemical Co., Ltd., dicyclopentenyloxyethyl methacrylate
YDCN-702: Toto Kasei Co., Ltd., cresol novolac type epoxy resin (epoxy equivalent 220)
EXA-830CRP: Dainippon Ink and Chemicals, bisphenol F type epoxy resin
H-1: Meiwa Kasei Co., Ltd., phenol novolac resin (OH equivalent 106)
CTBN-1300X8: Ube Industries, Ltd., carboxy-terminated acrylonitrile butadiene copolymer
PB-4700: Daicel Chemical Corporation, epoxidized polybutadiene
DICY: Dicyandiamide
2P4MHZ: Shikoku Kasei Kogyo Co., Ltd., Curesol
AEROSIL 380: Nippon Aerosil Co., Ltd., silica filler
AEROSIL R972: Nippon Aerosil Co., Ltd., silica filler micropearl SP with hydrophobic surface treatment: Sekisui Chemical Co., Ltd. (particle size: 100 micron product)

  From the results in Table 1, it was confirmed that the resin paste for die bonding of the present invention (Examples 1 to 3) can suppress the generation of voids after curing and the decrease in film thickness.

Claims (8)

  (A) Acrylic ester compound or methacrylic ester compound, (B) at least one liquid rubber component selected from epoxidized polybutadiene and carboxy-terminated acrylonitrile butadiene copolymer, (C) radical initiator, (D) It contains a non-conductive filler and (E) spacer filler, has a viscosity at 25 ° C. of 5 to 1000 Pa · s, a thixotropy index of 1.5 to 8.0, and a rate of change in viscosity at room temperature (48 hours) ± Resin paste for die bonding that is 20% or less.   The resin paste for die bonding according to claim 1, wherein the (E) spacer filler is a cross-linked copolymer resin containing divinylbenzene as a main component.   The resin paste for die bonding according to claim 1 or 2, wherein an average particle diameter of the (E) spacer filler is 80 to 100% of a design thickness of a die bonding layer to be formed.   The resin paste for die bonding according to any one of claims 1 to 3, wherein the non-conductive filler (D) contains silica, and the silica is subjected to a hydrophobic surface treatment.   The resin paste for die bonding according to claim 4, wherein the silica contains silica having an average primary particle size of 10.0 μm or less.   A semiconductor device comprising a semiconductor element mounted on a support member using the die bonding resin paste according to claim 1. Applying the resin paste for die bonding according to any one of claims 1 to 5 to a predetermined position on a support member to form a die bonding layer;
Drying the die bonding layer to form a B-stage;
A step of mounting a semiconductor element on the die bonding layer formed into a B stage, and a step of post-curing the die bonding layer;
A method for manufacturing a semiconductor device comprising: Applying the resin paste for die bonding according to any one of claims 1 to 5 to a predetermined position on a support member to form a die bonding layer;
Mounting a semiconductor element on the die bonding layer; and curing the die bonding layer;
A method for manufacturing a semiconductor device comprising: