JP2007110062A - Die bonding resin paste, semiconductor device manufacturing method using the same, and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide die bonding resin paste which is capable of being easily supplied and applied by a printing method to a support member that is required to be bonded at a comparatively low temperature, and restraining the generation of voids and a decrease in film thickness after it is hardened. <P>SOLUTION: The die bonding resin paste includes an acrylic ester compound or a methacrylic ester compound (A), epoxidized polybutadiene or a carboxy termination acrylonitrile butadiene copolymer (B), a radical initiator (C), and a non-conductive filler (D). Furthermore, the resin paste has a viscosity of 5 to 1,000 Pa s at a temperature of 25°C, and its rate of a change in viscosity with time (48 hours) is ±20% or below at room temperature. <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, and a method of manufacturing a semiconductor device using the same. The present invention relates to applications such as semiconductor devices.

Conventionally, Au—Si eutectic alloy, solder, silver paste, or the like is known as a bonding material between an IC or LSI and a lead frame.
In addition, the present applicant has previously proposed an adhesive film using a specific polyimide resin and an adhesive film for die bonding in which a conductive filler or an inorganic filler is added to a specific polyimide resin (see Patent Documents 1 to 3). ).

Japanese Patent Application Laid-Open No. 07-228697 Japanese Patent Laid-Open No. 06-145639 Japanese Patent Laid-Open No. 06-264035

The Au—Si eutectic alloy has high heat resistance and moisture resistance, but is easily cracked when applied to a large chip due to its large elastic modulus. There is also an expensive difficulty.
Although solder is inexpensive, its heat resistance is inferior, and its elastic modulus is as high as that of an Au—Si eutectic alloy, making it difficult to apply to a large chip.
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 currently the mainstream of die bonding materials. However, as ICs and LSIs become more highly integrated and the size of the chip grows, if you try to join the IC or LSI and the lead frame with silver paste, you must spread and apply this to the entire surface of the chip. It must be difficult.
The adhesive film for die bonding previously proposed by the present applicant can be suitably used for a 42 alloy lead frame for die bonding because it can be bonded at a relatively low temperature and has a good adhesive force during heat.
However, with the recent reduction in size and weight of packages, the use of insulating support substrates has become widespread, and in order to reduce manufacturing costs, die bonding materials have been tried to be supplied by a mass-productive printing method. The method to do is attracting attention. However, depending on the curing conditions of the die bonding material, voids are generated after the curing, resulting in a problem that the adhesive strength or the reliability of the package is lowered, and the film thickness of the paste is decreased after the curing.
Therefore, the present invention solves these problems, and can easily supply and apply by a printing method to a support member that needs to be bonded at a relatively low temperature, and suppresses void generation and film loss after curing. An object of the present invention is to provide a resin paste for die bonding. Another object of the present invention is to provide a method for manufacturing a semiconductor device using the resin paste for die bonding, a use of the semiconductor device, and the like.

In order to achieve the above object, the present invention has the following configuration.
That is, the present invention comprises (A) an acrylic ester compound or a methacrylic ester compound, (B) an epoxidized polybutadiene or a carboxy-terminated acrylonitrile butadiene copolymer, (C) a radical initiator, and (D) a non-conductive filler. The present invention relates to a resin paste for die bonding, characterized in that it has a viscosity at 25 ° C. of 5 to 1000 Pa · s, and the rate of change with time in viscosity at room temperature (48 hours) is ± 20% or less.
However, the above viscosity is a value when measured at 25 ° C. and a rotational speed of 0.5 rpm using an E-type rotational viscometer.
The viscosity of the resin paste is usually in the range of 5 to 1000 Pa · s, more preferably in the range of 5 to 500 Pa · s, more preferably a mesh or the like in the mask opening as in a screen mesh plate or the like. When it is stretched, it is preferably in the range of 5 to 200 Pa · s in consideration of the ability to remove the mesh portion, and in the case of a stencil plate or the like, it is preferably adjusted to the range of 20 to 500 Pa · s. When the viscosity of the resin paste is less than 5 Pa · s or more than 1000 Pa · s, the printing workability tends to be lowered.
Further, if the viscosity change rate when the resin paste is left at room temperature for 48 hours exceeds ± 20%, the usable time of the resin paste is very short and the usability is deteriorated.
The present invention also relates to the above-mentioned die bonding resin paste, wherein the non-conductive filler of the die bonding resin paste is a silica filler subjected to a hydrophobic treatment.
Moreover, this invention relates to the resin paste for die bonding of the said description whose average particle diameter of the primary particle of the silica filler of the resin paste for die bonding is 10 micrometers or less.
Further, the present invention includes a step of (1) applying the above-described resin bonding for die bonding on a support member, (2) mounting a semiconductor chip on the resin paste, and (3) curing the resin paste. The present invention relates to a method for manufacturing a semiconductor device.
In the present invention, (1) the die bonding paste is applied on a support member, (2) the resin paste is dried to form a B stage, and (3) a semiconductor chip is placed on the B stage resin paste. And (4) a method of manufacturing a semiconductor device including a step of curing the resin paste.
The present invention also relates to a semiconductor device using the die bonding resin paste described above.

  According to the present invention, it is possible to easily supply and apply by a printing method to a support member that needs to be bonded at a relatively low temperature, and to suppress the generation of voids and film loss after curing, for highly reliable die bonding. A resin paste can be provided. Further, the resin paste for die bonding of the present invention has heat resistance and whitening resistance, is easy to handle, and has excellent low-temperature adhesiveness. Further, the viscosity of the resin paste is stable even at room temperature, and it is easy to handle. Furthermore, since the adhesiveness with respect to a support member improves compared with a film adhesive, package reliability increases. It can be suitably used for an insulating support substrate such as an organic substrate and a copper lead frame for die bonding, and can also be used for a 42 alloy lead frame.

Hereinafter, the present invention will be described in more detail.
One embodiment of the present invention comprises (A) an acrylic ester compound or a methacrylic ester compound, (B) an epoxidized polybutadiene or a carboxy-terminated acrylonitrile butadiene copolymer, (C) a radical initiator, and (D) a non-conductive filler. And a viscosity of 5 to 1000 Pa · s at 25 ° C., and a change rate of viscosity with time (48 hours) at room temperature is ± 20% or less.

  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, and the following general formulas (I) to (I) A compound represented by X) can be used.

〔式中、Ｒ¹は水素又はメチル基を表し、Ｒ²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〕で示される化合物。 (1) General formula (I)

[Wherein R ¹ represents hydrogen or a methyl group, and R ² represents a divalent aliphatic or cyclic hydrocarbon structure having 1 to 100 carbon atoms, preferably 1 to 36 carbon atoms]. The compound shown.

The compounds 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, 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. ^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, iso Bornyl methacry Over DOO, tricyclo [5.2.1.0 ^{2, 6]} decyl methacrylate, 2- (tricyclo) [5.2.1.0 ^2,6] dec-3-ene -8 or 9-yl methacrylate And other methacrylate compounds.

〔式中、Ｒ¹及びＲ²はそれぞれ一般式（Ｉ）におけるものと同じものを表す〕で示される化合物。 (2) General formula (II)

[Wherein R ¹ and R ² are the same as those in formula (I), respectively].

  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, dimer diol monomethacrylate, and the like. Of methacrylate compounds.

〔式中、Ｒ¹は一般式（Ｉ）におけるものと同じものを表し、Ｒ³は水素、メチル基又はフェノキシメチル基を表し、Ｒ⁴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〕で示される化合物。 (3) General formula (III)

[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 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, methoxypolyethylene glycol acrylate, Acrylate compounds such as 2-phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxypolyethylene 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-benzoyloxyethyl methacrylate And methacrylate compounds such as 2-hydroxy-3-phenoxypropyl methacrylate.

〔式中、Ｒ¹は一般式（Ｉ）におけるものと同じものを表し、Ｒ⁵はフェニル基、ニトリル基、−Ｓｉ（ＯＲ⁶）₃（Ｒ⁶は炭素数１〜６のアルキル基を表す）、又は下記の式の基

（Ｒ⁷、Ｒ⁸及びＲ⁹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、Ｒ¹⁰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〕で示される化合物。 (4) General formula (IV)

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

(R ⁷ , R ⁸ and R ⁹ each independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms, R ¹⁰ represents hydrogen, an alkyl group having 1 to 6 carbon atoms or a phenyl group), m represents Represents a number of 0, 1, 2, or 3].

  The compounds 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-acryloyloxyethyl Acrylate compounds such as hydrogen phthalate, β-acryloyloxyethyl hydrogen succinate, benzyl methacrylate, 2-cyanoethyl 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. There are methacrylate compounds.

〔式中、Ｒ¹及びＲ²はそれぞれ独立に一般式（Ｉ）におけるものと同じものを表す〕で示される化合物。 (5) General formula (V)

[Wherein, R ¹ and R ² each independently represent the same as in general 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, and 1,3-butanediol. Diacrylate compounds such as 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 tricyclodecanedi There are dimethacrylate compounds such as methacrylate.

〔式中、Ｒ¹、Ｒ³及びｎはそれぞれ独立に一般式（ＩＩＩ）におけるものと同じものを表す〕で示される化合物。 (6) General formula (VI)

[Wherein, R ¹ , R ³ and n each independently represent the same as in general formula (III)].

  Examples of the compound represented by the general formula (VI) include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, and the like, diethylene glycol There are dimethacrylate compounds such as dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, and polypropylene glycol dimethacrylate.

〔式中、Ｒ¹はそれぞれ独立に一般式（Ｉ）におけるものと同じものを表し、Ｒ¹¹及びＲ¹²はそれぞれ独立に水素又はメチル基を表す〕で示される化合物。 (7) General formula (VII)

[Wherein, R ¹ independently 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, a reaction product of 1 mol of bisphenol A, bisphenol F or bisphenol AD and 2 mol of glycidyl methacrylate, and the like. There is.

〔式中、Ｒ¹、Ｒ¹¹及びＲ¹²はそれぞれ独立に一般式（ＶＩＩ）におけるものと同じものを表しＲ¹³及びＲ¹⁴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〕で示される化合物。 (8) General formula (VIII)

[Wherein R ¹ , R ¹¹ and R ¹² each independently represent the same as in general formula (VII), R ¹³ and R ¹⁴ each independently represent hydrogen or a methyl group, and p and q each independently Represents an integer of 1 to 20].

  The compounds represented by the 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, bisphenol. Examples include dimethacrylate of polyethylene oxide adduct of F or bisphenol AD, dimethacrylate of polypropylene oxide adduct of bisphenol A, bisphenol F or bisphenol AD.

〔式中、Ｒ¹はそれぞれ独立に一般式（Ｉ）におけるものと同じものを表し、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷及びＲ¹⁸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〕で示される化合物。 (9) General formula (IX)

[Wherein, R ¹ independently 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 1 to 20 Represents an integer of].

  Examples of the compound represented by the general formula (IX) include bis (acryloyloxypropyl) polydimethylsiloxane, bis (acryloyloxypropyl) methylsiloxane-dimethylsiloxane copolymer, bis (methacryloyloxypropyl) polydimethylsiloxane, and bis (methacryloyloxypropyl). ) Methylsiloxane-dimethylsiloxane copolymer.

〔式中、Ｒ¹はそれぞれ独立に一般式（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であり、ｓ＋ｕは１以上、好ましくは１〜１００である］で示される化合物。 (10) General formula (X)

[In the formula, each R ¹ independently represents the same thing as in the general formula (I), r, s, t and u are each independently a number of 0 or more indicating the average number of repetitions, and r + t is 0.1 or more, preferably 0.3 to 5, and s + u is 1 or more, preferably 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 a hydrogenated product thereof. For example, MM-1000-80, MAC-1000-80 (both are trade names of Nippon Petrochemical Co., Ltd.), etc.

  (A) As an acrylic ester compound or methacrylic ester compound of a component, said compound can be used individually or in combination of 2 or more types.

  In the present invention, at least one liquid rubber component selected from (B) an epoxidized polybutadiene and a carboxy-terminated acrylonitrile butadiene copolymer is used. The liquid rubber component (B) used in the present invention preferably has an epoxy equivalent of 1000 (g / eq) or less, more preferably 50 to 500 (g / eq), and a viscosity at room temperature of preferably 1000 Pa · epoxidized polybutadiene having a viscosity of s or less, more preferably 10 to 100 Pa · s, and a carboxy-terminated acrylonitrile butadiene copolymer having a viscosity at room temperature of preferably 1000 Pa · s or less, more preferably 50 to 500 Pa · s, either alone or Can be used in combination. The epoxy equivalent is determined by the perchloric acid method. The viscosity can be measured by the same method as the method for measuring the viscosity of the resin paste.

  Examples of the epoxidized polybutadiene include E-1000-8 (trade name of Shin Nippon Petrochemical Co., Ltd.) and PB-4700 (trade name of Daicel Chemical Co., Ltd.). Moreover, as a carboxy terminal acrylonitrile butadiene copolymer, Hycer CTB-2009X162, CTBN-1300X31, CTBN-1300X8, CTBN-1300X13, CTBNX-1300X9 (all are Ube Industries, Ltd. brand names), NISSO-PB-C- 2000 (Nippon Soda Co., Ltd. trade name).

  As the epoxidized polybutadiene, one having at least one hydroxyl group in the molecule may be used.

  (B) As for the compounding quantity of a component, it is preferable to use 10-100 weight part with respect to 100 weight part of (A) component, and 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.

  Although there is no restriction | limiting in particular as a radical initiator of (C) used for this invention, Peroxide is preferable from points, such as a void, Moreover, from the point of sclerosis | hardenability and viscosity stability of a resin paste, it is a rapid heating test. A decomposition temperature of the peroxide is preferably 70 to 170 ° C. Specific examples of the radical initiator include 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.

  The blending amount of the radical initiator is preferably 0.1 to 10 parts by weight, particularly preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total amount of the component (A). If this 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 tends to increase, 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 (D) used for invention, Various things can be used, for example, there exist a filler which consists of silica, an alumina, a titania, glass, iron oxide, a ceramic, etc. These non-conductive fillers impart low thermal expansion, low moisture absorption, and thixotropy to the resin paste.

Moreover, you may add an inorganic ion exchanger as a filler which improves the electrical reliability of a semiconductor device. When paste cured product is extracted in hot water, ions extracted into aqueous solution such as Na ⁺ , K ⁺ , Cl ⁻ , F ⁻ , RCOO ⁻ , Br ^−, etc. are recognized. It is. Examples of such ion exchangers include naturally produced zeolites, natural minerals such as zeolites, acid clay, dolomite, hydrotalcites, and artificially synthesized synthetic zeolites.

  The amount of the filler is usually 1 to 100 parts by weight, preferably 2 to 50 parts by weight with respect to the total amount of the resin paste. If it is less than 1 part by weight, it is difficult to impart sufficient thixotropy (thixotropy index: 1.5 or more) to the paste. Moreover, when it exceeds 100 weight part, adhesiveness may fall. Further, the elastic modulus of the cured product is increased, and as a result, the stress relaxation capability of the die bonding material is lowered and the mounting reliability of the semiconductor device may be lowered.

  One embodiment of the present invention is a die bonding resin comprising silica as a non-conductive filler of a die bonding resin paste, and the filler is subjected to a hydrophobic treatment (hydrophobic surface treatment). Regarding paste.

  As the non-conductive filler silica used in the invention, those having a hydrophobic surface treatment are preferred. Without a hydrophobic surface treatment, the paste easily absorbs moisture, the viscosity of the paste changes due to moisture absorption, and the rate of change in viscosity with time at room temperature tends to increase. The method of hydrophobic surface treatment is not particularly limited. For example, a method of introducing an alkyl group such as a methyl group or a hydrophobic group such as a trimethylsilyl group on the surface of a non-conductive filler, dimethyl silicone oil, octylsilane, or the like. For example, a surface treatment method may be used.

  Examples of the silica filler subjected to the hydrophobic surface treatment include Aerosil R972, R972V, R972CF, R974, RX200, RY200, and R805 (all are trade names of Nippon Aerosil Co., Ltd.).

  Moreover, one Embodiment of this invention is related with the resin paste for die bonding which contains the silica whose average particle diameter of a primary particle is 10 micrometers or less as a silica of the resin paste for die bonding.

  The silica used in the invention preferably has an average primary particle diameter of 10 μm or less, more preferably 1 μm or less, and particularly preferably 1 nm to 100 nm. When the average particle size of the primary particles exceeds 10 μm, it is difficult to impart sufficient thixotropy to the paste. In addition, the said average particle diameter can be measured by the particle size distribution measurement by a laser beam diffraction method, for example. Moreover, an average particle diameter can be calculated | required as a median diameter.

  Moreover, the resin paste of this invention can use a thermosetting resin, for example, an epoxy resin, and a phenol resin used together with an epoxy resin as required. The thermosetting resin is usually used together with a curing accelerator. Epoxy resins include bisphenol A, bisphenol AD, bisphenol S, bisphenol F or a condensed product of halogenated bisphenol A and epichlorohydrin, glycidyl ether of phenol novolac resin, glycidyl ether of cresol novolac resin, glycidyl ether of bisphenol A novolac resin, etc. is there.

  When using an epoxy resin, the amount thereof is preferably 0 to 100 parts by weight, particularly preferably 0 to 30 parts by weight, based on 100 parts by weight of the total amount of the component (A). When the blending ratio exceeds 100 parts by weight, there is a tendency that low stress characteristics are hardly exhibited.

  Examples of the phenol resin include a phenol novolak resin, a cresol novolak resin, a bisphenol A novolak resin, poly-p-vinylphenol, and a phenol aralkyl resin.

  The phenol resin is used in an amount of 0 to 150 parts by weight, preferably 0 to 120 parts by weight, based on 100 parts by weight of the epoxy resin. When this blending ratio exceeds 150 parts by weight, curability tends to be insufficient.

  Any curing accelerator may be used as long as it is used for curing the epoxy resin. Examples of such compounds include imidazoles, dicyandiamide derivatives, dicarboxylic acid dihydrazide, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole-tetraphenylborate, 1,8-diazabicyclo (5 , 4,0) Undecene-7-tetraphenylborate and the like are used.

  The amount of the curing accelerator is 0 to 50 parts by weight, preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the epoxy resin. When the blending ratio exceeds 50 parts by weight, the effect of low stress tends to be difficult to be exhibited.

  The resin paste according to the present invention further includes a toughness improving material such as acrylonitrile-butadiene rubber, styrene-butadiene rubber, urethane acrylate, a hygroscopic agent such as calcium oxide or magnesium oxide, a silane coupling agent, or a titanium coupling. Agents, adhesion improvers such as acid anhydrides, nonionic surfactants, wetting improvers such as fluorosurfactants, antifoaming agents such as silicone oil, spacer fillers and spacer resins to maintain the paste shape Etc. can be suitably added.

  Further, a solvent can be used as necessary. Examples of the solvent include N-methyl-2-pyrrolidinone, diethylene glycol dimethyl ether (also referred to as diglyme), triethylene glycol dimethyl ether (also referred to as triglyme), diethylene glycol diethyl ether, 2- (2-methoxyethoxy) ethanol, γ-butyrolactone, In addition to isophorone, carbitol, carbitol acetate, 1,3-dimethyl-2-imidazolidinone, 2- (2-butoxyethoxy) ethyl acetate, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, dioxane, cyclohexanone, anisole, There are solvents mainly composed of petroleum distillates used as solvents for printing inks.

  Production of the resin paste in the present invention includes (A) an acrylic ester compound or a methacrylic ester compound, (B) an epoxidized polybutadiene or a carboxy-terminated acrylonitrile butadiene copolymer, (C) a radical initiator, and (D) a non-conductive material. Along with various additives that are used as necessary, the filler is combined or divided into a suitable combination of a dispersing / dissolving device such as a stirrer, a raking device, a three-roll, a planetary mixer, etc., and heated as necessary. , Mixing, dissolving, kneading or dispersing. It is preferable to disperse each component uniformly.

  The viscosity of the resin paste is usually in the range of 5 to 1000 Pa · s, more preferably in the range of 5 to 500 Pa · s, more preferably a mesh or the like in the mask opening as in a screen mesh plate or the like. When it is stretched, it is preferably in the range of 5 to 200 Pa · s in consideration of the ability to remove the mesh portion, and in the case of a stencil plate or the like, it is preferably adjusted to the range of 20 to 500 Pa · s. When the viscosity of the resin paste is less than 5 Pa · s or more than 1000 Pa · s, the printing workability tends to be lowered. However, the above viscosity is a value when measured at 25 ° C. and a rotational speed of 0.5 rpm using an E-type rotational viscometer.

  In addition, the die bonding resin paste of the present invention has a rate of change in viscosity with time (48 hours) at room temperature of ± 20% or less. The room temperature is preferably 10 to 30 ° C. The rate of change in viscosity with time (48 hours) is the rate of change in viscosity before and after the resin paste is left at room temperature for 48 hours. The rate of change in viscosity with time can be measured at any time after the resin paste is created.

  The rate of change in viscosity with time is preferably ± 15% or less, more preferably ± 10% or less. If the rate of change in viscosity when the resin paste is allowed to stand at room temperature for 48 hours exceeds ± 20%, the usable time of the resin paste is very short, and the usability becomes poor. In order to set the rate of change in viscosity of the resin paste with time (48 hours) to ± 20% or less, for example, it is preferable to create the paste by avoiding highly hygroscopic materials as the composition of the resin paste.

  The present invention also includes the steps of (1) applying a die bonding resin paste obtained on a support member, (2) mounting a semiconductor chip on the resin paste, and (3) curing the resin paste. The present invention relates to a method for manufacturing a semiconductor device.

  Specifically, the obtained die bonding resin paste is a lead frame such as a 42 alloy lead frame or a copper lead frame, or a plastic film such as a polyimide resin, an epoxy resin or a polyimide resin, and further a glass nonwoven fabric or the like. The resin paste of the present invention is printed on a base material made by impregnating and curing a plastic such as polyimide resin, epoxy resin or polyimide resin, or a ceramic support member (plate-like) such as alumina. After supplying and applying, the semiconductor element is attached and then heated to bond the chip to the support member. Thereafter, the chip is mounted on the support member by a curing process. The curing step may be cured by the sealing material curing step within a range that does not affect the mounting reliability.

  The resin paste of the present invention can be cured at a relatively low temperature, and the curing temperature is preferably 140 to 200 ° C, more preferably 150 to 180 ° C.

  In addition, after supplying and applying the resin paste by a printing method, it is dried and semi-cured to obtain a support member with a B stage adhesive, and then a semiconductor element (chip) such as an IC or LSI is attached to the support member with the B stage adhesive. ) Can be attached and heated to bond the chip to the support member.

  Accordingly, in one embodiment of the method for manufacturing a semiconductor device of the present invention, (1) a resin paste for die bonding is applied on a support member, (2) the resin paste is dried to form a B stage, and (3) B The present invention relates to a method for manufacturing a semiconductor device, including a step of mounting a semiconductor chip on the staged resin paste and (4) curing the resin paste.

  Further, the structure of the semiconductor device of the present invention is not particularly limited as long as it is manufactured using the resin paste of the present invention. For example, the resin paste of the present invention in which a semiconductor element and a support member are bonded to each other. A semiconductor device containing

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

(Examples 1 to 5, Comparative Example 2)
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 a carbitol acetate (29 parts by weight) solution of 11 parts by weight of epoxy resin (YDCN-702) and 8 parts by weight of phenol resin (H-1) (the concentration of the solid content of the thermosetting resin is about 40% by weight). In addition, each material was put together with each material in 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.

  Properties of these resin pastes (viscosity, thixotropy index, viscosity after standing at room temperature for 2 days, hot die shear strength, void occupancy) were examined by the following methods. The results are shown in Table 1.

  (1) Viscosity: 0.4 ml of the resin paste was measured, and the viscosity (Pa · s) at 25 rpm at 25 ° C. was measured with an EHD viscometer (manufactured by Tokimec Co., Ltd.) using a 3 ° cone.

  (2) Viscosity after 2 days at room temperature (48 hours): 0.4 ml of paste left at 23 ° C. for 2 days (48 hours) with the paste-filled container sealed, and measured by EHD viscosity The viscosity (Pa · s) at 25 rpm at 25 ° C. was measured using a 3 ° cone with a meter (manufactured by Tokimec Co., Ltd.).

  (3) Nonvolatile content concentration: 1.5 g of resin paste is measured on a metal petri dish (diameter 60 mm, depth 10 mm), the weight is precisely weighed, and cured in an oven at 200 ° C. for 2 hours. Thereafter, the weight was precisely weighed, and the non-volatile content concentration was calculated by the following formula.

  (4) Die shear strength during heating: A resin paste is printed in a size of 5 × 5 mm on an 8 × 10 mm 42 alloy lead frame, and a 5 × 5 mm silicon chip (thickness 0.4 mm) is formed on the resin paste. A pressure of 50 g was applied for 1 second at room temperature. Thereafter, it was cured in an oven at 180 ° C. for 1 hour. This was measured for shear strength (kg / chip) at 250 ° C. using an automatic adhesive strength tester (manufactured by Daisy).

  (5) Void: A resin paste is printed on an 8 × 10 mm 42 alloy lead frame in a size of 8 × 10 mm, and an 8 mm × 10 mm silicon chip (thickness 0.4 mm) is applied with a load of 50 g. For 1 second. Then, it hardened for 1 hour in 180 degreeC oven, and created the sample. The paste layer portion of this sample was observed using a scanning ultrasonic microscope, and the occupied area of voids contained in the cured resin paste was determined.

  (6) Stability when the paste is released: About 12.0 g of resin paste is put into a metal petri dish (diameter 60 mm, depth 10 mm), and uniformly put into a constant temperature and humidity chamber of 85 ° C.-85% RH. After leaving for a predetermined time, the viscosity of the paste was measured by the method (1) above, and the time when the rate of change from the viscosity before being put into the constant temperature and humidity chamber exceeded 20% was determined.

In Table 1, various symbols have the following meanings.
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 Chemical Co., Ltd., 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 Co., Ltd., epoxidized polybutadiene 2P4MHZ: Shikoku Kasei Co., Ltd., Curesol DICY: Dicyandiamide AEROSIL 380: Nippon Aerosil Co., Ltd., silica filler AEROSIL R972: Nippon Aerosil Co., Ltd., silica filler with hydrophobic surface treatment

From the results in Table 1, the resin paste for die bonding (Examples 1 to 6) of the present invention has a good value in hot die shear strength compared to the resin paste (Comparative Example 1) using a conventional epoxy resin. It was also possible to suppress the generation of voids. Furthermore, since the non-volatile content concentration is high, it is possible to suppress a reduction in paste film due to curing. Moreover, compared with the resin paste (Comparative Example 2) using the silica filler which is not surface-treated as a nonelectroconductive filler, the stability at the time of paste release was able to be extended. From this, it was confirmed that the present invention can provide a highly reliable resin paste for die bonding that is easy to handle and suppresses void generation and film loss after curing.

Claims (6)

  (A) an acrylic ester compound or a methacrylic ester compound, (B) an epoxidized polybutadiene or a carboxy-terminated acrylonitrile butadiene copolymer, (C) a radical initiator, and (D) a non-conductive filler. A resin paste for die bonding having a viscosity at 5 ° C. of 5 to 1000 Pa · s and a rate of change in viscosity over time (48 hours) at room temperature of ± 20% or less.   The resin paste for die bonding according to claim 1, wherein the non-conductive filler is a silica filler that has been subjected to a hydrophobic treatment.   The resin paste for die bonding according to claim 2, wherein the average particle size of primary particles of the silica filler is 10 µm or less.   (1) A resin paste for die bonding according to any one of claims 1 to 3 is applied on a support member, (2) a semiconductor chip is mounted on the resin paste, and (3) the resin paste is cured. A manufacturing method of a semiconductor device including a process.   (1) The die bonding resin paste according to any one of claims 1 to 3 is applied onto a support member, (2) the resin paste is dried to form a B stage, and (3) the B stage is formed. A method for manufacturing a semiconductor device, comprising: mounting a semiconductor chip on a resin paste; and (4) curing the resin paste. The semiconductor device using the resin paste for die bonding as described in any one of Claims 1-3.