JP2001011107A - Resin paste composition and semiconductor device produced by using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin paste composition having high reactivity, curability and adhesivity and causing little bleed-out to a substrate such as metal frame, ceramic circuit board, glass epoxy circuit board and polyimide circuit board, and provide an easily manufacturable semiconductor device produced by using the composition. SOLUTION: The resin paste composition contains (A) an acrylic acid ester compound or a methacrylic acid ester compound, (B) a radical reaction initiator, (C) a fluorine-based surfactant having a perfluoroalkyl group and expressed by the formula F3C-(CF2)a-COOH ((a) is an integer of 2-20) and (D) a filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin paste composition, and more particularly, to a method for bonding semiconductor elements such as ICs and LSIs to substrates such as lead frames, ceramic wiring boards, glass epoxy wiring boards, and polyimide wiring boards. The present invention relates to a novel resin paste composition and a semiconductor device using the same.

[0002]

2. Description of the Related Art In recent years, ceramic wiring boards, glass epoxy wiring boards, polyimide wiring boards, and the like have been used as semiconductor substrates in addition to conventional metal frames.
The surface state of a substrate to which a semiconductor element is bonded has changed greatly. Also, with respect to the conventional metal frame, the plating process and the like have changed from the viewpoint of cost reduction, and the surface condition of the metal frame plating surface has changed greatly. For this reason, when a conventional resin paste composition is used, a phenomenon called a bleed-out, in which a resin component oozes out onto a substrate, may occur, causing a reduction in the reliability of a semiconductor device.

[0003]

SUMMARY OF THE INVENTION The present invention eliminates the above-mentioned problems of the prior art, and has high reactivity, good curability,
A resin paste composition which provides excellent adhesion, has little bleed-out to a substrate such as a metal frame, a ceramic wiring board, a glass epoxy wiring board, and a polyimide wiring board, and a semiconductor device which is easy to manufacture using the same. It is.

[0004]

The present invention comprises (A) an acrylate compound or a methacrylate compound (B) a radical initiator, and (C) a perfluoroalkyl group represented by the general formula (I). The present invention relates to a resin paste composition containing a fluorinated surfactant and (D) a filler.

[0005]

Embedded image (Where a is an integer of 2 to 20) The present invention also relates to a semiconductor device in which a semiconductor element is bonded to a substrate using the above-mentioned resin paste composition and then sealed.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The acrylate compound or methacrylate compound as the component (A) used in the present invention is, for example, a compound having at least one acryl or methacryl group in one molecule. The compounds represented by the general formulas (II) to (XI) can be used.

(1) General formula (II)

[0008]

Embedded image (Wherein, R ¹ represents hydrogen or a methyl group, and R ² has 1 carbon atom.
-100, preferably a divalent aliphatic or cyclic hydrocarbon group having a cyclic structure having 1 to 36 carbon atoms).

The compounds represented by the general formula (II) 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. 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 ] deca-
Acrylate compounds such as 3-ene-8 or 9-yl-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, isobornyl methacrylate, Cyclo [5.2.1.0 ^2,6]
Decyl methacrylate, 2- (tricyclo) [5.2.
1.0 ^2,6 ] methacrylate compounds such as deca-3-en-8 or 9-yl-oxyethyl methacrylate.

(2) General formula (III)

[0011]

Embedded image (Wherein, R ¹ and R ² represent the same as those in formula (II)).

The compound represented by the general formula (III) includes 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and the like.

(3) General formula (IV)

[0014]

Embedded image (Wherein, R ¹ represents the same as in general formula (II), R ³ represents hydrogen, a methyl group or a phenoxymethyl group, R ⁴ represents hydrogen, an alkyl group having 1 to 6 carbon atoms, dicycloalkyl, A pentenyl group, a phenyl group or a benzoyl group, and n represents an integer of 1 to 50).

The compound represented by the general formula (IV) includes diethylene glycol acrylate, polyethylene glycol acrylate, polypropylene glycol acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, methoxydiethylene glycol acrylate,
Acrylate compounds such as methoxypolyethylene glycol acrylate, dicyclopentenyloxyethyl acrylate, 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, methoxy polyethylene glycol methacrylate, dicyclopentenyloxyethyl meth Relate, 2-phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, phenoxy polyethylene glycol methacrylate, 2-benzoyloxy ethyl methacrylate, methacrylate compounds such as 2-hydroxy-3-phenoxypropyl methacrylate.

(4) General formula (V)

[0017]

Embedded image [Wherein, R ¹ represents the same as in the general formula (II), and R ⁵ represents a phenyl group, a nitrile group, -Si (O
R ⁶ ) ₃ (R ⁶ represents an alkyl group having 1 to ⁶ carbon atoms),

[0018]

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

The compound represented by the general formula (V) includes
Benzyl acrylate, 2-cyanoethyl acrylate, γ-acryloyloxypropyltrimethoxysilane, glycidyl acrylate, tetrahydrofurfuryl acrylate, tetrahydropyranyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, 1,2,2,6,6- Pentamethylpiperidinyl acrylate, 2,2,6,6-tetramethylpiperidinyl acrylate, acryloyloxyethyl phosphate, acryloyloxyethyl phenyl acid phosphate, β-acryloyloxyethyl hydrogen phthalate, β-acryloyloxyethyl hydro Acrylate compounds such as gen succinate, benzyl methacrylate, 2-cyanoethyl methacrylate, γ-meth Leroy Le trimethoxysilane, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, tetrahydropyranyl methacrylate, dimethylaminoethyl methacrylate,
Diethylaminoethyl methacrylate, 1,2,2
6,6, -pentamethylpiperidinyl methacrylate,
Methacrylates such as 2,2,6,6-tetramethylpiperidinyl methacrylate, methacryloyloxyethyl phosphate, methacryloyloxyethyl phenyl acid phosphate, β-methacryloyloxyethyl hydrogen phthalate, β-methacryloyloxyethyl hydrogen succinate and the like Methacrylate compounds.

(5) General formula (VI)

[0021]

Embedded image (Wherein, R ¹ and R ² represent the same as those in formula (II)).

The compounds represented by the general formula (VI) include ethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,3 A diacrylate compound such as butanediol diacrylate, neopentyl glycol diacrylate, dimer diol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonane Diol dimethacrylate, 1,3
-Dimethacrylate compounds such as butanediol dimethacrylate, neopentyl glycol dimethacrylate and dimer diol dimethacrylate.

(6) General formula (VII)

[0024]

Embedded image (Wherein, R ¹ and R ³ represent the same as in the general formula (IV), and n represents the same as in the general formula (IV)).

The compound represented by the general formula (VII) includes diacrylates such as diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol diacrylate. Compounds include dimethacrylate compounds such as diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, and polypropylene glycol dimethacrylate.

(7) General formula (VIII)

[0027]

Embedded image (Wherein, R ¹ represents the same as in general formula (II), and R ¹¹ and R ¹² each independently represent hydrogen or a methyl group).

The compound represented by the general formula (VIII) includes a reaction product of bisphenol A, bisphenol F or 1 mol of bisphenol AD and 2 mol of glycidyl acrylate, bisphenol A, bisphenol F or 1 mol of bisphenol AD and glycidyl methacrylate 2
There are reactants with moles.

(8) Formula (IX)

[0030]

Embedded image (Wherein, R ¹ represents the same as in the general formula (II), R ¹¹ and R ¹² represent the same as in the general formula (VIII), and R ¹³ and R ¹⁴ each independently represent hydrogen or Represents a methyl group, p and q each independently represents 1 to
Which represents an integer of 20).

Examples of the compound represented by the general formula (IX) include diacrylate of a polyethylene oxide adduct of bisphenol A, bisphenol F or bisphenol AD, diacrylate of a polypropylene oxide adduct of bisphenol A, bisphenol F or bisphenol AD, and bisphenol. A, a dimethacrylate of a polyethylene oxide adduct of bisphenol F or bisphenol AD, a dimethacrylate of a polypropylene oxide adduct of bisphenol A, bisphenol F or bisphenol AD, and the like.

(9) General formula (X)

[0033]

Embedded image (Wherein, R ¹ represents the same as those in the general formula ^{(II), R 15, R} 16, R 1 7 and R ¹⁸ each independently represent a hydrogen or a methyl group, x is an integer from 1 to 20 Which represents a).

The compound represented by the general formula (X) includes
Bis (acryloyloxypropyl) polydimethylsiloxane, bis (acryloyloxypropyl) methylsiloxane-dimethylsiloxane copolymer, bis (methacryloyloxypropyl) polydimethylsiloxane,
Bis (methacryloyloxypropyl) methylsiloxane-dimethylsiloxane copolymer and the like.

(10) General formula (XI)

[0036]

Embedded image (In the formula, R ¹ represents the same one as in the general formula (II), r, s, t and u are each independently a number of 0 or more indicating an average value of the number of repetitions, and r + t is 0.1 Or more, preferably from 0.3 to 5, and s + u is 1 or more, preferably from 1 to 100).

Examples of the compound represented by the general formula (XI) include a reaction product obtained by reacting polybutadiene to which maleic anhydride is added with an acrylate compound or a methacrylate compound having a hydroxyl group in a molecule, and a hydrogen product thereof. There is no particular limitation as long as it is a compound having an additive and having one or more acrylic or methacrylic groups in one molecule. For example, MM-1000-80, MAC-100
0-80 (both are trade names of Nippon Petrochemical Co., Ltd.) and the like.

As the acrylate compound or methacrylate compound as the component (A), the above compounds can be used alone or in combination of two or more.

The radical initiator (B) used in the present invention is not particularly limited, but is preferably a peroxide in terms of voids and the like, and in view of the curability and viscosity stability of the resin paste composition. Those having a peroxide decomposition temperature of 70 to 170 ° C in a rapid heating test are preferred.

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 mixing amount of the radical initiator is preferably from 0.1 to 10 parts by weight, particularly preferably from 0.5 to 5 parts by weight, based on 100 parts by weight of the total amount of the component (A). If the compounding ratio is less than 0.1 part by weight, the curability tends to decrease, and if it exceeds 10 parts by weight, the volatile content increases, and voids called voids tend to be easily generated in the cured product. .

Examples of the fluorine surfactant containing a perfluoroalkyl group represented by the general formula (I), which is the component (C) used in the present invention, include, for example, perfluorobutyric acid, perfluorocaproic acid, perfluorocaprylic acid , Perfluorocapric acid, perfluorolauric acid and the like.

The compounding amount of the compound represented by the general formula (I) is preferably 0.01 to 1.0% by weight based on the total amount of the components (A), (B) and (D). .03-
0.7% by weight is more preferred. If the amount is too small, the effect of suppressing bleed-out tends to decrease. If the amount is too large, the adhesive strength tends to decrease.

The filler (D) used in the present invention is not particularly limited, and various fillers can be used. Examples thereof include gold, silver, copper, nickel, iron, aluminum, stainless steel, silicon oxide, boron nitride, Powders such as aluminum oxide and aluminum borate are exemplified. The powder used as these fillers preferably has a particle size of 0.1 to 100 μm, more preferably 1 to 20 μm.
The amount of the filler is not particularly limited, but is preferably 20 to 90 parts by weight, more preferably 40 to 85 parts by weight, based on 100 parts by weight of the total amount of the resin paste composition. If this blending amount is 2
If the amount is less than 0 parts by weight, the adhesive strength when heated tends to decrease, and if it exceeds 90 parts by weight, the viscosity increases and the workability of the paste tends to decrease.

The resin paste composition according to the present invention may further contain, if necessary, a toughness improver such as polybutadiene, a polybutadiene derivative, acrylonitrile butadiene rubber, styrene butadiene rubber, urethane acrylate, a moisture absorbent such as calcium oxide and magnesium oxide, Adhesion enhancers such as silane coupling agents, titanium coupling agents, acid anhydrides, nonionic surfactants, wetting improvers such as higher fatty acids, defoamers such as silicone oil, and ion traps such as inorganic ion exchangers Agents or the like can be added alone or in combination of several types as appropriate.

To produce the resin paste of the present invention,
(A) an acrylate compound or a methacrylate compound, (B) a radical initiator (C) a general formula (I)
The fluorosurfactant containing a perfluoroalkyl group represented by the formula (I) and the filler (D) are collectively or divided, and a dispersing / dissolving device such as a stirrer, a grinder, a three-roller, or a planetary mixer is appropriately used. The paste may be mixed, melted, pulverized and kneaded or dispersed by heating, if necessary, into a uniform paste.

In the present invention, a semiconductor device can be obtained by bonding a semiconductor element and a substrate using the resin paste composition produced as described above, and then sealing it.

In order to adhere a semiconductor element to a support member such as a lead frame using the resin paste composition of the present invention, first, the resin paste composition is applied on the support member by a dispense method, a screen printing method, a stamping method or the like. After that, the semiconductor element can be press-bonded, and then heat-cured using a heating device such as an oven or a heat block. Further, after a wire bonding step, the semiconductor device is sealed by a usual method, whereby a completed semiconductor device can be obtained.

The above-mentioned heat curing differs depending on the case of long-term curing at a low temperature or the case of rapid curing at a high temperature, but it is usually 100 to 300 ° C., preferably 130 to 220 ° C.
It is preferable to carry out for 2 to 3 hours, preferably for 15 seconds to 1 hour.

[0050]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

The compounds used in the following examples are exemplified. (1) Acrylic ester compound and methacrylic ester compound R-551 (trade name of diacrylate manufactured by Nippon Kayaku Co., bisphenol A polyethylene glycol diacrylate), MAC-1000-80 (acrylated polybutadiene manufactured by Nippon Petrochemical Co., Ltd.) FA-512M (trade name of monomethacrylate manufactured by Hitachi Chemical Co., Ltd., 2- (tricyclo) [5.2.1.0 ^2,6 ])
Deca-3-en-8 or 9-yloxyethyl methacrylate), AMP-20G (trade name of monoacrylate manufactured by Shin-Nakamura Chemical Co., phenoxydiethylene glycol acrylate) A-174 (trade name of monoacrylate manufactured by Nippon Unicar, γ) -Methacryloxypropyltrimethoxysilane) (2) radical initiator dicumyl peroxide (decomposition temperature 126 ° C) (3) fluorinated surfactant perfluorocaprylic acid, perfluorolauric acid (4) filler TCG-1 (Tokuriki Chemical The respective materials were mixed at the mixing ratios shown in Table 1 and kneaded using a three-roll mill, followed by defoaming at 5 Torr (Torr) or less for 10 minutes to obtain a resin. A paste composition was obtained.

The properties (viscosity, adhesive strength and bleed-out) of this resin paste composition were examined by the following methods. Table 1 shows the results.

(1) Viscosity: The viscosity (Pa · s) at 25 ° C. was measured using an EHD type rotational viscometer (manufactured by Tokyo Keiki Co., Ltd.).

(2) Adhesive strength: A
Approximately 200 μg is applied on a copper lead frame provided with a g-plate, and a 2 mm × 2 mm Si chip (having a thickness of about 0.2 μm) is coated thereon.
4 mm), and then put into an oven set at 150 ° C. and heat-cured for 1 hour. The shear adhesive strength (kg / chip) at room temperature was measured using an automatic adhesive strength tester (BT100, manufactured by Dage).

(3) Bleed-out: 200 μg to 400 μg of the resin paste composition was applied to a copper lead frame with Ag plating and a polyimide substrate, left at 25 ° C. for 1 hour, and then put in an oven set at 150 ° C. Heat cured for hours. Using an optical microscope for this,
The bleeding width from the cured product to the Ag plating surface and the polyimide surface was observed and measured.

[0056]

[Table 1] In Comparative Examples 1 and 2 in Table 1, the occurrence of bleed-out is large. In contrast, in Examples 1 to 4, it was confirmed that the resin paste composition of the present invention had high adhesive strength and bleed-out was suppressed.

[0057]

When the resin paste composition of the present invention is used as a die bonding material for a semiconductor device, it can be used as a metal frame, a ceramic wiring board, a glass epoxy wiring board,
Bleed-out to a substrate such as a polyimide wiring board can be suppressed.

The semiconductor device of the present invention is excellent in reliability because it uses the above-mentioned resin paste composition.

Continued on front page F-term (reference) 4J011 PA03 PA07 PA13 PA14 PA28 PB22 PB40 PC08 QA03 QA34 4J040 DF031 DJ031 DL141 HA066 HA136 HA326 HB23 KA12 KA38 KA42 MA02 MA04 MA10 MB09 NA20 5F047 AA10 AA11 AA17 BA33

Claims (2)

[Claims] (A) an acrylate compound or a methacrylate compound, (B) a radical initiator,
(C) A resin paste composition containing a perfluoroalkyl group-containing fluorosurfactant represented by the general formula (I) and (D) a filler. Embedded image (Where a is an integer of 2 to 20) 2. A semiconductor device obtained by bonding a semiconductor element to a substrate using the resin paste composition according to claim 1, and then sealing the semiconductor element.