JP2000044774A - Epoxy resin composition for sealing semiconductor and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an epoxy resin composition for sealing a semiconductor, exhibiting high adhesion to a semiconductor member and excellent releasability in molding and capable of increasing reliability of a semiconductor, and a semiconductor device of high reliability sealed with the epoxy resin composition. SOLUTION: This epoxy resin composition for sealing a semiconductor comprises an epoxy resin (A), a curing agent (B), an inorganic filler (C), an amide compound (D) and an organopolysiloxane (E), wherein the content of the inorganic filler (C) is 50-95 wt.%, the amide compound (D) is the one comprising an 8-22C fatty acid and is contained in an amount of 0.01-2 wt.% in the composition, and the organopolysiloxane (E) is an epoxy group-containing organopolysiloxane obtained by reacting a carboxyl group-containing organopolysiloxane with an epoxy compound and is contained in an amount of 0.01-2 wt.% in the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition for semiconductor encapsulation, which has high adhesiveness to a semiconductor member, has excellent mold releasability during molding, and can enhance the reliability of semiconductors. The present invention relates to a semiconductor device sealed with a stopping composition.

[0002]

2. Description of the Related Art Epoxy resins are widely used as resin-sealing type semiconductor encapsulation resins because of their excellent heat resistance, moisture resistance, electrical properties, adhesiveness and the like. The main components of these epoxy resin compositions for semiconductor encapsulation generally include an epoxy resin, a phenolic curing agent, a curing accelerator, and an inorganic filler.

[0003] In the field of semiconductor integrated circuits, the degree of integration of IC chips has been further improved due to advances in microfabrication technology. However, in order to further increase the degree of integration, the occupation rate of IC chips in a package has been increasing. In addition, packages have become larger and have more pins.

On the other hand, the density of a semiconductor device package mounted on a printed wiring board has been increased.
Instead of the conventional “insertion mounting method” in which lead pins are inserted into holes in a substrate, “surface mounting method” in which a package is soldered to the surface of a substrate has become popular. Along with this, the package has become thinner and exposed to a high temperature of 200 ° C. or more during solder reflow in the surface mounting process.
The IC chip or the lead frame and the encapsulant are peeled off, cracks are generated in the package, and a defect that significantly impairs reliability has occurred.

[0005] For the above reasons, in the resin for encapsulating the semiconductor, it is essential to improve the adhesion to the package member such as the polyimide film or the silicon nitride film on the surface of the lead frame or the IC to improve the reliability of the semiconductor. It has become.

Recently, copper materials have been increasingly used as lead frames due to the need for heat dissipation and high-speed electrical characteristics. When a copper material is used for the lead frame, the adhesion between the lead frame and the sealing material is reduced due to oxidation of the copper, and therefore, further adhesion is required.

Conventionally, a method of adding a chelating component (Journal of Adhesion Science Technology, No. 10) has been used to improve the adhesion of an epoxy resin composition.
Vol. 1, No. 1, pp. 1-15, published in 1996), but their characteristics were not always satisfactory.

Further, in recent years, the shortening of the molding time in improving the productivity of the semiconductor device package has reduced the releasability from the mold, causing poor appearance of the semiconductor device package at the time of releasing, and impairing the continuous moldability. Problem.

[0009]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems in the prior art, and as a result,
Has been achieved.

[0010] Accordingly, an object of the present invention is to provide high adhesiveness to a semiconductor package member and excellent mold release properties.
An object of the present invention is to provide an epoxy resin composition for semiconductor encapsulation capable of improving the reliability of a semiconductor, and a semiconductor device sealed with the epoxy resin composition.

[0011]

In order to solve the above-mentioned problems, the epoxy resin composition for semiconductor encapsulation of the present invention mainly has the following constitution. That is, epoxy resin (A), curing agent (B), inorganic filler (C), amide compound (D),
In the resin composition for semiconductor encapsulation comprising the organopolysiloxane (E), the content of the inorganic filler (C) is 50 to 50%.
95% by weight, and the amide compound (D) has 8 to 2 carbon atoms.
A compound consisting of 2 fatty acids, wherein
1 to 2% by weight, and the organopolysiloxane (E) is an epoxy group-containing organopolysiloxane which is a reaction product of a carboxyl group-containing organopolysiloxane and an epoxy compound. % By weight of an epoxy resin composition for semiconductor encapsulation.

Further, the semiconductor device of the present invention mainly comprises the following:
It has any one of (1) to (3). That is, (1) a semiconductor device characterized in that a semiconductor element is sealed by a cured product of the epoxy resin composition for semiconductor encapsulation,
Or (2) a semiconductor device, wherein a semiconductor element on a lead frame made of a 42 alloy material is sealed by a cured product of the epoxy resin composition for semiconductor encapsulation, or (3) the semiconductor A semiconductor device characterized in that a semiconductor element on a lead frame made of a copper frame material is sealed with a cured product of an epoxy resin composition for sealing.

[0013]

Embodiments of the present invention will be described below. In the present invention, “weight” means “mass”.

The epoxy resin (A) according to the present invention comprises 1
The compound is not particularly limited as long as it has two or more epoxy groups in the molecule. For example, cresol novolak type epoxy resin, phenol novolak type epoxy resin, biphenyl type epoxy resin, phenol aralkyl type epoxy resin, naphthalene type epoxy resin, stilbene Epoxy resin, epoxy resin containing dicyclopentadiene skeleton,
Triphenylmethane type epoxy resin, bisphenol A
Epoxy resin, bisphenol F epoxy resin, tetramethyl bisphenol F epoxy resin, chain aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, halogenated epoxy resin, etc. Can be

Specific examples of the epoxy resin (A) include:
4,4'-bis (2,3-epoxypropoxy) biphenyl, 4,4'-bis (2,3-epoxypropoxy)
-3,3 ', 5,5'-tetramethylbiphenyl, 4,
4'-bis (2,3-epoxypropoxy) -3,3
', 5,5'-tetraethylbiphenyl, 4,4'-bis (2,3-epoxypropoxy) -3,3', 5,5
Biphenyl type epoxy resins such as' -tetramethyl-2-chlorobiphenyl, 1,5-di (2,3-epoxypropoxy) naphthalene, 1,6-di (2,3-epoxypropoxy) naphthalene, naphthol aralkyl type epoxy Naphthalene type epoxy resin such as resin, 3-t-butyl-2,4'-dihydroxy-3 ', 5', 6-glycidyl ether of 6-trimethylstilbene, 3-t-butyl-4,4'-dihydroxy-3 ', 5,5'-Diglycidyl ether of trimethylstilbene, 4,4'-
Diglycidyl ether of dihydroxy-3,3 ', 5,5'-tetramethylstilbene, diglycidyl ether of 4,4'-dihydroxy-3,3'-di-t-butyl-6,6'-dimethylstilbene and the like Stilbene type epoxy resin, 3,3′5,5′-tetramethyl-4,4
'Diglycidyl ether of dihydroxydiphenylmethane, 1,4-bis (3-methyl-4-hydroxycumyl)
Diglycidyl ether of benzene, diglycidyl ether of 4,4'-dihydroxydiphenyl ether 2,2
-Dimethyl-5,5'-di-tert-butyl-4,4
Examples thereof include bisphenol type epoxy resins such as' -dihydroxydiphenyl sulfide, and these may be used alone or in combination of two or more.

In the present invention, the epoxy resin (A) has a softening point of usually 50 to 130 ° C., preferably 50 to 130 ° C.
10 ° C. The viscosity at the time of melting is usually 0.05 to 50 poise at a value of 150 ° C., preferably 0.05 to 50 poise.
10 poise. If the softening point is out of the range of 50 to 130 ° C., or if the viscosity is out of the range of 0.05 to 50 poise, the workability deteriorates, which is not preferable.

In the present invention, the compounding amount of the epoxy resin (A) is 3 to 2 with respect to the entire epoxy resin composition.
5% by weight, further 3-10% by weight, especially 3-6%
% By weight is preferred. By setting the blending amount of the epoxy resin (A) in such a range, moldability becomes sufficient and crack resistance in a reflow test becomes excellent.

In the present invention, the curing agent (B) is not particularly limited as long as it is a compound that reacts with the epoxy resin. When a cured product is used, a phenol compound (b) is preferably used as a compound having a low water absorption. Phenol compound (b)
Examples of novolak resins such as phenol novolak resin, cresol novolak resin, naphthol novolak resin, tris (hydroxyphenyl) methane, 1,1,2-tris (hydroxyphenyl) ethane, 1,1,3-tris ( (Hydroxyphenyl) propane, a condensed compound of terpene and phenol, a phenol resin having a dicyclopentadiene skeleton, a phenol aralkyl resin, a naphthol aralkyl resin, a phenol aralkyl resin having a biphenyl skeleton, catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol and the like. These may be used alone or in combination of two or more.

In the present invention, the compounding amount of the curing agent (B) is usually 3 to 22% by weight, preferably 3 to 10% by weight, more preferably 3 to 6% by weight based on the whole epoxy resin composition. %. Further, the mixing ratio of the epoxy resin (A) and the phenolic compound (b) is such that the chemical equivalent ratio of (b) to (A) is 0.5 to 2, particularly 0.1 to 2 from the viewpoint of mechanical properties and moisture resistance reliability. It is preferably in the range of 7 to 1.5.

In the present invention, any known curing accelerator can be used as long as it promotes the reaction between the epoxy resin and the phenol compound. Specific examples of the curing accelerator include 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole,
-Imidazoles such as undecyl imidazole and salts thereof, tertiary amine compounds such as triethylamine, benzyldimethylamine and α-methylbenzylamine, 1,8-diazabicyclo (5,4,0) undecene-7,1,5 -Diazabicyclo (4,3,0) nonene,
7-methyl-1,5,7-triazabicyclo (4,4,
0) Amidine compounds such as decene-5 and salts thereof, phosphorus compounds such as triphenylphosphine, tris (2,6-dimethoxyphenyl) phosphine, tris (4-alkylphenyl) phosphine, trialkylphosphine and salts thereof and the like. Used. Two or more of these curing accelerators may be used in combination, or may be added after being melt-mixed with a phenol compound or an epoxy resin to be used in advance.

As the inorganic filler (C) in the present invention, amorphous silica, crystalline silica, calcium carbonate, magnesium carbonate, alumina, magnesia, silicon nitride, magnesium aluminum oxide, zirconia, zircon,
Examples include clay, talc, mica, calcium silicate, titanium oxide, antimony oxide, asbestos, glass fiber, and the like, and any of spherical, crushed, fibrous, and the like can be used.

The compounding amount of the inorganic filler (C) is 50 to 95% by weight in the resin composition, preferably 75 to 93% by weight, and particularly preferably 80 to 92% by weight. Less than 50% by weight of inorganic filler (C) or 9
If it exceeds 5% by weight, it cannot be put to practical use due to poor solder heat resistance and moldability.

In the present invention, it is preferable from the viewpoint of the reliability of a semiconductor device obtained that a coupling agent such as a silane coupling agent or a titanate coupling agent is mixed in the epoxy resin composition. The same effect can be expected when the coupling agent is blended as it is or when the inorganic filler (C) is surface-treated in advance.

As the coupling agent, a silane coupling agent in which an organic group and a hydrolyzable group are directly bonded to a silicon atom is preferably used.
Aminosilane, mercaptosilane, ureidosilane and the like. Among them, a silane coupling agent having an amino group is particularly preferably used. Specific examples of particularly preferred silane coupling agents having an amino group include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-amino Propylmethyldimethoxysilane, N-β (aminoethyl) γ
-Aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane and the like.

The addition amount of the coupling agent is usually 0.1 to 2% by weight based on the whole epoxy resin composition.

The amide compound (D) in the present invention is not particularly limited as long as it can be derived from a fatty acid having 8 to 22 carbon atoms. When the number of carbon atoms of the fatty acid is less than 8 or more than 22, the adhesion decreases. Specific examples of the amide compound (D) include lauric amide, behenic amide,
Monoamides such as oleic acid amide, N-stearyl stearic acid amide, methylol stearic acid amide,
Methylenebisstearic acid amide, ethylenebisstearic acid amide, hexamethylenebisstearic acid amide, N, N'-distearyladipamide, ethylenebisoleic acid amide, ethylenebisbehenic acid amide, m-xylylene bisstearic acid amide , N, N '
And bisamides such as distearyl isophthalic acid amide. The above compounds may be used alone or in combination of two or more.

The particularly preferred amide compound (D) is a polyvalent amide having two or more amide groups in one molecule. Specific examples thereof include methylenebisstearic acid amide, ethylenebisstearic acid amide, and ethylenebisbehenate. Acid amide, ethylenebisoleic acid amide, ethylenebiscaprylic acid amide, hexamethylenebisstearic acid amide, N, N'-distearyladipamide, and the like.

The amount of the amide compound (D) is 0.01 to 2% by weight, preferably 0.05 to 1% by weight, based on the whole epoxy resin composition. When the amount of the amide compound (D) is less than 0.01% by weight or more than 2% by weight, the solder heat resistance, which is an effect of the present invention, is insufficient.

The organopolysiloxane (E) in the present invention is obtained by reacting a carboxyl group-containing organopolysiloxane (e1) with an epoxy compound (e2).

Specific examples of the carboxyl group-containing organopolysiloxane (e1) include a carboxyl equivalent of 300
Siloxane compounds such as 5,000 to 5,000 side-chain type carboxyl-modified polydimethylsiloxane, one-terminal carboxyl-modified polydimethylsiloxane, and both-terminal carboxyl-modified polydimethylsiloxane;

As a specific example of the epoxy compound (e2), any compound having one or more epoxy groups in one molecule may be used. Particularly, a compound having two epoxy groups in one molecule is preferably used. Preferred specific examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, 4,4
'-Bis (2,3-epoxypropoxy) biphenyl,
4,4'-bis (2,3-epoxypropoxy) -3,
3 ', 5,5'-tetramethylbiphenyl, 1,5-di (2,3-epoxypropoxy) naphthalene, 1,6-
Di (2,3-epoxypropoxy) naphthalene, 2,7
-Di (epoxypropoxy) naphthalene, 9,9'-bis (2,3-epoxypropoxyphenyl) fluorene, and the like, and two or more kinds may be used at the same time.

The compounding ratio in the reaction between the carboxyl group-containing organopolysiloxane (e1) and the epoxy compound (e2) is such that the total amount of epoxy groups exceeds the total amount of carboxyl groups so that the epoxy groups remain after the reaction. The mixing ratio is preferably such that the epoxy equivalent of the reaction product is 400 to 3000. When the mixing ratio of the epoxy compound increases and the epoxy equivalent of the reaction product is smaller than the above range, sufficient releasability cannot be obtained when used in an epoxy resin composition, and the mixing ratio of the epoxy compound decreases to reduce the reaction. When the epoxy equivalent of the product is larger than the above range, when used in an epoxy resin composition for semiconductor encapsulation, the adhesiveness to a silicon chip or a lead frame tends to decrease.

The reaction between the carboxyl group-containing organopolysiloxane and the epoxy compound can be achieved by reacting at 100 to 200 ° C. for 3 to 60 minutes. In the above reaction, not only the components are simultaneously mixed and reacted, but also the carboxyl components may be sequentially reacted with the epoxy component, or the epoxy components may be sequentially reacted with the mixture of the carboxyl components. Tertiary amines, organic phosphine compounds, and the like are preferably used as the reaction catalyst, and the amount of the reaction catalyst to be added is preferably 0.1 to 1.0 weight based on the total amount of the mixture.

The amount of the organopolysiloxane (E) is 0.01 to 2% by weight, preferably 0.05 to 1.0% by weight, based on the whole epoxy resin composition. 0.01% by weight of organopolysiloxane (E)
If it is less than 2% or more than 2% by weight, the effect of the present invention is insufficient.

The epoxy resin composition of the present invention may contain, in addition to the organopolysiloxane (E), a metal salt of a long-chain fatty acid, an ester of a long-chain fatty acid, paraffin wax, or the like as long as the effects of the present invention are not impaired. Two or more release agents may be used in combination.

In the composition of the present invention, a bromo compound can be blended although it is not an essential component. The bromo compound is not particularly limited as long as it is usually added as a flame retardant to the epoxy resin composition for semiconductor encapsulation, and a known compound can be used.

Preferred specific examples of the bromo compound include:
Brominated bisphenol A-type epoxy resin, brominated epoxy resin such as brominated phenol novolak type epoxy resin, brominated polycarbonate resin, brominated polystyrene resin, brominated polyphenylene oxide resin, tetrabromobisphenol A, decabromodiphenyl ether, etc. Among them, brominated epoxy resins such as brominated bisphenol A type epoxy resin and brominated phenol novolak type epoxy resin,
It is preferable from the viewpoint of moldability.

The composition of the present invention may also contain an antimony compound. This is usually added as a flame retardant aid to the epoxy resin composition for semiconductor encapsulation, and is not particularly limited, and a known one can be used. Preferred specific examples of the antimony compound include antimony trioxide, antimony tetroxide, and antimony pentoxide.

The epoxy resin composition of the present invention includes a coloring agent such as carbon black and iron oxide, an ion scavenger such as hydrotalcite and bismuth, silicone rubber,
Elastomers such as olefin copolymers, modified nitrile rubber, modified polybutadiene rubber, etc., thermoplastic resins such as polyethylene, and crosslinking agents such as organic peroxides can be optionally added.

The method for producing the resin composition of the present invention includes:
For example, a method by melt kneading is used, and usually 60 to 1
It can be produced at 40 ° C. by a known kneading method using, for example, a Banbury mixer, a kneader, a roll, a single or twin screw extruder and a co-kneader. This resin composition is usually used for semiconductor encapsulation by molding from a powder or tablet state. As a method for sealing a semiconductor element, a low-pressure transfer molding method is generally used, but an injection molding method or a compression molding method is also possible.
As the molding conditions, for example, the resin composition is molded at a molding temperature of 150.
~ 200 ° C, molding pressure 5 ~ 15MPa, molding time 30 ~
A semiconductor device is manufactured by molding in 300 seconds to obtain a cured product of the resin composition. Further, if necessary, the molded product is subjected to additional heat treatment at 100 to 200 ° C. for 2 to 15 hours. Further, in a semiconductor device, it is preferable to use a 42 alloy material for a lead frame, a copper material for a lead frame, or a copper material used for a lead frame with a palladium-plated material. The effect of the present invention is more exhibited by using.

[0041]

The present invention will be described below in detail with reference to examples.

REFERENCE EXAMPLE 1 Preparation of Epoxy Group-Containing Organopolysiloxane 1 In a 1-liter three-necked flask equipped with a stirrer and a thermometer, 200 parts by weight of a polydimethylsiloxane having carboxyl equivalents at both ends and having a carboxyl equivalent of 780 and an epoxy equivalent of 185 were added. Add 95 parts by weight of bisphenol A type epoxy resin and add 1
After heating to 40 ° C., 3 parts by weight of triphenylphosphine was added while stirring the mixture and reacted for 1 hour to obtain an epoxy group-containing organopolysiloxane. FT-IR
From the spectrum analysis, the absorption of the carboxyl group (171
0-1720 cm ^-1 ) disappears and the absorption of ester groups (1
730-1740 cm ^-1 ) and the absorption of epoxy groups (910-920 cm ^-1 ), confirming that the desired epoxy group-containing organopolysiloxane 1 was obtained.

REFERENCE EXAMPLE 2 Preparation of Epoxy Group-Containing Organopolysiloxane 2 200 parts by weight of carboxyl-modified polydimethylsiloxane having a carboxyl equivalent of 430 and an epoxy equivalent of 170
The epoxy group-containing organopolysiloxane 2 was obtained in the same manner as in Reference Example 1 except that 158 parts by weight of the bisphenol F type epoxy resin was added.

Examples 1 to 10 and Comparative Examples 1 to 5 The components shown in Table 1 were dry-blended by a mixer at the composition ratios shown in Tables 2 to 4. The units of the numerical values in Tables 2 to 4 are parts by weight. This is a barrel temperature of 90 ° C.
The mixture was heated, melt-kneaded for 5 minutes using a twin screw extruder, and then cooled and pulverized to produce a resin composition for encapsulating a semiconductor.

[0045]

[Table 1]

Embedded image Using these compositions, a semiconductor device was obtained by molding at 175 ° C. × 2 minutes by low-pressure transfer molding. Various evaluations were performed by the following methods, and the results are shown in Tables 2 to 4.

Solder heat resistance test: 160 pin QFP (outer size: 28 × 28 × 3.3 mm, simulated semiconductor device: 10 × 1
0 × 0.5mm, frame material: 42 alloy or 250
8 pieces of copper (chip surface: polyimide film) oxidized at 3 ° C. for 3 minutes, and cured at 175 ° C. for 12 hours.
Under the conditions of 85 ° C. and 85% RH, the 42 alloy frame package was humidified for 192 hours, and the copper frame package was humidified for 144 hours.
Heat treatment was performed for 0 seconds. The die pad surface of the subsequent 160-pin QFP was observed using an ultrasonic flaw detector, and the area of the package where peeling occurred was calculated and defined as the peeling rate. × (poor) when the peeling rate was 16% or more, Δ (normal) when 9% or more and less than 16%, and ○ when 4% or more and less than 9%.
(Good) Less than 4% was represented by ◎ (Excellent).

Releasability: After sufficiently cleaning the mold, the diameter is 1 mm.
The molding of a cylinder having a length of 2 cm and a length of 2 cm was repeated 10 times, and the force required to protrude from the mold immediately after each molding was measured using a push-pull gauge. The average of the measured values is 20
Those weighing not less than kg were represented by x (poor), those weighing 10 kg or more but less than 20 kg were represented by △ (normal), those weighing 5 kg or more but less than 10 kg were represented by （(good), and those weighing less than 5 kg were represented by ◎ (excellent).

[0048]

[Table 2]

[Table 3] As can be seen from Tables 2 and 3, the epoxy resin compositions of Examples 1 to 10 have good adhesion to the lead frame and excellent solder heat resistance. Also, since the mold releasability from the mold at the time of molding is good, it is also excellent in continuous moldability. That is, it can be said that the balance between solder heat resistance and moldability is excellent.

[0049]

[Table 4] In contrast, Comparative Examples 1 to 5 shown in Table 4 have a poor balance between solder heat resistance and moldability and are not suitable for practical use.

[0050]

The epoxy resin composition of the present invention is a material suitable for encapsulating a semiconductor element because it has good adhesion to a semiconductor member during reflow mounting and good mold release during molding. Further, the semiconductor device sealed with the epoxy resin composition of the present invention has improved reliability.

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Claims (5)

[Claims] 1. A semiconductor sealing resin composition comprising an epoxy resin (A), a curing agent (B), an inorganic filler (C), an amide compound (D), and an organopolysiloxane (E). (C) is 50 to 95% by weight, the amide compound (D) is a compound comprising a fatty acid having 8 to 22 carbon atoms, and 0.01 to 2% by weight is contained in the composition; and Wherein the organopolysiloxane (E) is an epoxy group-containing organopolysiloxane which is a reaction product of a carboxyl group-containing organopolysiloxane and an epoxy compound, and is contained in the composition in an amount of 0.01 to 2% by weight. Epoxy resin composition for semiconductor encapsulation. 2. The epoxy resin composition for semiconductor encapsulation according to claim 1, wherein the amide compound (D) is a polyamide compound having two or more amide bonds in one molecule. 3. A semiconductor device comprising a semiconductor element encapsulated by a cured product of the epoxy resin composition for semiconductor encapsulation according to claim 1. 4. A semiconductor element on a lead frame made of a 42 alloy material is sealed with a cured product of the epoxy resin composition for semiconductor sealing according to claim 1. Semiconductor device. 5. A semiconductor element on a lead frame made of a copper frame material is sealed with a cured product of the epoxy resin composition for semiconductor sealing according to claim 1. Semiconductor device.