JP2003171529A - Epoxy resin composition and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition with improved resistance to soldering heat and a semiconductor device using the same. <P>SOLUTION: The epoxy resin composition comprises (A) an epoxy resin described by the formula, (B) a phenol resin, (C) a hardening accelerator, and (D) an inorganic filler and the semiconductor device manufactured by using the same is provided. In the formula, Rs are bivalent condensed ring aromatic hydrocarbon groups, n is an integer of one or greater, and the Rs in the molecule may be similar to or dissimilar from each other. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an epoxy resin composition used as a sealing resin material for electronic parts such as semiconductors, and a semiconductor device using the same.

[0002]

2. Description of the Related Art Conventionally, it has been widely practiced to seal electronic parts such as semiconductors with a thermosetting resin. For such encapsulating resin material, a composition in which a curing agent, a curing accelerator, and an inorganic filler or pigment such as silica powder are added to an epoxy resin as a base, has a high reliability and moldability. , Is generally used in terms of price.

By the way, in recent years, in the field of semiconductor integrated circuits, along with the high integration of chips, the chip size has become larger and the number of poles has increased. On the other hand, the package design is also a conventional pin insertion type DIP (Dual-In Line). Packag
e), surface mount type SOP (Small Outline Packag)
e), QFP (Quad Flat Package), SOJ (Small Ou)
tline J-lead Package), TSOP (Thin SOP),
LQFP (Large QFP), TQFP (Thin QFP)
And so on.

With such a change in the mounting method, cracks occur in the sealing resin portion of the package during mounting (solder process), or peeling occurs between the chip and the sealing resin or between the substrate and the sealing resin. The problem is occurring. This is because in the surface mount type package, the entire package is directly immersed in a high temperature (230 to 270 ℃) solder bath during mounting, so the sealing resin material has more severe solder heat resistance than the pin insertion type. Is required. That is, the conventional epoxy resin composition was slightly insufficient in solder heat resistance to be applied to the surface mount type package.

Therefore, there is a demand for the development of an epoxy resin composition having excellent solder heat resistance which does not cause cracks or peeling as described above even when applied to a surface mount type package.

On the other hand, this type of sealing resin material is required to have flame retardancy according to the UL standard from the viewpoint of safety.

Conventionally, in an epoxy resin composition, it is common to use a flame retardant containing a halogen element such as chlorine or bromine in combination with an antimony compound (usually antimony trioxide). However, these halogen-based flame retardants and antimony compounds have a problem of reducing the reliability of electronic parts. In addition, recently
These environmental impacts are beginning to be pointed out.

For this reason, development of flame retardant technology not containing a halogen flame retardant and an antimony compound, such as the combined use of a phosphorus flame retardant and a metal hydrate, is underway. However, conventional halogen flame retardants and antimony are not used. There is a problem that long-term moisture resistance reliability is reduced as compared with the combined use of compounds.

[0009]

As described above, there is a demand for an epoxy resin composition having excellent soldering heat resistance as the mounting method is changed from the pin insertion type to the surface mounting type. Further, in such an epoxy resin composition, development of a highly reliable flame retardant technique which is an alternative to the combined use of a halogen-based flame retardant and an antimony compound has been demanded in consideration of the environment.

The present invention has been made in view of the above conventional circumstances, and an epoxy resin composition having excellent solder heat resistance which does not cause cracking or peeling even when applied to a surface mount type package. Another object of the present invention is to provide a semiconductor device using the same. Another object of the present invention is to provide an epoxy resin composition which is excellent in flame retardancy, and which retains good moisture resistance for a long period of time and has no environmental problem, and a semiconductor device using the same. To do.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, by using a specific epoxy resin having a condensed ring aromatic hydrocarbon group, an epoxy resin composition is obtained. It is possible to improve the solder heat resistance of a product, and by combining such a specific epoxy resin with an aralkyl-type phenol resin, it imparts excellent flame retardancy to an epoxy resin composition without using a flame retardant. The inventors have completed the present invention by discovering that they can be achieved.

That is, the epoxy resin composition of the present invention comprises (A) the following general formula

[Chemical 4] (In the formula, R is a divalent condensed ring aromatic hydrocarbon group, n
Represents an integer of 1 or more, and Rs in the molecule may be the same or different. ) Epoxy resin, (B)
It is characterized by containing a phenol resin, (C) curing accelerator and (D) inorganic filler.

In the epoxy resin composition having the above structure, by using a specific epoxy resin having a condensed ring aromatic hydrocarbon group, it has excellent solder heat resistance which can be sufficiently applied to a surface mounting type package. be able to.

In the epoxy resin composition of the present invention, the component (B) has the following general formula:

[Chemical 5] (However, in the formula, n represents 0 or an integer of 1 or more.).

In the epoxy resin composition having the above constitution, by using a specific epoxy resin having a condensed ring aromatic hydrocarbon group and a specific phenol resin in combination,
Particularly, excellent flame retardancy can be imparted without using a flame retardant.

As the component (A), one in which R in the general formula [I] is at least one selected from naphthalene, anthracene, phenanthrene, bilene and benzanthracene is reliable and easy to handle. It is preferable from the point of view.

In the present invention, it is preferable to further contain (E) a biphenyl type epoxy resin. By including the biphenyl type epoxy resin, the solder heat resistance can be further improved.

The component (E) has the following formula

[Chemical 6] It is preferable that the compounding ratio (weight ratio) of the component (A) and the component (E) is 50:50 to 95: 5 from the viewpoint of solder heat resistance. The content of the inorganic filler as the component D) is preferably 65 to 93% by weight from the viewpoint of moldability.

The epoxy resin composition of the present invention is characterized in that the epoxy resin composition of the above invention contains substantially no flame retardant.

In such an epoxy resin composition, since the flame retardant is not substantially contained, the moisture resistance reliability and environmental problems associated with the use of the flame retardant are solved.

The semiconductor device of the present invention is characterized in that a semiconductor chip is sealed with a cured product of the epoxy resin composition of the present invention.

In the semiconductor device of the present invention, since the semiconductor chip is sealed by the cured product of the epoxy resin composition having excellent solder heat resistance, highly reliable mounting is possible by any mounting method. Become.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below.

The epoxy resin composition of the present invention comprises (A) the following general formula:

[Chemical 7] (In the formula, R is a divalent condensed ring aromatic hydrocarbon group, n
Represents an integer of 1 or more, and Rs in the molecule may be the same or different. ) Epoxy resin, (B)
Phenol resin, (C) curing accelerator and (D) inorganic filler are essential components.

As the epoxy resin (A), those having an epoxy equivalent of 170 to 270 are preferable, and those having an epoxy equivalent of 200 to 250 are more preferable. Also,
The softening temperature is preferably in the range of 40 to 100 ° C, more preferably the softening temperature is in the range of 55 to 75 ° C. Examples of R in the above general formula [I] include naphthalene, anthracene, phenanthrene, birene, and benzanthracene. Specifically, YL-6850 manufactured by Japan Epoxy Resins (trade name; epoxy equivalent 230, softening temperature 65 ° C.) and the like are preferably used. These epoxy resins may be used alone or in combination of two or more.

The phenol resin (B) is blended as a curing agent, and if it has two or more phenolic hydroxyl groups in the molecule capable of reacting with the epoxy groups of the epoxy resin (A), Used without particular limitation, for example, phenol novolac resin, cresol novolac resin, dicyclopentadiene modified phenol resin, para-xylene modified phenol resin, condensates of phenols and benzaldehyde, naphthyl aldehyde, triphenol methane compound, Examples include polyfunctional phenolic resins.

In the present invention, the aralkyl type phenol resin represented by the following general formula [II] is preferable, and the phenolic hydroxyl group equivalent thereof is preferably 130 to 250, more preferably 160 to 190. . Specifically, XL-225-3L (hydroxyl group equivalent 17 manufactured by Mitsui Chemicals, Inc.
4), XLC-LL (hydroxyl equivalent 176), XLC-3L
(Hydroxyl equivalent 172), XLC-4L (hydroxyl equivalent 167),
MEH-7800M manufactured by Meiwa Kasei Co. (hydroxyl equivalent 17
5), MEH-7800S (hydroxyl equivalent 175), MEH-
7800SS (hydroxyl equivalent 175), HE100C-10 (hydroxyl equivalent 168), HE100C manufactured by Sumikin Chemical Co., Ltd.
-15 (hydroxyl group equivalent 170), HE100C-30 (hydroxyl group equivalent 170) (all of which are trade names) are preferably used.

[Chemical 8] (However, in the formula, n represents 0 or an integer of 1 or more.)

These phenolic resins may be used alone or in combination of two or more. The (B) phenol resin has an epoxy group (including a hydroxyl group / (A) epoxy resin (which is included when other epoxy resins are used as described later)) from the viewpoint of reducing unreacted components. Equivalent ratio) is 0.5 ~
It is preferable to add an amount of 1.5, more preferably 0.7 to 1.1.

The curing accelerator (C) is not particularly limited as long as it has an action of promoting the reaction between the epoxy resins or between the epoxy resin and the phenol resin (B). Specifically, 1,8-diazabicyclo
[5,4,0] Undecene-7 (DBU), triethylenediamine, benzyldimethylamine, triethanolamine,
Tertiary amines such as dimethylaminoethanol, tris (dimethylaminomethyl) phenol, imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, tributylphosphine, diphenylphosphine, triphenylphosphine Examples thereof include organic phosphines, tetraphenylphosphonium tetraphenylborate, tetraphenylboron salts such as triphenylphosphine tetraphenylborate, and the like. These can be used alone or in combination of two or more.

The inorganic filler (D) is added for the purpose of improving and improving the properties such as the thermal expansion coefficient, thermal conductivity, water absorption and elastic modulus of the cured product. Fused silica, crystalline silica Powder of alumina, talc, calcium carbonate, titanium white, red iron oxide, silicon carbide, boron nitride, etc.
Examples thereof include spherical beads, single crystal fibers, and glass fibers. These can be used alone or in combination of two or more. In the present invention, among these, powdery ones having a maximum particle size of 100 μm or less and an average particle size of 40 μm or less are suitable, and a maximum particle size of 75 μm or less and an average particle size of 30 μm or less are further preferable. preferable. Maximum particle size exceeds 100 μm or average particle size is 40 μm
When it exceeds, the moldability tends to be deteriorated, for example, it becomes difficult to fill the narrow portion. In addition, it is more preferable that the shape of these powders be as spherical as possible from the viewpoint of fluidity, moldability, mold abrasivity, and the like. Fused silica is suitable for applications requiring low thermal expansion, and crystalline silica or alumina is suitable for applications requiring high thermal conductivity.

The content of the inorganic filler (D) is preferably 65 to 93% by weight, and more preferably 70 to 92% by weight, based on the total weight of the composition.
Is more preferable. If the blending amount is less than 65% by weight, the effect of improving or improving the properties such as the above-mentioned thermal expansion coefficient is small, and if the blending amount exceeds 93% by weight, the fluidity of the composition is lowered and the moldability is deteriorated. It becomes defective and practically difficult.

In the present invention, in order to further improve the solder heat resistance, (E) a biphenyl type epoxy resin, preferably a biphenyl type epoxy resin represented by the following formula [III] can be blended. Particularly preferred is a biphenyl type epoxy resin represented by the following formula [III], and the epoxy equivalent thereof is 140 to 250, preferably 15
It is in the range of 0 to 200. Specifically, YX-4000 (epoxy equivalent 18
5), YX-4000K (epoxy equivalent 185), YX-4
000H (Epoxy equivalent 193), YX-4000HK
(Epoxy equivalent 193), YL-6121H (epoxy equivalent 172) and the like are preferably used.

[Chemical 9]

The biphenyl type epoxy resin (E) is compounded such that the compounding ratio (weight ratio) of the epoxy resin of the component (A) and the epoxy resin of the component (E) is 50:50 to 95: 5. Preferably. The compounding ratio is more preferably 65:35 to 90:10.

In the epoxy resin composition of the present invention, in addition to the above-mentioned respective components, a coloring agent such as carbon black or cobalt blue which is generally blended with the composition of this type within a range not impairing the effects of the present invention. Silane coupling agents such as epoxy silane, amino silane, alkyl silane and vinyl silane, surface treatment agents such as alkyl titanate, mold release agents such as synthetic wax and natural wax, halogen trap agents, stress reduction of silicone oil and silicone rubber. Agents and the like can be blended as necessary.

When the epoxy resin composition of the present invention is prepared as a sealing material, the above components are thoroughly mixed (dry blended) with a mixer or the like, then melt-kneaded with a hot roll or kneader, cooled and pulverized. You can do it. When the component (E) is added,
It is preferable to premix with the epoxy resin as the component (A).

The semiconductor device of the present invention can be manufactured by sealing a semiconductor chip using the above-mentioned sealing material. Examples of semiconductor chips include integrated circuits, large-scale integrated circuits, transistors, thyristors, diodes, and the like. As a sealing method, a low-pressure transfer method is generally used, but sealing by injection molding, compression molding, casting or the like is also possible. After sealing with the sealing material, it is heated and cured, and finally a semiconductor device sealed with the cured product is obtained. The heating temperature for post-curing is
It is preferably 150 ° C. or higher. Furthermore, examples of the substrate on which the semiconductor chip is mounted include a ceramic substrate, a plastic substrate, a polyimide film, and a lead frame, but the substrate is not particularly limited to these.

[0037]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. Example 1 Epoxy resin YL-6850 (manufactured by Japan Epoxy Resin Co., Ltd. trade name, epoxy equivalent 230), novolac type phenol resin THE-1085 (manufactured by Meiwa Kasei Co., trade name, hydroxyl equivalent 106), triphenylphosphine, carnauba wax. , Carbon black, γ-glycidoxypropyltrimethoxysilane as silane coupling agent and fused spherical silica powder (maximum particle size 75 μm average particle size
18 μm) was mixed at a mixing ratio shown in Table 1 at room temperature and then kneaded by heating at 70 to 100 ° C. After cooling, it was pulverized to an appropriate size to obtain an epoxy resin composition.

Example 2 Epoxy resin YL-6850, aralkyl-type phenol resin represented by the general formula [II] XLC-LL (trade name of Mitsui Chemicals, hydroxyl equivalent 176), triphenylphosphine, carnauba wax, carbon Black, γ-glycidoxypropyltrimethoxysilane as silane coupling agent and fused spherical silica powder (maximum particle size 75μ
m average particle diameter 18 μm) were mixed at a mixing ratio shown in Table 1 at room temperature and then kneaded by heating at 70 to 100 ° C. After cooling
The epoxy resin composition was obtained by crushing into an appropriate size.

Example 3 YL-6850 of epoxy resin, YX-4000H of biphenyl type epoxy resin represented by the formula [III] (trade name of Japan Epoxy Resin Co., epoxy equivalent 193),
XLC-LL of aralkyl type phenol resin represented by the general formula [II], triphenylphosphine, carnauba wax, carbon black, γ-glycidoxypropyltrimethoxysilane as a silane coupling agent, and fused spherical silica powder (maximum particle size 75μm average particle size 18μm)
Are mixed at a mixing ratio shown in Table 1 at room temperature, and then 70-
The mixture was heated and kneaded at 100 ° C. After cooling, it was pulverized to an appropriate size to obtain an epoxy resin composition.

Examples 4 to 6 Epoxy resin compositions were obtained in the same manner as in Example 3 except that the compounding ratio was changed as shown in Table 1.

Comparative Example 1 cresol novolac type epoxy resin EOCN-10
20 (trade name of Nippon Kayaku Co., epoxy equivalent 199), Epiclon 1 of bisphenol A type brominated epoxy resin
53 (trade name, manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent: 400), a novolac type phenolic resin THE-10
Table 2 shows 85, triphenylphosphine, carnauba wax, carbon black, γ-glycidoxypropyltrimethoxysilane as a silane coupling agent, antimony trioxide and fused spherical silica powder (maximum particle size 75 μm average particle size 18 μm). Mixing was carried out at room temperature in the compounding ratios shown, and then kneading was carried out at 70-100 ° C. After cooling, it was pulverized to an appropriate size to obtain an epoxy resin composition.

Comparative Example 2 cresol novolac type epoxy resin EOCN-10
20, novolac type phenolic resin THE-108
5, triphenylphosphine, carnauba wax, carbon black, γ-glycidoxypropyltrimethoxysilane as a silane coupling agent, and fused spherical silica powder (maximum particle size 75 μm average particle size 18 μm) at the compounding ratio shown in Table 2. The mixture was mixed at room temperature and then kneaded by heating at 70 to 100 ° C. After cooling, it was pulverized to an appropriate size to obtain an epoxy resin composition.

Comparative Example 3 cresol novolac type epoxy resin EOCN-10
20, XLC-LL of aralkyl type phenol resin represented by the general formula [II], triphenylphosphine, carnauba wax, carbon black, γ-glycidoxypropyltrimethoxysilane as a silane coupling agent, and fused spherical silica powder (maximum Particle size 75μm Average particle size 18
[mu] m) were mixed at a mixing ratio shown in Table 2 at room temperature and then kneaded by heating at 70 to 100 ° C. After cooling, it was pulverized to an appropriate size to obtain an epoxy resin composition.

Comparative Example 4 YX of biphenyl type epoxy resin represented by the formula [III]
-4000H, XLC-LL of aralkyl type phenol resin represented by the general formula [II], triphenylphosphine, carnauba wax, carbon black, γ-glycidoxypropyltrimethoxysilane as a silane coupling agent, and fused spherical silica powder ( Maximum particle size 75 μm
The average particle size of 18 μm) was mixed at a mixing ratio shown in Table 2 at room temperature and then kneaded by heating at 70 to 100 ° C. After cooling, it was pulverized to an appropriate size to obtain an epoxy resin composition.

Comparative Example 5 An epoxy resin composition was obtained in the same manner as Comparative Example 4 except that the compounding ratio was changed as shown in Table 1.

The characteristics of the epoxy resin compositions obtained in the above Examples and Comparative Examples were measured as follows.

That is, regarding the water absorption, the epoxy resin composition was transfer-molded under the conditions of 175 ° C. for 90 seconds and then post-cured at 175 ° C. for 8 hours to cure a disc-shaped resin having a diameter of 50 mm and a thickness of 3 mm. The product was obtained and allowed to stand in saturated steam at 127 ° C. and 2.5 atm for 24 hours, and the increased weight was determined.

The barcol hardness of the epoxy resin composition is
Transfer molding was performed into a disk shape having a diameter of 50 mm and a thickness of 3 mm under the conditions of 175 ° C. for 90 seconds, and the mold was measured with a Barcol hardness meter immediately after opening.

Moisture resistance is measured by using an epoxy resin composition and using a silicon chip having two aluminum wirings.
2 Adhesion to an alloy frame, transfer molding at 175 ° C for 90 seconds and post-curing at 175 ° C for 8 hours, then the resulting molded product was tested for humidity resistance (PCT) in saturated steam at 127 ° C and 2.5 atmospheres. ) Was performed, and the time until 50% disconnection failure due to aluminum corrosion occurred was measured and evaluated.

The reflow resistance is measured by using an epoxy resin composition at 175 ° C. for 90 seconds in transfer molding and at 175 ° C.
QFA package (14mm × 14mm ×
1.0mm, chip size: 6.0mm x 6.0mm) was prepared, and this package was subjected to moisture absorption treatment at 85 ° C, 60% RH, 48, 72, 96, 168 hours, and then IR reflow at 240 ° C. The test was performed 3 times, and after cooling, the presence or absence of cracks was observed with an ultrasonic flaw detector to examine the occurrence rate.

The flame retardancy is obtained by using an epoxy resin composition at 175 ° C., 9
Transfer molding for 0 seconds, then 175 ℃, 8
120mm × 12mm × 0.8mm and 120mm after post-curing
A cured product of × 12 mm × 3.2 mm was obtained, and a combustion test based on UL-94 flame resistance test standard was performed.

The results are shown in the lower columns of Table 1 and Table 2, respectively.

[Table 1]

[Table 2]

[0053]

As described above, according to the present invention,
It is possible to obtain an epoxy resin composition having excellent solder heat resistance that does not cause cracking or peeling even when applied to a surface mount package, and a semiconductor device using the same.

Further, according to the present invention, it is possible to obtain an epoxy resin composition which is excellent in flame retardancy, has good moisture resistance for a long period of time, and has no environmental problem, and a semiconductor device using the same. You can

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01L 23/31 F term (reference) 4J002 CC032 CC052 CC072 CD061 CE002 FD01 FD09 FD14 FD15 FD16 GQ05 4J036 AF06 AF07 AF08 AF36 DC01 DC02 DC10 DC12 DC41 DD07 DD09 FA01 FB07 JA07 4M109 AA01 CA21 EA02 EB03 EB04 EB13 EC05

Claims (8)

[Claims] 1. (A) The following general formula: (In the formula, R is a divalent condensed ring aromatic hydrocarbon group, n
Represents an integer of 1 or more, and Rs in the molecule may be the same or different. ) Epoxy resin, (B)
An epoxy resin composition comprising a phenol resin, (C) a curing accelerator, and (D) an inorganic filler. 2. The component (B) has the following general formula: (However, in the formula, n represents 0 or an integer of 1 or more.) The epoxy resin composition according to claim 1, wherein 3. The epoxy resin composition according to claim 1, wherein R of the component (A) is at least one selected from naphthalene, anthracene, phenanthrene, bilene and benzanthracene. 4. The method according to claim 1, further comprising (E) a biphenyl type epoxy resin.
The epoxy resin composition according to item 1. 5. The component (E) has the following formula: And the compounding ratio (weight ratio) of the component (A) and the component (E) is 50:50 to 95: 5. object. 6. The content of the inorganic filler as the component (D) is from 65 to 65.
The epoxy resin composition according to claim 1, wherein the epoxy resin composition is 93% by weight. 7. The epoxy resin composition according to claim 1, which contains substantially no flame retardant. 8. A semiconductor device in which a semiconductor chip is encapsulated with the cured product of the epoxy resin composition according to claim 1.