KR950006638B1 - Epoxy resin composition for encapsulating semi-conductor - Google Patents

Abstract

The epoxy resin for semiconductor sealing is composed of 100 wt% ethylene oxide or propylene oxide added epoxy resin and 5-50 wt% silicone oil with a reaction group at each of both terminals, novolac resin as a curing agent, antimony oxide as a flame retardant, calcined clay, aluminum trihydrate, amorphous silica, or calcium carbonate as an inorganic filler, a releasing agent, carbon black as a coloring agent and triphenol phosphine curing accelerator. The epoxy resin is prepared by reacting the resin composition with silicone oil in the henkel mixer, mulling while heating the mixture at 70-80 deg.C at 3-15 min. The spherical dispersed particles in silicone oil has the range of 0.1-50 micrometer.

Description

Epoxy resin composition for semiconductor encapsulation and its manufacturing method

1 is a SEM image of the result of stirring at 2000 rpm using a Henkel mixer when mixing the epoxy resin and the silicone oil in the present invention.

FIG. 2 is a SEM result photograph when the epoxy resin and the silicone oil in the present invention are mixed at 100 rpm using a general stirrer.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition for semiconductor encapsulation, and a method of manufacturing the same, comprising an epoxy resin containing ethylene oxide or propylene oxide and a silicone oil having a reactive group at a sock end in preparing an epoxy resin composition for a semiconductor encapsulant. An object of the present invention is to provide an epoxy resin composition for encapsulating semiconductor electronic components, which reduces stress and improves moisture resistance reliability.

The pattern of the conventional IC chip has been reduced from 1.2μm to 0.5μm in the past 10 years, and the miniaturization has progressed rapidly, and the high integration of the chip has also progressed more rapidly, and the device is shifted from 1M bits to 4M bits at 16K, which is about 6 times higher integration Was achieved.

According to the IC mounting technology, the size of the VLSI chip has been enlarged to about four times (area ratio), but the size of the package (PKG) for mounting it has not changed significantly.

As a result, the development of VLSI and the diversification of packages have caused new mounting technology problems that cannot be dealt with by the prior art alone.

The biggest drawback of conventional resin encapsulation ICs is that Al wirings on IC chips are corroded and disconnected due to moisture in the encapsulation resin, or at the interface between the encapsulation resin and the lead frame, and ionic impurities such as Na ⁺ and Cl ^- in the resin. Deterioration of moisture resistance due to chip crackation (Passivation, PV) cracking due to thermal stress.

The recent increase in the size of the VLSI chip has led to the increase in the number of PV defects in the chip. As mentioned above, the chip size has increased, but the external size of the package has not changed. There is a cause that the step between each layer is increased.

In order to solve these problems, the high purity of the silane coupling agent of the resin, the change of the mixing order of the release agent or the modification, the modification by the modified resin that improves the adhesion, the additive application to delay the Al corrosion reaction and the chip package using the ceramic, Various studies have been conducted on material changes of lead frames.

The cause of PV and package cracks is mainly due to thermal stress generated between silicon, an IC chip material, and encapsulation resin, which is a package material.In order to reduce stress, the Young's modulus decreases, thermal expansion difference decreases, and glass transition temperature (Tg) It is necessary to prevent the thermal shock resistance and the disconnection of the binding wire by maintaining the temperature above a certain temperature (150 ℃).

In addition, when the filler is increased for low expansion, the coefficient of thermal expansion decreases, but conversely, the elastic modulus increases and the viscosity also increases.

However, the conventional technique was unable to obtain a sealing resin having a low elastic modulus and thermal expansion coefficient at a high glass transition temperature (Tg).

In the present invention, in order to solve such a problem, a novel epoxy resin containing ethylene oxide or propylene oxide is used, so that the flowability is good and the viscosity of the resin is lowered, so that the content of the filler can be increased compared to the conventional epoxy resin. A semiconductor device that can lower the coefficient of linear expansion to the maximum and at the same time uniformly disperse and react silicone oil with epoxy resin using Henkel mixer to maintain high glass transition temperature (Tg) and have low elasticity, excellent moisture resistance and thermal shock resistance. It is an object to provide an epoxy resin composition for sealing.

In addition, another object of the present invention to provide a method for producing the epoxy resin composition for sealing the semiconductor device.

In order to achieve the above object, the present invention is an epoxy resin composition used to seal a semiconductor device, (A) ethylene oxide (-OCH ₂ CH _2- ) or propylene oxide (O-CH ₂ CH ₂ CH _2- ) The present invention relates to an epoxy resin composition for semiconductor encapsulation, comprising an additional epoxy resin and (b) a silicone oil having a reactor at the sock end.

In addition, in the epoxy resin composition used to seal a semiconductor device, (A) ethylene oxide (-OCH ₂ CH _2- ) or propylene oxide (-OCH ₂ CH ₂ CH _2- ) addition epoxy resin, (B) sock end An epoxy resin composition for semiconductor encapsulation comprising a silicone oil having a reactor and (c) a curing agent, a flame retardant, an inorganic filler, a releasing agent, a coloring agent, and a curing accelerator.

In more detail, in the present invention, in the epoxy resin composition for encapsulating a semiconductor device, (A) intramolecular ethylene oxide (-OCH ₂ CH _2- ) or propylene oxide as shown in the following structural formula (I), (II) or (III) 100 parts by weight of an epoxy resin containing (-OCH ₂ CH ₂ CH _2- ), and (b) 5 to 50 parts by weight of silicone oil having a reactive group in a sock end having the following structural formula (IV) in a Henkel mixer. After the reaction for 1 to 5 hours at °, 1000 ~ 3000rpm (C) to the resin is prepared by adding a curing agent, flame retardant, inorganic filler, mold release agent, coloring agent (carbon black) curing accelerator.

In the above formulas (I), (II) and (III)

A는 (-OCH₂CH₂-)n 또는 (-OCH₂CH₂CH₂-)n

A is (-OCH ₂ CH _2- ) n or (-OCH ₂ CH ₂ CH _2- ) n

n은 0＜n＜20

n is 0 <n <20

이고, X는 -R'OH, -R'NH₂, -R'COOH,

여기서,R'는 탄소수가 1~3개인 알킬그룹 n은 2~200이다.In the formula (IV), R is -CH ₃ ,

X is -R'OH, -R'NH ₂ , -R'COOH,

Here, R 'is an alkyl group n having 1 to 3 carbon atoms is 2 to 200.

Hereinafter, the present invention will be described in detail.

Epoxy resin (A) used in the present invention is of the formula (I) to which ethylene oxide (-OCH ₂ CH ₂ CH _2- ) or propylene oxide (-OCH ₂ CH ₂ CH _2- ) is added to a conventional epoxy resin. Epoxy resin of bisphenol diglycidyl ether (DGEBA) type and phenol formaldehyde novolac epoxy of Formula (II) or tetrabromo bisphenol A diglycidyl ether of Formula (III) It is preferable to use by weight part.

의 반복 단위구조를 갖는 상온 액상형이 좋은데, 예를들면 디메틸 실리콘 오일이나 메틸 페닐 실리콘 오일로서 양 말단에 반응성기, 즉 아미노변성, 에폭시변성, 카르복실변성, 플루오르변성, 하이드록시변성, 메트켑토변성 또는 안하이드라이변성 실리콘 오일등을 사용할 수 있다.In addition, the silicone oil (IV) used in the present invention

A normal temperature liquid type having a repeating unit structure of is preferable, for example, dimethyl silicone oil or methyl phenyl silicone oil, and reactive groups at both ends, that is, amino modification, epoxy modification, carboxy modification, fluorine modification, hydroxy modification, and methamto modification. Or an anhydride-modified silicone oil can be used.

The silicone oil is used 5 to 50 parts by weight based on 100 parts by weight of the epoxy resin, particularly preferably 10 to 30 parts by weight.

If the use ratio is less than 5 parts by weight, the effect on moisture resistance, thermal shock resistance and low stress is not sufficient, and when it is 50 parts by weight or more, the silicone oil floats on the surface of the cured product, contaminating the encapsulant and lowering the strength.

In addition, the present invention is to prepare an epoxy resin composition used to seal a semiconductor device, (A) ethylene oxide (-OCH ₂ CH _2- ), or propylene oxide (O-CH ₂ CH ₂ CH _2- ) addition epoxy resin And (B) a method of producing an epoxy resin composition for semiconductor encapsulation, comprising reacting a silicone oil having a reactor at a sock end with a Henkel mixer at 100 to 150 ° C, 1000 to 3000 rpm, for 1 to 5 hours.

That is, in the present invention, in order to increase the effect of the invention (A) component and (B) component by mixing and heating using a Henkel mixer, when reacted using a general stirrer (100rpm) (A) component and (B) Uniform dispersion is difficult due to poor compatibility of the components, making it impossible to prepare a sufficiently low stress encapsulant. Also, if the reaction temperature is below 100 ℃, the load of the Henkel mixer becomes large and stirring is impossible, and above 3000rpm, the stirring is so strong that the reactant adheres to the base wall of the mixer and is easily gelled. Below, it becomes impossible to obtain particles that are sufficiently small and uniform (about 1 μm in average particle diameter).

In order to obtain a sufficient low stress effect, the dispersed silicone oil particle size is preferably 0.1 μm to 50 μm, and more preferably 0.5 μm to 10 μm.

After that, a curing agent, a flame retardant, an inorganic filler, a releasing agent, a coloring agent (carbon black), a curing accelerator, and the like are mixed with the reactants reacted using a Henkel mixer and melted for 3 to 15 minutes at 70 to 80 ° C with a heating heater or a near roller. It is prepared by kneading.

Phenolic resin was used as the curing agent used in the present invention. Since the curing agent is an important factor in determining the properties of the epoxy cured product, the curing method should be selected in consideration of the processing method, the size, form and required characteristics of the final molded product.

As the phenol resin, phenol novolac resin is the best, and any phenol novolac resin generally known is suitable. 5-15 weight part is preferable with respect to 100 weight part of whole sealing agents.

In the present invention, HRJ (166, HRJ 2210, manufactured by Schenectady, USA) and BRN 556,557,558 (manufactured by Japan Fire Union Co., Ltd.) were used as a curing accelerator. Bicyclo- (5,4,0) -Undeken-7 (manufactured by SanApro, Japan) was used. The amount of addition is preferably 0.1 to 1% by weight based on 100% by weight of the total sealing agent.

Flame retardants are used because the electrical and electronic materials may cause combustion due to overload. In the present invention, Sb ₂ O ₃ (manufactured by Japan Chusa) is used, and Patox-c (manufactured by Nihon Seiko Co., Ltd.), Sb ₂ O ₃ (Made by Hayashi Pure Co., Ltd.), AN-800, AN-900, and SR-700 (made by Daishi Tokyo Seiyaku Co., Ltd.) are also available.

Inorganic fillers include calcined clay, aluminum trihydrate, amorphous silica, alumina, fused silica, spheroidal silica, crystalline silica, hydrous clay calcium carbonate, magnesium oxide, barium sulfate, mica , Talc and the like can be used.

50-80 weight part is suitable with respect to 100 weight part of whole sealing agent compositions. If the amount is 50 parts by weight or less, the coefficient of thermal expansion of the cured product is increased, resulting in a large amount of defective products. When the amount is 80 parts by weight or more, the fluidity of the composition is significantly lowered, resulting in poor workability.

As a result, when the above-described composition range is arithmetic, it is preferable that the epoxy resin of (a) and the silicone oil of (b) are composed of 10 to 20% by weight based on the epoxy resin composition for final semiconductor encapsulation containing the additive. .

The present invention will be described in more detail with reference to the following examples and comparative examples. However, the following examples do not limit the scope of the present invention.

Example 1

(A) 100 parts by weight of an olso cresol novolac-type epoxy resin (softening temperature: 70 ° C., epoxy equivalent 240) in which A is (-OCH ₂ CH _2- ) n = 1 in the structure shown in formula (II) However, 15 parts by weight of amino-modified dimethyl silicone oil having a reactive group (brand name: X-22-161C, viscosity (25 ° C) 72 poise, specific gravity (25 ° C) 0.971, equivalent weight: 1940, ShinEtsu Co., Ltd. Japan) is 3000rpm at 120 ° C. After mixing, heating and reacting in a Henkel mixer for 3 hours, the mixture was cooled and pulverized. (C) 15 parts by weight of this was added to (D) flame retardant Sb ₂ O ₃ (trade name: Sb ₂ O _{3 manufactured by} JAPAN CO., LTD.) Part (e) 2 parts by weight of canava wax (trade name: product made by Canava wax, Blasil machado) (release) 70 parts by weight of inorganic filler (product name: Fuselex ZA-30, manufactured by Dasmori, Japan) 1 part by weight of carbon black as a coloring agent (h) 9 parts by weight of phenolic resin as a curing agent (product name: HRJ 1166, manufactured by Schenectady, USA) DBU (trade name: DBU, SanApro Japan Co., Ltd.) 1 part by weight was pre-cured by milling for 3 minutes in a 70 ℃ Henkel mixer at a heat roller (tworoll mill) were mixed at room temperature to produce a tablet by pulverization.

The composition prepared as described above is sealed using a low pressure transfer molding machine (175 ° C., 80 kg / cm 2, 120 seconds) to seal a sample element (8 mm × 8 mm) for evaluation of a large pellet having a PSG (phosphate silicate) film on its surface.

In order to evaluate the thermal shock resistance and moisture resistance of the sample element thus obtained, a thermal shock test (TCT) and a moisture deterioration test (PCT) are performed as follows.

1) Thermal shock resistance

% Of the number of cracked chips out of 50 chips that were alternately deposited for 30 seconds in -195 ℃ and 210 ℃ solutions, respectively.

2) P.C.T (moisture deterioration test)

The number of chips with aluminum wire corroded in 50 chips at 121 ° C x 100% relative humidity.

In addition, the items of mold contamination, virus PCT, stress, and gel particles are carried out as follows.

3) Mold contamination

Number of moldings that can work without mold cleaning

4) Bias P.C.T

The number of the chips which aluminum wire was corroded among 50 chips by applying DC 20V voltage to 121 degrees Celsius X relative humidity 100%

5) stress

The steel ring is attached to the inner wall using a steel ring with an inner diameter of 20 mm, a thickness of 1 mm, and a height of 20 mm by the steel ring method, and then formed into a 10 mm thickness at 170 ° C. and 75 kg / cm 2 and then cooled to 25 ° C. to deform the steel ring. Measuring.

6) gel particles

10 g of sample was added with 50 g of acetone and passed through an ultrasonic cleaner for 30 minutes and passed through 60 mesh sieves.

The results for these six items are listed in Table 1 below.

Example 2

In Example 1 (B) carboxy modified silicone oil having a reactive group in the sock end instead of 15 parts by weight of the amino modified silicone oil having a reactive group in the sock end (viscosity: 25 ℃, 207 poise, specific gravity (25 ℃): 0.980, Equivalent weight: 2330, trade name: X-22-162C, manufactured by ShinEtsu Co., Ltd.) Using 15 parts by weight, a composition was prepared in the same composition and method as in Example 1, and the same evaluation test was carried out. The results are shown in Table 1 below. .

Example 3

In Example 1, except that (a) in Example 1 except that 100 parts by weight of an epoxy resin in which A is propylene oxide (OCH ₂ CH ₂ CH ₂ ) n = 1 and an epoxy equivalent of 450 is used in Structural Formula (I). The composition was prepared in the same composition and method as described above, and the same evaluation test was carried out.

Example 4

Except for using 75 parts by weight instead of 70 parts by weight of the inorganic filler in (1) was prepared in the same composition and method as in Example 1 and subjected to the same evaluation test and the results are shown in Table 1 It was.

Comparative Example 1

In Example 1, instead of (A), an ordinary oxo cresol novolac polyglycidyl ether type epoxy resin without A in structural formula (II) (softening point 74 ° C, epoxy equivalent 205 to 230, trade name: EOCN-1025, Japanese painting) Except for using 100 parts by weight of a pharmacist product) was prepared in the same composition and method as in Example 1 and subjected to the same evaluation test are shown in Table 1 the results.

Comparative Example 2

In Example 1, instead of (A) and (B), an ordinary oxo cresol novolac poly glycidyl ether type epoxy resin without A in structural formula (II) (softening point 740 ° C, epoxy equivalent 205 to 230, trade name: EOCN- 1025, manufactured by Nippon Kayaku Pharmaceutical Co., Ltd.), except that 15 parts by weight were used, the composition was prepared in the same composition and method as in Example 1, and the same evaluation test was carried out.

TABLE 1

As described above, the epoxy resin composition for sealing a semiconductor device according to the present invention maintains a high glass transition temperature (Tg) and is excellent in low elasticity and moisture resistance heat shock resistance.

Claims (12)

(A) Ethylene oxide (-OCH ₂ CH _2- ), or propylene oxide (O-CH ₂ CH ₂ CH _2- ) addition epoxy resin and (B) silicone oil having a reactor at the end of the Epoxy resin composition for semiconductor encapsulation. The epoxy resin composition for semiconductor encapsulation according to claim 1, wherein the epoxy resin (a) is composed of the following structural formulas (I), (II) or (III).

In the above formulas (I), (II) and (III)

A is (OCH ₂ CH ₂ ) n or (OCH ₂ CH ₂ CH ₂ ) n

n is 0 <n <20 The epoxy resin composition for semiconductor encapsulation according to claim 1, wherein the structural formula of the silicone oil of (b) is composed of the following (IV).

In formula (IV), R is -CH ₃ ,

X is -R'OH, -R'NH ₂ , -R'COOH,

The epoxy resin composition for semiconductor encapsulation according to claim 1, wherein 5 to 50 parts by weight of the silicone oil of (b) is used relative to 100 parts by weight of the epoxy resin of (a). In the epoxy resin composition used to seal a semiconductor device, (A) ethylene oxide (-OCH ₂ CH _2- ), or propylene oxide (-OCH ₂ CH ₂ CH _2- ) addition epoxy resin, (B) sock end A semiconductor epoxy resin composition comprising a silicone oil having a reactor and (c) a curing agent, a flame retardant, an inorganic filler, a releasing agent, a coloring agent, and a curing accelerator. The epoxy resin composition for semiconductor encapsulation according to claim 5, wherein (a) the epoxy resin and (b) the silicone oil comprise 10 to 20% by weight based on the final epoxy resin composition. The epoxy resin composition for semiconductor encapsulation according to claim 5, wherein the epoxy resin (a) is composed of the following structural formulas (I), (II) or (III).

In the above formulas (I), (II) and (III)

A is (-OCH ₂ CH _2- ) n or (-OCH ₂ CH ₂ CH _2- ) n

n is 0 <n <20 The epoxy resin composition for semiconductor encapsulation according to claim 5, wherein the structural formula of the silicone oil of (b) is composed of the following (IV).

In formula (IV), R is -CH ₃ ,

X is -R'OH, -R'NH ₂ , -R'COOH, -R'-N

The epoxy resin composition for semiconductor encapsulation according to claim 5, wherein 5 to 50 parts by weight of the silicone oil of (b) is used relative to 100 parts by weight of the epoxy resin of (a). The epoxy resin composition for semiconductor encapsulation according to claim 5, wherein the curing agent is a phenol novolak resin. In preparing an epoxy resin composition used to seal a semiconductor device, (A) ethylene oxide (-OCH ₂ CH _2- ), or propylene oxide (O-CH ₂ CH ₂ CH _2- ) addition epoxy resin and (B) A method for producing an epoxy resin composition for semiconductor encapsulation, comprising reacting a silicone oil having a reactor at a sock end with a Henkel mixer at 100 to 150 ° C, 1000 to 3000 rpm, for 1 to 5 hours. The method for producing an epoxy resin composition for semiconductor encapsulation according to claim 11, wherein the dispersed particles of the silicone oil of (b) have a spherical shape of 0.1 to 50 µm.

Images