KR20190081986A - Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated by using the same - Google Patents

Abstract

The present invention is to provide an epoxy resin composition for encapsulating a semiconductor device with a low thermal expansion coefficient, hardening contraction ratio and flexural modulus and to a semiconductor device encapsulated by using the same. An epoxy resin composition for encapsulating a semiconductor device of the present invention comprises an epoxy resin, a hardener, an inorganic filler, a first silicon-based resin of which the viscosity at 25°C is 200 mm^2/s or less and a second silicon-based resin of which the viscosity at 25°C is 250 to 800 mm^2/s.

Description

TECHNICAL FIELD [0001] The present invention relates to an epoxy resin composition for encapsulating semiconductor devices, and a semiconductor device encapsulated with the epoxy resin composition. [0002] EPOXY RESIN COMPOSITION FOR ENCAPSULATING SEMICONDUCTOR DEVICE AND SEMICONDUCTOR DEVICE ENCAPSULATED BY USING THE SAME [

TECHNICAL FIELD The present invention relates to an epoxy resin composition for sealing a semiconductor device and a semiconductor device sealed by using the same.

A method for sealing a semiconductor element with an epoxy resin composition is commercially performed for the purpose of protecting the semiconductor element from external environmental factors such as moisture and mechanical impact. Recently, as small and thin digital devices become common, the degree of integration of semiconductor devices is improved day by day, and the chip is being stratified and densified.

As semiconductor chips become thinner, higher integration and / or surface mounting increases with the trend of miniaturization, weight reduction, and high performance, there is a problem that can not be solved by conventional epoxy resin compositions.

Particularly, there is a need for an epoxy resin composition for sealing a semiconductor element which can solve the problems caused by the warpage of the package due to thermal expansion and thermal shrinkage between the substrate and the epoxy resin composition and the defective problems such as chip breakage due to the high elasticity of the epoxy resin composition .

An object of the present invention is to provide an epoxy resin composition for sealing a semiconductor device having a low coefficient of thermal expansion, a hardening shrinkage percentage and a flexural modulus, and a semiconductor device sealed with the composition.

The above and other objects of the present invention can be achieved by the present invention described below.

One aspect of the present invention relates to an epoxy resin composition for sealing a semiconductor device.

According to one embodiment, the epoxy resin composition for encapsulating semiconductor devices comprises an epoxy resin, a curing agent, an inorganic filler, a first silicone resin having a viscosity at 25 캜 of 200 mm ² / s or less, and a viscosity at 25 캜 of 250 mm ² / Lt; ^{2 >} / s.

The first silicone resin and the second silicone resin may be contained in a weight ratio of 3: 1 to 1: 3.

The sum of the contents of the first silicone resin and the second silicone resin in the epoxy resin composition may be 0.2 wt% to 3 wt%.

The first silicone resin and the second silicone resin may be represented by the following general formula (1).

[Chemical Formula 1]

(Wherein R ₁ to R ₆ are each independently a C ₁ to C ₁₀ alkyl group, Y ₁ and Y ₂ each independently represent an amino group, an epoxy group, a carbinol group, a polyether group, a mercapto group, A hydroxy group or an acrylic group, and n is 0 to 50).

Wherein R ₁ to R ₆ are methyl groups, Y ₁ and Y ₂ are each independently -R (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b H, Wherein R is an alkyl or ether group having 1 to 10 carbon atoms, a is 0 to 50, and b may be 0 to 50.

Wherein the epoxy resin composition comprises 0.5 to 20 wt% of the epoxy resin, 0.1 to 13 wt% of the curing agent, 70 to 98 wt% of the inorganic filler, 0.1 to 2.9 wt% of the first silicone resin, 2 silicone resin in an amount of 0.1 to 2.9% by weight.

The epoxy resin composition may further include at least one of a curing accelerator, a coupling agent, a release agent, and a colorant.

Another aspect of the present invention relates to a semiconductor device.

In one embodiment, the semiconductor element may be sealed using the epoxy resin composition for semiconductor encapsulation.

The present invention has an effect of providing an epoxy resin composition for sealing a semiconductor element having a low thermal expansion coefficient, a hardening shrinkage percentage and a flexural modulus, and a semiconductor element sealed by using the composition.

Hereinafter, the present invention will be described in more detail.

In the following description of the present invention, detailed description of known related arts will be omitted when it is determined that the gist of the present invention may be unnecessarily obscured by the present invention.

In the case where the word 'includes', 'having', 'done', etc. are used in this specification, other parts can be added unless '~ only' is used. Unless the context clearly dictates otherwise, including the plural unless the context clearly dictates otherwise.

Also, in interpreting the constituent elements, even if there is no separate description, it is interpreted as including the error range.

In the present specification, 'X to Y' representing the range means 'X or more and Y or less'.

The epoxy resin composition for encapsulating semiconductor devices according to one embodiment of the present invention comprises an epoxy resin, a curing agent, an inorganic filler, a first silicone resin having a viscosity at 25 ° C of 200 mm ² / s or less and a viscosity at 25 ° C of 250 mm ² / To 800 mm < ² > / s.

Hereinafter, each component of the epoxy resin composition of the present invention will be described in detail.

Epoxy resin

And is not particularly limited as long as it is an epoxy resin generally used for sealing semiconductor devices. In an embodiment, the epoxy resin may be an epoxy compound containing two or more epoxy groups in the molecule. Examples of the epoxy resin include an epoxy resin obtained by epoxidizing a condensate of phenol or alkyl phenol and hydroxybenzaldehyde, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a multifunctional epoxy resin, a naphthol novolak Novolak type epoxy resins such as bisphenol A / bisphenol F / bisphenol AD, glycidyl ether of bisphenol A / bisphenol F / bisphenol AD, bishydroxybiphenyl type epoxy resin, dicyclopentadiene type epoxy resin, etc. . More specifically, the epoxy resin may be a cresol novolak type epoxy resin, a multifunctional epoxy resin, a phenol aralkyl type epoxy resin, a biphenyl type epoxy resin, or a mixture thereof.

The phenol aralkyl type epoxy resin may be, for example, a phenol aralkyl type epoxy resin having a novolak structure including a biphenyl derivative represented by the following formula (2).

(2)

In Formula 2, the average value of b is 1 to 7.

The epoxy resin may be used in an amount of 0.5 to 20% by weight, specifically 3 to 15% by weight, more preferably 3 to 12% by weight, based on the epoxy resin composition for encapsulating semiconductor devices.

Hardener

As the curing agent, curing agents generally used for sealing semiconductor devices may be used without limitation, for example, a curing agent having two or more reactors may be used.

Specific examples of the curing agent include phenol aralkyl type phenol resin, phenol novolak type phenol resin, xylok type phenol resin, cresol novolak type phenol resin, naphthol type phenol resin, terpene type phenol resin, Phenolic resin, dicyclopentadiene-based phenol resin, novolak-type phenol resin synthesized from bisphenol A and resole, polyhydric phenol compound including tris (hydroxyphenyl) methane, dihydroxybiphenyl, maleic anhydride and phthalic anhydride, , Aromatic amines such as methanophenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone, but are not limited thereto.

For example, the curing agent may include at least one of a phenol novolak type phenol resin, a xylock type phenol resin, a phenol aralkyl type phenol resin, and a multifunctional phenol resin.

The xylo-type phenol resin may be, for example, a xylok-type phenol resin represented by the following general formula (3).

  (3)

(In the formula 3, the average value of f is 0 to 7)

These curing agents may be used alone or in combination. Further, it can be used as an additional compound prepared by subjecting the above curing agent to a linear reaction such as an epoxy resin, a curing accelerator, a releasing agent, a coupling agent, a stress relieving agent and the like and a melt master batch.

The curing agent may be contained in an amount of 0.1 to 13% by weight, specifically 0.1 to 10% by weight, more specifically 0.1 to 8% by weight in the epoxy resin composition for sealing a semiconductor device.

The mixing ratio of the epoxy resin and the curing agent can be adjusted in accordance with the requirements of mechanical properties and moisture resistance reliability in the package. For example, the chemical equivalent ratio of the epoxy resin to the curing agent may be about 0.95 to about 3, specifically about 1 to about 2, more specifically about 1 to about 1.75. When the compounding ratio of the epoxy resin and the curing agent is in the above range, excellent strength can be realized after curing the epoxy resin composition.

Inorganic filler

The inorganic filler is a material used for improvement of mechanical properties and low stress of the epoxy resin composition. Examples of commonly used examples include fused silica, crystalline silica, calcium carbonate, magnesium carbonate, alumina, magnesia, clay, talc, calcium silicate, titanium oxide, antimony oxide and glass fiber.

In the specific example, fused silica having a low coefficient of linear expansion is used for low stress. The fused silica refers to amorphous silica having a true specific gravity of 2.3 or less and includes amorphous silica obtained by melting crystalline silica or synthesized from various raw materials. Although the shape and the particle diameter of the fused silica are not particularly limited, the fused silica containing 50 to 99% by weight of spherical fused silica having an average particle diameter of 5 to 30 탆 and the spherical fused silica having an average particle diameter of 0.001 to 1 탆 in an amount of 1 to 50% It is preferable that the mixture is contained in an amount of 40 to 100% by weight based on the total filler. Further, the maximum particle diameter can be adjusted to any one of 45 탆, 55 탆 and 75 탆 according to the application. Since the spherical fused silica may contain conductive carbon as a foreign substance on the surface of the silica, it is also important to select a substance having a small amount of polar foreign substances.

The amount of the inorganic filler to be used varies depending on required properties such as moldability, low stress, and high temperature strength. In an embodiment, the inorganic filler may be 70 to 95% by weight, more preferably 75 to 92% by weight, of the epoxy resin composition for sealing a semiconductor device.

The first silicone resin and the second silicone resin

The epoxy resin composition of the present invention comprises a first silicone resin having a viscosity at 25 ° C of 200 mm ² / s or less and a second silicone resin having a viscosity at 25 ° C of 250 mm ² / s to 800 mm ² / s, , There is an advantage that the coefficient of thermal expansion is low and the modulus is low, and the warping phenomenon can be improved. Specifically, the first silicone-based resin may have a viscosity at 25 ° C of from 30 mm ² / s to 200 mm ² / s, more specifically from 50 mm ² / s to 150 mm ² / s, and the second silicone- Can be from 300 mm ² / s to 700 mm ² / s, more specifically from 350 mm ² / s to 650 mm ² / s.

The first silicone resin and the second silicone resin may be represented by the following general formula (1). The viscosity of the first silicone resin and the second silicone resin may vary depending on the substituent and the value of n.

[Chemical Formula 1]

(Wherein R ₁ to R ₆ are each independently a C ₁ to C ₁₀ alkyl group, Y ₁ and Y ₂ each independently represent an amino group, an epoxy group, a carbinol group, a polyether group, a mercapto group, A hydroxy group or an acrylic group, and n is 0 to 50).

In embodiments, the first silicone resin and the second silicone resin is R ₁ to R ₆ is a methyl group, Y ₁ and Y ₂ are independently _{-R (C 2 H 4 O)} a (C 3 H 6 O) , respectively _b H, where R is an alkyl or ether group of 1 to 10 carbon atoms, a is 0 to 50, and b can be 0 to 50.

The first silicone resin and the second silicone resin may be contained in an amount of 0.1 to 2.9% by weight, specifically 0.2 to 2.5% by weight, respectively, in the epoxy resin composition for sealing a semiconductor device.

The first silicone resin and the second silicone resin may be contained in a weight ratio of 3: 1 to 1: 3, specifically, 1: 1 to 2: 1. The sum of the contents of the first silicone resin and the second silicone resin in the epoxy resin composition may be 0.2 wt% to 3 wt%. In the above range, the epoxy resin composition may have an advantage of improving the thermal expansion coefficient after curing.

Other ingredients

In addition to the above components, the epoxy resin composition according to the present invention may further include at least one of a curing accelerator, a coupling agent, a release agent, and a colorant.

Hardening accelerator

The curing accelerator is a substance that promotes the reaction between the epoxy resin and the curing agent. As the curing accelerator, for example, tertiary amines, organic metal compounds, organic phosphorus compounds, imidazoles, and boron compounds can be used. Tertiary amines include benzyldimethylamine, triethanolamine, triethylenediamine, diethylaminoethanol, tri (dimethylaminomethyl) phenol, 2-2- (dimethylaminomethyl) phenol, 2,4,6-tris ) Phenol and tri-2-ethylhexyl acid salt.

Specific examples of the organometallic compound include chromium acetylacetonate, zinc acetylacetonate, nickel acetylacetonate, and the like. Organic phosphorus compounds include tris-4-methoxyphosphine, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, phenylphosphine, diphenylphosphine, triphenylphosphine, triphenylphosphine triphenylborane, triphenylphosphine Pin-1,4-benzoquinone adducts and the like. Imidazoles include, but are not limited to, 2-phenyl-4 methylimidazole, 2-methylimidazole, 2-phenylimidazole, 2-aminoimidazole, -Methylimidazole, 2-heptadecylimidazole, and the like, but the present invention is not limited thereto. Specific examples of the boron compound include tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, tetraphenylboron salt, trifluoroborane-n-hexylamine, trifluoroborane monoethylamine, tetrafluoro Triethylamine, tetrafluoroborane amine, and the like. In addition, 1,5-diazabicyclo [4.3.0] non-5-ene (1,5-diazabicyclo [4.3.0] non-5-ene: DBN), 1,8-diazabicyclo [5.4. Diazabicyclo [5.4.0] undec-7-ene: DBU) and phenol novolac resin salt. However, the present invention is not limited thereto.

More specifically, organic phosphorus compounds, boron compounds, amine-based or imidazole-based curing accelerators may be used alone or in combination as the curing accelerator. As the curing accelerator, it is also possible to use an adduct made by reacting with an epoxy resin or a curing agent.

In the present invention, the amount of the curing accelerator to be used may be about 0.01 to about 2% by weight based on the total weight of the epoxy resin composition, specifically about 0.02 to 1.5% by weight, more specifically about 0.05 to 1% by weight . It may be advantageous that the curing of the epoxy resin composition is accelerated within the above-mentioned range and the curing degree is also good.

Coupling agent

The coupling agent is for improving the interface strength by reacting between the epoxy resin and the inorganic filler, and may be, for example, a silane coupling agent. The silane coupling agent is not particularly limited as long as it reacts between the epoxy resin and the inorganic filler to improve the interface strength between the epoxy resin and the inorganic filler. Specific examples of the silane coupling agent include epoxy silane, aminosilane, ureido silane, mercaptosilane, and the like. The coupling agent may be used alone or in combination.

The coupling agent may be contained in an amount of about 0.01 wt% to 5 wt%, specifically about 0.05 wt% to 3 wt%, and more specifically about 0.1 wt% to 2 wt%, based on the total weight of the epoxy resin composition. The strength of the cured product of the epoxy resin composition in the above range can be improved.

Release agent

As the release agent, at least one selected from the group consisting of paraffin wax, ester wax, higher fatty acid, higher fatty acid metal salt, natural fatty acid and natural fatty acid metal salt can be used.

The releasing agent may be contained in an amount of 0.1 to 1% by weight in the epoxy resin composition.

coloring agent

The coloring agent is for laser marking of a semiconductor element sealing material, and colorants well-known in the art can be used and are not particularly limited. For example, the colorant may include one or more of carbon black, titanium black, Nubian black, titanium nitride, dicopper hydroxide phosphate, iron oxide, mica.

The colorant may be contained in an amount of about 0.01% by weight to 5% by weight, specifically about 0.05% by weight to 3% by weight, and more specifically about 0.1% by weight to 2% by weight based on the total weight of the epoxy resin composition.

In addition, the epoxy resin composition of the present invention may contain a stress-relieving agent such as a modified silicone oil, a silicone powder, and a silicone resin to the extent that the object of the present invention is not impaired; Antioxidants such as Tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane; And the like may be further contained as needed.

The epoxy resin composition may be prepared by uniformly mixing the above components uniformly at a predetermined mixing ratio using a Hensel mixer or a Lodige mixer and then kneading the mixture in a roll mill or a kneader kneader, and then cooled and pulverized to obtain a final powder product.

The epoxy resin composition of the present invention as described above can be applied to sealing semiconductor devices, in particular, thin film type semiconductor devices. As a method of sealing a semiconductor element using the epoxy resin composition obtained in the present invention, a low pressure transfer molding method can be generally used. However, molding can also be performed by injection molding, casting, compression molding or the like.

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.

Example

The specifications of each component used in the following examples are as follows.

(A) Epoxy resin: phenol aralkyl type epoxy resin: NC-3000 product manufactured by Nippon Kayaku was used.

(B) Curing agent

Xyloclock type phenol resin: HE100C-10 manufactured by AIR WATER was used.

(C) Inorganic filler

Silica: Spherical fused silica having an average particle diameter of 45 탆 was used.

(D) First silicone-based resin: X-22-4952 manufactured by ShinEtsu Co., Ltd., having a viscosity of 100 mm ² / s at 25 캜 was used.

(E) Second silicone-based resin: KF-6123 manufactured by ShinEtsu having a viscosity of 420 mm ² / s at 25 ° C was used.

(F) Curing accelerator: Triphenylphosphine manufactured by Hokko Chemical Industry was used.

(G) Coupling agent: KBM-403 manufactured by Shin-Etsu Chemical was used.

(H) Colorant: Carbon black (MA600 manufactured by Mitsubishi Chemical)

(I) Release agent: powdered carnauba wax No. manufactured by S.Kato% Co. 1 was used.

Example  1 to 2 and Comparative Example  1 to 3

Each of the above components was weighed according to the composition shown in the following Table 1, and then uniformly mixed using a Henschel mixer to prepare a powdery primary composition. Thereafter, the mixture was melt-kneaded at 120 DEG C for 30 minutes using a continuous kneader, cooled to 10 to 15 DEG C and pulverized to prepare an epoxy resin composition for semiconductor encapsulation.

The epoxy resin composition for sealing semiconductor devices prepared above was evaluated for physical properties by the following methods, and the results are shown in Table 1 below.

Property evaluation method

(1) Spiral flow (inch): The mold was manufactured based on the EMMI standard, and the flow length was evaluated under the conditions of a molding temperature of 175 캜 and a molding pressure of 70 kgf / cm ² .

(2) Glass Transition Temperature (Tg, 占 폚) and Thermal Expansion Coefficients (? 1 and? 2, ppm / 占 폚): The TMA (Thermal Mechanical Analyzer) was used at a heating rate of 10 占 폚 / min.

(3) Curing Shrinkage (%): Flexural Strength A specimen (125 mm × 12.6 mm × 6.4 mm) was molded using an ASTM mold at 175 ° C. and 70 kgf / cm ² using a transfer molding press . The obtained specimens were post-cured (PMC) in an oven at 170 ° C to 180 ° C for 4 hours, cooled, and then the length of the specimens was measured with a caliper. The hardening shrinkage ratio was calculated from Equation 1 as follows.

[Formula 1]

Cure shrinkage (%) = A - B | / A × 100

(A is the mold length at 175 占 폚, and B is the length of the specimen obtained after curing the specimen at 170 占 폚 to 180 占 폚 for 4 hours and cooling)

(4) Flexural modulus (GPa (25 ° C), MPa (260 ° C)): A standard specimen (125 × 12.6 × 6.4 mm) was prepared in accordance with ASTM D-790 and cured at 175 ° C. for 4 hours. Testing Machine) at 25 ° C and 260 ° C, respectively.

(weight%) Example Comparative Example One 2 One 2 3 (A) 5.8 5.9 5.8 5.8 6.8 (B) 3.2 3.3 3.2 3.2 4.2 (C) 88 88 88 88 88 (D) One 0.6 2 0 0 (E) One 1.2 0 2 0 (F) 0.3 0.3 0.3 0.3 0.3 (G) 0.3 0.3 0.3 0.3 0.3 (H) 0.2 0.2 0.2 0.2 0.2 (I) 0.2 0.2 0.2 0.2 0.2 Spiral flow (inch) 175 ° C 51 49 42 49 36 125 ℃ 42 41 31 32 26 Coefficient of thermal expansion alpha 1 7.5 7.4 8.2 8.6 9.2 α2 30.1 30.5 33.8 31.1 31.0 Cure shrinkage (%) 0.11 0.12 0.17 0.18 0.24 Glass transition temperature (캜) 160 163 162 158 160 Flexural modulus 25 ° C (GPa) 9.6 10.0 15.6 12.3 17.6 260 DEG C (MPa) 743 783 974 738 1274

As shown in Table 1, a combination of a first silicone-based resin having a viscosity at 25 ° C of 200 mm ² / s or less and a second silicone-based resin having a viscosity at 25 ° C of 250 mm ² / s to 800 mm ² / s It can be seen that Examples 1 and 2 have a low coefficient of thermal expansion and a low flexural modulus.

However, Comparative Examples 1 to 3, which do not contain any of the first silicone resin and the second silicone resin, have a high thermal expansion coefficient and a high flexural modulus.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the embodiments described above are in all respects illustrative and not restrictive.

Claims (8)

Epoxy resin;
Curing agent;
Inorganic fillers;
A first silicone-based resin having a viscosity at 25 캜 of 200 mm ² / s or less; And
A second silicone-based resin having a viscosity at 25 캜 of 250 mm ² / s to 800 mm ² / s;
And an epoxy resin.
The method according to claim 1,
Wherein the first silicone resin and the second silicone resin are contained in a weight ratio of 3: 1 to 1: 3.
The method according to claim 1,
Wherein the sum of the contents of the first silicone resin and the second silicone resin in the epoxy resin composition is 0.2 wt% to 3 wt%.
The method according to claim 1,
Wherein the first silicone-based resin and the second silicone-based resin each have an epoxy resin composition for semiconductor encapsulation represented by the following formula (1)
[Chemical Formula 1]

(Wherein R ₁ to R ₆ are each independently a C ₁ to C ₁₀ alkyl group, Y ₁ and Y ₂ each independently represent an amino group, an epoxy group, a carbinol group, a polyether group, a mercapto group, A hydroxy group or an acrylic group, and n is 0 to 50).
5. The method of claim 4,
Wherein R ₁ to R ₆ are methyl groups, Y ₁ and Y ₂ are each independently -R (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b H, Wherein R is an alkyl or ether group having 1 to 10 carbon atoms, a is 0 to 50, and b is 0 to 50.
The epoxy resin composition according to claim 1,
0.5 to 20% by weight of the epoxy resin,
0.1 to 13% by weight of the curing agent,
70% to 98% by weight of the inorganic filler,
0.1 to 2.9% by weight of the first silicone-based resin, and
Based resin and 0.1 to 2.9 wt% of a second silicone-based resin.
The method according to claim 1,
Wherein the epoxy resin composition further comprises at least one of a curing accelerator, a coupling agent, a release agent, and a colorant.
8. A semiconductor device encapsulated with an epoxy resin composition for encapsulating semiconductor devices according to any one of claims 1 to 7.