KR20180076899A - Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated using the same - Google Patents

Abstract

The present invention relates to an epoxy resin composition for sealing semiconductor devices, and a semiconductor device sealed by using the same. To this end, the epoxy resin composition contains an epoxy resin, a hardener, and an inorganic filler. The hardener contains a phenolic hardener in which at least 0.1 mol% and not more than 30 mol% of total hydroxyl groups of total phenolic functional groups are modified with an alkoxysilane group-containing functional group.

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 USING THE SAME [

TECHNICAL FIELD The present invention relates to an epoxy resin composition for sealing a semiconductor device and a semiconductor device sealed with the epoxy resin composition. More particularly, the present invention relates to an epoxy resin composition for sealing a semiconductor device, which has a high hardening shrinkage ratio and a high modulus at a high temperature, thereby realizing excellent warpage characteristics and excellent reliability, and a semiconductor device sealed using the epoxy resin composition .

BACKGROUND ART As a method of packaging a semiconductor device such as IC and LSI and obtaining a semiconductor device, transfer molding using an epoxy resin composition is widely used because of its low cost and suitable for mass production. The epoxy resin composition for semiconductor encapsulation generally comprises an epoxy resin, a curing agent, an inorganic filler, and the like.

However, due to the miniaturization, light weight, and high performance of electronic products, semiconductor chips have become thinner, higher integration and / or surface mounting have increased, which can not be solved by conventional epoxy resin compositions. Particularly, there is a problem in that warpage and defects of the package are likely to occur due to thermal expansion and heat shrinkage between the substrate and the sealing layer as the semiconductor device is made thinner.

Depending on the kind of the semiconductor package, the modulus of the sealing layer and the curing shrinkage ratio of the composition may need to be increased in order to improve package bending and reliability. However, it is generally difficult to increase both modulus and hardening shrinkage because the modulus and cure shrinkage are in a trade-off relationship. The modulus can be increased by increasing the content of the inorganic filler in the epoxy resin composition. In this case, however, there is a problem that the flowability and moldability of the epoxy resin composition are deteriorated and the hardening shrinkage ratio decreases in proportion to the increase of the modulus. Further, in order to increase the hardening shrinkage ratio, a method of increasing the content of the epoxy resin having a low glass transition temperature may be considered. In this case, there is a problem that the modulus decreases most of the time.

Therefore, development of an epoxy resin composition capable of simultaneously realizing a high modulus and a high curing shrinkage ratio is desired.

An object of the present invention is to provide an epoxy resin composition for encapsulating semiconductor devices, which is capable of realizing a sealing layer having a high hardening shrinkage ratio and a high modulus at a high temperature.

Another object of the present invention is to provide an epoxy resin composition for sealing a semiconductor element, which has a high hardening shrinkage ratio, a high modulus sealing layer at a high temperature, and other physical properties such as moisture absorption rate, fluidity and adhesion.

It is still another object of the present invention to provide an epoxy resin composition for semiconductor device encapsulation which makes it possible to manufacture a semiconductor device having excellent bending characteristics and reliability.

Another object of the present invention is to provide a semiconductor device which is sealed with the epoxy resin composition as described above.

The epoxy resin composition for semiconductor device encapsulation according to the present invention comprises an epoxy resin; Curing agent; And an inorganic filler, wherein the curing agent may include a phenolic curing agent wherein at least 0.1 mol% and not more than 30 mol% of the total hydroxyl groups of the total phenol functional groups are modified with an alkoxysilane group-containing functional group.

The present invention provides a semiconductor device which is sealed using the epoxy resin composition for sealing a semiconductor device according to the present invention.

The present invention provides an epoxy resin composition for encapsulating a semiconductor device capable of realizing a sealing layer having a high hardening shrinkage ratio and a high modulus at a high temperature.

The present invention provides an epoxy resin composition for semiconductor device encapsulation which has a high hardening shrinkage ratio and a high modulus at a high temperature and which can improve other physical properties such as moisture absorption rate, fluidity and adhesion.

The present invention provides an epoxy resin composition for semiconductor device encapsulation which makes it possible to manufacture a semiconductor device having excellent bending characteristics and reliability.

The present invention provides a semiconductor device sealed with an epoxy resin composition as described above.

Generally, the epoxy resin composition for sealing a semiconductor device has a trade-off relationship between a curing shrinkage ratio and a modulus after curing. In other words, the epoxy resin composition for sealing a semiconductor device having a high hardening shrinkage ratio has a low modulus after curing and a high modulus after curing, and the epoxy resin composition for sealing a semiconductor device generally has a low hardening shrinkage ratio. Although there is a difference depending on the type of the semiconductor package, the higher the modulus and the hardening shrinkage ratio at high temperature, the better the warpage characteristic. In particular, a molded underfill (MUF) package in a semiconductor package has a higher flexural modulus as the modulus and hardening shrinkage ratio at high temperatures are higher.

As used herein, the term "substituted or unsubstituted" or "substituted" means that at least one hydrogen atom of the functional group is a hydroxyl group, a halogen (eg, F, Cl, Br or I), a nitro group, an imino group (= NH, = NR, R is C1 to C10 alkyl groups), amino groups _{(-NH 2, -NH (R '} ), -N (R ") (R"'), wherein R ', R ", A C1 to C20 alkyl group, a C6 to C30 aryl group, a C3 to C30 cycloalkyl group, a C3 to C30 alkyl group, a C3 to C30 aryl group, a C3 to C30 heteroaryl group, , Or a C2 to C30 heterocycloalkyl group, but is not limited thereto.

As used herein, "high temperature" may mean 260 ° C ± 5 ° C (255 ° C to 265 ° C), preferably 260 ° C.

In the present specification, "Me" is a methyl group and "Et" is an ethyl group.

The present inventors have conducted intensive studies to develop an epoxy resin for sealing semiconductor devices capable of simultaneously raising the curing shrinkage ratio and the modulus at a high temperature after curing. As a result, by using the modified curing agent described below, And the present invention has been completed.

The epoxy resin composition according to the present invention comprises an epoxy resin, a curing agent, and an inorganic filler, wherein the curing agent is modified by an alkoxysilane group-containing functional group in an amount of not less than 0.1 mol% and not more than 30 mol% of total hydroxyl groups (-OH) Phenolic < / RTI > curing agent. Within the above range, both the curing shrinkage ratio and the modulus at high temperature can be increased, and the curing property can be improved by preventing the composition from hardening or being hardened. Preferably, 5 mol% or more, 25 mol% or less, 7 mol% or more and 23 mol% or less, or 10 mol% or more and 20 mol% or less of the total hydroxyl groups of the total phenolic functional groups may be modified. Specifically, the epoxy resin composition according to the present invention may have a hardening shrinkage of 0.6% or more, for example, 0.6% or more and 1% or less. The epoxy resin composition according to the present invention may have a modulus of 700 MPa or more, for example, 700 MPa or more and 1,100 MPa or less at high temperature after curing. The epoxy resin composition according to the present invention has a glass transition temperature after curing of 180 占 폚 or higher, preferably 190 占 폚 or higher, For example, 190 deg. C or higher and 220 deg. C or lower. In the above range, the semiconductor package, particularly the MUF package, can have a good bending property and a high reliability.

As used herein, the term "phenol functional group" means the following structural formulas A1 to A3:

≪ Formula (A1)

≪   

<A3>

(Wherein * is a linking site, and one to four of the hydrogen atoms may be substituted by the same or different functional groups).

Hereinafter, the constituent components of the epoxy resin composition according to the present invention will be described in detail.

Epoxy resin

As the epoxy resin, epoxy resins generally used for sealing semiconductor devices can be used and are not particularly limited. Specifically, as the epoxy resin, an epoxy compound containing two or more epoxy groups in the molecule can be used. For example, the epoxy resin is an epoxy resin obtained by epoxidating a condensate of phenol or alkyl phenol and hydroxybenzaldehyde, a phenol aralkyl type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a multifunctional epoxy Resin, naphthol novolak type epoxy resin, novolak type epoxy resin of bisphenol A / bisphenol F / bisphenol AD, glycidyl ether of bisphenol A / bisphenol F / bisphenol AD, bishydroxybiphenyl type epoxy resin, dicyclopenta Diene-based epoxy resins, and biphenyl-type epoxy resins. More specifically, the epoxy resin may include at least one of a cresol novolak-type epoxy resin, a multifunctional epoxy resin, a phenol aralkyl-type epoxy resin, and a biphenyl-type epoxy resin. Most preferably, the epoxy resin may be an orthocresol novolak type epoxy resin.

The epoxy resin may be used singly or in combination, and may be added in the form of an additive compound prepared by subjecting an epoxy resin to a linear reaction such as a curing agent, a curing accelerator, a releasing agent, a coupling agent, and a stress relieving agent and a melt master batch .

The epoxy resin may be contained in an amount of 0.5 to 20% by weight, specifically 3 to 15% by weight in the epoxy resin composition for sealing a semiconductor device. Within this range, the curability of the composition may not be deteriorated.

Hardener

The hardener At least 0.1 mol% and not more than 30 mol% of the total hydroxyl groups of the total phenolic functional groups may be modified with an alkoxysilane group-containing functional group. The phenolic curing agent can increase both the curing shrinkage ratio of the epoxy resin composition for sealing a semiconductor device and the modulus at a high temperature after curing.

The phenolic curing agent may be contained in an amount of more than 0 wt% to 100 wt%, preferably 60 wt% to 100 wt% of the total curing agent. Within the above range, both the curing shrinkage ratio and the modulus at high temperature after curing can be increased.

The alkoxysilane group-containing functional group may be represented by the following Formula 1:

&Lt; Formula 1 >

* -O-X-Y-Z

(Wherein * is a moiety connected to the aromatic carbon of the phenol functional group,

X is -C (= O) -NH-, or _{-CH 2 CH (OH) CH 2} -O-,

Y is a single bond or a divalent organic group,

And Z is an alkoxysilane group having 1 to 3 alkoxy groups of 1 to 10 carbon atoms. The divalent organic group may be a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms or a substituted or unsubstituted oxyalkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 5 carbon atoms.

For example, the phenolic curing agent may include at least one alkoxysilane group-containing functional group represented by any one of the following formulas (1-1) to (1-4).

&Lt; Formula 1-1 >

* -OC (= O) -NH- (CH ₂ ) ₃ -Si (OMe) ₃

(1-2)

* -OC (= O) -NH- ( CH 2) 3 -Si (OEt) 3

<Formula 1-3>

-O-CH ₂ -CH (OH) -CH ₂ -O- (CH ₂ ) ₃ -Si (OMe) ₃

<Formula 1-4>

-O-CH ₂ -CH (OH) -CH ₂ -O- (CH ₂ ) ₃ -Si (OEt) ₃

In one embodiment, the phenolic curing agent may include one or more of the following structures:

(2)

(Note that in the above, X is -C (= O) -NH-, or _{-CH 2 CH (OH) CH 2} -O-,

Y is a single bond or a divalent organic group,

R _a , R _b and R _c are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, and at least one of R _a , R _b and R _c And at least one is a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms).

A phenolic curing agent is a -C (= O) -NH-, or _{-CH 2 CH (OH) CH 2} -O- can be coupled to the phenol functional group.

Preferably, the phenolic curing agent may comprise units of the formula:

(3)

(Wherein X, Y, R _a , R _b , and R _c are the same as defined in Formula 2,

n is an average value of 1 to 7).

For example, the phenolic curing agent may include one or more of the following formulas (3-1) and (3-2):

&Lt; Formula 3-1 >

(Wherein n is the same as defined in the above formula (3)).

(3-2)

(Wherein n is the same as defined in the above formula (3)).

Phenolic curing agents can be prepared by conventional methods known to those skilled in the art. For example, the phenolic curing agent may be prepared by reacting at least one phenolic curing agent having a hydroxyl group with an alkoxysilane having an isocyanate group or a glycidoxy group at the terminal. In order to increase the yield of the phenolic curing agent, the temperature, time, etc. of the reaction conditions can be controlled. Wherein the at least one hydroxyl group-containing phenolic curing agent is selected from the group consisting of a phenol aralkyl type phenol resin, a phenol novolac type phenol resin, a xylok type phenol resin, a cresol novolak type phenol resin, a naphthol type phenol resin, A phenol resin, a novolac phenol resin synthesized from bisphenol A and resole, a polyhydric phenol compound including tris (hydroxyphenyl) methane, and dihydroxybiphenyl, . Preferably, the phenolic curing agent may comprise a multifunctional phenolic resin. The alkoxysilane may comprise at least one of 3-isocyanate propyltrimethoxysilane, 3-isocyanate propyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane have.

In addition to the modified phenolic curing agent, the curing agent may further include a curing agent generally used for sealing semiconductor devices (hereinafter, unreformed curing agent). Specifically, as the curing agent, 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 modified phenolic curing agent and the unmodified curing agent may be used alone or in combination. Further, it can be used as an additional compound prepared by subjecting the above-mentioned curing agent to a linear reaction such as an epoxy resin, a curing accelerator, a releasing 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, preferably 0.1 to 10% by weight, more preferably 0.1 to 9% by weight in the epoxy resin composition for encapsulating semiconductor devices. Within this range, there is an effect that the curability of the composition is not lowered.

The blending ratio of the epoxy resin and the curing agent can be adjusted according to 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 from 0.95 to 3, and may be specifically from 1 to 2, more specifically from 1 to 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 intended to improve the mechanical properties and low stress of the epoxy resin composition. As the inorganic filler, general inorganic fillers used for the semiconductor encapsulant can be used without limitation and are not particularly limited. Examples of the inorganic filler include fused silica, crystalline silicate, calcium carbonate, magnesium carbonate, alumina, magnesia, clay, talc, calcium silicate, titanium oxide, antimony oxide, glass fiber and the like . These may be used alone or in combination.

Preferably, fused silica having a low linear expansion coefficient 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 spherical fused silica having an average particle diameter of 5 to 30 탆 is contained in an amount of 50 to 99% by weight, the spherical fused silica having an average particle diameter of 0.001 to 1 탆 is contained in an amount of 1 to 50% To 40% by weight to 100% by weight with respect to 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 included in the epoxy resin composition for encapsulating semiconductor devices in an amount of 70% by weight to 95% by weight, such as 75% by weight to 94% by weight or 75% by weight to 93% by weight. Within this range, there can be obtained an effect of ensuring the fluidity and reliability of the composition.

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, a tertiary amine, an organometallic compound, an organic phosphorus compound, an imidazole, and a boron compound 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.

The curing accelerator may be 0.01% by weight to 2% by weight, specifically 0.02% by weight to 1.5% by weight, more specifically 0.05% by weight to 1% by weight in the epoxy resin composition for encapsulating semiconductor devices. In the above range, the curing of the epoxy resin composition is promoted 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, ureidosilane, mercaptosilane, and alkylsilane. The coupling agent may be used alone or in combination.

The coupling agent may be contained in an amount of 0.01 to 5 wt%, preferably 0.05 to 3 wt%, and more preferably 0.1 to 2 wt% in the epoxy resin composition for encapsulating semiconductor devices. The strength of the cured product of the epoxy resin composition in the above range can be improved.

Release agent

As the releasing 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 release agent may be contained in an amount of 0.1 wt% to 1 wt% in the epoxy resin composition for sealing a semiconductor device.

coloring agent

The coloring agent is for laser marking of the semiconductor element sealing material, and coloring agents 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, titanium nitride, dicopper hydroxide phosphate, iron oxide, mica.

The colorant may be contained in an amount of 0.01 to 5 wt%, preferably 0.05 to 3 wt%, and more preferably 0.1 to 2 wt% in the epoxy resin composition for encapsulating semiconductor devices.

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; A flame retardant such as aluminum hydroxide, and the like may be further added as needed.

The epoxy resin composition is prepared by sufficiently mixing the above components uniformly at a predetermined mixing ratio using a Hensel mixer or a Lodige mixer and then melt-kneading the mixture with a roll mill or a kneader Followed by cooling and grinding to obtain a final powder product.

The epoxy resin composition of the present invention as described above can be applied to semiconductor devices, particularly semiconductor devices requiring high shrinkage and high elasticity properties. 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, it is also possible to perform molding by an injection molding method or a casting method.

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

Specific specifications of the components used in the following examples and comparative examples are as follows.

(A) an epoxy resin

YDCN-500-4P (Kukdo Chemical), an orthocresol novolak type epoxy resin, was used.

(B) Curing agent

(b1) A mixture of 74 g of alkoxysilane KBE-9007 (Shinetsu) having an isocyanate group in 310 g of a phenolic curing agent MEH-7500-3S (Meiwa) was melted at a temperature of 90 ° C and stirred for 30 minutes. The mixture was cooled at room temperature and then pulverized to obtain 380 g of modified resin PS-110 (solid compound). The modified resin PS-110 is a curing agent having an alkoxysilane group introduced therein in an amount of 10 mol% of the total phenolic functional groups of the phenolic curing agent, and includes the following Formula 3-1.

&Lt; Formula 3-1 >

(b2) To 310 g of a phenolic curing agent MEH-7500-3S (Meiwa) were mixed 148 g of an alkoxysilane KBE-9007 (Shinetsu) having an isocyanate group, and the temperature was raised to 90 캜 and melted, followed by stirring for 30 minutes. After cooling at room temperature, the mixture was pulverized to obtain 456 g of a modified PS-120 (solid compound). The modified PS-120 is a curing agent having an alkoxysilane group introduced therein in an amount of 20 mol% of the total phenolic functional groups of the phenolic curing agent.

(b3) 310 g of a phenolic curing agent MEH-7500-3S (manufactured by Meiwa) and 71 g of an alkoxysilane A-187 having an epoxy group (Momentive) were mixed and heated at 90 DEG C for melting and stirring for 30 minutes. Cooled at room temperature and then pulverized to obtain 379 g of a modified resin ES-110 (solid compound). The modified resin ES-110 is a curing agent having an alkoxysilane group introduced therein in an amount of 20 mol% of the total phenolic functional groups of the phenolic curing agent, and includes the following Formula 3-2.

(3-2)

(b4) phenolic curing agent MEH-7500-3S (Meiwa) without an alkoxysilane group was used.

(b5) 260 g of an alkoxysilane KBE-9007 (Shinetsu) having an isocyanate group was mixed with 310 g of a phenolic curing agent MEH-7500-3S (Meiwa), and the mixture was heated at 90 캜 for melting and then stirred for 30 minutes. The mixture was cooled at room temperature and then pulverized to obtain 551 g of a modified resin. The modified resin is a curing agent in which an alkoxysilane group is introduced in an amount of 35 mol% of the total phenolic functional groups of the phenolic curing agent.

(C) Inorganic filler: A 9: 1 (weight ratio) mixture of spherical fused silica having an average particle diameter of 18 탆 and spherical fused silica having an average particle diameter of 0.5 탆 was used.

(D) Curing accelerator: Triphenylphosphine (Hoko Chemical) was used.

 (E) Coupling agent: A mixture of KBM-403 (Shin-Etsu) (e1), an epoxy group-containing trimethoxysilane, and SZ-6070 (Dow Corning Chemicals), e2, methyltrimethoxysilane was used.

(F) Colorant: Carbon black MA-600B (manufactured by Mitsubishi Chemical Corporation) was used.

(G) Release agent: Carnauba wax was used.

Example  And Comparative Example

Each of the components was weighed according to the composition (unit: parts by weight) 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 90 to 110 ° C using a continuous kneader, followed by cooling and pulverization, thereby preparing an epoxy resin composition for sealing semiconductor devices.

Example Comparative Example One 2 3 One 2 (A) 14.7 14.7 14.7 14.7 14.7 (B) (b1) 8.6 - - - - (b2) - 8.6 - - - (b3) - - 8.6 - - (b4) - - - 8.6 - (b5) - - - - 8.6 (C) 75 75 75 75 75 (D) 0.6 0.6 0.6 0.6 0.6 (E) (e1) 0.3 0.3 0.3 0.3 0.3 (e2) 0.2 0.2 0.2 0.2 0.2 (F) 0.3 0.3 0.3 0.3 0.3 (G) 0.3 0.3 0.3 0.3 0.3

The physical properties of the epoxy resin compositions of the examples and comparative examples thus prepared were measured according to the following properties evaluation methods. The measurement results are shown in Table 2.

Property evaluation method

(1) Flowability (inch): An epoxy resin composition was injected into a mold for spiral flow measurement according to EMMI-1-66 at a molding temperature of 175 캜 and a molding pressure of 70 kgf / cm ² using a low pressure transfer molding machine, (Length of idle motion) (unit: inch) was measured. The higher the measured value, the better the fluidity.

(2) Curing Shrinkage (%): Flexural Strength Using a transfer molding press at 175 ° C and 70 kgf / cm ² using an ASTM mold for specimen preparation, the specimen (length x width x thickness, 125 mm x 12.6 mm x 6.4 mm). 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 ratio = A - B | / A x 100

Wherein A is a length of a specimen obtained by transfer molding pressing the epoxy resin composition at 175 DEG C and 70 kgf / cm &lt; ² &gt;, B is a temperature at which the specimen is cured at 170 DEG C to 180 DEG C for 4 hours, The length of the psalm).

(3) High temperature modulus: The epoxy resin composition was cured at a mold temperature of 175 ° C ± 5 ° C, an injection pressure of 1000 psi ± 200psi and a curing time of 120 seconds using a transfer molding machine to prepare a specimen (length x width x thickness x 20 mm x 13 mm x 1.6 mm). The specimens were post cured for 2 hours in a hot air drier at 175 ° C ± 5 ° C and then measured with a dynamic mechanical analyzer (DMA) using a Q8000 (TA). In the measurement of the modulus, the temperature raising rate was increased from -10 ° C to 300 ° C at a rate of 5 ° C / minute, and the value at 260 ° C was obtained as a storage modulus.

(4) Glass transition temperature (占 폚): The glass transition temperature was determined in the same manner as in (3).

(5) moisture absorption: Examples and Comparative Examples the epoxy resin composition to a mold temperature of 170 ℃ to 180 ℃, the clamp pressure 70kgf / cm ^2, feed pressure 1000psi, feed rate 0.5 to 1cm / sec, the curing time of 120 seconds, a molding diameter 50mm , And a disk-shaped specimen having a thickness of 1.0 mm were obtained. The obtained specimens were placed in an oven at 170 to 180 DEG C and post-cured for 4 hours. The specimens were allowed to stand for 168 hours at 85 DEG C and 85% relative humidity to be moisture-absorbed, Respectively.

<Formula 2> Moisture absorption rate = | C - D | / D x 100

(Where C is the weight of the specimen after moisture absorption and D is the weight of the specimen before moisture absorption).

6, adhesive force: preparing a standard for the mold for the adhesion measurement of copper metal element, and held in the prepared specimen examples and the comparative example epoxy resin composition to a mold temperature of 170 ℃ to 180 ℃, the clamp pressure 70kgf / cm ^2, feed pressure 1000psi , A feed rate of 0.5 to 1 cm / sec, and a curing time of 120 seconds to obtain specimens. The obtained specimen was post-cured in an oven at 170 ° C to 180 ° C for 4 hours. The area of the epoxy resin composition contacting the specimen was 40 ± 1 mm ² . Adhesion was measured using a universal testing machine (UTM) for 12 specimens per each measurement step and then calculated as an average value.

(7) Hardening degree by curing time: Using an eTQFP (exposed thin quad flat package) machine having a width of 24 mm, a length of 24 mm and a thickness of 1 mm including a copper metal element at 70 ° C., 80 seconds, 90 seconds, 100 After curing the composition to be evaluated for a second, the hardness of the cured product with the curing time was measured using a Shore-D type hardness meter directly on the package on the mold. The higher the hardness, the better the hardness.

(8) Storage stability: The flow lengths of the epoxy resin compositions of the examples and comparative examples were measured at the intervals of 24 hours in the same manner as in the flowability measurement of the above (1) while being stored in a thermo-hygrostat set at 25 ° C and 50% . The flow length immediately after preparation was determined as the ratio of the flow length to the storage time. The larger the value obtained, the better the storage stability.

(9) Warpage: The epoxy resin composition was molded by transfer molding at 175 DEG C for 70 seconds using an MPS (Multi Plunger System) molding machine to obtain a molded under fill (MUF) package having a width of 20 mm and a length of 20 mm and a thickness of 1 mm Respectively. After the molded package was post-cured, 10 packages heated at 175 ° C for 2 hours were heated from 25 ° C to 260 ° C to observe the flexural characteristic behavior. Differences in warpage characteristics were observed by taking point values of warpage at room temperature (25 ℃) and warpage at high temperature (260 ℃). │High warpage - The smaller the warpage at room temperature, the better the bending property.

Evaluation items Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Flowability (inch) 115 140 121 93 - Cure shrinkage (%) 0.63 0.75 0.62 0.43 - High temperature modulus (MPa) 730 1060 742 479 - Glass transition temperature (캜) 192 201 194 188 - Moisture absorption rate (%) 0.36 0.42 0.34 0.33 - Adhesion (kgf) 54 52 52 53 - By hardening time
Hardness (Shore-D) 70 seconds 62 60 63 65 - 80 seconds 65 63 66 67 - 90 seconds 68 67 68 69 - 100 seconds 71 70 72 72 - Storage stability (%) 24 hours 96 96 97 98 - 48 hours 93 91 94 94 - 72 hours 90 88 91 91 - warp 25 占 폚 warpage (占 퐉) -5 0 -10 -45 - 260 占 폚 warpage (占 퐉) 60 70 65 95 -

As shown in Table 2, the epoxy resin composition of the present invention has high curing shrinkage, high modulus at high temperature, and good physical properties such as moisture absorption rate, fluidity, adhesion, and storage stability. In particular, although the modified phenolic curing agent modifies part of the phenolic hydroxyl groups involved in the curing reaction of the composition with an alkoxysilane group, it does not affect the degree of cure within the curing time (100 sec) The modulus of shrinkage and the modulus after curing could be increased. In addition, the epoxy resin composition of the present invention can produce a semiconductor device having excellent bending property and excellent reliability.

On the other hand, Comparative Example 1 using a phenolic curing agent having no alkoxysilane group had both a high temperature modulus and a hardening shrinkage.

In Comparative Example 2, in which 35 mol% of the total hydroxyl groups of the total phenolic functional groups were modified with an alkoxysilane group-containing functional group, the curing was not completed within the curing time (100 sec) 9) could not be evaluated.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

Epoxy resin; Curing agent; And an inorganic filler,
Wherein the curing agent comprises a phenolic curing agent wherein at least 0.1 mol% and not more than 30 mol% of the total hydroxyl groups of the total phenolic functional groups are modified with an alkoxysilane group-containing functional group.
The epoxy resin composition for sealing a semiconductor device according to claim 1, wherein the phenolic curing agent is modified by 10 mol% or more and 20 mol% or less of the total hydroxyl groups of the total phenolic functional groups.
The epoxy resin composition for sealing a semiconductor device according to claim 1, wherein the alkoxysilane group-containing functional group is represented by the following formula (1)
&Lt; Formula 1 >
* -OXYZ
(Wherein * is a moiety connected to the aromatic carbon of the phenol functional group,
X is -C (= O) -NH-, or _{-CH 2 CH (OH) CH 2} -O-,
Y is a single bond or a divalent organic group,
And Z is an alkoxysilane group having 1 to 3 alkoxy groups of 1 to 10 carbon atoms.
2. The epoxy resin composition for sealing a semiconductor element according to claim 1, wherein the phenolic curing agent comprises at least one of the following structures:
(2)

(Note that in the above, X is -C (= O) -NH-, or _{-CH 2 CH (OH) CH 2} -O-,
Y is a single bond or a divalent organic group,
R _a , R _b and R _c are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, and at least one of R _a , R _b and R _c And at least one is a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms).
The epoxy resin composition for sealing a semiconductor element according to claim 1, wherein the phenolic curing agent comprises a unit represented by the following formula (3):
(3)

(Note that in the above, X is -C (= O) -NH-, or _{-CH 2 CH (OH) CH 2} -O-,
Y is a single bond or a divalent organic group,
R _a , R _b and R _c are each independently hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, and at least one of R _a , R _b and R _c At least one is a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms,
n is an average value of 1 to 7).
The phenolic resin composition according to claim 1, wherein the phenolic curing agent is selected from the group consisting of phenol aralkyl type phenol resin, phenol novolak type phenol resin, xylok type phenol resin, cresol novolak type phenol resin, naphthol type phenol resin, A polyhydric phenol resin, a dicyclopentadiene type phenol resin, a novolak type phenol resin synthesized from bisphenol A and resole, and a polyhydric phenol compound including tris (hydroxyphenyl) methane and dihydroxybiphenyl By weight based on the total weight of the epoxy resin composition.
The composition of claim 1, wherein the composition comprises
0.5 to 20% by weight of the epoxy resin,
0.1 to 13% by weight of the curing agent,
And 70 to 95% by weight of the inorganic filler.
The epoxy resin composition for sealing a semiconductor element according to claim 1, wherein the epoxy resin composition has a curing shrinkage rate of 0.6% or more and a modulus at 260 占 폚 of 700 MPa or more after the curing process,
&Lt; Formula 1 > Cure shrinkage ratio = | A - B | / A x 100
Wherein A is a length of a specimen obtained by transfer molding pressing the epoxy resin composition at 175 DEG C and 70 kgf / cm &lt; ² &gt;, B is a temperature at which the specimen is cured at 170 DEG C to 180 DEG C for 4 hours, The length of the psalm).
The epoxy resin composition for sealing a semiconductor device according to claim 1, wherein the epoxy resin composition has a glass transition temperature of 180 DEG C or higher after curing.
A semiconductor device encapsulated with an epoxy resin composition for sealing a semiconductor element according to any one of claims 1 to 9.