KR102112868B1 - Epoxy resin composition for encapsulating semiconductor device and semiconductor device prepared using the same - Google Patents

Abstract

An epoxy resin composition for sealing a semiconductor device comprising an epoxy resin, a curing agent, a curing accelerator, an inorganic filler, and a (meth) acrylate-based compound, and the (meth) acrylate-based compound is 0.1 weight in the epoxy resin composition for sealing the semiconductor device. % To 2% by weight, an epoxy resin composition for sealing a semiconductor device and a semiconductor device manufactured using the same are provided.

Description

EPOXY RESIN COMPOSITION FOR ENCAPSULATING SEMICONDUCTOR DEVICE AND SEMICONDUCTOR DEVICE PREPARED USING THE SAME}

The present invention relates to an epoxy resin composition for sealing a semiconductor device and a semiconductor device manufactured using the same. In more detail, the present invention includes a (meth) acrylic compound in an epoxy resin composition for sealing semiconductor devices, thereby increasing toughness, improving reliability of a semiconductor package, and sealing semiconductor devices capable of increasing fluidity. It relates to an epoxy resin composition for use and a semiconductor device manufactured using the same.

As a method of packaging semiconductor elements such as IC and LSI and obtaining a semiconductor device, transfer molding using an epoxy resin composition is widely used in that it is suitable for low cost and mass production. The epoxy resin composition for semiconductor sealing is generally made of an epoxy resin, a curing agent, an inorganic filler, and the like.

However, according to the trend of miniaturization, light weight, and high performance of electronic products, semiconductor chips become thinner, and higher integration and / or surface mounting increases, and thus, problems that cannot be solved with conventional epoxy resin compositions occur. In particular, when the toughness of the epoxy resin composition is low, reliability of the semiconductor package may be reduced.

There has been a conventional method of increasing the rigidity by adjusting the content of the inorganic filler. However, when adjusting the content of the inorganic filler, there was a problem that the moisture absorption rate is increased.

An object of the present invention is to provide an epoxy resin composition for semiconductor device sealing that can increase the rigidity of the semiconductor package.

Another object of the present invention is to provide an epoxy resin composition for semiconductor device sealing that can increase the reliability of the semiconductor package.

Another object of the present invention is to provide a semiconductor device sealed using the epoxy resin composition.

The epoxy resin composition for sealing a semiconductor device of the present invention includes an epoxy resin, a curing agent, a curing accelerator, an inorganic filler, and a (meth) acrylate-based compound, and the (meth) acrylate-based compound is an epoxy resin composition for sealing the semiconductor device Of 0.1 to 2% by weight may be included.

The semiconductor device of the present invention may be sealed using the epoxy resin composition of the present invention.

The present invention provides an epoxy resin composition for semiconductor device sealing that can increase the rigidity of the semiconductor package.

The present invention provides an epoxy resin composition for semiconductor device sealing that can increase the reliability of the semiconductor package.

The present invention provides a sealed semiconductor device using the epoxy resin composition.

1 is a cross-sectional view of a semiconductor device according to an embodiment of the present invention.
2 is a cross-sectional view of a semiconductor device according to another embodiment of the present invention.

As used herein, "(meth) acrylate-based" means an acrylate-based and / or methacrylate-based.

The inventors of the present invention have found that the curable (meth) acrylate-based compound is contained in 0.1% to 2% by weight of the composition to increase toughness, increase the reliability of the semiconductor package, and increase the fluidity. Was completed.

The epoxy resin composition for sealing a semiconductor device of the present invention includes an epoxy resin, a curing agent, a curing accelerator, an inorganic filler and a (meth) acrylate-based compound, and the (meth) acrylate-based compound is an epoxy resin composition for sealing the semiconductor device Of 0.1 to 2% by weight may be included. In the above range, it is possible to increase the rigidity and increase the reliability of the semiconductor package, and to prevent the decrease in fluidity of the composition. Preferably 0.1 It may be included in weight% to 1% by weight.

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

Epoxy resin

The epoxy resins are biphenyl type epoxy resins, polyfunctional epoxy resins, biphenyl novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins and other bisphenol type epoxy resins, phenol novolac type epoxy resins, and tert-butyl Catechol type epoxy resin, naphthalene type epoxy resin, glycidylamine type epoxy resin, phenol aralkyl type epoxy resin, cresol novolac type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy Resins, cyclohexanedimethanol type epoxy resins, halogenated epoxy resins, and the like. These may be included alone or in combination of two or more.

In one embodiment, the epoxy resin may be one or more of the biphenyl-type epoxy resin of Formula 2, polyfunctional epoxy resin:

<Formula 2>

(In Formula 2, R is an alkyl group having 1 to 4 carbon atoms, and the average value of n is 0 to 7).

The epoxy resin may be included in an amount of 0.5% to 20% by weight, preferably 3% to 15% by weight of the epoxy resin composition, based on the solid content. In the above range, the curability of the composition may not be lowered.

Epoxy resins may be used alone, or may be included as a compound formed by pre-reaction such as a melt master batch with additives such as a curing agent, a curing accelerator, a release agent, a coupling agent, and a stress reliever.

Hardener

Curing agents include polyfunctional phenol resins, phenol aralkyl type phenol resins, 페놀 phenol novolac type phenol resins, xylox type phenol resins, ortho cresol novolac type phenol resins, etc., cresol novolac type phenol resins, naphthol type phenol resins, terpenes Polyphenolic phenolic compounds, including type phenolic resins, polyfunctional phenolic resins, dicyclopentadiene-based phenolic resins, novolac-type phenolic resins synthesized from bisphenol A and resol, tris (hydroxyphenyl) methane, and dihydroxybiphenyl, And aromatic amines such as maleic anhydride and anhydride-containing phthalic anhydride, meta-phenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone. The curing agent may be a phenol resin having one or more hydroxyl groups.

In one embodiment, the curing agent may include one or more of a polyfunctional phenolic resin of Formula 3, ortho cresol novolac-type phenolic resin.

<Formula 3>

(In the formula (3), the average value of n is 1 to 7).

The curing agent may be included in an amount of 0.1 wt% to 13 wt%, preferably 0.1 wt% to 10 wt% in the epoxy resin composition, based on the solid content. In the above range, the curability of the composition may not be lowered.

The curing agent may be used alone, or an additive such as an epoxy resin, a curing accelerator, a release agent, a coupling agent, and a stress relieving agent and a pre-reaction such as a melt master batch may also be included as a compound.

Curing accelerator

The curing accelerator may be a tertiary amine, an organometallic compound, an organophosphorus compound, an imidazole compound, and a boron compound. Tertiary amines include benzyldimethylamine, triethanolamine, triethylenediamine, diethylaminoethanol, tri (dimethylaminomethyl) phenol, 2-2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) ) Phenol and tri-2-ethylhexyl acid. Organic metal compounds include chromium acetylacetonate, zinc acetylacetonate, and nickel acetylacetonate. Organophosphorus compounds include tris (4-methoxyphenyl) phosphine, triphenylphosphine, triphenylborane, and triphenylphosphine-1,4-benzoquinone adducts. The imidazole compound includes 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-methylimidazole, 2-phenylimidazole, 2-aminoimidazole, 2 - methyl-1-vinyl imida Sol, 2-ethyl-4-methylimidazole, 2-heptadecylimidazole, and the like. Examples of boron compounds include triphenylphosphine tetraphenylborate, tetraphenylboron salt, trifluoroborane-n-hexylamine, trifluoroboranomonoethylamine, tetrafluoroboranetriethylamine, tetrafluoroboraneamine, 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. 0] Undec-7-ene (1,8-diazabicyclo [5.4.0] undec-7-ene: DBU) and phenol novolak resin salts. It is also possible to use an additive made by pre-reacting with the epoxy resin or curing agent.

The curing accelerator may be included in an amount of 0.01% to 10% by weight, for example, 0.01% to 5% by weight in the composition based on solids. In the above range, the curing reaction time is not delayed, the fluidity of the composition can be secured.

Inorganic filler

Inorganic fillers can improve the mechanical properties and lower stress of the composition. Examples of the inorganic filler may include one or more of fused silica, crystalline silica, calcium carbonate, magnesium carbonate, alumina, magnesia, clay, talc, calcium silicate, titanium oxide, antimony oxide, and glass fibers. have.

Preferably, for low stress, fused silica having a low coefficient of linear expansion is used. Fused silica refers to amorphous silica having a true specific gravity of 2.3 MPa or less, and includes amorphous silica produced by melting crystalline silica or synthesized from various raw materials. The shape and particle size of the fused silica are not particularly limited, but 50% to 99% by weight of spherical fused silica having an average particle size of 5 to 30 μm, and 1% to 50% by weight of spherical fused silica having an average particle diameter of 0.001 to 1 μm. It is preferable to include the fused silica 포함한 mixture containing to 40 wt% to 100 wt% based on the total filler. Further, the maximum particle size can be adjusted to any one of 45 µm, 55 µm, and 75 µm according to the application. In the fused spherical silica, since conductive carbon may be included as a foreign substance on the silica surface, it is also important to select a substance with less polar foreign matter mixing.

The amount of the inorganic filler used depends on physical properties such as moldability, low stress, and high temperature strength. In an embodiment, the inorganic filler may be included in an amount of 70% to 95% by weight, for example, 75% to 92% by weight of the epoxy resin composition based on solid content. In the above range, flame retardancy, fluidity and reliability of the epoxy resin composition can be secured.

( Met ) Acrylate series  compound

The (meth) acrylate-based compound is curable and polymerized through a crosslinking reaction, thereby increasing the rigidity of the epoxy resin composition for sealing semiconductor devices, thereby increasing the reliability of the semiconductor package. The (meth) acrylate-based compound may be a compound having a bifunctional or more preferably 5-functional to 6-functional (meth) acrylate group.

In one embodiment, the (meth) acrylate-based compound may be represented by the formula (1).

<Formula 1>

(In Formula 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently hydrogen or a methyl group).

The compound of Formula 1 includes a linking structure of carbon and oxygen excluding the (meth) acrylate group and a curable (meth) acrylate group. For this reason, it is possible to increase the reliability of the semiconductor package by adding a small amount and increasing the rigidity during curing without impairing the fluidity of the composition. In addition, there is no increase in the moisture absorption rate by adjusting the content of the inorganic filler in order to increase the conventional rigidity.

The (meth) acrylate-based compound of Formula 1 may be synthesized by a conventional method known to those skilled in the art, or a commercially available product may be used.

The (meth) acrylate-based compound may be included in an amount of 0.1 wt% to 2 wt%, for example, 0.1 wt% to 1 wt% of the epoxy resin composition based on solid content. In the above range, it is possible to increase the rigidity of the composition, increase the reliability of the semiconductor package, and prevent a decrease in fluidity of the composition.

additive

The epoxy resin composition may contain conventional additives. In embodiments, the additive may include one or more of a coupling agent, a release agent, a stress reliever, a colorant, a crosslinking enhancer, and a leveling agent.

The coupling agent may use one or more of epoxy silane, amino silane, mercapto silane, alkyl silane, and alkoxy silane, but is not limited thereto. Coupling agent may be included in 0.1% to 1% by weight of the epoxy resin composition based on solids.

The mold release agent may be one or more 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. The release agent may be included in an amount of 0.1% to 1% by weight of the epoxy resin composition based on solid content.

The stress reliever may be one or more selected from the group consisting of modified silicone oil, silicone elastomer, silicone powder and silicone resin, but is not limited thereto. The stress relieving agent may be contained in an amount of 0 to 6.5% by weight, for example, 0 to 1% by weight, for example, 0.1 to 1% by weight of the epoxy resin composition on a solid content basis.

The colorant may be carbon black or the like, and may be included in an amount of 0.1% to 3% by weight in the epoxy resin composition based on solid content.

The additive may be included in an amount of 0.1% to 10% by weight, for example, 0.1% to 3% by weight of the epoxy resin composition based on solid content.

The method for preparing the epoxy resin composition is not particularly limited, but after mixing the components contained in the composition uniformly using a Henschel mixer or a Lödige mixer, melt-kneading at 90 ° C to 120 ° C with a roll mill or a kneader And may be manufactured through a cooling and grinding process.

The epoxy resin composition of the present invention can be used for sealing semiconductor devices. As a method of sealing a semiconductor device using the composition of the present invention, a low pressure transfer molding method may be most commonly used. However, it can also be molded by a method such as an injection molding method or a casting method. A semiconductor device of a copper leadframe, an iron leadframe, or a preframe pre-plated with one or more materials selected from the group consisting of nickel, copper, and palladium on the leadframe, or an organic laminate frame by the above method can do.

The semiconductor device of the present invention can be sealed using the epoxy resin composition.

1 is a cross-sectional view of a semiconductor device according to an embodiment of the present invention. Referring to FIG. 1, a semiconductor device 100 according to an embodiment of the present invention includes a wiring board 10, a bump 30 formed on the wiring board 10, and a semiconductor chip 20 formed on the bump 30, The gap between the wiring substrate 10 and the semiconductor chip 20 may be sealed with the epoxy resin composition 40, and the epoxy resin composition may be the epoxy resin composition of the embodiment of the present invention.

2 is a cross-sectional view of a semiconductor device according to another embodiment of the present invention. 2, the semiconductor device 200 of another embodiment of the present invention includes a wiring board 10, a bump 30 formed on the wiring board 10, a semiconductor chip 20 formed on the bump 30, The gap between the wiring board 10 and the semiconductor chip 20 and the entire upper surface of the semiconductor chip 30 may be sealed with the epoxy resin composition 40, and the epoxy resin composition is an epoxy resin composition for sealing a semiconductor device of an embodiment of the present invention. It may include.

In FIG. 1 and FIG. 2, the size of each of the wiring board, the bump, and the semiconductor chip, the number of bumps, and the like are arbitrarily illustrated and may be changed.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by examples.

Specific specifications of the components used in Examples and Comparative Examples are as follows.

(A) Epoxy resin

(A1) Biphenyl epoxy resin: YX-4000, JER

(A2) Multifunctional epoxy resin: EPPN-501, Nippon kayaku

(B) curing agent

(B1) polyfunctional phenolic resin: MEH-7500, MEIWA

(B2) Ortho cresol novolac type phenolic resin: HF-1,4,5M, MEIWA

(C) curing accelerator: phosphonium-based (TPP, HOKKO company)

(D) Inorganic filler: 9: 1 (weight ratio) mixture of spherical fused silica having an average particle diameter of 20 µm and spherical fused silica having an average particle diameter of 0.5 µm (Tathumori, MSR Series)

(E) (meth) acrylate-based compound: Compounds in which R ₁ to R ₆ are all hydrogen in Formula 1 (Nippon Kayaku, Kayarad series)

(F) Coloring agent: Carbon black (MA-100R, Mitsubishi Chemical Corporation)

(G) Mold release agent: Carnauba wax

(H) Coupling agent: Epoxy silane (KBM-303, Shinetsu), mercapto silane (KBM-803, Shinetsu)

Example  One

Each component was mixed according to the following Table 1 (unit: parts by weight), and uniformly mixed using a Henschel mixer to obtain a powdery composition. Then, using a continuous kneader, melt-kneaded at 95 ° C, and then cooled and pulverized to prepare an epoxy resin composition.

Example  2 to Example  4 and Comparative example  1 to Comparative example  3

In Example 1, except for changing the content of each component as shown in Table 1, an epoxy resin composition was prepared in the same manner.

The physical properties of Table 1 below were evaluated for the epoxy resin compositions prepared in Examples and Comparative Examples.

(1) Flowability (unit: inch): The flow length was measured using a transfer molding press at 175 ° C and 70 kgf / cm ² using an evaluation mold according to EMMI-1-66. The higher the measured value, the better the fluidity.

(2) Toughness (unit: kgf / mm): the resin composition prepared in Examples and Comparative Examples is 170 ° C to 180 ° C, clamp pressure 70kgf / cm ² , feed pressure 1,000psi, feed speed 0.5 to 1cm / s , Molded under the conditions of a curing time of 120 seconds to obtain a cured specimen having a diameter of 12.78 mm, a thickness of 6.43 mm, and a length of 127.1 mm. The hardened specimen is measured using a UTM (Universal Testing Machine) device using a 3-point vending method to obtain the toughness value using the area value of the displacement value (mm) to the breaking point and the load value (kgf) to the breaking point. (At this time, the descending speed of Jig at 3 point vending was 1 mm / min).

(3) Hygroscopicity (unit:%): the resin composition prepared in Examples and Comparative Examples is mold temperature 170 ° C to 180 ° C, clamp pressure 70 kgf / cm ² , transfer pressure 1000 psi, transfer speed 0.5 to 1 cm / s, curing It was molded under the conditions of time 120 seconds to obtain a hardened specimen in the form of a disc having a diameter of 50 mm and a thickness of 1 mm. The obtained specimen was placed in an oven at 170 ° C to 180 ° C and post-cured for 4 hours (PMC: post molding cure), then left at 85 ° C and 85% relative humidity for 168 hours, and then measured for weight change due to moisture absorption. The moisture absorption rate was calculated by Equation 1.

<Equation 1>

Absorption rate (%) = (weight of specimen after moisture absorption-weight of specimen before moisture absorption) ÷ (weight of specimen before moisture absorption) × 100

(4) Reliability: BOC Type (14 mm horizontal, 12 mm vertical, 0.45 mm thick) package was dried at 125 ° C. for 24 hours, followed by 5 cycles (1 cycle is 10 minutes at -65 ° C. and 10 minutes at 25 ° C.) Thermal shock test was performed). Thereafter, the package was left for 168 hours at 85 ° C and 60% relative humidity, and then the presence or absence of appearance cracks in the package was observed after the pre-conditioning condition of repeating the IR reflow once three times at 260 ° C for 30 seconds. It was observed under a microscope. Subsequently, the presence or absence of peeling between the epoxy resin composition and the lead frame was evaluated using a non-destructive test, C-SAM (Scanning Acoustic Microscopy). When the appearance crack of the package occurs or peeling occurs between the epoxy resin composition and the lead frame, the reliability of the package cannot be secured.

Example Comparative example One 2 3 4 One 2 3 Epoxy resin Biphenyl type epoxy resin 5.151 5.013 4.89 4.545 5.236 4.199 5.219 Polyfunctional epoxy resin 5.151 5.013 4.89 4.545 5.236 4.199 5.219 Hardener Polyfunctional phenolic resin 2.284 2.222 2.146 1.992 2.299 1.839 2.291 Ortho cresol novolac type phenolic resin 2.284 2.222 2.146 1.992 2.299 1.839 2.291 Curing accelerator 0.03 0.03 0.028 0.026 0.03 0.024 0.03 Inorganic filler 84 84 84 84 84 84 84 (Meth) acrylate compound 0.1 0.5 One 2 0 3 0.05 coloring agent 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Release agent 0.3 0.3 0.2 0.2 0.2 0.2 0.2 Coupling agent
(Epoxy silane) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Coupling agent
(Mercapto Silane) 0.2 0.2 0.2 0.2 0.2 0.2 0.2 total 100 100 100 100 100 100 100 liquidity 40 38 35 30 42 21 40 rigidity 32 46 55 48 27 46 30 Moisture absorption rate 0.35 0.33 0.34 0.35 0.36 0.35 0.34 responsibility

Number of appearance cracks 0 0 0 0 2 0 2 Number of peeling 0/146 0/146 0/146 0/146 3/146 0/146 3/146 Number of semiconductors tested 146 146 146 146 146 146 146

As shown in Table 1, the epoxy resin composition for sealing a semiconductor device of the present invention has high rigidity, excellent reliability for a semiconductor package, and excellent fluidity.

On the other hand, Comparative Example 1, which did not contain a (meth) acrylate-based compound, had poor rigidity and poor reliability. Comparative Example 2 containing more than 2% by weight, including 3% by weight of the (meth) acrylate-based compound, had poor flowability. In Comparative Example 3, which contained (meth) acrylate-based compound in an amount of 0.05% by weight or less and less than 0.1% by weight, the reliability of the semiconductor package was not good because the rigidity was not high.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.

Claims (6)

It is an epoxy resin composition for sealing semiconductor devices comprising an epoxy resin, a curing agent, a curing accelerator, an inorganic filler and a (meth) acrylate-based compound,
Among the epoxy resin composition for sealing the semiconductor device,
The epoxy resin is 0.5% to 20% by weight, the curing agent is 0.1% to 13% by weight, the curing accelerator is 0.01% to 10% by weight, the inorganic filler is 70% to 95% by weight, the (meth ) The acrylate-based compound is contained in 0.1% to 2% by weight,
The (meth) acrylate-based compound is represented by the following formula (1), an epoxy resin composition for semiconductor device sealing:
<Formula 1>

(In the formula 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently hydrogen or a methyl group).
delete The epoxy resin composition for sealing a semiconductor device of claim 1, wherein the (meth) acrylate-based compound is included in an amount of 0.1% to 1% by weight of the epoxy resin composition for sealing the semiconductor device.
delete The epoxy resin composition for sealing a semiconductor device of claim 1, wherein the composition further comprises at least one of a coupling agent, a release agent, a colorant, a stress reliever, a crosslinking enhancer, and a leveling agent.
A semiconductor device sealed using the epoxy resin composition for sealing a semiconductor device according to any one of claims 1, 3, and 5.

Images