KR102137553B1 - Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated using the same - Google Patents

Abstract

The epoxy resin composition for sealing a semiconductor device of the present invention includes an epoxy resin; Curing agent; Inorganic fillers; And a compound of Formula 1:
[Formula 1]

Description

Epoxy resin composition for sealing semiconductor devices and semiconductor devices sealed using the same{EPOXY RESIN COMPOSITION FOR ENCAPSULATING SEMICONDUCTOR DEVICE AND SEMICONDUCTOR DEVICE ENCAPSULATED USING THE SAME}

The present invention relates to an epoxy resin composition for sealing a semiconductor element and a semiconductor device sealed using the same. More specifically, the present invention relates to an epoxy resin composition for sealing a semiconductor device having excellent adhesion and reliability with a metal and a semiconductor device sealed using the same.

A method of sealing a semiconductor element with an epoxy resin composition for the purpose of protecting the semiconductor element from external environments such as moisture or mechanical impact has been commercially performed. The epoxy resin composition requires excellent adhesion to a lead frame or chip, but when the adhesion to the lead frame is poor, there is a problem that the reliability of the semiconductor device is lowered.

Conventionally, in order to increase the adhesive strength, the ratio of the equivalent ratio of the epoxy resin and the phenol resin is not adjusted to 1:1, and the ratio is varied to make the unreacted functional groups participate in the adhesion, or to increase the adhesive strength by changing the type of coupling agent and increasing the content. The back was tried. However, in the conventional method, there is a problem that the basic properties required for the epoxy resin composition for sealing semiconductor devices are deteriorated even if the adhesive force is insufficient or the adhesive force is secured.

The object of the present invention Excellent adhesion with improved adhesion to metal It is to provide an epoxy resin composition for sealing a semiconductor device.

Another object of the present invention is to provide an epoxy resin composition for sealing a semiconductor device suitable for a package for a lead frame.

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

One aspect of the present invention relates to an epoxy resin composition for sealing semiconductor devices. The epoxy resin composition for sealing a semiconductor device is an epoxy resin; Curing agent; Inorganic fillers; And a compound of Formula 1:

[Formula 1]

In an embodiment, the compound of Formula 1 may be included in an amount of 0.01% to 1% by weight of the epoxy resin composition for sealing the semiconductor device.

In an embodiment, the epoxy resin is an epoxy resin obtained by epoxidizing a condensation product of phenol or alkyl phenols with hydroxybenzaldehyde, a phenol aralkyl type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, and a polyfunctional type Epoxy resin, naphthol novolac type epoxy resin, bisphenol A/bisphenol F/bisphenol AD novolac type epoxy resin, bisphenol A/bisphenol F/bisphenol AD glycidyl ether, bishydroxybiphenyl epoxy resin, dicyclo It may include one or more of a pentadiene-based epoxy resin, biphenyl-type epoxy resin resin.

In a specific embodiment, the curing agent is a phenol aralkyl type phenol resin, 　phenol novolac type phenol resin, xylotype phenol resin, cresol novolac type phenol resin, naphthol type phenol resin, terpene type phenol resin, polyfunctional phenol resin, dicyclopenta It may include one or more of diene-based phenol resins, novolac-type phenol resins synthesized from bisphenol A and resol, tris(hydroxyphenyl)methane, and polyhydric phenol compounds.

In an embodiment, the inorganic filler comprises a fused silica 　 mixture consisting of 50% to 99% by weight of spherical fused silica having an average particle diameter of 5 to 30㎛ and 1% to 50% by weight of spherical fused silica having an average particle diameter of 0.001 to 1㎛ can do.

In an embodiment, the epoxy resin composition for sealing a semiconductor device, the epoxy resin 0.5 wt% to 20 wt%, the curing agent 0.1 wt% to 10 wt%, the inorganic filler 70 wt% to 95 wt%, the formula (1) It may contain from 0.01% to 1% by weight of the compound.

In an embodiment, 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 invention relates to a semiconductor device. The semiconductor device is sealed using the epoxy resin composition for sealing the semiconductor element.

The present invention It has the effect of the invention to provide an epoxy resin composition for sealing a semiconductor element suitable for a package for a lead frame and a semiconductor device sealed with the epoxy resin composition by significantly improving adhesion to metal.

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 commonly used for sealing semiconductor devices may be used, and are not particularly limited. Specifically, the epoxy resin may be used an epoxy compound containing two or more epoxy groups in the molecule. For example, the epoxy resin is an epoxy resin obtained by epoxidizing a condensation product of phenol or alkyl phenols with hydroxybenzaldehyde, a phenol aralkyl type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a polyfunctional type epoxy Resin, naphthol novolac-type epoxy resin, bisphenol A/bisphenol F/bisphenol AD, novolac-type epoxy resin, bisphenol A/bisphenol F/bisphenol AD glycidyl ether, bishydroxybiphenyl-based epoxy resin, dicyclopenta And diene-based epoxy resins and biphenyl-type epoxy resins. More specifically, the epoxy resin may include at least one of biphenyl type epoxy resin, phenol aralkyl type epoxy resin, cresol novolak type epoxy resin, and polyfunctional epoxy resin. Most preferably, the epoxy resin may be a cresol novolac-type epoxy resin or a polyfunctional epoxy resin.

The epoxy resin may be an epoxy resin having an epoxy equivalent of 100 g/eq to 500 g/eq when considering curability. In the above range, the degree of curing can be increased.

The epoxy resin may be included in 0.5 to 20% by weight, specifically 3 to 15% by weight of the epoxy resin composition for sealing semiconductor devices. In the above range, the curability of the composition may not be lowered.

Hardener

Hardener Curing agents generally used for sealing semiconductor devices may be used, and are not particularly limited. Specifically, a curing agent may be a phenolic curing agent, for example, a phenolic curing agent may be a phenol aralkyl type phenol resin, a phenol novolak type phenol resin, a xylotype phenol resin, a cresol novolak type phenol resin, a naphthol type phenol resin, Terpene-type phenolic resin, polyfunctional phenolic resin, dicyclopentadiene-based phenolic resin, bisphenol A and novolak-type phenolic resin synthesized from resol, tris (hydroxyphenyl) methane, polyhydric phenolic compound may include one or more of . Preferably, the phenolic curing agent may be one or more of a xylophone type phenol resin, a phenol aralkyl type phenol resin, a phenol novolak type phenol resin, or a polyfunctional type phenol resin, most preferably a xylotype phenol resin.

The curing agent may have a hydroxyl group equivalent of 90 g/eq to 250 g/eq when considering curability. In the above range, the degree of curing can be increased.

The curing agent may be included in 0.1% to 10% by weight, preferably 1% to 5% by weight of the epoxy resin composition for sealing semiconductor devices. In the above range, there may be an effect that the curability of the composition does not decrease.

The mixing 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 0.95 to 3, specifically 1 to 2, and more specifically 1 to 1.75. When the equivalent ratio of the epoxy resin and the curing agent satisfies the above range, excellent strength can be achieved after curing the epoxy resin composition.

Inorganic filler

The inorganic filler is for improving the mechanical properties and low stress of the epoxy resin composition. As the inorganic filler, general inorganic fillers used in semiconductor device encapsulants can be used without limitation, and are not particularly limited. For example, the inorganic filler may include at least one of fused silica, crystalline silica, calcium carbonate, magnesium carbonate, alumina, magnesia, clay, talc, calcium silicate, titanium oxide, antimony oxide, and glass fiber. It may include.

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. In an embodiment, the inorganic filler is a fused silica 　 mixture containing 50% to 99% by weight of spherical fused silica having an average particle diameter of 5 to 30㎛, and 1% to 50% by weight of spherical fused silica having an average particle diameter of 0.001 to 1㎛. It is preferred to include 　40% to 100% by weight, relative to the total inorganic filler. Further, the maximum particle size can be adjusted to any one of 45 µm, 55 µm, 　, and 　75 µm according to the application. Since the spherical fused silica may contain conductive carbon as a foreign substance on the silica surface, it is also important to select a substance with little polar foreign matter mixing.

The amount of the inorganic filler used depends on the required 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 of the epoxy resin composition, for example, 75% to 92% by weight. In the above range, flame retardancy, fluidity and reliability of the epoxy resin composition can be secured.

Adhesion promoter

In the present invention, the compound of Formula 1 is used as an adhesion promoter:

[Formula 1]

The compound of Formula 1 is commercially available and can be prepared using conventional synthetic methods known to those skilled in the art.

The compound of Formula 1 may be included in an amount of 0.01% to 1% by weight, for example, 0.05% to 0.5% by weight of the epoxy resin composition for sealing semiconductor devices. In the above range, adhesion and reliability can be greatly improved without deteriorating the inherent physical properties of the epoxy resin composition.

In addition to this, 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 coloring agent.

Curing accelerator

The curing accelerator is a substance that promotes the reaction of the epoxy resin and the curing agent. As the curing accelerator, for example, a tertiary amine, an organometallic compound, an organophosphorus 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(diaminomethyl) ) Phenol and tri-2-ethylhexyl acid. Specific examples of the organometallic compound include chromium acetylacetonate, zinc acetylacetonate, and nickel acetylacetonate. Organophosphorus compounds include tris-4-methoxyphosphine, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, phenylphosphine, diphenylphosphine, triphenylphosphine, triphenylphosphine triphenylborane, triphenylphosphine And pin-1,4-benzoquinone　 adducts. The imidazoles include 2-phenyl-4-methylimidazole, 2-methylimidazole,　2-phenylimidazole,　2-aminoimidazole, 2-methyl-1-vinylimidazole, 2-ethyl- 4-methylimidazole, 2-heptadecylimidazole　, and the like, but is not limited thereto. Specific examples of the boron compound include tetraphenylphosphonium-tetraphenylborate, triphenylphosphine tetraphenylborate, tetraphenylborone salt, trifluoroborane-n-hexylamine, trifluoroboranemonoethylamine, tetrafluoro Borane triethylamine, 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 phenol novolak resin salts, and the like, but are not limited thereto.

It is also possible to use an epoxy resin or an adduct made by pre-reacting with a curing agent.

The curing accelerator may be included in an amount of 0.01% to 2% by weight, specifically 0.02% to 1.5% by weight of the epoxy resin composition for sealing semiconductor devices. In the above range, the curing of the epoxy resin composition may be accelerated, and the degree of curing may also be good.

Coupling agent

The coupling agent reacts between the epoxy resin and the inorganic filler to improve interface strength, and may be, for example, a silane coupling agent. The silane coupling agent may be one that reacts between the epoxy resin and the inorganic filler, and improves the interfacial strength of the epoxy resin and the inorganic filler, and the type is not particularly limited. Specific examples of the silane coupling agent include epoxysilane, aminosilane, ureidosilane, mercaptosilane, and alkylsilane. The coupling agents can be used alone or in combination.

The coupling agent may be included in an amount of 0.01% to 5% by weight, preferably 0.05% to 3% by weight of the epoxy resin composition for sealing semiconductor devices. In the above range, the strength of the cured product of the epoxy resin composition may be improved.

Release agent

As the release agent, 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 can be used.

The mold release agent may be included in an amount of 0.1% to 1% by weight in the epoxy resin composition for semiconductor device sealing.

coloring agent

The colorant 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, titanium nitride, copper hydroxide phosphate, iron oxide, and mica.

The colorant may be included in an amount of 0.01% to 5% by weight, preferably 0.05% to 3% by weight of the epoxy resin composition for sealing semiconductor devices.

In addition to this, the epoxy resin composition of the present invention is an antioxidant such as Tetrakis[methylene-3-(3,5-di-tertbutyl-4-hydroxyphenyl)propionate]methane in the range not detrimental to the object of the present invention; Flame retardants, such as aluminum hydroxide, etc., can be further included as needed.

The epoxy resin composition is uniformly sufficiently mixed at a predetermined compounding ratio using a Hensel mixer or a Lodige mixer, and then roll-mill or kneader. After melt-kneading, it may be manufactured through a cooling and grinding process.

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 may also be molded by a method such as an injection molding method or a casting method. By this method, a lead frame pre-plated with one or more materials selected from the group consisting of copper, lead, or palladium on a copper lead frame, an iron lead frame, or an organic laminate frame can be manufactured. Can.

Hereinafter, the configuration and operation of the present invention will be described in more detail through preferred embodiments of the present invention. However, this is provided as a preferred example of the present invention and cannot be interpreted as limiting the present invention in any sense.

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

(a) Epoxy resin

(a1) YDCN-500-4P, a cresol novolak-type epoxy resin (Kukdo Chemical)

(a2) Multifunctional epoxy resin EPPN-501HY (Nippon Kayaku)

(b) Curing agent: HE100C-10 (Air Water), a xylophone type phenolic resin

(c) Inorganic filler: 9:1 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

(d) adhesion promoter

(d1) Compound of Formula 1

[Formula 1]

AMT-ZP (Zheda Panaco chemical engineering Co. Ltd.)

(d2) Compound of Formula 2

[Formula 2]

(d3) Compound of Formula 3

[Formula 3]

(e) Curing accelerator: 2-phenyl-4-methylimidazole (2P4MHZ, Nippon-Gosei)

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

(g) Coupling agent:

(g1) Epoxysilane (A-187, Momentive Performance Materials Korea Co., Ltd.)

(g2) Mercaptosilane coupling agent KBM-803 (Shin Etsu)

(h) Additive: Mixture of ion trapper (DHT-4A), release agent (Carnauba wax)

Examples and comparative examples

Each component was weighed according to the composition (unit: weight %) of Tables 1 and 2 below, and then uniformly mixed using a Henschel mixer to prepare a primary composition in a powder state. Then, using a continuous kneader, the mixture was melt-kneaded at 90 to 110°C, then cooled and crushed to prepare an epoxy resin composition for sealing semiconductor devices.

Ingredient Example 1 Example 2 Example 3 (a) epoxy resin (a1) 4.9 4.88 4.835 (a2) 4.9 4.88 4.835 (b) hardener 3.42 3.41 3.40 (c) inorganic filler 85 85 85 (d) adhesion promoter (d1) 0.05 0.1 0.2 (d2) - - - (d3) - - - (e) Curing accelerator 0.93 0.93 0.93 (f) Coloring agent 0.3 0.3 0.3 (g) Coupling agent (g1) 0.3 0.3 0.3 (g2) 0.1 0.1 0.1 additive Ion trapper 0.05 0.05 0.05 Release agent 0.05 0.05 0.05 sum 100 100 100 100

Ingredient Comparative Example 1 Comparative Example 2 Comparative Example 3 (a) epoxy resin (a1) 4.92 4.9 4.9 (a2) 4.92 4.9 4.9 (b) hardener Xylok 3.43 3.42 3.42 (c) inorganic filler Silica 85 85 85 (d) adhesion promoter (d1) - - - (d2) - 0.05 - (d3) - - 0.05 (e) Curing accelerator 0.93 0.93 0.93 (f) Coloring agent 0.3 0.3 0.3 (g) Coupling agent (g1) 0.3 0.3 0.3 (g2) 0.1 0.1 0.1 additive Ion trapper 0.05 0.05 0.05 Release agent 0.05 0.05 0.05 sum 100 100 100 100

The physical properties of the epoxy resin compositions of Examples and Comparative Examples prepared as described above were measured according to the following physical property evaluation methods. The measurement results are shown in Tables 3 and 4.

Method for evaluating physical properties

(1) Fluidity (inch, spiral flow): Using a low pressure transfer molding press, the epoxy resin composition was injected at a molding temperature of 175°C and a molding pressure of 50 kgf/cm ² into a mold for measuring spiral flow according to EMMI-1-66. Then, the flow field (unit: inch) was measured. The higher the measured value, the better the fluidity.

(2) Adhesion (kgf): Prepare the metal element in a standard suitable for the mold for measurement of adhesion, and transfer the resin composition prepared in the above Examples and Comparative Examples to the prepared element at a mold temperature of 180° C., a transfer pressure of 50 kgf/cm ² , and transfer Cured specimens were obtained by molding under the conditions of a speed of 0.5 to 1 cm/s, a transfer time of 24 seconds, and a curing time of 145 seconds. The obtained specimen was placed in an oven at 175°C and post-cured (PMC) for 5 hours. At this time, the area of the epoxy resin composition contacting the metal element was 40±1 mm 2, and the adhesion force was measured by using a Universal Testing Machine (UTM) for 12 specimens per each measuring process and then calculated as an average value. Measured for copper and nickel metal, respectively.

(3) Reliability: After drying the BOC type semiconductor package made of an epoxy resin composition at 125°C for 24 hours, after undergoing a thermal shock test of 5 cycles and standing at 30°C under 60% relative humidity conditions for 120 hours, at 260°C The presence or absence of package peeling under precondition conditions was first evaluated by passing the IR reflow three times for 10 seconds. After pre-conditioning, leave at 10 minutes at -65°C, 5 minutes at 25°C, and 10 minutes at 150°C in a thermal cycle environment tester (Temperature Cycle Test) for 1 cycle, and apply 1,000 cycles of conditions. Acoustic Tomograph).

Basic properties unit Example 1 Example 2 Example 3 liquidity inch 32 31 27 Adhesion Cu(kgf) 31 29 27 Ni(kgf) 28 17 15 Reliability delamination
(ea/10ea) 0 0 0

Basic properties unit Comparative Example 1 Comparative Example 2 Comparative Example 3 liquidity inch 33 31 31 Adhesion Cu(kgf) 15 13 8 Ni(kgf) 2 One 2 Reliability delamination
(ea/10ea) 8 7 9

As shown in Tables 3 and 4, it can be seen that the epoxy resin composition of the present invention has excellent adhesion and reliability while maintaining the basic properties of the epoxy resin composition.

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 (8)

0.5 to 20 wt% epoxy resin;
0.1% to 10% by weight of curing agent;
70% to 95% by weight of an inorganic filler; And
Epoxy resin composition for sealing a semiconductor device comprising 0.01% to 1% by weight of the compound of Formula 1:
[Formula 1]

.
delete According to claim 1, The epoxy resin is an epoxy resin obtained by epoxidizing a condensation product of phenol or alkyl phenols with hydroxybenzaldehyde, phenol aralkyl type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, Polyfunctional epoxy resin, naphthol novolac type epoxy resin, bisphenol A/bisphenol F/bisphenol AD novolac type epoxy resin, bisphenol A/bisphenol F/bisphenol AD glycidyl ether, bishydroxybiphenyl type epoxy resin, Dicyclopentadiene-based epoxy resin, a biphenyl-type epoxy resin containing at least one of the epoxy resin composition for sealing semiconductor devices.
The curing agent according to claim 1, wherein the curing agent is a phenol aralkyl type phenol resin, a phenol novolak type phenol resin, a xylotype phenol resin, a cresol novolak type phenol resin, a naphthol type phenol resin, a terpene type phenol resin, a polyfunctional phenol resin, and a dish. An epoxy resin composition for sealing a semiconductor device, comprising at least one of clopentadiene-based phenol resin, bisphenol A and a novolac-type phenol resin synthesized from resol, tris(hydroxyphenyl)methane, and a polyhydric phenol compound.
The method of claim 1, wherein the inorganic filler is a fused silica mixture consisting of 50% to 99% by weight of spherical fused silica having an average particle diameter of 5 to 30㎛ and 1% to 50% by weight of spherical fused silica having an average particle diameter of 0.001 to 1㎛. It comprises, an epoxy resin composition for sealing a semiconductor device.
delete The epoxy resin composition for sealing a semiconductor device of 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.
A semiconductor device sealed by using the epoxy resin composition for sealing a semiconductor element according to any one of claims 1, 3 to 5, and 7.