KR101574836B1 - Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated by using the same - Google Patents

Abstract

The present invention relates to an epoxy resin composition for sealing a semiconductor element, which comprises an epoxy resin, a curing agent, an inorganic filler, and a colorant, wherein the colorant comprises a mixture of titanium oxide, iron oxide and mica, and a semiconductor element .

Description

TECHNICAL FIELD [0001] The present invention relates to an epoxy resin composition for encapsulating a semiconductor device and a semiconductor device encapsulated using the epoxy resin composition.

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. More specifically, the present invention includes a mixture of titanium oxide, iron oxide, and mica as a coloring agent, thereby achieving excellent markability even for a laser having a low output during manufacturing of a sealing material of a semiconductor element, reducing the content of carbon black, And an epoxy resin composition for sealing a semiconductor device which can reduce occurrence of soot at the time of use, and a semiconductor device sealed by using the composition.

A method for sealing a semiconductor element with an epoxy resin composition is commercially performed for the purpose of protecting the semiconductor element from moisture or mechanical impact, and the semiconductor element package is used to record information such as the manufacturer, product name, The surface of the molded epoxy resin sealing material is subjected to marking. There has been a method of marking using a marking ink such as an ultraviolet curing ink on the surface of a molded epoxy resin sealing material by a marking method used from the past, but there has been a problem that a process time is long and a cost is high due to a hardening and cleaning process.

In order to solve such a problem, a method of marking the surface of a sealing material of a semiconductor device package by using a laser has been introduced. This method is rapidly used because of its advantages such as high processing speed, semi-permanent marking, and low cost.

In the conventional laser marking, an effective coloring agent such as carbon black has already been developed and produced. However, in order to reduce the cost of the marking process, it is necessary to lower the laser output and to reduce the cost of the marking process due to the deflection characteristic of a map-type single-sided molding substrate package such as FBGA (fine pitch ball grid array) The lowering of the marking contrast can not be overcome simply by a method of controlling the content of carbon black, the particle size distribution, etc., and the desired contrast can not be sufficiently obtained. For example, when the amount of carbon black added to the resin composition is small, incomplete marking occurs due to insufficient absorption of heat energy generated during the marking. Conversely, if the amount of carbon black is too large, the electrical insulation of the resin composition is reduced, In addition, there has been a problem that it becomes difficult to identify the characters because the marking area is contaminated by the increase of soot generation at the time of marking. Therefore, there is a demand for a resin composition for encapsulating semiconductor devices having excellent laser marking property in order to perform more clear marking.

It is an object of the present invention to provide an epoxy resin composition for sealing a semiconductor device which can realize excellent markability even in a carbon dioxide gas laser having a low output.

Another object of the present invention is to provide an epoxy resin composition for sealing a semiconductor device which can reduce the content of carbon black, which is a conventional coloring agent, and reduce the occurrence of soot during laser marking.

It is still another object of the present invention to provide an epoxy resin composition for sealing a semiconductor device which can increase electrical insulation.

An epoxy resin composition for sealing a semiconductor element which is an aspect of the present invention includes an epoxy resin, a curing agent, an inorganic filler, and a colorant, and the colorant may include a mixture of titanium oxide, iron oxide and mica.

A semiconductor element which is another aspect of the present invention can be sealed with the above epoxy resin composition.

The present invention can realize excellent markability even in a carbon dioxide gas laser having a low output and can reduce the content of carbon black which is a conventional coloring agent so that the occurrence of soot can be reduced during laser marking, Thereby providing an epoxy resin composition for sealing semiconductor devices.

The epoxy resin composition for semiconductor device encapsulation of the present invention is characterized by comprising a colorant mixture comprising an epoxy resin, a curing agent, an inorganic filler, and a colorant, wherein the colorant comprises a mixture of titanium oxide, iron oxide and mica.

Epoxy resin

The epoxy resin is not particularly limited as long as it is an epoxy resin generally used for sealing semiconductor devices. In an embodiment, the epoxy resin is preferably an epoxy compound containing two or more epoxy groups in the molecule.

For example, the epoxy resin is an epoxy resin obtained by epoxidating 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 type epoxy Novolak type epoxy resins such as bisphenol A / bisphenol F / bisphenol AD, glycidyl ether of bisphenol A / bisphenol F / bisphenol AD, bishydroxybiphenyl epoxy resin, dicyclopentadiene epoxy resin, etc. .

Preferably, the epoxy resin may include at least one of an orthocresol novolak type epoxy resin, a biphenyl type epoxy resin, and a phenol aralkyl type epoxy resin.

For example, a biphenyl type epoxy resin represented by the following formula (1) can be used:

≪ Formula 1 >

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

Preferably, R is a methyl group or an ethyl group, more preferably a methyl group.

For example, a phenol aralkyl type epoxy resin represented by the following formula (2) can be used:

(2)

(In the above, the average value of n is 1 to 7)

These epoxy resins may be used alone or in combination of two or more.

The above-mentioned epoxy resin may be used singly or an additional compound prepared by a linear reaction such as a hardening agent, a curing accelerator, a releasing agent, a coupling agent, and a stress relaxation agent and a melt master batch may be used. In order to improve the moisture resistance, it is preferable to use a resin having a low chloride ion, sodium ion, and other ionic impurities contained in the epoxy resin.

The epoxy resin may be contained in an amount of 2 to 17% by weight, preferably 2 to 15% by weight or 3 to 15% by weight, more preferably 3 to 12% by weight in the epoxy resin composition for sealing a semiconductor device.

Hardener

The curing agent is generally used for sealing semiconductor devices and is not particularly limited as long as it has two or more reactors.

Specific examples thereof include phenol aralkyl type phenol resin, phenol novolac type phenol resin, xylok type phenol resin, cresol novolak type phenol resin, naphthol type phenol resin, terpene type phenol resin, Novolac phenol resins synthesized from bisphenol A and resole, polyhydric phenol compounds including tris (hydroxyphenyl) methane, dihydroxybiphenyl, acid anhydrides including maleic anhydride and phthalic anhydride, And aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone.

Preferably, a xylylene phenolic resin represented by the following formula (3) can be used:

(3)

(Wherein the average value of n is 0 to 7).

Preferably, a phenol aralkyl phenolic resin represented by the following general formula (4) can be used:

≪ Formula 4 >

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

These curing agents may be used alone or in combination of two or more.

The curing agent can also be used as an additive compound prepared by a linear reaction such as an epoxy resin, a curing accelerator, a releasing agent, a coupling agent, and a stress relaxation agent, and a melt master batch.

The curing agent may be contained in an amount of 0.5 to 13% by weight, preferably 1 to 10% by weight, more preferably 2 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. In a specific example, the chemical equivalent ratio of the epoxy resin to the curing agent may be from 0.75 to 2, and preferably from 0.85 to 1.75.

Inorganic filler

The inorganic filler is a material used for improving the 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.

Preferably, 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, it is preferable that 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 탆 to 1 탆 containing 1 to 50% It is preferable that the silica 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. In the molten spherical silica, conductive carbon may be contained as a foreign substance on the surface of silica, but 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 in the present invention depends on required properties such as moldability, low stress, and high temperature strength. In the specific examples, 70 to 95% by weight, preferably 75 to 92% by weight, of the epoxy resin composition for sealing a semiconductor device can be included.

coloring agent

The colorant may comprise a colorant mixture comprising a mixture of titanium oxide, iron oxide and mica.

The above-mentioned mixture replaces the use of only a large amount of carbon black as a conventional coloring agent, increases laser marking property, reduces soot generated by excessive use of carbon black, and improves reliability and moldability.

The titanium oxide is an oxide of titanium and does not limit the oxidation number of titanium. For example, the titanium oxide may be TiO ₂ .

The iron oxide is iron-oxidized and does not limit the oxidation number of iron. For example, the iron oxide may be FeO ₃ , Fe ₂ O ₃ , and the like.

The mixture may have a cumulative weight fraction of 98% or more, preferably 98 to 99% by weight in terms of particle size distribution, having a particle diameter of 15 탆 or less.

The titanium oxide in the colorant mixture may be contained in an amount of 1 to 20% by weight, preferably 3 to 15% by weight, more preferably 5 to 10% by weight.

The iron oxide in the colorant mixture may be contained in an amount of 10 to 70% by weight, preferably 30 to 60% by weight, more preferably 40 to 55% by weight.

The mica in the colorant mixture may be contained in an amount of 10 to 70% by weight, preferably 30 to 60% by weight, more preferably 40 to 55% by weight.

The colorant mixture in the epoxy resin composition may be contained in an amount of 0.1 to 3% by weight, preferably 0.2 to 2.5% by weight, more preferably 0.5 to 2% by weight.

In addition to the colorant mixture, the colorant may further include a conventional colorant. For example, the conventional colorant may further include carbon black, organic or inorganic dyes.

The conventional colorant may be contained in an amount of 0.1 to 1% by weight, preferably 0.1 to 0.4% by weight in the epoxy resin composition. When carbon black is used together with the above colorant mixture, there may be a better effect on the marking properties.

The total colorant may be contained in an amount of 0.2 to 4% by weight in the epoxy resin composition. In the above range, incomplete marking can be prevented from occurring, marking can be prevented from occurring due to occurrence of soot at the time of marking, and deterioration in electrical insulation of the resin composition can be prevented.

The resin composition may further include a curing accelerator.

Hardening accelerator

The curing accelerator is a substance that promotes the reaction between the epoxy resin and the curing agent.

For example, tertiary amines, organometallic 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. Organometallic compounds 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-methylimidazole, 2-phenylimidazole, 2-aminoimidazole, 2 - methyl- Imidazole and the like. Examples of the boron compound include tetraphenylphosphonium-tetraphenylborate, triphenylphosphine tetraphenylborate, tetraphenylboron salt, trifluoroborane-n-hexylamine, trifluoroborane monoethylamine, tetrafluoroborane 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. 1,8-diazabicyclo [5.4.0] undec-7-ene: DBU) and phenol novolak resin salts. Particularly preferable curing accelerators include organic phosphorus compounds, boron compounds, amine-based compounds, and imidazole-based curing accelerators, either alone or in combination. 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 contained in an amount of 0.01 to 2% by weight, preferably 0.02 to 1.5% by weight, more preferably 0.05 to 1% by weight in the epoxy resin composition.

The resin composition may further include an additive.

additive

The epoxy resin composition may further include conventional additives included in the epoxy resin composition. In embodiments, it may further comprise additives such as coupling agents, release agents, stress relieving agents, crosslinking enhancers, leveling agents and the like.

As the coupling agent, at least one selected from the group consisting of an epoxy silane, an aminosilane, a mercaptosilane, an alkylsilane, and an alkoxysilane can be used, but the present invention is not limited thereto.

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

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

The stress relieving agent may be at least one 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 included in an amount of 0.1 to 6.5% by weight, preferably 0.1 to 1% by weight based on the whole epoxy resin composition. As the modified silicone oil, a silicone polymer having excellent heat resistance is preferable, and a silicone oil having an epoxy functional group, a silicone oil having an amine functional group, and a silicone oil having a carboxyl functional group, or the like, 0.05 to 1.5% by weight based on the total weight of the composition. However, when the amount of the silicone oil is more than 1.5% by weight, surface contamination is liable to occur and the resin bleed may be prolonged. When the silicone oil is used in an amount of less than 0.05% by weight, a sufficient low elastic modulus may not be obtained have. The silicone powder having a center particle diameter of 15 탆 or less is particularly preferable because it does not act as a cause of the deterioration of the moldability and is preferably contained in an amount of 0.05 to 5% by weight based on the whole resin composition.

The additive may be included in the epoxy resin composition in an amount of 0.1 to 10% by weight, preferably 1 to 7% by weight.

The sealed semiconductor element which is another aspect of the present invention may be one which is sealed using the epoxy resin composition for sealing the semiconductor element. As a method of sealing a semiconductor element using the epoxy resin composition, a conventionally known method can be used.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

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

1) Epoxy resin

Orcocresol novolak type epoxy resin (EOCN-1020-55, Japanese explosive)

Biphenyl-type epoxy resin (YX-4000, Japan Epoxy Resin)

Phenol aralkyl type epoxy resin (NC-3000, Japanese explosive)

2) Hardener

Phenol novolak resin (HF-1, Meiwa)

Xylo-type phenol resin (MEH-7800SS, Meiwa)

Phenol aralkyl type phenol resin (MEH-7851SS, Meiwa)

3) Inorganic filler

Silica: A 9: 1 mixture of spherical fused silica having an average particle diameter of 20 占 퐉 and spherical fused silica having an average particle diameter of 0.5 占 퐉

4) Curing accelerator

Triphenylphosphine: TPP, Hokko Chemical

5) Colorant

Carbon black: MA-600B, Mitsubishi Chemical

Titanium oxide, iron oxide, mica mixture: Iriodin 600,

Iron oxide, mica mixture: LASERFLAIR 835,

Metal complex salt pigments: ORIPACS B-1, Orient Chemical

6) Coupling agent

Epoxy silane: S-510, CHISSO

Mercapt Tosilan: KBM-803, Shin Etsu

7) Releasing agent

Carnauba wax

8) Stress relieving agent

Silicone powder: E-601, Toray

Examples Comparative Example

The mixture was uniformly mixed using a Henschel mixer (KEUM SUNG MACHINERY CO. LTD. (KSM-22)) according to the composition of the following Table 1 (unit: parts by weight), and then melt kneaded Followed by cooling and pulverization to prepare an epoxy resin composition for sealing semiconductor devices.

Example Comparative Example Constituent One 2 3 4 5 One 2 3 4 5 6 7 Epoxy resin Orcocresol novolak type epoxy resin 4 2.6 7.8 5 0 4.5 4.5 3.5 3.1 8.2 3.5 2.5 Biphenyl-type epoxy resin 2.3 0 0 1.5 2 1.7 2 3 0 0 2.7 1.5 Phenol aralkyl type epoxy resin 0 2.7 0 0 3.5 0 0 0 2 0 0 0 Hardener Phenol novolak resin 2.1 1.9 6.4 5.1 0 3.2 3.5 3.7 2.5 6.1 4 2 Xylock type phenol resin 1.5 1.8 0 0 4.1 1.9 1.5 1.75 1.8 0 One 2.2 Phenol aralkyl phenolic resin 0 0 0 0 One 0 0 0 0 0 0 0 Hardening accelerator Triphenylphosphine 0.1 0.1 0.3 0.2 0.2 0.1 0.1 0.2 0.1 0.4 0.1 0.1 Inorganic filler Silica 88 88 82 86 87 87 87 87 88 82 87 88 Coupling agent Epoxy silane 0.3 0.3 0.2 0.15 0.35 0.2 0.3 0.15 0.2 0.35 0.2 0.25 Mercaptosilane 0.2 0.2 0.3 0.35 0.15 0.3 0.2 0.35 0.3 0.15 0.3 0.25 coloring agent Carbon black 0.2 0.1 0.1 0.2 0.4 0.4 0.2 0.05 0.1 0.1 0.2 0 Total weight of titanium oxide, iron oxide, mica mixture 0.5 1.5 2 One One 0 0 0 0 0 0 0 Titanium oxide weight% 7 7 7 7 7 - - - - - - - Iron oxide 50 50 50 50 50 - - - - - - - mica 43 43 43 43 43 - - - - - - - Mixture of iron oxide and mica 0 0 0 0 0 0 0 0 1.5 2 0 2.5 Metal complex salt pigment 0 0 0 0 0 0 0 0 0 0 0.1 0.1 Release agent Carnauba wax 0.3 0.3 0.4 0.2 0.3 0.3 0.4 0.3 0.2 0.2 0.4 0.3 Stress relieving agent Silicone powder 0.5 0.5 0.5 0.3 0 0.4 0.3 0 0.2 0.5 0.5 0.3 sum 100 100 100 100 100 100 100 100 100 100 100 100

The epoxy resin composition for sealing semiconductor devices was evaluated for physical properties by the following method.

That is, the epoxy resin composition prepared above was molded for 120 seconds at 175 ° C using a MPS (multi plunger system) molding machine for each package, and then the epoxy resin composition for sealing semiconductor devices was evaluated by the following method.

That is, the epoxy resin composition thus prepared was molded at 175 ° C for 120 seconds using MPS (multi plunger system) molding machine for each package, followed by post-curing at 175 ° C for 6 hours, followed by laser marking.

[Assessment Methods]

1. YAG laser mark: pulse type, manufactured by EO-Tech

Wavelength: 1060 nm / pulse width: 120 μsec / laser beam output: 1.3 J / pulse

2. FIBER Laser Mark: EO-Tech

 Wavelength: 1060 nm / laser output: 40 W

 The laser marking performance and the soot generation amount were observed with an optical microscope and a naked eye after observing the appearance of a molded product obtained by molding a semiconductor package with an epoxy resin composition and then performing a laser marking process.

The case where the laser markability is very good and the degree of soot generation is low is very good, the case where the laser markability is good and the degree of soot generation is low is good, the case where laser markability is poor and the case where it is slightly faint, Respectively.

division Applicable package Laser marking property Yag laser Fiber laser Example 1 BOC ◎ ◎ Example 2 BOC ◎ ◎ Example 3 BOC ◎ ◎ Example 4 TSOP ◎ ◎ Example 5 FBGA ◎ ◎ Comparative Example 1 BOC ○ △ Comparative Example 2 BOC △ × Comparative Example 3 BOC × × Comparative Example 4 BOC ○ ○ Comparative Example 5 BOC ○ ○ Comparative Example 6 TSOP × ○ Comparative Example 7 FBGA ○ △

* BOC: Board On Chip

* FBGA: Fine Pitch Ball Grid Array

* TSOP: Thin <52> Small Out Package

As shown in Table 2, it can be confirmed that the epoxy resin composition of the present invention has good laser marking property even if both the YAG laser and the fiber laser are applied.

On the other hand, it can be confirmed that the resin composition of Comparative Example using only carbon black has a poor laser marking or a lot of soot.

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 (10)

An epoxy resin, a curing agent, an inorganic filler, and a colorant,
Wherein the colorant comprises a mixture of titanium oxide, iron oxide and mica.
The epoxy resin composition for sealing a semiconductor device according to claim 1, wherein the titanium oxide is contained in an amount of 1 to 20% by weight, the iron oxide is contained in an amount of 10 to 70% by weight, and the mica is contained in an amount of 10 to 70% by weight.
The epoxy resin composition for sealing a semiconductor device according to claim 1, wherein the mixture has an aggregate weight fraction of 98% or more in particle size distribution of 15 占 퐉 or less.
The epoxy resin composition for sealing a semiconductor device according to claim 1, wherein the mixture comprises 0.1 to 3% by weight of the epoxy resin composition.
The epoxy resin composition for sealing a semiconductor element according to claim 1, wherein the colorant further comprises carbon black.
The epoxy resin composition for sealing a semiconductor device according to claim 5, wherein the carbon black is contained in an amount of 0.1 to 1% by weight based on the resin composition.
The epoxy resin composition for sealing a semiconductor device according to claim 1, wherein the colorant is contained in an amount of 0.2 to 4 wt% of the epoxy resin composition.
The semiconductor device according to claim 1, wherein the epoxy resin composition comprises 2 to 17 wt% of the epoxy resin, 0.5 to 13 wt% of the curing agent, 70 to 95 wt% of the inorganic filler, and 0.2 to 4 wt% Epoxy resin composition for sealing.
The epoxy resin composition for sealing a semiconductor device according to claim 1, wherein the epoxy resin composition further comprises a curing accelerator.
A semiconductor element sealed by using the epoxy resin composition for sealing a semiconductor element according to any one of claims 1 to 9.