KR20170115414A - Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated by using the same - Google Patents
Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated by using the same Download PDFInfo
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- KR20170115414A KR20170115414A KR1020160043083A KR20160043083A KR20170115414A KR 20170115414 A KR20170115414 A KR 20170115414A KR 1020160043083 A KR1020160043083 A KR 1020160043083A KR 20160043083 A KR20160043083 A KR 20160043083A KR 20170115414 A KR20170115414 A KR 20170115414A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
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Abstract
The present invention relates to an epoxy resin composition for semiconductor encapsulation comprising an epoxy resin containing a fluorene-based epoxy compound represented by the following formula (1) or (2), a curing agent, and an inorganic filler, and a semiconductor device sealed with the composition.
[Chemical Formula 1]
(Wherein A is hydrogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and 0 < n < = 4)
(2)
(Wherein B is hydrogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, 0 < m < = 4)
Description
TECHNICAL FIELD The present invention relates to an epoxy resin composition for semiconductor encapsulation and a semiconductor device sealed with the composition. More particularly, the present invention relates to an epoxy resin composition for semiconductor encapsulation having low shrinkage and low elasticity, and a semiconductor device sealed with the 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 it is suitable for a low cost and mass production.
Conventionally, due to the characteristics of the semiconductor packaging process, aliphatic or aromatic epoxy resins having a softening point of 50 to 130 占 폚 have been mainly used. When the softening point of the epoxy resin is out of the above range, molding is difficult and defects tend to occur.
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, as the semiconductor device is made thinner, the package tends to be warped due to thermal expansion or heat shrinkage between the substrate and the sealing layer, and the sealing layer has high elasticity properties, causing problems such as damage or breakage of the chip by the sealing layer .
In order to solve the above problems, a method of suppressing the curing shrinkage of the resin composition by increasing the glass transition temperature of the epoxy resin composition using an epoxy resin and / or a phenol resin having a high glass transition temperature, To decrease the linear expansion coefficient of the epoxy resin composition.
However, when an epoxy resin composition having a high glass transition temperature is used, there is a problem that the modulus of elasticity is greatly increased and is vulnerable to external stress due to heat or external impact. When the content of the inorganic filler is increased, A problem arises.
Therefore, development of an epoxy resin composition for encapsulating a semiconductor device which has a low hardening shrinkage ratio and an elastic modulus and is excellent in fluidity and moldability has been demanded.
An object of the present invention is to provide an epoxy resin composition capable of realizing low shrinkage and low elasticity properties after curing.
Another object of the present invention is to provide an epoxy resin composition having excellent flowability and fast curability at low temperatures.
It is still another object of the present invention to provide an epoxy resin composition having excellent dispersibility.
Still another object of the present invention is to provide a semiconductor device sealed with the epoxy resin composition as described above.
In one aspect, the present invention provides an epoxy resin composition for semiconductor encapsulation comprising an epoxy resin comprising a fluorene-based epoxy compound represented by the following general formula (1) or (2), a curing agent, and an inorganic filler.
[Chemical Formula 1]
(Wherein A is hydrogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and 0 < n < = 4)
(2)
(Wherein B is hydrogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and 0 < m < = 4)
The epoxy resin composition may further include a non-fluorene-based epoxy compound that does not contain a fluorene structure. The fluorene-based epoxy compound may be included in the epoxy resin in an amount of 10 to 80% by weight, and the non-fluorene-based epoxy compound may be included in the epoxy resin in an amount of 20 to 90% by weight. Preferably, the epoxy resin may include a fluorene-based epoxy compound and a non-fluorene-based epoxy compound in a weight ratio of 1: 9 to 4: 1.
The fluorene-based epoxy compound may have a softening point of 80 ° C to 100 ° C, and the epoxy resin composition may have a softening point of 50 ° C to 130 ° C.
Specifically, the epoxy resin composition for semiconductor encapsulation according to the present invention comprises 0.5 to 20% by weight of an epoxy resin containing the fluorene-based epoxy compound, 0.1 to 13% by weight of a curing agent, and 70 to 95% by weight of an inorganic filler can do.
The epoxy resin composition for semiconductor encapsulation according to the present invention may have a curing shrinkage of 0.3% or less as measured by the following formula (1).
(1): Cure shrinkage ratio (%) = {(L 0 -L 1 ) / L 0 } × 100
In the formula (1), L 0 is the length of the molded specimen obtained by molding the epoxy resin composition at 175 ° C and 70 kgf / cm 2 using a transfer molding press, and L 1 is the length of the molded specimen at 175 ° C Length of the specimen after post molding curing in the oven for 4 hours and after cooling.
The elastic modulus measured on the specimen prepared by molding the epoxy resin composition for semiconductor encapsulation according to the present invention using a transfer molding machine and post-curing may be 900 MPa or less and the glass transition temperature may be 150 ° C or more.
In another aspect, the present invention provides a sealed semiconductor device using the above epoxy resin composition for semiconductor encapsulation of the present invention.
The epoxy resin composition according to the present invention is an epoxy resin composition containing an epoxy resin and a fluorene epoxy compound having a specific structure and exhibiting excellent low shrinkage and low elasticity properties after curing and minimizing deterioration of fluidity, have.
In addition, the epoxy resin composition according to the present invention has excellent flowability at a low temperature of 200 ° C or lower, and has a rapid curing ability to be cured within 1 to 30 minutes, so that it can be usefully used in a low temperature curing process.
Hereinafter, the present invention will be described in more detail.
In the following description of the present invention, detailed description of known related arts will be omitted when it is determined that the gist of the present invention may be unnecessarily obscured by the present invention.
In the case where the word 'includes', 'having', 'done', etc. are used in this specification, other parts can be added unless '~ only' is used. Unless the context clearly dictates otherwise, including the plural unless the context clearly dictates otherwise.
Also, in interpreting the constituent elements, even if there is no separate description, it is interpreted as including the error range.
In the present specification, " X to Y " representing the range means " X or more and Y or less ".
The inventors of the present invention have conducted studies to develop a material for semiconductor encapsulation having low shrinkage and low elasticity so as to minimize the occurrence of warping of the semiconductor package due to thermal expansion and heat shrinkage and chip breakage caused by external impact, Of the fluorene-based epoxy compound is used, the above-mentioned object can be achieved. Thus completing the present invention.
Specifically, the epoxy resin composition of the present invention comprises an epoxy resin containing a fluorene-based epoxy compound represented by the general formula (1) or (2), a curing agent, and an inorganic filler. Hereinafter, each component of the epoxy resin composition of the present invention will be described in detail.
(A) an epoxy resin
In the present invention, the epoxy resin includes a fluorene-based epoxy compound (A-1) represented by the following general formula (1) or (2)
[Chemical Formula 1]
In Formula 1, A is hydrogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and 0 < n? 4. Preferably, A may be hydrogen, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. More preferably, A may be a hydrogen, a methyl group or a methoxy group.
(2)
In Formula 2, B is hydrogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and 0 < m? 4. Preferably, B may be hydrogen, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. More preferably, B may be a hydrogen, a methyl group or a methoxy group.
Specific examples of the fluorene-based epoxy compound represented by the formula (1) include compounds represented by the following formulas (1-1) to (1-3), but are not limited thereto.
[Formula 1-1]
[Formula 1-2]
[Formula 1-3]
In the above Chemical Formulas 1-1 to 1-3, 0 <n? 4.
Specific examples of the fluorene-based epoxy compound represented by the formula (2) include compounds represented by the following formulas (2-1) to (2-3), but are not limited thereto.
[Formula 2-1]
[Formula 2-2]
[Formula 2-3]
In the above formulas (2-1) to (2-3), 0 < m? 4.
Since the fluorene-based epoxy compound represented by the above-described formula (1) or (2) has a bulky structure including a plurality of ring structures together with a fluorene structure, the fluorene- Shrinkage after curing is low. In addition, as compared with an epoxy resin containing only a fluorene structure, it has a low softening point and is excellent in moldability. Particularly, at a low temperature of 200 ° C or less, for example, 120 to 180 ° C or 120 to 150 ° C, There is an effect to be improved. Specifically, the fluorene-based epoxy compound has a softening point of 90 ° C or lower, for example, 80 ° C to 90 ° C or 80 ° C to 89 ° C.
When the fluorene-based epoxy compound represented by the above formula (1) or (2) is used, the curing property at low temperature is excellent. Specifically, the epoxy resin composition containing the fluorene-based epoxy compound represented by the above formula (1) or (2) has a fast curability that is cured at 200 ° C or less, for example, at 150 ° C to 200 ° C within 1 minute to 30 minutes .
Meanwhile, the epoxy resin of the present invention may further contain a fluorene-based epoxy compound (A-2) which does not contain a fluorene structure, in addition to the fluorene-based epoxy compound represented by the above formula (1) or (2).
As the non-fluorene-based epoxy compound, epoxy compounds not containing a fluorene structure generally used in the art can be used, and there is no particular limitation. Examples of the non-fluorene epoxy compound include epoxy resins obtained by epoxidating phenol or condensed products of alkyl phenols and hydroxybenzaldehyde, phenol novolak type epoxy resins, cresol novolak type epoxy resins, Novolak type epoxy resins, naphthol novolak type epoxy resins, novolak type epoxy resins such as bisphenol A / bisphenol F / bisphenol AD, glycidyl ethers of bisphenol A / bisphenol F / bisphenol AD, bishydroxybiphenyl type epoxy resins, And chloropentadiene-based epoxy resins. More specifically, the epoxy resin may be a cresol novolak type epoxy resin, a multifunctional epoxy resin, a phenol aralkyl type epoxy resin, a biphenyl type epoxy resin, or a mixture thereof.
The polyfunctional epoxy resin may be, for example, an epoxy resin represented by the following formula (3).
(3)
Wherein R 1, R 2, R 3, R 4 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R 6 and R 7 are each independently a hydrogen atom, a methyl group or an ethyl group, to be. Preferably, each of R 1, R 2, R 3, R 4 and R 5 is independently selected from the group consisting of hydrogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, , And R6 and R7 may be hydrogen, but are not necessarily limited thereto.
More specifically, the multifunctional epoxy resin composition may be a triphenolalkane type epoxy resin such as a triphenolmethane type epoxy resin, a triphenolpropane type epoxy resin, or the like.
The phenol aralkyl type epoxy resin may be, for example, a phenol aralkyl type epoxy resin having a novolac structure including a biphenyl derivative represented by the following formula (4).
[Chemical Formula 4]
In Formula 4, the average value of b is 1 to 7.
The biphenyl type epoxy resin may be, for example, a biphenyl type epoxy resin represented by the following formula (5).
[Chemical Formula 5]
Wherein R 8, R 9, R 10, R 11, R 12, R 13, R 14 and R 15 are each independently an alkyl group having 1 to 4 carbon atoms, and the average value of c is 0 to 7.
As described above, when a mixture of the fluorene-based epoxy compound and the non-fluorene-based epoxy compound is used, the fluorene-based epoxy compound may be contained in the epoxy resin in an amount of 10 to 80% by weight, preferably 10 to 70% And the non-fluorene-based epoxy compound may be contained in the epoxy resin in an amount of 20 to 90% by weight, preferably 30 to 90% by weight.
Preferably, the epoxy resin (A) may contain a fluorene-based epoxy compound (A-1) and a non-fluorene-based epoxy compound (A-2) in a weight ratio of 1: 9 to 4: , Preferably from 1: 5 to 3: 1, more preferably from 1: 2 to 2: 1. When the content of the fluorene-based epoxy compound and the non-fluorene-based epoxy compound is in the above range, the shrinkage, the elastic modulus and the moldability are excellent.
On the other hand, the epoxy resin (A) is used in an amount of about 0.5 to 20% by weight, specifically about 3 to 15% by weight, more specifically about 3 to 12% by weight .
(B) Curing agent
As the curing agent, curing agents generally used for sealing semiconductor devices may be used without limitation, and preferably, 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 phenol novolak type phenol resin may be, for example, a phenol novolak type phenol resin represented by the following formula (6).
[Chemical Formula 6]
(D in the general formula (6) is 1 to 7).
The phenol novolak type phenol resin represented by the above formula (6) has a short crosslinking point interval, and when it reacts with an epoxy resin, the crosslinking density becomes high to increase the glass transition temperature of the cured product, The warping of the package can be suppressed more effectively.
The phenol aralkyl type phenol resin may be, for example, a phenol aralkyl type phenol resin having a novolak structure including a biphenyl derivative in a molecule represented by the following formula (7).
(7)
(In the above formula (7), the average value of e is 1 to 7).
The phenol aralkyl type phenol resin represented by the above formula (7) reacts with an epoxy resin to form a carbon layer (char), thereby blocking the transfer of heat and oxygen to the periphery, thereby achieving flame retardancy.
The xylo-type phenol resin may be, for example, a xylok-type phenol resin represented by the following formula (8).
[Chemical Formula 8]
(In Formula 8, the average value of f is 0 to 7)
The xylyl type phenol resin represented by the above formula (8) is preferable in terms of enhancing the fluidity and reliability of the resin composition.
The multifunctional phenol resin may be, for example, a multifunctional phenol resin containing a repeating unit represented by the following formula (9).
[Chemical Formula 9]
(The average value of g in the above formula (9) is 1 to 7.)
The multifunctional phenol resin containing the repeating unit represented by the above formula (9) is preferable in terms of reinforcing the high temperature bending property of the epoxy resin composition.
These curing agents may be used alone or in combination. Further, it can be used as an additional compound prepared by subjecting the above curing agent to a linear reaction such as an epoxy resin, a curing accelerator, a releasing agent, a coupling agent, a stress relieving agent and the like and a melt master batch.
The curing agent may be contained in an amount of 0.1 to 13% by weight, preferably 0.1 to 10% by weight, more preferably 0.1 to 8% by weight in the epoxy resin composition for sealing a semiconductor device.
The mixing ratio of the epoxy resin and the curing agent can be adjusted in accordance with the requirements of mechanical properties and moisture resistance reliability in the package. For example, the chemical equivalent ratio of the epoxy resin to the curing agent may be about 0.95 to about 3, specifically about 1 to about 2, more specifically about 1 to about 1.75. When the compounding ratio of the epoxy resin and the curing agent is in the above range, excellent strength can be realized after curing the epoxy resin composition.
Inorganic filler
The inorganic filler is 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 sealing material 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 fused silica containing 50 to 99% by weight of spherical fused silica having an average particle diameter of 5 to 30 탆 and the spherical fused silica having an average particle diameter of 0.001 to 1 탆 in an amount of 1 to 50% It is preferable that the mixture is contained in an amount of 40 to 100% by weight based on the total filler. Further, the maximum particle diameter can be adjusted to any one of 45 탆, 55 탆 and 75 탆 according to the application. In the spherical fused silica, conductive carbon may be included 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 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 in an amount of 70 wt% to 95 wt%, for example, 80 wt% to 90 wt% or 83 wt% to 97 wt%.
Other ingredients
In addition to the above components, the epoxy resin composition according to the present invention may further include at least one of a curing accelerator, a coupling agent, a release agent, and a colorant.
Hardening accelerator
The curing accelerator is a substance that promotes the reaction between the epoxy resin and the curing agent. As the curing accelerator, for example, 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.
In the present invention, the amount of the curing accelerator to be used may be about 0.01 to about 2% by weight based on the total weight of the epoxy resin composition, specifically about 0.02 to 1.5% by weight, more specifically about 0.05 to 1% by weight . 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, ureido silane, mercaptosilane, and the like. The coupling agent may be used alone or in combination.
The coupling agent may be contained in an amount of about 0.01 wt% to 5 wt%, preferably about 0.05 wt% to 3 wt%, and more preferably about 0.1 wt% to 2 wt%, based on the total weight of the epoxy resin composition . The strength of the epoxy resin composition cured product is improved in the above range.
Release agent
As the release agent, at least one selected from the group consisting of paraffin wax, ester wax, higher fatty acid, higher fatty acid metal salt, natural fatty acid and natural fatty acid metal salt can be used.
The releasing agent may be contained in an amount of 0.1 to 1% by weight in the epoxy resin composition.
coloring agent
The coloring agent is for laser marking of a semiconductor element sealing material, and colorants well-known in the art can be used and are not particularly limited. For example, the colorant may comprise at least one of carbon black, titanium black, titanium nitride, dicopper hydroxide phosphate, iron oxide, mica.
The colorant may be contained in an amount of about 0.01% by weight to 5% by weight, preferably about 0.05% by weight to 3% by weight, and more preferably about 0.1% by weight to 2% by weight based on the total weight of the epoxy resin composition.
In addition, the epoxy resin composition of the present invention may contain a stress-relieving agent such as a modified silicone oil, a silicone powder, and a silicone resin to the extent that the object of the present invention is not impaired; Antioxidants such as Tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane; And the like may be further contained as needed.
Since the epoxy resin composition for semiconductor encapsulation according to the present invention has a low shrinkage ratio and modulus of elasticity after curing, package bending due to shrinkage and expansion due to heat after semiconductor sealing and chip breakage due to external impact can be minimized.
Specifically, the epoxy resin composition for semiconductor encapsulation according to the present invention has a low shrinkage specificity of not more than 0.3%, preferably not more than 0.27%, as measured by the following formula (1).
(1): Cure shrinkage ratio (%) = {(L 0 -L 1 ) / L 0 } × 100
In the formula (1), L 0 is the length of the molded specimen obtained by molding the epoxy resin composition at 175 ° C and 70 kgf / cm 2 using a transfer molding press, and L 1 is the length of the molded specimen at 175 ° C This is the length of the specimen measured after post molding curing in the oven for 4 hours and cooling.
The epoxy resin composition for semiconductor encapsulation according to the present invention is molded using a transfer molding machine, and after post curing, the elastic modulus measured on the specimen is 900 MPa or less, preferably 850 MPa or less, more preferably 800 MPa or less And has low elasticity properties after curing. The transfer molding was performed under the conditions of a mold temperature of 170 to 180 ° C., an injection pressure of 800 to 1200 psi, and a curing time of 120 seconds. The size of the molded specimen was 20 × 13 × 1.6 mm. The post curing was carried out in a hot air drier at 170 to 180 ° C for 2 hours. The modulus of elasticity was measured using a Dynamic Mechanical Analyzer (TA, Q8000 DMA) at a temperature rising rate of 5 ° C / And was measured in a temperature range of 10 ° C to 300 ° C.
Further, since the epoxy resin composition for semiconductor encapsulation according to the present invention has a high glass transition temperature after curing, shrinkage after curing can be minimized. Concretely, the epoxy resin composition for semiconductor encapsulation is molded using a transfer molding machine, and after post-curing, the glass transition temperature measured for the specimen is 150 ° C or higher, preferably 170 ° C or higher, Lt; 0 > C to 250 < 0 & The transfer molding was performed under the conditions of a mold temperature of 170 to 180 ° C., an injection pressure of 800 to 1200 psi, and a curing time of 120 seconds. The size of the molded specimen was 20 × 13 × 1.6 [mm]. The post curing was carried out for 2 hours in a hot air drier at 170-180 ° C. The glass transition temperature was measured using a Dynamic Mechanical Analyzer (TA Corporation, Q8000 DMA) at a temperature raising rate of 5 ° C./minute Lt; 0 > C to 300 < 0 > C.
Further, the epoxy resin composition for semiconductor encapsulation according to the present invention has a softening point of 50 캜 to 130 캜 and is suitable for a semiconductor packaging process. When the softening point exceeds 130 캜, the moldability is deteriorated and it is difficult to apply to the semiconductor packaging process.
The epoxy resin composition may be prepared by uniformly mixing the above components uniformly at a predetermined mixing ratio using a Hensel mixer or a Lodige mixer and then kneading the mixture in a roll mill or a kneader kneader, and then cooled and pulverized to obtain a final powder product.
The epoxy resin composition of the present invention as described above can be usefully applied to semiconductor devices, particularly thin film type semiconductor devices requiring low shrinkage and low elasticity characteristics. 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
Hereinafter, the present invention will be described in detail with reference to specific examples.
Specific specifications of the components used in the following examples and comparative examples are as follows.
(A) an epoxy resin
(a1) A fluorene-based epoxy compound represented by the following formula (I) (softening point: 75 to 80 ° C) was used.
(I)
(a2) A fluorene-based epoxy compound represented by the following formula (II) (softening point: 85 to 90 캜) was used.
≪ RTI ID = 0.0 &
(a3) A fluorene-based epoxy compound represented by the following formula (III) (softening point: 88 to 90 캜) was used.
(III)
(a4) A fluorene-based epoxy compound represented by the following formula (IV) (softening point: 150 to 155 ° C) was used.
(IV)
(a5) A fluorene-based epoxy compound represented by the following formula (V) (softening point: 130-135 ° C) was used.
(V)
(a6) NC-3000 (Nippon Kayaku) was used.
(B) Curing agent
Multifunctional phenol resin MEH 7500-3S (Meiwa) was used.
(C) Curing accelerator
The curing accelerator was synthesized and prepared as follows
42.6 g of salicylamide and 21.6 g of 25% sodium methoxide solution were added to 50 g of methanol (MeOH) and reacted at room temperature for 30 minutes to completely dissolve. Then, 50 g of (4-hydroxyphenyl (4-hydroxyphenyl) triphenyl phosphonium bromide) was slowly added thereto, and the mixture was gradually added thereto. After further reaction for 1 hour, water was added to form a precipitate, which was then filtered to obtain a white solid compound. . (Yield: 85%).
(D) Inorganic filler: A 9: 1 (weight ratio) mixture of spherical fused silica having an average particle diameter of 18 μm and spherical fused silica having an average particle diameter of 0.5 μm was used.
(E) Coupling agent
(e1) was mixed with KBM-803 (Shinetsu), which is a mercaptopropyltrimethoxysilane, and SZ-6070 (Dow Corning chemical), which is e2) methyltrimethoxysilane.
(F) Additive: Carbon black MA-600 (Matsusita Chemical) was used as the (f1) carnauba wax and (f2) colorant.
Example 1 to 4 and Comparative Example One
Each of the components was weighed according to the composition shown in Table 1, and then uniformly mixed using a Henschel mixer to prepare a powdery first composition. Thereafter, the mixture was melt-kneaded at 120 ° C using a continuous kneader, followed by cooling and pulverization to prepare an epoxy resin composition for semiconductor encapsulation.
The properties of the epoxy resin compositions for semiconductor encapsulation of Examples 1 to 2 and Comparative Examples 1 to 4 were measured by the following measurement methods. The measurement results are shown in Table 2.
Property evaluation method
(1) Dispersibility: Flexural Strength An epoxy resin composition of Examples and Comparative Examples was molded by using a transfer molding press at 175 DEG C and 70 kgf / cm < 2 > × 6.4 mm). The obtained molded specimen was cut in half, and the presence or absence of particles due to micro dispersion was visually confirmed in the outer tube and inside. The results are shown in Table 1. The results are shown in Table 1. The results are shown in Table 1.
(2) Flowability (inch): An epoxy resin composition of Examples and Comparative Examples was molded by a transfer molding press at 175 DEG C and 70 kgf / cm < 2 > using an evaluation mold according to EMMI- The length was measured. The higher the measured value, the better the fluidity.
(3) Curing shrinkage ratio (%) Bending strength specimens produced 175 ℃ using ASTM mold for, 70kgf / 2 transfer molding press (transfer molding press) in cm of Examples and Comparative Examples the epoxy resin composition formed by molding the specimen to a ( 125 x 12.6 x 6.4 mm). The obtained specimens were post-cured (PMC) in a 170-180 oven for 4 hours, cooled, and then the length of the specimens was measured with calipers. The hardening shrinkage was calculated from the following equation (1).
(1): Cure shrinkage ratio (%) = {(L 0 -L 1 ) / L 0 } × 100
L 0 is the length of the molded specimen obtained by molding the epoxy resin composition with a transfer molding press at 175 ° C and 70 kgf / cm 2 , and L 1 is the length of the molded specimen in an oven at 175 ° C After post molding curing for 4 hours, it is the length of the specimen after cooling.
(4) Modulus of Elasticity (MPa) and Glass Transition Temperature (占 폚) The epoxy resin compositions of Examples and Comparative Examples were molded using a transfer molding machine under conditions of a mold temperature of 170 to 180 占 폚, an injection pressure of 800 to 1200 psi, and a curing time of 120 seconds 20 × 13 × 1.6 [mm] was prepared. The specimens for measurement were cured in a hot air dryer at 170 to 180 ° C for 2 hours, and then the glass transition temperature (Tg) and the elastic modulus of the specimens were measured using a Q8000 DMA (Dynamic Mechanical Analyzer) manufactured by TA Corporation. At this time, the temperature increase was 5 ° C / min, and the temperature was measured from -10 ° C to 300 ° C.
(5) Moisture absorption rate (%): The epoxy resin compositions of the above examples and comparative examples were subjected to a heat treatment under the conditions of a mold temperature of 170 to 180, a clamp pressure of 70 kgf / cm 2 , a transfer pressure of 1000 psi, a feed rate of 0.5 to 1 cm / And a disk-shaped cured specimen having a diameter of 50 mm and a thickness of 1.0 mm was obtained. The obtained specimens were placed in an oven at 170 to 180 ° C. and post-cured for 4 hours. The samples were allowed to stand at 85 ° C. and 85 RH% relative humidity for 168 hours, and the weight change due to moisture absorption was measured. (2), the moisture absorption rate was calculated.
(2): moisture absorption rate = (weight of sample after moisture absorption-weight of sample before moisture absorption) / (weight of sample before moisture absorption) × 100
(6) Shore-D: Using an MPS (Multi Plunger System) molding machine equipped with a mold for an eTQFP (exposed thin quad flat package) package having a width of 24 mm, a length of 24 mm and a thickness of 1 mm including a copper metal element After curing the epoxy resin composition to be evaluated at 175 ° C for 50, 60, 70, 80 and 90 seconds, the hardness of the cured product was measured by a Shore-D type hardness meter directly on the lap on the mold. The higher the value, the better the degree of cure.
(7) Adhesive force (kgf): A copper metal element was prepared in accordance with the mold for measurement of adhesion, and the resin composition prepared in the above-mentioned Examples and Comparative Examples was pressed at a mold temperature of 170 to 180 DEG C and a clamp pressure of 70 kgf / cm 2 , a feed pressure of 1000 psi, a feed rate of 0.5 to 1 cm / s, and a curing time of 120 seconds to obtain cured specimens. The obtained specimens were post-cured (PMC) in an oven at 170 to 180 ° C. for 4 hours. In this case, the area of the epoxy resin composition contacting the specimen was 40 ± 1 mm 2 , and the adhesion was measured by using a universal testing machine (UTM) for 12 specimens per each measuring step, and then the average value was calculated.
(8) Storage stability: The flow length was measured at the intervals of 24 hours in the same manner as in the fluidity measurement in the above (1) while the prepared epoxy resin composition was stored in a thermostatic hygrostat set at 25 ° C / 50RH% for 1 week, Percentage (%) of flow length was obtained. The larger this percentage value, the better the storage stability.
Properties
evaluation
stability(%)
As shown in Table 2, in Examples 1 and 2 using the epoxy resin composition containing the compound represented by Chemical Formula 1 or 2, it is possible to provide a resin composition which is excellent in dispersibility, has excellent low shrinkage and low elasticity properties after curing, And quickly cured even at a low temperature of 200 ° C or lower. On the contrary, the composition of Comparative Example 1 showed a high elastic modulus after curing and a low temperature curing property, and in Comparative Example 4 using a non-fluorene epoxy resin alone, the elastic modulus and shrinkage ratio after curing were high . On the other hand, in the case of Comparative Examples 2 and 3, it was possible to produce the first-order composition, but in the continuous kneader, an abnormal manufacturing due to insufficient melting property occurred during melting and kneading, A reliable physical property evaluation could not be performed.
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 (12)
[Chemical Formula 1]
(Wherein A is hydrogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and 0 < n < = 4)
(2)
(Wherein B is hydrogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and 0 < m < = 4)
Wherein the epoxy resin further comprises a non-fluorene-based epoxy compound that does not include a fluorene structure.
Wherein the fluorene-based epoxy compound is contained in an amount of 10 to 80% by weight in the epoxy resin.
Wherein the non-fluorene epoxy compound is contained in an amount of 20 to 90% by weight in the epoxy resin.
Wherein the epoxy resin comprises a fluorene-based epoxy compound and a non-fluorene-based epoxy compound in a weight ratio of 1: 9 to 4: 1.
Wherein the fluorene-based epoxy compound has a softening point of 80 to 90 占 폚.
Wherein the epoxy resin composition has a softening point of 50 占 폚 to 130 占 폚.
0.5 to 20% by weight of an epoxy resin containing the fluorene-based epoxy compound,
0.1 to 13% by weight of a curing agent, and
And 70 to 95% by weight of an inorganic filler.
Wherein the epoxy resin composition has a curing shrinkage of 0.3% or less as measured by the following formula (1).
(1): Cure shrinkage ratio (%) = {(L 0 -L 1 ) / L 0 } × 100
In the formula (1), L 0 is the length of the molded specimen obtained by molding the epoxy resin composition at 175 ° C and 70 kgf / cm 2 using a transfer molding press, and L 1 is the length of the molded specimen at 175 ° C Length of the specimen after post molding curing in the oven for 4 hours and after cooling.
The epoxy resin composition for semiconductor encapsulation having a modulus of elasticity of 900 MPa or less as measured on a specimen produced by molding the epoxy resin composition using a transfer molding machine and then curing the epoxy resin composition.
Wherein the epoxy resin composition is molded using a transfer molding machine and then post cured to measure a glass transition temperature of 150 占 폚 or more.
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| KR20170127814A (en) * | 2016-05-12 | 2017-11-22 | 삼성에스디아이 주식회사 | Epoxy resin composition for encapsulating semicomductor device and semiconductor device encapsulated using the same |
| KR20190081992A (en) * | 2017-12-29 | 2019-07-09 | 삼성에스디아이 주식회사 | Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated using the same |
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| JP5363704B2 (en) | 2006-09-19 | 2013-12-11 | 大阪瓦斯株式会社 | Epoxy resin for sealing and its use |
| KR101563827B1 (en) | 2011-07-06 | 2015-10-27 | 미쓰이 가가쿠 가부시키가이샤 | Epoxy polymerizable composition and organic el device |
| JP6087738B2 (en) | 2013-06-06 | 2017-03-01 | 大阪ガスケミカル株式会社 | Fluorene compound having phenolic hydroxyl group and epoxy compound thereof |
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| KR20170127814A (en) * | 2016-05-12 | 2017-11-22 | 삼성에스디아이 주식회사 | Epoxy resin composition for encapsulating semicomductor device and semiconductor device encapsulated using the same |
| KR20190081992A (en) * | 2017-12-29 | 2019-07-09 | 삼성에스디아이 주식회사 | Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated using the same |
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