KR101627019B1 - 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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- KR101627019B1 KR101627019B1 KR1020130120853A KR20130120853A KR101627019B1 KR 101627019 B1 KR101627019 B1 KR 101627019B1 KR 1020130120853 A KR1020130120853 A KR 1020130120853A KR 20130120853 A KR20130120853 A KR 20130120853A KR 101627019 B1 KR101627019 B1 KR 101627019B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
- H01L21/563—Encapsulation of active face of flip-chip device, e.g. underfilling or underencapsulation of flip-chip, encapsulation preform on chip or mounting substrate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
- H01L2224/161—Disposition
- H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
- H01L2224/321—Disposition
- H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73201—Location after the connecting process on the same surface
- H01L2224/73203—Bump and layer connectors
- H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/181—Encapsulation
Abstract
The present invention relates to an epoxy resin composition for encapsulating semiconductor devices and a semiconductor device sealed with the epoxy resin composition, which comprises an epoxy resin, a curing agent, an inorganic filler and a curing catalyst, and the curing catalyst comprises a compound of the formula (1).
Description
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.
BACKGROUND ART [0002] Transfer molding of an epoxy resin composition is widely used as a method of packaging semiconductor devices such as IC (integrated circuit) and LSI (large scale integration) and obtaining a semiconductor device because of its low cost and suitable for mass production. Improvement of the characteristics and reliability of the semiconductor device can be achieved by improving the phenolic resin which is an epoxy resin or a curing agent. The epoxy resin composition may include an epoxy resin, a curing agent, a curing catalyst and the like.
As the curing catalyst, amine compounds such as tertiary amines, imidazoles compounds, phosphine compounds, phosphonium salts and the like are used. Specifically, triphenylphosphine and 1,4-benzoquinone addition reactants are used. These curing catalysts cause the curing accelerating effect to appear at relatively low temperatures. For example, when the epoxy resin composition before curing is mixed with the other components, the curing reaction progresses partially due to heat generated from outside or heat from the outside, and the curing reaction proceeds even when the epoxy resin composition is stored at room temperature after completion of the mixing . The progress of the partial curing reaction can lead to an increase in viscosity or a decrease in fluidity when the composition is a liquid, and a viscosity can be expressed when the composition is solid. It is possible to change the properties of each part of the composition upon curing. This partial change leads to a decrease in the mechanical, electrical, or chemical properties of the molded article when the thermosetting epoxy resin composition is formed by advancing the curing reaction to a high temperature. Therefore, when such a curing accelerator is used, strict quality control of each component mixing time, storage and transportation at a low temperature, and precise management of molding conditions are indispensable.
In this regard, Korean Patent No. 10-0290448 discloses an epoxy resin curing catalyst which is a carboxylic acid salt of bicyclic amidine.
An object of the present invention is to provide an epoxy resin composition for semiconductor device sealing that can be cured even at a low temperature.
Another object of the present invention is to provide an epoxy resin composition for semiconductor device encapsulation which exhibits a rapid curing reaction at a low temperature, does not lower its fluidity, and has a good hardening strength.
Another object of the present invention is to provide an epoxy resin composition for sealing a semiconductor device which catalyzes curing only when a desired curing temperature is reached, and eliminates curing catalyst activity when the curing temperature is not a desired curing temperature.
It is still another object of the present invention to provide a semiconductor device which minimizes viscosity change even under a predetermined range of time and temperature conditions and which is free from deterioration of moldability due to lowering of fluidity and mechanical, And an epoxy resin composition for sealing.
The epoxy resin composition for semiconductor device encapsulation of the present invention comprises an epoxy resin, a curing agent, an inorganic filler, and a curing catalyst, and the curing catalyst may include a compound of the following formula 1:
≪ Formula 1 >
R 1 , R 2 , R 3 , R 4 , Y, W, M, m and n are as defined in the following description.
The semiconductor device of the present invention can be sealed using the epoxy resin composition for sealing semiconductor devices.
The present invention provides an epoxy resin composition for semiconductor device sealing that can be cured even at a low temperature.
The present invention provides an epoxy resin composition for semiconductor device encapsulation which exhibits a rapid curing reaction at low temperature, does not deteriorate flowability, and has a good hardening strength.
The present invention provides an epoxy resin composition for semiconductor device encapsulation that catalyzes curing only when a desired curing temperature is reached, and eliminates curing catalyst activity when the curing temperature is not a desired temperature, thereby achieving long-term storage stability.
The present invention relates to an epoxy resin for semiconductor device encapsulation, which is capable of minimizing the change in viscosity even under a predetermined range of time and temperature conditions and preventing degradation in moldability due to lowering of fluidity and mechanical, electrical, Lt; / RTI >
1 is a cross-sectional view of a semiconductor device according to an embodiment of the present invention.
2 is a cross-sectional view of a semiconductor device according to another embodiment of the present invention.
The present invention will now be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments of the invention are shown. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and the same or similar components are denoted by the same reference numerals throughout the specification.
As used herein, the term "substituted" means that the hydrogen atom of the functional group is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, a halogen, Substituted by hydroxyl group.
The epoxy resin composition for semiconductor device encapsulation according to one embodiment of the present invention comprises an epoxy resin, a curing agent, an inorganic filler, and a curing catalyst, wherein the curing catalyst is an anion in which a phosphonium or ammonium cations and a metal and a ligand are chelated ≪ / RTI >
The salt containing a cation and an anion can be used as a curing catalyst in an epoxy resin composition. When exposed to external energy such as heat, it is decomposed into cations and anions at 80 to 120 ° C, for example, and the resulting cations and anions It is possible to exhibit an excellent degree of curing even in a short period of time during the curing reaction of the epoxy resin as compared with the conventional catalysts and to improve the low temperature curing property and the storage stability of the epoxy resin composition. Said "storage stability" catalyzes curing only when the desired curing temperature is reached, and when not the desired curing temperature, there is no curing catalytic activity, so that the epoxy resin composition can be stored for a prolonged period of time without viscosity changes. In general, the progress of the curing reaction may lead to an increase in the viscosity and a decrease in the fluidity when the epoxy resin composition is a liquid, and to develop viscosity when the epoxy resin composition is solid.
Specifically, the salt containing the cation and the anion may be represented by the following formula (1): < EMI ID =
≪ Formula 1 >
(Wherein, A is N or P,
R 1 , R 2 , R 3 and R 4 each represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms , A substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted heteroaryl group having 4 to 20 carbon atoms,
M is Fe, Cu, Zn or Co,
W is H 2 O or NH 3 ,
Y is an organic functional group capable of forming a chelate bond with M n + in the above formula (1)
m, n and k are integers, m > n > 0, 2 < m &
Specifically, n may be 2 or 3, and m may be 2, 3, or 4.
In one embodiment, Y can be represented by the formula:
(2)
(Wherein X is a substituted or unsubstituted alkylene group having 1 to 12 carbon atoms or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms,
R 5 , R 6 , R 7 and R 8 are each independently an alkylene group having 1 to 3 carbon atoms or an arylene group having 6 to 10 carbon atoms,
Of, -NRaRb * (and in the above, and * connections, Ra, Rb are each independently hydrogen or C 1 -C 5 - Y 1, Y 2, Y 3, Y 4 are each independently a carboxylate (COO) an alkyl group), or * -R 10 -O - (in the above, * is a connection portion, and, R 10 is an arylene group having from 1 to 5 carbon atoms or an alkylene group having a carbon number of 6 to 10)
Y 1, Y 2, Y 3 , Y 4 has one or more of the carboxylate or * -R 10 -O - a).
More specifically, Y may be an anion of ethylenediaminetetraacetic acid (EDTA).
In another embodiment, Y is selected from the group consisting of diethylene triamine pentaacetic acid, nitrilotriacetic acid, glutamic-N, N-diacetic acid, methylglycine N, N- diacetic acid, ethylene glycol- , N, N ', N'-tetraacetic acid, cyclohexanediamine tetraacetic acid, triethylenetetraamine hexa (N, N' And examples thereof include acetic acid, N- (2-hydroxyethyl) ethylenediamine-N, N ', N'-triacetic acid, ethylenediaminetetramethylenesulfonic acid, diethylenetriaminepentamethylenesulfonic acid, aminotrimethylenesulfonic acid, , Diethylene triamine penta methylene phosphonic acid, and anion of aminotrimethylene phosphonic acid.
The compound represented by the formula (1) is a salt containing a phosphonium or ammonium cation and an anion in which a metal and a ligand are chelated with each other. Specifically, M n + in formula (1) may be chelated with at least one of Y and W, And has a chelate bond with one or more Y's. More specifically, the anion of the compound of formula (1) may be represented by the following formula (3): < EMI ID =
(3)
(Wherein M, n, R 5 , R 6 , R 7 , R 8 , Y 1 , Y 2 , Y 3 , Y 4 and X are as defined in the above formulas 1 and 2).
The compound of formula (1) can be prepared by a conventional method. For example, it can be prepared by reacting a phosphonium-based or ammonium-based cation-containing compound of Formula 1 with a metal chelated anion-containing compound of Formula 1.
The phosphonium-based or ammonium-based cation-containing compound is a salt of a phosphonium-based or ammonium-based cation and a halogen anion, respectively, and the halogen may be fluorine, chlorine, bromine or iodine. The phosphonium-based or ammonium-based cation-containing compound can be produced by coupling an alkyl halide, an aryl halide, or an aralkyl halide with a phosphonium or alkylamine compound in a solvent. The metal chelated anion-containing compound can be prepared by a conventional method as a salt of a metal chelated anion and an alkali metal or alkaline earth metal cation.
The reaction of the phosphonium or ammonium cation-containing compound with the metal chelated anion-containing compound may be carried out in an aqueous solvent such as water, alcohol, or a mixture thereof, and may be carried out at a temperature of 10 to 40 ° C, To 30 hours For example, 20 to 30 hours, and the phosphonium-based or ammonium-based cation-containing compound: metal chelated anion-containing compound can be reacted at a molar ratio of 1: 0.9 to 1: 2. Within this range, the synthesis of the compound of formula (1) may be possible.
The compound of the formula (1) may be contained in an amount of 0.01 to 5% by weight, specifically 0.01 to 2% by weight, more specifically 0.05 to 1.0% by weight in the epoxy resin composition. Within this range, the curing reaction time is not delayed and the fluidity of the composition can be ensured.
The epoxy resin is not particularly limited as long as it has two or more epoxy groups in the molecule. Specifically, the epoxy resin may be one of a monomer, an oligomer and a polymer in a liquid or solid phase Or more.
In an embodiment, the epoxy resin is selected from the group consisting of phenol aralkyl type epoxy resin, orthocresol novolak type epoxy resin, epoxy resin obtained by epoxidating a condensate of phenol or alkyl phenol and hydroxybenzaldehyde, phenol novolak type epoxy resin, Novolak type epoxy resins, naphthol novolak type epoxy resins, novolak type epoxy resins of bisphenol A / bisphenol F / bisphenol AD, glycidyl ethers of bisphenol A / bisphenol F / bisphenol AD, A biphenyl type epoxy resin, a polyaromatic modified epoxy resin, a bisphenol A type epoxy resin, and a naphthalene type epoxy resin. The epoxy resin may be at least one selected from the group consisting of a phenol-based epoxy resin, a dicyclopentadiene-based epoxy resin,
In one embodiment, the epoxy resin may be a biphenyl type epoxy resin of the following formula:
≪ Formula 4 >
(Wherein R represents an alkyl group having 1 to 4 carbon atoms, and n has an average value of 0 to 7).
The epoxy resin may be included in the composition in an amount of from 2 to 17% by weight, for example, from 3 to 15% by weight, for example, from 3 to 12% by weight, based on the solid content. Within this range, the curability of the composition may not be deteriorated.
The curing agent is selected from the group consisting of phenol aralkyl type phenol resin, phenol novolac type phenol resin, xylock type phenol resin, cresol novolak type phenol resin, naphthol type phenol resin, terpene type phenol resin, Novolak type phenol resins synthesized from bisphenol A and resole, polyhydric phenol compounds including tris (hydroxyphenyl) methane, dihydroxybiphenyl, acid anhydrides including maleic anhydride and phthalic anhydride, metaphenylenediamine, di Aminodiphenylmethane, diaminodiphenylsulfone, and other aromatic amines. Preferably, the curing agent may be a phenolic resin having at least one hydroxyl group.
In one embodiment, the curing agent may comprise a xylock type phenolic resin of formula 5:
≪ Formula 5 >
(In the formula (5), the average value of n is 0 to 7.)
The curing agent may be contained in an amount of 0.5 to 13% by weight, for example, 1 to 10% by weight, for example, 2 to 8% by weight, based on the solid content in the epoxy resin composition. Within this range, the curability of the composition may not be deteriorated.
The weight ratio of the curing agent to the curing catalyst in the composition may be from 5 to 15. Within this range, the curability of the composition may not be deteriorated.
The inorganic filler can improve mechanical properties and low stress of the composition. Examples of the inorganic filler may include at least one of fused silica, crystalline silicate, calcium carbonate, magnesium carbonate, alumina, magnesia, clay, talc, calcium silicate, titanium oxide, antimony oxide, have.
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 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 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 to 95% by weight, for example, 75 to 92% by weight. Within the above range, the flowability and reliability of the epoxy resin composition can be secured.
The epoxy resin composition may further include a non-pyridinium curing catalyst which catalyzes the reaction of the epoxy resin with the curing agent and does not contain the pyridinium cation. As the non-pyridinium curing catalyst, 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. Organophosphorous compounds include tris-4-methoxyphosphine, phenylphosphine, diphenylphosphine, triphenylphosphine, triphenylphosphine triphenylborane, triphenylphosphine-1,4-benzoquinone adduct and the like have. 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 triphenylphosphine tetraphenylborate, tetraphenylboron salt, trifluoroborane-n-hexylamine, trifluoroboron monoethylamine, tetrafluoroborantriethylamine, 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 preferred curing catalysts include those using organic phosphorus compounds, boron compounds, amine-based or imidazole-based curing catalysts, alone or in combination. It is also possible to use adducts formed by a linear reaction with an epoxy resin or a curing agent. In the total curing catalyst, the compound of Chemical Formula 1 may be contained in an amount of 10 to 100% by weight, for example, 10 to 70% by weight. In this range, the curing reaction time is not delayed and the fluidity of the composition can be ensured. The curing catalyst may be included in the epoxy resin composition in an amount of 0.01 to 5 wt%, specifically 0.01 to 3 wt%, more specifically 0.05 to 1.0 wt%. Within this range, the curing reaction time is not delayed and the fluidity of the composition can be ensured.
The composition of the present invention may further include conventional additives included in the composition. In embodiments, the additive may include at least one of a coupling agent, a release agent, a stress relieving agent, a crosslinking enhancer, a leveling agent, and a colorant.
The coupling agent may be at least one selected from the group consisting of epoxy silane, aminosilane, mercaptosilane, alkylsilane and alkoxysilane, but 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 releasing agent, at least one selected from the group consisting of paraffin wax, ester wax, higher fatty acid, higher fatty acid metal salt, natural fatty acid and natural fatty acid metal salt can be used. The release agent may be contained in an amount of 0.05 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 is preferably contained in the epoxy resin composition in an amount of 0 to 6.5% by weight, for example, 0 to 1% by weight, for example, 0.1 to 1% by weight, and may be contained selectively or both . 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 median particle diameter of 15 탆 or less is particularly preferable because it does not act as a cause of degradation in moldability and may be contained in an amount of 0 to 5% by weight, for example, 0.1 to 5% by weight, based on the whole resin composition . The colorant may be carbon black or the like and may be contained in an amount of 0.1 to 1% by weight based on the total composition.
The additive may be included in the epoxy resin composition in an amount of 0.1 to 10% by weight, for example, 0.1 to 3% by weight.
The epoxy resin composition can be cured at a low temperature, for example, the curing initiation temperature can be 80 to 130 占 폚. Within this range, there is an advantage that the curing proceeds sufficiently even at a low temperature.
The epoxy resin composition has high storage stability by containing the compound of formula (1) as a curing catalyst, so that even if stored at a predetermined temperature for a predetermined time, hardening does not proceed and the viscosity change of the epoxy resin composition is low. According to one embodiment, the epoxy resin composition may have a viscosity change ratio of 20% or less, for example, 10% or less, for example, 0% to 10%
<Formula 1>
Viscosity change rate = | B-A | / A
(Unit: cPs), B is the viscosity (unit: cPs) measured at 25 占 폚 after the epoxy resin composition is allowed to stand at 25 占 폚 for 48 hours under the condition of 25 占 폚, to be)
In the above range, the curing is catalyzed only when the curing temperature is high due to high storage stability. When the curing temperature is not the desired curing temperature, there is no curing catalyst activity, and when the curing reaction is actually carried out at a high temperature, , There may be no deterioration in electrical and chemical properties. In embodiments, A may be between 100 and 3000 cPs, and B may be between 100 and 3000 cPs.
The epoxy resin composition may be in the EMMI-1-66 in 150 ℃, the flow length of a transfer molding press 55 at 70kgf / cm 2 to 75inch, particularly 60 to 72 inch. Within this range, it can be used for the use of epoxy resin composition.
The method for producing the epoxy resin composition is not particularly limited, but the constituent components contained in the composition are uniformly mixed using a Henschel mixer or a Lodige mixer, and then melt-kneaded at 90 to 120 캜 in a roll mill or kneader , Cooling and milling processes. As a method of sealing a semiconductor element using an epoxy resin composition, a low pressure transfer molding method is most commonly used. However, it can also be formed by a method such as an injection molding method or a casting method. According to the above method, a lead frame pre-plated with a copper lead frame, an iron lead frame, or at least one material selected from the group consisting of nickel and palladium on the lead frame, or a semiconductor element of an organic laminate frame is manufactured .
The sealed semiconductor element 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. 1 is a cross-sectional view of a semiconductor device according to an embodiment of the present invention. 1, a
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Manufacturing example One
Synthesis is described in Chem . commun . 2011, vol47, pp2300-2302.
41.9 g of tetraphenylphosphonium bromide and 55 g of ethylenediaminetetraacetic acid chelated iron (III) sodium salt were dissolved in 200 mL of ethanol and 200 mL of distilled water, respectively. The two solutions were mixed and reacted at 25 ° C for 24 hours. After that, ethanol and water were removed by distillation under reduced pressure, and dichloromethane was added again. Then, dichloromethane was distilled under reduced pressure to obtain 54.0 g of a pale red powder of the following formula (6).
(6)
Manufacturing example 2
In Example 1, 48.2 g of white pale red powder of Formula 7 was obtained in the same manner as in Example 1, except that 43.3 g of triphenylbenzylphosphonium bromide and 55 g of ethylenediaminetetraacetic acid chelated iron (III) sodium salt were used.
≪ Formula 7 >
Manufacturing example 3
In Example 1, 42.2 g of a sticky red solid of the following Formula 8 was obtained in the same manner as in Example 1 except that 41.9 g of tetrabutylphosphonium bromide and 30 g of ethylenediaminetetraacetic acid chelated iron (III) sodium salt were used.
(8)
Manufacturing example 4
In Example 1, 36.8 g of a sticky yellow solid of the following formula (9) was obtained in the same manner as in Example 1 except that 32.2 g of tetraoctylammonium bromide and 55 g of ethylenediaminetetraacetic acid chelated iron (III) sodium salt were used.
≪ Formula 9 >
Manufacturing example 5
In Example 1, 58 g of a purple solid of the following
≪
Example One
, 8.2 parts by weight of biphenyl type epoxy resin (NC-3000, Nippon Kayaku), 4.4 parts by weight of xylo-type phenol resin (HE100C-10, Air Water), 0.3 part by weight of the compound of Preparation Example 1, 86 parts by weight of an inorganic filler which is a mixture of spherical fused silica having an average particle diameter of 0.5 m and a mixture of spherical fused silica having an average particle diameter of 0.5 m, 0.2 part by weight of mercaptopropyltrimethoxysilane (KBM-803, Shinetsu) and methyl trimethoxysilane (SZ- , 0.4 parts by weight of a coupling agent which is a mixture of 0.2 parts by weight of a coloring agent (Dow Corning Chemical), 0.3 parts by weight of carnauba wax as a release agent, and 0.4 parts by weight of carbon black (MA-600, manufactured by Matsusita Chemical) The mixture was homogeneously mixed to obtain a powdery composition. Then, the mixture was melt-kneaded at 95 ° C using a continuous kneader, and then cooled and pulverized to prepare an epoxy resin composition for sealing a semiconductor device.
Example 2 to 5
An epoxy resin composition for semiconductor device encapsulation was prepared in the same manner as in Example 1, except that the compound (unit: parts by weight) shown in the following Table 1 was used instead of the compound of Preparation Example 1.
Comparative Example One
An epoxy resin composition for semiconductor device encapsulation was prepared in the same manner as in Example 1, except that adduct of triphenylphosphine and 1,4-benzoquinone was used instead of the compound of Preparation Example 1.
Comparative Example 2
An epoxy resin composition for semiconductor device encapsulation was prepared in the same manner as in Example 1, except that tetraphenylphosphonium tetraphenylborate was used instead of the compound of Preparation Example 1.
Curing catalyst: adduct of triphenylphosphine and 1,4-benzoquinone
** Curing catalyst: tetraphenylphosphonium tetraphenylborate
(1) Flowability (inch): The flow length was measured by using a transfer molding press at 150 ° C and 70 kgf / cm 2 using an evaluation mold according to EMMI-1-66 for the epoxy resin composition . The higher the measured value, the better the fluidity.
(2) Curing shrinkage (%): Flexural strength Using a transfer molding press at 175 ° C and 70 kgf / cm 2 using a mold for forming a specimen, a specimen (125 mm × 12.6 mm × 6.4 mm, x thickness). The obtained specimens were post-cured (PMC) in an oven at 170 to 180 ° C for 4 hours, cooled, and then the length of the specimens was measured with a caliper. The hardening shrinkage ratio was calculated from Equation 2 as follows.
[Formula 2]
Cure shrinkage rate = | C - D | /
C is the length of the specimen obtained by transfer molding pressing the epoxy resin composition at 175 DEG C and 70 kgf / cm < 2 >, D is the specimen after curing at 170 to 180 DEG C for 4 hours, Lt; / RTI >
(3) Glass transition temperature (占 폚): The epoxy resin composition was measured using a thermomechanical analyzer (TMA). At this time, the TMA was set to a condition of measuring up to 300 DEG C by raising the temperature by 10 DEG C per minute at 25 DEG C. [
(4) Moisture absorption rate (%): The epoxy resin composition was molded under the conditions of a mold temperature of 170 to 180 占 폚, a clamping pressure of 70 kgf / cm2, a feed pressure of 1000 psi, a feed rate of 0.5 to 1 cm / A disk-shaped cured specimen having 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 for 168 hours at 85 ° C. and 85 RH% relative humidity, and the weight change due to moisture absorption was measured. 3, the moisture absorption rate was calculated.
[Formula 3]
Moisture absorption rate = (weight of test piece after moisture absorption - weight of test piece before moisture absorption) ÷ (weight of test piece before moisture absorption) × 100
(5) Adhesive force (kgf): A copper metal element was prepared for the epoxy resin composition in accordance with the measurement mold, and the resin composition prepared in the above-mentioned Examples and Comparative Examples was heated to a mold temperature of 170 to 180 ° C, A clamping 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 a cured specimen. 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.
(6) Storage stability: The flow length was measured in the same manner as in the fluidity measurement in (1) after 48 hours while the prepared epoxy resin composition was stored in a thermo-hygrostat set at 25 DEG C and 50RH% (%) Of the surface area of the test piece was obtained by the following formula (4). The higher this percentage value is, the better the storage stability is.
[Formula 4]
Storage stability = (flow length after 48 hours) / (flow length immediately after preparation) x 100
(7) Hardness (shore-D): The epoxy resin composition was subjected to MPL (Multi Plunger System) equipped with a mold for an eTQFP (exposed thin quad flat package) package having a width of 24 mm, a length of 24 mm, ) After curing the epoxy resin composition to be evaluated at 150 ° C for 70, 80, 90, 100 and 110 seconds using a molding machine, the hardness of the cured product is measured by a Shore-D type hardness meter Respectively. The higher the value, the better the degree of cure.
Properties
(inch)
(kgf)
evaluation
As shown in Table 2, the epoxy resin composition for encapsulating semiconductor devices of the present invention has high flowability, low hardening shrinkage rate, and has a high hardening strength even in a short curing time compared to conventional phosphonium catalysts Respectively. Also, it was confirmed that the rate of change of viscosity after 48 hours was small, and thus, it has high storage stability. On the other hand, it was confirmed that the composition of the comparative example has low storage stability, high shrinkage ratio, low fluidity and can not achieve the effect of the present invention when used in a package.
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
Wherein the curing catalyst comprises a compound represented by the following formula (1): < EMI ID =
≪ Formula 1 >
(Wherein, A is N or P,
R 1 , R 2 , R 3 and R 4 each independently represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted 6 to 20 carbon atom A substituted or unsubstituted arylalkyl group, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted heteroaryl group having 4 to 20 carbon atoms,
M is Fe, Cu, Zn or Co,
W is H 2 O or NH 3 ,
Y is an organic functional group capable of forming a chelate bond with M n + in the above formula (1)
m, n and k are integers, m > n > 0, 2 < m &
(2)
(Wherein X is a substituted or unsubstituted alkylene group having 1 to 12 carbon atoms or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms,
R 5 , R 6 , R 7 and R 8 are each independently an alkylene group having 1 to 3 carbon atoms or an arylene group having 6 to 10 carbon atoms,
Y 1, Y 2, Y 3 , Y 4 are independently a carboxylate, respectively (C (= O) O - ), * -NRaRb ( In the above, * is a connection portion, Ra, Rb are each independently hydrogen or an alkyl group having 1 to 5 in), or * -R 10 -O - (in the above, * is a connection portion, and, R 10 is an arylene group having from 1 to 5 carbon atoms or an alkylene group having a carbon number of 6 to 10)
Y 1, Y 2, Y 3 , Y 4 has one or more of the carboxylate or * -R 10 -O - a).
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| KR1020130120853A KR101627019B1 (en) | 2013-10-10 | 2013-10-10 | Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated by using the same |
| PCT/KR2014/003845 WO2015053453A1 (en) | 2013-10-10 | 2014-04-30 | Epoxy resin composition for sealing semiconductor device, and semiconductor device sealed using same |
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| KR1020130120853A KR101627019B1 (en) | 2013-10-10 | 2013-10-10 | Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated by using the same |
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| JP2008280492A (en) | 2007-05-14 | 2008-11-20 | Sumitomo Bakelite Co Ltd | Epoxy resin composition for semiconductor sealing and semiconductor device |
| JP2010047741A (en) | 2008-07-22 | 2010-03-04 | Hitachi Chem Co Ltd | Thermosetting resin composition, substrate for loading photosemiconductor element using the same, method for producing the substrate, and photosemiconductor device |
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| JP3883146B2 (en) * | 1997-10-16 | 2007-02-21 | 住友ベークライト株式会社 | Epoxy resin composition and semiconductor device |
| KR100504604B1 (en) * | 1999-04-06 | 2005-08-04 | 제일모직주식회사 | Epoxy molding compound for sealing of semiconductor device |
| JP5585760B2 (en) * | 2007-07-31 | 2014-09-10 | 住友ベークライト株式会社 | Liquid resin composition for adhesive, semiconductor device, and method for manufacturing semiconductor device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2008280492A (en) | 2007-05-14 | 2008-11-20 | Sumitomo Bakelite Co Ltd | Epoxy resin composition for semiconductor sealing and semiconductor device |
| JP2010047741A (en) | 2008-07-22 | 2010-03-04 | Hitachi Chem Co Ltd | Thermosetting resin composition, substrate for loading photosemiconductor element using the same, method for producing the substrate, and photosemiconductor device |
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