KR101933264B1 - Tetrazolium compound, epoxy resin composition comprising the same and semiconductor device encapsulated with the same - Google Patents
Tetrazolium compound, epoxy resin composition comprising the same and semiconductor device encapsulated with the same Download PDFInfo
- Publication number
- KR101933264B1 KR101933264B1 KR1020150112734A KR20150112734A KR101933264B1 KR 101933264 B1 KR101933264 B1 KR 101933264B1 KR 1020150112734 A KR1020150112734 A KR 1020150112734A KR 20150112734 A KR20150112734 A KR 20150112734A KR 101933264 B1 KR101933264 B1 KR 101933264B1
- Authority
- KR
- South Korea
- Prior art keywords
- epoxy resin
- group
- resin composition
- formula
- compound represented
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D257/04—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
-
- 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
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- H01L51/5237—
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
The tetrazolium compound of the present invention is characterized by being represented by the following general formula (1). The tetrazolium compound is capable of accelerating the curing of the epoxy resin even at a low temperature. The epoxy resin composition containing the tetrazolium compound as a curing catalyst has little occurrence of micropores when cured, and has excellent bending properties.
[Chemical Formula 1]
Wherein R 1 , R 2 and R 3 each independently represent a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms containing a hetero atom or a halogen group And R 4 is a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms including a hetero atom, a, b, and c are each independently 0 to 5 It is an integer.
Description
TECHNICAL FIELD The present invention relates to a tetrazolium compound, an epoxy resin composition containing the same, and a semiconductor device sealed using the composition. More specifically, the present invention relates to a tetrazolium compound capable of accelerating curing of an epoxy resin even at low temperatures, a process for producing the same, an epoxy resin composition containing the same, and a semiconductor device sealed using the same.
A transfer molding method using an epoxy resin composition as a method for packaging a semiconductor device such as an IC (integrated circuit) and an LSI (large scale integration) and manufacturing a semiconductor device is low in cost and suitable for mass production Widely used. Particularly, the transfer molding method can improve the characteristics and reliability of the semiconductor device by improving the phenolic resin which is the epoxy resin or the curing agent to be used.
The epoxy resin composition used in this molding method may generally include an epoxy resin, a curing agent, a curing catalyst and the like. As the curing catalyst, an imidazole-based catalyst, an amine-based catalyst and a phosphine-based catalyst are used.
However, due to the trend toward miniaturization, weight saving and high performance of electronic devices, the high integration of semiconductors is accelerating every year, and as the demand for surface mounting of semiconductor devices increases, problems that can not be solved by conventional epoxy resin compositions It is happening. In recent years, materials used for packaging semiconductor devices must be capable of fast curability and curing at a low temperature in order to improve productivity, and can prevent or reduce the occurrence of micro voids in curing, And warping characteristics should be excellent.
The background art of the present invention is disclosed in Korean Patent Registration No. 1266536 and the like.
An object of the present invention is to provide a tetrazolium compound capable of accelerating curing of an epoxy resin even at a low temperature and a process for producing the same.
Another object of the present invention is to provide an epoxy resin composition containing the tetrazolium compound as a curing catalyst, which is less susceptible to micropores during curing and has excellent bending properties.
It is still another object of the present invention to provide a semiconductor device which is sealed by using the epoxy resin composition.
The above and other objects of the present invention can be achieved by the present invention described below.
One aspect of the present invention relates to tetrazolium compounds. The tetrazolium compound is represented by the following Formula 1:
[Chemical Formula 1]
Wherein R 1 , R 2 and R 3 each independently represent a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms containing a hetero atom or a halogen group And R 4 is a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms including a hetero atom, a, b, and c are each independently 0 to 5 It is an integer.
In an embodiment, the tetrazolium compound may be a fluorine group in which R 1 , R 2 and R 3 in the formula (1) may be a fluorine group.
In an embodiment, the tetrazolium compound may include at least one compound selected from the group consisting of a compound represented by the following formula (1a), a compound represented by the following formula (1b), a compound represented by the following formula (1c) and a compound represented by the following formula (1d).
[Formula 1a]
[Chemical Formula 1b]
[Chemical Formula 1c]
≪ RTI ID = 0.0 &
Another aspect of the present invention relates to a process for preparing a tetrazolium compound. The preparation method comprises reacting a compound represented by the following formula (2) and a compound represented by the following formula (3)
(2)
Wherein R 1 , R 2 , R 3 , R 4 , a, b and c are as defined in Formula 1, and X is a halogen atom;
(3)
In Formula 3, R 4 is as defined in Formula 1, and Y is an alkali metal or silver (Ag).
Another aspect of the present invention relates to an epoxy resin composition. The epoxy resin composition comprises an epoxy resin; Curing agent; Curing catalyst; And an inorganic filler, wherein the curing catalyst comprises the tetrazolium compound.
In an embodiment, the epoxy resin composition comprises, on a solid basis, 2 to 17% by weight of the epoxy resin; 0.5 to 13% by weight of the curing agent; 0.01 to 5% by weight of the curing catalyst; And 70 to 95% by weight of the inorganic filler.
In an embodiment, the epoxy resin is selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolak epoxy resin, tert-butyl catechol epoxy resin, naphthalene epoxy resin, glycidylamine epoxy resin, A phenol aralkyl type epoxy resin, a cycloaliphatic epoxy resin, a cycloaliphatic epoxy resin, a heterocyclic epoxy resin, a spiro ring containing epoxy resin, a cyclohexanedimethanol type epoxy resin, a trimethylol type epoxy resin And a halogenated epoxy resin.
In embodiments, the curing agent may comprise a phenolic resin.
In an embodiment, the curing agent is selected from the group consisting of a phenol aralkyl type phenol resin, a phenol novolak type phenol resin, a xylock type phenol resin, a cresol novolak type phenol resin, a naphthol type phenol resin, a terpene type phenol resin, Diene phenol resins, novolak phenol resins synthesized from bisphenol A and resole, polyhydric phenol compounds including tris (hydroxyphenyl) methane, dihydroxybiphenyl, acid anhydrides including maleic anhydride and phthalic anhydride, Phenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone. The term " a "
In an embodiment, the tetrazolium compound may be present in an amount of 10 wt% or more in 100 wt% of the curing catalyst.
In an embodiment, the tetrazolium compound may be contained in an amount of 0.01 to 5% by weight based on 100% by weight of the solid content of the epoxy resin composition.
In an embodiment, the epoxy resin composition may have a curing temperature of 155 ° C or less.
Another aspect of the present invention relates to a semiconductor element sealed with the epoxy resin composition.
The present invention relates to a tetrazolium compound capable of accelerating the curing of an epoxy resin even at a low temperature (155 캜 or lower), a process for producing the tetrazolium compound and a tetrazolium compound as a curing catalyst, The present invention has the effect of providing the excellent epoxy resin composition and the semiconductor element sealed by using the same.
1 is a cross-sectional view of a semiconductor device according to one embodiment of the present invention.
2 is a cross-sectional view of a semiconductor device according to another embodiment of the present invention.
3 is a cross-sectional view of a semiconductor device according to another embodiment of the present invention.
Hereinafter, the present invention will be described in detail.
The tetrazolium compound (tetrazolium salt) according to the present invention is represented by the following general formula (1).
[Chemical Formula 1]
Wherein R 1 , R 2 and R 3 each independently represent a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms containing a hetero atom or a halogen group , A substituted or unsubstituted aromatic hydrocarbon group (aryl group), a substituted or unsubstituted aliphatic hydrocarbon group (alkyl group) having 1 to 30 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group (aryl group) having 6 to 30 carbon atoms, A substituted or unsubstituted aliphatic hydrocarbon group (heteroalkyl group) having 1 to 30 carbon atoms which contains at least one hetero atom such as a sulfur atom (S) and a phosphorus atom (P), a nitrogen atom (N) Substituted or unsubstituted aromatic hydrocarbon group (heteroaryl group) or fluorine group (-F) containing at least one hetero atom such as a sulfur atom (S) or phosphorus atom (P) (-Cl), an iodine group (-I), and a bromo group (-Br). And, R 4 is a substituted or unsubstituted 1 to 30 carbon atoms substituted in the containing hydrocarbon group or a heteroatom or unsubstituted group of 1 to 30 carbon atoms unsubstituted hydrocarbon, e.g., substituted or unsubstituted C1 to 30 ring A substituted or unsubstituted aromatic hydrocarbon group (aryl group) having 6 to 30 carbon atoms, a nitrogen atom (N), an oxygen atom (O), a sulfur atom (S), and a phosphorus atom (P) A substituted or unsubstituted aliphatic hydrocarbon group (heteroalkyl group) having 1 to 30 hetero atoms, a nitrogen atom (N), an oxygen atom (O), a sulfur atom (S) (Heteroaryl group) having 6 to 30 carbon atoms, and a, b, and c are each independently an integer of 0 to 5, which may be a substituted or unsubstituted aromatic hydrocarbon group (heteroaryl group) having at least one heteroatom.
As used herein, the term "substituted" means that the hydrogen atom is replaced by a halogen group, a hydroxyl group, an amino group, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, Quot; means an aryl group having from 3 to 30 carbon atoms, a heteroaryl group having from 3 to 30 carbon atoms, an arylalkyl group having from 7 to 30 carbon atoms, or a combination thereof, and the like. And may be in the form of a ring. In the case of "branched type", the number of carbon atoms may be 2 or more, and in the case of "cyclic type", the number of carbon atoms may be 3 or more. "Hetero" includes one or more of an oxygen atom (O), a sulfur atom (S), a nitrogen atom (N) and the like, and "halo" means fluorine, chlorine, iodine or bromine.
In the specific examples, examples of the aryl group include, but are not limited to, a phenyl group, a biphenyl group, a naphthyl group, a naphthol group, and an anthracenyl group.
Examples of the heteroaryl group include a pyridinyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group, a quinoxalinyl group, an acridinyl group, a quinazolinyl group A thiazolyl group, a benzothiazolyl group, a benzisoxazolyl group, an oxazolyl group, a benzoxazolyl group, a pyrazolyl group, an imidazolyl group, an imidazolyl group, , A benzimidazolyl group, a purinyl group, a thiophenyl group, a benzothiophenyl group, a furanyl group, a benzofuranyl group, and an isobenzofuranyl group, but the present invention is not limited thereto.
The tetrazolium compound of the present invention comprises a tetrazolium series cation moiety and a sulfonamide series anion moiety and is a (curable) curing catalyst capable of accelerating the curing of the epoxy resin even at a low temperature of 155 ° C or lower Can be used. For example, the tetrazolium compound (curing catalyst) may contain at least one compound represented by the above formula (1).
In an embodiment, the tetrazolium compound may be a fluorine group (-F) in which R 1 , R 2 and R 3 in the formula (1) are fluorine groups.
In an embodiment, the tetrazolium compound may include at least one compound selected from the group consisting of a compound represented by the following formula (1a), a compound represented by the following formula (1b), a compound represented by the following formula (1c) and a compound represented by the following formula (1d).
[Formula 1a]
[Chemical Formula 1b]
[Chemical Formula 1c]
≪ RTI ID = 0.0 &
The tetrazolium compound according to one embodiment of the present invention can be prepared by reacting a compound represented by the following formula (2) and a compound represented by the following formula (3). For example, the compound represented by the formula (2) is dissolved in a solvent containing water and / or an alcohol having 1 to 3 carbon atoms, the compound represented by the formula (3) is added, To < RTI ID = 0.0 > 10 hours. ≪ / RTI > The tetrazolium compound prepared can be in the form of a white precipitate, which can be used by filtration and drying.
(2)
In Formula 2, R 1, R 2, R 3, R 4, a, b and c have the same meanings as defined in formula 1, X is a halogen atom, for example, fluorine (F), chlorine (Cl ), An iodine atom (I) or a bromine atom (Br).
(3)
In formula (3), R 4 is as defined in formula (1), and Y is an alkali such as lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium Metal or silver (Ag).
The epoxy resin composition according to the present invention can be used for sealing semiconductor devices and includes (A) an epoxy resin, (B) a curing agent, (C) a curing catalyst and (D) an inorganic filler.
(A) an epoxy resin
As the epoxy resin of the present invention, one or more epoxy resins commonly used in the field of epoxy resin composition for sealing semiconductor devices can be used. For example, it is not particularly limited as long as it has two or more epoxy groups in the molecule.
Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, tert-butyl catechol type epoxy resin, naphthalene type epoxy resin, glycidylamine type epoxy resin, Novolak type epoxy resins, biphenyl type epoxy resins, phenol aralkyl type epoxy resins, linear aliphatic epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, spirocyclic epoxy resins, cyclohexanedimethanol type epoxy resins, trimethylol epoxy Resins, halogenated epoxy resins, and the like. These may be used alone or in combination of two or more.
In an embodiment, the epoxy resin may be an epoxy resin having two or more epoxy groups in the molecule and at least one hydroxyl group, and may be a solid epoxy resin, a liquid epoxy resin, or a combination thereof. Specifically, a solid epoxy resin can be used.
In one embodiment, the epoxy resin may include at least one of a biphenyl type epoxy resin represented by the following formula (4) and a phenol aralkyl type epoxy resin represented by the following formula (5).
[Chemical Formula 4]
In Formula 4, R is an alkyl group having 1 to 4 carbon atoms, and an average value of n is 0 to 7.
[Chemical Formula 5]
In Formula 5, the average value of n is 1 to 7.
In an embodiment, the epoxy resin may be contained in an amount of 2 to 17% by weight, for example, 3 to 15% by weight, specifically 3 to 12% by weight, based on the solid content in the epoxy resin composition. Within the above range, the epoxy resin composition may have excellent curability.
(B) Curing agent
As the curing agent of the present invention, a conventional curing agent used in an epoxy resin composition for sealing a semiconductor element can be used without limitation. For example, it is not particularly limited as long as it has two or more phenolic hydroxyl groups, amino groups, and the like.
Examples of the curing agent include phenol aralkyl type phenol resin, phenol novolak type phenol resin, xylock type phenol resin, cresol novolac type phenol resin, naphthol type phenol resin, terpene type phenol resin, Pentadiene type phenol resin, novolak type phenol resin synthesized from bisphenol A and resole; Tris (hydroxyphenyl) methane, and dihydroxybiphenyl; Acid anhydrides including maleic anhydride and phthalic anhydride; And aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, and the like. For example, the curing agent may be a phenolic resin having at least one hydroxyl group.
In one embodiment, the curing agent may include at least one of a xylyl phenol resin represented by the following formula (6) and a phenol aralkyl phenol resin represented by the following formula (7).
[Chemical Formula 6]
In the above formula (6), the average value of n is 0 to 7.
(7)
In Formula 7, the average value of n is 1 to 7.
In an embodiment, the curing agent may be contained in an amount of 0.5 to 13% by weight, for example, 1 to 10% by weight, specifically 2 to 8% by weight, based on the solid content in the epoxy resin composition. Within the above range, the thermoplastic resin composition may have excellent curability.
(C) Curing catalyst
The curing catalyst of the present invention is a (curable) curing catalyst capable of promoting curing of the epoxy resin even at a low temperature of 155 ° C or lower, and is characterized by containing the tetrazolium compound.
In an embodiment, the curing catalyst may further include a curing catalyst used in a conventional epoxy resin composition for sealing a semiconductor element in addition to the tetrazolium compound. For example, a tertiary amine, an organic metal compound, an organic phosphorus compound, an imidazole, a boron compound, a combination thereof, and the like can be used, but the present invention is not limited thereto. Examples of the tertiary amine include benzyldimethylamine, triethanolamine, triethylenediamine, diethylaminoethanol, tri (dimethylaminomethyl) phenol, 2-2- (dimethylaminomethyl) phenol, 2,4,6-tris Diaminomethyl) phenol and tri-2-ethylhexyl acid salt. Examples of the organic metal compound include chromium acetylacetonate, zinc acetylacetonate, nickel acetylacetonate and the like. Triphenylphosphine triphenylborane, triphenylphosphine-1,4-benzoquinone adduct, and the like. Examples of imidazoles include 2- Methylimidazole, 2-phenylimidazole, 2-aminoimidazole, 2-methyl-1-vinylimidazole, 2-ethyl-4-methylimidazole and 2-heptadecylimidazole As the boron compound, triphenylphosphine tetraphenyl borate, tetraphenylboron salt, triflue Robo is the like can be given -n- hexyl amine, trifluoroacetic borane monoethylamine, tetrafluoroethylene borane triethylamine, borane amine tetrafluoroborate. 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. Specifically, in addition to the tetrazolium compound, organic phosphorus compounds, boron compounds, tertiary amines, imidazoles, combinations thereof, and the like can be further used.
In an embodiment, the curing catalyst may be used in the form of an adduct formed by pre-reacting with an epoxy resin and / or a curing agent.
In an embodiment, the tetrazolium compound may comprise at least 10 wt%, such as 20 to 100 wt%, of 100 wt% of the total cure catalyst. Within the above range, the low temperature curing property of the epoxy resin composition can be excellent, the occurrence of micropores after curing can be prevented or reduced, and the flexural characteristics and the like can be excellent.
In an embodiment, the curing catalyst may be included in an amount of 0.01 to 5% by weight, for example 0.02 to 1.5% by weight, for example 0.05 to 1.5% by weight, based on the solid content in the epoxy resin composition. Within the above range, the low temperature curing property of the epoxy resin composition can be excellent, the occurrence of micropores after curing can be prevented or reduced, and the flexural characteristics and the like can be excellent.
In an embodiment, the tetrazolium compound may be contained in an amount of 0.01 to 5% by weight, for example, 0.02 to 1.5% by weight, specifically 0.05 to 1.5% by weight, based on the solid content in the epoxy resin composition. Within the above range, the low temperature curing property of the epoxy resin composition can be excellent, the occurrence of micropores after curing can be prevented or reduced, and the flexural characteristics and the like can be excellent.
(D) Inorganic filler
The inorganic filler of the present invention can improve the mechanical properties and the like of the epoxy resin composition and lower the stress, and an inorganic filler used in a typical epoxy resin composition for semiconductor device sealing can be used. Examples of the inorganic filler include fused silica, crystalline silica, calcium carbonate, magnesium carbonate, alumina, magnesia, clay, talc, calcium silicate, titanium oxide, antimony oxide, glass fiber, But is not limited thereto. These may be used alone or in combination of two or more.
For example, fused silica having a low linear expansion coefficient can be used for low stress. Fused silica means amorphous silica having a true specific gravity of 2.3 or less and can be made by melting crystalline silica or synthesizing it from various raw materials. Although the shape and the particle diameter of the fused silica are not particularly limited, a fused silica mixture comprising 50 to 99% by weight of spherical fused silica having an average particle diameter of 5 to 30 탆 and 1 to 50% by weight of spherical fused silica having an average particle diameter of 0.001 to 1 탆 Is used in an amount of 40 to 100% by weight based on the total inorganic filler. Further, the maximum particle diameter can be adjusted to any one of 45, 55, and 75 占 퐉 according to the application. Since the spherical fused silica may contain the conductive carbon as a foreign substance on the surface of the silica, it is important to select a substance having a small amount of polar foreign substances.
In the specific examples, the inorganic filler may vary depending on the moldability, low stress, and high temperature strength required for the epoxy resin composition, but it is preferably 70 to 95 wt%, for example, 72 to 92 wt% %. ≪ / RTI > Within the above range, the epoxy resin composition of the epoxy resin composition may have excellent mechanical properties, low stress, flame retardancy, fluidity, reliability and the like.
The epoxy resin composition according to one embodiment of the present invention may further contain an additive contained in a conventional epoxy resin composition, as needed, so long as the effect of the present invention is not impaired. Examples of the additive include, but are not limited to, a coupling agent, a releasing agent, a stress relieving agent, a crosslinking promoter, a leveling agent, a colorant, and combinations thereof.
In the specific examples, examples of the coupling agent include, but are not limited to, epoxy silane, aminosilane, mercaptosilane, alkylsilane, alkoxysilane, combinations thereof, and the like. When the coupling agent is used, its content may be 0.1 to 1% by weight based on the total epoxy resin composition.
Examples of the mold release agent include, but are not limited to, paraffin wax, ester wax, higher fatty acid, higher fatty acid metal salt, natural fatty acid, natural fatty acid metal salt, and combinations thereof. When the releasing agent is used, the content thereof may be 0.1 to 1% by weight based on the whole epoxy resin composition.
Examples of the stress relieving agent include, but are not limited to, modified silicone oil, silicone elastomer, silicone powder, silicone resin, combinations thereof, and the like. When the stress relieving agent is used, the content thereof may be 6.5 wt% or less, for example, 0.1 to 1 wt%, based on the entire epoxy resin composition. Specifically, the modified silicone oil is preferably a silicone polymer having excellent heat resistance, and more specifically, a silicone oil having an epoxy functional group, a silicone oil having an amine functional group, a silicone oil having a carboxyl functional group, etc., To 0.05 to 1.5% by weight based on the whole epoxy resin composition. The silicone powder having a center particle diameter of 15 탆 or less is preferable for improvement in moldability and may be contained in an amount of 5% by weight or less, for example, 0.1 to 5% by weight, based on the whole epoxy resin composition.
In an embodiment, the total amount of the additive may be 0.1 to 10% by weight, for example 0.1 to 3% by weight, of the total epoxy resin composition.
The epoxy resin composition of the present invention is capable of curing at a low temperature, and the curing temperature may be 155 占 폚 or lower, for example, 135 to 155 占 폚. The epoxy resin composition can be sufficiently cured even at a low temperature (155 캜 or less) in the above range, and the occurrence of micropores can be prevented or reduced when the epoxy resin composition is cured, and the flexural characteristics and the like can be excellent.
In the specific examples, the epoxy resin composition is prepared by homogeneously mixing the respective components using a Henschel mixer, a Lodige mixer or the like, melt-kneading the mixture at 90 to 120 ° C in a roll mill or a kneader, It may be manufactured. Here, the constituent components of the epoxy resin and the like may be used alone, or the epoxy resin may be added together with a curing agent, a curing catalyst and, if necessary, additives such as release agent, coupling agent and stress relieving agent, such as a melt master batch, And can be used in the form of an addition compound prepared by the reaction.
The epoxy resin composition of the present invention can be used for a wide range of uses in which epoxy resin compositions can be used such as insulating resin sheets, circuit boards, solder resists, underfill materials, die bonding materials, Lt; / RTI > For example, it can be used for sealing semiconductor devices.
The semiconductor device according to the present invention is sealed using the above epoxy resin composition.
Hereinafter, a semiconductor device of the present invention will be described with reference to the accompanying drawings. However, the techniques disclosed in the present invention are not limited to the embodiments described herein but may be embodied in other forms. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art. In the drawings, the width, thickness, and the like of the components are slightly enlarged in order to clearly illustrate the components. In addition, although only a part of the components is shown for convenience of explanation, those skilled in the art can easily grasp the rest of the components. It is to be understood that when an element is described as being located at the top or bottom of another element, it is to be understood that the element may be located directly above or below another element, or where additional elements may be interposed between elements Quot; upper "and" lower "are based on the drawings. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention. In the drawings, the same reference numerals denote substantially the same elements.
Also, the singular " include "should be understood to include plural representations unless the context clearly dictates otherwise, and the terms" comprises, " It should be understood that they are intended to specify the presence of a combination of both, and do not preclude the presence or addition of one or more other features, numbers, steps, operations, components, or combinations thereof.
1 is a cross-sectional view of a semiconductor device according to an embodiment of the present invention. 1, the
2 is a cross-sectional view of a semiconductor device according to another embodiment of the present invention. 2, the
3 is a cross-sectional view of a semiconductor device according to another embodiment of the present invention. 3, the
In a specific example, a method of sealing a semiconductor element using the epoxy resin composition of the present invention may be a low pressure transfer molding method, a compression molding method, an injection molding method, a casting molding method, or the like And preferably a low pressure transfer molding method can be used. According to the molding method, a semiconductor device including a copper lead frame, an iron lead frame, a lead frame pre-plated with at least one of nickel, copper, and palladium in the lead frame, and an organic laminate frame can be manufactured.
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.
Example
Manufacturing example 1: Tetrazolium Preparation of compounds
3.4 g of 2,3,5-triphenyl-tetrazolium chloride solids were dissolved in 50 ml of MeOH / H 2 O, then 3.5 g of sulfadiazine sodium And the reaction was allowed to proceed at room temperature for 2 hours. After completion of the reaction, the resulting white precipitate was filtered through a filter paper to obtain 6 g of a tetrazolium compound represented by the following formula (1a) in the form of a white solid (yield: 88%, 1 H NMR (400 MHz, DMSO): 8.38 , J = 2.4Hz, 2H), 7.42 (d, J = 6.6Hz, 2H), 7.40 (m, 2H), 7.32-7.28 (m, 13H), 6.58 (m, 1H), 6.47 (d, J = 6.6Hz, 2H), 5.54 (br , 2H) ppm; 13 C NMR (100 MHz, DMSO): 169.3, 163.5, 157.9, 151.6, 139.3, 130.7, 129.9, 129.3, 128.9, 128.8, 127.5, 116.6, 110.3 ppm ; LC-MS m / z = 548 (M + ); Anal. Calcd for C 29 H 24 N 8 O 2 S: C, 63.49; H, 4.41; N, 20.42; Found: C, 63.44; N, 20.73).
[Formula 1a]
Manufacturing example 2: < RTI ID = 0.0 > Tetrazolium Preparation of compounds
3.4 g of 2,3,5-triphenyl-tetrazolium chloride solid was dissolved in 50 ml of MeOH / H 2 O, and sulfamethazine sodium 4 g and reacted at room temperature for 2 hours. After completion of the reaction, the resulting white precipitate was filtered through a filter paper to obtain 6.5 g of a tetrazolium compound represented by the following Formula 1b in the form of a white solid (yield: 86%, 1 H NMR (400 MHz, DMSO): 7.42 , J = 6.6Hz, 2H), 7.40 (m, 2H), 7.32-7.28 (m, 13H), 6.47 (d, J = 6.6Hz, 2H), 6.28 (d, J = 2.4Hz, 1H), 5.54 (br, 2H), 2.35 (s, 6H) ppm; 13 C NMR (100 MHz, DMSO) 168.5,165.3,163.5,151.6,139.3,131.7,129.9,129.3,128.9,128.8,125. ppm; LC-MS m / z = 576 (M +); Anal Calcd for C 31 H 28 N 8 O 2 S:. C, 64.57; H, 4.89; N, 19.43; Found: C, 64.41; H, 4.55 N, 19.85).
[Chemical Formula 1b]
Manufacturing example 3: Tetrazolium Preparation of compounds
3.4 g of 2,3,5-triphenyl-tetrazolium chloride solids were dissolved in 50 ml of MeOH / H 2 O, and then sulfacetamide sodium 3 g and reacted at room temperature for 2 hours. After completion of the reaction, the resulting white precipitate was filtered through a filter paper to obtain 6 g of a tetrazolium compound represented by the following formula (1c) in the form of a white solid (yield: 83%, 1 H NMR (400 MHz, DMSO): 7.42 , J = 6.6Hz, 2H), 7.40 (m, 2H), 7.32-7.28 (m, 13H), 6.47 (d, J = 6.6 Hz, 2H), 5.54 (br, 2H), 1.66 (s, 3H) ppm; 13 C NMR (100 MHz, DMSO): 173.0, 163.5, 151.6, 139.3, 130.7, 129.9, 129.3, 128.9, 128.8, 127.5, 116.6, 21.9 ppm; LC-MS m / z = 512 (M + ); Calcd for C 27 H 24 N 6 O 3 S: C, 63.27, H, 4.72, N, 16.40, Found: C, 63.43, H, 4.76, N, 15.99).
[Chemical Formula 1c]
Manufacturing example 4: Tetrazolium Preparation of compounds
2- (4-fluorophenyl) -3- (4-fluorophenyl) -5-phenyl-2H-tetrazolium chloride. 2H-tetrazolium chloride) 5 g of solid was dissolved in 50 ml of MeOH / H 2 O, and 3 g of sulfacetamide sodium was added thereto, followed by reaction at room temperature for 2 hours. After completion of the reaction, the resulting white precipitate was filtered through a filter paper to obtain 6 g of a tetrazolium compound represented by the following formula (1d) in the form of a white solid (yield: 88%, 1 H NMR (400 MHz, DMSO): 7.42 , J = 6.6 Hz, 2H) , 7.40 (m, 2H), 7.32-7.20 (m, 7H), 7.00 (m, 4H), 6.47 (d, J = 6.6 Hz, 2H), 5.54 (br, 2H) , 1.66 (s, 3H) ppm; 13 C NMR (100 MHz, DMSO): 173.0, 163.5, 162.9, 151.6, 134.9, 131.5, 130.5, 129.7, 129.3, 128.8, 128.1, 127.5, 116.6, 115.5, 21.9 ppm; LC-MS m / z = 548 (M +); Anal Calcd for C 27 H 22 F 2 N 6 O 3 S:. C, 59.12; H, 4.04; N, 15.32; Found: C, 59.43; H, 4.40 N, 15.31).
≪ RTI ID = 0.0 &
Specific specifications of the components used in Examples and Comparative Examples are as follows.
(A) an epoxy resin
(a1) phenol aralkyl type epoxy resin NC-3000 (Nippon Kayaku) was used.
(a2) biphenyl type epoxy resin YX-4000 (Japan Epoxy Resin) was used.
(B) Curing agent
(b1) A xylock type phenol resin (KPH-F3065, Kolon Chemical Industries, Ltd.) was used.
(b2) phenol aralkyl type phenol resin (Meiwa, MEH-7851) was used.
(C) Curing catalyst
(c1) The tetrazolium compound represented by the formula (1a) prepared in Preparation Example 1 was used.
(c2) The tetrazolium compound represented by the formula 1b prepared in Preparation Example 2 was used.
(c3) The tetrazolium compound represented by the formula (1c) prepared in Preparation Example 3 was used.
(c4) A tetrazolium compound represented by the formula (1d) prepared in Preparation Example 4 was used.
(c5) triphenyl phosphine (Hokko Chemical, TPP-k) was used.
(c6) adduct of triphenylphosphine and 1,4-benzoquinone (Aldrich) was used.
(c7) adduct of triphenylphosphine and 2,3-dihydroxynaphthalene (Aldrich) was used.
(D) Inorganic filler
A 9: 1 (weight ratio) mixture of spherical fused silica having an average particle diameter of 20 μm and spherical fused silica having an average particle diameter of 0.5 μm was used.
(E) Coupling agent
(e1) mercaptopropyltrimethoxysilane (Shin-Etsu, KBM-803) was used.
(e2) methyltrimethoxysilane (Dow-Corning, SZ-6070) was used.
(e3) N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu, KBM-573) was used.
(F) Colorant
Carbon black (Matsusita Chemical Co., MA-600B) was used.
Example 1 to 4 and Comparative Example 1 to 3: Preparation of epoxy resin composition
The components were homogeneously mixed at 25 to 30 ° C for 30 minutes using a Henschel mixer (KEUM SUNG MACHINERY, KSM-22) according to the composition and content (unit: wt%) shown in the following Table 1, A composition was prepared. Next, the primary composition was melted and kneaded at 110 ° C for 30 minutes using a self-made continuous kneader, and then cooled and pulverized at 10 to 15 ° C to prepare an epoxy resin composition in the form of a solid powder.
Experimental Example
The physical properties of the epoxy resin composition prepared in Examples 1 to 4 and Comparative Examples 1 to 3 and the package to which the epoxy resin composition was applied were measured and evaluated by the following physical property measuring method, and the results are shown in Table 2 below.
Property evaluation method
(1) Curing temperature (unit: 占 폚): Measured using differential scanning calorimeter (DSC, TA Instrument, 2910). 1 mg of the epoxy resin composition (solid powder) was placed in a Hermetic pan made of aluminum (Al) and sealed with an encapsulating press to prepare a measurement specimen. Indium metal (mp: 156.4 캜, heat of fusion: 781 cal / mol) was used for the measurement of the prepared specimen in a He gas at a heating rate of 10 캜 / min. The He gas flow rate was maintained at 50 to 60 ml / And the curing temperature was measured.
(2) Frequency of Cull-Broken Occurrence: We confirmed the occurrence of cull-broken by using a self-fabricated press molding machine (KPS) applicable to actual semiconductor packages. The molding temperature was measured by a thermocouple after setting the temperature of the press molding machine (KPS) at 175 ° C. Cull-broken when using a press-forming machine may cause insufficient formability and decrease productivity. The number of cull-broken pieces was measured for a total of 40 specimens.
(3) Gel Time (unit: sec): 3 g of the epoxy resin composition (solid powder) was measured with a small number of four-point scales, taken on an herbarium, and hot plate temperature (thermocouple final confirmation) 135 ° C, drop the pre-weighed sample onto a hot plate, press it with ointment spatula (stainless steel) to make a thin film, and then when the sample is thinly drawn with a probe (brass material) Stopwatch was used to measure the time when the point at which the line was no longer drawn was terminated. The mean value was taken three times and the deviation was measured twice for the second time. If the gel time is short, the curing speed is high, the moldability is excellent, and the productivity is high.
(4) Spiral Flow (Unit: inch): A mold for measuring a spiral flow according to EMMI-1-66 was used at a mold temperature of 135 ° C, an injection pressure of 9 MPa, and a curing time The epoxy resin composition was injected under the conditions of 90 seconds, and the flow length (spiral flow) was measured. The higher the measured value, the better the fluidity.
(5) Evaluation of Micropores (Unit: 占 퐉) 4.2 g of an epoxy resin composition (solid tablet,? = 14 mm (tablet outer diameter)) was measured with a small number of four- Narrow gap filling) was used to measure the number of voids and incidence. The conditions of the NGF mold are as follows: Block 1 (a: 150 μm, b: 450) with respect to a (mold gap thickness: distance between the upper mold and the upper end of the row located in the mold) b (mold thickness: distance between the mold and the mold) Block a (100 μm, b: 450 μm), Block 3 (a: 150 μm, b: 850 μm), Block 4 (a: 100 μm, b: 850 μm). The molding conditions were a molding temperature of 175 ° C, a curing time of 120 seconds, a transfer time of 14 seconds, a transfer speed of 1.2 mm / sec, a clamping pressure of 40 tons, and a transfer pressure of 1.0 ton. The void size was measured with a high magnification of the voids of the molded specimen with the ultrasonic imaging equipment (SAT, Scanning acoustic tomography, Hitachi, FineSAT-III) for semiconductor / electronic parts, and the average size (unit: 탆) was measured.
(6) Evaluation of warpage (unit: 占 퐉): An epoxy resin composition (solid tablet,? = 14 mm (tablet outer diameter)) and 4.2 g were assembled into a semiconductor package through transfer molding. The packaged package test conditions used in the present invention were a package dimension of 18 × 14 mm, a chip size of 13 × 11 mm (thickness: 150 μm) and a mold cap of 350 μm. The package specimen was prepared using Shadow moire (IPO AKRO MATRIX) The flexural behavior was measured by measuring the profile according to JESD22-B112. Warpage (-): cry direction, warpage (+): direction of smile) were obtained by taking point values of warpage at room temperature (30 ℃) and warpage at high temperature (260 ℃).
(%)
(탆)
From the results, the epoxy resin compositions (Examples 1 to 4) containing the curing catalyst (tetrazolium compound) of the present invention and the semiconductor device (semiconductor package) produced using the epoxy resin composition of the present invention were cured at a temperature of 155 ° C or less, It was found that no cull broken occurred, the gel time was short, the generation rate of micro voids was low, the size was small, and the warping property was excellent.
On the other hand, Comparative Examples 1 to 3, which did not include the curing catalyst of the present invention, had a high curing temperature and a large cracking, a long gel time, a large number of micro voids, a large size, You can see that there is a vulnerability.
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 (15)
[Chemical Formula 1]
Wherein R 1 , R 2 and R 3 are each independently a halogen group and R 4 is a substituted or unsubstituted aromatic hydrocarbon group (heteroaryl group) having 6 to 30 carbon atoms or a substituted or unsubstituted acetyl group And a, b, and c are each independently an integer of 0 to 5.
[Formula 1a]
[Chemical Formula 1b]
[Chemical Formula 1c]
≪ RTI ID = 0.0 &
[Chemical Formula 1]
Wherein R 1 , R 2 and R 3 are each independently a halogen group and R 4 is a substituted or unsubstituted aromatic hydrocarbon group (heteroaryl group) having 6 to 30 carbon atoms or a substituted or unsubstituted acetyl group A, b and c are each independently an integer of 0 to 5;
(2)
Wherein R 1 , R 2 , R 3 , R 4 , a, b and c are as defined in Formula 1, and X is a halogen atom;
(3)
In Formula 3, R 4 is as defined in Formula 1, and Y is an alkali metal or silver (Ag).
Wherein the curing catalyst comprises a tetrazolium compound represented by the following formula (1): < EMI ID =
[Chemical Formula 1]
Wherein R 1 , R 2 and R 3 are each independently a halogen group and R 4 is a substituted or unsubstituted aromatic hydrocarbon group (heteroaryl group) having 6 to 30 carbon atoms or a substituted or unsubstituted acetyl group And a, b, and c are each independently an integer of 0 to 5.
[Formula 1a]
[Chemical Formula 1b]
[Chemical Formula 1c]
≪ RTI ID = 0.0 &
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150112734A KR101933264B1 (en) | 2015-08-10 | 2015-08-10 | Tetrazolium compound, epoxy resin composition comprising the same and semiconductor device encapsulated with the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150112734A KR101933264B1 (en) | 2015-08-10 | 2015-08-10 | Tetrazolium compound, epoxy resin composition comprising the same and semiconductor device encapsulated with the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20170019031A KR20170019031A (en) | 2017-02-21 |
| KR101933264B1 true KR101933264B1 (en) | 2018-12-28 |
Family
ID=58313717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020150112734A KR101933264B1 (en) | 2015-08-10 | 2015-08-10 | Tetrazolium compound, epoxy resin composition comprising the same and semiconductor device encapsulated with the same |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101933264B1 (en) |
-
2015
- 2015-08-10 KR KR1020150112734A patent/KR101933264B1/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| KR20170019031A (en) | 2017-02-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101835937B1 (en) | Epoxy resin composition for encapsulating semiconductor device and semiconductor device prepared from using the same | |
| US9896465B2 (en) | Phosphonium compound, preparation method thereof, epoxy resin composition including the same, and semiconductor device prepared by using the same | |
| KR101768305B1 (en) | Phosphonium compound, epoxy resin composition comprising the same and semiconductor device prepared from using the same | |
| KR101802583B1 (en) | Epoxy resin composition for encapsulating semiconductor device and semiconductor device prepared from using the same | |
| KR101955754B1 (en) | Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated by using the same | |
| KR101854503B1 (en) | Phosphonium compound, epoxy resin composition comprising the same and semiconductor device prepared from using the same | |
| KR101933264B1 (en) | Tetrazolium compound, epoxy resin composition comprising the same and semiconductor device encapsulated with the same | |
| KR101702704B1 (en) | Compound comprising phosphonium ion, epoxy resin composition comprising the same and apparatus prepared from using the same | |
| KR101768287B1 (en) | Phosphonium compound, epoxy resin composition comprising the same and semiconductor device prepared from using the same | |
| KR101845134B1 (en) | Phosphonium compound, epoxy resin composition comprising the same and semiconductor device prepared from using the same | |
| KR101706823B1 (en) | Compound comprising sulfonium ion, epoxy resin composition comprising the same and apparatus prepared using the same | |
| KR101627019B1 (en) | Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated by using the same | |
| KR101622016B1 (en) | Catalyst for curing epoxy resin composition, epoxy resin composition comprising the same and apparatus prepared using the same | |
| KR101768303B1 (en) | Phosphonium compound, epoxy resin composition comprising the same and semiconductor device prepared from using the same | |
| KR101802577B1 (en) | Phosphonium compound, epoxy resin composition comprising the same and semiconductor device prepared from using the same | |
| KR101768281B1 (en) | Phosphonium compound, epoxy resin composition comprising the same and semiconductor device prepared from using the same | |
| KR101900552B1 (en) | Epoxy resin composition for encapsulating semicomductor device and semiconductor device encapsulated using the same | |
| KR101992006B1 (en) | Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated using the same | |
| KR101731681B1 (en) | Phosphonium compound, epoxy resin composition comprising the same and semiconductor device prepared from using the same | |
| KR101871574B1 (en) | Epoxy resin composition for encapsulating semicomductor device and semiconductor device encapsulated using the same | |
| KR101706822B1 (en) | Curing catalyst, epoxy resin composition comprising the same for encapsulating semiconductor device and semiconductor device prepared from using the same | |
| KR101780532B1 (en) | Compound comprising phosphonium ion, epoxy resin composition comprising the same and apparatus prepared using the same | |
| KR20210088377A (en) | Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant |