KR100826107B1 - Epoxy resin composition for encapsulating semiconductor device - Google Patents
Epoxy resin composition for encapsulating semiconductor device Download PDFInfo
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- KR100826107B1 KR100826107B1 KR1020060134172A KR20060134172A KR100826107B1 KR 100826107 B1 KR100826107 B1 KR 100826107B1 KR 1020060134172 A KR1020060134172 A KR 1020060134172A KR 20060134172 A KR20060134172 A KR 20060134172A KR 100826107 B1 KR100826107 B1 KR 100826107B1
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- South Korea
- Prior art keywords
- epoxy resin
- resin composition
- formula
- coupling agent
- semiconductor device
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 62
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 62
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 239000004065 semiconductor Substances 0.000 title claims abstract description 33
- 239000007822 coupling agent Substances 0.000 claims abstract description 19
- 238000007789 sealing Methods 0.000 claims abstract description 16
- -1 Triazole Compound Chemical class 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 150000003852 triazoles Chemical class 0.000 claims abstract description 9
- 239000011256 inorganic filler Substances 0.000 claims abstract description 8
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 6
- 239000005011 phenolic resin Substances 0.000 claims description 10
- 125000003277 amino group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000005641 methacryl group Chemical group 0.000 claims description 3
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 abstract description 9
- 238000007747 plating Methods 0.000 abstract description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000704 physical effect Effects 0.000 abstract description 6
- 239000006229 carbon black Substances 0.000 abstract description 4
- 229910052736 halogen Inorganic materials 0.000 abstract description 4
- 150000002367 halogens Chemical class 0.000 abstract description 4
- 239000012766 organic filler Substances 0.000 abstract description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract 3
- 229910052709 silver Inorganic materials 0.000 abstract 3
- 239000004332 silver Substances 0.000 abstract 3
- 239000002184 metal Substances 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 19
- 230000007797 corrosion Effects 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000006087 Silane Coupling Agent Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910000679 solder Inorganic materials 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000011417 postcuring Methods 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910020816 Sn Pb Inorganic materials 0.000 description 2
- 229910020922 Sn-Pb Inorganic materials 0.000 description 2
- 229910008783 Sn—Pb Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- NFVPEIKDMMISQO-UHFFFAOYSA-N 4-[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC=C(O)C=C1 NFVPEIKDMMISQO-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000010800 human waste Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- UPRXAOPZPSAYHF-UHFFFAOYSA-N lithium;cyclohexyl(propan-2-yl)azanide Chemical compound CC(C)N([Li])C1CCCCC1 UPRXAOPZPSAYHF-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000009659 non-destructive testing Methods 0.000 description 1
- 238000010428 oil painting Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
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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
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/226—Mixtures of di-epoxy compounds
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/72—Fillers; Inorganic pigments; Reinforcing additives
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
본 발명은 반도체 소자 밀봉용 에폭시 수지 조성물에 관한 것으로, 보다 상세하게는 무기 충전제 뿐만 아니라 카본 블랙과 같은 유기 충전제와의 결합력을 향상시켜 물성을 높이기 위하여 화학식 1의 구조를 갖는 커플링제를 사용하는 동시에, 사전 도금된 프레임(Pre-Plated frame) 및 은 도금된(Ag plated) 패드 면에 대한 부착력을 향상시키기 위하여 화학식 2의 구조를 갖는 트리아졸(triazole)계 화합물을 사용하는 것을 특징으로 하는 반도체 소자 밀봉용 에폭시 수지 조성물에 관한 것이다.The present invention relates to an epoxy resin composition for sealing semiconductor devices, and more particularly, to use a coupling agent having a structure of Formula 1 to improve physical properties by improving bonding strength with organic fillers such as carbon black as well as inorganic fillers. In order to improve the adhesion to the surface of the pre-plated frame (Pre-Plated frame) and silver plated (Ag plated) pad semiconductor device characterized in that using a triazole-based compound having a structure of formula (2) It relates to an epoxy resin composition for sealing.
본 발명의 에폭시 수지 조성물은 사전 도금된 프레임 및 은 도금된 패드 면에 있어서의 부착력을 향상시키고 무기 및 유기 충전제에서 동시에 커플링제의 역할을 수행할 수 있어 물리적 강도의 향상에 효과적인 동시에 별도의 할로겐계, 삼산화 안티몬 등의 난연제를 사용하지 않아도 우수한 난연성이 확보되므로 수지 밀봉형 반도체 소자 제조에 유용하다.The epoxy resin composition of the present invention can improve the adhesion on the surface of the pre-plated frame and the silver plated pad and can simultaneously act as a coupling agent in inorganic and organic fillers, which is effective for improving physical strength and at the same time separate halogen-based. Excellent flame retardancy is secured even without the use of flame retardants such as antimony trioxide and the like.
커플링제, 트리아졸계 화합물, 사전 도금, 은 도금, 부착력, 신뢰도, 난연성, 반도체 소자 Coupling Agent, Triazole Compound, Pre Plating, Silver Plating, Adhesion, Reliability, Flame Retardant, Semiconductor Device
Description
도 1은 기존 주석-납 도금 후의 땜납 공정을 나타내는 단면도이다.1 is a cross-sectional view showing a soldering process after conventional tin-lead plating.
본 발명은 반도체 소자 밀봉용 에폭시 수지 조성물에 관한 것으로, 보다 상세하게는 우수한 내땜납성을 가짐과 동시에 Ni, Ni-Pd, Ni-Pd-Au, Ni-Pd-Au/Ag 등의 사전 도금된 리드 프레임과의 부착성이 우수하며 자기 소화성의 난연 특성을 나타내는 반도체 봉지용 에폭시 수지 조성물에 관한 것이다. The present invention relates to an epoxy resin composition for sealing semiconductor elements, and more particularly, has a good solder resistance and at the same time pre-plated such as Ni, Ni-Pd, Ni-Pd-Au, Ni-Pd-Au / Ag The present invention relates to an epoxy resin composition for semiconductor encapsulation having excellent adhesion to a lead frame and exhibiting self-extinguishing flame retardant properties.
근래 폐기되는 전기/전자제품 내의 납성분의 인체에 대한 치명적인 영향이 현실화됨에 따라 국가별로 지하수 1리터당 납 용출량을 0.05~0.3㎎으로 규제하고 있다. 특히 유럽을 중심으로 납 규제에 대한 법제화가 활발히 진행되고 있으며 환경 유해 물질로서 납, 수은, 카드뮴, 6가 크롬 등의 무기 원소와, 브롬계 유기 난연제 등 6가지를 제한하는 RoHS(Restriction of Hazardous Substances)를 2006년 7월에 전면 시행할 예정이다. As the fatal effects of lead in human waste products have been realized in recent years, the amount of lead leached per liter of groundwater is regulated to 0.05 ~ 0.3mg. Restriction of Hazardous Substances (RoHS), which is particularly active in Europe, is leading the legislation of lead regulation. ) Will be fully implemented in July 2006.
따라서 규제법이 시행되기 이전에 전기/전자 제품 내 유해물질이 함유된 부 품 전부를 환경 친화적으로 교체하여야 하므로 무연(Pb free)제품의 활발한 개발이 필요한 실정이다. 전기/전자 부품 메이커(Maker) 및 셋메이커(Set Maker)에서 전자 부품내 무연(Pb-free)화하여야 할 대상은 다음과 같다. Therefore, active development of lead-free products is required because all parts containing hazardous substances in electrical / electronic products must be replaced with environment-friendly products before the enforcement of the regulation law. Pb-free electronic components in electric / electronic parts makers and set makers are as follows.
현재 땜납(Solder)의 경우 해외에서는 거의 무연 땜납(Pb-free Solder)으로 진행된 상태이며, Sn-Pb 도금(Plating)도 점차 무연(Pb free)화가 진행되고 있는 단계이다. 기존의 Sn-Pb 도금의 현재 개발되고 있는 무연(Pb free)화 방법은 크게 순주석도금(Pure Sn plating)과 Ni-Pd 사전도금(Pre-plating)을 들 수 있다. In the case of solders, Pb-free solders have been developed in foreign countries, and Sn-Pb plating is gradually becoming lead-free. Currently developed Pb free method of Sn-Pb plating is pure Sn plating and Ni-Pd pre-plating.
삼성전자, NEC, Sony 등에서는 Alloy42 및 Cu에 순주석도금(Pure Sn plating)을 하는 방법을 적극적으로 검토하고 있는 단계이나 휘스커(whisker)문제를 극복하여야 하는 과제가 남아 있어 양산까지는 상당 시간이 소요될 것으로 예상된다. Ni-Pd Pre-plating(일명 PPF)은 이러한 문제점 극복을 위한 대안으로 제시되고 있는데, 특히 유럽을 중심으로 Cu L/F에 대한 PPF 대체가 활발히 진행되고 있으며 PPF 사용량이 2005년에는 큰 폭으로 증가할 것으로 예상되고 있다. Samsung, NEC, Sony, etc., perform Pure Sn plating on Alloy42 and Cu. It is expected that it will take a long time to mass-produce due to the active step of reviewing the method and the challenge of overcoming the whisker problem. Ni-Pd pre-plating (aka PPF) has been suggested as an alternative to overcome this problem. In particular, PPF replacement for Cu L / F is actively underway, especially in Europe, and PPF usage has increased significantly in 2005. It is expected to do.
그러나 PPF 리드 프레임은 기존 Alloy42 및 Cu 리드 프레임에 비하여 에폭시 수지 조성물과의 계면 부착력이 크게 낮아 후경화 및 신뢰도 테스트 후 박리가 발생하는 등 신뢰도가 현저하게 저하되는 문제를 안고 있었다. However, the PPF lead frame had a significantly lower interface adhesion strength with the epoxy resin composition than the existing Alloy42 and Cu lead frames, resulting in a significant decrease in reliability such as peeling after post-curing and reliability tests.
일반적으로 용접 후의 신뢰도 저하를 개선하기 위하여 무기 충전재의 충전량을 증가시켜 저흡습 및 저열팽창화를 달성하여 내땜납성을 향상시킴과 동시에 저점도 수지를 사용하여 고유동성을 유지하는 방법을 적용하나, 용접 처리 후의 신뢰성은 에폭시 수지 조성물의 경화물과 반도체 장치 내부에 존재하는 반도체 소자나 리 드 프레임 등의 기재와의 계면의 부착성이 더 큰 영향을 미치게 된다. 만약 이 계면의 부착력이 약하다면 용접 처리 후의 기재와의 계면에서 박리가 발생하고 나아가서는 이 박리에 의하여 반도체 장치에 크랙이 발생하게 되는 것이다. In general, in order to improve the reliability reduction after welding, a method of maintaining high fluidity by using a low viscosity resin while improving the solder resistance by increasing the amount of the inorganic filler to achieve low moisture absorption and low thermal expansion, The reliability after the welding treatment has a greater influence on the adhesion between the cured product of the epoxy resin composition and a substrate such as a semiconductor element or a lead frame existing inside the semiconductor device. If the adhesion of this interface is weak, peeling occurs at the interface with the base material after the welding treatment, and further cracking occurs in the semiconductor device due to this peeling.
따라서 종래로부터 계면 접착력 향상을 목적으로 아민계 커플링제등이 수지 조성물에 첨가되어 왔으나(JP2000-304430; JP2000-352727) Pb Free화에 의한 용접 처리 온도의 상승(215~240℃ → 260℃)이나 PPF 등의 출현으로 적합한 부착력을 유지하는 데에 한계에 도달하게 되었다. Therefore, amine coupling agents and the like have been conventionally added to resin compositions for the purpose of improving interfacial adhesion (JP2000-304430; JP2000-352727). The advent of PPF has reached a limit in maintaining adequate adhesion.
본 발명은 상기와 같은 종래 기술의 문제점을 해결하기 위한 것으로, 반도체 소자, 리드 프레임 등의 각종 부재와의 부착성을 향상시키고, 기판 실장시의 내땜납성을 향상시킨 반도체 밀봉용 에폭시 수지 조성물 및 이것을 이용한 반도체 장치를 제공하는 것이다. The present invention is to solve the problems of the prior art as described above, the epoxy resin composition for semiconductor sealing to improve the adhesion to various members such as semiconductor elements, lead frames, etc., and to improve the solder resistance at the time of mounting the substrate and It is to provide a semiconductor device using the same.
그러므로 본 발명은 트리아졸(triazole)계 화합물을 첨가하여 기재와의 부착력을 획기적으로 향상시킴과 동시에 부가적으로 무기 및 유기 충전제에서도 커플링제의 역할 수행이 가능한 특정 구조의 커플링제를 병용하여 물성을 향상을 도모하여, 인체나 기기에 유해한 할로겐계 난연제 및 인계 난연제를 일절 사용하지 않는 환경 친화적인 반도체 밀봉용 에폭시 수지 조성물을 제공하고자 한다. Therefore, the present invention improves the adhesion to the substrate by adding a triazole-based compound, and at the same time, in addition to using a coupling agent of a specific structure that can perform the role of the coupling agent in inorganic and organic fillers The present invention aims to provide an environmentally friendly epoxy resin composition for semiconductor encapsulation that does not use any halogen-based flame retardants or phosphorus-based flame retardants that are harmful to humans or devices.
본 발명의 에폭시 수지 조성물은 사전 도금된 프레임에 있어서의 부착력을 향상시켜 신뢰도를 높임과 동시에 별도의 할로겐계, 삼산화 안티몬 등의 난연제를 사용하지 않아도 우수한 난연성이 확보되므로 수지 밀봉형 반도체 소자 제조에 유용하다.The epoxy resin composition of the present invention is useful for manufacturing a resin-sealed semiconductor device because it improves the adhesion in the pre-plated frame to improve the reliability and at the same time excellent flame resistance without using a flame retardant such as halogen-based, antimony trioxide, etc. Do.
본 발명에 의하면 화학식 1의 구조를 갖는 커플링제와 화학식 2의 구조를 갖는 트리아졸(triazole)계 화합물을 병용하는 것을 특징으로 하는 반도체 소자 밀봉용 에폭시 수지 조성물이 제공된다.According to the present invention, there is provided an epoxy resin composition for sealing a semiconductor device, comprising using a coupling agent having a structure of formula (1) and a triazole compound having a structure of formula (2) in combination.
(M은 4가의 티타늄 혹은 지르코늄이고, R1은 탄소수 1~12의 알킬기이고; R2는 [단, n은 1~8의 정수], 중 어느 하나이며; X 및 Y는 아크릴, 메타크릴, 머캅토, 아미노기 중 어느 하나이고, n은 1~3의 정수이다.)(M is tetravalent titanium or zirconium, R 1 is an alkyl group having 1 to 12 carbon atoms; R 2 is [Where n is an integer of 1 to 8], Any one of; X and Y are any of acryl, methacryl, mercapto, and an amino group, and n is an integer of 1-3.)
(R1은 수소원자, 머캅토기, 아미노기, 하이드록시기, 탄소수 1~8의 탄화수소 쇄 중 어느 하나이다.)(R1 is any one of a hydrogen atom, a mercapto group, an amino group, a hydroxyl group and a hydrocarbon chain having 1 to 8 carbon atoms.)
상기 커플링제의 함량이 전체 에폭시 수지 조성물을 기준으로 0.05 ~ 0.8 중량%, 상기 트리아졸계 화합물의 함량이 전체 에폭시 수지 조성물을 기준으로 0.01 ~ 2 중량%인 것을 특징으로 한다.The content of the coupling agent is 0.05 to 0.8% by weight based on the total epoxy resin composition, the content of the triazole-based compound is characterized in that 0.01 to 2% by weight based on the total epoxy resin composition.
상기 반도체 소자 밀봉용 에폭시 수지 조성물은 하기 화학식 3으로 표시되는 다방향족 에폭시 수지와 하기 화학식 4로 표시되는 다방향족 페놀 수지를 사용하는 것을 특징으로 한다.
삭제delete
(상기 식에서, n의 평균치는 1 내지 7이다.)(In the above formula, the average value of n is 1 to 7.)
(상기 식에서, n의 평균치는 1 내지 7이다.)(In the above formula, the average value of n is 1 to 7.)
상기 반도체 소자 밀봉용 에폭시 수지 조성물은 무기충전제를 전체 에폭시 수지 조성물 대비 82 ~ 92 중량%로 사용하는 것을 특징으로 한다.The epoxy resin composition for sealing the semiconductor device is characterized in that the inorganic filler is used in 82 ~ 92% by weight compared to the total epoxy resin composition.
이하 본 발명을 상세히 설명하고자 한다.Hereinafter, the present invention will be described in detail.
본 발명에 의하면 화학식 1의 구조를 갖는 커플링제와 화학식 2의 구조를 갖는 트리아졸(triazole)계 화합물을 병용하는 것을 특징으로 하는 반도체 소자 밀봉용 에폭시 수지 조성물이 제공된다.According to the present invention, there is provided an epoxy resin composition for sealing a semiconductor device, comprising using a coupling agent having a structure of formula (1) and a triazole compound having a structure of formula (2) in combination.
[화학식 1][Formula 1]
(R1O)n-M-(OXR2Y)4-n (R 1 O) n -M- (OXR 2 Y) 4-n
(M은 4가의 티타늄 혹은 지르코늄이고, R1은 탄소수 1~12의 알킬기이고; R2는 [단, n은 1~8의 정수], 중 어느 하나이며; X 및 Y는 아크릴, 메타크릴, 머캅토, 아미노기 중 어느 하나이고, n은 1~3의 정수이다.)(M is tetravalent titanium or zirconium, R 1 is an alkyl group having 1 to 12 carbon atoms; R 2 is [Where n is an integer of 1 to 8], Any one of; X and Y are any of acryl, methacryl, mercapto, and an amino group, and n is an integer of 1-3.)
[화학식 2][Formula 2]
(R1은 수소원자, 머캅토기, 아미노기, 하이드록시기, 탄소수 1~8의 탄화수소쇄 중 어느 하나이다.)(R1 is any one of a hydrogen atom, a mercapto group, an amino group, a hydroxyl group and a hydrocarbon chain having 1 to 8 carbon atoms.)
기존의 실란 커플링제는 실리카에 대해서만 그 효과가 발현되는 반면에, 상기 화학식 1의 커플링제는 카본 블랙과 같은 유기 충전제에 대해서도 커플링제로서의 역할 수행이 가능하며 또한 촉매로서의 역할도 가능하므로 기존에 사용되는 촉매의 양을 절감할 수 있는 이점이 있다. 상기 커플링제는 특별히 한정하는 것은 아니지만 구성내에 머캅토기(-SH)를 갖는 것이 바람직하다. 사용량은 전체 에폭시 수지 조성물에 대하여 0.05 ~ 0.8중량%가 바람직하다. 상기 실란 커플링제의 함량이 0.05 중량% 미만일 경우에는 원하는 효과를 얻을 수 없으며, 0.8 중량%를 초과할 경우에는 경화 속도가 너무 빨라지고, 점도가 높아지는 등의 문제점이 발생할 수 있다.While the existing silane coupling agent has an effect only on silica, the coupling agent of Chemical Formula 1 can be used as a coupling agent and also as a catalyst for organic fillers such as carbon black, and thus can be used as a catalyst. There is an advantage that can reduce the amount of catalyst to be. Although the said coupling agent does not specifically limit, It is preferable to have a mercapto group (-SH) in a structure. As for the usage-amount, 0.05-0.8 weight% is preferable with respect to the whole epoxy resin composition. If the content of the silane coupling agent is less than 0.05% by weight, the desired effect may not be obtained. If the content of the silane coupling agent is more than 0.8% by weight, the curing rate may be too high, and the viscosity may increase.
상기 화학식 2의 트리아졸계 화합물은 범용적인 금속의 부식 억제제이다. 반도체 패키지 흡습 신뢰도 평가 시 발생하는 리드 프레임의 부식이 계면 간의 결합을 방해하여 부착력을 저하시키고 이후 신뢰도에 악영향을 미칠 수 있으므로 본 발명에서는 리드프레임의 부식을 막고 기재와의 계면 부착력을 유지하기 위하여 상기 물질을 적용한다. 일반적으로 부식은 금속이 접하고 있는 주위 환경에 존재하는 성분과 반응하여 화합물로 변해 소모됨으로써 금속 제품의 성능이 저하되는 현상으로 일반적으로 부식을 억제하기 위해 산/염기 부식액 중에 용해시킨 후 금속에 표면 처리하는 방법이 사용된다. 즉, 부식 억제제의 흡착기는 부식액과 금속 표면과의 사이에서 활성을 나타내는 물질(흡착기는 친금속성 및 친무기성, 탄화 수소기는 소금속성 및 친유기성)로 금속에 부착하기 이전의 단계에서는 부식액 중에 잘 분산되어 흡착이 용이하고, 금속면에 강하게 흡착한 후에는 쉽게 금속으로부터 탈착되지 않는 성질을 이용한 것이다. 따라서 본 발명에서는 부식액 대신 에폭시 수지 조성물에 상기 트리아졸계 화합물을 원할히 분산시켜, 금속면에 부착된 후 금속으로부터의 탈착을 막을 수 있도록 하였다. 이를 통하여 기재와 금속간의 부착력의 저하를 막아 고 신뢰성의 반도체 봉지재료를 제공하고자 한 것이다. 또한, 이러한 흡착의 강도는 흡착에 관여하는 원자에 따른 영향이 크나 흡착 중심이 되는 원자에 따르는 다른 원자의 영향도 무시할 수 없다. 흡착기 중심원자가 금속에 전자를 공여하는 것이 흡착이기 때문에 부식 억제에 사용되는 물질의 흡착기는 전자 밀도가 높은 원소가 중심이 된다. 따라서 부식 억제제에 사용되는 물질의 흡착기는 전자 밀도가 높은 주기유표의 제 V족 및 제 VI족의 원소가 중심이 되며 특히 N이 포함된 화학식 2의 트리아졸(triazole)계 화합물은 높은 전기음성도를 가지고 있어 금속(Cu, Alloy, Ag등)의 부식을 억제하여 금속과 에폭시 수지 조성물 간의 계면에서의 부착력의 저하를 방지하게 된다. The triazole-based compound of Formula 2 is a corrosion inhibitor of a general metal. In the present invention, since the corrosion of the lead frame generated when evaluating the moisture absorption reliability of the semiconductor package may interfere with the interfacial bonding, thereby lowering the adhesion and adversely affecting the reliability, the present invention may prevent the corrosion of the leadframe and maintain the interface adhesion with the substrate. Apply the substance. In general, corrosion is a phenomenon in which the performance of a metal product is degraded by reacting with a component present in the surrounding environment where the metal is in contact with the metal. In general, corrosion is dissolved in an acid / base corrosion solution to suppress corrosion and then surface treatment on the metal. Method is used. That is, the adsorbent of the corrosion inhibitor is a substance exhibiting activity between the corrosion solution and the metal surface (the adsorbent is electrometallic and non-organic, and the hydrocarbon group is small metal and organic). It is dispersed and easily adsorbed, and after being strongly adsorbed on the metal surface, the property is not easily desorbed from the metal. Therefore, in the present invention, the epoxy resin composition instead of The triazole-based compound was smoothly dispersed to prevent desorption from the metal after adhered to the metal surface. Through this, to reduce the adhesion between the substrate and the metal to provide a highly reliable semiconductor sealing material. In addition, the strength of the adsorption is largely influenced by the atoms involved in the adsorption, but the influence of other atoms depending on the atoms serving as the adsorption center cannot be ignored. Since the adsorption center atom donates electrons to the metal, the adsorption center of the material used for suppressing corrosion is centered on an element having a high electron density. Therefore, the adsorption group of the material used for the corrosion inhibitor is centered on the elements of Group V and VI of the periodic index with high electron density, and especially the triazole compound of Formula 2 containing N has high electronegativity. It has a corrosion resistance of the metal (Cu, Alloy, Ag, etc.) to prevent the degradation of adhesion at the interface between the metal and the epoxy resin composition.
상기 트리아졸계 화합물은 분자량이 100~200인 것이 바람직하며, 전체 에폭시 수지 조성물을 기준으로 0.01 ~ 2 중량% 사용되는데, 그 함량이 전체 조성물의 0.01 중량% 미만인 경우에는 PPF 등 금속과의 부착성 향상효과를 충분히 가질 수 없는 반면, 2 중량%를 초과하여 사용할 경우에는 원재료 혼합문제의 발생 및 경화반응 저하를 초래할 수 있다. Preferably, the triazole-based compound has a molecular weight of 100 to 200, and is used in an amount of 0.01 to 2% by weight based on the total epoxy resin composition. When the content is less than 0.01% by weight of the total composition, adhesion to metals such as PPF is improved. While the effect may not be sufficiently, when used in excess of 2% by weight it may lead to the occurrence of raw material mixing problems and lowering of the curing reaction.
본 발명의 반도체 밀봉용 에폭시 수지 조성물의 에폭시 수지는 다방향족 에폭시 수지, 크레졸 노볼락형 에폭시 수지, 페놀 노볼락형 에폭시 수지, 바이페닐계 에폭시 수지, 비스페놀계 에폭시 수지, 디시클로펜타디엔계 에폭시 수지, 나프탈렌 계 에폭시 수지 등의 임의의 에폭시수지를 적어도 한 종 이상 사용한다. 그 중에 다방향족 에폭시 수지가 난연성 향상을 위하여 바람직한데, 다방향족 에폭시 수지는 하기 화학식 3의 구조를 갖는다. The epoxy resin of the epoxy resin composition for semiconductor sealing of the present invention may be a polyaromatic epoxy resin, a cresol novolac epoxy resin, a phenol novolac epoxy resin, a biphenyl epoxy resin, a bisphenol epoxy resin, or a dicyclopentadiene epoxy resin. And at least one arbitrary epoxy resin such as naphthalene epoxy resin. Among them, a polyaromatic epoxy resin is preferred for improving flame retardancy, and the polyaromatic epoxy resin has a structure of Formula 3 below.
[화학식 3] [Formula 3]
(상기 식에서, n의 평균치는 1 내지 7이다.)(In the above formula, the average value of n is 1 to 7.)
상기 다방향족 에폭시 수지는 바이페닐렌 노볼락형 구조를 형성하여, 흡습성, 인성 내산화성, 및 내크랙성도 우수하며, 가교 밀도가 낮아서 고온에서 연소 시 탄소층(char)을 형성하면서 그 자체로도 어느 정도 수준의 난연성을 확보할 수 있는 장점이 있다. 본 발명에서 상기 전체 에폭시 수지의 사용량은 전체 수지 조성물 중 3.5 ~ 15 중량%가 바람직하다.The polyaromatic epoxy resin forms a biphenylene novolak-type structure, has excellent hygroscopicity, toughness oxidation resistance, and crack resistance, and has a low crosslinking density, thereby forming a carbon layer (char) upon combustion at high temperature. There is an advantage to secure a certain level of flame retardancy. In the present invention, the amount of the total epoxy resin is preferably 3.5 to 15% by weight of the total resin composition.
본 발명의 반도체 밀봉용 에폭시 수지 조성물의 경화제로는 다방향족 페놀 수지, 페놀 노볼락형 수지, 크레졸 노볼락형 수지, 자일록형 수지, 디시클로펜타디엔계 페놀 수지, 나프탈렌계 수지 등의 임의의 페놀 수지를 적어도 한 종 이상 사용한다. 그 중에 다방향족 페놀 수지가 난연성 향상을 위하여 바람직한데, 다방향족 페놀 수지는 하기 화학식 4의 구조를 갖는다.As a hardening | curing agent of the epoxy resin composition for semiconductor sealing of this invention, arbitrary phenols, such as a polyaromatic phenol resin, a phenol novolak-type resin, a cresol novolak-type resin, a xyloxic resin, a dicyclopentadiene type phenol resin, a naphthalene type resin, etc. At least one resin is used. Among them, a polyaromatic phenol resin is preferred for improving flame retardancy, and the polyaromatic phenol resin has a structure of the following Chemical Formula 4.
[화학식 4] [Formula 4]
(상기 식에서, n의 평균치는 1 내지 7이다.)(In the above formula, the average value of n is 1 to 7.)
상기 다방향족 페놀 수지는 다방향족 에폭시 수지와 반응하여 탄소층(char)을 형성하면서 주변의 열 및 산소의 전달을 차단함으로써 난연성을 향상시키는 장점이 있다. 본 발명에서 상기 전체 페놀 수지의 사용량은 전체 수지 조성물 중 0.6 ~ 10.5 중량%가 바람직하다. The polyaromatic phenolic resin has the advantage of improving flame retardancy by blocking the transfer of heat and oxygen around the reaction while forming a carbon layer (char) by reacting with the polyaromatic epoxy resin. In the present invention, the total amount of the phenol resin is preferably 0.6 to 10.5% by weight in the total resin composition.
본 발명의 조성물에서 사용 가능한 경화 촉진제는 상기 다방향족 에폭시 수지와 다방향족 페놀 수지의 경화반응을 촉진하기 위한 촉매 성분으로, 예를 들면 벤질디메틸아민, 트리에탄올아민, 트리에틸렌디아민, 디메틸아미노에탄올, 트리(디메틸아미노메틸)페놀 등의 3급 아민류; 2-메틸이미다졸, 2-페닐이미다졸 등의 이미다졸류; 트리페닐포스핀, 디페닐포스핀, 페닐포스핀 등의 유기 포스핀류; 테트라페닐포스포니움 테트라페닐보레이트, 트리페닐포스핀 테트라페닐보레이트 등의 테트라페닐보론염 등이 있다. 이 중에서 1종 또는 2종 이상을 병용할 수 있으며, 사용량은 전체 에폭시 수지 조성물에 대하여 0.1 ~ 0.5 중량%가 바람직하다. The curing accelerator usable in the composition of the present invention is a catalyst component for promoting the curing reaction of the polyaromatic epoxy resin and the polyaromatic phenol resin, for example benzyldimethylamine, triethanolamine, triethylenediamine, dimethylaminoethanol, tri Tertiary amines such as (dimethylaminomethyl) phenol; Imidazoles such as 2-methylimidazole and 2-phenylimidazole; Organic phosphines such as triphenylphosphine, diphenylphosphine and phenylphosphine; Tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate. Among these, 1 type, or 2 or more types can be used together, 0.1-0.5 weight% is preferable with respect to the whole epoxy resin composition.
본 발명에서는 화학식 1 이외의 실란 커플링제를 사용할 수 있는데, 통상의 에폭시 실란 커플링제, 머켑토 실란 커플링제, 아민계 커플링제 및 메틸 트리 메톡 시 실란 커플링제로 구성된 군에서 1종 또는 2종 이상을 병용하여 사용할 수 있으며 사용량은 전체 에폭시 수지 조성물에 대하여 0.2~0.8중량%가 바람직하다.In the present invention, a silane coupling agent other than Chemical Formula 1 may be used, and in the group consisting of a conventional epoxy silane coupling agent, a merceto silane coupling agent, an amine coupling agent, and a methyl trimethoxy silane coupling agent, one or two or more kinds thereof may be used. It can be used in combination and the amount of use is preferably 0.2 to 0.8% by weight based on the total epoxy resin composition.
본 발명에서 사용할 수 있는 무기충전제로서는 그 평균입자가 0.1 ~ 35 ㎛인 용융 또는 합성실리카를 사용하는 것이 바람직하며, 충전량은 조성물 전체에 대해 82 ~ 92중량%가 바람직하다.As the inorganic filler which can be used in the present invention, it is preferable to use molten or synthetic silica having an average particle of 0.1 to 35 µm, and the filling amount is preferably 82 to 92% by weight based on the whole composition.
본 발명의 성형재료에는 고급 지방산, 고급 지방산 금속염, 에스테르계 왁스 등의 이형제, 카본블랙, 유·무기염료 등의 착색제, 변성 실리콘 오일 또는 실리콘 파우더, 실리콘 레진 등의 응력완화제 등이 필요에 따라 사용될 수 있다.In the molding material of the present invention, release agents such as higher fatty acids, higher fatty acid metal salts, ester waxes, colorants such as carbon black and inorganic dyes, modified silicone oils or stress relief agents such as silicone powders and silicone resins may be used as necessary. Can be.
이상과 같은 원재료를 이용하여 에폭시 수지 조성물을 제조하는 일반적인 방법으로는 소정의 배합량을 헨셀믹서나 슈퍼 믹서를 이용하여 균일하게 충분히 혼합한 뒤, 롤밀이나 니이더로 용융혼련하며, 냉각, 분쇄과정을 거쳐 최종 분말 제품을 얻는 방법이 사용되고 있다. As a general method for producing an epoxy resin composition using the raw materials as described above, a predetermined amount is uniformly mixed sufficiently using a Henschel mixer or a super mixer, melt-kneaded with a roll mill or a kneader, and then cooled and pulverized. The method of obtaining a final powder product is used.
본 발명에서 얻어진 에폭시 수지 조성물을 사용하여 반도체 소자를 밀봉하는 방법으로써는 저압 트랜스퍼 성형법이 가장 일반적으로 사용되는 방법이나, 인젝션(Injection) 성형법이나 캐스팅(Casting) 등의 방법으로도 성형 가능하다. As a method of sealing a semiconductor element using the epoxy resin composition obtained by this invention, the low pressure transfer molding method is the most commonly used method, It can also be shape | molded by the methods, such as injection molding method and casting.
이하 본 발명을 실시예에 의거 상세히 설명하나, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by Examples.
[실시예 1 ~ 3 및 비교예 1 ~ 2] [Examples 1-3 and Comparative Examples 1-2]
반도체 소자 밀봉용 에폭시 수지 조성물을 제조하기 위해 표 1에 나타낸 바 와 같이 각 성분들을 평량한 뒤, 헨셀 믹서를 이용, 균일하게 혼합하여 분말 상태의 1차 조성물을 제조하였으며, 믹싱 2-롤밀을 이용하여 100℃에서 7분간 용융혼련한 뒤, 냉각 및 분쇄과정을 거쳐 에폭시 수지 조성물을 제조하였다. In order to prepare an epoxy resin composition for semiconductor device sealing, the components were weighed as shown in Table 1, and then uniformly mixed using a Henschel mixer to prepare a powdery primary composition, using a mixing 2-roll mill. After melt kneading at 100 ° C. for 7 minutes, an epoxy resin composition was prepared by cooling and pulverizing.
이렇게 하여 얻어진 에폭시 수지 조성물에 대하여 다음과 같은 방법으로 물성 및 신뢰성을 평가하였으며, 신뢰성 시험을 위해 MQFP형 반도체 소자 성형 시 MPS(Multi Plunger System)성형기를 이용하여 175℃에서 70초간 성형시킨 후, 175℃에서 4시간 동안 후경화시켜, MQFP형 반도체 소자를 제작하였다. The epoxy resin composition thus obtained was evaluated for physical properties and reliability by the following method, and was molded for 70 seconds at 175 ° C. using an MPS (Multi Plunger System) molding machine for molding an MQFP type semiconductor device for reliability test. After post-curing at 4 ° C. for 4 hours, an MQFP semiconductor device was produced.
실시예 및 비교예에 의한 에폭시수지 조성물의 물성 및 난연성, 신뢰성, 성형성 시험결과를 표 2에 나타내었다. 신뢰성 시험은 프리컨디션 조건 하에서의 다이의 박리 및 패키지 크랙 발생 정도로 나타내었다.Table 2 shows the physical properties and flame retardancy, reliability, and moldability test results of the epoxy resin compositions according to Examples and Comparative Examples. Reliability testing was indicated to the extent of die peeling and package cracking under precondition conditions.
[물성평가 방법][Property evaluation method]
* 스파이럴 플로우 (Spiral Flow): EMMI 규격을 기준으로 금형을 제작하여 성형온도 175℃, 성형압력 70Kgf/㎠에서 유동 길이를 평가하였다.* Spiral Flow (Spiral Flow): The mold was manufactured based on the EMMI standard, and the flow length was evaluated at a molding temperature of 175 ° C and a molding pressure of 70Kgf / cm 2.
* 유리전이온도 (Tg): TMA(Thermomechanical Analyser)로 평가하였다.* Glass transition temperature (Tg): evaluated by TMA (Thermomechanical Analyser).
* 부착력: 측정하고자 하는 금속 소자를 부착 측정용 금형에 맞는 규격으로 준비하고, 측정 대상인 에폭시 수지 성형물을 금형온도 170 ~ 180℃, 이송압력 1000psi, 이송속도 0.5 ~ 1.0cm/sec, 경화시간 120초의 조건으로 성형하여 경화물을 얻은 후, 시편을 170 ~ 180℃의 오븐에 넣어 4시간 동안 후경화 시킨 직후와, 60℃, 60% 상대습도 조건 하에서 120시간 동안 방치시킨 후 260℃, 30초 동안 IR 리플로우를 3회 통과시킨 후의 부착력을 각각 측정하였다. 이때 금속 시편에 닿는 에폭시 수지 조성물의 면적은 33~40㎟이며 부착력 측정은 각 측정 공정당 10개 이상의 시편에 대하여 UTM을 이용하여 측정하였다.* Adhesion: Prepare the metal element to be measured in a standard suitable for the attachment measurement mold, and measure the epoxy resin molding to be measured with a mold temperature of 170 to 180 ° C, a transfer pressure of 1000psi, a transfer rate of 0.5 to 1.0cm / sec, and a curing time of 120 seconds. After molding under the condition to obtain a cured product, the specimen was placed in an oven at 170 to 180 ° C. for 4 hours, after curing for 4 hours, and left at 60 ° C. and 60% relative humidity for 120 hours, and then at 260 ° C. for 30 seconds. The adhesion force after three passes of IR reflow was measured. At this time, the area of the epoxy resin composition in contact with the metal specimen is 33 ~ 40 ㎜ and the adhesion measurement was measured using UTM for 10 or more specimens per each measurement process.
* 난연성: UL 94 V-0 규격에 준하여 1/8인치 두께를 기준으로 평가하였다.* Flame retardancy: Based on the UL 94 V-0 standard was evaluated based on 1/8 inch thickness.
* 내크랙성 평가 (신뢰성 시험): 에폭시 수지 조성물로 제조한 MQFP형 반도체 소자를 125℃에서 24시간 건조시킨 후, 60℃, 60% 상대습도 조건 하에서 120시간 동안 방치시킨 후 260℃, 30초 동안 IR 리플로우를 3회 통과시켜 1차로 프리컨디션 조건 하에서의 패키지 크랙발생 유무를 평가하였다. 프리컨디션 후 열충격 환경시험기(Temperature Cycle Test)에서 -65℃에서 10분, 25℃에서 5분, 150℃에서 10분씩 방치하는 것을 1 사이클로 하여 1,000사이클을 진행한 후 비파괴 검사기인 SAT (Scanning Acoustic Tomograph)로 크랙발생 유무를 평가하였다.* Crack resistance evaluation (reliability test): The MQFP type semiconductor device made of an epoxy resin composition was dried at 125 ° C. for 24 hours, and then left at 60 ° C. and 60% relative humidity for 120 hours and then 260 ° C. for 30 seconds. IR reflow was passed three times during the first time to evaluate the presence of package cracking under precondition conditions. Non-destructive testing machine SAT (Scanning Acoustic Tomograph) after 1,000 cycles after preconditioning for 10 cycles at -65 ° C, 5 minutes at 25 ° C, and 10 minutes at 150 ° C in a thermal shock environment tester. ) Cracks were evaluated.
주 1) NC-3000, Nippon Kayaku Note 1) NC-3000, Nippon Kayaku
주 2) YX-4000, Japan Epoxy Resin Note 2) YX-4000, Japan Epoxy Resin
주 3) KPH-F3060, Kolon 유화 Note 3) KPH-F3060, Kolon Oil Painting
주 4) MEH-7851, Meiwa Note 4) MEH-7851, Meiwa
주 5) TPP-k, Hokko Chemical Note 5) TPP-k, Hokko Chemical
주 6) SZ-6070, Dow corning chemical Note 6) SZ-6070, Dow corning chemical
주 7) KBM-573, Shin Etsu silicone Note 7) KBM-573, Shin Etsu silicone
주 8) LICA 01, KENRICH Petrochemicals, INC Note 8) LICA 01, KENRICH Petrochemicals, INC
상기 표 2에 나타난 바와 같이 본 발명에 의한 에폭시 수지 조성물은 화학식의 2의 트리아졸(triazole)계 화합물을 첨가할 경우 기존의 비교예에 비하여 후경화 직후 및 60℃, 60% 상대습도 조건하에서 120시간 동안 방치시킨 후 260℃, 30초 동안 IR 리플로우를 3회 통과시킨 후의 부착력을 충분히 확보하며, 화학식 1의 커플링제를 첨가할 경우 강도 등의 물성 향상을 보인다. 또한 두 가지 성분을 동시에 적용할 경우 PPF 부착력 향상 및 강도 등의 물성 향상에도 효과적임을 알 수 있다. 그러나 트리아졸계 화합물만을 적용했을 경우에는 상온 및 고온에서의 굴곡강도가 충분치 않으며, 화학식 1의 커플링제를 단독으로 적용할 경우에는 PPF 및 Ag에서의 부착력 향상에는 한계가 있으므로 주의하여야 한다. 또한 별도의 난연제를 적용하지 않으면서도 우수한 난연성을 확보하고 있음을 알 수 있었다.As shown in Table 2, when the epoxy resin composition according to the present invention is added with a triazole-based compound of Formula 2, 120 ° C immediately after post-curing and at 60 ° C. and 60% relative humidity under the conditions of the conventional comparative example. After leaving for a period of time to secure enough adhesion after passing through the IR reflow three times for 260 ℃, 30 seconds, and when the coupling agent of the formula (1) is added to improve physical properties such as strength. In addition, when the two components are applied at the same time it can be seen that it is effective in improving the physical properties such as PPF adhesion and strength. However, when only the triazole-based compound is applied, the flexural strength at room temperature and high temperature is not sufficient, and when the coupling agent of Formula 1 alone is used, care should be taken because there is a limit in improving adhesion in PPF and Ag. In addition, it was found that excellent flame retardancy was secured without applying a separate flame retardant.
본 발명의 에폭시 수지 조성물은 사전 도금(Pre-Plated) 리드 프레임에 있어서의 부착력을 향상시키고 강도 등의 물성을 향상시켜 신뢰도를 높임과 동시에 별도의 할로겐계, 삼산화 안티몬 등의 난연제를 사용하지 않아도 우수한 난연성이 확보되므로 환경 친화성 수지 밀봉형 반도체 소자 제조에 유용하다.The epoxy resin composition of the present invention improves adhesion by pre-plated lead frame, improves physical properties such as strength, and improves reliability, and does not have to use a flame retardant such as a halogen-based antimony trioxide. Since flame retardance is ensured, it is useful for manufacturing an environmentally friendly resin-sealed semiconductor device.
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