KR100430195B1 - Epoxy Resin Composition for Sealing Semiconductor Devices with Excellent Crack Resistance - Google Patents
Epoxy Resin Composition for Sealing Semiconductor Devices with Excellent Crack Resistance Download PDFInfo
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- KR100430195B1 KR100430195B1 KR10-1998-0062767A KR19980062767A KR100430195B1 KR 100430195 B1 KR100430195 B1 KR 100430195B1 KR 19980062767 A KR19980062767 A KR 19980062767A KR 100430195 B1 KR100430195 B1 KR 100430195B1
- Authority
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- South Korea
- Prior art keywords
- epoxy resin
- resin composition
- weight
- parts
- crack resistance
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 42
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 239000004065 semiconductor Substances 0.000 title claims abstract description 21
- 238000007789 sealing Methods 0.000 title claims abstract description 11
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000011256 inorganic filler Substances 0.000 claims abstract description 9
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 9
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000853 adhesive Substances 0.000 abstract description 10
- 230000001070 adhesive effect Effects 0.000 abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052802 copper Inorganic materials 0.000 abstract description 8
- 239000010949 copper Substances 0.000 abstract description 8
- 238000005538 encapsulation Methods 0.000 abstract description 3
- 238000005336 cracking Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 15
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 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 6
- 239000004593 Epoxy Substances 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000035882 stress Effects 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
- 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
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 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 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000008393 encapsulating agent Substances 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
- 239000000945 filler Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 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 description 1
- CIPOCPJRYUFXLL-UHFFFAOYSA-N 2,3,4-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC=C(O)C(CN(C)C)=C1CN(C)C CIPOCPJRYUFXLL-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000001638 boron Chemical class 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
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229960002887 deanol Drugs 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
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 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
- 230000002265 prevention Effects 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
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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
-
- 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
- C08G59/40—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 curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4085—Curing agents not provided for by the groups C08G59/42 - C08G59/66 silicon containing compounds
-
- 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
- C08G59/40—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 curing agents used
- C08G59/66—Mercaptans
-
- 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
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
-
- 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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- Chemical & Material Sciences (AREA)
- 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)
- Compositions Of Macromolecular Compounds (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
본 발명은 에폭시수지, 경화제, 경화촉진제, 무기충전제로 이루어진 에폭시 수지 조성물에 2-머캅토벤즈이미다졸을 에폭시 수지 100중량부에 대하여 0.1 내지 3.0중량부 및 3-머캅토프로필트리메톡시실란을 전체 100중량부에 대하여 0.1 내지 0.5중량부 추가로 포함하여 구성되는 반도체 소자 밀봉용 에폭시 수지 조성물에 관한 것으로, 반도체 소자 봉지용으로 사용하였을 때 반도체용 구리 리드프레임과의 접착강도가 우수하고 저응력화를 달성할 수 있어 반도체 패키지의 크랙발생을 억제할 수 있게된다.The present invention is 0.1 to 3.0 parts by weight of 2-mercaptobenzimidazole in 100 parts by weight of epoxy resin composition consisting of an epoxy resin, a curing agent, a curing accelerator, an inorganic filler and 3-mercaptopropyltrimethoxysilane The present invention relates to an epoxy resin composition for sealing semiconductor elements, which comprises 0.1 to 0.5 parts by weight based on 100 parts by weight of the total, and when used for encapsulation of semiconductor elements, has excellent adhesive strength with copper lead frames for semiconductors and low stress. As a result, the cracking of the semiconductor package can be suppressed.
Description
본 발명은 반도체소자 밀봉용 에폭시 수지 조성물에 관한 것으로, 더욱 상세하게는 에폭시 수지, 경화제, 경화촉진제, 무기충전제로 이루어진 에폭시 수지 조성물에, 에폭시 수지 100중량부에 대하여 2-머캅토벤즈이미다졸(2-mercaptobenzimidazole, MBI)0.1 내지 3.0중량부 및 3-머캅토프로필트리메톡시실란을 전체 100중량부에 대하여 0.1 내지 0.5중량부 추가로 첨가함으로써 내크랙성을 향상시킨 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 an epoxy resin composition consisting of an epoxy resin, a curing agent, a curing accelerator, and an inorganic filler, based on 100 parts by weight of 2-mercaptobenzimidazole ( 2-mercaptobenzimidazole, MBI) Epoxy resin composition for sealing semiconductor elements with improved crack resistance by adding 0.1 to 3.0 parts by weight and 3-mercaptopropyltrimethoxysilane in an amount of 0.1 to 0.5 parts by weight based on 100 parts by weight. It is about.
최근 반도체 소자의 집적도는 나날이 향상되고 있으며, 이에 따른 배선의 미세화, 소자크기의 대형화, 셀면적의 축소 및 다층배선화가 급속히 진전되고 있다. 한편, 반도체 소자를 외부 환경으로부터 보호하는 패키지(package)는 프린트 기판으로의 고밀도실장 즉, 표면실장이라는 관점으로부터 소형, 박형화가 가속화되고 있다.In recent years, the degree of integration of semiconductor devices has been improved day by day, and thus the size of wirings, the size of devices, the size of cells, and the number of multilayer wirings are rapidly progressing. On the other hand, the package for protecting a semiconductor element from the external environment is accelerating its size and thickness from the viewpoint of high-density mounting to the printed board, that is, surface mounting.
이와 같이 대형 반도체 소자를 소형, 박형 패키지에 밀봉한 수지 밀봉형 반도체 장치에서는 외부환경의 온도 및 습도변화에 따른 열응력에 기인하여 패키지 크랙 또는 알루미늄 패드 부식발생등으로 고장발생의 빈도가 높아지게 된다. 이에 따라서 밀봉용 에폭시 수지 봉지재료의 내크랙성, 저응력화를 통한 고신뢰성 반도체 소자 에폭시 봉지재가 요구되어왔다.As described above, in the resin encapsulated semiconductor device in which a large semiconductor device is sealed in a small and thin package, the frequency of failure is increased due to package cracks or aluminum pad corrosion due to thermal stress caused by temperature and humidity changes in the external environment. Accordingly, there has been a demand for a highly reliable semiconductor element epoxy encapsulant through crack resistance and low stress of the epoxy resin encapsulation material for sealing.
이와 같은 요구를 만족하기 위해 종래의 기술로 제안되어 있는 것으로는 저응력화를 달성하기 위해 탄성율을 낮추는 방법, 열팽창계수를 낮추는 방법등이 있고, 외부 수분의 흡습을 방지하기 위하여 무기충진재를 고충전하여 수분 흡습량을 저하시키는 방법과 에폭시 수지 종류 및 기타 첨가제를 이용하여 칩 또는 리드프레임과 반도체 소자 밀봉용 봉지재와의 밀착성을 증가시키는 방법등도 제안되어 있다.In order to satisfy such demands, there are methods proposed in the related art to lower the elastic modulus and lower the coefficient of thermal expansion in order to achieve low stress, and high filling inorganic fillers to prevent moisture absorption from external moisture. A method of reducing the moisture absorption amount and a method of increasing the adhesion between the chip or lead frame and the encapsulant for sealing a semiconductor device by using an epoxy resin type and other additives have also been proposed.
저응력화를 위해 탄성율을 낮추는 방법으로, 일본국 특개소 63-1894호 및 일본국 특개평 5-291436호에서는 각종 고무성분에 의한 개질을 제안하며 열적 안정성이 우수한 실리콘 중합체를 배합하여 개질시킨 에폭시 수지 성형재료를 제시하였다. 이 방법에서 실리콘 오일은 성형재료의 기초수지인 에폭시수지 및 경화제와 상용성이 없기 때문에 기초수지중에 미립자가 분산되므로 내열성을 유지한채 저탄성율을 이룰 수 있었다.As a method of lowering the elastic modulus for reducing stress, Japanese Patent Application Laid-Open No. 63-1894 and Japanese Patent Application Laid-open No. 5-291436 propose modifications by various rubber components and modify epoxy compounded with a silicone polymer having excellent thermal stability. A resin molding material was presented. In this method, since silicone oil is incompatible with epoxy resin and curing agent which are the basic resins of the molding material, the microparticles were dispersed in the basic resins, thus achieving low modulus while maintaining heat resistance.
또, 저열팽창화에 대해서는 열팽창계수가 낮은 무기충전제의 충전량을 늘리는 방법이 제안되어 있는데, 무기충전제의 충전량 증가에 따른 에폭시 수지 성형재료의 저유동성과 고탄성이 문제가 되나 일본국 특개소 64-11355호에서는 구형 충전제를 사용하고 그 입도 분포와 입자크기의 조절함으로써 다량의 충전제를 배합할 수 있는 기술을 제안하였다.In addition, a method of increasing the filling amount of the inorganic filler having a low coefficient of thermal expansion has been proposed for low thermal expansion, but the low flowability and high elasticity of the epoxy resin molding material caused by the increase of the filling amount of the inorganic filler have been a problem. The issue proposes a technique for the formulation of large amounts of fillers by using spherical fillers and controlling their particle size distribution and particle size.
에폭시 수지 조성물과 리드프레임과의 접착강도를 강화시키는 방법으로 현재까지 제시된 것은 그다지 많지는 않으나, 고접착성의 에폭시 또는 경화제를 적용함으로써 접착성을 향상시키는 방법이 가장 일반적으로 사용되는 방법중 하나이다. 그외에 일본국 특개소 52-71543호에서는 열경화성 수지 조성물에 벤조트리아졸 등의 안식산 유도체(benzoic acid derivatives)를 방청효과를 위한 첨가제로서 적용하여 금속과의 접착력을 향상시키는 방법을 제안하고 있으나, 반도체 봉지용 에폭시 수지 조성물에서는 이와 같은 경우를 찾아볼 수 없고, 특히 구리 리드프레임에 대해서는 그 접착력이나 열선 팽창계수에 대한 개선이 이루어지지 않고 있는 실정이다.As a method of strengthening the adhesive strength between the epoxy resin composition and the lead frame has not been suggested so far, one of the most commonly used method of improving the adhesiveness by applying a high adhesive epoxy or a curing agent. In addition, Japanese Patent Application Laid-Open No. 52-71543 proposes a method of improving adhesion to metals by applying benzoic acid derivatives such as benzotriazole to the thermosetting resin composition as an additive for rust prevention effect. Such a case cannot be found in the epoxy resin composition for encapsulation. In particular, the copper lead frame has not been improved in its adhesive strength or thermal expansion coefficient.
본 발명의 목적은 상기와 같은 종래 문제점을 해결하기 위한 것으로, 에폭시 수지 조성물에 2-머캅토벤즈이미다졸 및 3-머캅토프로필트리메톡시실란을 첨가하여 구리 리드프레임과의 접착강도를 향상시킴으로써 솔더 내크랙성이 우수한 반도체 소자 밀봉용 에폭시 수지 조성물을 제공하는 것이다.An object of the present invention is to solve the conventional problems as described above, by adding 2-mercaptobenzimidazole and 3-mercaptopropyltrimethoxysilane to the epoxy resin composition to improve the adhesive strength with the copper lead frame It is to provide an epoxy resin composition for sealing semiconductor elements excellent in solder crack resistance.
즉, 본 발명은 에폭시수지, 경화제, 경화촉진제, 무기충진제로 이루어진 에폭시 수지 조성물에 에폭시 수지 100중량부에 대하여 2-머캅토벤즈이미다졸을 0.1 내지 3.0중량부 및 3-머캅토프로필트리메톡시실란을 전체 100중량부에 대하여 0.1 내지 0.5중량부 첨가하여 구성되는 고접착강도 및 내크랙성이 우수한 반도체 소자 밀봉용 에폭시 수지 조성물에 관한 것이다.That is, the present invention is 0.1 to 3.0 parts by weight of 2-mercaptobenzimidazole and 3-mercaptopropyltrimethoxy with respect to 100 parts by weight of epoxy resin in the epoxy resin composition consisting of an epoxy resin, a curing agent, a curing accelerator, an inorganic filler. The present invention relates to an epoxy resin composition for sealing semiconductor elements excellent in high adhesion strength and crack resistance, which is formed by adding 0.1 to 0.5 parts by weight of silane based on 100 parts by weight of the total.
이하, 본 발명을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.
본 발명에 사용되는 에폭시 수지는 당량이 100 내지 200이며, 불순물 함량이 10ppm이하인 고순도의 에폭시 수지로서 1분자중 2개 이상의 에폭시기를 갖는 것이면 특별히 한정되지 않고 어느 것이라도 적용가능하다. 즉, 예를 들면 일반적으로 사용되는 크레졸 노볼락수지, 페놀 노볼락수지, 바이페닐, 비스페놀A, 디사이클로펜타디엔 등을 단독 또는 2종 이상 병행하여 사용할 수 있지만 내열크랙성, 성형성의 관점에서 에폭시 당량이 180∼220인 올소크레놀 노볼락형 에폭시 수지를 50중량% 이상 사용하는 것이 바람직하고, 전체 조성물에 대하여는 3.5 내지 10.0중량%로 사용한다.The epoxy resin used in the present invention is a high purity epoxy resin having an equivalent weight of 100 to 200 and an impurity content of 10 ppm or less, and any one of them is not particularly limited as long as it has two or more epoxy groups in one molecule. That is, for example, cresol novolak resin, phenol novolak resin, biphenyl, bisphenol A, dicyclopentadiene, and the like, which are generally used, may be used alone or in combination of two or more thereof. It is preferable to use 50 weight% or more of the allocrerenol novolak-type epoxy resins whose equivalent is 180-220, and it is used at 3.5-10.0 weight% with respect to the whole composition.
본 발명에서 사용되는 경화제로는 2개 이상의 수산기를 갖고 수산기 당량이 100∼200인 통상의 페놀 노볼락수지, 크레졸 노볼락수지, 자일록수지, 디사이클로펜타디엔 수지 등으로부터 1종 또는 2종 이상 선택하여 사용할 수 있으나 가격 및 성형성 관점에서 볼 때 페놀 노볼락형 수지를 경화제 전체의 50중량% 이상 사용하는 것이 바람직하다. 에폭시 수지와 경화제의 조성비는 수산기 당량에 대한 에폭시 당량이 0.8 내지 1.2인 것이 바람직하며, 그 사용량은 전체 조성물에 대하여 2.0 내지 10.0중량%로 사용하는 것이 바람직하다.As the curing agent used in the present invention, one or two or more kinds of conventional phenol novolak resins, cresol novolak resins, xylox resins, dicyclopentadiene resins having two or more hydroxyl groups and a hydroxyl group equivalent of 100 to 200 Although it may be selected and used, it is preferable to use at least 50% by weight of the entire phenolic novolak-type resin from the viewpoint of price and moldability. The composition ratio of the epoxy resin and the curing agent is preferably 0.8 to 1.2 of epoxy equivalent to hydroxyl equivalent, and the amount of the epoxy resin and the curing agent is preferably used in an amount of 2.0 to 10.0% by weight based on the total composition.
본 발명에서 사용되는 경화촉진제는 상기 에폭시 수지와 경화제의 경화반응을 촉진하기 위해 필요한 성분으로, 예를 들면 벤질디메틸아민, 트리에탄올아민, 트리에틸렌디아민, 디메틸아미노에탄올, 트리(디메틸아미노메틸)페놀 등의 3급 아민류, 2-메틸이미다졸, 2-페닐이미다졸 등의 이미다졸류, 트리페닐포스핀, 디페닐포스핀, 페닐포스핀 등의 유기포스핀류, 테트라페닐포스포니움테트라페닐보레이트, 트리페닐포스핀테트라페닐보레이트 등의 테트라페닐보론염등으로부터 1종 또는 2종 이상 선택하여 사용할 수 있으며, 사용량은 전체 에폭시 수지 조성물에 대하여 0.10 내지 0.35중량%이다.The curing accelerator used in the present invention is a component necessary for promoting the curing reaction of the epoxy resin and the curing agent, for example benzyldimethylamine, triethanolamine, triethylenediamine, dimethylaminoethanol, tri (dimethylaminomethyl) phenol, and the like. Imidazoles such as tertiary amines, 2-methylimidazole and 2-phenylimidazole, organic phosphines such as triphenylphosphine, diphenylphosphine and phenylphosphine, and tetraphenylphosphonium tetraphenyl It can select 1 type (s) or 2 or more types from tetraphenyl boron salts, such as a borate and a triphenyl phosphine tetraphenyl borate, and the use amount is 0.10 to 0.35 weight% with respect to the whole epoxy resin composition.
본 발명에서 사용되는 무기충전제는 그 평균입자가 0.1 내지 35.0㎛인 용융 또는 합성실리카를 사용하는 것이 바람직하며, 충전량은 조성물 전체에 대하여 72중량% 이상 사용하는 것이 좋은데, 이는 72중량% 미만으로 사용하는 경우에는 충분한 강도와 저열팽창화를 실현할 수 없기 때문이다. 아울러, 무기충전제의 충전량 상한선은 성형성을 고려하여 선정하는 것이 바람직하며, 88중량% 이하로 사용하는 것이 바람직하다. 또한, 각형과 구형의 실리카를 구성 조성비를 7/3 내지 0/10로 하여 혼합한 형태가 좋으며 고순도의 제품일 것이 요구된다.Inorganic fillers used in the present invention preferably use molten or synthetic silica having an average particle of 0.1 to 35.0㎛, it is preferable to use at least 72% by weight based on the total amount of the composition, which is used less than 72% by weight This is because sufficient strength and low thermal expansion cannot be achieved. In addition, the upper limit of the filling amount of the inorganic filler is preferably selected in consideration of moldability, it is preferable to use at 88% by weight or less. In addition, it is preferable that the square and spherical silicas are mixed in a constituent composition ratio of 7/3 to 0/10, and a high purity product is required.
본 발명에서 사용되는 2-머캅토벤즈이미다졸(MBI)은 니이딩 공정에서 충분한 혼련이 일어날 수 있는 성질을 갖는 것으로써 에폭시 수지 100중량부에 대해 0.1 내지 3.0중량부를 분말상태 또는 용융 마스터 배치로 사용하고, 3-머캅토프로필트리메톡시실란은 믹싱공정에서 0.1 내지 0.5중량부의 양으로 분무하여 첨가한다. 2-머캅토벤즈이미다졸의 사용량이 0.1중량부 미만인 경우에는 충분한 내크랙성을 발현할 수 없으며, 반면에 3.0중량부를 초과하는 경우에는 오히려 접착강도의 저하를 초래하여 내크랙성이 감소하게 된다. 한편, 3-머캅토프로필트리메톡시실란의 함량이 0.1중량부 미만으로 사용하는 경우에는 2-머캅토벤즈이미다졸과의 상승효과를 기대하기 어렵고, 0.5중량부를 초과하는 경우에는 초과하는 분량만큼의 효과상승이 증가하지 않으므로 경제적 측면에서 바람직하지 못하다.2-mercaptobenzimidazole (MBI) used in the present invention has a property that sufficient kneading can occur in the kneading process, 0.1 to 3.0 parts by weight based on 100 parts by weight of the epoxy resin in a powder or melt master batch 3-mercaptopropyltrimethoxysilane is added by spraying in an amount of 0.1 to 0.5 parts by weight in the mixing step. When the amount of 2-mercaptobenzimidazole is less than 0.1 part by weight, sufficient crack resistance cannot be expressed. On the other hand, when the amount of 2-mercaptobenzimidazole is less than 3.0 parts by weight, the adhesive strength is lowered and crack resistance is reduced. . On the other hand, when the content of 3-mercaptopropyltrimethoxysilane is used less than 0.1 parts by weight, it is difficult to expect a synergistic effect with 2-mercaptobenzimidazole, and when it exceeds 0.5 parts by weight, an amount exceeding The increase in effectiveness does not increase, which is undesirable from an economic point of view.
이상, 상술한 각 구성성분외에도 본 발명에서는 브로모에폭시의 난연제, 삼산화안티몬, 수산화알루미나, 오산화안티몬 등의 난연조제, 고급지방산, 고급지방산금속염, 에스테르계 왁스 등의 이형제, 카본블랙, 유.무기염료 등의 착색제, 에폭시실란, 아미노실란, 알킬실란 등의 커플링제 등을 필요에 따라 사용할 수 있음은 물론이다.In addition to the above components, in the present invention, flame retardants such as bromoepoxy flame retardant, antimony trioxide, alumina hydroxide and antimony pentoxide, release agents such as higher fatty acids, higher fatty acid metal salts, and ester waxes, carbon black, organic and inorganic substances. Of course, coupling agents, such as coloring agents, such as dye, epoxysilane, aminosilane, and alkylsilane, can be used as needed.
또한, 상기와 같은 원재료를 이용하여 에폭시 수지 조성물을 제조하는 일반적인 방법으로는 소정의 배합량으로 헨셀믹서나 뢰디게 믹서를 이용하여 균일하게 충분히 혼합한 뒤 롤밀이나, 니이더로 용융 혼련하며 냉각, 분쇄과정을 거쳐 최종 분말제품을 얻는 방법을 사용할 수 있다.In addition, as a general method for producing an epoxy resin composition using the raw materials as described above, uniformly and sufficiently mixed using a Henschel mixer or a Rödige mixer at a predetermined compounding amount, melt kneading with a roll mill or a kneader, and then cooling and grinding Process can be used to obtain the final powder product.
상기와 같이 제조된 에폭시 수지 조성물을 사용하여 반도체 소자를 봉지하는 방법으로는 저압트랜스퍼 성형법이 가장 일반적으로 사용되는 방법이나, 인젝션(injection)성형법이나, 캐스팅(casting) 등의 방법으로도 성형이 가능하다.As a method of encapsulating a semiconductor device using the epoxy resin composition prepared as described above, the low pressure transfer molding method is the most commonly used method, but molding may be performed by injection molding or casting. Do.
이하, 본 발명을 실시예를 들어 더욱 상세히 설명하고자 하나 본 발명이 하기 실시예에 의하여 제한되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples.
실시예 1∼3Examples 1 to 3
본 발명의 반도체 소자 밀봉용 에폭시 수지 조성물을 제조하기 위해 표 1에 나타낸 것과 같이 각 성분들을 평량한 뒤, 헨셀믹서를 이용하여 균일하게 혼합하여 분말상태의 1차 조성물을 제조하였으며, 믹싱 2-롤밀을 이용하여 100℃에서 7분간 용융 혼련한 뒤, 냉각 및 분쇄과정을 거쳐 최종 에폭시 수지 조성물을 제조하였다.In order to prepare the epoxy resin composition for sealing a semiconductor device of the present invention, as shown in Table 1, each component was weighed, and then uniformly mixed using a Henschel mixer to prepare a powdery primary composition. After melt kneading at 100 ° C. for 7 minutes, a final epoxy resin composition was prepared by cooling and grinding.
이와 같이 수득된 에폭시 수지 조성물에 대하여 시험편을 제작하여 175℃에서 6시간 후경화시킨 뒤, 얼로이 42와 구리 리드프레임과의 접착강도 및 굴곡계수를 측정하였다. 또한, 구리의 리드프레임을 사용하여 48 TQFP를 성형하였으며, 후경화시킨 후 85℃, 85%RH의 조건에서 각각 168시간 동안 흡습시킨 뒤, 245℃에서 10초동안 IR리플로우를 통과시켜 전처리를 실시하고 패키지 크랙을 관찰하여 표 1에 함께 나타내었다.After the test piece was prepared for the epoxy resin composition thus obtained and cured at 175 ° C. for 6 hours, the adhesive strength between the alloy 42 and the copper lead frame and the bending coefficient were measured. In addition, 48 TQFP was formed by using a lead frame of copper, and after curing, after absorbing for 168 hours at 85 ° C. and 85% RH, respectively, and pretreatment was performed by passing an IR reflow at 245 ° C. for 10 seconds. The package cracks were observed and shown in Table 1 together.
비교예 1∼3Comparative Examples 1 to 3
표 1에 표시한 바와 같이 각 성분을 주어진 조성대로 정량하여 실시예와 같은 방법으로 에폭시 수지 조성물을 제조하였으며, 접착강도와 굴곡계수의 측정 및 패키지크랙을 관찰하였다.As shown in Table 1, each component was quantified according to a given composition to prepare an epoxy resin composition in the same manner as in Example, and the measurement of adhesive strength and bending coefficient and package cracks were observed.
이상에서 살펴본 바와 같이 본 발명에 따라 제조된 에폭시 수지 조성물을 사용하여 반도체 소자를 봉지하는 경우 구리 리드프레임과의 접착강도가 우수하게되고, 이로 인해 크랙발생을 억제할 수 있는 양호한 반도체 소자를 수득할 수 있게된다.As described above, when the semiconductor device is encapsulated using the epoxy resin composition prepared according to the present invention, the adhesive strength with the copper lead frame is excellent, thereby obtaining a good semiconductor device capable of suppressing cracking. Will be.
Claims (3)
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| Application Number | Priority Date | Filing Date | Title |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5759366A (en) * | 1980-09-26 | 1982-04-09 | Nitto Electric Ind Co Ltd | Epoxy resin composition for sealing semiconductor |
| JPS604527A (en) * | 1983-06-21 | 1985-01-11 | Denki Kagaku Kogyo Kk | Epoxy resin composition |
| JPS61203160A (en) * | 1985-03-06 | 1986-09-09 | Fujitsu Ltd | Epoxy resin composition for sealing semiconductor |
| JPH02219815A (en) * | 1989-02-21 | 1990-09-03 | Three Bond Co Ltd | Epoxy resin composition |
| KR19980064257A (en) * | 1996-12-19 | 1998-10-07 | 카나가와치히로 | Epoxy Resin Compositions and Semiconductor Devices |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5759366A (en) * | 1980-09-26 | 1982-04-09 | Nitto Electric Ind Co Ltd | Epoxy resin composition for sealing semiconductor |
| JPS604527A (en) * | 1983-06-21 | 1985-01-11 | Denki Kagaku Kogyo Kk | Epoxy resin composition |
| JPS61203160A (en) * | 1985-03-06 | 1986-09-09 | Fujitsu Ltd | Epoxy resin composition for sealing semiconductor |
| JPH02219815A (en) * | 1989-02-21 | 1990-09-03 | Three Bond Co Ltd | Epoxy resin composition |
| KR19980064257A (en) * | 1996-12-19 | 1998-10-07 | 카나가와치히로 | Epoxy Resin Compositions and Semiconductor Devices |
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