WO2022104878A1 - 一种半导体芯片五边保护用液态模封胶及制备方法 - Google Patents
一种半导体芯片五边保护用液态模封胶及制备方法 Download PDFInfo
- Publication number
- WO2022104878A1 WO2022104878A1 PCT/CN2020/132155 CN2020132155W WO2022104878A1 WO 2022104878 A1 WO2022104878 A1 WO 2022104878A1 CN 2020132155 W CN2020132155 W CN 2020132155W WO 2022104878 A1 WO2022104878 A1 WO 2022104878A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mass
- parts
- epoxy resin
- semiconductor chip
- molding compound
- Prior art date
Links
- 238000000465 moulding Methods 0.000 title claims abstract description 37
- 239000004065 semiconductor Substances 0.000 title claims abstract description 20
- 239000000565 sealant Substances 0.000 title abstract description 7
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 43
- 239000003822 epoxy resin Substances 0.000 claims abstract description 30
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 30
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 19
- 239000012745 toughening agent Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000007822 coupling agent Substances 0.000 claims abstract description 14
- 239000011256 inorganic filler Substances 0.000 claims abstract description 12
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 12
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 10
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical group [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005011 phenolic resin Substances 0.000 claims abstract description 9
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims abstract description 7
- 239000004305 biphenyl Substances 0.000 claims abstract description 5
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003086 colorant Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- UXMYUFHUUYBDLL-UHFFFAOYSA-N 2,2-dimethyl-3-(oxiran-2-ylmethoxy)propan-1-ol Chemical compound OCC(C)(C)COCC1CO1 UXMYUFHUUYBDLL-UHFFFAOYSA-N 0.000 claims description 3
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 claims description 3
- -1 curing accelerator Substances 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000004848 polyfunctional curative Substances 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052710 silicon Inorganic materials 0.000 abstract description 11
- 239000010703 silicon Substances 0.000 abstract description 11
- 238000005336 cracking Methods 0.000 abstract description 4
- 239000004842 bisphenol F epoxy resin Substances 0.000 abstract description 2
- 230000002787 reinforcement Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 description 2
- 101150091203 Acot1 gene Proteins 0.000 description 2
- 102100025854 Acyl-coenzyme A thioesterase 1 Human genes 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 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
- 239000000945 filler Substances 0.000 description 2
- 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 2
- 239000010410 layer Substances 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on 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
- C08G59/62—Alcohols or phenols
-
- 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
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
Definitions
- the invention belongs to the technical field of edge protection of semiconductor chips, and in particular relates to a liquid molding compound for protecting the five edges of a semiconductor chip and a preparation method thereof.
- silicon chip edge protection technology is widely used in advanced packaging manufacturing processes, especially in the lithography process related to silicon chip metal plating, such as BUMP (bump process), RDL (redistribution layer technology) and other lithography
- silicon chip edge protection technology is required.
- a more effective method is: referring to FIG. 1, several chips 2 are arranged on the substrate 1, and an adhesive layer 3 is filled around the chips 2 to protect the edges of the chips 2 and avoid damage to the chips 2, thereby improving product reliability.
- the filled adhesive layer 3 can be quickly cured by natural flow, acting on the weirs around the chip, increasing the shock absorption performance of the chip, and can effectively reduce the overall temperature expansion between the chip and the substrate. impact, while preventing solder joint oxidation.
- the molding compound used for edge protection of silicon chips it needs to have good impact resistance, good adhesion and toughness.
- the purpose of the present invention is to provide a liquid molding compound for protecting the five sides of a semiconductor chip and a preparation method, so as to solve the common problem of easy cracking or even falling off when the molding compound is filled around the silicon chip.
- the present invention provides a liquid molding compound for protecting the five sides of a semiconductor chip, which comprises the following components:
- Curing accelerator 0.1-3 parts by mass
- Toughening agent 4 ⁇ 15 parts by mass
- Inorganic filler 75 ⁇ 150 parts by mass
- Coupling agent 0.1 ⁇ 5 parts by mass
- the epoxy resin is one or more of bisphenol A epoxy resin, double F epoxy resin, and biphenyl epoxy resin;
- the toughening agent is an adduct of epoxy resin and carboxyl-terminated liquid nitrile rubber
- the curing agent adopts phenolic resin.
- the toughening agent can be the adduct of cyclohexyl dimethanol diglycidyl ether and carboxyl-terminated liquid nitrile rubber, the adduct of neopentyl glycol glycidyl ether and carboxyl-terminated liquid nitrile rubber, bisphenol A One or more of the adduct of epoxy resin and carboxyl-terminated liquid nitrile rubber, and the adduct of phenolic epoxy resin and carboxyl-terminated liquid nitrile rubber.
- Carboxy-terminated liquid nitrile rubber can be polymerized from 2-acrylic acid, 1,3-butadiene and 2-acrylonitrile as monomers.
- the curing agent is preferably a phenol-aralkylphenol resin.
- the curing accelerator adopts imidazole curing accelerator.
- the inorganic filler is silica, preferably silica with a particle size of 0.1-30 ⁇ m.
- the coupling agent adopts a silane coupling agent.
- silane coupling agent is ⁇ -glycidyl etheroxypropyltrimethoxysilane.
- the above-mentioned liquid molding compound further includes 0.1 to 3 parts by mass of a colorant.
- the preparation method of a liquid molding compound for protecting the five sides of a semiconductor chip provided by the present invention is as follows:
- Epoxy resin, curing agent, curing accelerator, toughening agent, inorganic filler and coupling agent are mixed in parts by mass, ground to a jelly-like substance, and vacuum degassed to obtain a liquid molding compound.
- the present invention has the following characteristics and beneficial effects:
- the molding compound of the present invention has a lower coefficient of thermal expansion, and its silicon adhesive force, fracture toughness and impact strength are significantly enhanced. Using it for edge protection and reinforcement of semiconductor chips can avoid molding compounds. cracking and peeling of the mold sealant.
- Figure 1 is a schematic diagram of edge protection of silicon chips, in the figure, 1-substrate, 2-chip, 3-adhesive layer.
- the liquid molding compound for protecting the five sides of a semiconductor chip comprises 15-40 parts by mass of epoxy resin, 15-35 parts by mass of curing agent, 0.1-3 parts by mass of curing accelerator, and 4-15 parts by mass of of toughening agent, 75-150 parts by mass of inorganic filler, and 0.1-5 parts by mass of coupling agent.
- the epoxy resin adopts one or more of bisphenol A epoxy resin, double F epoxy resin and biphenyl epoxy resin
- the toughening agent adopts epoxy resin and carboxyl-terminated liquid nitrile rubber.
- Adduct the curing agent is a phenolic resin, preferably a phenol-aralkylphenolic resin, such as a commercially available liquid phenolic resin MEH-8000H product.
- the consumption of epoxy resin is preferably 15 ⁇ 30 mass parts, 30 ⁇ 40 mass parts;
- the consumption of curing agent is preferably 15 ⁇ 25 mass parts, 25 ⁇ 35 mass parts;
- the consumption of toughening agent is preferably 4 ⁇ 6 mass parts, 4 to 10 parts by mass, 6 to 10 parts by mass, 6 to 15 parts by mass, and 10 to 15 parts by mass;
- the amount of the inorganic filler is preferably 75 to 100 parts by mass, 75 to 110 parts by mass, 75 to 150 parts by mass, and 100 to 100 parts by mass. 110 parts by mass, 100-150 parts by mass, 110-150 parts by mass.
- the toughening agent can be selected from the adduct of cyclohexyl dimethanol diglycidyl ether and carboxyl-terminated liquid nitrile rubber CTBN1300X13 (such as HyPox RM22 products on the market), neopentyl glycol glycidyl ether and carboxyl-terminated liquid nitrile rubber Adducts of CTBN1300X8 (such as HyPox RM20 products on the market), adducts of bisphenol A epoxy resin and carboxyl-terminated liquid nitrile rubber CTBN1300X8 (such as HyPox RA 840 products on the market), phenolic epoxy resins and terminal Adduct of carboxylated liquid nitrile rubber CTBN1300X13 (eg HyPox RA 928 on the market).
- CTBN1300X13 such as HyPox RM22 products on the market
- CTBN1300X8 such as HyPox RM20 products on the market
- the curing accelerator is preferably an imidazole type curing accelerator, for example, imidazole type curing accelerators of 2E4MZ, 2PZ, 2PHZ and other types on the market can be selected, and the amount of the curing accelerator can be conventionally used.
- the inorganic filler conventional inorganic fillers can be used, such as silica, calcium silicate, boron nitride, etc., preferably silica.
- the coupling agent is used to form the bonding layer of the organic matrix-coupling agent-inorganic matrix, so as to connect the two materials with different properties.
- the coupling agent is preferably a silane coupling agent, specifically ⁇ -glycidyl ether can be used Oxypropyltrimethoxysilane.
- the liquid molding adhesive of the present invention may further include 0.1-3 parts by mass of a colorant, and the colorant is used to provide color to the filler. Specifically, a pigment such as carbon black can be used, and the colorant is an optional component.
- a specific preparation process of the liquid molding adhesive of the present invention is as follows: mixing epoxy resin, curing agent, curing accelerator, toughening agent, inorganic filler and coupling agent according to the above-mentioned dosages, grinding to a jelly, and vacuumizing Degassing, that is, to obtain a liquid molding compound.
- the curing agent adopts the liquid phenolic resin MEH-8000H and methyl hexahydrophthalic anhydride
- the curing accelerator adopts the 2E4MZ type curing accelerator on the market
- the toughening agent adopts the HyPox RM22 type on the market.
- the test method for the thermal expansion coefficient CTE1 is: after curing the liquid molding compound at 150C/1H, prepare a sample that meets the requirements of the standard ASTM E831-2019, and test the thermal expansion coefficient of the sample. Fracture toughness K1c was tested according to ASTM E1820-2015 standard method. Impact strength was tested according to ASTM D256-2010 (R2018) standard method.
- the test method of silicon bonding force is: refer to the standard ASTM D1002-2010, point the liquid molding glue on the test interface silicon wafer in a square area of 5mm ⁇ 5mm, after curing at 180 ° C for 1 hour, test with a universal tensile machine Shear bond strength.
- the molding compound when phenolic resin is used as the curing agent and epoxy-modified nitrile rubber is used as the toughening agent, the molding compound has lower thermal expansion coefficient, higher silicon adhesion, fracture toughness and impact strength. , which is beneficial to avoid cracking and shedding of the mold sealant.
- the curing accelerator, coupling agent and colorant in the present invention have no decisive influence on the performance of the liquid molding compound, and can be added according to the conventional dosage.
- the dosage of curing accelerator, coupling agent and colorant remains unchanged.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
一种半导体芯片（2）五边保护用液态模封胶（3）及制备方法，该液态模封胶（3）包括15～40质量份的环氧树脂，15～35质量份的固化剂，0.1～3质量份的固化促进剂，4～15质量份的增韧剂，75～150质量份的无机填料，以及0.1～5质量份的偶联剂。所述环氧树脂采用双酚A环氧树脂、双酚F环氧树脂、联苯环氧树脂中的一种或多种；所述增韧剂采用环氧树脂与端羧基液态丁腈橡胶的加成物；所述固化剂采用酚醛树脂。所述的模封胶（3）具有更低的热膨胀系数，且其硅接着力、断裂韧性及冲击强度都得到显著增强，将其利用于半导体芯片（2）的边缘保护和加固补强，可避免模封胶（3）的开裂和脱落。
Description
本发明属于半导体芯片边缘保护技术领域，具体涉及一种半导体芯片五边保护用液态模封胶及制备方法。
半导体领域中，硅芯片边缘保护技术广泛被应用于先进封装制造流程，特别是在硅芯片金属电镀相关的光刻工序中，如BUMP（凸块工艺）、RDL（重布线层技术）等光刻关键工序中，均需使用硅芯片边缘保护技术。目前，比较有效的方法是：参见图1，基板1上布设若干芯片2，在芯片2周围填充胶层3，来保护芯片2的边缘，避免芯片2出现损伤，从而提高产品可靠性。填充的胶层3能通过自然流动快速固化，作用于芯片四周围堰上，增加芯片的缓震性能，并能有效降低由于芯片与基板之间的总体温度膨胀特性不匹配或芯片切割外力造成的冲击，同时还能防止焊点氧化。对应用于硅芯片边缘保护的模封胶，其需具有良好的耐冲击性、良好的粘着力、强韧性。但目前的模封胶由于韧性不强，耐冲击性及粘着力不够，当其填充于硅芯片周围时普遍存在易裂开甚至脱落的问题。
本发明的目的是提供一种半导体芯片五边保护用液态模封胶及制备方法，以解决模封胶填充于硅芯片周围时普遍存在的易裂开甚至脱落的问题。
本发明提供的一种半导体芯片五边保护用液态模封胶，其包括如下组分：
环氧树脂 15~40质量份；
固化剂 15~35质量份；
固化促进剂 0.1-3质量份；
增韧剂 4~15质量份；
无机填料 75~150质量份；
偶联剂 0.1~5质量份；
所述环氧树脂为双酚A环氧树脂、双份F环氧树脂、联苯环氧树脂中的一种或多种；
所述增韧剂为环氧树脂与端羧基液态丁腈橡胶的加成物；
所述固化剂采用酚醛树脂。
进一步的，增韧剂可为环己基二甲醇二缩水甘油醚与端羧基液态丁腈橡胶的加成物、新戊二醇缩水甘油醚与端羧基液态丁腈橡胶的加成物、双酚A环氧树脂与端羧基液态丁腈橡胶的加成物、酚醛环氧树脂与端羧基液态丁腈橡胶的加成物中的一种或多种。
端羧基液态丁腈橡胶可以2-丙烯酸、1,3-丁二烯、2-丙烯腈为单体聚合而成。
进一步的，固化剂优选苯酚-芳烷基酚醛树脂。
进一步的，固化促进剂采用咪唑类固化促进剂。
进一步的，无机填料采用二氧化硅，优选粒径0.1~30μm的二氧化硅。
进一步的，偶联剂采用硅烷偶联剂。
进一步的，硅烷偶联剂为γ-缩水甘油醚氧丙基三甲氧基硅烷。
进一步的，上述液态模封胶还包括0.1~3质量份的着色剂。
本发明提供的一种半导体芯片五边保护用液态模封胶的制备方法为：
按质量份混合环氧树脂、固化剂、固化促进剂、增韧剂、无机填料、偶联剂，并研磨至胶状物，经真空脱泡，即得液态模封胶。
和现有技术相比，本发明具有如下特点和有益效果：
（1）选择直链环氧树脂（例如双酚A环氧树脂、双酚F环氧树脂、联苯环氧树脂）与酚醛树脂搭配，可显著降低模封胶的热膨胀系数；添加环氧改性的丁腈橡胶，环氧改性的丁腈橡胶与直链环氧树脂、酚醛树脂配合，可显著改善模封胶的韧性，提高冲击强度，增强粘合能力。
（2）本发明模封胶具有更低的热膨胀系数，且其硅接着力、断裂韧性及冲击强度都得到显著增强，将其利用于半导体芯片的边缘保护和加固补强，可避免模封胶的开裂和脱落模封胶。
图1为硅芯片边缘保护的示意图，图中，1-基板，2-芯片，3-胶层。
为了使本发明的目的、技术方案及有益效果更加清楚明白，以下将对本发明的具体实施方式做进一步详细说明。应当理解，所描述的具体实施方式仅用以解释本发明，并不用于限定本发明。
本发明提供的半导体芯片五边保护用液态模封胶，包括15~40质量份的环氧树脂，15~35质量份的固化剂，0.1~3质量份的固化促进剂，4~15质量份的增韧剂，75~150质量份的无机填料，以及0.1~5质量份的偶联剂。所述环氧树脂采用双酚A环氧树脂、双份F环氧树脂、联苯环氧树脂中的一种或多种；所述增韧剂采用环氧树脂与端羧基液态丁腈橡胶的加成物；所述固化剂采用酚醛树脂，优选苯酚-芳烷基酚醛树脂，例如市面上的液态酚醛树脂MEH-8000H产品。
环氧树脂的用量优选为15~30质量份、30~40质量份；固化剂的用量优选为15~25质量份，25~35质量份；增韧剂的用量优选为4~6质量份、4~10质量份、6~10质量份、6~15质量份、10~15质量份；无机填料的用量优选为75~100质量份、75~110质量份、75~150质量份、100~110质量份、100~150质量份、110~150质量份。
增韧剂具体可选择环己基二甲醇二缩水甘油醚与端羧基液态丁腈橡胶CTBN1300X13的加成物（例如市面上的HyPox RM22产品）、新戊二醇缩水甘油醚与端羧基液态丁腈橡胶CTBN1300X8的加成物（例如市面上的HyPox RM20产品）、双酚A环氧树脂与端羧基液态丁腈橡胶CTBN1300X8的加成物（例如市面上的HyPox RA 840产品）、酚醛环氧树脂与端羧基液态丁腈橡胶CTBN1300X13的加成物（例如市面上的HyPox RA 928产品）。
固化促进剂优选咪唑类固化促进剂，例如可选择市面上2E4MZ、2PZ、2PHZ等型号的咪唑类固化促进剂，固化促进剂的用量按常规用量即可。无机填料采用常规无机填料即可，例如二氧化硅、硅酸钙、氮化硼等，优选二氧化硅。偶联剂用来形成有机基体-偶联剂-无机基体的结合层，从而把两种性质悬殊的材料连接起来，本发明中偶联剂优选硅烷偶联剂，具体可采用γ-缩水甘油醚氧丙基三甲氧基硅烷。本发明液态模封胶还可包括0.1~3质量份的着色剂，着色剂用来给填充胶提供颜色，具体可采用炭黑等颜料，着色剂为非必要组分。
本发明液态模封胶的一种具体制备工艺如下：按上述用量份混合环氧树脂、固化剂、固化促进剂、增韧剂、无机填料、偶联剂，并研磨至胶状物，经真空脱泡，即得液态模封胶。
为进一步证明本发明液态模封胶的优点，进行如下对比试验。下述实施例及对比例中，固化剂均采用液态酚醛树脂MEH-8000H和甲基六氢苯酐，固化促进剂均采用市面上的2E4MZ型号固化促进剂；增韧剂采用市面上的HyPox RM22型号产品；填料均采用二氧化硅，着色剂均采用炭黑，偶联剂均采用γ-缩水甘油醚氧丙基三甲氧基硅烷。
实施例及对比例的配比见表1，对实施例及对比例所得产品，测试热膨胀系数CTE1、硅接着力、断裂韧行、冲击强度，所得测试数据列于表1。
本实施例中，热膨胀系数CTE1的测试方法为：将液态模封胶经150C/1H固化后，制备符合标准ASTM E831-2019要求的样品，测试样品的热膨胀系数。断裂韧性K1c根据ASTM E1820-2015标准方法测试。冲击强度根据ASTM D256-2010(R2018)标准方法测试。硅接着力的测试方法为：参考标准ASTM D1002-2010，将液态模封胶分别点在测试界面硅片上大小为5mm×5mm的方形区域，经180℃固化1小时后，用万能拉力机测试剪切粘结强度。
表1 实施例及对比例的配比及检测结果
从表1可以看出，当固化剂采用酚醛树脂同时增韧剂采用环氧改性的丁腈橡胶时，模封胶具有更低的热膨胀系数、更高的硅接着力、断裂韧性及冲击强度，有利于避免模封胶的开裂和脱落。
针对上述实施例，需要说明的是，本发明中固化促进剂、偶联剂、着色剂对液态模封胶性能无决定性影响，按常规用量添加即可，为便于比较所以几组实施例中固定固化促进剂、偶联剂、着色剂的用量不变。
上述实施例仅为多种实施例中的一种，对于本领域内的技术人员，在上述说明基础上还可以做出其他不同形式的变化或变动，而这些属于本发明实质精神而衍生出的其他变化或变动仍属于本发明保护范围。
Claims (9)
- 一种半导体芯片五边保护用液态模封胶，其特征是，包括如下组分：环氧树脂 15~40质量份；固化剂 15~35质量份；固化促进剂 0.1-3质量份；增韧剂 4~15质量份；无机填料 75~150质量份；偶联剂 0.1~5质量份；所述环氧树脂为双酚A环氧树脂、双份F环氧树脂、联苯环氧树脂中的一种或多种；所述增韧剂为环氧树脂与端羧基液态丁腈橡胶的加成物；所述固化剂采用酚醛树脂。
- 如权利要求1所述的半导体芯片五边保护用液态模封胶，其特征是：增韧剂为环己基二甲醇二缩水甘油醚与端羧基液态丁腈橡胶的加成物、新戊二醇缩水甘油醚与端羧基液态丁腈橡胶的加成物、双酚A环氧树脂与端羧基液态丁腈橡胶的加成物、酚醛环氧树脂与端羧基液态丁腈橡胶的加成物中的一种或多种。
- 如权利要求1所述的半导体芯片五边保护用液态模封胶，其特征是：所述固化剂为苯酚-芳烷基酚醛树脂。
- 如权利要求1所述的半导体芯片五边保护用液态模封胶，其特征是：所述固化促进剂采用咪唑类固化促进剂。
- 如权利要求1所述的半导体芯片五边保护用液态模封胶，其特征是：所述无机填料为粒径0.1~30μm的二氧化硅。
- 如权利要求1所述的半导体芯片五边保护用液态模封胶，其特征是：所述偶联剂为硅烷偶联剂。
- 如权利要求6所述的半导体芯片五边保护用液态模封胶，其特征是：所述硅烷偶联剂为γ-缩水甘油醚氧丙基三甲氧基硅烷。
- 如权利要求1所述的半导体芯片五边保护用液态模封胶，其特征是：还包括0.1~3质量份的着色剂。
- 如权利要求1所述的半导体芯片五边保护用液态模封胶的制备方法，其特征是：按质量份混合环氧树脂、固化剂、固化促进剂、增韧剂、无机填料、偶联剂，并研磨至胶状物，经真空脱泡，即得液态模封胶。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US17/911,431 US11643499B2 (en) | 2020-11-20 | 2020-11-27 | Liquid molding compound for protecting five edges of semiconductor chip and preparation method thereof |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011313095.4A CN112409971B (zh) | 2020-11-20 | 2020-11-20 | 一种半导体芯片五边保护用液态模封胶及制备方法 |
| CN202011313095.4 | 2020-11-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2022104878A1 true WO2022104878A1 (zh) | 2022-05-27 |
Family
ID=74778220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2020/132155 WO2022104878A1 (zh) | 2020-11-20 | 2020-11-27 | 一种半导体芯片五边保护用液态模封胶及制备方法 |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US11643499B2 (zh) |
| CN (1) | CN112409971B (zh) |
| WO (1) | WO2022104878A1 (zh) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113150730B (zh) * | 2021-05-13 | 2022-07-29 | 湖北三选科技有限公司 | 一种晶圆切割用保护胶 |
| CN113403013B (zh) * | 2021-06-30 | 2022-09-02 | 武汉市三选科技有限公司 | 半导体封装用底部填充胶及芯片倒装的半导体封装结构 |
| CN113462128B (zh) * | 2021-06-30 | 2022-10-21 | 湖北三选科技有限公司 | 一种树脂组合物、功能膜及其应用 |
| CN115305038B (zh) * | 2021-09-02 | 2023-11-28 | 天台复志新材料科技有限公司 | 一种高粘接强度的环氧胶及其制备方法 |
| CN113604184B (zh) * | 2021-10-09 | 2022-09-02 | 武汉市三选科技有限公司 | 芯片封装材料、芯片封装结构及封装方法 |
| CN114292613A (zh) * | 2022-02-16 | 2022-04-08 | 武汉市三选科技有限公司 | 复合膜、倒装led芯片及其制造方法 |
| CN115260963B (zh) * | 2022-09-27 | 2022-12-27 | 武汉市三选科技有限公司 | 低模量垂直堆叠封装用薄膜黏晶胶、其制备方法及应用 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005002311A (ja) * | 2003-02-17 | 2005-01-06 | Mitsui Chemicals Inc | 硬化剤組成物およびその用途 |
| CN104927733A (zh) * | 2015-06-24 | 2015-09-23 | 深圳先进技术研究院 | 底部填充胶及其制备方法 |
| CN104962224A (zh) * | 2015-07-06 | 2015-10-07 | 深圳先进技术研究院 | 底部填充胶及其制备方法 |
| CN110527046A (zh) * | 2019-08-19 | 2019-12-03 | 湖北三选科技有限公司 | 改质双胺型苯并恶嗪树脂及制备方法、及其在液态晶圆级封装材料中作为应力释放剂的应用 |
| CN111518499A (zh) * | 2020-06-08 | 2020-08-11 | 武汉市三选科技有限公司 | 一种高温下粘着力稳定的底部填充胶及其制备方法 |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11199841A (ja) * | 1998-01-19 | 1999-07-27 | Nitto Denko Corp | 半導体装置用接着シ―ト類と面実装型半導体装置 |
| US6565969B1 (en) * | 1999-10-21 | 2003-05-20 | 3M Innovative Properties Company | Adhesive article |
| CN100365813C (zh) * | 2004-02-03 | 2008-01-30 | 旺宏电子股份有限公司 | 光感测芯片及半导体芯片堆叠封装结构 |
| CN101286462B (zh) * | 2008-05-27 | 2010-10-20 | 北京海升天达科技有限公司 | 集成电路芯片的封胶装置、封胶方法和封装方法 |
| TW201032297A (en) * | 2009-02-20 | 2010-09-01 | Advanced Semiconductor Eng | Semiconcductor package and manufacturing method thereof and encapsulating method thereof |
| CN102086365B (zh) * | 2010-12-27 | 2013-01-23 | 东莞市腾威电子材料技术有限公司 | 一种胶黏剂及其制备方法和在集成线路板灌封中的应用 |
| CN102391813B (zh) * | 2011-09-27 | 2014-04-16 | 英特沃斯(北京)科技有限公司 | 一种单组分环氧树脂导电胶粘剂 |
| US20150017359A1 (en) * | 2013-07-11 | 2015-01-15 | Ppg Industries Ohio, Inc. | Coating compositions with improved adhesion to containers |
| CN103436210B (zh) * | 2013-08-08 | 2015-10-28 | 深圳丹邦科技股份有限公司 | 一种用于芯片封装的电绝缘树脂浆及其制备方法 |
| TWI642746B (zh) * | 2017-07-27 | 2018-12-01 | 武漢市三選科技有限公司 | 底部塡充膠組成物及使用其之底部塡充方法與電子組裝元件 |
| CN107474770A (zh) * | 2017-08-04 | 2017-12-15 | 烟台信友新材料股份有限公司 | 一种单组分高导热绝缘结构胶黏剂及其制备方法 |
| KR102621099B1 (ko) * | 2018-11-07 | 2024-01-04 | 삼성전자주식회사 | 반도체 패키지 |
| CN110845980A (zh) * | 2019-10-09 | 2020-02-28 | 深圳大学 | 一种cob封装胶及其制备方法 |
| CN111440579A (zh) * | 2019-12-24 | 2020-07-24 | 武汉市三选科技有限公司 | 一种高柔性环氧树脂胶粘剂、其制备方法以及应用 |
| CN111876111B (zh) * | 2020-07-29 | 2022-03-22 | 武汉市三选科技有限公司 | 一种高导热率的底部填充胶及其制备方法 |
-
2020
- 2020-11-20 CN CN202011313095.4A patent/CN112409971B/zh active Active
- 2020-11-27 US US17/911,431 patent/US11643499B2/en active Active
- 2020-11-27 WO PCT/CN2020/132155 patent/WO2022104878A1/zh active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005002311A (ja) * | 2003-02-17 | 2005-01-06 | Mitsui Chemicals Inc | 硬化剤組成物およびその用途 |
| CN104927733A (zh) * | 2015-06-24 | 2015-09-23 | 深圳先进技术研究院 | 底部填充胶及其制备方法 |
| CN104962224A (zh) * | 2015-07-06 | 2015-10-07 | 深圳先进技术研究院 | 底部填充胶及其制备方法 |
| CN110527046A (zh) * | 2019-08-19 | 2019-12-03 | 湖北三选科技有限公司 | 改质双胺型苯并恶嗪树脂及制备方法、及其在液态晶圆级封装材料中作为应力释放剂的应用 |
| CN111518499A (zh) * | 2020-06-08 | 2020-08-11 | 武汉市三选科技有限公司 | 一种高温下粘着力稳定的底部填充胶及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| US11643499B2 (en) | 2023-05-09 |
| US20230094916A1 (en) | 2023-03-30 |
| CN112409971B (zh) | 2022-03-22 |
| CN112409971A (zh) | 2021-02-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2022104878A1 (zh) | 一种半导体芯片五边保护用液态模封胶及制备方法 | |
| US6724091B1 (en) | Flip-chip system and method of making same | |
| JP2001519838A (ja) | エポキシシロキサン及びポリエポキシ樹脂のダイス接着剤又はカプセル材 | |
| JP3469446B2 (ja) | 樹脂組成物およびこれを用いた樹脂封止型半導体装置の製造方法 | |
| WO2017181447A1 (zh) | 一种流动型芯片级底部填充胶及其制备方法 | |
| WO2012105071A1 (ja) | 半導体樹脂封止材 | |
| JP2013006893A (ja) | 高熱伝導樹脂組成物、高熱伝導性硬化物、接着フィルム、封止用フィルム、及びこれらを用いた半導体装置 | |
| CN1732225A (zh) | 不流动的增韧的环氧树脂－酸酐底层填料密封剂 | |
| WO2010029726A1 (ja) | 半導体装置および半導体装置に用いる樹脂組成物 | |
| CN108641645A (zh) | 一种半导体密封用封装胶及其制备方法 | |
| WO2021248724A1 (zh) | 高温下粘着力稳定的底部填充胶及其制备方法 | |
| JP2009091510A (ja) | 液状エポキシ樹脂組成物及び該組成物を用いた半導体装置 | |
| CN113150730A (zh) | 一种晶圆切割用保护胶 | |
| CN106633631B (zh) | 一种高密度封装用底部填充胶及其制备方法 | |
| JP2001019745A (ja) | 半導体装置の製造方法及び半導体装置 | |
| JP2006169395A (ja) | アンダーフィル樹脂組成物 | |
| JPH06345847A (ja) | エポキシ樹脂組成物及び半導体装置 | |
| JP3819148B2 (ja) | エポキシ封止用樹脂組成物、それを用いた半導体装置、半導体チップモジュール、および半導体チップパッケージ | |
| JP2011192818A (ja) | 半導体チップ接合用接着フィルム | |
| JP2002226675A (ja) | 絶縁性ペースト | |
| JP2001226455A (ja) | 液状封止用樹脂組成物 | |
| JP2004518796A (ja) | アンダーフィル組成物 | |
| JP2010209266A (ja) | 半導体封止用液状エポキシ樹脂組成物、及びそれをアンダーフィル材として用いて封止したフリップチップ型半導体装置 | |
| JP2008277631A (ja) | 半導体装置 | |
| JP3578592B2 (ja) | 半導体用ダイアタッチ樹脂ペースト |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 20962169 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 20962169 Country of ref document: EP Kind code of ref document: A1 |