CN114196359A - Chip-level underfill with low thermal expansion coefficient - Google Patents
Chip-level underfill with low thermal expansion coefficient Download PDFInfo
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- CN114196359A CN114196359A CN202111435897.7A CN202111435897A CN114196359A CN 114196359 A CN114196359 A CN 114196359A CN 202111435897 A CN202111435897 A CN 202111435897A CN 114196359 A CN114196359 A CN 114196359A
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- 239000003822 epoxy resin Substances 0.000 claims abstract description 49
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 49
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 9
- 150000001412 amines Chemical class 0.000 claims abstract description 7
- 239000007822 coupling agent Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 15
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- MEVBAGCIOOTPLF-UHFFFAOYSA-N 2-[[5-(oxiran-2-ylmethoxy)naphthalen-2-yl]oxymethyl]oxirane Chemical compound C1OC1COC(C=C1C=CC=2)=CC=C1C=2OCC1CO1 MEVBAGCIOOTPLF-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- -1 m-aminomethane Chemical compound 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 2
- CBEVWPCAHIAUOD-UHFFFAOYSA-N 4-[(4-amino-3-ethylphenyl)methyl]-2-ethylaniline Chemical compound C1=C(N)C(CC)=CC(CC=2C=C(CC)C(N)=CC=2)=C1 CBEVWPCAHIAUOD-UHFFFAOYSA-N 0.000 claims description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 2
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- IPRDLZOQLUYGNI-UHFFFAOYSA-N n-benzyl-n-(dibenzylamino)oxy-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(ON(CC=1C=CC=CC=1)CC=1C=CC=CC=1)CC1=CC=CC=C1 IPRDLZOQLUYGNI-UHFFFAOYSA-N 0.000 claims 1
- 239000013638 trimer Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 36
- 239000000945 filler Substances 0.000 abstract description 13
- 229920005989 resin Polymers 0.000 description 31
- 239000011347 resin Substances 0.000 description 31
- 238000002360 preparation method Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 239000006229 carbon black Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000006087 Silane Coupling Agent Substances 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- 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 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011049 filling Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 3
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- 101150091203 Acot1 gene Proteins 0.000 description 2
- 102100025854 Acyl-coenzyme A thioesterase 1 Human genes 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
Classifications
-
- 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
- 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
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
The invention relates to a chip-level underfill with low thermal expansion coefficient, which comprises the following raw materials in parts by weight: 22-33 parts of epoxy resin, 0.5-1 part of coupling agent, 0.5-1 part of defoaming agent, 0.5-1 part of black paste, 65-70 parts of various spherical silicon dioxide and 8-12 parts of amine curing agent. The invention introduces the epoxy resin with a special structure, adopts the combination of various fillers, and can obviously reduce the thermal expansion coefficient of the chip-level underfill material while ensuring the good fluidity of the underfill.
Description
Technical Field
The invention relates to a chip-level underfill material with a low thermal expansion coefficient, and belongs to the field of single-component and thermosetting epoxy electronic adhesive materials.
Background
In the chip packaging technology, a bonding layer of an IC chip and an organic substrate is composed of a large number of welding spots with micro sizes, the welding spots have poor deformation adaptability and are extremely sensitive to thermal stress, and the problem of structural reliability is more prominent. The use of polymer underfill to improve the reliability of packaged chips is a new approach developed in recent years. The method is economical and easy, and during the chip packaging process, the Underfill material (Underfill) is gradually solidified and formed in the slit between the IC chip and the organic substrate by thermosetting action, and the connected welding spots are protected. Meanwhile, the impact load can be effectively reduced, the performances of deformation resistance, moisture resistance, chemical corrosion resistance and the like of the packaged chip are improved, and the fatigue life of the packaged chip can be greatly prolonged, so that the chip packaging structure has great development potential.
The chip-level underfill material is a single-component liquid material before being cured at normal temperature, and mainly comprises epoxy resin and spherical silicon dioxide with a large amount of addition. The chip-level underfill material has a high viscosity at normal temperature, and at a high process operation temperature, the viscosity becomes very low, and the material can easily flow into a gap between a silicon chip and a PCB substrate through capillary action, and then is cured to form a filling-type protective layer. The chip-level underfill material can be directly contacted with three different materials, namely a silicon chip, a PCB (printed Circuit Board) base material and a soldering tin ball, and the three materials simultaneously cover inorganic non-metallic materials, polymer composite materials and metal materials. Because of the difference in thermal expansion coefficients of these three materials, the thermal expansion coefficients of the chip-level underfill material are required to be "balanced" to better protect the chip material. Therefore, the lower the thermal expansion coefficient of the chip-level underfill material is, the more the chip-level underfill material can play a role in balancing, and the warping degree of the material can be reduced, so that the material can be ensured to pass reliability experiments, and the problem of reliability failure of a semiconductor packaging part can be guided to be solved.
Disclosure of Invention
Aiming at the technical problems, the invention provides a chip-level underfill with a low thermal expansion coefficient and a preparation method thereof. By adding a proper amount of the special epoxy resin and optimizing the addition of the spherical silicon dioxide in different proportion forms, the level of the thermal expansion coefficient of the material can be fully reduced from the two directions of the molecular structure after curing and the addition of the filler.
The specific technical scheme is as follows:
one of the purposes of the invention is to provide a chip-level underfill with a low thermal expansion coefficient, which comprises the following raw materials in parts by weight:
22-33 parts of epoxy resin, 0.5-1 part of coupling agent, 0.5-1 part of defoaming agent, 0.5-1 part of black paste, 65-70 parts of various spherical silicon dioxide and 8-12 parts of amine curing agent.
Further, the epoxy resin comprises 10-15 parts of conventional epoxy resin and 12-18 parts of special epoxy resin; the mass ratio of the conventional epoxy resin to the special epoxy resin is preferably 1: (1-3).
Still further, the plurality of spherical silicas are preferably 3 to 4, with average particle diameters of preferably 0.5 μm, 1 μm, 2 μm, 5 μm, and maximum particle diameters of preferably 5 μm, 10 μm, 20 μm.
Wherein the conventional epoxy resin is bisphenol A type epoxy resin or/and bisphenol F type epoxy resin; specifically, it may be one or a combination of two or more of EXA-830 CRP of DIC, 370 resin of friendship from Shanghai, RE-303S-L (bisphenol F type epoxy resin) of Japan chemical, EXA-850 CRP of DIC, 328 resin of friendship from Shanghai, RE-310S (bisphenol A type epoxy resin) of Japan chemical, EXA-830 LVP, EXA-835 LVP, and KF-8110 (bisphenol A/bisphenol F mixed type epoxy resin) of DIC from Japan. In the above resins, bisphenol a epoxy resin and bisphenol F epoxy resin are main resins of the entire adhesive, and as a skeleton function, the bisphenol a epoxy resin has higher strength but higher viscosity, and the bisphenol F epoxy resin has lower viscosity but lower strength, compared with the bisphenol a epoxy resin and the bisphenol F epoxy resin.
Wherein the special epoxy resin is one or more of ELM-100H of Sumitomo Japan, MY0510 and MY0500 of Hunsmann USA, AFG-90H, EBA-65 of the friendship of Shanghai, SW-0510, SW-70, SW-80, SWE90 of Sagnan Severv, YLSE-900S of GLK of Korea, HP-4032D of DIC Japan, and CER-3000-L of Nippon Chemicals. Some of the resins contain a multifunctional group structure, which can improve the curing crosslinking density, and some contain a rigid structure, which can reduce the thermal expansion coefficient of the material in both directions. The epoxy resin composition is characterized in that ELM-100H, MY0510 and AFG-90H, SW-0510 are trifunctional epoxy resin, SW-70 and SW-80 are tetrafunctional epoxy resin, MY0500 and SWE90 are alicyclic trifunctional epoxy resin, and the multifunctional structure can improve curing crosslinking density and further reduce thermal expansion coefficient. Wherein EBA-65 and YLSE-900S, HP-4032D are naphthalene type epoxy resin, CER-3000-L is biphenyl type epoxy resin, and the epoxy resin with rigid structure can improve the heat resistance of the material and reduce the coefficient of thermal expansion. The ratio of multifunctional epoxy resin to rigid-structure-containing epoxy resin is here 1: (0.5-2), wherein 1: 1.
further, the coupling agent is one or more than two of gamma-aminopropyl triethoxysilane, gamma-mercaptopropyl trimethoxysilane, gamma-mercaptopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane and gamma-aminopropyl trimethoxysilane. The black paste is preferably carbon black. The antifoaming agent is 1799 of the mai chart.
Further, the amine curing agent is one or more than two of 4, 4 '-diamino-3, 3' -diethyl diphenylmethane, diethyl toluenediamine, diamino diphenyl sulfone, m-amino methylamine, xylylene diamine tripolymer, dibenzyl amino ether and diethyl toluenediamine.
Further, the spherical silicon dioxide is compounded by multiple of FE 920A-SQ, SE6050, SE 6050-SED, SE 6050-STE, SE 5050-SEJ, SE 505G-SEJ, SE-203G-SEJ and SO-E2/24C of Yayuma, Japan. One or more than two types of models. In the above spherical silica, the average particle diameter is selected from the group consisting of 0.5 μm, 1 μm, 2 μm, 5 μm, and 10 μm, and the maximum particle diameter is selected from the group consisting of 5 μm, 10 μm, and 20 μm. The optimal filler compounding ratio can be obtained through calculation of a Horsfield spherical stacking model, more fillers can be added into the whole system, lower viscosity can be obtained, and the filling fluidity at high temperature can be better. While ensuring a high loading, the spherical silica is packed as densely as possible, which results in a low coefficient of thermal expansion, in addition to satisfying the flow-filling properties of the material.
Another object of the present invention is to provide a method for preparing the chip-scale underfill adhesive, which comprises the following steps:
blending epoxy resin, coupling agent, black paste and defoaming agent, stirring for 1-2 h, adding various spherical silicon dioxide, heating and stirring for 4-6 h at 70-90 ℃, cooling to normal temperature, adding amine curing agent, controlling the temperature to be 25-30 ℃, and stirring for 1-2 h to obtain the epoxy resin-modified epoxy resin.
Further, the whole preparation process is carried out under vacuum condition, preferably, the whole process is maintained at vacuum degree of not less than-0.08 MPa.
The invention has the beneficial effects that: the special epoxy resin is introduced into the formula of the chip-level underfill material according to the optimal proportion, and a plurality of spherical silica fillers are introduced at the same time, so that the thermal expansion coefficient of the chip-level underfill material after curing can be obviously reduced. The invention is more novel and special in that the special epoxy resin is used in a matching proportion and a plurality of spherical silicon dioxide fillers are used in a compounding proportion in a combined way.
The coefficient of thermal expansion CTE1 of the conventional chip-level underfill material is 25-35 ppm/DEG C, the CTE2 is 90-100 ppm/DEG C, when the conventional chip-level underfill material is applied to a large-size chip packaging test, the intrinsic stress of the underfill material exists, and the coefficient of thermal expansion between the underfill material and a silicon chip, a PCB substrate and a solder ball cannot be well matched. After curing, reliability tests are performed on the packaged chip assembly for the reasons, such as cold and hot cycles, high-temperature storage, high temperature and high humidity, the underfill materials under the two opposite corners of the chip are easy to warp, and failure modes such as stripping delamination and cracks occur. The chip-scale underfill prepared in this patent can have a CTE1 as low as 18-20 ppm/deg.C and a CTE2 as low as 70-80 ppm/deg.C under the same test conditions, which can largely eliminate failure modes caused by the failure to match the thermal expansion coefficients of the materials well.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
12g of EXA-830 CRP resin, 6g of SW-70 resin, 6g of YLSE-900S resin, 0.5g of KH560 silane coupling agent, 0.5g of defoaming agent and 0.5g of carbon black are added into a high-speed planetary stirrer, after stirring for 2 hours, FE 920A-SQ 40g and SE 6050-STE 26g are sequentially added into the stirrer in three times, the temperature is set to be 85 ℃, the stirring is carried out for 4 hours by heating, the heating is stopped, the stirrer is cooled to the normal temperature by condensed water, 8.5g of curing agent diethyltoluenediamine is added, after the stirring is carried out for 2 hours at the normal temperature by controlling the temperature, the preparation process is ended, and the vacuum degree is not lower than-0.08 MPa in the whole process.
Example 2
8g of EXA-830 CRP resin, 8g of SW-70 resin, 8g of YLSE-900S resin, 0.5g of KH560 silane coupling agent, 0.5g of defoaming agent and 0.5g of carbon black are added into a high-speed planetary stirrer, after stirring for 2 hours, FE 920A-SQ 40g and SE 6050-STE 26g are sequentially added into the stirrer in three times, the temperature is set to be 85 ℃, the stirring is carried out for 4 hours by heating, the heating is stopped, the stirrer is cooled to the normal temperature by condensed water, 8.5g of curing agent diethyl toluenediamine is added, after the stirring is carried out for 2 hours at the normal temperature by controlling the temperature, the preparation process is ended, and the vacuum degree is not lower than-0.08 MPa in the whole process.
Example 3
6g of EXA-830 CRP resin, 9g of SW-70 resin, 9g of YLSE-900S resin, 0.5g of KH560 silane coupling agent, 0.5g of defoaming agent and 0.5g of carbon black are added into a high-speed planetary stirrer, after stirring for 2 hours, FE 920A-SQ 40g and SE 6050-STE 26g are sequentially added into the stirrer in three times, the temperature is set to be 85 ℃, the stirring is carried out for 4 hours by heating, the heating is stopped, the stirrer is cooled to the normal temperature by condensed water, 8.5g of curing agent diethyltoluenediamine is added, after the stirring is carried out for 2 hours at the normal temperature by controlling the temperature, the preparation process is ended, and the vacuum degree is not lower than-0.08 MPa in the whole process.
Example 4
6G of EXA-830 CRP resin, 9G of SW-70 resin, 9G of YLSE-900S resin, 0.5G of KH560 silane coupling agent, 0.5G of defoaming agent and 0.5G of carbon black are added into a high-speed planetary stirrer, after stirring for 2 hours, FE 920A-SQ 35G, SE 6050-STE 25G and SE-203G-SEJ 8G are sequentially added into the stirrer in three times, the temperature is set to be 85 ℃, the stirring is heated and stirred for 4 hours, the heating is closed, the stirrer is cooled to the normal temperature by condensed water, 8.5G of curing agent diethyl toluenediamine is added, the temperature is controlled and the stirring is maintained at the normal temperature for 2 hours, the preparation process is ended, and the vacuum degree is not lower than-0.08 MPa in the whole process.
Example 5
6G of EXA-830 CRP resin, 9G of SW-70 resin, 9G of YLSE-900S resin, 0.5G of KH560 silane coupling agent, 0.5G of defoaming agent and 0.5G of carbon black are added into a high-speed planetary stirrer, after stirring for 2 hours, FE 920A-SQ 35G, SE 6050-STE 25G, SE-203G-SEJ 10G and SO-E2/24C 6G are sequentially added into the stirrer in three times, the stirring is carried out at a set temperature of 85 ℃, the heating and stirring are carried out for 4 hours, the heating are stopped, the stirrer is cooled to the normal temperature by introducing condensed water, 8.5G of curing agent diethyl toluenediamine is added, after the stirring is carried out for 2 hours at the normal temperature, the preparation process is ended, and the vacuum degree is not lower than-0.08 MPa in the whole process.
Example 6
6G of EXA-830 CRP resin, 9G of SW-70 resin, 9G of YLSE-900S resin, 0.5G of KH560 silane coupling agent, 0.5G of defoaming agent and 0.5G of carbon black are added into a high-speed planetary stirrer, after stirring for 2 hours, SE 6050-STE 35G, SE-203G-SEJ 25G and SO-E2/24C 8G are sequentially added into the stirrer in three times, the temperature is set to be 85 ℃, the stirring is heated and stirred for 4 hours, the heating is stopped, the stirrer is cooled to the normal temperature by condensed water, 8.5G of curing agent diethyl toluenediamine is added, after the stirring is maintained for 2 hours at the normal temperature, the preparation process is ended, and the vacuum degree is not lower than-0.08 MPa in the whole process.
Comparative example 1
Adding 24g of EXA-830 CRP resin, 0.5g of KH560 silane coupling agent, 0.5g of defoaming agent and 0.5g of carbon black into a high-speed planetary stirrer, stirring for 2 hours, sequentially adding FE 920A-SQ 40g and SE 6050-STE 26g for three times, setting the temperature to be 85 ℃, heating and stirring for 4 hours, closing the heating, cooling the stirrer to the normal temperature by introducing condensed water, adding 8.5g of curing agent diethyl toluenediamine, stirring for 2 hours at the normal temperature under controlled temperature, finishing the preparation process, and keeping the vacuum degree not lower than-0.08 MPa in the whole process.
Comparative example 2
6g of EXA-830 CRP resin, 9g of MY0510 resin, 9g of YLSE-900S resin, 0.5g of KH560 silane coupling agent, 0.5g of defoaming agent and 0.5g of carbon black are added into a high-speed planetary stirrer, after stirring for 2 hours, only FE 920A-SQ 66g is added, the temperature is set to be 85 ℃, the stirring is heated for 4 hours, the heating is closed, the stirrer is cooled to the normal temperature through condensed water, 8.5g of curing agent diethyl toluenediamine is added, after the stirring is maintained at the normal temperature for 2 hours, the preparation process is ended, and the vacuum degree is not lower than-0.08 MPa in the whole process.
Testing
The viscosities of the products obtained in examples 1 to 6 and comparative examples 1 and 2 are shown in Table 1; the thermal expansion coefficient test results of the cured samples are shown in table 2.
And (3) viscosity testing: measuring at room temperature for 20s with Haake viscometer (Thermofeisher, USA) and C20/2 rotor-1Viscosity of water; the viscosity at 110 ℃ was measured using a TA rheometer.
A sample preparation process: preheating a 5mm by 5mm polytetrafluoroethylene mold in a drying oven at 110-130 ℃, injecting glue into the mold after preheating, and properly beating the mold to discharge air bubbles possibly generated in the glue.
And (3) curing process: and (3) placing the dispensed simulation chip in a blast oven, raising the temperature from room temperature to 165 ℃ at the speed of 5 ℃/min, maintaining the temperature at 165 ℃ for 2 hours, naturally cooling to room temperature to finish curing, taking out the sample after curing and forming, observing each surface, grinding possible defects and then testing.
The thermal expansion coefficient test method comprises the following steps: the test was carried out using a static thermomechanical analyzer (TMA) and, after the sample was placed in the furnace, the program was set up as: firstly, the temperature in the furnace is reduced to-20 ℃, the temperature is increased to 150 ℃ from-20 ℃ at the speed of 3 ℃/min, and then is reduced to-20 ℃ at the speed of 3 ℃/min, in order to eliminate the internal stress of the material, the temperature is increased to 260 ℃ at the speed of 3 ℃/min, and then is reduced to-20 ℃ at the speed of 3 ℃/min, and the whole process is finished.
The thermal expansion coefficient value taking method comprises the following steps: and (3) carrying out data processing on TMA data processing software, and in order to ensure that the performance parameters of all the materials can be compared in parallel, the unified value taking method comprises the following steps: taking the value on the last cooling curve, wherein the slope obtained at 0-40 ℃ is the thermal expansion coefficient below the Tg temperature of the material and is recorded as CTE1The slope taken at 170-200 ℃ is the coefficient of thermal expansion above the Tg of the material, denoted CTE2。
TABLE 1 test results of room temperature viscosity and 110 ℃ viscosity of examples and comparative examples
TABLE 2 thermal expansion coefficient and Tg test results after curing for examples and comparative examples
The viscosity is one of the important indexes of the chip-level underfill, and is directly related to the flow property and the filling effect when filling the bottom of the chip, as can be seen from the data in Table 1 for examples 1-3, as the room temperature viscosity and the viscosity at 110 ℃ of the glue increased with the addition of the specialty epoxy resin to the formulation, this is because the special epoxy resin contains a rigid structure such as a benzene ring or a naphthalene ring, for example, YLSE-900S contains a rigid structure, and has a large steric hindrance, therefore, the adhesive has higher viscosity per se, and as can be seen from the data of examples 4 to 6, the viscosity of the adhesive at room temperature and the viscosity at 110 ℃ are obviously increased along with the addition of the filler with smaller particle size, this is because, at the same mass, smaller particle size fillers have a greater specific surface area, require more resin or adjuvant to wet, equivalent to "taking up" more resin and adjuvant, and therefore increase in viscosity is significant.
As shown by the data of examples 1-3 in Table 2, the coefficient of thermal expansion gradually decreased with increasing amounts of specialty epoxy resin added because of the: SW-70 contains polyfunctional groups, the crosslinking density can be effectively increased, the rigid structure in YLSE-900S can enable the material to have larger volume steric hindrance after curing, and the synergistic effect between the two can enable the material to have lower thermal expansion coefficient, and as can be seen from the data of examples 4-6, the thermal expansion coefficient can be further reduced along with the addition of the filler with small particle size, because the filler with smaller particle size can be filled in the adjacent gaps of the filler with larger particle size, the resin and the filler can be better infiltrated, the filler is prevented from settling or resin enrichment to a certain extent, and thus the thermal expansion coefficient can reach a lower level.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. The chip-level underfill with low thermal expansion coefficient is characterized by comprising the following raw materials in parts by weight:
22-33 parts of epoxy resin, 0.5-1 part of coupling agent, 0.5-1 part of defoaming agent, 0.5-1 part of black paste, 65-70 parts of various spherical silicon dioxide and 8-12 parts of amine curing agent.
2. The chip scale underfill according to claim 1, wherein the epoxy resin comprises 10-15 parts of a conventional epoxy resin and 12-18 parts of a specialty epoxy resin; the mass ratio of the conventional epoxy resin to the special epoxy resin is 1: (1-3).
3. The chip scale underfill according to claim 2, wherein said conventional epoxy resin is bisphenol a type epoxy resin or/and bisphenol F type epoxy resin; the special epoxy resin is one or more of ELM-100H of Sumitomo Japan, MY0510 and MY0500 of Hunsmann, AFG-90H, EBA-65 of Shanghai Walker, SW-0510, SW-70 and SW-80 of Hunan Severv, YLSE-900S of Korea GLK, HP-4032D of DIC Japan and CER-3000-L of Japan chemical; wherein ELM-100H, MY0510, AFG-90H, SW-0510, SW-70, SW-80, MY0500 and SWE90 are multifunctional epoxy resin, EBA-65 and YLSE-900S, HP-4032D, CER-3000-L are epoxy resin containing a rigid structure, and the ratio of the multifunctional epoxy resin to the epoxy resin containing the rigid structure is 1: (0.5-2).
4. The chip-scale underfill according to claim 1, wherein the coupling agent is one or more of γ -aminopropyltriethoxysilane, γ -mercaptopropyltrimethoxysilane, γ -mercaptopropyltriethoxysilane, γ -glycidoxypropyltrimethoxysilane, and γ -aminopropyltrimethoxysilane.
5. The chip scale underfill according to claim 1, wherein said amine curing agent is one or more of 4, 4 '-diamino-3, 3' -diethyldiphenylmethane, diethyltoluenediamine, diaminodiphenylsulfone, m-aminomethane, xylylenediamine trimer, dibenzylaminoether, diethyltoluenediamine.
6. The chip scale underfill according to claim 1, wherein said plurality of spherical silicas are a plurality of combinations of SE6050, SE 6050-SED, SE 6050-STE, SE 5050-SEJ, SE 605G-SEJ, SE 505G-SEJ, SE-203G-SEJ, SO-E2/24C, manufactured by the company Admatechs, japan.
7. The chip scale underfill of claim 1, wherein the anti-foaming agent is michael 1799.
8. A method of preparing the chip scale underfill according to any one of claims 1 to 7, comprising the steps of:
blending epoxy resin, coupling agent, black paste and defoaming agent, stirring for 1-2 h, adding various spherical silicon dioxide, heating and stirring for 4-6 h at 70-90 ℃, cooling to normal temperature, adding amine curing agent, controlling the temperature to be 25-30 ℃, and stirring for 1-2 h to obtain the epoxy resin-modified epoxy resin.
9. The method of claim 8, wherein the whole process is performed under vacuum.
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| CN117186820A (en) * | 2023-11-03 | 2023-12-08 | 武汉市三选科技有限公司 | Adjustable underfill, preparation method thereof and chip packaging structure |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105295796A (en) * | 2015-11-27 | 2016-02-03 | 烟台德邦科技有限公司 | High-reliability epoxy bottom filling glue and preparation method thereof |
| CN112724899A (en) * | 2020-12-30 | 2021-04-30 | 深圳先进电子材料国际创新研究院 | Underfill adhesive |
-
2021
- 2021-11-29 CN CN202111435897.7A patent/CN114196359A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105295796A (en) * | 2015-11-27 | 2016-02-03 | 烟台德邦科技有限公司 | High-reliability epoxy bottom filling glue and preparation method thereof |
| CN112724899A (en) * | 2020-12-30 | 2021-04-30 | 深圳先进电子材料国际创新研究院 | Underfill adhesive |
Non-Patent Citations (1)
| Title |
|---|
| 叶青萱 等: "《胶粘剂》", vol. 1, 中国物资出版社, pages: 129 - 130 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117186820A (en) * | 2023-11-03 | 2023-12-08 | 武汉市三选科技有限公司 | Adjustable underfill, preparation method thereof and chip packaging structure |
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