CN104212365B - A kind of no-flow underfill material and preparation method thereof - Google Patents
A kind of no-flow underfill material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of no-flow underfill material and preparation method thereof, described a kind of no-flow underfill material is with acrylate monomer, bismaleimides, maleation polyhutadiene, silane coupling agent, ball-shaped silicon micro powder, initiator, stopper is raw material, by joining in stirred vessel respectively, stir under vacuum conditions, namely discharging obtains product, obtained no-flow underfill material has and helps weldering effect preferably, there is high-modulus, high reliability, high glass-transition temperature, low linear expansion coefficient, be applicable to chip size larger, tin sphere gap is less, the encapsulation of the less low k flip-chip of tin ball.
Description
Technical field
The present invention relates to a kind of no-flow underfill material and preparation method thereof, belong to electronics adhesive field.
Background technology
Normal capillary pipe underfill uses after the interconnected formation of flip-chip; under capillary action; resin flows in the gap of chip and substrate; then be heating and curing; space big area bottom flip-chip is filled up; thus the stress reduced on solder joint and chip, and protect IC and solder joint, extend its work-ing life.Along with semiconductor packages develops to lower than 0.1 μm of characteristic dimension, the demand of encapsulation is also being improved, narrow in flip-chip tin ball distance, under tin ball size is less, chip size is larger trend, the flowing of normal capillary pipe underfill will face huge challenge.
In addition, along with IC manufactures towards small size and high-density future development, interconnectedly postponed into principal contradiction, therefore brought the demand to interconnecting material and interlevel dielectric material.People successfully adopt low K(specific inductivity) flip-chip to be to improve the working speed of electronic devices and components and to reduce power consumption.But low-k materials has the shortcomings such as porous, frangible and physical strength be low mostly, so the selection of underfill is particularly crucial.Because it does not protect solder joint by means of only the mode of stress redistribution, but also protection to be provided for low k dielectric and with the interface of silicon.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of no-flow underfill material and preparation method thereof is provided, this no-flow underfill material is first applying glue on substrate before chip attachment, is then aimed at by chip and is placed on substrate, more whole assembly is passed through reflow soldering.Formed interconnected in reflow ovens chips with being welded by solder bump between substrate, simultaneously underfill is solidified.After using this underfill, avoid and use discharging and two of cleaning scaling powder processing steps of common bottom packing material, and avoid Capillary Flow, thus improve the production efficiency of underfill technique.Simultaneously, obtained no-flow underfill material has and helps weldering effect preferably, has high-modulus, high reliability, high glass-transition temperature, low linear expansion coefficient, is applicable to chip size larger, tin sphere gap is less, the encapsulation of the less low k flip-chip of tin ball.
The technical scheme that the present invention solves the problems of the technologies described above is as follows:
A kind of no-flow underfill material, is made up of the former material of following mass parts: acrylate monomer 20-40 part, bismaleimides 5-10 part, maleation polyhutadiene 1-10 part, silane coupling agent 0.1-1 part, ball-shaped silicon micro powder 50-70 part, initiator 0.1-1 part, stopper 0.01-0.1 part.
Further, described acrylate monomer is isobornyl methacrylate, 1,4 butylene glycol diacrylates, 1, a kind of or several arbitrarily mixture in 6 hexanediyl esters, dihydroxyphenyl propane ethoxy acid diacrylate, diglycidyl rthers of bisphenol-A diacrylate, Viscoat 295, pentaerythritol triacrylate.
Further, the structural formula of described bismaleimides is
Wherein R is one or more in aliphatic alkane, aromatic hydrocarbon.
Further, described maleation polyhutadiene is a kind of or several arbitrarily mixture in 130MA8,130MA13,130MA20 of CaryValley.
Further, described silane coupling agent is a kind of or several arbitrarily mixture in γ-(methacryloxypropyl) propyl trimethoxy silicane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-aminopropyl triethoxysilane.
Further, described ball-shaped silicon micro powder is a kind of or several arbitrarily mixture in SE2030, SE2050, SC2500SQ of Admatechs company.
Further, described initiator is a kind of or several arbitrarily mixture in dibenzoyl peroxide (BPO), the peroxidation-2-ethyl acid tert-butyl ester, peroxidation-2 ethyl hexanoic acid tert-pentyl ester, percarbonic acid two (2-ethylhexyl), peroxidized t-butyl perbenzoate.
Further, described stopper is a kind of or several arbitrarily mixture in Resorcinol, para benzoquinone, toluhydroquinone, MEHQ, 2-Tert. Butyl Hydroquinone, 5-di-tert-butyl hydroquinone.
A kind of preparation method of no-flow underfill material, comprise: first by acrylate monomer 20-40 part, bismaleimides 5-10 part, maleation polyhutadiene 1-10 part, stopper 0.01-0.1 part joins in stirred vessel, 20min is stirred under room temperature in vacuo state, and then add after ball-shaped silicon micro powder 50-70 part mixes and stir 1h under vacuum conditions, carry out three rollers again and grind 3 times, again the material after grinding is joined in stirred vessel, last add silane coupling agent 0.1-1 part successively and initiator 0.1-1 part stirs, discharging after 2h is stirred again under vacuum state.
The invention has the beneficial effects as follows: the present invention is by acrylate resin and bismaleimides free radical polymerization, toughness reinforcing and improve the consistency of acrylate and bismaleimides with maleation polyhutadiene, silane coupling agent improves the sticking power of underfill and chip and substrate, the little loading level of ball-shaped silicon micro powder thickening is large, significantly can reduce again the coefficient of expansion of underfill to obtain high reliability simultaneously, stopper is obtaining the means such as good stability in storage, obtained no-flow underfill material has high-modulus, high reliability, high glass-transition temperature, low linear expansion coefficient, better can protect low k flip-chip.Can be applicable to chip size larger, tin sphere gap is less, chip and substrate gap less, common bottom packing material cannot by the flip-chip of Capillary Flow.Eliminate the coating of common bottom packing material and the step of cleaning scaling powder, additionally reduce the time of Capillary Flow, thus improve the efficiency of Flip-Chip Using.
Embodiment
Be described principle of the present invention and feature below, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment 1
Raw material is taken according to following mass parts
Viscoat 295 15 parts
Isobornyl methacrylate 5 parts
N, N'-(4,4'-methylenediphenyl) bismaleimides 10 parts
130MA810 part
Resorcinol 0.1 part
Ball-shaped silicon micro powder SE203050 part
γ-(methacryloxypropyl) propyl trimethoxy silicane 1 part
The benzoyl peroxide tert-butyl ester 1 part
First by Viscoat 295, isobornyl methacrylate, N, N'-(4, 4'-methylenediphenyl) bismaleimides, 130MA8, Resorcinol joins in stirred vessel, 20min is stirred under room temperature in vacuo state, and then add ball-shaped silicon micro powder SE2030 mix after high-speed stirring 1h under vacuum conditions, and then grind 3 times through three rollers, again the material after grinding is joined in stirred vessel, finally add γ-(methacryloxypropyl) propyl trimethoxy silicane successively, the benzoyl peroxide tert-butyl ester stirs, vacuumize again and stir discharging after 2h.
Embodiment 2
Raw material is taken according to following mass parts
Pentaerythritol triacrylate 20 parts
Isosorbide-5-Nitrae butylene glycol diacrylate 20 parts
N, N'-penylene bismaleimides 5 parts
130MA136 part
Para benzoquinone 0.05 part
Ball-shaped silicon micro powder SE205060 part
γ-glycidyl ether oxygen propyl trimethoxy silicane 0.5 part
Peroxidation-2 ethyl hexanoic acid tert-pentyl ester 0.5 part
First by pentaerythritol triacrylate, 1,4 butylene glycol diacrylates, N, a N'-penylene bismaleimides, 130MA13, para benzoquinone join in stirred vessel, stir 20min under room temperature in vacuo state and then add ball-shaped silicon micro powder SE2050 mix after high-speed stirring 1h under vacuum conditions, and then grind 3 times through three rollers, again the material after grinding is joined in stirred vessel, finally add γ-glycidyl ether oxygen propyl trimethoxy silicane successively, peroxidation-2 ethyl hexanoic acid tert-pentyl ester stirs, then vacuumize and stir discharging after 2h.
Embodiment 3
Raw material is taken according to following mass parts
Diglycidyl rthers of bisphenol-A diacrylate 10 parts
Viscoat 295 25 parts
2,2 '-bis-[4-(4-maleimide phenoxyl) phenyl] 8 parts, propane
130MA201 part
Toluhydroquinone 0.01 part
Ball-shaped silicon micro powder SC2500SQ70 part
γ-aminopropyl triethoxysilane 0.1 part
Peroxidation-2-ethyl acid the tert-butyl ester 0.1 part
First by Viscoat 295, diglycidyl rthers of bisphenol-A diacrylate, 2, 2 '-bis-[4-(4-maleimide phenoxyl) phenyl] propane, 130MA20, toluhydroquinone joins in stirred vessel, 20min is stirred under room temperature in vacuo state, and then add ball-shaped silicon micro powder SC2500SQ mix after high-speed stirring 1h under vacuum conditions, and then grind 3 times through three rollers, again the material after grinding is joined in stirred vessel, finally add γ-aminopropyl triethoxysilane successively, peroxidation-2-ethyl acid the tert-butyl ester stirs, vacuumize again and stir discharging after 2h.
table 1 embodiment and comparative example test result
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Common bottom packing material | |
| Modulus (Gpa) | 7.5 | 5.6 | 6.5 | 3.0 |
| Tg（℃） | 195 | 176 | 183 | 70 |
| The coefficient of expansion (ppm/ DEG C) | 42 | 35 | 28 | 65 |
As can be seen from Table 1, the underfill of gained of the present invention has high-modulus, high glass-transition temperature, the advantages such as low-expansion coefficient compared with common bottom packing material, can be widely used in low k dielectric Flip-Chip Using technique.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. a no-flow underfill material, it is characterized in that, be made up of the starting material of following mass parts: acrylate monomer 20-40 part, bismaleimides 5-10 part, maleation polyhutadiene 1-10 part, silane coupling agent 0.1-1 part, ball-shaped silicon micro powder 50-70 part, initiator 0.1-1 part, stopper 0.01-0.1 part.
2. a kind of no-flow underfill material according to claim 1, it is characterized in that, described acrylate monomer is isobornyl methacrylate, 1, a kind of or several arbitrarily mixture in 4-butylene glycol diacrylate, 1,6 hexanediol diacrylate, dihydroxyphenyl propane ethoxy acid diacrylate, diglycidyl rthers of bisphenol-A diacrylate, Viscoat 295, pentaerythritol triacrylate.
3. a kind of no-flow underfill material according to claim 1, it is characterized in that, the structural formula of described bismaleimides is as follows:
Wherein R is one or more in aliphatic alkane, aromatic hydrocarbon.
4. a kind of no-flow underfill material according to claim 1, is characterized in that, described maleation polyhutadiene is a kind of or several arbitrarily mixture in 130MA8,130MA13,130MA20 of CaryValley.
5. a kind of no-flow underfill material according to claim 1, it is characterized in that, described silane coupling agent is a kind of or several arbitrarily mixture in γ-(methacryloxypropyl) propyl trimethoxy silicane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-aminopropyl triethoxysilane.
6. a kind of no-flow underfill material according to claim 1, is characterized in that, described ball-shaped silicon micro powder is a kind of or several arbitrarily mixture in SE2030, SE2050, SC2500SQ of Admatechs company.
7. a kind of no-flow underfill material according to claim 1, it is characterized in that, described initiator is a kind of or several arbitrarily mixture in dibenzoyl peroxide (BPO), the peroxidation-2-ethyl acid tert-butyl ester, peroxidation-2 ethyl hexanoic acid tert-pentyl ester, peroxy dicarbonate two (2-ethyl) ester, peroxidized t-butyl perbenzoate.
8. a kind of no-flow underfill material according to claim 1, it is characterized in that, described stopper is a kind of or several arbitrarily mixture in Resorcinol, para benzoquinone, toluhydroquinone, MEHQ, 2-Tert. Butyl Hydroquinone, 2,5 di tert butyl hydroquinone.
9. the preparation method of a kind of no-flow underfill material according to claim 1, comprise: first by acrylate monomer 20-40 part, bismaleimides 5-10 part, maleation polyhutadiene 1-10 part, stopper 0.01-0.1 part joins in stirred vessel, 20min is stirred under room temperature in vacuo state, and then add after ball-shaped silicon micro powder 50-70 part mixes and stir 1h under vacuum conditions, carry out three rollers again and grind 3 times, again the material after grinding is joined in stirred vessel, last add silane coupling agent 0.1-1 part successively and initiator 0.1-1 part stirs, discharging after 2h is stirred again under vacuum state.
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| CN108966522A (en) * | 2018-07-17 | 2018-12-07 | 天津瑞爱恩科技有限公司 | QFN chip welding spot reinforcement means and element solder joint intensifying method |
| CN115141504A (en) * | 2021-03-30 | 2022-10-04 | 宁波江北激智新材料有限公司 | Maleic anhydride polybutadiene modified ultraviolet-curing polyacrylate coating composition and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1676564A (en) * | 2004-04-01 | 2005-10-05 | 国家淀粉及化学投资控股公司 | Method to improve high temperature cohesive strength with adhesive having multi-phase system |
| CN102002209A (en) * | 2010-10-26 | 2011-04-06 | 深圳市库泰克电子材料技术有限公司 | Bottom filling glue for packaging inverted chip type semiconductor |
| CN102010686A (en) * | 2010-09-30 | 2011-04-13 | 烟台德邦电子材料有限公司 | Double-solidification system fast-flowing underfill and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1676564A (en) * | 2004-04-01 | 2005-10-05 | 国家淀粉及化学投资控股公司 | Method to improve high temperature cohesive strength with adhesive having multi-phase system |
| CN102010686A (en) * | 2010-09-30 | 2011-04-13 | 烟台德邦电子材料有限公司 | Double-solidification system fast-flowing underfill and preparation method thereof |
| CN102002209A (en) * | 2010-10-26 | 2011-04-06 | 深圳市库泰克电子材料技术有限公司 | Bottom filling glue for packaging inverted chip type semiconductor |
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