CN115818652A - Silicon dioxide filler for chip-level underfill adhesive and preparation method and application thereof - Google Patents
Silicon dioxide filler for chip-level underfill adhesive and preparation method and application thereof Download PDFInfo
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- CN115818652A CN115818652A CN202211477172.9A CN202211477172A CN115818652A CN 115818652 A CN115818652 A CN 115818652A CN 202211477172 A CN202211477172 A CN 202211477172A CN 115818652 A CN115818652 A CN 115818652A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 69
- 239000000945 filler Substances 0.000 title claims abstract description 49
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000853 adhesive Substances 0.000 title claims abstract description 5
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 5
- 239000000243 solution Substances 0.000 claims abstract description 53
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000006184 cosolvent Substances 0.000 claims abstract description 45
- 239000000843 powder Substances 0.000 claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 40
- 239000010703 silicon Substances 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 29
- 239000000725 suspension Substances 0.000 claims abstract description 26
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000004806 packaging method and process Methods 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 6
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 6
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 5
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 claims description 5
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 5
- 238000011085 pressure filtration Methods 0.000 claims description 5
- 238000004062 sedimentation Methods 0.000 claims description 5
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 claims description 5
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 150000007529 inorganic bases Chemical class 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 2
- 239000002245 particle Substances 0.000 abstract description 19
- 238000009826 distribution Methods 0.000 abstract description 13
- 229910004298 SiO 2 Inorganic materials 0.000 abstract description 7
- 239000012535 impurity Substances 0.000 abstract description 7
- 230000001276 controlling effect Effects 0.000 abstract description 6
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- 238000011112 process operation Methods 0.000 abstract description 3
- 238000007873 sieving Methods 0.000 abstract description 2
- 238000011049 filling Methods 0.000 abstract 1
- 238000004880 explosion Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000000280 densification Methods 0.000 description 5
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 5
- 239000011863 silicon-based powder Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000002285 radioactive effect Effects 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910021488 crystalline silicon dioxide Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- -1 siloxane, siloxane Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
The invention relates to a silicon dioxide filler for chip-level underfill adhesive and a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing the cosolvent solution with a silicon source compound to obtain a solution A; mixing the catalyst aqueous solution with the obtained solution A to obtain a suspension; performing solid-liquid separation to obtain suspension, and drying to obtain powder A; calcining the obtained powder A to obtain the chip-level SiO 2 And (4) filling. The chip-level silicon dioxide filler prepared by the preparation method provided by the invention has the advantages of high purity, high sphericity and low impurity ion content, and the particle size distribution meets the requirement of flip chip packaging. And the average particle size and the cut-off point of the prepared silicon dioxide can be controlled by regulating and controlling the proportion of the cosolvent, the catalyst and the silicon source compound, and subsequent grading, sieving and grading process operations are not needed.
Description
Technical Field
The invention belongs to the technical field of semiconductors, relates to silicon dioxide, and particularly relates to a silicon dioxide filler for chip-level underfill, and a preparation method and application thereof.
Background
Silicon dioxide (SiO) 2 ) The inorganic filler is widely applied to chip-level underfill, and is of great importance to stress matching, mechanical protection, reliability and the like after chip packaging. With the development of electronic devices towards thinning, high integration and multi-functionalization, the packaging form of Integrated Circuits (ICs) has begun to transition from 2D packaging to 2.1D, 2.5D and 3D packaging, and under the development trend of high-density interconnection, the distances between chips, between micro bumps and between chip and substrate become narrower and narrower, and SiO is applied to the integrated circuits 2 The particle size, the content of impurity elements and radioactive elements put new demands. At present, siO is prepared 2 The method comprises a melting method, an explosion method and a chemical synthesis method, although SiO with different grain diameters can be prepared 2 But still has certain disadvantages.
Production of SiO by fusion 2 Using crystalline silicon dioxide as raw material to prepare SiO 2 Firstly, crushing, ultrafine crushing, screening and purifying the crystalline silicon dioxide, then sending the purified powder into a high-temperature field generated by combustible gas-oxygen, regulating and controlling the surface tension of the powder in the cooling process by controlling conditions after high-temperature melting, and finally cooling and solidifying the powder into spherical SiO 2 。
But SiO obtained by the melt process 2 Has a large average particle diameter and a low sphericity, and has a high content of the radioactive element U because the crystalline silica is derived from natural quartz ore.
The burning explosion method uses superfine silicon powder as raw material to prepare spherical SiO 2 Before, the silicon powder needs to be subjected to superfine grinding and screening, combustible gas such as methane, propane, hydrogen or acetylene is combusted in oxygen-containing atmosphere through a burner by a combustion explosion method to form flame, meanwhile, the superfine silicon powder is fed into the flame to form dust cloud, and the spherical SiO is obtained by initiating combustion explosion 2 Ultrafine particles. SiO obtained by combustion and explosion method 2 The sphericity of the superfine silicon powder is high, the surface is smooth, but the superfine silicon powder is easy to cause dust explosion, and the requirements on the safety of space and equipment are extremely high. Furthermore, if a spherical SiO with a defined particle size distribution is to be obtained 2 And also to SiO 2 The products are classified, screened and graded again, and the production process is complicated.
The chemical synthesis method is that silicon compound is used as raw material, and high-purity spherical SiO is obtained through nucleation and growth processes under the action of dispersant, control agent, catalyst and the like 2 . The chemical synthesis method can be used for synthesizing SiO by controlling factors such as reaction temperature, raw material proportion, addition sequence and the like 2 The shape, the particle size and the like of the SiO are regulated and controlled, and simultaneously, the SiO 2 The content of impurity ions, radioactive elements and the like in the raw materials can be further reduced by purifying the raw materials.
The invention provides SiO based on a chemical synthesis method 2 Preparation method of (1), siO obtained by the preparation method 2 The purity of the silicon dioxide is high, the sphericity is high, the content of impurity ions is low, and the particle size distribution meets the scene requirement of flip chip packaging. Moreover, the preparation method provided by the invention can flexibly control SiO 2 Without the need for subsequent classification, sieving and grading processes.
Disclosure of Invention
The invention aims to provide a silicon dioxide filler for chip-level underfill adhesive as well as a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a silica filler for a chip-level underfill, the method comprising the steps of:
(1) Mixing the cosolvent solution with a silicon source compound to obtain a solution A;
(2) Mixing a catalyst aqueous solution with the solution A obtained in the step (1) to obtain a suspension;
(3) Performing solid-liquid separation on the suspension obtained in the step (2), and drying to obtain powder A;
(4) And (4) calcining the powder A obtained in the step (3) to obtain the chip-level silicon dioxide filler.
The preparation method provided by the invention comprises the steps of firstly, mixing a silicon source compound and a cosolvent, and gradually hydrolyzing and condensing the silicon source compound under the action of a catalyst aqueous solution to obtain a stable sol system; after solid-liquid separation, drying and sintering are carried out on gel formed by sol polymerization, the formed chip-level silicon dioxide has high purity and good sphericity, and the particle size distribution meets the packaging requirement of the flip chip.
Preferably, the cosolvent solution in step (1) comprises a cosolvent and water in a mass ratio (10-50) of (10-100), which can be, for example, 50.
Preferably, the co-solvent comprises any one of methanol, ethanol, isopropanol, or cyclohexane, or a combination of at least two of these, typical but non-limiting combinations include a combination of methanol and ethanol, a combination of ethanol and isopropanol, a combination of isopropanol and cyclohexane, a combination of methanol, ethanol and isopropanol, a combination of ethanol, isopropanol and cyclohexane, or a combination of methanol, ethanol, isopropanol and cyclohexane.
Preferably, the mass ratio of the cosolvent solution to the silicon source compound in step (1) is (1-50): 1, which can be, for example, 1:1, 5:1, 10, 1, 20, 1, 30, 1, 40, or 50.
Preferably, the silicon source compound in step (1) comprises any one of or a combination of at least two of organosilicon, siloxane or silicate, and may be, for example, a combination of organosilicon and siloxane, siloxane and silicate, organosilicon and silicate, or organosilicon, siloxane and silicate.
Preferably, the silicone comprises any one or a combination of at least two of vinyltrimethoxysilane, vinyltriethoxysilane, (3-mercaptopropyl) trimethoxysilane, allyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, or dodecyltrimethoxysilane, typical but non-limiting combinations include a combination of vinyltrimethoxysilane and vinyltriethoxysilane, (3-mercaptopropyl) trimethoxysilane and allyltrimethoxysilane, a combination of 3-glycidoxypropyltrimethoxysilane and dodecyltrimethoxysilane, a combination of vinyltrimethoxysilane, vinyltriethoxysilane and (3-mercaptopropyl) trimethoxysilane, a combination of allyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and dodecyltrimethoxysilane, or a combination of vinyltrimethoxysilane, vinyltriethoxysilane, (3-mercaptopropyl) trimethoxysilane, allyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and dodecyltrimethoxysilane.
Preferably, the siloxane comprises any one or a combination of at least two of tetramethoxysilane, tetraethoxysilane or tetrapropoxysilane, typical but non-limiting combinations include combinations of tetramethoxysilane and tetraethoxysilane, tetraethoxysilane and tetrapropoxysilane, tetramethoxysilane and tetrapropoxysilane, or tetramethoxysilane, tetraethoxysilane and tetrapropoxysilane.
Preferably, the silicate comprises sodium silicate.
Preferably, the temperature of the mixing in step (2) is 30 to 60 ℃, for example 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃ or 60 ℃, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the mass ratio of the aqueous catalyst solution to the silicon source compound in step (2) is (1-20): 1, and may be, for example, 1:1, 3:1, 5:1, 8:1, 1, 12.
Preferably, the concentration of the aqueous catalyst solution in step (2) is 0.1 to 20wt%, for example 0.1wt%, 1wt%, 3wt%, 5wt%, 8wt%, 10wt%, 12wt%, 15wt%, 16wt%, 18wt% or 20wt%, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the aqueous catalyst solution in step (2) comprises any one of an aqueous inorganic acid solution, an aqueous inorganic base solution or an aqueous organic acid solution, or a combination of at least two of them.
Preferably, the mixing in step (2) includes stirring and mixing until a suspension is obtained, and then stirring is continued for 10-300min, such as 10min, 30min, 50min, 60min, 80min, 100min, 120min, 150min, 160min, 180min, 200min, 210min, 240min, 250min, 270min, 280min or 300min, but not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the rotational speed of the stirring and mixing is 150 to 250rpm, which may be, for example, 150rpm, 160rpm, 180rpm, 200rpm, 210rpm, 240rpm or 250rpm, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the suspension obtained in step (2) is a white suspension.
Preferably, the solid-liquid separation method in step (3) comprises any one or a combination of at least two of pressure filtration, centrifugation or sedimentation, and typical but non-limiting combinations include a combination of pressure filtration and centrifugation, a combination of centrifugation and sedimentation, a combination of pressure filtration and sedimentation, or a combination of pressure filtration, centrifugation and sedimentation.
Preferably, the drying temperature in step (3) is 30-220 ℃, for example 30 ℃, 50 ℃,60 ℃, 80 ℃, 100 ℃,120 ℃,150 ℃, 160 ℃,180 ℃,200 ℃ or 220 ℃, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the drying time in step (3) is 1 to 24 hours, and may be, for example, 1 hour, 2 hours, 3 hours, 5 hours, 6 hours, 8 hours, 10 hours, 12 hours, 15 hours, 16 hours, 18 hours, 20 hours, 21 hours or 24 hours, but is not limited to the enumerated values, and other unrecited values within the numerical range are also applicable.
The invention realizes the removal of physically adsorbed water by drying after solid-liquid separation, thereby obtaining the powder A.
Further preferably, the preparation method comprises washing the obtained solid after solid-liquid separation to remove impurities in the silicon source compound, so that the purity requirement on the silicon source compound can be reduced, and the purity of the finally obtained chip-grade silica filler can be ensured.
Preferably, the temperature of the calcination treatment in step (4) is 500 to 1300 ℃, and may be, for example, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃ or 1300 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the time of the calcination treatment in step (4) is 10-300min, such as 10min, 30min, 50min, 60min, 80min, 100min, 120min, 150min, 160min, 180min, 200min, 210min, 240min, 250min, 270min, 280min or 300min, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the calcining device used in the calcining in the step (4) comprises any one of a tube furnace, a box furnace, a tunnel furnace, a push plate furnace or a track furnace or a combination of at least two of the two.
According to the invention, the powder A is calcined, organic matters in the powder A are removed, and the powder A is densified, so that dense spherical silicon dioxide, namely the chip-level silicon dioxide filler, is obtained.
As a preferable technical solution of the preparation method of the first aspect of the present invention, the preparation method comprises the steps of:
(1) Mixing a cosolvent solution and a silicon source compound in a mass ratio of (1-50) to 1 to obtain a solution A; the cosolvent solution comprises a cosolvent and water in a mass ratio of (10-50) to (10-100);
(2) Stirring and mixing the catalyst aqueous solution and the solution A obtained in the step (1) at the rotating speed of 150-250rpm under the condition of 30-60 ℃ until white suspension is obtained, and then continuously stirring for 10-300min; the mass ratio of the catalyst aqueous solution to the silicon source compound is (1-20) to 1;
(3) Carrying out solid-liquid separation on the suspension obtained in the step (2), and drying at 30-220 ℃ for 1-24h to obtain powder A;
(4) And (3) calcining the powder A obtained in the step (3) at 500-1300 ℃ to obtain the chip-level silicon dioxide filler, wherein the calcining time is 10-300min.
In a second aspect, the invention provides a silica filler for a chip-scale underfill, the chip-scale silica filler being obtained by the preparation method of the first aspect.
The purity of the silicon dioxide filler for the chip-level underfill provided by the invention is more than or equal to 99.9wt% and the sphericity is more than or equal to 98%; the particle size distribution D50 is 0.3-8 μm, and D100 is 1-20 μm, which meets the requirements of flip chip packaging.
In a third aspect, the present invention provides a use of a silica filler for a chip-level underfill for chip packaging.
Compared with the prior art, the invention has the following beneficial effects:
the purity of the silicon dioxide filler for the chip-level underfill prepared by the preparation method is more than or equal to 99.9 percent, the sphericity is more than or equal to 98 percent, and the content of impurity ions is low; and the particle size distribution D50 is 0.3-8 μm, and D100 is 1-20 μm, which meets the requirements of flip chip packaging. And the average particle size and the cut-off point of the prepared silicon dioxide can be controlled by regulating and controlling the proportioning of the cosolvent, the catalyst and the silicon source compound, and subsequent grading, screening and grading process operations are not needed.
Drawings
FIG. 1 is a scanning electron micrograph of a chip-scale silica filler obtained in example 1 of the present invention;
FIG. 2 is a graph of particle size distribution for the chip-scale silica filler obtained in example 1 of the present invention;
FIG. 3 is a scanning electron micrograph of a chip-scale silica filler obtained in example 2 of the present invention;
FIG. 4 is a graph of particle size distribution for the chip-scale silica filler obtained in example 2 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of a chip-scale silica filler, which comprises the following steps:
(1) Mixing a cosolvent solution and a silicon source compound according to a mass ratio of 30; the cosolvent solution consists of a cosolvent and deionized water in a mass ratio of 2:5; the cosolvent is cyclohexane; the silicon source compound is (3-mercaptopropyl) trimethoxysilane;
(2) Stirring and mixing 10wt% of catalyst water solution and the solution A obtained in the step (1) at the temperature of 40 ℃ at 200rpm until white suspension is obtained, and then continuously stirring for 120min; the catalyst aqueous solution is ammonia water; the mass ratio of the catalyst aqueous solution to the silicon source compound is 10;
(3) Centrifuging the white suspension obtained in the step (2) to obtain white mud, drying at 60 ℃ for 14h, and removing physically adsorbed water to obtain powder A;
(4) And (4) calcining the powder A obtained in the step (3) in a tunnel furnace, wherein the temperature in the tunnel furnace is increased to 1000 ℃ within 100min, the powder A stays in the tunnel furnace for 120min, in the process, organic matters in the powder A are removed, densification of the powder A is realized, and the chip-level silicon dioxide filler is obtained.
The SEM image of the chip scale silica filler obtained in this example is shown in FIG. 1, and the particle size distribution diagram is shown in FIG. 2.
Example 2
The embodiment provides a preparation method of a chip-scale silica filler, which comprises the following steps:
(1) Mixing a cosolvent solution and a silicon source compound according to a mass ratio of 15; the cosolvent solution consists of a cosolvent and deionized water in a mass ratio of 1:5; the cosolvent is cyclohexane; the silicon source compound is (3-mercaptopropyl) trimethoxysilane;
(2) Stirring and mixing the 5wt% catalyst aqueous solution and the solution A obtained in the step (1) at the temperature of 35 ℃ at 180rpm until a white suspension is obtained, and then continuously stirring for 200min; the catalyst aqueous solution is ammonia water; the mass ratio of the catalyst aqueous solution to the silicon source compound is 15;
(3) Carrying out filter pressing on the white suspension obtained in the step (2) to obtain a white block, drying at 120 ℃ for 12h, and removing physically adsorbed water to obtain powder A;
(4) And (4) calcining the powder A obtained in the step (3) in a box type furnace, raising the temperature in the tunnel furnace to 1100 ℃ within 120min, and keeping the powder A in the tunnel furnace for 90min, wherein in the process, organic matters in the powder A are removed, and the densification of the powder A is realized, so that the chip-level silicon dioxide filler is obtained.
The SEM image of the chip scale silica filler obtained in this example is shown in FIG. 3, and the particle size distribution diagram is shown in FIG. 4.
Example 3
The embodiment provides a preparation method of a chip-scale silica filler, which comprises the following steps:
(1) Mixing a cosolvent solution and a silicon source compound according to a mass ratio of 40; the cosolvent solution consists of a cosolvent and deionized water in a mass ratio of 1:8; the cosolvent is cyclohexane; the silicon source compound is (3-mercaptopropyl) trimethoxysilane;
(2) Stirring and mixing a 15wt% catalyst aqueous solution and the solution A obtained in the step (1) at 210rpm under the condition of 50 ℃ until a white suspension is obtained, and then continuously stirring for 300min; the catalyst aqueous solution is ammonia water; the mass ratio of the catalyst aqueous solution to the silicon source compound is 5:1;
(3) Carrying out filter pressing on the white suspension obtained in the step (2) to obtain a white block, drying at 180 ℃ for 9h, and removing physically adsorbed water to obtain powder A;
(4) And (4) calcining the powder A obtained in the step (3) in a push plate furnace, raising the temperature in a tunnel furnace to 1000 ℃ in 240min, and keeping the powder A in the tunnel furnace for 300min, wherein in the process, organic matters in the powder A are removed, the densification of the powder A is realized, and the chip-level silicon dioxide filler is obtained.
Example 4
The embodiment provides a preparation method of a chip-scale silica filler, which comprises the following steps:
(1) Mixing the cosolvent solution and the silicon source compound according to the mass ratio of 1:1 to obtain a solution A; the cosolvent solution consists of a cosolvent and deionized water in a mass ratio of 1; the cosolvent is cyclohexane; the silicon source compound is (3-mercaptopropyl) trimethoxysilane;
(2) Stirring and mixing 0.1wt% catalyst water solution and the solution A obtained in the step (1) at the temperature of 60 ℃ at 150rpm until white suspension is obtained, and then continuing stirring for 60min; the catalyst aqueous solution is ammonia water; the mass ratio of the catalyst aqueous solution to the silicon source compound is 20;
(3) Carrying out filter pressing on the white suspension obtained in the step (2) to obtain a white block, drying at 200 ℃ for 16h, and removing physically adsorbed water to obtain powder A;
(4) And (4) calcining the powder A obtained in the step (3) in a push plate furnace, raising the temperature in a tunnel furnace to 900 ℃ within 160min, and keeping the powder A in the tunnel furnace for 240min, wherein in the process, organic matters in the powder A are removed, the densification of the powder A is realized, and the chip-level silicon dioxide filler is obtained.
Example 5
The embodiment provides a preparation method of a chip-scale silica filler, which comprises the following steps:
(1) Mixing a cosolvent solution and a silicon source compound according to a mass ratio of 50; the cosolvent solution consists of a cosolvent and deionized water in a mass ratio of 1:1; the cosolvent is cyclohexane; the silicon source compound is (3-mercaptopropyl) trimethoxysilane;
(2) Stirring and mixing the 20wt% catalyst aqueous solution and the solution A obtained in the step (1) at 250rpm under the condition of 30 ℃ until a white suspension is obtained, and then continuously stirring for 100min; the catalyst aqueous solution is ammonia water; the mass ratio of the catalyst aqueous solution to the silicon source compound is 1:1;
(3) Carrying out filter pressing on the white suspension obtained in the step (2) to obtain a white block, drying at 120 ℃ for 20h, and removing physically adsorbed water to obtain powder A;
(4) And (4) calcining the powder A obtained in the step (3) in a box type furnace, raising the temperature in the tunnel furnace to 1200 ℃ within 200min, and keeping the powder A in the tunnel furnace for 180min, wherein in the process, organic matters in the powder A are removed, the densification of the powder A is realized, and the chip-level silicon dioxide filler is obtained.
Example 6
This example provides a method for preparing a chip-scale silica filler, which is the same as in example 1 except that the co-solvent and the like were replaced by isopropanol by mass.
Example 7
This example provides a process for preparing a chip-scale silica filler, which is the same as example 1 except that the co-solvent and the like are replaced by methanol.
Example 8
This example provides a method of preparing a chip-scale silica filler, which is the same as example 1 except that the co-solvent and the like were replaced by ethanol.
Example 9
This example provides a process for preparing a chip-scale silica filler similar to that of example 1 except that the silicon source compound and the like were replaced by vinyltrimethoxysilane.
Example 10
This example provides a process for preparing a chip-scale silica filler, which is the same as example 1 except that an equal mass of a silicon source compound is replaced with tetramethoxysilane.
Example 11
This example provides a process for preparing a chip-scale silica filler similar to that of example 1 except that the silicon source compound and the like were replaced by tetrapropoxysilane.
Example 12
This example provides a method for preparing a chip-scale silica filler, which is the same as in example 1 except that sodium silicate is substituted for silicon source compounds of the same mass.
Comparative example 1
This comparative example provides a process for the preparation of a silica filler, which is the same as example 1, except that a co-solvent solution is not used, but a silicon source compound is directly mixed with an aqueous catalyst solution.
Performance testing
The silica fillers of the above examples and comparative examples were tested for purity, sphericity and particle size distribution, with purity being tested as SJ/T3228.4-2016, sphericity being tested as GB/T32661-2016 and particle size distribution being tested as GB/T19077-2016.
The results obtained are shown in table 1.
TABLE 1
| Purity (wt%) | Sphericity (%) | D50(μm) | D100(μm) | D100/D50 | |
| Example 1 | 99.98 | 99.62 | 3.05 | 7.42 | 2.43 |
| Example 2 | 99.96 | 99.56 | 1.02 | 2.77 | 2.72 |
| Example 3 | 99.95 | 98.51 | 0.36 | 1.03 | 2.86 |
| Example 4 | 99.91 | 98.43 | 0.53 | 1.74 | 3.28 |
| Example 5 | 99.9 | 98.29 | 0.81 | 2.62 | 3.23 |
| Example 6 | 99.94 | 99.52 | 1.42 | 3.66 | 2.58 |
| Example 7 | 99.93 | 99.26 | 1.76 | 6.16 | 3.50 |
| Example 8 | 99.95 | 99.37 | 1.65 | 5.37 | 3.25 |
| Example 9 | 99.92 | 98.93 | 2.35 | 6.78 | 2.89 |
| Example 10 | 99.95 | 99.31 | 2.73 | 6.98 | 2.56 |
| Example 11 | 99.94 | 99.42 | 1.98 | 5.39 | 2.72 |
| Example 12 | 99.93 | 98.74 | 2.29 | 6.12 | 2.67 |
| Comparative example 1 | 99.35 | 97.3 | 3.61 | 9.52 | 2.64 |
In conclusion, the purity of the silicon dioxide filler for the chip-level underfill prepared by the preparation method is more than or equal to 99.9%, the sphericity degree is more than or equal to 98%, and the content of impurity ions is low; and the particle size distribution D50 is 0.3-8 μm, and D100 is 1-20 μm, which meets the requirements of flip chip packaging. And the average particle size and the cut-off point of the prepared silicon dioxide can be controlled by regulating and controlling the proportioning of the cosolvent, the catalyst and the silicon source compound, and subsequent grading, screening and grading process operations are not needed.
The above description is only for the specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure of the present invention.
Claims (10)
1. A preparation method of a silicon dioxide filler for a chip-level underfill adhesive is characterized by comprising the following steps:
(1) Mixing the cosolvent solution with a silicon source compound to obtain a solution A;
(2) Mixing a catalyst aqueous solution with the solution A obtained in the step (1) to obtain a suspension;
(3) Performing solid-liquid separation on the suspension obtained in the step (2), and drying to obtain powder A;
(4) And (4) calcining the powder A obtained in the step (3) to obtain the chip-level silicon dioxide filler.
2. The method according to claim 1, wherein the cosolvent solution of step (1) comprises a cosolvent and water in a mass ratio of (10-50) to (10-100);
preferably, the co-solvent comprises any one of methanol, ethanol, isopropanol or cyclohexane or a combination of at least two thereof.
3. The preparation method according to claim 1 or 2, wherein the mass ratio of the cosolvent solution to the silicon source compound in the step (1) is (1-50): 1;
preferably, the silicon source compound of step (1) comprises any one of or a combination of at least two of an organosilicon, a siloxane, or a silicate;
preferably, the organosilicon comprises any one or a combination of at least two of vinyltrimethoxysilane, vinyltriethoxysilane, (3-mercaptopropyl) trimethoxysilane, allyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, or dodecyltrimethoxysilane;
preferably, the siloxane comprises any one of tetramethoxysilane, tetraethoxysilane or tetrapropoxysilane, or a combination of at least two of them;
preferably, the silicate comprises sodium silicate.
4. The method according to any one of claims 1 to 3, wherein the temperature of the mixing in the step (2) is 30 to 60 ℃;
preferably, the mass ratio of the catalyst aqueous solution to the silicon source compound in the step (2) is (1-20): 1;
preferably, the concentration of the catalyst aqueous solution in the step (2) is 0.1 to 20wt%;
preferably, the aqueous catalyst solution in step (2) comprises any one of an aqueous inorganic acid solution, an aqueous inorganic base solution or an aqueous organic acid solution, or a combination of at least two of them.
5. The method according to any one of claims 1 to 4, wherein the mixing in step (2) comprises stirring and mixing until a suspension is obtained, and then continuing stirring for 10 to 300min;
preferably, the rotation speed of the stirring and mixing is 150-250rpm;
preferably, the suspension obtained in step (2) is a white suspension.
6. The production method according to any one of claims 1 to 5, wherein the solid-liquid separation method in step (3) comprises any one of pressure filtration, centrifugation or sedimentation or a combination of at least two thereof;
preferably, the temperature of the drying in the step (3) is 30-220 ℃;
preferably, the drying time in step (3) is 1-24h.
7. The production method according to any one of claims 1 to 6, wherein the temperature of the calcination treatment in step (4) is 500 to 1300 ℃;
preferably, the time of the calcination treatment in the step (4) is 10-300min;
preferably, the calcining device used in the calcining in the step (4) comprises any one of a tube furnace, a box furnace, a tunnel furnace, a push plate furnace or a track furnace or a combination of at least two of the two.
8. The production method according to any one of claims 1 to 7, characterized by comprising the steps of:
(1) Mixing a cosolvent solution and a silicon source compound in a mass ratio of (1-50) to 1 to obtain a solution A; the cosolvent solution comprises cosolvent and water in a mass ratio of (10-50) to (10-100);
(2) Stirring and mixing the catalyst aqueous solution and the solution A obtained in the step (1) at the rotating speed of 150-250rpm under the condition of 30-60 ℃ until white suspension is obtained, and then continuously stirring for 10-300min; the mass ratio of the catalyst aqueous solution to the silicon source compound is (1-20) to 1;
(3) Carrying out solid-liquid separation on the suspension obtained in the step (2), and drying at 30-220 ℃ for 1-24h to obtain powder A;
(4) And (3) calcining the powder A obtained in the step (3) at 500-1300 ℃ to obtain the chip-level silicon dioxide filler, wherein the calcining time is 10-300min.
9. A silica filler for chip-scale underfill, wherein said chip-scale silica filler is obtained by the method of any one of claims 1 to 8.
10. Use of a silica filler for a chip-scale underfill, wherein the chip-scale silica filler is used for chip packaging.
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