JP2022001545A - Method for producing silica particles, method for producing silica sol, polishing method, method for producing semiconductor wafer, and method for producing semiconductor device - Google Patents
Method for producing silica particles, method for producing silica sol, polishing method, method for producing semiconductor wafer, and method for producing semiconductor device Download PDFInfo
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- JP2022001545A JP2022001545A JP2020107122A JP2020107122A JP2022001545A JP 2022001545 A JP2022001545 A JP 2022001545A JP 2020107122 A JP2020107122 A JP 2020107122A JP 2020107122 A JP2020107122 A JP 2020107122A JP 2022001545 A JP2022001545 A JP 2022001545A
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- Prior art keywords
- silica particles
- mass
- solution
- polishing
- producing
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- Granted
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 225
- 238000005498 polishing Methods 0.000 title claims abstract description 109
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 78
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000004065 semiconductor Substances 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 239000006185 dispersion Substances 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000003054 catalyst Substances 0.000 claims description 34
- 238000006460 hydrolysis reaction Methods 0.000 claims description 31
- 238000006482 condensation reaction Methods 0.000 claims description 30
- 239000002612 dispersion medium Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 17
- 239000003513 alkali Substances 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 239000011362 coarse particle Substances 0.000 abstract description 11
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 109
- 235000012431 wafers Nutrition 0.000 description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 28
- 229910052710 silicon Inorganic materials 0.000 description 28
- 239000010703 silicon Substances 0.000 description 28
- 239000011164 primary particle Substances 0.000 description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- 239000011163 secondary particle Substances 0.000 description 19
- 239000002904 solvent Substances 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000002245 particle Substances 0.000 description 18
- 229920003169 water-soluble polymer Polymers 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 14
- 238000004220 aggregation Methods 0.000 description 13
- 230000002776 aggregation Effects 0.000 description 13
- 125000005372 silanol group Chemical group 0.000 description 12
- 239000000377 silicon dioxide Substances 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 239000003139 biocide Substances 0.000 description 10
- 239000012535 impurity Substances 0.000 description 10
- 229910021529 ammonia Inorganic materials 0.000 description 9
- 230000000844 anti-bacterial effect Effects 0.000 description 9
- 150000007514 bases Chemical class 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 230000003115 biocidal effect Effects 0.000 description 4
- 238000002296 dynamic light scattering Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 4
- 238000000108 ultra-filtration Methods 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000417 fungicide Substances 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- -1 polyoxyethylene Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000012085 test solution Substances 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000006174 pH buffer Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical group C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 241001553178 Arachis glabrata Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000896 Ethulose Polymers 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 208000000260 Warts Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 150000002433 hydrophilic molecules Chemical class 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 1
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 201000010153 skin papilloma Diseases 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 229960002218 sodium chlorite Drugs 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
Description
本発明は、シリカ粒子の製造方法、シリカゾルの製造方法、研磨方法、半導体ウェハの製造方法及び半導体デバイスの製造方法に関する。 The present invention relates to a method for producing silica particles, a method for producing silica sol, a polishing method, a method for producing a semiconductor wafer, and a method for producing a semiconductor device.
金属や無機化合物等の材料の表面を研磨する方法として、研磨液を用いた研磨方法が知られている。中でも、半導体用のプライムシリコンウェハやこれらの再生シリコンウェハの最終仕上げ研磨、及び、半導体デバイス製造時の層間絶縁膜の平坦化、金属プラグの形成、埋め込み配線形成等の化学的機械的研磨（ＣＭＰ）では、その表面状態が半導体特性に大きく影響するため、これらの部品の表面や端面は、極めて高精度に研磨されることが要求されている。 As a method for polishing the surface of a material such as a metal or an inorganic compound, a polishing method using a polishing liquid is known. Among them, chemical mechanical polishing (CMP) such as final finish polishing of prime silicon wafers for semiconductors and these recycled silicon wafers, flattening of interlayer insulating films during semiconductor device manufacturing, metal plug formation, embedded wiring formation, etc. In), the surface condition thereof greatly affects the semiconductor characteristics, so that the surfaces and end faces of these parts are required to be polished with extremely high precision.
このような精密研磨においては、シリカ粒子を含む研磨組成物が採用されており、その主成分である砥粒として、コロイダルシリカが広く用いられている。コロイダルシリカは、その製造方法の違いにより、四塩化珪素の熱分解によるもの（ヒュームドシリカ等）、水ガラス等の珪酸アルカリの脱イオンによるもの、アルコキシシランの加水分解反応及び縮合反応（一般に「ゾルゲル法」と称される）によるもの等が知られている。 In such precision polishing, a polishing composition containing silica particles is adopted, and colloidal silica is widely used as the abrasive grains which are the main components thereof. Colloidal silica is produced by thermal decomposition of silicon tetrachloride (hummed silica, etc.), by deionization of alkali silicate such as water glass, hydrolysis reaction and condensation reaction of alkoxysilane (generally, "" The method by (called the sol-gel method) is known.
シリカ粒子の製造方法に関し、これまで多くの検討がなされてきた。例えば、特許文献１及び特許文献２には、アルコキシシランの加水分解反応及び縮合反応によりシリカ粒子を製造する方法が開示されている。 Many studies have been made on the method for producing silica particles. For example, Patent Document 1 and Patent Document 2 disclose a method for producing silica particles by a hydrolysis reaction and a condensation reaction of alkoxysilane.
アルコキシシランの加水分解反応及び縮合反応によりシリカ粒子を製造する方法では、その製造条件次第で、反応槽の壁面に付着するシリカ粒子が発生したり、シリカ粒子同士が凝集した粗大粒子が発生したりすることがある。反応槽の壁面に付着するシリカ粒子が発生すると、生産性が低下するという課題が生じる。また、シリカ粒子同士が凝集した粗大粒子が発生すると、精製時に濾過性が悪化し、研磨時に被研磨体にスクラッチが生じるという課題が生じる。 In the method of producing silica particles by hydrolysis reaction and condensation reaction of alkoxysilane, depending on the production conditions, silica particles adhering to the wall surface of the reaction tank may be generated, or coarse particles in which silica particles are aggregated may be generated. I have something to do. When silica particles adhering to the wall surface of the reaction tank are generated, there arises a problem that productivity is lowered. Further, when coarse particles in which silica particles are aggregated are generated, the filterability is deteriorated during purification, and there arises a problem that scratches are generated on the object to be polished during polishing.
従来、アルコキシシランの加水分解反応及び縮合反応によるシリカ粒子の製造において、反応槽の壁面へのシリカ粒子の付着、シリカ粒子同士の凝集による粗大粒子の発生を抑制し得る製造条件についての提案はなされておらず、特許文献１，２でも、このような製造条件について何ら記載されていない。このため、特許文献１及び特許文献２に開示されているシリカ粒子の製造方法では、製造条件次第では反応槽の壁面に付着するシリカ粒子が発生したり、シリカ粒子同士が凝集した粗大粒子が発生したりするという課題があった。 Conventionally, in the production of silica particles by hydrolysis reaction and condensation reaction of alkoxysilane, a proposal has been made on production conditions capable of suppressing the adhesion of silica particles to the wall surface of the reaction tank and the generation of coarse particles due to aggregation of silica particles. In addition, Patent Documents 1 and 2 do not describe such manufacturing conditions. Therefore, in the methods for producing silica particles disclosed in Patent Document 1 and Patent Document 2, depending on the production conditions, silica particles adhering to the wall surface of the reaction tank may be generated, or coarse particles in which silica particles are aggregated may be generated. There was a problem of doing it.
本発明は、このような課題を鑑みてなされたものであり、本発明の目的は、反応槽の壁面に付着するシリカ粒子の発生を抑制し、シリカ粒子同士が凝集した粗大粒子の発生を抑制するシリカ粒子の製造方法を提供することにある。 The present invention has been made in view of such problems, and an object of the present invention is to suppress the generation of silica particles adhering to the wall surface of the reaction vessel and to suppress the generation of coarse particles in which silica particles are aggregated with each other. It is an object of the present invention to provide a method for producing silica particles.
本発明者らは、鋭意検討を重ねた結果、テトラアルコキシシランの加水分解反応及び縮合反応によりシリカ粒子を製造するに当たり、撹拌動力を好適化することで、反応槽の壁面に付着するシリカ粒子を抑制し、シリカ粒子同士が凝集した粗大粒子の発生を抑制することができることを見出し、本発明を完成するに至った。 As a result of diligent studies, the present inventors have made silica particles adhering to the wall surface of the reaction vessel by optimizing the stirring power in producing silica particles by the hydrolysis reaction and condensation reaction of tetraalkoxysilane. We have found that it is possible to suppress the generation of coarse particles in which silica particles are aggregated with each other, and have completed the present invention.
即ち、本発明の要旨は、以下の通りである。
［１］ ２０Ｗ／ｍ３〜２００Ｗ／ｍ３の撹拌動力でテトラアルコキシシランを加水分解反応及び縮合反応させる工程を含む、シリカ粒子の製造方法。
［２］ アルカリ触媒を含む溶液（Ａ）に、テトラアルコキシシランを含む溶液（Ｂ）及びアルカリ触媒を含む溶液（Ｃ）を添加し、撹拌下にテトラアルコキシシランを加水分解反応及び縮合反応させる、［１］に記載のシリカ粒子の製造方法。
［３］ 加水分解反応及び縮合反応の反応温度が、２０℃〜５０℃である、［１］又は［２］に記載のシリカ粒子の製造方法。
［４］ 加水分解反応及び縮合反応の反応系内の水の濃度を、３質量％〜３０質量％に維持する、［１］〜［３］のいずれかに記載のシリカ粒子の製造方法。
［５］ 更に、以下の工程（１）を含む、［１］〜［４］のいずれかに記載のシリカ粒子の製造方法。
工程（１）：得られたシリカ粒子の分散液を濃縮し、分散媒を添加する工程
［６］ 更に、以下の工程（２）を含む、［５］に記載のシリカ粒子の製造方法。
工程（２）：工程（１）で得られたシリカ粒子の分散液を加圧加熱処理する工程
［７］ ［１］〜［６］のいずれかに記載のシリカ粒子の製造方法を含む、シリカゾルの製造方法。
［８］ シリカゾル中のシリカ粒子の含有率が、３質量％〜５０質量％である、［７］に記載のシリカゾルの製造方法。
［９］ ［７］又は［８］に記載のシリカゾルの製造方法で得られたシリカゾルを含む研磨組成物を用いて研磨する、研磨方法。
［１０］ ［９］に記載の研磨方法を含む、半導体ウェハの製造方法。
［１１］ ［９］に記載の研磨方法を含む、半導体デバイスの製造方法。
That is, the gist of the present invention is as follows.
[1] 20W / m 3 tetraalkoxysilane in stirring power ~200W / m 3 comprising the step of hydrolysis and condensation reactions, the production method of the silica particles.
[2] A solution (B) containing tetraalkoxysilane and a solution (C) containing an alkali catalyst are added to the solution (A) containing an alkali catalyst, and the tetraalkoxysilane is hydrolyzed and condensed under stirring. The method for producing silica particles according to [1].
[3] The method for producing silica particles according to [1] or [2], wherein the reaction temperature of the hydrolysis reaction and the condensation reaction is 20 ° C to 50 ° C.
[4] The method for producing silica particles according to any one of [1] to [3], wherein the concentration of water in the reaction system of the hydrolysis reaction and the condensation reaction is maintained at 3% by mass to 30% by mass.
[5] The method for producing silica particles according to any one of [1] to [4], further comprising the following step (1).
Step (1): Step of concentrating the obtained dispersion of silica particles and adding a dispersion medium [6] Further, the method for producing silica particles according to [5], which comprises the following step (2).
Step (2): A silica sol comprising the method for producing silica particles according to any one of [7] [1] to [6], wherein the dispersion liquid of the silica particles obtained in the step (1) is pressure-heated. Manufacturing method.
[8] The method for producing silica sol according to [7], wherein the content of silica particles in the silica sol is 3% by mass to 50% by mass.
[9] A polishing method for polishing using a polishing composition containing the silica sol obtained by the method for producing a silica sol according to [7] or [8].
[10] A method for manufacturing a semiconductor wafer, which comprises the polishing method according to [9].
[11] A method for manufacturing a semiconductor device, including the polishing method according to [9].
本発明のシリカ粒子の製造方法によれば、テトラアルコキシシランの加水分解反応及び縮合反応によりシリカ粒子を製造するに当たり、反応槽の壁面に付着するシリカ粒子の発生を抑制し、シリカ粒子同士が凝集した粗大粒子の発生を抑制することができる。従って、本発明のシリカ粒子の製造方法によれば、粗大粒子の少ない高品質のシリカ粒子を歩留りよく効率的に製造することができる。 According to the method for producing silica particles of the present invention, in producing silica particles by hydrolysis reaction and condensation reaction of tetraalkoxysilane, the generation of silica particles adhering to the wall surface of the reaction tank is suppressed, and the silica particles aggregate with each other. It is possible to suppress the generation of coarse particles. Therefore, according to the method for producing silica particles of the present invention, high-quality silica particles having a small amount of coarse particles can be produced efficiently and with good yield.
以下に本発明について詳述するが、本発明は、以下の実施の形態に限定されるものではなく、その要旨の範囲内で種々に変更して実施することができる。尚、本明細書において「〜」という表現を用いる場合、その前後の数値又は物性値を含む表現として用いる。 The present invention will be described in detail below, but the present invention is not limited to the following embodiments, and can be variously modified and carried out within the scope of the gist thereof. When the expression "~" is used in the present specification, it is used as an expression including numerical values or physical property values before and after the expression.
（シリカ粒子の製造方法）
本発明のシリカ粒子の製造方法は、２０Ｗ／ｍ３〜２００Ｗ／ｍ３の撹拌動力でテトラアルコキシシランを加水分解反応及び縮合反応させる工程を含む。
本発明における撹拌動力は、反応液の単位体積あたりの撹拌動力である。
(Manufacturing method of silica particles)
Method for producing silica particles of the present invention, comprising the step of hydrolysis and condensation reactions tetraalkoxysilane in stirring power 20W / m 3 ~200W / m 3 .
The stirring power in the present invention is the stirring power per unit volume of the reaction solution.
該撹拌動力は、２０Ｗ／ｍ３〜２００Ｗ／ｍ３であり、２５Ｗ／ｍ３〜１５０Ｗ／ｍ３が好ましく、３０Ｗ／ｍ３〜１００Ｗ／ｍ３がより好ましい。撹拌動力が上記下限値以上であると、シリカ粒子同士が凝集した粗大粒子の発生を抑制することができる。また、撹拌動力が上記上限値以下であると、反応槽の壁面に付着するシリカ粒子の発生を抑制することができる。 The stirring power is 20W / m 3 ~200W / m 3 , preferably 25W / m 3 ~150W / m 3 , 30W / m 3 ~100W / m 3 and more preferably. When the stirring power is at least the above lower limit value, it is possible to suppress the generation of coarse particles in which silica particles are aggregated with each other. Further, when the stirring power is not more than the above upper limit value, the generation of silica particles adhering to the wall surface of the reaction tank can be suppressed.
撹拌動力は、撹拌翼の種類、撹拌回転数を調整することで、所望の範囲に設定することができる。 The stirring power can be set in a desired range by adjusting the type of stirring blade and the stirring rotation speed.
本発明のシリカ粒子の製造方法は、加水分解反応及び縮合反応の制御性に優れることから、アルカリ触媒を含む溶液（Ａ）に、前述の撹拌動力で撹拌しながら、テトラアルコキシシランを含む溶液（Ｂ）及びアルカリ触媒を含む溶液（Ｃ）を添加し、前述の撹拌動力で撹拌しながら、テトラアルコキシシランを加水分解反応及び縮合反応させることが好ましい。なお、溶液（Ａ）への溶液（Ｂ）と溶液（Ｃ）の添加は、ほぼ同時に同程度の時間をかけて行うことが好ましい。 Since the method for producing silica particles of the present invention is excellent in controllability of hydrolysis reaction and condensation reaction, a solution containing tetraalkoxysilane (A) containing an alkali catalyst while stirring with the above-mentioned stirring power (A). It is preferable to add the solution (C) containing B) and the alkali catalyst, and hydrolyze and condense the tetraalkoxysilane while stirring with the above-mentioned stirring power. It is preferable that the solution (B) and the solution (C) are added to the solution (A) at almost the same time over the same period of time.
溶液（Ａ）は、アルカリ触媒を含む。
溶液（Ａ）中のアルカリ触媒としては、例えば、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラアミン、アンモニア、尿素、エタノールアミン、テトラメチル水酸化アンモニウム等が挙げられる。これらのアルカリ触媒は、１種を単独で用いてもよく、２種以上を併用してもい。これらのアルカリ触媒の中でも、触媒作用に優れ、粒子形状を制御しやすく、金属不純物の混入を抑制することができ、揮発性が高く加水分解反応及び縮合反応後の除去性に優れることから、アンモニアが好ましい。
The solution (A) contains an alkaline catalyst.
Examples of the alkaline catalyst in the solution (A) include ethylenediamine, diethylenetriamine, triethylenetetraamine, ammonia, urea, ethanolamine, and tetramethylammonium hydroxide. One of these alkaline catalysts may be used alone, or two or more of them may be used in combination. Among these alkaline catalysts, ammonia has excellent catalytic action, easy control of particle shape, suppression of metal impurities, high volatility, and excellent removal after hydrolysis reaction and condensation reaction. Is preferable.
溶液（Ａ）は、テトラアルコキシシランの加水分解反応及び縮合反応進行させることができることから、水を含むことが好ましい。 The solution (A) preferably contains water because it can promote the hydrolysis reaction and the condensation reaction of tetraalkoxysilane.
溶液（Ａ）は、反応液中でのテトラアルコキシシランの分散性に優れることから、水以外の溶媒を含むことが好ましい。
溶液（Ａ）中の水以外の溶媒としては、例えば、メタノール、エタノール、プロパノール、イソプロパノール、エチレングリコール等のアルコールや、アセトン、メチルエチルケトン等のケトン、酢酸エチル等のエステルなどが挙げられる。これらの溶媒は、１種を単独で用いてもよく、２種以上を併用してもよい。これらの溶媒の中でも、テトラアルコキシシランを溶解しやすく、加水分解反応及び縮合反応で用いるものと副生するものとが同一で、製造上の利便性に優れることから、アルコールが好ましく、メタノール、エタノールがより好ましく、メタノールが更に好ましい。
The solution (A) preferably contains a solvent other than water because it has excellent dispersibility of tetraalkoxysilane in the reaction solution.
Examples of the solvent other than water in the solution (A) include alcohols such as methanol, ethanol, propanol, isopropanol and ethylene glycol, ketones such as acetone and methyl ethyl ketone, and esters such as ethyl acetate. These solvents may be used alone or in combination of two or more. Among these solvents, alcohol is preferable, and methanol and ethanol are preferable because they are easy to dissolve tetraalkoxysilane, and the one used in the hydrolysis reaction and the condensation reaction is the same as the one used as a by-product and is excellent in manufacturing convenience. Is more preferable, and methanol is even more preferable.
溶液（Ａ）中のアルカリ触媒の濃度は、溶液（Ａ）１００質量％中、０．５質量％〜２．０質量％が好ましく、０．６質量％〜１．５質量％がより好ましい。溶液（Ａ）中のアルカリ触媒の濃度が上記下限値以上であると、シリカ粒子の凝集を抑制し、得られる分散液中のシリカ粒子の分散安定性に優れる。また、溶液（Ａ）中のアルカリ触媒の濃度が上記上限値以下であると、反応が過度に速く進行せず、反応制御性に優れる。 The concentration of the alkaline catalyst in the solution (A) is preferably 0.5% by mass to 2.0% by mass, more preferably 0.6% by mass to 1.5% by mass, based on 100% by mass of the solution (A). When the concentration of the alkaline catalyst in the solution (A) is at least the above lower limit value, the aggregation of silica particles is suppressed, and the dispersion stability of the silica particles in the obtained dispersion is excellent. Further, when the concentration of the alkaline catalyst in the solution (A) is not more than the above upper limit value, the reaction does not proceed excessively fast and the reaction controllability is excellent.
溶液（Ａ）中の水の濃度は、溶液（Ａ）１００質量％中、３質量％〜３０質量％が好ましく、５質量％〜２５質量％がより好ましい。溶液（Ａ）中の水の濃度が上記下限値以上であると、加水分解反応で生成するケイ酸の反応液中での分散性に優れる。また、溶液（Ａ）中の水の濃度が上記上限値以下であると、反応液中でのテトラアルコキシシランの分散性に優れる。 The concentration of water in the solution (A) is preferably 3% by mass to 30% by mass, more preferably 5% by mass to 25% by mass in 100% by mass of the solution (A). When the concentration of water in the solution (A) is at least the above lower limit, the dispersibility of silicic acid produced in the hydrolysis reaction in the reaction solution is excellent. Further, when the concentration of water in the solution (A) is not more than the above upper limit value, the dispersibility of tetraalkoxysilane in the reaction solution is excellent.
溶液（Ａ）中の水以外の溶媒の濃度は、アルカリ触媒と水の残部とすることが好ましい。 The concentration of the solvent other than water in the solution (A) is preferably an alkaline catalyst and the balance of water.
溶液（Ｂ）は、テトラアルコキシシランを含む。
溶液（Ｂ）中のテトラアルコキシシランとしては、例えば、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトライソプロポキシシラン等のアルコキシ基の炭素数が１〜１２のテトラアルコキシシランが挙げられる。これらのテトラアルコキシシランは、１種を単独で用いてもよく、２種以上を併用してもよい。これらのテトラアルコキシシランの中でも、加水分解反応が速く、未反応物が残留し難く、生産性に優れ、安定なシリカゾルを容易に得ることができることから、テトラメトキシシラン、テトラエトキシシランが好ましく、テトラメトキシシランがより好ましい。
The solution (B) contains tetraalkoxysilane.
Examples of the tetraalkoxysilane in the solution (B) include tetraalkoxysilanes having an alkoxy group having 1 to 12 carbon atoms such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetraisopropoxysilane. These tetraalkoxysilanes may be used alone or in combination of two or more. Among these tetraalkoxysilanes, tetramethoxysilane and tetraethoxysilane are preferable because the hydrolysis reaction is fast, unreactant is hard to remain, the productivity is excellent, and a stable silica sol can be easily obtained. More preferred is methoxysilane.
溶液（Ｂ）は、反応液中でのテトラアルコキシシランの分散性に優れることから、溶媒を含むことが好ましい。
溶液（Ｂ）中の溶媒としては、例えば、メタノール、エタノール、プロパノール、イソプロパノール、エチレングリコール等のアルコールや、アセトン、メチルエチルケトン等のケトン、酢酸エチル等のエステルなどが挙げられる。これらの溶媒は、１種を単独で用いてもよく、２種以上を併用してもよい。これらの溶媒の中でも、加水分解反応及び縮合反応で用いるものと副生するものとが同一で、製造上の利便性に優れることから、アルコールが好ましく、メタノール、エタノールがより好ましく、メタノールが更に好ましい。
The solution (B) preferably contains a solvent because it has excellent dispersibility of tetraalkoxysilane in the reaction solution.
Examples of the solvent in the solution (B) include alcohols such as methanol, ethanol, propanol, isopropanol and ethylene glycol, ketones such as acetone and methyl ethyl ketone, and esters such as ethyl acetate. These solvents may be used alone or in combination of two or more. Among these solvents, those used in the hydrolysis reaction and the condensation reaction are the same as those used in the condensation reaction, and because they are excellent in manufacturing convenience, alcohol is preferable, methanol and ethanol are more preferable, and methanol is further preferable. ..
溶液（Ｂ）中のテトラアルコキシシランの濃度は、溶液（Ｂ）１００質量％中、７６質量％〜８９質量％が好ましく、７７質量％〜８８質量％がより好ましい。溶液（Ｂ）中のテトラアルコキシシランの濃度が上記下限値以上であると、用いる溶媒の量を低減することができ、シリカ粒子の生産性に優れる。また、溶液（Ｂ）中のテトラアルコキシシランの濃度が上記上限値以下であると、反応液中でのテトラアルコキシシランの分散性に優れる。 The concentration of tetraalkoxysilane in the solution (B) is preferably 76% by mass to 89% by mass, more preferably 77% by mass to 88% by mass in 100% by mass of the solution (B). When the concentration of tetraalkoxysilane in the solution (B) is at least the above lower limit, the amount of the solvent used can be reduced, and the productivity of silica particles is excellent. Further, when the concentration of the tetraalkoxysilane in the solution (B) is not more than the above upper limit value, the dispersibility of the tetraalkoxysilane in the reaction solution is excellent.
溶液（Ｂ）中の溶媒の濃度は、溶液（Ｂ）１００質量％中、１１質量％〜２４質量％が好ましく、１２質量％〜２３質量％がより好ましい。溶液（Ｂ）中の溶媒の濃度が上記下限値以上であると、反応液中でのテトラアルコキシシランの分散性に優れる。また、溶液（Ｂ）中の溶媒の濃度が上記上限値以下であると、用いる溶媒の量を低減することができ、シリカ粒子の生産性に優れる。なお、溶液（Ｂ）中の溶媒の濃度は、通常、溶液（Ｂ）のテトラアルコキシシランの残部であることが好ましい。 The concentration of the solvent in the solution (B) is preferably 11% by mass to 24% by mass, more preferably 12% by mass to 23% by mass in 100% by mass of the solution (B). When the concentration of the solvent in the solution (B) is at least the above lower limit, the dispersibility of the tetraalkoxysilane in the reaction solution is excellent. Further, when the concentration of the solvent in the solution (B) is not more than the above upper limit value, the amount of the solvent used can be reduced and the productivity of the silica particles is excellent. The concentration of the solvent in the solution (B) is usually preferably the balance of the tetraalkoxysilane in the solution (B).
溶液（Ａ）への溶液（Ｂ）の添加速度は、５０ｇシリカ／時／ｋｇ溶液〜１５０ｇシリカ／時／ｋｇ溶液が好ましく、７０ｇシリカ／時／ｋｇ溶液〜１３０ｇシリカ／時／ｋｇ溶液がより好ましい。溶液（Ｂ）の添加速度が上記下限値以上であると、反応時間が短縮され、生産性に優れる。また、溶液（Ｂ）の添加速度が上記上限値以下であると、反応液中でのテトラアルコキシシランの分散性に優れる。
ここで、「ｇシリカ／時／ｋｇ溶液」とは、溶液（Ａ）１ｋｇに対して、１時間当たりに添加する溶液（Ｂ）中のテトラアルコキシシランの質量をシリカの質量に換算した値（ｇ）を表す。
The rate of addition of the solution (B) to the solution (A) is preferably 50 g silica / hour / kg solution to 150 g silica / hour / kg solution, more preferably 70 g silica / hour / kg solution to 130 g silica / hour / kg solution. preferable. When the addition rate of the solution (B) is at least the above lower limit value, the reaction time is shortened and the productivity is excellent. Further, when the addition rate of the solution (B) is not more than the above upper limit value, the dispersibility of the tetraalkoxysilane in the reaction solution is excellent.
Here, "g silica / hour / kg solution" is a value obtained by converting the mass of tetraalkoxysilane in the solution (B) added per hour with respect to 1 kg of the solution (A) into the mass of silica (the mass of silica). Represents g).
溶液（Ｃ）は、アルカリ触媒を含む。
溶液（Ｃ）中のアルカリ触媒としては、例えば、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラアミン、アンモニア、尿素、エタノールアミン、テトラメチル水酸化アンモニウム等が挙げられる。これらのアルカリ触媒は、１種を単独で用いてもよく、２種以上を併用してもよい。溶液（Ｃ）中のアルカリ触媒は溶液（Ａ）中のアルカリ触媒と同種のアルカリ触媒が好ましく、溶液（Ａ）におけると同様に、これらのアルカリ触媒の中でも、触媒作用に優れ、粒子形状を制御しやすく、金属不純物の混入を抑制することができ、揮発性が高く加水分解反応及び縮合反応後の除去性に優れることから、アンモニアが好ましい。
The solution (C) contains an alkaline catalyst.
Examples of the alkaline catalyst in the solution (C) include ethylenediamine, diethylenetriamine, triethylenetetraamine, ammonia, urea, ethanolamine, and tetramethylammonium hydroxide. One of these alkaline catalysts may be used alone, or two or more of them may be used in combination. The alkaline catalyst in the solution (C) is preferably an alkaline catalyst of the same type as the alkaline catalyst in the solution (A), and as in the solution (A), among these alkaline catalysts, it has excellent catalytic action and controls the particle shape. Ammonia is preferable because it is easy to carry out, it is possible to suppress the mixing of metal impurities, it is highly volatile, and it is excellent in removability after a hydrolysis reaction and a condensation reaction.
溶液（Ｃ）は、反応液の組成の変動を小さくすることができることから、溶媒を含むことが好ましい。
溶液（Ｃ）中の溶媒としては、例えば、水、メタノール、エタノール、プロパノール、イソプロパノール、エチレングリコール等のアルコールなどが挙げられる。これらの溶媒は、１種を単独で用いてもよく、２種以上を併用してもよい。これらの溶媒の中でも、加水分解反応及び縮合反応で用いるものと副生するものとが同一で、製造上の利便性に優れることから、水、アルコールが好ましく、水がより好ましい。
The solution (C) preferably contains a solvent because the variation in the composition of the reaction solution can be reduced.
Examples of the solvent in the solution (C) include water, methanol, ethanol, propanol, isopropanol, alcohols such as ethylene glycol, and the like. These solvents may be used alone or in combination of two or more. Among these solvents, those used in the hydrolysis reaction and the condensation reaction are the same as those used in the condensation reaction, and since they are excellent in manufacturing convenience, water and alcohol are preferable, and water is more preferable.
溶液（Ｃ）中のアルカリ触媒の濃度は、溶液（Ｃ）１００質量％中、２質量％〜５質量％が好ましく、３質量％〜４質量％がより好ましい。溶液（Ｃ）中のアルカリ触媒の濃度が上記下限値以上であると、シリカ粒子の凝集を抑制し、得られる分散液中のシリカ粒子の分散安定性に優れる。また、溶液（Ｃ）中のアルカリ触媒の濃度が上記上限値以下であると、反応が過度に速く進行せず、反応制御性に優れる。 The concentration of the alkaline catalyst in the solution (C) is preferably 2% by mass to 5% by mass, more preferably 3% by mass to 4% by mass in 100% by mass of the solution (C). When the concentration of the alkaline catalyst in the solution (C) is at least the above lower limit value, the aggregation of silica particles is suppressed, and the dispersion stability of the silica particles in the obtained dispersion is excellent. Further, when the concentration of the alkaline catalyst in the solution (C) is not more than the above upper limit value, the reaction does not proceed excessively fast and the reaction controllability is excellent.
溶液（Ｃ）中の水の濃度は、溶液（Ｃ）１００質量％中、９５質量％〜９８質量％が好ましく、９６質量％〜９７質量％がより好ましい。溶液（Ｃ）中の水の濃度が上記下限値以上であると、加水分解反応で生成するケイ酸の反応液中での分散性に優れる。また、溶液（Ｃ）中の水の濃度が上記上限値以下であると、反応液中でのテトラアルコキシシランの分散性に優れる。 The concentration of water in the solution (C) is preferably 95% by mass to 98% by mass, more preferably 96% by mass to 97% by mass in 100% by mass of the solution (C). When the concentration of water in the solution (C) is at least the above lower limit, the dispersibility of silicic acid produced in the hydrolysis reaction in the reaction solution is excellent. Further, when the concentration of water in the solution (C) is not more than the above upper limit value, the dispersibility of tetraalkoxysilane in the reaction solution is excellent.
溶液（Ａ）への溶液（Ｃ）の添加速度は、２ｇアルカリ触媒／時／ｋｇ溶液〜６ｇアルカリ触媒／時／ｋｇ溶液が好ましく、３ｇアルカリ触媒／時／ｋｇ溶液〜５ｇアルカリ触媒／時／ｋｇ溶液がより好ましい。溶液（Ｃ）の添加速度が上記下限値以上であると、シリカ粒子の凝集を抑制し、得られる分散液中のシリカ粒子の分散安定性に優れる。また、溶液（Ｃ）の添加速度が上記上限値以下であると、反応が過度に速く進行せず、反応制御性に優れる。
ここで、「ｇアルカリ触媒／時／ｋｇ溶液」とは、溶液（Ａ）１ｋｇに対して、１時間当たりに添加する溶液（Ｃ）中のアルカリ触媒の質量（ｇ）を表す。
The rate of addition of the solution (C) to the solution (A) is preferably 2 g alkaline catalyst / hour / kg solution to 6 g alkaline catalyst / hour / kg solution, 3 g alkaline catalyst / hour / kg solution to 5 g alkaline catalyst / hour /. A kg solution is more preferred. When the addition rate of the solution (C) is at least the above lower limit value, the aggregation of silica particles is suppressed, and the dispersion stability of the silica particles in the obtained dispersion liquid is excellent. Further, when the addition rate of the solution (C) is not more than the above upper limit value, the reaction does not proceed excessively fast, and the reaction controllability is excellent.
Here, "g alkaline catalyst / hour / kg solution" represents the mass (g) of the alkaline catalyst in the solution (C) added per hour with respect to 1 kg of the solution (A).
テトラアルコキシシランの加水分解反応及び縮合反応の反応温度（反応液の温度）は、２０℃〜５０℃が好ましく、２５℃〜４５℃がより好ましい。反応温度が上記下限値以上であると、反応が過度に遅く進行せず、制御性に優れる。また、反応温度が上記上限値以下であると、加水分解反応速度と縮合反応速度のバランスに優れる。
ここで反応系内の反応液とは、溶液（Ａ）、溶液（Ｂ）及び溶液（Ｃ）の混合液に相当する。
The reaction temperature (temperature of the reaction solution) of the hydrolysis reaction and the condensation reaction of tetraalkoxysilane is preferably 20 ° C to 50 ° C, more preferably 25 ° C to 45 ° C. When the reaction temperature is equal to or higher than the above lower limit, the reaction does not proceed excessively slowly and the controllability is excellent. Further, when the reaction temperature is not more than the above upper limit value, the balance between the hydrolysis reaction rate and the condensation reaction rate is excellent.
Here, the reaction solution in the reaction system corresponds to a mixed solution of the solution (A), the solution (B) and the solution (C).
加水分解反応及び縮合反応の反応系内の水の濃度は、反応系内の反応液１００質量％中、３質量％〜３０質量％に維持することが好ましく、５質量％〜２５質量％に維持することがより好ましい。反応系内の水の濃度が上記下限値以上であると、中間生成物であるケイ酸の反応液中での分散性に優れる。また、反応系内の水の濃度が上記上限値以下であると、反応液中でのテトラアルコキシシランの分散性に優れる。
ここで反応系内の反応液とは、溶液（Ａ）、溶液（Ｂ）及び溶液（Ｃ）の混合液に相当する。
The concentration of water in the reaction system of the hydrolysis reaction and the condensation reaction is preferably maintained at 3% by mass to 30% by mass, preferably 5% by mass to 25% by mass, based on 100% by mass of the reaction solution in the reaction system. It is more preferable to do so. When the concentration of water in the reaction system is at least the above lower limit, the dispersibility of silicic acid, which is an intermediate product, in the reaction solution is excellent. Further, when the concentration of water in the reaction system is not more than the above upper limit value, the dispersibility of tetraalkoxysilane in the reaction solution is excellent.
Here, the reaction solution in the reaction system corresponds to a mixed solution of the solution (A), the solution (B) and the solution (C).
加水分解反応及び縮合反応の反応系内のアルカリ触媒の濃度は、反応系内の反応液１００質量％中、０．５質量％〜２．０質量％に維持することが好ましく、０．６質量％〜１．５質量％に維持することがより好ましい。反応系内のアルカリ触媒の濃度が上記下限値以上であると、シリカ粒子の凝集を抑制し、得られる分散液中のシリカ粒子の分散安定性に優れる。また、反応系内のアルカリ触媒の濃度が上記上限値以下であると、反応が過度に速く進行せず、反応制御性に優れる。 The concentration of the alkali catalyst in the reaction system of the hydrolysis reaction and the condensation reaction is preferably maintained at 0.5% by mass to 2.0% by mass, preferably 0.6% by mass, based on 100% by mass of the reaction solution in the reaction system. More preferably, it is maintained at% to 1.5% by mass. When the concentration of the alkaline catalyst in the reaction system is at least the above lower limit, the aggregation of silica particles is suppressed, and the dispersion stability of the silica particles in the obtained dispersion is excellent. Further, when the concentration of the alkaline catalyst in the reaction system is not more than the above upper limit value, the reaction does not proceed excessively fast and the reaction controllability is excellent.
（工程（１））
本発明のシリカ粒子の製造方法は、不必要な成分を除去し、必要な成分を添加することができることから、上記テトラアルコキシシランの加水分解反応及び縮合反応工程後に、更に、以下の工程（１）を含むことが好ましい。
工程（１）：テトラアルコキシシランの加水分解反応及び縮合反応で得られたシリカ粒子の分散液を濃縮し、分散媒を添加する工程
(Step (1))
Since the method for producing silica particles of the present invention can remove unnecessary components and add necessary components, the following steps (1) are further performed after the hydrolysis reaction and condensation reaction steps of the tetraalkoxysilane. ) Is preferably included.
Step (1): A step of concentrating the dispersion liquid of the silica particles obtained by the hydrolysis reaction and the condensation reaction of tetraalkoxysilane and adding the dispersion medium.
工程（１）のシリカ粒子の分散液の濃縮と分散媒の添加とはいずれを先に行ってもよい。 Either the concentration of the dispersion liquid of the silica particles or the addition of the dispersion medium in the step (1) may be performed first.
シリカ粒子の分散液を濃縮する方法は特に限定されず、例えば、加熱濃縮法、膜濃縮法などが挙げられる。
加熱濃縮法によってシリカ粒子の分散液を濃縮するには、該分散液を常圧下、又は減圧下で加熱濃縮すればよい。
膜濃縮法によってシリカ粒子の分散液を濃縮するには、限外濾過法による膜分離が好ましい。ここで用いる限外濾過膜の分画分子量は、分散液中のシリカ粒子の粒径に合わせてシリカ粒子を濾過分離して濃縮できるものを選択する。
限外濾過膜の材質としては、ポリスルホン、ポリアクリルニトリル、焼結金属、セラミック、カーボンなどが挙げられる。限外濾過膜の形態としては、スパイラル型、チューブラー型、中空糸型等が挙げられる。
The method for concentrating the dispersion liquid of silica particles is not particularly limited, and examples thereof include a heat concentration method and a membrane concentration method.
In order to concentrate the dispersion liquid of silica particles by the heat concentration method, the dispersion liquid may be heated and concentrated under normal pressure or reduced pressure.
In order to concentrate the dispersion of silica particles by the membrane concentration method, membrane separation by the ultrafiltration method is preferable. The fractional molecular weight of the ultrafiltration membrane used here is selected so that the silica particles can be filtered and separated and concentrated according to the particle size of the silica particles in the dispersion liquid.
Examples of the material of the ultrafiltration membrane include polysulfone, polyacrylic nitrile, sintered metal, ceramic, and carbon. Examples of the form of the ultrafiltration membrane include a spiral type, a tubular type, and a hollow fiber type.
また、シリカ粒子の分散液に添加する分散媒としては、例えば、水、メタノール、エタノール、プロパノール、イソプロパノール、エチレングリコール等のアルコールなどが挙げられる。これらの分散媒は、１種を単独で用いてもよく、２種以上を併用してもよい。これらの分散媒の中でも、シリカ粒子との親和性に優れることから、水、アルコールが好ましく、水がより好ましい。 Examples of the dispersion medium added to the dispersion liquid of silica particles include water, methanol, ethanol, propanol, isopropanol, and alcohols such as ethylene glycol. These dispersion media may be used alone or in combination of two or more. Among these dispersion media, water and alcohol are preferable, and water is more preferable, because they have an excellent affinity with silica particles.
（工程（２））
本発明のシリカ粒子の製造方法は、シリカ粒子の縮合度を高めることができることから、更に、以下の工程（２）を含むことが好ましい。
工程（２）：工程（１）で得られたシリカ粒子の分散液を加圧加熱処理する工程
(Step (2))
Since the method for producing silica particles of the present invention can increase the degree of condensation of silica particles, it is preferable to further include the following step (2).
Step (2): A step of pressurizing and heat-treating the dispersion liquid of the silica particles obtained in the step (1).
工程（２）における加圧加熱処理の圧力は、０．１０ＭＰａ〜２．３ＭＰａが好ましく、０．１４ＭＰａ〜１．０ＭＰａがより好ましい。加圧加熱処理の圧力が０．１０ＭＰａ以上であると、シリカ粒子の縮合度を高めることができる。また、加圧加熱処理の圧力が２．３ＭＰａ以下であると、平均１次粒子径、平均２次粒子径、ｃｖ値、会合比を大きく変化させることなくシリカ粒子を製造することができ、シリカゾルの分散安定性に優れる。 The pressure of the pressure heat treatment in the step (2) is preferably 0.10 MPa to 2.3 MPa, more preferably 0.14 MPa to 1.0 MPa. When the pressure of the pressure heat treatment is 0.10 MPa or more, the degree of condensation of the silica particles can be increased. Further, when the pressure of the pressure heat treatment is 2.3 MPa or less, silica particles can be produced without significantly changing the average primary particle diameter, average secondary particle diameter, cv value, and association ratio, and the silica sol. Excellent dispersion stability.
加圧は、密閉した状態でシリカ粒子の分散液を分散媒の沸点以上に加熱すればよい。密閉した状態でシリカ粒子の水分散液を１００℃以上に加熱した場合、圧力は、その温度の飽和水蒸気圧となる。 For pressurization, the dispersion liquid of silica particles may be heated above the boiling point of the dispersion medium in a sealed state. When the aqueous dispersion of silica particles is heated to 100 ° C. or higher in a closed state, the pressure becomes the saturated water vapor pressure at that temperature.
加圧加熱処理の温度は、１００℃〜２２０℃が好ましく、１１０℃〜１８０℃がより好ましい。加圧加熱処理の温度が１００℃以上であると、シリカ粒子の縮合度を高めることができる。加圧加熱処理の温度が２２０℃以下であると、平均１次粒子径、平均２次粒子径、ｃｖ値、会合比を大きく変化させることなくシリカ粒子を製造することができ、シリカゾルの分散安定性に優れる。 The temperature of the pressure heat treatment is preferably 100 ° C. to 220 ° C., more preferably 110 ° C. to 180 ° C. When the temperature of the pressure heat treatment is 100 ° C. or higher, the degree of condensation of the silica particles can be increased. When the temperature of the pressure heat treatment is 220 ° C. or lower, silica particles can be produced without significantly changing the average primary particle size, average secondary particle size, cv value, and association ratio, and the dispersion of silica sol is stable. Excellent in sex.
加圧加熱処理の時間は、０．２５時間〜１０時間が好ましく、０．５時間〜８時間がより好ましい。加圧加熱処理の時間が０．２５時間以上であると、シリカ粒子の縮合度を高めることができる。加圧加熱処理の時間が１０時間以下であると、平均１次粒子径、平均２次粒子径、ｃｖ値、会合比を大きく変化させることなくシリカ粒子を製造することができ、シリカゾルの分散安定性に優れる。 The time of the pressure heat treatment is preferably 0.25 hours to 10 hours, more preferably 0.5 hours to 8 hours. When the pressure heat treatment time is 0.25 hours or more, the degree of condensation of the silica particles can be increased. When the pressure heat treatment time is 10 hours or less, silica particles can be produced without significantly changing the average primary particle size, average secondary particle size, cv value, and association ratio, and the dispersion of silica sol is stable. Excellent in sex.
加圧加熱処理は、平均１次粒子径、平均２次粒子径、ｃｖ値、会合比を大きく変化させることなくシリカ粒子の縮合度を高めることができることから、水分散液中で行うことがより好ましい。 Since the pressure heat treatment can increase the degree of condensation of silica particles without significantly changing the average primary particle size, average secondary particle size, cv value, and association ratio, it is more suitable to perform the pressure heat treatment in an aqueous dispersion. preferable.
加圧加熱処理を水分散液中で行う際のｐＨは、６．０〜８．０が好ましく、６．５〜７．８がより好ましい。加圧加熱処理を水分散液中で行う際のｐＨが６．０以上であると、シリカゾルのゲル化を抑制することができる。また、加圧加熱処理を水分散液中で行う際のｐＨが８．０以下であると、平均１次粒子径、平均２次粒子径、ｃｖ値、会合比を大きく変化させることなくシリカ粒子の縮合度を高めることができる。 The pH when the pressure heat treatment is carried out in the aqueous dispersion is preferably 6.0 to 8.0, more preferably 6.5 to 7.8. When the pH when the pressure heat treatment is performed in the aqueous dispersion is 6.0 or more, gelation of the silica sol can be suppressed. Further, when the pH when the pressure heat treatment is performed in the aqueous dispersion is 8.0 or less, the silica particles do not significantly change the average primary particle size, average secondary particle size, cv value, and association ratio. The degree of condensation can be increased.
（シリカ粒子の物性）
本発明のシリカ粒子の製造方法により製造されるシリカ粒子（以下、「本発明のシリカ粒子」と称す場合がある。）の平均１次粒子径は、５ｎｍ〜１００ｎｍが好ましく、１０ｎｍ〜６０ｎｍがより好ましい。シリカ粒子の平均１次粒子径が５ｎｍ以上であると、シリカゾルの保存安定性に優れる。また、シリカ粒子の平均１次粒子径が１００ｎｍ以下であると、シリコンウェハに代表される被研磨体の表面粗さや傷を低減でき、シリカ粒子の沈降を抑制することができる。
(Physical characteristics of silica particles)
The average primary particle diameter of the silica particles produced by the method for producing silica particles of the present invention (hereinafter, may be referred to as "silica particles of the present invention") is preferably 5 nm to 100 nm, more preferably 10 nm to 60 nm. preferable. When the average primary particle diameter of the silica particles is 5 nm or more, the storage stability of the silica sol is excellent. Further, when the average primary particle diameter of the silica particles is 100 nm or less, the surface roughness and scratches of the object to be polished represented by the silicon wafer can be reduced, and the sedimentation of the silica particles can be suppressed.
シリカ粒子の平均１次粒子径は、ＢＥＴ法により測定する。具体的には、比表面積自動測定装置を用いてシリカ粒子の比表面積を測定し、下記式（１）を用いて平均１次粒子径を算出する。
平均１次粒子径（ｎｍ）＝６０００／(比表面積(ｍ２／ｇ)×密度(ｇ／ｃｍ３))
・・・ （１）
The average primary particle size of the silica particles is measured by the BET method. Specifically, the specific surface area of the silica particles is measured using an automatic specific surface area measuring device, and the average primary particle diameter is calculated using the following formula (1).
Average primary particle diameter (nm) = 6000 / (specific surface area (m 2 / g) x density (g / cm 3 ))
... (1)
シリカ粒子の平均１次粒子径は、公知の条件・方法により、所望の範囲に設定することができる。 The average primary particle diameter of the silica particles can be set in a desired range according to known conditions and methods.
本発明のシリカ粒子の平均２次粒子径は、１０ｎｍ〜２００ｎｍが好ましく、２０ｎｍ〜１００ｎｍがより好ましい。シリカ粒子の平均２次粒子径が１０ｎｍ以上であると、研磨後の洗浄における粒子等の除去性に優れ、シリカゾルの保存安定性に優れる。シリカ粒子の平均２次粒子径が２００ｎｍ以下であると、研磨時のシリコンウェハに代表される被研磨体の表面粗さや傷を低減でき、研磨後の洗浄における粒子等の除去性に優れ、シリカ粒子の沈降を抑制することができる。 The average secondary particle diameter of the silica particles of the present invention is preferably 10 nm to 200 nm, more preferably 20 nm to 100 nm. When the average secondary particle diameter of the silica particles is 10 nm or more, the removal property of particles and the like in washing after polishing is excellent, and the storage stability of the silica sol is excellent. When the average secondary particle diameter of the silica particles is 200 nm or less, the surface roughness and scratches of the object to be polished represented by a silicon wafer during polishing can be reduced, and the removal of particles and the like during cleaning after polishing is excellent, and silica is used. It is possible to suppress the sedimentation of particles.
シリカ粒子の平均２次粒子径は、ＤＬＳ法（動的光散乱法）により測定する。具体的には、動的光散乱粒子径測定装置を用いて測定する。 The average secondary particle diameter of silica particles is measured by the DLS method (dynamic light scattering method). Specifically, the measurement is performed using a dynamic light scattering particle size measuring device.
シリカ粒子の平均２次粒子径は、公知の条件・方法により、所望の範囲に設定することができる。 The average secondary particle diameter of the silica particles can be set in a desired range according to known conditions and methods.
本発明のシリカ粒子のｃｖ値は、１０〜５０が好ましく、１５〜４０がより好ましく、２０〜３５が更に好ましい。シリカ粒子のｃｖ値が下限値以上であると、シリコンウェハに代表される被研磨体に対する研磨レートに優れ、生産性に優れる。また、シリカ粒子のｃｖ値が上記上限値以下であると、研磨時のシリコンウェハに代表される被研磨体の表面粗さや傷を低減でき、研磨後の洗浄における粒子等の除去性に優れる。 The cv value of the silica particles of the present invention is preferably 10 to 50, more preferably 15 to 40, and even more preferably 20 to 35. When the cv value of the silica particles is at least the lower limit value, the polishing rate for the object to be polished represented by the silicon wafer is excellent, and the productivity is excellent. Further, when the cv value of the silica particles is not more than the above upper limit value, the surface roughness and scratches of the object to be polished represented by the silicon wafer during polishing can be reduced, and the removal property of particles and the like in cleaning after polishing is excellent.
シリカ粒子のｃｖ値は、動的光散乱粒子径測定装置を用いてシリカ粒子の平均２次粒子径を測定し、下記式（２）を用いて算出する。
ｃｖ値＝（標準偏差（ｎｍ）／平均２次粒子径（ｎｍ））×１００ ・・・ （２）
The cv value of the silica particles is calculated by measuring the average secondary particle size of the silica particles using a dynamic light scattering particle size measuring device and using the following formula (2).
cv value = (standard deviation (nm) / average secondary particle size (nm)) x 100 ... (2)
本発明のシリカ粒子の会合比は、１．０〜４．０が好ましく、１．１〜３．０がより好ましい。シリカ粒子の会合比が下限値以上であると、シリコンウェハに代表される被研磨体に対する研磨レートに優れ、生産性に優れる。また、シリカ粒子の会合比が上記上限値以下であると、研磨時のシリコンウェハに代表される被研磨体の表面粗さや傷を低減でき、シリカ粒子の凝集を抑制することができる。 The association ratio of the silica particles of the present invention is preferably 1.0 to 4.0, more preferably 1.1 to 3.0. When the association ratio of the silica particles is at least the lower limit value, the polishing rate for the object to be polished represented by a silicon wafer is excellent, and the productivity is excellent. Further, when the association ratio of the silica particles is not more than the above upper limit value, the surface roughness and scratches of the object to be polished represented by the silicon wafer at the time of polishing can be reduced, and the aggregation of the silica particles can be suppressed.
シリカ粒子の会合比は、前述の測定方法にて測定した平均１次粒子径と前述の測定方法にて測定した平均２次粒子径とから、下記式（３）を用いて算出される。
会合比＝平均２次粒子径／平均１次粒子径 ・・・ （３）
The association ratio of the silica particles is calculated from the average primary particle diameter measured by the above-mentioned measuring method and the average secondary particle diameter measured by the above-mentioned measuring method by using the following formula (3).
Association ratio = average secondary particle diameter / average primary particle diameter ... (3)
本発明のシリカ粒子の表面シラノール基密度は、０．１個／ｎｍ２〜１０個／ｎｍ２が好ましく、０．５個／ｎｍ２〜７．５個／ｎｍ２がより好ましく、２．０個／ｎｍ２〜７．０個／ｎｍ２が更に好ましい。シリカ粒子の表面シラノール基密度が０．１個／ｎｍ２以上であると、シリカ粒子が適度な表面反発を有し、シリカゾルの分散安定性に優れる。また、シリカ粒子の表面シラノール基密度が１０個／ｎｍ２以下であると、シリカ粒子が適度な表面反発を有し、シリカ粒子の凝集を抑制することができる。 The surface silanol group density of the silica particles of the present invention is preferably 0.1 pieces / nm 2 to 10 pieces / nm 2, more preferably 0.5 pieces / nm 2 to 7.5 pieces / nm 2 , and 2.0. More preferably, 2 to 7.0 pieces / nm 2. When the surface silanol group density of the silica particles is 0.1 element / nm 2 or more, the silica particles have an appropriate surface repulsion and the dispersion stability of the silica sol is excellent. Further, when the surface silanol group density of the silica particles is 10 pieces / nm 2 or less, the silica particles have an appropriate surface repulsion, and the aggregation of the silica particles can be suppressed.
シリカ粒子の表面シラノール基密度は、シアーズ法により測定する。具体的には、下記に示す条件で測定、算出する。 The surface silanol group density of the silica particles is measured by the Sears method. Specifically, it is measured and calculated under the conditions shown below.
シリカ粒子１．５ｇに相当するシリカゾルを採取し、純水を加えて液量を９０ｍＬにする。２５℃の環境下、ｐＨが３．６になるまで０．１ｍｏｌ／Ｌの塩酸水溶液を加え、塩化ナトリウム３０ｇを加え、純水を徐々に加えながら塩化ナトリウムを完全に溶解させ、最終的に試験液の総量が１５０ｍＬになるまで純水を加え、試験液を得る。
得られた試験液を自動滴定装置に入れ、０．１ｍｏｌ／Ｌの水酸化ナトリウム水溶液を滴下して、ｐＨが４．０から９．０になるのに要する０．１ｍｏｌ／Ｌの水酸化ナトリウム水溶液の滴定量Ａ（ｍＬ）を測定する。
下記式（４）を用いて、シリカ粒子１．５ｇあたりのｐＨが４．０から９．０になるのに要した０．１ｍｏｌ／Ｌの水酸化ナトリウム水溶液の消費量Ｖ（ｍＬ）を算出し、下記式（５）を用いて、シリカ粒子の表面シラノール基密度ρ（個／ｎｍ２）を算出する。
Ｖ＝（Ａ×ｆ×１００×１．５）／（Ｗ×Ｃ） ・・・ （４）
Ａ：シリカ粒子１．５ｇあたりのｐＨが４．０から９．０になるのに要した０．１ｍｏｌ／Ｌの水酸化ナトリウム水溶液の滴定量（ｍＬ）
ｆ：用いた０．１ｍｏｌ／Ｌの水酸化ナトリウム水溶液の力価
Ｃ：シリカゾル中のシリカ粒子の濃度（質量％）
Ｗ：シリカゾルの採取量（ｇ）
ρ＝（Ｂ×ＮＡ）／（１０１８×Ｍ×ＳＢＥＴ） ・・・ （５）
Ｂ：Ｖから算出したシリカ粒子１．５ｇあたりのｐＨが４．０から９．０になるのに要した水酸化ナトリウム量（ｍｏｌ）
ＮＡ：アボガドロ数（個／ｍｏｌ）
Ｍ：シリカ粒子量（１．５ｇ）
ＳＢＥＴ：平均１次粒子径の算出の際に測定したシリカ粒子の比表面積（ｍ２／ｇ）
A silica sol corresponding to 1.5 g of silica particles is collected, and pure water is added to make the liquid volume 90 mL. In an environment of 25 ° C, add a 0.1 mol / L hydrochloric acid aqueous solution until the pH reaches 3.6, add 30 g of sodium chloride, and gradually add pure water to completely dissolve the sodium chloride, and finally the test. Add pure water until the total volume of the solution reaches 150 mL to obtain a test solution.
The obtained test solution is placed in an automatic titrator, and a 0.1 mol / L sodium hydroxide aqueous solution is added dropwise to obtain 0.1 mol / L sodium hydroxide required for the pH to change from 4.0 to 9.0. Titration A (mL) of the aqueous solution is measured.
Using the following formula (4), calculate the consumption V (mL) of 0.1 mol / L sodium hydroxide aqueous solution required for the pH per 1.5 g of silica particles to change from 4.0 to 9.0. Then, the surface silanol group density ρ (pieces / nm 2 ) of the silica particles is calculated using the following formula (5).
V = (A × f × 100 × 1.5) / (W × C) ・ ・ ・ (4)
A: Titration (mL) of 0.1 mol / L sodium hydroxide aqueous solution required for the pH per 1.5 g of silica particles to change from 4.0 to 9.0.
f: Titer of 0.1 mol / L sodium hydroxide aqueous solution used C: Concentration (mass%) of silica particles in silica sol
W: Amount of silica sol collected (g)
ρ = (B × N A) / (10 18 × M × S BET) ··· (5)
B: Amount of sodium hydroxide (mol) required for the pH per 1.5 g of silica particles calculated from V to change from 4.0 to 9.0.
N A: Avogadro's number (number / mol)
M: Amount of silica particles (1.5 g)
SBET : Specific surface area (m 2 / g) of silica particles measured when calculating the average primary particle size.
尚、前記シリカ粒子の表面シラノール基密度の測定、算出方法は、「Ｇ．Ｗ．Ｓｅａｒｓ，Ｊｒ．，Ａｎａｌｙｔｉｃａｌ Ｃｈｅｍｉｓｔｒｙ，Ｖｏｌ．２８，Ｎｏ．１２，ｐｐ．１９８１−１９８３（１９５６）．」、「羽場真一， 半導体集積回路プロセス用研磨剤の開発,高知工科大学博士論文，ｐｐ．３９−４５，２００４年３月」、「特許第５９６７１１８号公報」、「特許第６０４７３９５号公報」を参考にした。 The method for measuring and calculating the surface silanol group density of the silica particles is described in "GW Sears, Jr., Analytical Chemistry, Vol. 28, No. 12, pp. 1981-1983 (1956).", ". Shinichi Haba, Development of Polishing Agents for Semiconductor Integrated Circuit Processes, Kochi University of Technology Doctoral Thesis, pp.39-45, March 2004 ”,“ Patent No. 5967118 ”,“ Patent No. 6047395 ” ..
シリカ粒子の表面シラノール基密度は、アルコキシシランの加水分解反応及び縮合反応の条件を調整することで、所望の範囲に設定することができる。 The surface silanol group density of the silica particles can be set in a desired range by adjusting the conditions of the hydrolysis reaction and the condensation reaction of the alkoxysilane.
本発明のシリカ粒子の金属不純物含有率は、５ｐｐｍ以下が好ましく、２ｐｐｍ以下がより好ましい。 The metal impurity content of the silica particles of the present invention is preferably 5 ppm or less, more preferably 2 ppm or less.
半導体デバイスのシリコンウェハの研磨において、金属不純物が被研磨体の表面に付着、汚染することで、ウェハ特性に悪影響を及ぼすと共に、ウェハ内部に拡散して品質が劣化するため、このようなウェハによって製造された半導体デバイスの性能が著しく低下する。
また、シリカ粒子に金属不純物が存在すると、酸性を示す表面シラノール基と金属不純物とが配位的な相互作用が発生し、表面シラノール基の化学的性質（酸性度等）を変化させたり、シリカ粒子表面の立体的な環境（シリカ粒子の凝集のしやすさ等）を変化させたり、研磨レートに影響を及ぼす。
In polishing a silicon wafer of a semiconductor device, metal impurities adhere to and contaminate the surface of the object to be polished, which adversely affects the wafer characteristics and diffuses inside the wafer to deteriorate the quality. The performance of manufactured semiconductor devices is significantly reduced.
In addition, when metal impurities are present in the silica particles, a coordinated interaction occurs between the surface silanol groups showing acidity and the metal impurities, which changes the chemical properties (acidity, etc.) of the surface silanol groups, or silica. It changes the three-dimensional environment of the particle surface (easiness of aggregation of silica particles, etc.) and affects the polishing rate.
シリカ粒子の金属不純物含有率は、高周波誘導結合プラズマ質量分析法（ＩＣＰ−ＭＳ）により測定する。具体的には、シリカ粒子０．４ｇ含むシリカゾルを正確に量り取り、硫酸とフッ酸を加え、加温、溶解、蒸発させ、残存した硫酸滴に総量が正確に１０ｇとなるよう純水を加えて試験液を作成し、高周波誘導結合プラズマ質量分析装置を用いて測定する。対象の金属は、ナトリウム、カリウム、鉄、アルミニウム、カルシウム、マグネシウム、亜鉛、コバルト、クロム、銅、マンガン、鉛、チタン、銀、ニッケルとし、これらの金属の含有率の合計を金属不純物含有率とする。 The metal impurity content of the silica particles is measured by high frequency inductively coupled plasma mass spectrometry (ICP-MS). Specifically, the silica sol containing 0.4 g of silica particles is accurately weighed, sulfuric acid and hydrofluoric acid are added, heated, dissolved and evaporated, and pure water is added to the remaining sulfuric acid droplets so that the total amount is exactly 10 g. Prepare a test solution and measure using a high-frequency inductively coupled plasma mass spectrometer. The target metals are sodium, potassium, iron, aluminum, calcium, magnesium, zinc, cobalt, chromium, copper, manganese, lead, titanium, silver, and nickel, and the total content of these metals is the metal impurity content. do.
シリカ粒子の金属不純物含有率は、アルコキシシランを主原料として加水分解反応及び縮合反応を行ってシリカ粒子を得ることで、５ｐｐｍ以下とすることができる。
水ガラス等の珪酸アルカリの脱イオンによる方法では、原料由来のナトリウム等が残存するため、シリカ粒子の金属不純物含有率を５ｐｐｍ以下とすることが極めて困難である。
The metal impurity content of the silica particles can be 5 ppm or less by performing a hydrolysis reaction and a condensation reaction using alkoxysilane as a main raw material to obtain silica particles.
In the method by deionization of alkali silicate such as water glass, it is extremely difficult to reduce the metal impurity content of silica particles to 5 ppm or less because sodium or the like derived from the raw material remains.
シリカ粒子の形状としては、例えば、球状、鎖状、繭状（こぶ状や落花生状とも称される）、異形状（例えば、疣状、屈曲状、分岐状等）等が挙げられる。これらのシリカ粒子の形状の中でも、研磨時のシリコンウェハに代表される被研磨体の表面粗さや傷を低減させたい場合は、球状が好ましく、シリコンウェハに代表される被研磨体に対する研磨レートをより高めたい場合は、異形状が好ましい。 Examples of the shape of the silica particles include a spherical shape, a chain shape, a cocoon shape (also referred to as a hump shape or a peanut shape), and an irregular shape (for example, a wart shape, a bent shape, a branched shape, etc.). Among the shapes of these silica particles, if it is desired to reduce the surface roughness and scratches of the object to be polished represented by a silicon wafer during polishing, a spherical shape is preferable, and the polishing rate for the object to be polished represented by a silicon wafer is set. If you want to increase it, a different shape is preferable.
本発明のシリカ粒子は、機械的強度、保存安定性に優れることから、細孔を有しないことが好ましい。
シリカ粒子の細孔の有無は、窒素を吸着ガスとした吸着等温線を用いたＢＥＴ多点法解析により確認する。
Since the silica particles of the present invention are excellent in mechanical strength and storage stability, it is preferable that they do not have pores.
The presence or absence of pores in the silica particles is confirmed by BET multipoint analysis using an adsorption isotherm using nitrogen as an adsorption gas.
（シリカゾルの製造方法）
本発明のシリカゾルの製造方法は、本発明のシリカ粒子の製造方法を含む。
(Manufacturing method of silica sol)
The method for producing a silica sol of the present invention includes a method for producing silica particles of the present invention.
シリカゾルは、本発明のシリカ粒子の製造方法で得られたシリカ粒子の分散液をそのまま用いてもよく、得られたシリカ粒子の分散液中の成分のうち、不必要な成分の除去や必要な成分の添加をして製造してもよい。 As the silica sol, the dispersion liquid of the silica particles obtained by the method for producing silica particles of the present invention may be used as it is, and among the components in the dispersion liquid of the obtained silica particles, unnecessary components may be removed or necessary. It may be manufactured by adding an ingredient.
シリカゾルは、シリカ粒子及び分散媒を含むことが好ましい。
シリカゾル中の分散媒は、例えば、水、メタノール、エタノール、プロパノール、イソプロパノール、エチレングリコール等のアルコールなどが挙げられる。これらのシリカゾル中の分散媒は、１種を単独で用いてもよく、２種以上を併用してもよい。これらのシリカゾル中の分散媒の中でも、シリカ粒子との親和性に優れることから、水、アルコールが好ましく、水がより好ましい。
The silica sol preferably contains silica particles and a dispersion medium.
Examples of the dispersion medium in the silica sol include water, methanol, ethanol, propanol, isopropanol, and alcohols such as ethylene glycol. As the dispersion medium in these silica sol, one kind may be used alone, or two or more kinds may be used in combination. Among the dispersion media in these silica sol, water and alcohol are preferable, and water is more preferable, because they have an excellent affinity with silica particles.
シリカゾル中のシリカ粒子の含有率は、シリカゾル全量１００質量％中、３質量％〜５０質量％が好ましく、４質量％〜４０質量％がより好ましく、５質量％〜３０質量％が更に好ましい。シリカゾル中のシリカ粒子の含有率が３質量％以上であると、シリコンウェハに代表される被研磨体に対する研磨レートに優れる。また、シリカゾル中のシリカ粒子の含有率が５０質量％以下であると、シリカゾルや研磨組成物中のシリカ粒子の凝集を抑制することができ、シリカゾルや研磨組成物の保存安定性に優れる。 The content of the silica particles in the silica sol is preferably 3% by mass to 50% by mass, more preferably 4% by mass to 40% by mass, still more preferably 5% by mass to 30% by mass, based on 100% by mass of the total amount of the silica sol. When the content of silica particles in the silica sol is 3% by mass or more, the polishing rate for the object to be polished represented by a silicon wafer is excellent. Further, when the content of the silica particles in the silica sol is 50% by mass or less, the aggregation of the silica particles in the silica sol or the polishing composition can be suppressed, and the storage stability of the silica sol or the polishing composition is excellent.
シリカゾル中の分散媒の含有率は、シリカゾル全量１００質量％中、５０質量％〜９７質量％が好ましく、６０質量％〜９６質量％がより好ましく、７０質量％〜９５質量％が更に好ましい。シリカゾル中の分散媒の含有率が５０質量％以上であると、シリカゾルや研磨組成物中のシリカ粒子の凝集を抑制することができ、シリカゾルや研磨組成物の保存安定性に優れる。また、シリカゾル中の分散媒の含有率が９７質量％以下であると、シリコンウェハに代表される被研磨体に対する研磨レートに優れる。 The content of the dispersion medium in the silica sol is preferably 50% by mass to 97% by mass, more preferably 60% by mass to 96% by mass, still more preferably 70% by mass to 95% by mass, based on 100% by mass of the total amount of the silica sol. When the content of the dispersion medium in the silica sol is 50% by mass or more, aggregation of silica particles in the silica sol or the polishing composition can be suppressed, and the storage stability of the silica sol or the polishing composition is excellent. Further, when the content of the dispersion medium in the silica sol is 97% by mass or less, the polishing rate for the object to be polished represented by the silicon wafer is excellent.
シリカゾル中のシリカ粒子や分散媒の含有率は、得られたシリカ粒子の分散液中の成分のうち、不必要な成分を除去し、必要な成分を添加することで、所望の範囲に設定することができる。 The content of the silica particles and the dispersion medium in the silica sol is set to a desired range by removing unnecessary components from the components in the obtained dispersion liquid of the silica particles and adding the necessary components. be able to.
シリカゾルは、シリカ粒子及び分散媒以外に、その性能を損なわない範囲において、必要に応じて、酸化剤、防腐剤、防黴剤、ｐＨ調整剤、ｐＨ緩衝剤、界面活性剤、キレート剤、抗菌殺生物剤等の他の成分を含んでもよい。
特に、シリカゾルの保存安定性に優れることから、シリカゾル中に抗菌殺生物剤を含ませることが好ましい。
In addition to silica particles and dispersion media, silica sol can be used as an oxidizing agent, preservative, fungicide, pH adjuster, pH buffer, surfactant, chelating agent, antibacterial agent, if necessary, as long as its performance is not impaired. It may contain other components such as biocides.
In particular, it is preferable to include an antibacterial biocide in the silica sol because the silica sol is excellent in storage stability.
抗菌殺生物剤としては、例えば、過酸化水素、アンモニア、第四級アンモニウム水酸化物、第四級アンモニウム塩、エチレンジアミン、グルタルアルデヒド、ｐ−ヒドロキシ安息香酸メチル、亜塩素酸ナトリウム等が挙げられる。これらの抗菌殺生物剤は、１種を単独で用いてもよく、２種以上を併用してもよい。これらの抗菌殺生物剤の中でも、シリカゾルとの親和性に優れることから、過酸化水素が好ましい。
抗菌殺生物剤は、一般に殺菌剤と言われるものも含む。
Examples of the antibacterial killing agent include hydrogen peroxide, ammonia, quaternary ammonium hydroxide, quaternary ammonium salt, ethylenediamine, glutaraldehyde, methyl p-hydroxybenzoate, sodium chlorite and the like. These antibacterial biocides may be used alone or in combination of two or more. Among these antibacterial biocides, hydrogen peroxide is preferable because it has an excellent affinity with silica sol.
Antibacterial biocides also include what are commonly referred to as fungicides.
シリカゾル中の抗菌殺生物剤の含有率は、シリカゾル全量１００質量％中、０．０００１質量％〜１０質量％が好ましく、０．００１質量％〜１質量％がより好ましい。シリカゾル中の抗菌殺生物剤の含有率が０．０００１質量％以上であると、シリカゾルの保存安定性に優れる。シリカゾル中の抗菌殺生物剤の含有率が１０質量％以下であると、シリカゾルの本来の性能を損なわない。 The content of the antibacterial biocide in the silica sol is preferably 0.0001% by mass to 10% by mass, more preferably 0.001% by mass to 1% by mass, based on 100% by mass of the total amount of the silica sol. When the content of the antibacterial biocide in the silica sol is 0.0001% by mass or more, the storage stability of the silica sol is excellent. When the content of the antibacterial biocide in the silica sol is 10% by mass or less, the original performance of the silica sol is not impaired.
シリカゾルのｐＨは、６．０〜８．０が好ましく、６．５〜７．８がより好ましい。シリカゾルのｐＨが６．０以上であると、分散安定性に優れ、シリカ粒子の凝集を抑制することができる。また、シリカゾルのｐＨが８．０以下であると、シリカ粒子の溶解を防ぎ、長期間の保存安定性に優れる。
シリカゾルのｐＨは、ｐＨ調整剤を添加することで、所望の範囲に設定することができる。
The pH of the silica sol is preferably 6.0 to 8.0, more preferably 6.5 to 7.8. When the pH of the silica sol is 6.0 or more, the dispersion stability is excellent and the aggregation of silica particles can be suppressed. Further, when the pH of the silica sol is 8.0 or less, the dissolution of the silica particles is prevented and the storage stability for a long period of time is excellent.
The pH of the silica sol can be set in a desired range by adding a pH adjuster.
（研磨組成物）
本発明のシリカ粒子の製造方法で得られたシリカ粒子は、研磨組成物として好適に用いることができる。
研磨組成物は、前述したシリカゾル及び水溶性高分子を含むことが好ましい。
(Polishing composition)
The silica particles obtained by the method for producing silica particles of the present invention can be suitably used as a polishing composition.
The polishing composition preferably contains the above-mentioned silica sol and a water-soluble polymer.
水溶性高分子は、シリコンウェハに代表される被研磨体に対する研磨組成物の濡れ性を高める。水溶性高分子は、水親和性の高い官能基を保有する高分子であることが好ましく、この水親和性の高い官能基とシリカ粒子の表面シラノール基との親和性が高く、研磨組成物中でより近傍にシリカ粒子と水溶性高分子とが安定して分散する。そのため、シリコンウェハに代表される被研磨体への研磨の際、シリカ粒子と水溶性高分子との効果が相乗的に機能する。 The water-soluble polymer enhances the wettability of the polishing composition with respect to the object to be polished represented by a silicon wafer. The water-soluble polymer is preferably a polymer having a functional group having a high water affinity, and the functional group having a high water affinity has a high affinity with the surface silanol group of the silica particles, and is contained in the polishing composition. The silica particles and the water-soluble polymer are stably dispersed in the vicinity. Therefore, the effects of the silica particles and the water-soluble polymer function synergistically when polishing the object to be polished represented by a silicon wafer.
水溶性高分子としては、例えば、セルロース誘導体、ポリビニルアルコール、ポリビニルピロリドン、ポリビニルピロリドン骨格を有する共重合体、ポリオキシアルキレン構造を有する重合体等が挙げられる。 Examples of the water-soluble polymer include cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone, copolymers having a polyvinylpyrrolidone skeleton, and polymers having a polyoxyalkylene structure.
セルロース誘導体としては、例えば、ヒドロキシエチルセルロース、加水分解処理を施したヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシエチルメチルセルロース、ヒドロキシプロピルメチルセルロース、メチルセルロース、エチルセルロース、エチルヒドロキシエチルセルロース、カルボキシメチルセルロース等が挙げられる。
ポリビニルピロリドン骨格を有する共重合体としては、例えば、ポリビニルアルコールとポリビニルピロリドンとのグラフト共重合体等が挙げられる。
ポリオキシアルキレン構造を有する重合体としては、例えば、ポリオキシエチレン、ポリオキシプロピレン、エチレンオキサイドとプロピレンオキサイドとの共重合体等が挙げられる。
Examples of the cellulose derivative include hydroxyethyl cellulose, hydrolyzed hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropylmethyl cellulose, methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose and the like.
Examples of the copolymer having a polyvinylpyrrolidone skeleton include a graft copolymer of polyvinyl alcohol and polyvinylpyrrolidone.
Examples of the polymer having a polyoxyalkylene structure include polyoxyethylene, polyoxypropylene, and a copolymer of ethylene oxide and propylene oxide.
これらの水溶性高分子は、１種を単独で用いてもよく、２種以上を併用してもよい。これらの水溶性高分子の中でも、シリカ粒子の表面シラノール基との親和性が高く、相乗的に作用して被研磨体の表面に良好な親水性を与えることから、セルロース誘導体が好ましく、ヒドロキシエチルセルロースがより好ましい。 These water-soluble polymers may be used alone or in combination of two or more. Among these water-soluble polymers, a cellulose derivative is preferable because it has a high affinity with the surface silanol group of the silica particles and acts synergistically to give good hydrophilicity to the surface of the object to be polished. Is more preferable.
水溶性高分子の質量平均分子量は、１，０００〜３，０００，０００が好ましく、５，０００〜２，０００，０００がより好ましく、１０，０００〜１，０００，０００が更に好ましい。水溶性高分子の質量平均分子量が１，０００以上であると、研磨組成物の親水性が向上する。また、水溶性高分子の質量平均分子量が３，０００，０００以下であると、シリカゾルとの親和性に優れ、シリコンウェハに代表される被研磨体に対する研磨レートに優れる。 The mass average molecular weight of the water-soluble polymer is preferably 1,000 to 3,000,000, more preferably 5,000 to 2,000,000, and even more preferably 10,000 to 1,000,000. When the mass average molecular weight of the water-soluble polymer is 1,000 or more, the hydrophilicity of the polishing composition is improved. Further, when the mass average molecular weight of the water-soluble polymer is 3,000,000 or less, the affinity with the silica sol is excellent, and the polishing rate for the object to be polished represented by the silicon wafer is excellent.
水溶性高分子の質量平均分子量は、ポリエチレンオキサイド換算で、０．１ｍｏｌ／ＬのＮａＣｌ溶液を移動相とする条件で、サイズ排除クロマトグラフィーにより測定する。 The mass average molecular weight of the water-soluble polymer is measured by size exclusion chromatography under the condition that a 0.1 mol / L NaCl solution is used as a mobile phase in terms of polyethylene oxide.
研磨組成物中の水溶性高分子の含有率は、研磨組成物全量１００質量％中、０．０２質量％〜１０質量％が好ましく、０．０５質量％〜５質量％がより好ましい。研磨組成物中の水溶性高分子の含有率が０．０２質量％以上であると、研磨組成物の親水性が向上する。また、研磨組成物中の水溶性高分子の含有率が１０質量％以下であると、研磨組成物調製時のシリカ粒子の凝集を抑制することができる。 The content of the water-soluble polymer in the polishing composition is preferably 0.02% by mass to 10% by mass, more preferably 0.05% by mass to 5% by mass, based on 100% by mass of the total amount of the polishing composition. When the content of the water-soluble polymer in the polishing composition is 0.02% by mass or more, the hydrophilicity of the polishing composition is improved. Further, when the content of the water-soluble polymer in the polishing composition is 10% by mass or less, the aggregation of silica particles at the time of preparing the polishing composition can be suppressed.
研磨組成物は、シリカゾル及び水溶性高分子以外に、その性能を損なわない範囲において、必要に応じて、塩基性化合物、研磨促進剤、界面活性剤、親水性化合物、防腐剤、防黴剤、ｐＨ調整剤、ｐＨ緩衝剤、界面活性剤、キレート剤、抗菌殺生物剤等の他の成分を含んでもよい。
特に、シリコンウェハに代表される被研磨体の表面に化学的な作用を与えて化学的研磨（ケミカルエッチング）ができ、シリカ粒子の表面シラノール基との相乗効果により、シリコンウェハに代表される被研磨体の研磨速度を向上させることができることから、研磨組成物中に塩基性化合物を含ませることが好ましい。
In addition to silica sol and water-soluble polymers, the polishing composition may contain basic compounds, polishing accelerators, surfactants, hydrophilic compounds, preservatives, fungicides, as necessary, as long as the performance is not impaired. It may contain other components such as pH regulators, pH buffers, surfactants, chelating agents, antibacterial killing agents and the like.
In particular, it is possible to perform chemical polishing (chemical etching) by giving a chemical action to the surface of the object to be polished represented by a silicon wafer, and due to the synergistic effect with the surface silanol groups of silica particles, the surface of the object to be polished is represented by a silicon wafer. Since the polishing speed of the polished body can be improved, it is preferable to include a basic compound in the polishing composition.
塩基性化合物としては、例えば、有機塩基性化合物、アルカリ金属水酸化物、アルカリ金属炭酸水素塩、アルカリ金属炭酸塩、アンモニア等が挙げられる。これらの塩基性化合物は、１種を単独で用いてもよく、２種以上を併用してもよい。これらの塩基性化合物の中でも、水溶性が高く、シリカ粒子や水溶性高分子との親和性に優れることから、アンモニア、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、炭酸水素アンモニウム、炭酸アンモニウムが好ましく、アンモニア、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウムがより好ましく、アンモニアが更に好ましい。 Examples of the basic compound include organic basic compounds, alkali metal hydroxides, alkali metal hydrogen carbonates, alkali metal carbonates, ammonia and the like. These basic compounds may be used alone or in combination of two or more. Among these basic compounds, ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, ammonium hydrogencarbonate, and ammonium carbonate are preferable because they are highly water-soluble and have excellent affinity with silica particles and water-soluble polymers. , Ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide are more preferable, and ammonia is even more preferable.
研磨組成物中の塩基性化合物の含有率は、研磨組成物全量１００質量％中、０．００１質量％〜５質量％が好ましく、０．０１質量％〜３質量％がより好ましい。研磨組成物中の塩基性化合物の含有率が０．００１質量％以上であると、シリコンウェハに代表される被研磨体の研磨速度を向上させることができる。また、研磨組成物中の塩基性化合物の含有率が５質量％以下であると、研磨組成物の安定性に優れる。 The content of the basic compound in the polishing composition is preferably 0.001% by mass to 5% by mass, more preferably 0.01% by mass to 3% by mass, based on 100% by mass of the total amount of the polishing composition. When the content of the basic compound in the polishing composition is 0.001% by mass or more, the polishing speed of the object to be polished represented by a silicon wafer can be improved. Further, when the content of the basic compound in the polishing composition is 5% by mass or less, the stability of the polishing composition is excellent.
研磨組成物のｐＨは、８．０〜１２．０が好ましく、９．０〜１１．０がより好ましい。研磨組成物のｐＨが８．０以上であると、研磨組成物中のシリカ粒子の凝集を抑制することができ、研磨組成物の分散安定性に優れる。また、研磨組成物のｐＨが１２．０以下であると、シリカ粒子の溶解を抑制することができ、研磨組成物の安定性に優れる。
研磨組成物のｐＨは、ｐＨ調整剤を添加することで、所望の範囲に設定することができる。
The pH of the polishing composition is preferably 8.0 to 12.0, more preferably 9.0 to 11.0. When the pH of the polishing composition is 8.0 or more, the aggregation of silica particles in the polishing composition can be suppressed, and the dispersion stability of the polishing composition is excellent. Further, when the pH of the polishing composition is 12.0 or less, the dissolution of silica particles can be suppressed and the stability of the polishing composition is excellent.
The pH of the polishing composition can be set in a desired range by adding a pH adjuster.
研磨組成物は、本発明のシリカゾルの製造方法で得られたシリカゾル、水溶性高分子、及び、必要に応じて、他の成分を混合することで得られるが、保管、運搬を考慮し、一旦高濃度で調製し、研磨直前に水等で希釈してもよい。 The polishing composition can be obtained by mixing the silica sol obtained by the method for producing a silica sol of the present invention, a water-soluble polymer, and other components as necessary, but once considering storage and transportation. It may be prepared at a high concentration and diluted with water or the like immediately before polishing.
（研磨方法）
本発明の研磨方法は、本発明のシリカゾルの製造方法で得られたシリカゾルを含む研磨組成物を用いて研磨する方法である。
研磨組成物は、前述した研磨組成物を用いることが好ましい。
具体的な研磨の方法としては、例えば、シリコンウェハの表面を研磨パッドに押し付け、研磨パッド上に本発明の研磨組成物を滴下し、シリコンウェハの表面を研磨する方法が挙げられる。
(Polishing method)
The polishing method of the present invention is a method of polishing using a polishing composition containing a silica sol obtained by the method for producing a silica sol of the present invention.
As the polishing composition, it is preferable to use the above-mentioned polishing composition.
Specific examples of the polishing method include a method in which the surface of a silicon wafer is pressed against a polishing pad, the polishing composition of the present invention is dropped onto the polishing pad, and the surface of the silicon wafer is polished.
（半導体ウェハの製造方法）
本発明の半導体ウェハの製造方法は、本発明の研磨方法を含む方法であり、具体的な研磨方法は、前述した通りである。
半導体ウェハとしては、例えば、シリコンウェハ、化合物半導体ウェハ等が挙げられる。
(Manufacturing method of semiconductor wafer)
The method for manufacturing a semiconductor wafer of the present invention is a method including the polishing method of the present invention, and the specific polishing method is as described above.
Examples of the semiconductor wafer include a silicon wafer and a compound semiconductor wafer.
（半導体デバイスの製造方法）
本発明の半導体デバイスの製造方法は、本発明の研磨方法を含む方法であり、具体的な研磨方法は、前述した通りである。
(Manufacturing method of semiconductor device)
The method for manufacturing a semiconductor device of the present invention is a method including the polishing method of the present invention, and the specific polishing method is as described above.
（用途）
本発明のシリカ粒子の製造方法で得られたシリカ粒子、本発明のシリカゾルの製造方法で得られたシリカゾルは、研磨用途に好適に用いることができ、例えば、シリコンウェハ等の半導体材料の研磨、ハードディスク基板等の電子材料の研磨、集積回路を製造する際の平坦化工程における研磨（化学的機械的研磨）、フォトマスクや液晶に用いる合成石英ガラス基板の研磨、磁気ディスク基板の研磨等に用いることができる。中でもシリコンウェハの研磨や化学的機械的研磨に特に好適に用いることができる。
(Use)
The silica particles obtained by the method for producing silica particles of the present invention and the silica sol obtained by the method for producing a silica sol of the present invention can be suitably used for polishing applications, for example, polishing a semiconductor material such as a silicon wafer. Used for polishing electronic materials such as hard disk substrates, polishing in the flattening process when manufacturing integrated circuits (chemical mechanical polishing), polishing synthetic quartz glass substrates used for photomasks and liquid crystals, polishing magnetic disk substrates, etc. be able to. Above all, it can be particularly preferably used for polishing silicon wafers and chemical mechanical polishing.
以下、実施例を用いて本発明を更に具体的に説明するが、本発明は、その要旨を逸脱しない限り、以下の実施例の記載に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the description of the following examples as long as it does not deviate from the gist thereof.
（平均１次粒子径の測定）
実施例及び比較例で得られたシリカ粒子の分散液を１５０℃で乾燥し、比表面積自動測定装置「ＢＥＬＳＯＲＰ−ＭＲ１」（機種名、マイクロトラック・ベル株式会社）を用いて、シリカ粒子の比表面積を測定し、下記式（１）を用い、密度を２．２ｇ／ｃｍ３として平均１次粒子径を算出した。
平均１次粒子径（ｎｍ）＝６０００／(比表面積(ｍ２／ｇ)×密度(ｇ／ｃｍ３))
・・・ （１）
(Measurement of average primary particle size)
The dispersions of silica particles obtained in Examples and Comparative Examples were dried at 150 ° C., and the specific surface area automatic measuring device "BELSORP-MR1" (model name, Microtrac Bell Co., Ltd.) was used to ratio the silica particles. The surface area was measured, and the average primary particle size was calculated using the following formula (1) with a density of 2.2 g / cm 3.
Average primary particle diameter (nm) = 6000 / (specific surface area (m 2 / g) x density (g / cm 3 ))
... (1)
（平均２次粒子径、ｃｖ値の測定）
実施例及び比較例で得られたシリカ粒子の分散液を、動的光散乱粒子径測定装置「ゼーターサイザーナノＺＳ」（機種名、マルバーン社製）を用いて、シリカ粒子の平均２次粒子径を測定し、下記式（２）を用いてｃｖ値を算出した。
ｃｖ値＝（標準偏差（ｎｍ）／平均２次粒子径（ｎｍ））×１００ ・・・ （２）
(Measurement of average secondary particle diameter and cv value)
Using the dynamic light scattering particle size measuring device "Zetersizer Nano ZS" (model name, manufactured by Malvern), the dispersions of silica particles obtained in Examples and Comparative Examples were used to measure the average secondary particle size of the silica particles. Was measured, and the cv value was calculated using the following formula (2).
cv value = (standard deviation (nm) / average secondary particle size (nm)) x 100 ... (2)
（会合比の算出）
測定した平均１次粒子径と平均２次粒子径とから、下記式（３）を用いて会合比を算出した。
会合比＝平均２次粒子径／平均１次粒子径 ・・・ （３）
(Calculation of meeting ratio)
From the measured average primary particle diameter and average secondary particle diameter, the association ratio was calculated using the following formula (3).
Association ratio = average secondary particle diameter / average primary particle diameter ... (3)
（シリカ粒子同士が接合した凝集粒子量の測定）
実施例及び比較例で得られたシリカ粒子の分散液を超純水で５０００倍に希釈し、希釈したシリカ粒子の分散液５μＬをシリコン基板上に滴下し乾燥させた。次いで、電界放出型走査電子顕微鏡（機種名「Ｓ−５２００型」、株式会社日立ハイテクノロジーズ製、ＦＥ−ＳＥＭ）を用いて、シリコン基板に加速電圧５ｋＶで電子線を照射し、倍率５万倍で観測される二次電子像を撮影した。撮影した写真を、画像解析式粒度分布測定ソフト（ソフト名「Ｍａｃ−Ｖｉｅｗ Ｖｅｒ．４」、株式会社マウンテック製）に取り込み、同一視野に含まれる全シリカ粒子（８０個〜１２０個）の面積を測定した。シリカ粒子が２個以上接合した粒子を凝集粒子と定義し、全粒子の面積の総和に対する凝集粒子の面積の割合（面積％）を算出した。
(Measurement of agglomerated particles in which silica particles are bonded together)
The dispersions of silica particles obtained in Examples and Comparative Examples were diluted 5000 times with ultrapure water, and 5 μL of the diluted dispersions of silica particles was dropped onto a silicon substrate and dried. Next, using a field emission scanning electron microscope (model name "S-5200", manufactured by Hitachi High-Technologies Co., Ltd., FE-SEM), the silicon substrate was irradiated with electron beams at an acceleration voltage of 5 kV, and the magnification was 50,000 times. The secondary electron image observed in was taken. The photograph taken is taken into the image analysis type particle size distribution measurement software (software name "Mac-View Ver.4", manufactured by Mountech Co., Ltd.), and the area of all silica particles (80 to 120) contained in the same field of view is captured. It was measured. Particles in which two or more silica particles are bonded are defined as agglomerated particles, and the ratio of the area of the agglomerated particles (area%) to the total area of all the particles is calculated.
（反応槽の壁面状態の測定）
実施例及び比較例でシリカ粒子を得るために用いた反応槽の壁面を目視で観察し、以下のような指標で評価した。
Ａ：反応槽の壁面へのシリカ粒子の付着がほぼ確認できなかった。
Ｂ：反応槽の壁面への少量のシリカ粒子の付着が確認された。
Ｃ：反応槽の壁面への多量のシリカ粒子の付着が確認された。
(Measurement of wall surface condition of reaction tank)
The wall surface of the reaction vessel used to obtain silica particles in Examples and Comparative Examples was visually observed and evaluated by the following indexes.
A: Almost no adhesion of silica particles to the wall surface of the reaction tank could be confirmed.
B: Adhesion of a small amount of silica particles to the wall surface of the reaction tank was confirmed.
C: It was confirmed that a large amount of silica particles adhered to the wall surface of the reaction vessel.
［実施例１］
反応槽に供給した純水３．９質量部、メタノール７７．８質量部及び１０質量％アンモニア水１１．１質量部を混合した溶液（Ａ−１）に、テトラメトキシシラン１００質量部及びメタノール２５．０質量部を混合した溶液（Ｂ−１）（テトラメトキシシランの濃度８０質量％）と、純水２９．１質量部及び１０質量％アンモニア水１５．６質量部を混合した溶液（Ｃ−１）とを、２５３分かけてそれぞれ等速で滴下した（溶液（Ｂ−１）の添加速度：１００ｇシリカ／時／ｋｇ溶液、溶液（Ｃ−１）の添加速度：４ｇアルカリ触媒／時／ｋｇ溶液）。滴下中、反応液の温度を３７℃に保ったまま、反応液を撹拌動力７８Ｗ／ｍ３で撹拌した。滴下終了後、反応液の温度を３７℃に保ったまま、更に反応液を同じ撹拌動力で３０分間撹拌した。反応液を濾過し、シリカ粒子濃度１６質量％のシリカ粒子の分散液を得た。
得られたシリカ粒子の評価結果を、表１に示す。
[Example 1]
A solution (A-1) in which 3.9 parts by mass of pure water, 77.8 parts by mass of methanol and 11.1 parts by mass of 10% by mass aqueous ammonia supplied to the reaction vessel are mixed with 100 parts by mass of tetramethoxysilane and 25 parts by mass of methanol. .0 parts by mass mixed solution (B-1) (tetramethoxysilane concentration 80% by mass) mixed with 29.1 parts by mass of pure water and 15.6 parts by mass of 10% by mass ammonia water (C- 1) and 1) were added dropwise at a constant velocity over 253 minutes (addition rate of solution (B-1): 100 g silica / hour / kg solution, addition rate of solution (C-1): 4 g alkali catalyst / hour / kg solution). During the dropping, the reaction solution was stirred with a stirring power of 78 W / m 3 while keeping the temperature of the reaction solution at 37 ° C. After completion of the dropping, the reaction solution was further stirred with the same stirring power for 30 minutes while keeping the temperature of the reaction solution at 37 ° C. The reaction solution was filtered to obtain a dispersion of silica particles having a silica particle concentration of 16% by mass.
The evaluation results of the obtained silica particles are shown in Table 1.
［比較例１］
撹拌動力を１２Ｗ／ｍ３とした以外は、実施例１と同様に操作した。
得られたシリカ粒子の評価結果を、表１に示す。
[Comparative Example 1]
The operation was performed in the same manner as in Example 1 except that the stirring power was set to 12 W / m 3.
The evaluation results of the obtained silica particles are shown in Table 1.
［比較例２］
撹拌動力を４０３Ｗ／ｍ３とした以外は、実施例１と同様に操作した。
得られたシリカ粒子の評価結果を、表１に示す。
[Comparative Example 2]
The operation was performed in the same manner as in Example 1 except that the stirring power was set to 403 W / m 3.
The evaluation results of the obtained silica particles are shown in Table 1.
表１から分かるように、実施例１のシリカ粒子の製造方法は、比較例１〜２のシリカ粒子の製造方法と比較して、反応槽の壁面に付着するシリカ粒子を抑制すると共に、シリカ粒子同士が凝集した粗大粒子の発生を抑制することができた。 As can be seen from Table 1, the method for producing silica particles of Example 1 suppresses the silica particles adhering to the wall surface of the reaction vessel and suppresses the silica particles as compared with the method for producing silica particles of Comparative Examples 1 and 2. It was possible to suppress the generation of coarse particles in which they aggregated with each other.
本発明のシリカ粒子の製造方法で得られたシリカ粒子、本発明のシリカゾルの製造方法で得られたシリカゾルは、研磨用途に好適に用いることができ、例えば、シリコンウェハ等の半導体材料の研磨、ハードディスク基板等の電子材料の研磨、集積回路を製造する際の平坦化工程における研磨（化学的機械的研磨）、フォトマスクや液晶に用いる合成石英ガラス基板の研磨、磁気ディスク基板の研磨等に用いることができる。中でもシリコンウェハの研磨や化学的機械的研磨に特に好適に用いることができる。 The silica particles obtained by the method for producing silica particles of the present invention and the silica sol obtained by the method for producing a silica sol of the present invention can be suitably used for polishing applications, for example, polishing a semiconductor material such as a silicon wafer. Used for polishing electronic materials such as hard disk substrates, polishing in the flattening process when manufacturing integrated circuits (chemical mechanical polishing), polishing synthetic quartz glass substrates used for photomasks and liquid crystals, polishing magnetic disk substrates, etc. be able to. Above all, it can be particularly preferably used for polishing silicon wafers and chemical mechanical polishing.
Claims (11)
工程（１）：得られたシリカ粒子の分散液を濃縮し、分散媒を添加する工程 The method for producing silica particles according to any one of claims 1 to 4, further comprising the following step (1).
Step (1): A step of concentrating the obtained dispersion of silica particles and adding a dispersion medium.
工程（２）：工程（１）で得られたシリカ粒子の分散液を加圧加熱処理する工程 The method for producing silica particles according to claim 5, further comprising the following step (2).
Step (2): A step of pressurizing and heat-treating the dispersion liquid of the silica particles obtained in the step (1).
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