JP2009188058A - Colloidal silica for polishing semiconductor wafer and method for producing the same - Google Patents
Colloidal silica for polishing semiconductor wafer and method for producing the same Download PDFInfo
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- JP2009188058A JP2009188058A JP2008024375A JP2008024375A JP2009188058A JP 2009188058 A JP2009188058 A JP 2009188058A JP 2008024375 A JP2008024375 A JP 2008024375A JP 2008024375 A JP2008024375 A JP 2008024375A JP 2009188058 A JP2009188058 A JP 2009188058A
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- colloidal silica
- polishing
- silica
- alanine
- semiconductor wafer
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 235
- 238000005498 polishing Methods 0.000 title claims abstract description 106
- 239000008119 colloidal silica Substances 0.000 title claims abstract description 89
- 239000004065 semiconductor Substances 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000002245 particle Substances 0.000 claims abstract description 56
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims abstract description 52
- 235000004279 alanine Nutrition 0.000 claims abstract description 51
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000004471 Glycine Substances 0.000 claims abstract description 43
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 41
- 239000007864 aqueous solution Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 27
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 6
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 57
- 235000012431 wafers Nutrition 0.000 claims description 38
- 239000003513 alkali Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 15
- 230000005540 biological transmission Effects 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 13
- 230000003139 buffering effect Effects 0.000 claims description 9
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 9
- -1 (B-1) Next Substances 0.000 claims description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- 238000005530 etching Methods 0.000 abstract description 14
- 230000003746 surface roughness Effects 0.000 abstract description 2
- 229960003767 alanine Drugs 0.000 description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- 229960002449 glycine Drugs 0.000 description 39
- 239000000203 mixture Substances 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 20
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000010949 copper Substances 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 8
- 239000004115 Sodium Silicate Substances 0.000 description 7
- 239000006061 abrasive grain Substances 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- 229910052911 sodium silicate Inorganic materials 0.000 description 7
- QNAYBMKLOCPYGJ-UHFFFAOYSA-N Alanine Chemical compound CC([NH3+])C([O-])=O QNAYBMKLOCPYGJ-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910021485 fumed silica Inorganic materials 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000001788 irregular Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000007517 polishing process Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000000108 ultra-filtration Methods 0.000 description 5
- 229910000881 Cu alloy Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000006174 pH buffer Substances 0.000 description 4
- 238000004438 BET method Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 239000007853 buffer solution Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000012510 hollow fiber Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 238000011085 pressure filtration Methods 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229950010030 dl-alanine Drugs 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 235000013905 glycine and its sodium salt Nutrition 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002649 leather substitute Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- HMBHAQMOBKLWRX-UHFFFAOYSA-N 2,3-dihydro-1,4-benzodioxine-3-carboxylic acid Chemical compound C1=CC=C2OC(C(=O)O)COC2=C1 HMBHAQMOBKLWRX-UHFFFAOYSA-N 0.000 description 1
- KIZQNNOULOCVDM-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CCO KIZQNNOULOCVDM-UHFFFAOYSA-M 0.000 description 1
- 208000032368 Device malfunction Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940024606 amino acid Drugs 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229940027991 antiseptic and disinfectant quinoline derivative Drugs 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229940075419 choline hydroxide Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- GICLSALZHXCILJ-UHFFFAOYSA-N ctk5a5089 Chemical compound NCC(O)=O.NCC(O)=O GICLSALZHXCILJ-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- LOAUVZALPPNFOQ-UHFFFAOYSA-N quinaldic acid Chemical compound C1=CC=CC2=NC(C(=O)O)=CC=C21 LOAUVZALPPNFOQ-UHFFFAOYSA-N 0.000 description 1
- LISFMEBWQUVKPJ-UHFFFAOYSA-N quinolin-2-ol Chemical compound C1=CC=C2NC(=O)C=CC2=C1 LISFMEBWQUVKPJ-UHFFFAOYSA-N 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
【課題】半導体ウエハ表面に生じる過剰エッチングを抑制し、かつ高い研磨速度を維持しつつ、良好な面粗さが得られる半導体ウエハの鏡面研磨用コロイダルシリカおよびその製造方法を提供する。
【解決手段】シリカ粒子の長径／短径比が１．２〜２０であって、長径／短径比の平均値が３〜１５である非球状の異形粒子群となっているコロイダルシリカである。これは、珪酸アルカリ水溶液とカチオン交換樹脂とを接触させて、活性珪酸水溶液を調製した後、この活性珪酸水溶液にグリシンまたはアラニンを加えて加熱し、ビルドアップの手法で粒子成長を行うことにより製造することができる。
【選択図】なしDisclosed is a colloidal silica for mirror polishing of a semiconductor wafer and a method for producing the same, which can suppress the excessive etching generated on the surface of a semiconductor wafer and maintain a high polishing rate while obtaining good surface roughness.
The colloidal silica is a non-spherical deformed particle group having a major axis / minor axis ratio of 1.2 to 20 and an average value of major axis / minor axis ratio of 3 to 15. . This is made by bringing an alkali silicate aqueous solution and a cation exchange resin into contact with each other to prepare an active silicic acid aqueous solution, adding glycine or alanine to the active silicic acid aqueous solution and heating it, and performing particle growth by a build-up method. can do.
[Selection figure] None
Description
本発明は、シリコンウエハあるいは表面に金属膜、酸化物膜、窒化物膜等（以下、金属膜等と記載する）が形成された半導体デバイス基板等の半導体ウエハの平面およびエッジ部分に研磨加工を施す半導体ウエハ研磨用コロイダルシリカ及びその製造方法に関する。
以下「半導体ウエハ研磨用コロイダルシリカ」を「研磨用コロイダルシリカ」と略記することがある。
The present invention polishes the planar and edge portions of a semiconductor wafer such as a semiconductor device substrate on which a silicon film or a metal film, oxide film, nitride film, etc. (hereinafter referred to as a metal film) is formed. The present invention relates to a semiconductor wafer polishing colloidal silica to be applied and a manufacturing method thereof.
Hereinafter, “semiconductor wafer polishing colloidal silica” may be abbreviated as “polishing colloidal silica”.
シリコン単結晶等半導体素材を原材料としたＩＣ、ＬＳＩあるいは超ＬＳＩ等の電子部品は、シリコンあるいはその他の化合物半導体の単結晶インゴットを薄い円板状にスライスしたウエハに多数の微細な電気回路を書き込み分割した小片状の半導体素子チップを基に製造されるものである。インゴットからスライスされたウエハは、ラッピング、エッチング、更には研磨（以下ポリッシングと記載することもある）という工程を経て、平面およびエッジ面が鏡面に仕上げられた鏡面ウエハに加工される。ウエハは、その後のデバイス工程にてその鏡面仕上げされた表面に微細な電気回路が形成されて行くのであるが、現在、ＬＳＩの高速化の観点から、配線材料は従来のＡｌからより電気抵抗の低いＣｕに、配線間の絶縁膜は、シリコン酸化膜からより誘電率の低い低誘電率膜に、更にＣｕと低誘電率膜の間に、Ｃｕが低誘電率膜中に拡散することを防止するためのタンタルや窒化タンタルによるバリア膜を介した構造を有する配線形成プロセスに移行しつつある。こうした配線構造の形成と高集積化のために、層間絶縁膜の平坦化、多層配線の上下配線間の金属接続部（プラグ）形成や埋め込み配線形成などに繰り返し頻繁に研磨工程が行われる。この平面の研磨においては、合成樹脂発泡体あるいはスウェード調合成皮革等よりなる研磨布を展張した定盤上に半導体ウエハを載置し、押圧回転しつつ研磨用組成物溶液を定量的に供給しながら加工を行なう方法が一般的である。
エッジ面は上記の金属膜等が不規則に堆積した状態となっている。半導体素子チップに分割されるまではウエハは最初の円板状の形状を保ったままエッジ部を支えにした搬送等の工程が入る。搬送時にウエハの外周側面エッジが不規則な構造形状であると、搬送装置との接触により微小破壊が起こり微細粒子を発生する。その後の工程で発生した微粒子が散逸して精密加工を施した面を汚染し、製品の歩留まりや品質に大きな影響を与える。この微粒子汚染を防止するために、金属膜等の形成後に半導体ウエハのエッジ部分を鏡面研磨する加工が必要となっている。
Electronic parts such as ICs, LSIs, or VLSIs that are made from silicon single crystal semiconductor materials, etc., write a large number of fine electric circuits on a wafer sliced from a single crystal ingot of silicon or other compound semiconductor into a thin disk shape. It is manufactured based on the divided piece-like semiconductor element chip. The wafer sliced from the ingot is processed into a mirror surface wafer whose surface and edge surface are mirror-finished through processes of lapping, etching, and polishing (hereinafter also referred to as polishing). In the wafer process, a fine electrical circuit is formed on the mirror-finished surface in the subsequent device process. Currently, from the viewpoint of increasing the speed of LSI, the wiring material is more resistant than conventional Al. Low Cu, insulating film between wiring prevents silicon from diffusing into low dielectric constant film from silicon oxide film to low dielectric constant film with lower dielectric constant, and between Cu and low dielectric constant film Therefore, the process is moving to a wiring formation process having a structure through a barrier film of tantalum or tantalum nitride. In order to form such a wiring structure and achieve high integration, a polishing process is frequently performed repeatedly for flattening an interlayer insulating film, forming a metal connection part (plug) between upper and lower wirings of a multilayer wiring, and forming a buried wiring. In this flat surface polishing, a semiconductor wafer is placed on a surface plate on which a polishing cloth made of a synthetic resin foam or a suede-like synthetic leather is stretched, and a polishing composition solution is quantitatively supplied while pressing and rotating. However, the method of processing is common.
The edge surface is in a state where the above metal film or the like is irregularly deposited. Until the wafer is divided into semiconductor element chips, the wafer is subjected to a process such as conveyance with the edge portion supported while maintaining the original disk shape. If the outer peripheral side edge of the wafer has an irregular structure at the time of transfer, micro-breakage occurs due to contact with the transfer device, and fine particles are generated. The fine particles generated in the subsequent processes are dissipated and contaminate the surface that has been subjected to precision processing, greatly affecting the product yield and quality. In order to prevent this fine particle contamination, it is necessary to perform mirror polishing of the edge portion of the semiconductor wafer after the formation of the metal film or the like.
上述のエッジ研磨は、研磨布支持体の表面に、合成樹脂発泡体、合成皮革あるいは不織布等からなる研磨布を貼付した研磨加工機に、半導体ウエハのエッジ部分を押圧しながら、シリカ等の研磨砥粒を主成分とする研磨用組成物溶液を供給しつつ、研磨布支持体とウエハもしくはどちらか一方を回転させて達成される。この際用いられる研磨用組成物の砥粒としては、シリコンウエハのエッジ研磨に用いられるものと同等のコロイダルシリカや、デバイスウエハの平面研磨に用いられるヒュームドシリカやセリア、アルミナなどが提案されている。特にコロイダルシリカやヒュームドシリカは微細な粒子であるため平滑な鏡面を得られ易く注目されている。
このような研磨用組成物は「スラリー」とも呼ばれ、以下にそのように記載することもある。
The above-mentioned edge polishing is performed by polishing silica or the like while pressing the edge portion of a semiconductor wafer on a polishing machine in which a polishing cloth made of synthetic resin foam, synthetic leather or nonwoven fabric is attached to the surface of the polishing cloth support. This is achieved by rotating a polishing pad support and / or a wafer while supplying a polishing composition solution containing abrasive grains as a main component. As abrasive grains of the polishing composition used at this time, colloidal silica equivalent to that used for edge polishing of silicon wafers, fumed silica, ceria, alumina, etc. used for planar polishing of device wafers have been proposed. Yes. In particular, colloidal silica and fumed silica are fine particles, and are attracting attention because they can easily obtain a smooth mirror surface.
Such a polishing composition is also referred to as a “slurry” and may be described as such below.
シリカ砥粒を主成分とする研磨用組成物は、アルカリ成分を含む溶液が一般的で、加工の原理は、アルカリ成分による化学的作用、具体的には酸化珪素膜や金属膜等の表面に対する浸蝕作用とシリカ砥粒の機械的な研磨作用を併用したものである。具体的には、アルカリ成分の侵食作用により、ウエハ等被加工物表面に薄い軟質の浸蝕層が形成される。その浸蝕層を微細砥粒粒子の機械的研磨作用により除去する機構と推定されており、この工程を繰り返すことにより加工が進むと考えられている。 A polishing composition mainly composed of silica abrasive grains is generally a solution containing an alkali component, and the principle of processing is chemical action by the alkali component, specifically, the surface of a silicon oxide film, a metal film or the like. This is a combination of the erosion action and the mechanical polishing action of silica abrasive grains. Specifically, a thin soft erosion layer is formed on the surface of a workpiece such as a wafer by the erosion action of an alkali component. It is presumed to be a mechanism for removing the eroded layer by the mechanical polishing action of fine abrasive grains, and it is considered that the processing proceeds by repeating this process.
また、デバイス配線の微細化は年々顕著になってきており、国際半導体技術ロードマップ（International Technology Roadmap for Semiconductors）によれば、デバイスの配線幅の目標値として２０１０年５０ｎｍ、２０１３年３５ｎｍが示されている。デバイスの配線幅の微細化に対応して、配線材料に銅や銅合金が使用されつつある。半導体ウエハの研磨に用いる研磨剤には、アルカリ成分以外に銅の酸化成分や選択的エッチング成分の使用が推奨されている。なかでもアミノ酸は過剰エッチングを起こしにくい薬剤として注目されてきたが、問題の解決には至っていない。半導体ウエハ表面の配線に対する過剰エッチングはデバイスの動作不良をもたらすため、深刻な課題となっている。 Further, miniaturization of device wiring is becoming more and more noticeable year by year, and according to the International Technology Roadmap for Semiconductors, the target value of the device wiring width is 50 nm in 2010 and 35 nm in 2013. ing. In response to the miniaturization of device wiring width, copper and copper alloys are being used as wiring materials. As an abrasive used for polishing a semiconductor wafer, it is recommended to use a copper oxidizing component or a selective etching component in addition to an alkali component. Of these, amino acids have been attracting attention as agents that are unlikely to cause excessive etching, but the problem has not been solved. Excessive etching of the wiring on the surface of the semiconductor wafer is a serious problem because it causes device malfunction.
従来から半導体ウエハの鏡面研磨では、様々な研磨用組成物が提案されている。特許文献１には、銅または銅合金の浸漬時において前記銅または銅合金を殆どエッチングせず、かつ研磨処理時に前記銅または銅合金を溶解して浸漬時と研磨処理時との間で数倍ないし数十倍のエッチング速度差を示す銅系金属用研磨液として、アミノ酢酸(グリシン)およびアミド硫酸から選ばれる少なくとも１種の有機酸と酸化剤と水とを含有するが研磨液が記載されている。特許文献２には、ディッシングの発生を抑制し、高い研磨速度で信頼性の高い導体膜を形成することができる研磨方法として、表面に凹部を有する基体上に前記凹部を充填するように金属を主成分とする材料からなる膜を形成し、金属主成分と反応して金属膜表面に保護膜を形成する化学試薬およびエッチング剤を含有する研磨剤を用いた化学機械的研磨方法が記載されており、保護膜を形成する化学試薬はアミノ酢酸またはアミド硫酸と酸化剤であると記載されている。特許文献３には、銅膜に対する研磨速度が大きく、一方、タンタル含有化合物に対する研磨速度が小さく、高い選択比を有し、かつ平滑性が優れた被研磨面を得ることができる研磨用組成物であって、α−アラニンを含む研磨用組成物であると記載されている。 Conventionally, various polishing compositions have been proposed for mirror polishing of semiconductor wafers. In Patent Document 1, the copper or copper alloy is hardly etched during the immersion of copper or copper alloy, and the copper or copper alloy is dissolved during the polishing process to be several times between the immersion and the polishing process. As a polishing liquid for copper-based metals exhibiting an etching rate difference of several to several tens of times, at least one organic acid selected from aminoacetic acid (glycine) and amidosulfuric acid, an oxidizing agent, and water is described. ing. In Patent Document 2, as a polishing method capable of suppressing the occurrence of dishing and forming a highly reliable conductor film at a high polishing rate, a metal is used to fill the recesses on a substrate having recesses on the surface. A chemical mechanical polishing method using an abrasive containing a chemical reagent and an etching agent that forms a film made of a material as a main component and reacts with a metal main component to form a protective film on the metal film surface is described. In addition, it is described that the chemical reagent forming the protective film is aminoacetic acid or amidosulfuric acid and an oxidizing agent. Patent Document 3 discloses a polishing composition capable of obtaining a polished surface having a high polishing rate for a copper film, a low polishing rate for a tantalum-containing compound, a high selectivity, and excellent smoothness. However, it is described as a polishing composition containing α-alanine.
上記特許文献１〜３記載のように、グリシンやアラニンは銅配線研磨に有利な薬剤である。 As described in Patent Documents 1 to 3, glycine and alanine are agents that are advantageous for copper wiring polishing.
また、非球状のシリカ粒子からなるコロイダルシリカも、数多く提案されている。特許文献４には、電子顕微鏡観察による５〜４０ミリミクロンの範囲内の一様な太さで一平面内のみの伸長を有する細長い形状の非晶質コロイダルシリカ粒子が液状媒体中に分散されてなる安定なシリカゾルが記載されている。特許文献５には、珪酸液添加工程の前、添加工程中または添加工程後に、アルミニウム塩などの金属化合物を添加する製法によって得られる細長い形状のシリカ粒子から成るシリカゾルが記載されている。特許文献６には、アルコキシシランの加水分解による長径／短径比が１．４〜２．２の繭型のシリカ粒子から成るコロイダルシリカが記載されている。特許文献７には、水ガラス法の活性珪酸水溶液に代替して、アルコキシシランの加水分解液を使用し、アルカリには水酸化テトラアルキルアンモニウムを使用して、非球状のシリカ粒子を含有するコロイダルシリカが得られることが記載されている。 Many colloidal silicas composed of non-spherical silica particles have also been proposed. In Patent Document 4, elongated colloidal silica particles having a uniform thickness within a range of 5 to 40 millimicrons observed by an electron microscope and extending only in one plane are dispersed in a liquid medium. A stable silica sol is described. Patent Document 5 describes a silica sol composed of elongated silica particles obtained by a manufacturing method in which a metal compound such as an aluminum salt is added before, during or after a silicic acid solution addition step. Patent Document 6 describes colloidal silica composed of cage-shaped silica particles having a major axis / minor axis ratio of 1.4 to 2.2 by hydrolysis of alkoxysilane. In Patent Document 7, a colloidal containing non-spherical silica particles using a hydrolyzed liquid of alkoxysilane instead of an active silicic acid aqueous solution of the water glass method and using tetraalkylammonium hydroxide as an alkali. It is described that silica is obtained.
特許文献４に記載のコロイダルシリカは、その製造において、水溶性のカルシウム塩、マグネシウム塩またはこれらの混合物を添加する工程があり、製品にはそれらが不純物として残存している。特許文献５に記載のコロイダルシリカはその製造において、水溶性のアルミニウム塩を添加する工程があり、製品にはそれらが不純物として残存している。特許文献６及び特許文献７に記載のコロイダルシリカはアルコキシシランをシリカ源とするので高純度で好ましいが、副生するアルコールの除去や価格など不利な一面がある。 In the production of colloidal silica described in Patent Document 4, there is a step of adding a water-soluble calcium salt, magnesium salt or a mixture thereof, and these remain as impurities in the product. In the production of colloidal silica described in Patent Document 5, there is a step of adding a water-soluble aluminum salt, and these remain as impurities in the product. The colloidal silicas described in Patent Document 6 and Patent Document 7 are preferable because of high purity because alkoxysilane is used as a silica source, but there are disadvantageous aspects such as removal of by-produced alcohol and cost.
本発明の目的は、半導体ウエハ表面に生じる過剰エッチングを抑制し、かつ高い研磨速度を維持しつつ、良好な面粗さが得られる半導体ウエハの平面およびエッジ部分の鏡面研磨用コロイダルシリカおよびその製造方法を提供することにある。 SUMMARY OF THE INVENTION An object of the present invention is to provide a colloidal silica for mirror polishing of the planar and edge portions of a semiconductor wafer that can provide a good surface roughness while suppressing excessive etching occurring on the surface of the semiconductor wafer and maintaining a high polishing rate It is to provide a method.
本発明者等は、グリシンまたはアラニンとアルカリ金属水酸化物を含み、２５℃においてｐＨ９．０〜１０．５の間で緩衝作用を有することを特徴とする半導体ウエハ研磨用コロイダルシリカを用いることにより、半導体ウエハの平面およびエッジ部分の鏡面研磨加工が効果的に行なえることを見出し、本発明を完成するに到った。 By using colloidal silica for polishing a semiconductor wafer, the present inventors include glycine or alanine and an alkali metal hydroxide and have a buffering action at 25 ° C. between pH 9.0 and 10.5. The present inventors have found that mirror polishing of the plane and edge portions of a semiconductor wafer can be performed effectively, and the present invention has been completed.
即ち、本発明の第一の発明は、珪酸アルカリ水溶液からアルカリを除去して得られた活性珪酸水溶液とグリシンまたはアラニンおよびアルカリ金属水酸化物によって製造され、２５℃においてｐＨ９．０〜１０．５の間でｐＨ緩衝作用を有するコロイダルシリカを含有する半導体ウエハ研磨用コロイダルシリカである。シリカ／グリシンまたはシリカ／アラニンのモル比が１０〜１５００であることがより好ましい。また、製造工程ではアルカリ金属水酸化物の一部を水酸化第４アンモニウムに代替することも好ましい。
この研磨用コロイダルシリカは非球状のシリカ粒子を含有することが好ましい。さらに、非球状のシリカ粒子は、透過型電子顕微鏡観察によるシリカ粒子の長径／短径比が１．２〜２０であって、長径／短径比の平均値が３〜１５である非球状の異形粒子群シリカ粒子であることが好ましい。透過型電子顕微鏡観察によるシリカ粒子の平均短径は５〜３０ｎｍであることが好ましい。この半導体ウエハ研磨用コロイダルシリカは、コロイド溶液全体に対してシリカ濃度が２〜５０重量％の水分散液であることが好ましい。
That is, the first invention of the present invention is produced from an active silicic acid aqueous solution obtained by removing alkali from an alkali silicate aqueous solution, glycine or alanine and an alkali metal hydroxide, and has a pH of 9.0 to 10.5 at 25 ° C. It is the colloidal silica for semiconductor wafer polishing containing the colloidal silica which has a pH buffer action between. The molar ratio of silica / glycine or silica / alanine is more preferably 10 to 1500. In the production process, it is also preferable to substitute a part of the alkali metal hydroxide with quaternary ammonium hydroxide.
The polishing colloidal silica preferably contains non-spherical silica particles. Further, the non-spherical silica particles are non-spherical having a major axis / minor axis ratio of 1.2 to 20 and an average major axis / minor axis ratio of 3 to 15 by observation with a transmission electron microscope. It is preferable that they are irregularly shaped particle group silica particles. The average minor axis of the silica particles by observation with a transmission electron microscope is preferably 5 to 30 nm. The semiconductor wafer polishing colloidal silica is preferably an aqueous dispersion having a silica concentration of 2 to 50% by weight based on the entire colloidal solution.
また、本発明の第二の発明は、（ａ）珪酸アルカリ水溶液をカチオン交換樹脂に接触させて活性珪酸水溶液を調製する工程、（ｂ−１）次いで前記活性珪酸水溶液にグリシンまたはアラニンとアルカリ金属水酸化物を添加してアルカリ性とした後、加熱してコロイド粒子を形成させ、（ｂ−２）続いて加熱下にアルカリ性を維持して前記活性珪酸水溶液とアルカリ剤または、前記活性珪酸水溶液とグリシンまたはアラニンとアルカリ剤を添加して粒子成長を行う工程、
を有することを特徴とする半導体ウエハ研磨用コロイダルシリカの製造方法である。さらに、（ｂ）工程の後、
（ｃ）シリカを濃縮する工程を行うことを特徴とする半導体ウエハ研磨用コロイダルシリカの製造方法である。
なお、コロイド粒子を形成と粒子成長の双方をあわせて、以下で「粒子成長」あるいは「成長」と記載することがある。
The second invention of the present invention includes (a) a step of bringing an aqueous alkali silicate solution into contact with a cation exchange resin to prepare an active silicic acid aqueous solution, and (b-1) glycine or alanine and an alkali metal in the active silicic acid aqueous solution. After adding a hydroxide to make it alkaline, the mixture is heated to form colloidal particles. (B-2) Subsequently, while maintaining the alkalinity under heating, the active silicic acid aqueous solution and the alkali agent or the active silicic acid aqueous solution and A step of growing particles by adding glycine or alanine and an alkaline agent,
It is a manufacturing method of the colloidal silica for semiconductor wafer polishing characterized by having. Furthermore, after the step (b),
(C) A method for producing colloidal silica for polishing a semiconductor wafer, comprising performing a step of concentrating silica.
In the following, the formation of colloidal particles and the growth of particles may be collectively referred to as “particle growth” or “growth”.
グリシンは別名アミノ酢酸であり、またアラニンは別名アミノプロピオン酸である。グリシンまたはアラニンの１％水溶液はｐＨが６の弱酸性であるが、水酸化ナトリウムのようなアルカリの共存下で範囲が９．０〜１０．５の弱いｐＨ緩衝作用を示す。アラニンはＤ-、Ｌ-、ＤＬ−アラニンのいずれでもよく、ＤＬ−アラニンが安価で好ましい。 Glycine is also known as aminoacetic acid and alanine is also known as aminopropionic acid. A 1% aqueous solution of glycine or alanine is weakly acidic with a pH of 6, but exhibits a weak pH buffering action in the range of 9.0 to 10.5 in the presence of an alkali such as sodium hydroxide. Alanine may be any of D-, L-, and DL-alanine, and DL-alanine is inexpensive and preferable.
本発明による研磨用コロイダルシリカを用いれば、半導体ウエハ等の研磨において過剰エッチングを起こしにくいという卓越した効果が得られる。「過剰エッチング」とは、配線金属および絶縁膜、バリア膜の研磨中に、配線金属部分だけを腐食してへこみを作ってしまう現象で、砥粒による研削とアルカリ成分による腐食の速度バランスが崩れたときに発生する。過剰エッチングは腐食ピット、配線コロージョン、タングステン配線のキーホールなどと称される不良品発生の原因とされている。本発明により、平面部の平坦度を改善し、ウエハの鏡面研磨加工において優れた研磨力とその持続性をもった研磨用コロイダルシリカが得られたものであり、関連業界に及ぼす効果は極めて大である。 By using the colloidal silica for polishing according to the present invention, an excellent effect that excessive etching is hardly caused in polishing of a semiconductor wafer or the like can be obtained. “Excessive etching” is a phenomenon in which only the wiring metal part is corroded during polishing of the wiring metal, insulating film, and barrier film, and the rate balance between grinding by abrasive grains and corrosion by alkali components is lost. Occurs when Excessive etching is considered to cause defective products called corrosion pits, wiring corrosion, tungsten wiring keyholes, and the like. According to the present invention, it is possible to obtain a colloidal silica for polishing which has improved flatness of a flat portion and has excellent polishing power and durability in mirror polishing of a wafer, and has an extremely large effect on related industries. It is.
本発明においては、実際の研磨加工時に安定な研磨力を持続するために、溶液全体のｐＨをｐＨ９．０〜１０．５の範囲に保つことが好ましい。ｐＨが９．０未満であると研磨速度は低下し実用の範囲からは外れることがある。また、ｐＨが１０．５を超えると、研磨部以外でのエッチングが強くなりすぎウエハの平坦度が低下しこれも実用の範囲から外れることがある。 In the present invention, it is preferable to maintain the pH of the entire solution in the range of pH 9.0 to 10.5 in order to maintain a stable polishing force during actual polishing. When the pH is less than 9.0, the polishing rate decreases and may be out of the practical range. On the other hand, when the pH exceeds 10.5, the etching at the portion other than the polishing portion becomes too strong, and the flatness of the wafer is lowered, which may be out of the practical range.
さらに、このｐＨは摩擦、熱、外気との接触あるいは他の成分との混合等、考えられる外的条件により容易に変化しないことが好ましい。特にエッジ研磨においては、研磨剤は循環流として使用される。すなわち、スラリータンクから研磨部位へ供給された研磨剤は、スラリータンクへ戻す方式で使用される。アルカリ剤だけを含む研磨剤は、循環使用中の純水希釈により短時間でｐＨが低下してしまう。これは、洗浄水である純水の混入によるもので、ｐＨの変動がもたらす研磨速度の変動は、研磨不足もしくは、研磨を行いすぎるために生じるオーバーポリッシュを起こしやすくなる。 Furthermore, it is preferable that this pH does not change easily due to possible external conditions such as friction, heat, contact with outside air, or mixing with other components. Especially in edge polishing, the abrasive is used as a circulating flow. That is, the polishing agent supplied from the slurry tank to the polishing site is used in a manner of returning to the slurry tank. The polishing agent containing only the alkaline agent is lowered in pH in a short time due to dilution with pure water during circulation use. This is due to the mixing of pure water as cleaning water, and the fluctuation in the polishing rate caused by the change in pH tends to cause insufficient polishing or over-polishing due to excessive polishing.
本発明の研磨用コロイダルシリカのｐＨを一定に保つために好ましくは、ｐＨ９．０〜１０．５の間で緩衝作用を有することが好ましい。従って、本発明においては研磨用コロイダルシリカ自体を、外的条件の変化に対してｐＨ変化の幅が少ない、所謂緩衝作用の強い液とすることが好ましい。緩衝溶液を形成するためには、シリカ／グリシンまたはシリカ／アラニンのモル比が１０〜１５００となるようにし、アルカリ金属水酸化物を添加してｐＨｐＨ９．０〜１０．５の範囲の任意のｐＨに調節するようにする。 In order to keep the pH of the polishing colloidal silica of the present invention constant, it preferably has a buffering action between pH 9.0 and 10.5. Therefore, in the present invention, the colloidal silica for polishing itself is preferably a liquid having a so-called buffering action having a small range of pH change with respect to changes in external conditions. In order to form a buffer solution, the silica / glycine or silica / alanine molar ratio is 10 to 1500 and an alkali metal hydroxide is added to any pH in the range of pH pH 9.0 to 10.5. To adjust to.
本発明のコロイダルシリカの製造方法は、珪酸アルカリ水溶液をカチオン交換樹脂に接触させて活性珪酸水溶液を調製し、次いでこの活性珪酸水溶液にグリシンまたはアラニンとアルカリ金属水酸化物を添加してアルカリ性とした後、加熱してコロイド粒子を成長させ（種粒子生成工程、請求項７の（ｂ−１）工程）、続いて加熱下にアルカリ性を維持しつつ、活性珪酸水溶液とアルカリ剤または、活性珪酸水溶液とグリシンまたはアラニンとアルカリ剤を添加して粒子成長（粒子成長工程、請求項７の（ｂ−２）工程）を行う研磨用コロイダルシリカの製造方法である。種粒子形成工程ではアルカリ金属水酸化物を使用するが、粒子成長工程ではアルカリ金属水酸化物以外のアルカリ剤を使用することができる。 In the method for producing colloidal silica of the present invention, an aqueous silicic acid solution is contacted with a cation exchange resin to prepare an active silicic acid aqueous solution, and then glycine or alanine and an alkali metal hydroxide are added to the active silicic acid aqueous solution to make it alkaline. Thereafter, the colloidal particles are grown by heating (seed particle generation step, step (b-1) of claim 7), and subsequently, the active silicic acid aqueous solution and the alkali agent or the active silicic acid aqueous solution are maintained while maintaining the alkalinity. And glycine or alanine, and an alkali agent are added to carry out particle growth (particle growth step, step (b-2) of claim 7) for producing colloidal silica for polishing. In the seed particle forming step, an alkali metal hydroxide is used, but in the particle growth step, an alkali agent other than the alkali metal hydroxide can be used.
上記研磨用コロイダルシリカの製造方法は、常法であるアルカリ金属水酸化物や珪酸アルカリをアルカリ剤に用いた製造方法と概略同一である。すなわち、珪酸ソーダより活性ゾルを製造する工程はまったく同一であり、種粒子形成工程ではグリシンまたはアラニンの存在下でアルカリ金属水酸化物を使用する点だけが異なり、粒子成長工程ではグリシンまたはアラニンの存在を必要条件としないだけではなく、いかなるアルカリ剤も使用できる。
粒子成長工程では、アルカリ剤としては常法である水酸化アルカリ金属水酸化物でもよく、あるいは有機アルカリでもよい。アルカリ金属は少ない方が好ましいので、有機アルカリを使用するほうが好ましい。有機アルカリとしては、水酸化第４アンモニウムが好ましく、なかでも、水酸化テトラメチルアンモニウムや水酸化テトラエチルアンモニウム、水酸化トリメチル−２−ヒドロキシエチルアンモニウム（別名、水酸化コリン）が好ましい。
The manufacturing method of the said colloidal silica for grinding | polishing is substantially the same as the manufacturing method which used the alkali metal hydroxide and alkali silicate which are the usual methods for an alkali agent. That is, the process for producing an active sol from sodium silicate is exactly the same, except that the seed particle formation process uses an alkali metal hydroxide in the presence of glycine or alanine, and the particle growth process uses glycine or alanine. Not only is presence a prerequisite, but any alkaline agent can be used.
In the particle growth step, the alkali agent may be a conventional alkali metal hydroxide or organic alkali. Since it is preferable that the amount of alkali metal is small, it is preferable to use an organic alkali. As the organic alkali, quaternary ammonium hydroxide is preferable, and tetramethylammonium hydroxide, tetraethylammonium hydroxide, and trimethyl-2-hydroxyethylammonium hydroxide (also known as choline hydroxide) are particularly preferable.
グリシンまたはアラニンは１重量％水溶液でｐＨが６程度であって、アルカリではないので粒子成長には寄与しない。しかしながら、粒子成長時の粒子形状に影響を及ぼす。グリシンまたはアラニンは成長中のシリカ粒子表面に結合もしくは吸着して、結合部位の粒子成長を阻害し、球状成長をできないようにしているようである。シリカ／グリシンまたはシリカ／アラニンのモル比は１０〜１５００であることが好ましい。シリカ／グリシンまたはアラニンのモル比が１０より小さいと、全く粒子成長ができないためシリカのゲルが発生する。粒子成長時に１５００を超えてグリシンまたはアラニンが少ない場合には、シリカ粒子の形状が球状に近くなる。
したがって、上記範囲で存在することが望ましい。水相に溶解しているグリシンまたはアラニンは限外濾過による濃縮工程で水とともに減少する。緩衝作用の強い液とする場合には、濃縮後に各成分を添加補充することも好ましい。
Glycine or alanine is a 1% by weight aqueous solution having a pH of about 6 and is not alkaline, so it does not contribute to particle growth. However, it affects the particle shape during particle growth. Glycine or alanine appears to bind or adsorb to the growing silica particle surface, inhibiting particle growth at the binding site and preventing spherical growth. The molar ratio of silica / glycine or silica / alanine is preferably 10 to 1500. If the silica / glycine or alanine molar ratio is less than 10, particle growth is impossible and a silica gel is generated. If the amount of glycine or alanine is less than 1500 at the time of particle growth, the shape of the silica particles becomes nearly spherical.
Therefore, it is desirable to exist in the above range. Glycine or alanine dissolved in the aqueous phase decreases with water in the concentration step by ultrafiltration. In the case of a liquid having a strong buffering action, it is also preferable to add and replenish each component after concentration.
ただし、有機物の存在は廃水処理などで二次的な弊害を発生することもある。そのような場合を配慮するとグリシンまたはアラニンを除去した製品も必要となる。限外濾過を有効に活用してグリシンまたはアラニンを極力減らす方法も本発明の製造方法のひとつとして範疇に含まれる。 However, the presence of organic matter may cause secondary problems in wastewater treatment. Considering such a case, a product from which glycine or alanine has been removed is also required. A method of effectively using ultrafiltration to reduce glycine or alanine as much as possible is also included in the category as one of the production methods of the present invention.
非球状の異形粒子群となっているコロイダルシリカとは、芋虫のような形もしくは屈曲した棒状の形であって、個々に異なる形をした粒子のコロイダルシリカを表し、具体的には図１または図２に示されるような形状のシリカ粒子を含有するコロイダルシリカである。長径／短径比は１．２〜２０の範囲にある。その粒子は、直線状に伸長していない粒子が大半を占めており、一部は伸長していない粒子も存在する。これは一例であって、製造条件によってその形状はさまざまとなるが、真球状でない粒子が大半を占めている。 Colloidal silica that is a group of non-spherical irregularly shaped particles refers to a colloidal silica having a worm-like shape or a bent rod-like shape, each having a different shape, and specifically, FIG. Colloidal silica containing silica particles having a shape as shown in FIG. The major axis / minor axis ratio is in the range of 1.2-20. Most of the particles are particles that do not extend linearly, and some particles do not extend. This is an example, and the shape varies depending on the manufacturing conditions, but most of them are non-spherical particles.
本発明の研磨用コロイダルシリカのシリカ粒子は長径／短径比の平均値が３〜１５であり、研磨用の砥粒として好ましい形状をしている。１５よりも大きいと粒子が絡みあって凝集しやすくなり、３より小さいと研磨速度が低くなる。
研磨加工においては、シリカ粒子の形状は重要なファクターとなる。すなわち、被加工物表面はアルカリによって腐食され薄層が形成されてゆくのであるが、この薄層の除去速度はシリカ粒子の形状によって大きく変化する。シリカ粒子の粒子径を大きくすれば、除去速度は速くなるが、研磨面にスクラッチが発生しやすくなる。また、形状は真球状よりも異形の粒子の方が除去速度は速くなるが、研磨面にスクラッチが発生しやすくなる。ゆえに、その粒子は適度なサイズを有し、適当な形状であって、容易に破壊したり、あるいは高次に凝集してゲル化するものであってはならない。
本発明の研磨用コロイダルシリカのシリカ粒子はヒュームドシリカのシリカ粒子とよく似た形状である。ヒュームドシリカのシリカ粒子は、一般に長径／短径比が５〜１５の細長い異形粒子群となっている。ヒュームドシリカの一次粒子径（単に粒子径とも記載されることがある）と言われるものは、一次粒子の短径（太さ）であって通常７〜４０ｎｍである。さらに、その粒子は凝集して二次粒子を形成しており、スラリーの外観は白色になっている。そのためスラリーを長時間放置すると粒子が沈降する不具合、研磨面にスクラッチを発生しやすいなどの欠点がある。
The silica particles of the colloidal silica for polishing of the present invention have an average value of the major axis / minor axis ratio of 3 to 15, and have a preferable shape as abrasive grains for polishing. If it is larger than 15, the particles are entangled and easily aggregated, and if it is smaller than 3, the polishing rate becomes low.
In the polishing process, the shape of the silica particles is an important factor. That is, the surface of the workpiece is corroded by alkali and a thin layer is formed, but the removal rate of this thin layer varies greatly depending on the shape of the silica particles. Increasing the particle size of the silica particles increases the removal rate, but tends to cause scratches on the polished surface. Moreover, although the removal rate of the irregularly shaped particles is higher than that of the true spherical shape, scratches are likely to occur on the polished surface. Therefore, the particles should have an appropriate size and have an appropriate shape and cannot be easily broken or highly aggregated and gelled.
The silica particles of the colloidal silica for polishing of the present invention have a shape very similar to the silica particles of fumed silica. The silica particles of fumed silica are generally a group of elongated irregular particles having a major axis / minor axis ratio of 5 to 15. What is referred to as the primary particle size of fumed silica (sometimes simply referred to as the particle size) is the short diameter (thickness) of the primary particles and is usually 7 to 40 nm. Further, the particles are aggregated to form secondary particles, and the appearance of the slurry is white. For this reason, there are disadvantages such as a problem that the particles settle when the slurry is left for a long time, and a scratch is easily generated on the polished surface.
しかし、本発明のシリカ粒子は、ヒュームドシリカの一次粒子に似た形状をしているが、凝集による二次粒子の形成はなく、スラリーの外観は透明ないし半透明になっている。粒子が沈降する不具合はなく、研磨面にスクラッチを発生することもない。
本発明シリカ粒子よりなる研磨用コロイダルシリカは、好ましくは電子顕微鏡観察によるシリカ粒子の平均短径が５〜３０ｎｍであり、かつシリカ粒子の濃度が２〜５０重量％である。シリカ粒子の平均短径が５ｎｍより小さいと、研磨速度が低く、粒子の凝集が起こりやすくコロイドの安定性に欠ける。また、３０nmよりも大きいとスクラッチが発生しやすく、研磨面の平坦性も低くなる。
However, the silica particles of the present invention have a shape similar to the primary particles of fumed silica, but secondary particles are not formed by aggregation, and the appearance of the slurry is transparent or translucent. There is no problem that the particles settle, and no scratches are generated on the polished surface.
The colloidal silica for polishing made of the silica particles of the present invention preferably has an average minor axis of silica particles of 5 to 30 nm as observed by an electron microscope, and a concentration of silica particles of 2 to 50% by weight. When the average minor axis of the silica particles is smaller than 5 nm, the polishing rate is low, the particles are likely to aggregate and the stability of the colloid is lacking. On the other hand, if it is larger than 30 nm, scratches are likely to occur, and the flatness of the polished surface will be lowered.
本発明では上述の研磨用コロイダルシリカを含有し、さらに研磨性能を改善する成分を加えて研磨用組成物を構成することが出来る。
本発明においては、研磨用組成物溶液の導電率を高くすることにより、研磨加工速度を著しく向上することができる。導電率とは液中の電気の通り易さを示す数値であり、単位長さあたりの電気抵抗値の逆数値である。本発明においては単位長あたりの導電率の数値（ｍｉｃｒｏ・Ｓｉｅｍｅｎｓ）をシリカ１重量％当たりに換算した数値で示す。本発明においては、２５℃における導電率が１５ｍＳ／ｍ／１％−ＳｉＯ２以上であれば研磨加工速度の向上に対して好ましく、２０ｍＳ／ｍ／１％−ＳｉＯ２以上であれば更に好ましい。塩類の添加はコロイドの安定性を低下させるため、添加には上限がある。上限はシリカの粒子径によって異なるが、概ね６０ｍＳ／ｍ／１％−ＳｉＯ２程度である。
In the present invention, the polishing composition can be constituted by adding the above-described polishing colloidal silica and further adding a component for improving the polishing performance.
In the present invention, the polishing process speed can be remarkably improved by increasing the conductivity of the polishing composition solution. The electrical conductivity is a numerical value indicating the ease of passing electricity in the liquid, and is an inverse value of the electrical resistance value per unit length. In the present invention, the numerical value of conductivity per unit length (micro · Siemens) is shown as a numerical value converted to 1% by weight of silica. In the present invention, further preferably equal to preferably against improvement of polishing rate if the conductivity at 25 ° C. is 15mS / m / 1% -SiO 2 or more, 20mS / m / 1% -SiO 2 or more. Since the addition of salts reduces the stability of the colloid, there is an upper limit for the addition. The upper limit varies depending particle size of silica is approximately 60mS / m / 1% -SiO 2 approximately.
導電率を上昇させる方法としては、次の二方法がある。一つは緩衝溶液の濃度を高くする方法、もう一つは塩類を添加する方法である。緩衝溶液の濃度を高くするには、グリシンまたはアラニンとアルカリ金属水酸化物とのモル比を変えずに濃度のみを高くすればよい。塩類を添加する方法に用いる塩類は、酸及び塩基の組み合わせより構成されるが、酸としては、強酸、弱酸いずれであってもかまわず、鉱酸および、有機酸が使用でき、その混合物でもよい。塩基としては、アルカリ金属水酸化物を増やすことは好ましくないので、水溶性の第４アンモニウムの水酸化物の使用が好ましい。
強酸と第４アンモニウム塩基の塩としては、硫酸第４アンモニウム、硝酸第４アンモニウムまたはフッ化第４アンモニウムの少なくとも一つであることが好ましい。第４アンモニウム強塩基を構成する陽イオンはコリンイオン、テトラメチルアンモニウムイオンまたはテトラエチルアンモニウムイオンが好ましい。
There are the following two methods for increasing the conductivity. One is a method of increasing the concentration of the buffer solution, and the other is a method of adding salts. In order to increase the concentration of the buffer solution, it is only necessary to increase the concentration without changing the molar ratio of glycine or alanine to the alkali metal hydroxide. The salt used in the method of adding salts is composed of a combination of an acid and a base, but the acid may be either a strong acid or a weak acid, and a mineral acid and an organic acid can be used, or a mixture thereof may be used. . As the base, since it is not preferable to increase the alkali metal hydroxide, it is preferable to use a water-soluble quaternary ammonium hydroxide.
The salt of the strong acid and the quaternary ammonium base is preferably at least one of quaternary ammonium sulfate, quaternary ammonium nitrate, or quaternary ammonium fluoride. The cation constituting the quaternary ammonium strong base is preferably choline ion, tetramethylammonium ion or tetraethylammonium ion.
また、本発明の研磨用コロイダルシリカを含有する研磨用組成物は、銅と水不溶性のキレート化合物を形成するキレート化剤を含有していることも好ましい。例えば、キレート化剤としては、ベンゾトリアゾールのようなアゾール類やキノリノール、キナルジン酸のようなキノリン誘導体など公知の化合物が好ましい。 Moreover, it is also preferable that the polishing composition containing the colloidal silica for polishing of the present invention contains a chelating agent that forms a water-insoluble chelate compound with copper. For example, as the chelating agent, known compounds such as azoles such as benzotriazole, quinoline derivatives such as quinolinol and quinaldic acid are preferable.
本発明の研磨用コロイダルシリカの物性を改良するため、界面活性剤、水溶性高分子化合物、消泡剤などを併用することができる。
界面活性剤としては、ノニオン界面活性剤が好ましい。ノニオン界面活性剤は過剰エッチングの防止効果がある。ノニオン界面活性剤としては、ポリオキシエチレンラウリルエーテルなどのポリオキシアルキレンアルキルエーテル、グリセリンエステルなどの脂肪酸エステル、ジ（ポリオキシエチレン）ラウリルアミンなどのポリオキシアルキレンアルキルアミンが使用できる。研磨用コロイダルシリカを含有する研磨用組成物における濃度は０．００１〜０．１重量％である。
水溶性高分子化合物としては、ヒドロキシエチルセルロース、ポリエチレングリコール、ポリビニルアルコールのいずれかひとつであることが好ましい。これらには過剰エッチングの防止効果がある。エチレンオキサイド・プロピレンオキサイドトリブロックコポリマーも好ましい。研磨用組成物が１００倍希釈されたとき、例えば、ヒドロキシエチルセルロースであれば３０〜３００ｐｐｍで効果がある。従って、研磨用組成物における濃度は０．３〜３重量％である。同じく、ポリエチレングリコールでは０．３〜５重量％、ポリビニルアルコールでは１〜５重量％である。
消泡剤としては、シリコーンエマルジョンであることが好ましい。シリコーンエマルジョンとしては、ポリジメチルシロキサンを主要成分とするシリコーンオイルのＯ／Ｗ型エマルジョンである市販のシリコーン消泡剤が使用できる。研磨用組成物における濃度は０．００１〜０．１重量％である。
また、本発明の研磨用コロイダルシリカを含有する研磨用組成物は水溶液としているが、有機溶媒を添加してもかまわない。本発明の研磨用コロイダルシリカを含有する研磨用組成物は、研磨時にコロイダルアルミナ、コロイダルセリア、コロイダルジルコニア等の他の研磨剤、塩基、添加剤、水等を混合して調製してもよい。
In order to improve the physical properties of the polishing colloidal silica of the present invention, a surfactant, a water-soluble polymer compound, an antifoaming agent and the like can be used in combination.
As the surfactant, a nonionic surfactant is preferable. Nonionic surfactants have an effect of preventing excessive etching. As the nonionic surfactant, polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether, fatty acid esters such as glycerin ester, and polyoxyalkylene alkyl amines such as di (polyoxyethylene) laurylamine can be used. The concentration in the polishing composition containing the colloidal silica for polishing is 0.001 to 0.1% by weight.
The water-soluble polymer compound is preferably any one of hydroxyethyl cellulose, polyethylene glycol, and polyvinyl alcohol. These have the effect of preventing excessive etching. Ethylene oxide / propylene oxide triblock copolymers are also preferred. When the polishing composition is diluted 100 times, for example, hydroxyethyl cellulose is effective at 30 to 300 ppm. Therefore, the concentration in the polishing composition is 0.3 to 3% by weight. Similarly, it is 0.3 to 5% by weight for polyethylene glycol and 1 to 5% by weight for polyvinyl alcohol.
The antifoaming agent is preferably a silicone emulsion. As the silicone emulsion, a commercially available silicone antifoaming agent which is an O / W type emulsion of silicone oil containing polydimethylsiloxane as a main component can be used. The concentration in the polishing composition is 0.001 to 0.1% by weight.
The polishing composition containing the polishing colloidal silica of the present invention is an aqueous solution, but an organic solvent may be added. The polishing composition containing the polishing colloidal silica of the present invention may be prepared by mixing other polishing agents such as colloidal alumina, colloidal ceria, colloidal zirconia, a base, an additive, water, and the like during polishing.
本発明の研磨用コロイダルシリカを含有する研磨用組成物は、シリカ濃度２０〜５０重量％で製造し、その使用時に純水で希釈し必要に応じてｐＨ調整剤及び導電率調整のための塩類等を適宜加えて研磨用組成物とすることが好ましい。 The polishing composition containing the colloidal silica for polishing according to the present invention is produced at a silica concentration of 20 to 50% by weight, diluted with pure water at the time of use, and a pH adjuster and salts for adjusting conductivity as necessary. Etc. are preferably added to obtain a polishing composition.
以下、実施例により本発明をさらに詳細に説明する。実施例での測定は以下の装置を使用した。
（１）ＴＥＭ観察：（株）日立製作所、透過型電子顕微鏡Ｈ−７５００型を使用した。
（２）ＢＥＴ法比表面積：（株）島津製作所、フローソーブ２３００型を使用した。
（３）グリシンまたはアラニン分析：（株）島津製作所、全有機体炭素計ＴＯＣ−５０００Ａ、ＳＳＭ−５０００Ａを使用した。炭素量よりグリシンまたはアラニンに換算した。具体的には、全有機体炭素量（ＴＯＣ）は、全炭素量（ＴＣ）と無機体炭素量（ＩＣ）を測定後ＴＯＣ＝ＴＣ−ＩＣにより求めた。ＴＣ測定の標準として炭素量１重量％のグルコース水溶液を用い、ＩＣ測定の標準として炭素量１重量％の炭酸ナトリウムを用いた。超純水を炭素量０重量％の標準とし、それぞれ先に示した標準を用い、ＴＣは１５０μｌと３００μｌ、またＩＣは２５０μｌで検量線を作成した。サンプルのＴＣ測定ではサンプルを約１００ｍｇ採取し、９００℃燃焼炉で燃焼させた。また、ＩＣ測定ではサンプルを約２０ｍｇ採取し、（１＋１）燐酸を約１０ｍｌ添加し２００℃燃焼炉で反応を促進した。
（４）水酸化テトラメチルアンモニウム(ＴＭＡＯＨ)の分析：ダイオネクス社、イオンクロマトＩＣＳ−１５００を使用した。具体的には、液相ＴＭＡＯＨは、サンプルを１０００倍から５０００倍に純水で希釈し測定を行った。全ＴＭＡＯＨの測定には前処理としてサンプル５ｇに３ｇの２０重量％ＮａＯＨと純水を加え、８０℃で加熱しシリカを完全に溶解させた。この溶解液を１０００倍から５０００倍に純水で希釈し測定を行い、ＴＭＡＯＨ量を求めた。
Hereinafter, the present invention will be described in more detail with reference to examples. The following apparatus was used for the measurement in the examples.
(1) TEM observation: Hitachi, Ltd., transmission electron microscope H-7500 type was used.
(2) BET specific surface area: Shimadzu Corporation, Flowsorb 2300 type was used.
(3) Glycine or alanine analysis: Shimadzu Corporation, Total Organic Carbon Meter TOC-5000A, SSM-5000A were used. The amount of carbon was converted to glycine or alanine. Specifically, the total organic carbon amount (TOC) was obtained by measuring TOC = TC-IC after measuring the total carbon amount (TC) and the inorganic carbon amount (IC). A glucose aqueous solution having a carbon content of 1% by weight was used as a standard for TC measurement, and sodium carbonate having a carbon content of 1% by weight was used as a standard for IC measurement. A calibration curve was prepared using ultrapure water as a standard with 0% by weight of carbon, using the above-mentioned standards, TC of 150 μl and 300 μl, and IC of 250 μl. In the TC measurement of the sample, about 100 mg of the sample was collected and burned in a 900 ° C. combustion furnace. In IC measurement, about 20 mg of a sample was collected, about 10 ml of (1 + 1) phosphoric acid was added, and the reaction was promoted in a 200 ° C. combustion furnace.
(4) Analysis of tetramethylammonium hydroxide (TMAOH): Dionex Corporation, ion chromatography ICS-1500 was used. Specifically, the liquid phase TMAOH was measured by diluting a sample with pure water from 1000 times to 5000 times. To measure total TMAOH, 3 g of 20 wt% NaOH and pure water were added to 5 g of sample as a pretreatment, and heated at 80 ° C. to completely dissolve silica. This dissolved solution was diluted 1000 times to 5000 times with pure water and measured, and the amount of TMAOH was determined.
（実施例１）
脱イオン水２８ｋｇにＪＩＳ３号珪酸ソーダ（ＳｉＯ２：２８．８重量％、Ｎａ２Ｏ：９．７重量％、Ｈ２Ｏ：６１．５重量％）５.２ｋｇを加えて均一に混合しシリカ濃度４．５重量％の希釈珪酸ソーダを作成した。この希釈珪酸ソーダを予め塩酸によって再生したＨ型強酸性カチオン交換樹脂（オルガノ（株）製アンバーライトＩＲ１２０Ｂ）２０リットルのカラムに通して脱アルカリし、シリカ濃度３．７重量％でｐＨ２．９の活性珪酸４０ｋｇを得た。
別途、グリシン(試薬)を純水に加えて１０重量％グリシン水溶液を調製した。
次いで、ビルドアップの方法をとり、コロイド粒子を成長させた。すなわち、得られた活性珪酸の一部５００ｇに攪拌下５重量％水酸化ナトリウム水溶液を添加してｐＨを８．５とし、１０重量％グリシン水溶液１６ｇを加えたところｐＨは８．４となった。次いで、１００℃に１時間保ち、放冷した。得られた液は、水の蒸発で４６０ｇとなっており、シリカ濃度は４．０重量％となっていた。また、２５℃でのｐＨが９．５であり、透過型電子顕微鏡（ＴＥＭ）観察では短径が約５〜７ｎｍで、長径／短径比が５〜２０の不規則に連結した非球状シリカの異形粒子群となっており、長径／短径比の平均値が１５であった。
このコロイダルシリカは、活性珪酸およびグリシンの使用量から、シリカ／グリシンのモル比は１４．５と算出された。
Example 1
Silica was obtained by adding 5.2 kg of JIS No. 3 sodium silicate (SiO 2 : 28.8 wt%, Na 2 O: 9.7 wt%, H 2 O: 61.5 wt%) to 28 kg of deionized water and mixing uniformly. Diluted sodium silicate having a concentration of 4.5% by weight was prepared. This dilute sodium silicate was passed through a 20 liter column of H-type strongly acidic cation exchange resin (Amberlite IR120B manufactured by Organo Co., Ltd.) regenerated with hydrochloric acid in advance to remove alkali, and the silica concentration was 3.7% by weight and the pH was 2.9. 40 kg of active silicic acid was obtained.
Separately, glycine (reagent) was added to pure water to prepare a 10 wt% glycine aqueous solution.
Next, the build-up method was taken to grow colloidal particles. That is, 5 wt% sodium hydroxide aqueous solution was added to 500 g of a part of the obtained active silicic acid with stirring to make pH 8.5, and when 10 wt% glycine aqueous solution 16 g was added, pH became 8.4. . Subsequently, it kept at 100 degreeC for 1 hour, and stood to cool. The obtained liquid was 460 g by evaporation of water, and the silica concentration was 4.0% by weight. Moreover, the nonspherical silica which has a pH of 9.5 at 25 ° C., is irregularly linked and has a minor axis of about 5 to 7 nm and a major axis / minor axis ratio of 5 to 20 as observed with a transmission electron microscope (TEM). The average value of the major axis / minor axis ratio was 15.
In this colloidal silica, the silica / glycine molar ratio was calculated to be 14.5 from the amounts of active silicic acid and glycine used.
（実施例２）
上記実施例１で得られたコロイダルシリカを再度加熱して９８℃とし、１０００ｇの活性珪酸を２．５時間かけて添加した。活性珪酸の添加中は９８℃を維持し、５重量％水酸化ナトリウム水溶液を同時添加しｐＨ９〜１０を維持した。添加中の水の蒸発により放冷後には１２００ｇのコロイダルシリカを得た。シリカ濃度は４．６重量％となっていた。このコロイダルシリカは２５℃でのｐＨが９．５であり、透過型電子顕微鏡（ＴＥＭ）観察では短径が約９ｎｍで、長径／短径比が５〜１５の不規則に連結した非球状シリカの異形粒子群よりなり、長径／短径比の平均値が１０であった。
このコロイダルシリカは、活性珪酸およびグリシンの使用量から、シリカ／グリシンのモル比は４３と算出された。
(Example 2)
The colloidal silica obtained in Example 1 was heated again to 98 ° C., and 1000 g of active silicic acid was added over 2.5 hours. During the addition of active silicic acid, the temperature was maintained at 98 ° C., and a 5 wt% aqueous sodium hydroxide solution was added simultaneously to maintain pH 9-10. After cooling by evaporation of water during addition, 1200 g of colloidal silica was obtained. The silica concentration was 4.6% by weight. This colloidal silica has a pH of 9.5 at 25 ° C., and is irregularly linked non-spherical silica having a minor axis of about 9 nm and a major axis / minor axis ratio of 5 to 15 as observed with a transmission electron microscope (TEM). The average value of the ratio of major axis / minor axis was 10.
The colloidal silica was calculated to have a silica / glycine molar ratio of 43 based on the amounts of active silicic acid and glycine used.
（実施例３）
実施例１で得られた活性珪酸の一部５００ｇに攪拌下５重量％水酸化ナトリウム水溶液を添加してｐＨを８．５とし、１０重量％グリシン水溶液１６ｇを加えたところｐＨは８．４となった。次いで、加熱して９８℃とし、４０００ｇの活性珪酸を１０時間かけて添加した。活性珪酸の添加中は９８℃を維持し、５重量％水酸化ナトリウム水溶液を同時添加しｐＨ９〜１０を維持した。添加中の水の蒸発により放冷後には２４２０ｇのコロイダルシリカを得た。シリカ濃度は６．８８重量％となっていた。このコロイダルシリカは２５℃でのｐＨが９．７であり、透過型電子顕微鏡（ＴＥＭ）観察では短径が約１５ｎｍで、長径／短径比が５〜１５の不規則に連結した非球状シリカの異形粒子群よりなり、長径／短径比の平均値が７であった。ＴＥＭ写真を図１に示した。
このコロイダルシリカは、活性珪酸およびグリシンの使用量から、シリカ／グリシンのモル比は１３０と算出された。
(Example 3)
To 500 g of a part of the active silicic acid obtained in Example 1, a 5 wt% aqueous sodium hydroxide solution was added with stirring to a pH of 8.5, and 16 g of a 10 wt% aqueous glycine solution was added, resulting in a pH of 8.4. became. Then it was heated to 98 ° C. and 4000 g of active silicic acid was added over 10 hours. During the addition of active silicic acid, the temperature was maintained at 98 ° C., and a 5 wt% aqueous sodium hydroxide solution was added simultaneously to maintain pH 9-10. After cooling by evaporation of water during addition, 2420 g of colloidal silica was obtained. The silica concentration was 6.88% by weight. This colloidal silica has a pH of 9.7 at 25 ° C., and is irregularly linked non-spherical silica having a minor axis of about 15 nm and a major axis / minor axis ratio of 5 to 15 as observed with a transmission electron microscope (TEM). The average value of the ratio of major axis / minor axis was 7. A TEM photograph is shown in FIG.
The colloidal silica was calculated to have a silica / glycine molar ratio of 130 based on the amounts of active silicic acid and glycine used.
（実施例４）
上記実施例３で得られたコロイダルシリカの濃縮を行った。分画分子量６０００の中空糸型限外濾過膜（旭化成（株）製マイクローザＵＦモジュールＳIＰ−１０１３）を用いてポンプ循環送液による加圧濾過を行い、シリカ濃度２７．１重量％まで濃縮し、コロイダルシリカ約５８０ｇを回収した。このコロイダルシリカは２５℃でのｐＨが９．２であり、透過型電子顕微鏡（ＴＥＭ）観察では短径が約１５ｎｍで、長径／短径比が５〜１５の不規則に連結した非球状の異形粒子群となっており、長径／短径比の平均値が７であった。また、ＢＥＴ法による比表面積換算の粒子径は１６．５ｎｍであった。
コロイダルシリカのグリシンの含有量は０．０２５重量％であり、シリカ／グリシンのモル比は１３５５であった。
ｐＨの緩衝能についても確認をおこなった。上記のシリカ濃度２７．３重量％でのｐＨは９．２であり、純水で１０倍に希釈したときのｐＨは９．６であり、１００倍に希釈したときのｐＨは９．２であった。グリシンと水酸化ナトリウムの混合溶液でｐＨの緩衝系が形成されていた。
Example 4
The colloidal silica obtained in Example 3 was concentrated. Using a hollow fiber type ultrafiltration membrane with a molecular weight cut off of 6000 (Microsa UF module SIP-1013 manufactured by Asahi Kasei Co., Ltd.), pressure filtration by pump circulation is performed, and the silica concentration is concentrated to 27.1% by weight. About 580 g of colloidal silica was recovered. This colloidal silica has a pH of 9.2 at 25 ° C., a transmission electron microscope (TEM) observation has a minor axis of about 15 nm, and an irregularly connected non-spherical shape having a major axis / minor axis ratio of 5 to 15. It was an irregularly shaped particle group, and the average value of the major axis / minor axis ratio was 7. The particle diameter in terms of specific surface area by BET method was 16.5 nm.
The colloidal silica had a glycine content of 0.025 wt% and a silica / glycine molar ratio of 1355.
The buffering ability of pH was also confirmed. The pH at the silica concentration of 27.3% by weight is 9.2, the pH when diluted 10 times with pure water is 9.6, and the pH when diluted 100 times is 9.2. there were. A pH buffer system was formed with a mixed solution of glycine and sodium hydroxide.
（実施例５）
脱イオン水２８ｋｇにＪＩＳ３号珪酸ソーダ（ＳｉＯ２：２８．８重量％、Ｎａ２Ｏ：９．７重量％、Ｈ２Ｏ：６１．５重量％）５.２ｋｇを加えて均一に混合しシリカ濃度４．５重量％の希釈珪酸ソーダを作成した。この希釈珪酸ソーダを予め塩酸によって再生したＨ型強酸性カチオン交換樹脂（オルガノ（株）製アンバーライトＩＲ１２０Ｂ）２０リットルのカラムに通して脱アルカリし、シリカ濃度３．７重量％でｐＨ２．９の活性珪酸４０ｋｇを得た。
別途、アラニン(ＤＬ-α−アラニン、試薬)を純水に加えて１０重量％アラニン水溶液を調製した。
次いで、ビルドアップの方法をとり、コロイド粒子を成長させた。すなわち、得られた活性珪酸の一部５００ｇに攪拌下５重量％水酸化ナトリウム水溶液を添加してｐＨを８．３とし、１０重量％アラニン水溶液１９ｇを加えたところｐＨは８．２となった。次いで、１００℃に１時間保ち、放冷した。得られた液は、水の蒸発で４６０ｇとなっており、シリカ濃度は４．０重量％となっていた。また、２５℃でのｐＨが９．５であり、透過型電子顕微鏡（ＴＥＭ）観察では短径が約５ｎｍで、長径／短径比が５〜２０の不規則に連結した非球状シリカの異形粒子群となっており、長径／短径比の平均値が１０であった。
このコロイダルシリカは、活性珪酸およびアラニンの使用量から、シリカ／アラニンのモル比は１４．４と算出された。
(Example 5)
Silica was obtained by adding 5.2 kg of JIS No. 3 sodium silicate (SiO 2 : 28.8 wt%, Na 2 O: 9.7 wt%, H 2 O: 61.5 wt%) to 28 kg of deionized water and mixing uniformly. Diluted sodium silicate having a concentration of 4.5% by weight was prepared. This dilute sodium silicate was passed through a 20 liter column of H-type strongly acidic cation exchange resin (Amberlite IR120B manufactured by Organo Co., Ltd.) regenerated with hydrochloric acid in advance to remove alkali, and the silica concentration was 3.7% by weight and the pH was 2.9. 40 kg of active silicic acid was obtained.
Separately, alanine (DL-α-alanine, reagent) was added to pure water to prepare a 10 wt% alanine aqueous solution.
Next, the build-up method was taken to grow colloidal particles. That is, 5 wt% sodium hydroxide aqueous solution was added to 500 g of a part of the obtained active silicic acid with stirring to make the pH 8.3, and when 19 g of 10 wt% alanine aqueous solution was added, the pH was 8.2. . Subsequently, it kept at 100 degreeC for 1 hour, and stood to cool. The obtained liquid was 460 g by evaporation of water, and the silica concentration was 4.0% by weight. Further, the irregular shape of irregularly connected non-spherical silica having a pH of 9.5 at 25 ° C., a short axis of about 5 nm, and a major axis / minor axis ratio of 5 to 20 as observed with a transmission electron microscope (TEM). The average particle size of the major axis / minor axis ratio was 10.
In this colloidal silica, the silica / alanine molar ratio was calculated to be 14.4 from the amounts of active silicic acid and alanine used.
（実施例６）
上記実施例１で得られたコロイダルシリカを再度加熱して１００℃とし、１０００ｇの活性珪酸を２．５時間かけて添加した。活性珪酸の添加中は１００℃を維持し、５重量％水酸化ナトリウム水溶液を同時添加しｐＨ９〜１０を維持した。添加中の水の蒸発により放冷後には１２００ｇのコロイダルシリカを得た。シリカ濃度は４．６重量％となっていた。このコロイダルシリカは２５℃でのｐＨが９．５であり、透過型電子顕微鏡（ＴＥＭ）観察では短径が約９ｎｍで、長径／短径比が３〜１０の不規則に連結した非球状シリカの異形粒子群よりなり、長径／短径比の平均値が５であった。
このコロイダルシリカは、活性珪酸およびアラニンの使用量から、シリカ／アラニンのモル比は４３と算出された。
(Example 6)
The colloidal silica obtained in Example 1 was heated again to 100 ° C., and 1000 g of active silicic acid was added over 2.5 hours. During the addition of activated silicic acid, the temperature was maintained at 100 ° C., and a 5 wt% aqueous sodium hydroxide solution was added simultaneously to maintain pH 9-10. After cooling by evaporation of water during addition, 1200 g of colloidal silica was obtained. The silica concentration was 4.6% by weight. This colloidal silica has a pH of 9.5 at 25 ° C., and is an irregularly linked non-spherical silica having a minor axis of about 9 nm and a major axis / minor axis ratio of 3 to 10 as observed with a transmission electron microscope (TEM). The average value of the major axis / minor axis ratio was 5.
This colloidal silica was calculated to have a silica / alanine molar ratio of 43 based on the amounts of active silicic acid and alanine used.
（実施例７）
実施例１で得られた活性珪酸の一部５００ｇに攪拌下５重量％水酸化ナトリウム水溶液を添加してｐＨを８．３とし、１０重量％アラニン水溶液１９ｇを加えたところｐＨは８．２となった。次いで、加熱して１００℃とし、４０００ｇの活性珪酸を８時間かけて添加した。活性珪酸の添加中は１００℃を維持し、５重量％水酸化ナトリウム水溶液を同時添加しｐＨ９〜１０を維持した。添加中の水の蒸発により放冷後には１８８０ｇのコロイダルシリカを得た。シリカ濃度は８．８６重量％となっていた。このコロイダルシリカは２５℃でのｐＨが９．８であり、透過型電子顕微鏡（ＴＥＭ）観察では短径が約１５ｎｍで、長径／短径比が１．２〜７の不規則に連結した非球状シリカの異形粒子群よりなり、長径／短径比の平均値が３であった。ＴＥＭ写真を図２に示した。
このコロイダルシリカは、活性珪酸およびアラニンの使用量から、シリカ／アラニンのモル比は１３０と算出された。
(Example 7)
To 500 g of a part of the active silicic acid obtained in Example 1, a 5 wt% aqueous sodium hydroxide solution was added with stirring to adjust the pH to 8.3, and 19 g of 10 wt% alanine aqueous solution was added, resulting in a pH of 8.2. became. Next, the mixture was heated to 100 ° C., and 4000 g of active silicic acid was added over 8 hours. During the addition of activated silicic acid, the temperature was maintained at 100 ° C., and a 5 wt% aqueous sodium hydroxide solution was added simultaneously to maintain pH 9-10. After cooling by evaporation of water during addition, 1880 g of colloidal silica was obtained. The silica concentration was 8.86% by weight. This colloidal silica has a pH of 9.8 at 25 ° C., a transmission electron microscope (TEM) observation shows that the minor axis is about 15 nm and the ratio of the major axis / minor axis ratio is 1.2-7. It consisted of a group of irregularly shaped particles of spherical silica, and the average value of the major axis / minor axis ratio was 3. A TEM photograph is shown in FIG.
In this colloidal silica, the molar ratio of silica / alanine was calculated as 130 from the amounts of active silicic acid and alanine used.
（実施例８）
上記実施例３で得られたコロイダルシリカの濃縮を行った。分画分子量６０００の中空糸型限外濾過膜（旭化成（株）製マイクローザＵＦモジュールＳIＰ−１０１３）を用いてポンプ循環送液による加圧濾過を行い、シリカ濃度２７．７重量％まで濃縮し、コロイダルシリカ約５７０ｇを回収した。このコロイダルシリカは２５℃でのｐＨが９．４であり、透過型電子顕微鏡（ＴＥＭ）観察では短径が約１５ｎｍで、長径／短径比が１．２〜５の不規則に連結した非球状の異形粒子群となっており、長径／短径比の平均値が３であった。また、ＢＥＴ法による比表面積換算の粒子径は１６．４ｎｍであった。
コロイダルシリカのアラニンの含有量は０．０４９重量％であり、シリカ／アラニンのモル比は８３３であった。
ｐＨの緩衝能についても確認をおこなった。上記のシリカ濃度２７．７重量％でのｐＨは９．４であり、純水で１０倍に希釈したときのｐＨは９．７であり、１００倍に希釈したときのｐＨは９．５であった。アラニンと水酸化ナトリウムの混合溶液でｐＨの緩衝系が形成されていた。
(Example 8)
The colloidal silica obtained in Example 3 was concentrated. Using a hollow fiber type ultrafiltration membrane with a molecular weight cut off of 6000 (Microsa UF module SIP-1013 manufactured by Asahi Kasei Co., Ltd.), pressure filtration by pump circulation is performed, and the silica concentration is concentrated to 27.7% by weight. About 570 g of colloidal silica was recovered. This colloidal silica has a pH of 9.4 at 25 ° C., and when observed with a transmission electron microscope (TEM), the minor axis has a minor axis of about 15 nm, and the major axis / minor axis ratio is 1.2-5. A group of spherical irregular particles was formed, and the average value of the major axis / minor axis ratio was 3. The particle diameter in terms of specific surface area by the BET method was 16.4 nm.
The alanine content of the colloidal silica was 0.049% by weight, and the silica / alanine molar ratio was 833.
The buffering ability of pH was also confirmed. The pH at the silica concentration of 27.7% by weight is 9.4, the pH when diluted 10 times with pure water is 9.7, and the pH when diluted 100 times is 9.5. there were. A pH buffer system was formed with a mixed solution of alanine and sodium hydroxide.
（実施例９）
実施例１で得られた活性珪酸の一部５００ｇに攪拌下５重量％水酸化ナトリウム水溶液を添加してｐＨを８．３とし、１０重量％アラニン水溶液１９ｇを加えたところｐＨは８．２となった。次いで、加熱して１００℃とし、３８００ｇの活性珪酸を８時間かけて添加した。活性珪酸の添加中は１００℃を維持し、２５重量％水酸化テトラメチルアンモニウム水溶液を同時添加しｐＨ９〜１０を維持した。添加中の水の蒸発により放冷後には１６８０ｇのコロイダルシリカを得た。シリカ濃度は９．４７重量％となっていた。このコロイダルシリカは２５℃でのｐＨが９．８５であり、透過型電子顕微鏡（ＴＥＭ）観察では短径が約１５ｎｍで、長径／短径比が１．２〜７の不規則に連結した非球状シリカの異形粒子群よりなり、長径／短径比の平均値が３であった。
このコロイダルシリカは、活性珪酸およびアラニンの使用量から、シリカ／アラニンのモル比は１２４と算出された。
Example 9
To 500 g of a part of the active silicic acid obtained in Example 1, a 5 wt% aqueous sodium hydroxide solution was added with stirring to adjust the pH to 8.3, and 19 g of 10 wt% alanine aqueous solution was added, resulting in a pH of 8.2. became. Next, the mixture was heated to 100 ° C., and 3800 g of active silicic acid was added over 8 hours. During the addition of active silicic acid, the temperature was maintained at 100 ° C., and a 25 wt% tetramethylammonium hydroxide aqueous solution was simultaneously added to maintain pH 9-10. After cooling by evaporation of water during addition, 1680 g of colloidal silica was obtained. The silica concentration was 9.47% by weight. This colloidal silica has a pH of 9.85 at 25 ° C., and when observed with a transmission electron microscope (TEM), the minor axis has a minor axis of about 15 nm and the major axis / minor axis ratio is 1.2-7. It consisted of spherical silica irregularly shaped particles, and the average value of the ratio of major axis / minor axis was 3.
This colloidal silica was calculated to have a silica / alanine molar ratio of 124 based on the amounts of active silicic acid and alanine used.
（実施例１０）
上記実施例９で得られたコロイダルシリカの濃縮を行った。分画分子量６０００の中空糸型限外濾過膜（旭化成（株）製マイクローザＵＦモジュールＳIＰ−１０１３）を用いてポンプ循環送液による加圧濾過を行い、シリカ濃度２５．６重量％まで濃縮し、コロイダルシリカ約６０４ｇを回収した。このコロイダルシリカは２５℃でのｐＨが９．７５であり、透過型電子顕微鏡（ＴＥＭ）観察では短径が約１５ｎｍで、長径／短径比が１．２〜７の不規則に連結した非球状の異形粒子群となっており、長径／短径比の平均値が３であった。また、ＢＥＴ法による比表面積換算の粒子径は１８．２ｎｍであった。
コロイダルシリカのアラニンの含有量は０．２７重量％であり、シリカ／アラニンのモル比は１４１であった。また、水酸化テトラメチルアンモニウムの含有量は０．８５重量％であった。水酸化テトラメチルアンモニウムの存在はアラニンの残存量を増やすことが判明した。
ｐＨの緩衝能についても確認をおこなった。上記のシリカ濃度２５．６重量％でのｐＨは９．７５であり、純水で１０倍に希釈したときのｐＨは９．７６であり、１００倍に希釈したときのｐＨは９．６０であった。アラニンと水酸化ナトリウムおよび水酸化テトラメチルアンモニウムの混合溶液でｐＨの緩衝系が形成されていた。
(Example 10)
The colloidal silica obtained in Example 9 was concentrated. Using a hollow fiber type ultrafiltration membrane with a molecular weight cut off of 6000 (Microsa UF module SIP-1013 manufactured by Asahi Kasei Co., Ltd.), pressure filtration by pump circulation is performed, and the silica concentration is concentrated to 25.6% by weight. About 604 g of colloidal silica was recovered. This colloidal silica has a pH of 9.75 at 25 ° C., and when observed with a transmission electron microscope (TEM), the minor axis has a minor axis of about 15 nm and the major axis / minor axis ratio is 1.2-7. A group of spherical irregular particles was formed, and the average value of the major axis / minor axis ratio was 3. The particle diameter in terms of specific surface area by the BET method was 18.2 nm.
The alanine content of the colloidal silica was 0.27% by weight, and the silica / alanine molar ratio was 141. The content of tetramethylammonium hydroxide was 0.85% by weight. The presence of tetramethylammonium hydroxide was found to increase the residual amount of alanine.
The buffering ability of pH was also confirmed. The pH at the above silica concentration of 25.6% by weight is 9.75, the pH when diluted 10 times with pure water is 9.76, and the pH when diluted 100 times is 9.60. there were. A pH buffer system was formed with a mixed solution of alanine, sodium hydroxide and tetramethylammonium hydroxide.
Claims (9)
（ａ）珪酸アルカリ水溶液をカチオン交換樹脂に接触させて活性珪酸水溶液を調製する工程、
（ｂ−１）次いで前記活性珪酸水溶液にグリシンまたはアラニンとアルカリ金属水酸化物を添加してアルカリ性とした後、加熱してコロイド粒子を形成させる工程、
（ｂ−２）加熱条件下で、前工程で形成したコロイド粒子に、アルカリ性を維持しながら前記活性珪酸水溶液とアルカリ剤または、前記活性珪酸水溶液とグリシンまたはアラニンとアルカリ剤を添加してコロイド粒子を成長させる工程、
を有することを特徴とする、請求項１〜７に記載の半導体ウエハ研磨用コロイダルシリカの製造方法。 The following step (a) a step of bringing an aqueous alkali silicate solution into contact with a cation exchange resin to prepare an active silicate aqueous solution,
(B-1) Next, glycine or alanine and an alkali metal hydroxide are added to the active silicic acid aqueous solution to make it alkaline, and then heated to form colloidal particles.
(B-2) Colloidal particles obtained by adding the active silicic acid aqueous solution and the alkali agent or the active silicic acid aqueous solution and glycine or alanine and the alkali agent to the colloidal particles formed in the previous step under heating conditions while maintaining alkalinity. Growing the process,
The manufacturing method of the colloidal silica for semiconductor wafer grinding | polishing of Claims 1-7 characterized by having.
（ｃ）コロイダルシリカを濃縮する工程、
を有することを特徴とする請求項８に記載の半導体ウエハ研磨用コロイダルシリカの製造方法。 (B) After the process,
(C) a step of concentrating colloidal silica;
The method for producing colloidal silica for polishing a semiconductor wafer according to claim 8, comprising:
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