CN101068901B - Adjuvant for chemical mechanical polishing slurry - Google Patents
Adjuvant for chemical mechanical polishing slurry Download PDFInfo
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- CN101068901B CN101068901B CN2005800410698A CN200580041069A CN101068901B CN 101068901 B CN101068901 B CN 101068901B CN 2005800410698 A CN2005800410698 A CN 2005800410698A CN 200580041069 A CN200580041069 A CN 200580041069A CN 101068901 B CN101068901 B CN 101068901B
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- Prior art keywords
- polyelectrolyte
- ethylenically unsaturated
- graft type
- unsaturated monomers
- auxiliary
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- 239000002002 slurry Substances 0.000 title claims abstract description 83
- 238000005498 polishing Methods 0.000 title claims abstract description 40
- 239000000126 substance Substances 0.000 title claims abstract description 24
- 239000002671 adjuvant Substances 0.000 title abstract 4
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 101
- 239000002801 charged material Substances 0.000 claims abstract description 49
- 150000003839 salts Chemical class 0.000 claims abstract description 41
- 239000002245 particle Substances 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000001179 sorption measurement Methods 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims description 77
- 150000002500 ions Chemical class 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 36
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 22
- 238000006116 polymerization reaction Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- 238000007334 copolymerization reaction Methods 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 6
- 238000007517 polishing process Methods 0.000 claims description 6
- 238000002955 isolation Methods 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- 239000003518 caustics Substances 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 description 30
- 229910052581 Si3N4 Inorganic materials 0.000 description 28
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 28
- 238000005516 engineering process Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- -1 fluoro-phenylbenzene glyoximes Chemical class 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 150000004767 nitrides Chemical class 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 229910052814 silicon oxide Inorganic materials 0.000 description 9
- 239000003999 initiator Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 150000004696 coordination complex Chemical class 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000012986 chain transfer agent Substances 0.000 description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 4
- 238000004377 microelectronic Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000003556 assay Methods 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- LJHFIVQEAFAURQ-ZPUQHVIOSA-N (NE)-N-[(2E)-2-hydroxyiminoethylidene]hydroxylamine Chemical compound O\N=C\C=N\O LJHFIVQEAFAURQ-ZPUQHVIOSA-N 0.000 description 2
- DUJMVKJJUANUMQ-UHFFFAOYSA-N 4-methylpentanenitrile Chemical compound CC(C)CCC#N DUJMVKJJUANUMQ-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- NBMYFZIWNCAUJL-UHFFFAOYSA-N (3-hydroxyiminobutan-2-ylideneamino) hypofluorite Chemical class FON=C(C(=NO)C)C NBMYFZIWNCAUJL-UHFFFAOYSA-N 0.000 description 1
- PDRQTUDUXNVBSM-UHFFFAOYSA-N 1,1'-biphenyl;4-methylpent-1-ene Chemical compound CC(C)CC=C.C1=CC=CC=C1C1=CC=CC=C1 PDRQTUDUXNVBSM-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- DSCFFEYYQKSRSV-UHFFFAOYSA-N 1L-O1-methyl-muco-inositol Natural products COC1C(O)C(O)C(O)C(O)C1O DSCFFEYYQKSRSV-UHFFFAOYSA-N 0.000 description 1
- ARCORKUYHGATHB-UHFFFAOYSA-N 2-(2-methylpentan-2-ylperoxy)ethyl hexanoate Chemical compound CCCCCC(=O)OCCOOC(C)(C)CCC ARCORKUYHGATHB-UHFFFAOYSA-N 0.000 description 1
- AQKYLAIZOGOPAW-UHFFFAOYSA-N 2-methylbutan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCC(C)(C)OOC(=O)C(C)(C)C AQKYLAIZOGOPAW-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229950010765 pivalate Drugs 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
Disclosed is an adjuvant for use in simultaneous polishing of a cationically charged material and an anionically charged material, which forms a adsorption layer on the cationically charged material in order to increase the polishing selectivity of the anionically charged material to cationically charged material, wherein the adjuvant comprises a polyelectrolyte salt containing: (a) a graft type polyelectrolyte that has a weight average molecular weight of 1,000-20,000 and comprises a backbone and a side chain; and (b) a basic material. CMP (chemical mechanical polishing) slurry comprising the above adjuvant and abrasive particles is also disclosed.
Description
Technical field
The present invention relates to the auxiliary of a kind of CMP of being used for (chemically machinery polished) slurry; Or being used for the auxiliary that positively charged ion charged materials and negatively charged ion charged materials are polished simultaneously, it forms adsorption layer to improve the polishing selectivity of negatively charged ion charged materials to the positively charged ion charged materials on the positively charged ion charged materials.
Background technology
When microelectronic device constantly was endowed higher integrated level, the planarization process that is used to make such microelectronic device became more and more important.As in order to obtaining the part effort of high integrated micro device, multiple interconnect technology (multiple interconnection technique) and multilayer laminated technology (multilayer stacking technique) are generally used for semiconductor wafer.But the non-leveling of implementing a kind of back generation in the above-mentioned technology causes a lot of problems.Therefore, in a plurality of steps of microelectronic device ME, use planarization process, so that the irregular of wafer surface minimizes.
A kind of in the planarization techniques is CMP (chemically machinery polished).In the CMP technological process, wafer surface is pressed with the polishing pad with respect to the surface rotation, and in polishing process, known chemical reagent as the CMP slurry is introduced in the polishing pad.Such CMP technology is accomplished the leveling of wafer surface through the mode of chemistry and physical action.In other words, the CMP technology be through will being pressed on wafer surface with respect to the polishing pad of surface rotation, and simultaneously through providing the chemically reactive slurry to accomplish the leveling of wafer surface to the wafer surface with pattern.
An embodiment using the CMP technology is STI (shallow-trench isolation).In the STI technology, form shallow relatively groove, such groove is used to form the field region (field region) of the zone of action (activeregion) on separating wafer surface.
As shown in Figure 1, in STI technology, on semiconductor wafer, form liner oxidation silicon (SiO continuously
2) layer 101 and silicon nitride (SiN) layer 102.Then, on SiN layer 102, form the photoresist material pattern.Then, through making with photoresist pattern as sheltering, partially-etched SiN layer 102, pad silicon oxide layer 101 and semiconductor wafer 100 are to form a plurality of grooves 103.
In addition; In order to form the field region; Method deposition insulating oxide silicon layer 104 through LPCVD (low-pressure chemical vapor deposition), PECVD (plasma reinforced chemical vapour deposition) or HDPCVD (high density plasma CVD) technology; So that layer 104 filling slot 103, and the surperficial tegillum 104 of SiN layer 102 covers.
Subsequently, polishing insulating oxide silicon layer 104 is up to exposing SiN layer 102.In addition, SiN layer 102 places between the two adjacent zone of action, removes pad silicon oxide layer 101 through etching simultaneously.At last, on the surface of semiconductor wafer, form gate (gate) silicon oxide layer 105.
Here, carry out in the process in the CMP technology of removing insulating oxide silicon layer 104, because different chemistry and physical propertiess, insulating oxide silicon layer 104 demonstrates the different rates of removing with SiN layer 102.
The rate of removing of insulating oxide silicon layer and the ratio of the rate of removing of silicon nitride layer are called as the selectivity of CMP slurry.
When the selectivity of CMP slurry reduced, the amount of the SiN layer of removing through slurry increased.Preferably, the SiN layer is not removed.In other words, the insulating oxide silicon layer should be infinity to the selectivity of SiN layer.But the insulating oxide silicon layer of conventional CMP slurry is low to the polishing selectivity of SiN layer, and it is approximately 4: 1.Therefore, in actual CMP technology, the SiN layer is polished to the degree that surpasses acceptable scope.
As a result, in the CMP process,, remove the SiN layer pattern unevenly according to the position in the wafer.Therefore, the thickness of SiN layer changes in entire wafer.Especially at the same time have that this is a serious problem under the situation of semiconductor wafer of high density patterns and sparse pattern.
Because the problems referred to above, the final structure with field region has level error (level difference) between zone of action and field region, causes making surplus (margin) reduction and the transistor and the device quality deterioration of the subsequent step of semiconducter device.In brief, the problem of conventional CMP technology is, even remove the SiN layer pattern that can not obtain to have uniform thickness behind the oxide skin through CMP technology.
For addressing the above problem, a lot of effort have been made in the recent period, to develop the paste compound that a kind of rate of removing of controlling the insulating oxide silicon layer is higher than the polishing rate of SiN layer.For example, in U.S. Patent number 5,614,444; Japan publication 1998-106988,1998-154672,1998-270401,2001-37951,2001-35820 and 2001-319900; With such paste compound is disclosed among Korea S publication 2001-108048,2002-0015697,2004-0057653,2004-0013299 and the 2003-0039999.
Although constantly the CMP paste compound is carried out deep research and development up to now, to improve the selectivity of being represented by the polishing rate of insulation silicon dioxide layer and the ratio of the polishing rate of SiN layer, this paste compound still has very big room for improvement.
Summary of the invention
Technical problem
Therefore, consider that the problems referred to above make the present invention.An object of the present invention is to provide the auxiliary that the structure of a kind of structure that is used for the positively charged ion charged materials and negatively charged ion charged materials is polished simultaneously, it forms adsorption layer to increase the polishing selectivity of negatively charged ion charged materials structure on the structure of positively charged ion charged materials.The present invention's use comprises weight-average molecular weight and is controlled to be 1,000～20, and the polyelectrolyte salt of 000 graft type polyelectrolyte (ionic polymer or macroion) is so that the reunion of abrasive particle minimizes.
Technical scheme
According to a technical scheme of the present invention; A kind of auxiliary that positively charged ion charged materials and negatively charged ion charged materials are polished simultaneously that is used for is provided; It forms adsorption layer to improve the polishing selectivity of negatively charged ion charged materials on the positively charged ion charged materials, this auxiliary comprises polyelectrolyte salt, and said polyelectrolyte salt comprises: (a) weight-average molecular weight is 1; 000～20,000 and comprise the graft type polyelectrolyte of main chain and side chain; And (b) base material.The CMP that comprises this auxiliary and abrasive particle also is provided slurry.
According to another technical scheme of the present invention, a kind of auxiliary that comprises polyelectrolyte salt of the CMP of being used for slurry is provided, said polyelectrolyte salt comprises: (a) weight-average molecular weight is 1,000～20,000 and comprises the graft type polyelectrolyte of main chain and side chain; And (b) base material.The CMP that comprises this auxiliary and abrasive particle also is provided slurry.
According to another technical scheme of the present invention, a kind of STI (shallow-trench isolation) method of using above-mentioned CMP slurry is provided.
According to a technical scheme more of the present invention; A kind of polished method of positively charged ion charged materials that in polishing process, suppresses through using polyelectrolyte salt is provided; Said polyelectrolyte salt comprises: (a) weight-average molecular weight is 1; 000～20,000 and comprise the graft type polyelectrolyte of main chain and side chain; And (b) base material.
Description of drawings
Fig. 1 is the schema of explanation conventional STI (shallow-trench isolation) method.
Fig. 2 is the synoptic diagram of demonstration according to the structure of the graft type polyelectrolyte of preferred implementation of the present invention.
Embodiment
Hereinafter illustrates in greater detail the present invention.
The invention is characterized in that in polishing process, using weight-average molecular weight is 1,000～20,000 the charged graft type polyelectrolyte of negatively charged ion, polished with the structure of effective inhibition positively charged ion charged materials, the reunion like the particle of abrasive particle is minimized.
Usually, the surface of silicon nitride is that positively charged ion is charged, and silicon oxide surface is that negatively charged ion is charged.Therefore; For improving the polishing selectivity of silicon oxide to silicon nitride; To be adsorbed in like the negatively charged ion electropolymer of polyelectrolyte on the charged silicon nitride of positively charged ion through electrostatic force, to stop the charged silicon nitride of positively charged ion polished, it is polished that the charged silicon oxide of negatively charged ion more is prone to.
Among the present invention, if the molecular weight of negatively charged ion electropolymer is too low, then this polymkeric substance sparsely or with the form that approaches adsorption layer is adsorbed on the positively charged ion charged materials structure.Therefore, can not in glossing, the adequately protect structure of positively charged ion charged materials.
For in glossing, guaranteeing the protection to the positively charged ion charged materials, the negatively charged ion electropolymer preferably has HMW.But if molecular weight is too high, then polymkeric substance partly is adsorbed onto the reunion that causes particle on the abrasive particle through Van der Waals force.The particle of reuniting so in addition, can bring scratch in CMP technology.
Therefore; The invention is characterized in; For making the electrostatic adhesion maximization of negatively charged ion electropolymer on the structure of positively charged ion charged materials, make simultaneously because the absorption of Van der Waals force minimizes, use the graft type polyelectrolyte that comprises main chain and side chain to replace the linear polymerization ionogen.When relatively at the graft type polyelectrolyte of same molecular weight range and linear polymerization ionogen, the backbone length of graft type polyelectrolyte makes agglomeration minimize less than the electrolytical chain length of linear polymerization.In addition, proportional with side chain lengths, the graft type polymer electrolyte mass-energy with the side chain that is grafted on the main chain forms adsorption layer with density polymer higher on the per unit area on the structure of positively charged ion charged materials, and forms bigger thickness (see figure 2).
In brief, according to the present invention, use the graft type polyelectrolyte to replace the linear polymerization ionogen.Said graft type polyelectrolyte can optionally be adsorbed onto on the structure of positively charged ion charged materials with big thickness, and need not increase its molecular weight.Therefore; In glossing; Protected the structure that has optionally applied the positively charged ion charged materials of graft type polyelectrolyte through electrostatic force, thereby improved the polishing selectivity of negatively charged ion charged materials (for example silicon oxide) positively charged ion charged materials (for example silicon nitride).
Simultaneously, if use, not only can improve the polishing selectivity of negatively charged ion charged materials, and can improve the not polishing selectivity of charged materials according to auxiliary of the present invention.Therefore, as the equivalent of negatively charged ion charged materials, not charged structure is also included within the scope of the present invention.
As shown in Figure 2, be used for graft type polyelectrolyte of the present invention and comprise main chain 200 and side chain 201.Said graft type polyelectrolyte can form polyelectrolyte salt with base material.Can use the graft type polyelectrolyte of other form except that graft type polyelectrolyte salt within the scope of the invention.
According to the present invention, the weight-average molecular weight of said graft type polyelectrolyte is 1,000～20,000, is preferably 3,000～15,000.If the weight-average molecular weight of said graft type polyelectrolyte is lower than 1,000 or be higher than 20,000, then can not obtain stable paste compound.In addition, if the weight-average molecular weight of polyelectrolyte is higher than 20,000, then abrasive particle can be reunited.In addition, under latter event, polyelectrolyte is adsorbed onto on the structure of negatively charged ion charged materials (for example silicon oxide), also be adsorbed onto on the structure of positively charged ion charged materials (for example silicon nitride), so polyelectrolyte is used as resist in glossing.Therefore, the polishing rate of the polishing rate of positively charged ion charged materials structure and negatively charged ion charged materials structure reduces simultaneously, thereby causes polishing selectivity to reduce.
Preferably, it is 500～2,000 length that the side chain on the graft type polyelectrolyte preferably has corresponding to molecular weight, and it is 500～15,000 length that the main chain on the graft type polyelectrolyte has corresponding to molecular weight.If the length of side chain is too short, said polyelectrolyte can not fully be exercised defencive function because cladding thickness is little.On the other hand, if the length of side chain is long, then particle aggregation can take place.In addition, if the length of main chain is too short, cause polyelectrolyte absorption poor.On the other hand, if backbone length is long, abrasive particle then can takes place reunite.
The main chain of polyelectrolyte is the main point of participating in electrostatic adhesion.Therefore, in order to be adsorbed onto the structural purpose of positively charged ion charged materials, main chain preferably comprises a large amount of anionic units.For example, such anionic units comprises functional group like hydroxy-acid group as a part.
Compare with main chain, side chain is less to the influence degree of electrostatic adhesion.Therefore, to need not to be negatively charged ion charged for side chain.But side chain should not be cationic.Side chain mainly plays the purpose of the adsorptive coating of the bigger thickness of formation.
The side chain of said graft type polyelectrolyte preferably comprises by polymerization that contains hydroxyl, carboxyl and/or sulfonic ethylenically unsaturated monomers or co-polymerization deutero-big unit.In addition, the main chain of said graft type polyelectrolyte comprises by the ethylenically unsaturated monomers deutero-unit that contains carboxyl.
Usually, the slurry that is used to polish makes water as dispersion medium.Thereby preferred said graft type polyelectrolyte is water-soluble.Therefore, the big unit that also is preferably formed graft type polyelectrolyte side chain is hydrophilic, and preferably comprises the unit (for example comprising hydroxyl, carboxyl and/or sulfonic ethylenically unsaturated monomers) by the monomer derived of high-hydrophilic.
Said big unit is a short chain polymer, and is formed by big monomer derived, and 8～16 inferior monomer polymerizations of said big monomer form and use functional group dead-end.If because it is long to comprise the side chain of big unit, agglomeration takes place then, if it is too short to comprise the side chain of big unit, then polyelectrolyte can not be exercised defencive function.
PH according to polyelectrolyte salt of the present invention is 4.5～8.8, is preferably 6.0～7.5.If this pH is less than 4.5 or greater than 8.8, then polishing selectivity can not reach competent level.
For example, said graft type polyelectrolyte can make through the method that comprises following steps: (i) at least a inferior monomer of polymerization forms the big monomer of the side chain of graft type polymkeric substance with acquisition; And the monomer copolymerizable of the main chain of (ii) said big monomer and formation graft type polymkeric substance.
Preparation comprises step according to the preferred implementation of the method for graft type polyelectrolyte of the present invention: (i) comprise the radical polymerization of hydroxyl, carboxyl and/or sulfonic ethylenically unsaturated monomers, form the big monomer of the side chain of graft type polymkeric substance with acquisition; And the ethylenically unsaturated monomers copolymerization that comprises carboxyl of the main chain of (ii) said big monomer and formation graft type polymkeric substance.
Usually; Said big monomer obtains through following method: comprise through using and like the chain-transfer agent of thiohydracrylic acid carboxyl is introduced polymer ends, the ethylenic unsaturated group is introduced the method (Japanese publication number clear 43-11224) of polymer ends to wherein adding SY-Monomer G then; Through using as 2 of addition-breaking type (addition-cleavage type) chain-transfer agent, 4-phenylbenzene-4-methyl-1-pentene prepares big monomer methods (Japanese publication number flat 7-002954); Or through using metal complex to prepare big monomer methods (Japanese publication number flat 6-23209 peace 7-35411 and U.S. Patent number 4,694,054 and 4,886,861) based on cobalt.But in the present invention, the preferred use at the metal complex based on cobalt that shows excellent specific property aspect control MWD and the big monomeric purity of gained prepares big monomer.
Preferably, the ethylenically unsaturated monomers that comprises hydroxyl that is used for step (i) is C1～C12 hydroxyalkyl methacrylate, and its object lesson comprises Rocryl 400, Rocryl 410, methylacrylic acid hydroxy butyl ester etc.In addition, the operable ethylenically unsaturated monomers that comprises carboxyl comprises the carboxylic acid monomer like vinylformic acid, methylacrylic acid, methylene-succinic acid or toxilic acid.In addition, operablely comprise sulfonic ethylenically unsaturated monomers and comprise styrene sulfonic acid or naphthene sulfonic acid.
If desired, can comprise hydroxyl and/or sulfonic ethylenically unsaturated monomers and the big monomer of the incompatible preparation of ethylenically unsaturated monomers copolymerization that comprises carboxyl through making.In this case, preferably use methylacrylic acid or vinylformic acid.
Preferably will comprise hydroxyl and/or sulfonic ethylenically unsaturated monomers is mixed with the ethylenically unsaturated monomers that comprises carboxyl with 100: 0～70: 30, more preferably 95: 5～85: 15 weight ratio.If the amount to be higher than 30 weight parts is used the ethylenically unsaturated monomers that comprises carboxyl, then the gained paste compound can not provide highly selective stable with fully.
Can use metal complex to come the said ethylenically unsaturated monomers of polymerization as chain-transfer agent based on cobalt.In the presence of radical polymerization initiator, carry out polyreaction through solution polymerization with organic solvent.In addition, can in water, come the said ethylenically unsaturated monomers of polymerization through letex polymerization.Especially preferably use solution polymerization.
The metal complex based on cobalt of effect chain-transfer agent comprises two hydrations two (boron two fluoro-dimethyl glyoximes) cobalt (II) or two hydrations two (boron two fluoro-phenylbenzene glyoximes) cobalt (II).
Based on being used for the big monomeric total amount of preparation, preferably with 5～1, the amount of 000ppm is used the metal complex based on cobalt.If this amount is lower than 5ppm, then the big monomeric molecular weight of gained improves rapidly.If this amount is higher than 1,000ppm then has disadvantageous effect based on the metal complex of cobalt to the quality of final paste compound.
Operable polymerization starter comprises the initiator of organo-peroxide or azo-based.More preferably use as 2 2-azo two-4-methoxyl group-2,4-methyl pentane nitrile, 2; 2-azo two-2,4-methyl pentane nitrile, 2,2-azo two-isopropyl cyanide, 2; 2-azo two-2-methyl-butyronitrile, 2, and 2-azo two-hexamethylene formonitrile HCN (2,2-azobis-cyclohexanecarbonitrile) or 2; 2-azo two-cyanogen pentane (2, the initiator of azo-based 2-azobis-cyanopentane).
Based on being used for the big monomeric total amount of preparation, use said polymerization starter with the amount of 0.1～5 weight part.If this amount is lower than 0.1 weight part, then monomeric transformation efficiency is low.If this amount is higher than 5 weight parts, then the big monomeric purity of gained is low.
Operable organic solvent comprises aromatic compound, fatty compounds, ketone, glycol ether, acetic ester, alcohol etc.The object lesson of organic solvent comprises methyl ethyl ketone, Virahol, propylene glycol monomethyl ether and propyl carbinol.
Then, the big monomer that obtains as stated with as comprise the monomer polymerization of the main chain that can form the graft type polymkeric substance of the ethylenically unsaturated monomers of carboxyl, so that final graft type polyelectrolyte to be provided.
As the ethylenically unsaturated monomers that comprises carboxyl, preferably use methylacrylic acid or vinylformic acid.Based on the main chain gross weight,, more preferably use the ethylenically unsaturated monomers that comprises carboxyl with the amount of 70 weight parts with the amount of 65～100 weight parts.If this amount is less than 65 weight parts, then can not obtain enough static avidity, so resulting polymers can not be adsorbed on optionally on the structure of positively charged ion charged materials (for example silicon nitride).Therefore, can not prevent that such structure is polished, cause polishing selectivity to reduce.
If desired, when fashionable with big monomer copolymerization, comprise carboxyl ethylenically unsaturated monomers can with can unite use with the polymerisable monomer that comprises vinyl of its copolymerization.
Although to the not concrete restriction of the polymerisable monomer that comprises vinyl, it is because good reactivity and preferred (methyl) acrylate monomer that uses, and based on the gross weight of main chain, uses such monomer with the amount of 35 weight parts at the most.If this amount is higher than 35 weight parts, then can not accomplish absorption through static avidity.In addition, as being used as tensio-active agent, the hydrophobic monomer that comprises vinyl has increased the hydrophobicity of main chain, therefore in final paste compound, has increased the generation of bubble.
Be used to form the initiator of the main chain of graft type polyelectrolyte, preferably use the organic peroxy initiator.The object lesson of said initiator comprises Lucidol, lauryl peroxide, t-butylperoxy pivarate, t-amyl peroxy pivalate, uncle's hexyl peroxo-pivalate, tert-butyl hydroperoxide neodecanoic acid ester, uncle's hexyl peroxo-ethylhexoate (t-hexylperoxyethyl hexanoate) etc.
The organic solvent that in the main chain of preparation graft type polyelectrolyte, uses comprises and prepares the solvent phase example together that uses in the side chain of same polyelectrolyte.
In addition, through using base material, can said graft type polyelectrolyte be converted into graft type polyelectrolyte salt at aqueous phase.
When auxiliary of the present invention was used for the CMP slurry, spendable base material comprised being selected from and comprises volatile caustic (NH
4OH) with like at least a material of the group of the basic amine of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide.
Except above-mentioned auxiliary, the present invention also provides a kind of CMP slurry, and it comprises: (i) comprise (a) weight-average molecular weight and be 1,000～20,000 and comprise the graft type polyelectrolyte of main chain and side chain and (b) auxiliary of base material; (ii) abrasive particle; And (iii) water.
Preferably in the CMP slurry, use said polyelectrolyte salt with the amount of 0.1～10wt%.If this amount is lower than 0.1wt%, then polishing selectivity reduces.On the other hand, if this amount is higher than 10wt%, then polishing selectivity reduces, and the reunion of abrasive particle takes place.
Amount with 0.1～10wt% is used said abrasive particle in the CMP slurry.If this amount is lower than 0.1wt%, the height that then can not fully obtain oxide skin is removed rate.Another invention, if this amount is higher than 10wt%, then slurry presents poor stability.
As abrasive particle, can use nano-scale ceramic abrasive grain like silicon-dioxide, aluminum oxide, zirconium white, titanium oxide and cerium oxide particles.The preferred cerium oxide particles that uses.
Can be by the polyelectrolyte salt that is dissolved in the solvent (for example water), or prepare said CMP slurry by the abrasive particle that is scattered in the dispersion medium (for example water).Preferably, the concentration of the aqueous solution of polyelectrolyte salt is 3～3.5wt%, and the concentration of the aqueous dispersion of abrasive particle is 4～6wt%.
Therefore, the water that forms the CMP slurry can come the water in the compsn that comprises polyelectrolyte salt or abrasive particle that is present in of the aqueous solution freely.The amount that is adjusted to 100wt% with the gross weight with slurry makes water.Preferably the amount with 94～99.8wt% makes water.If this amount is lower than 94wt%, then said slurry stability decreases.If this amount is higher than 99.8wt%, the rate of then removing reduces.
In addition, the present invention provides a kind of STI (shallow-trench isolation) method of using said CMP slurry.
When using, because silicon oxide layer is to the highly selective of silicon nitride layer, so can in the entire area of wafer, remove the SiN layer equably in the CMP technological process according to CMP slurry of the present invention.Therefore, can make the minimize variations of thickness.As a result, the level of zone of action (lcvel) is little with the horizontal difference of field region, can disadvantageous effect not arranged to the quality of transistor and microelectronic device simultaneously.In addition, can use and have high polishing selectivity and the low paste compound of abrasive particle reunion degree advances new CMP technology.Therefore, the present invention is suitable for being applied in the manufacturing of the semiconducter device that needs miniature image (micropattcrn), has therefore formed high-quality miniature image, and has improved safety and productive rate.
In addition; The present invention provides a kind of polyelectrolyte salt that in polishing process, uses to suppress the polished method of positively charged ion charged materials; Said polyelectrolyte salt comprises: (a) weight-average molecular weight is 1,000～20,000 and comprises the graft type polyelectrolyte of main chain and side chain and (b) base material.
The charged graft type polymkeric substance of positively charged ion that in polishing process, comprises main chain and side chain through use suppresses the polished method of negatively charged ion charged materials and is also included within the scope of the present invention.
In detail with reference to preferred implementation of the present invention.Should be appreciated that following embodiment is merely illustrative, the invention is not restricted to this.
Embodiment 1. is used for the preparation of the auxiliary of CMP slurry
(big monomeric preparation)
In the 500mL four-hole boiling flask that has been equipped with whisking appliance, TM, nitrogen inlet and condensing surface, add 75 weight part Virahols, and this Virahol bubbled about 20 minutes with nitrogen under reflux temperature.Then, with 0.032g two (boron difluorodiphenyl base glyoxime) cobalt (II) (bis (borondifluorodiphenyl glyoxime) CoII)) be dissolved in the methyl ethyl ketone of 80g, and with about 270 minutes it is dropwise joined in the above-mentioned reactor drum.Meanwhile; Respectively with about 240 minutes and 270 minutes dropwise add the methylacrylic acid that comprises 10 weight parts and 90 weight parts Rocryl 400 monomer be dissolved in the 49g Virahol, comprise 1g 2, the polymerization starter solution of 2-azo two-2-methyl-butyronitrile.After adding polymerization starter solution, reaction mixture kept under reflux temperature about 30 minutes, was cooled to room temperature then, was 35% large monomer solution with the acquisition solid content.Use the said big monomer of NMR spectrometer analysis, and big monomeric molecular weight is 1,300, the polymkeric substance degree is 10.Behind this big monomer of thermogravimetry analysis, big monomeric purity is about 92%.
(preparation of graft type polyelectrolyte)
The methylacrylic acid of TEB 3K, 2.9 parts by weight of acrylic and 4.2 weight parts of the above-mentioned big monomer of the Virahol of adding 120 weight parts, 30 weight parts, 2.9 weight parts in the 500mL four-hole boiling flask that has been equipped with whisking appliance, TM, nitrogen inlet and condensing surface, this mixture bubbled under reflux temperature about 10 minutes
In mixture, add the peroxo-PIVALIC ACID CRUDE (25) tert-pentyl ester of 0.2 weight part as initiator, and with the monomer of the methylacrylic acid that dropwise added the TEB 3K, 17.2 parts by weight of acrylic and 25.6 weight parts that comprise 17.2 weight parts in about 2 hours and the peroxo-PIVALIC ACID CRUDE (25) tert-pentyl ester of 1.0 weight parts.Then, with 10 minutes dropwise to the peroxo-PIVALIC ACID CRUDE (25) tert-pentyl ester that wherein adds 0.3 weight part, reaction mixture placed under the reflux temperature about 10 minutes, was cooled to room temperature then, was about 38% graft type polyelectrolyte solution to obtain solid content.After GPC (GPC) assay products, the weight-average molecular weight of this graft type polyelectrolyte is 10,000.The characteristic peak that the NMR analysis of product and thermogravimetric analysis do not show unsaturated carbon atom.
(preparation of graft type polyelectrolyte salt)
In the solution of the graft type polyelectrolyte that makes as stated, add ammonium hydroxide aqueous solution; Polyelectrolyte is converted into polyelectrolyte salt; And under vacuum decompression, remove remaining Virahol, the aqueous solution that be 10.5% to obtain solid content, pH is 6.5 graft type polyelectrolyte salt.
(being used for the preparation of the auxiliary of CMP slurry)
In the solution of graft type polyelectrolyte salt, add entry, reach 3wt% up to ultimate density.In the solution of dilution, adding volatile caustic, is 7.1 with the pH that controls solution.At last, obtain to be used for the final auxiliary of CMP slurry.
Embodiment 2 is used for the preparation of the auxiliary of CMP slurry
(big monomeric preparation)
To prepare big monomer with embodiment 1 said same procedure.
(preparation of graft type polyelectrolyte)
In the 500mL four-hole boiling flask that has been equipped with whisking appliance, TM, nitrogen inlet and condensing surface, add the Virahol of 120 weight parts, the above-mentioned big monomer of 30 weight parts, the TEB 3K and 7.1 parts by weight of acrylic of 2.9 weight parts, this mixture bubbled under reflux temperature about 10 minutes.
In mixture, add the peroxo-PIVALIC ACID CRUDE (25) tert-pentyl ester of 0.2 weight part as initiator, and with about 2 hours dropwise adding comprise TEB 3K and the monomer of 42.8 parts by weight of acrylic and the peroxo-PIVALIC ACID CRUDE (25) tert-pentyl ester of 1.0 weight parts of 17.2 weight parts.Then, with 10 minutes dropwise to the peroxo-PIVALIC ACID CRUDE (25) tert-pentyl ester that wherein adds 0.3 weight part, reaction mixture placed under the reflux temperature about 10 minutes, was cooled to room temperature then, was about 37% graft type polyelectrolyte solution to obtain solid content.After GPC (GPC) assay products, the weight-average molecular weight of this graft type polyelectrolyte is 10,000.The characteristic peak that the NMR analysis of product and thermogravimetric analysis do not show unsaturated carbon atom.
(preparation of graft type polyelectrolyte salt)
To obtain graft type polyelectrolyte salt with embodiment 1 said same procedure.
(being used for the preparation of the auxiliary of CMP slurry)
To obtain to be used for the auxiliary of CMP slurry with the said same procedure of embodiment 1.
Embodiment 3 is used for the preparation of the auxiliary of CMP slurry
(big monomeric preparation)
The methylacrylic acid that replaces comprising 10 weight parts except that the Rocryl 400 that uses 100 weight parts and the Rocryl 400 blended monomer of 90 weight parts, with embodiment 1 said same procedure acquisition large monomer solution.The big monomeric molecular weight that obtains among this embodiment is 1,000, and the polymerization degree is 8, and purity is about 96%.
(preparation of graft type polyelectrolyte)
In the 500mL four-hole boiling flask that has been equipped with whisking appliance, TM, nitrogen inlet and condensing surface, add the Virahol of 120 weight parts, the above-mentioned big monomer of 30 weight parts, the TEB 3K and 5.3 parts by weight of acrylic of 4.3 weight parts, this mixture bubbled under reflux temperature about 10 minutes.
In mixture, add the peroxo-PIVALIC ACID CRUDE (25) tert-pentyl ester of 0.2 weight part as initiator, and with the monomer of the methylacrylic acid that dropwise added the TEB 3K, 34.3 parts by weight of acrylic and 25.6 weight parts that comprise 25.7 weight parts in about 2 hours and the peroxo-PIVALIC ACID CRUDE (25) tert-pentyl ester of 1.0 weight parts.Then, with 10 minutes dropwise to the peroxo-PIVALIC ACID CRUDE (25) tert-pentyl ester that wherein adds 0.3 weight part, reaction mixture placed under the reflux temperature about 10 minutes, was cooled to room temperature then, was about 38% graft type polyelectrolyte solution to obtain solid content.
After GPC (GPC) assay products, the weight-average molecular weight of this graft type polyelectrolyte is 10,000.The characteristic peak that the NMR analysis of product and thermogravimetric analysis do not show unsaturated carbon atom.
(preparation of graft type polyelectrolyte salt)
To obtain graft type polyelectrolyte salt with embodiment 1 said same procedure.
(being used for the preparation of the auxiliary of CMP slurry)
To obtain to be used for the auxiliary of CMP slurry with the said same procedure of embodiment 1.
The preparation of embodiment 4.CMP slurry
With volume ratio is to mix the ceria slurry compsn as abrasive particle composition (HIHC-1, LG Chemical Ltd.) of 5wt% at 1: 3: 3, prepare the CMP slurry according to auxiliary that is used for the CMP slurry and the water of embodiment 1.
The preparation of embodiment 5.CMP slurry
Except that using the auxiliary that is used for the CMP slurry to replace the auxiliary that is used for the CMP slurry according to embodiment 1, to prepare the CMP slurry with embodiment 4 said identical methods according to embodiment 2.
The preparation of embodiment 6.CMP slurry
Except that using the auxiliary that is used for the CMP slurry to replace the auxiliary that is used for the CMP slurry according to embodiment 1, to prepare the CMP slurry with embodiment 4 said identical methods according to embodiment 3.
Use is carried out following test according to each CMP slurry of the foregoing description 4～6, and (
/min), nitride layer are removed rate (
/min) and polishing selectivity to remove rate with mensuration pH, average agglomerated particles size (nm), oxide skin.The result is listed in the table below 1.
(a) use pH measuring apparatus (healthy and free from worry pH meter 445) to measure pH.
(b) use light scattering device (dynamic light scattering, Microtrap UPA150, Honeywell Inc., the U.S.) to measure average agglomerated particles size.
(c) use the Nanospec 6100 that buys from Nai Nuo company, before and after polishing, measure the thickness of oxide skin, then calculated thickness difference and obtain oxide skin and remove rate.
(d) use the Nanospec 6100 that buys from Nai Nuo company, before and after polishing, measure the thickness of nitride layer, then calculated thickness difference and obtain nitride layer and remove rate.
(c) record selectivity with the oxide skin rate of removing divided by the nitride layer rate of removing.
[table 1]
| Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| The concentration (wt%) that is used for the auxiliary of CMP slurry | 1.3 | 1.3 | 1.3 |
| PH | 7.66 | 7.35 | 7.00 |
| Average agglomerated particles size (nm) | 535 | 685 | 734 |
Oxide skin remove rate (
 | 3,134 | 3,935 | 3,201 |
Nitride layer remove rate (
 | 42 | 43 | 43 |
| Selectivity | 74.6 | 91.5 | 74.4 |
The preparation of comparative example 1 and embodiment 7～10 CMP slurries
At first, be to mix the ceria slurry compsn (abrasive particle composition, HIHC-1, LG Chemical Ltd.) of 5wt% at 1: 7 and with volume ratio according to the auxiliary that is used for the CMP slurry of embodiment 1.Then, water mixture diluted is used for the CMP slurry with adjustment the concentration of auxiliary to 0wt% (comparative example 1), 0.42wt% (embodiment 7), 0.85wt% (embodiment 8), 1.3wt% (embodiment 9) and 1.5wt% (embodiment 10).
Measure pH with method same as described above according to each CMP slurry of comparative example 1 and embodiment 7～10; Average agglomerated particles size (nm); Oxide skin is removed rate (
/min); Nitride layer is removed rate (
/min) and polishing selectivity.The result is listed in the table below 2.
[table 2]
| The comparative example 1 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | |
| The concentration (wt%) that is used for the auxiliary of CMP slurry | 0.0 | 0.42 | 0.85 | 1.3 | 1.5 |
| PH | 7.84 | 7.93 | 7.83 | 7.72 | 7.67 |
| Average agglomerated particles size (nm) | 240 | 881 | 835 | 617 | 557 |
Oxide skin remove rate (
 | 3,854 | 3,516 | 3,145 | 2,944 | 2,761 |
Nitride layer remove rate (
 | 829 | 66 | 37 | 38 | 40 |
| Selectivity | 5 | 53 | 85 | 77 | 69 |
The comparative example 2
(being used for the preparation of the auxiliary of CMP slurry)
Remove to use to comprise outside the solution of polyelectrolyte salt that weight-average molecular weight is 10,000 polyacrylic linear anionoid polymerization ionogen and sodium hydroxide, repetition embodiment 1 is to be provided for the auxiliary of CMP slurry.
(preparation of CMP slurry)
With volume ratio is to mix the auxiliary that is used for the CMP slurry and the water of the ceria slurry compsn as abrasive particle composition (HIHC-1, LG Chemical Ltd.) of 5wt%, above-mentioned acquisition at 1: 3: 3 and prepare the CMP slurry.
The comparative example 3
(being used for the preparation of the auxiliary of CMP slurry)
Except using the commercially available glidant that gets (glidant) (trade(brand)name CD-WB; LG Chemical Ltd.); Be that weight-average molecular weight is 21,000, and comprise outside the polyelectrolyte salts solution of the anionoid polymerization ionogen represented by structure shown in Figure 2 and sodium hydroxide; Repeat embodiment 1, to be provided for the auxiliary of CMP slurry.
(preparation of CMP slurry)
With volume ratio is to mix the auxiliary that is used for the CMP slurry and the water of the ceria slurry compsn as abrasive particle composition (HIHC-1, LG Chemical Ltd.) of 5wt%, above-mentioned acquisition at 1: 3: 3 and prepare the CMP slurry.
The comparative example 4
(being used for the preparation of the auxiliary of CMP slurry)
Except using commercially available glidant (the trade(brand)name CD-WR that gets; LG Chemical Ltd.); Be that weight-average molecular weight is 25,000, and comprise outside the polyelectrolyte salts solution of the anionoid polymerization ionogen represented by structure shown in Figure 2 and sodium hydroxide; Repeat embodiment 1, to be provided for the auxiliary of CMP slurry.
(preparation of CMP slurry)
With volume ratio is to mix the auxiliary that is used for the CMP slurry and the water of the ceria slurry compsn as abrasive particle composition (HIHC-1, LG Chemical Ltd.) of 5wt%, above-mentioned acquisition at 1: 3: 3 and prepare the CMP slurry.
Measure pH with method same as described above according to each CMP slurry of comparative example 2～4; Average agglomerated particles size (nm); Oxide skin is removed rate (
/min); Nitride layer is removed rate (
/min) and polishing selectivity.The result is listed in the table below 3.
[table 3]
| The comparative example 2 | The comparative example 3 | The comparative example 4 | |
| The concentration (wt%) that is used for the auxiliary of CMP slurry | 1.3 | 1.3 | 1.3 |
| PH | 7.29 | 8.25 | 7.93 |
| Average agglomerated particles size (nm) | 967 | 806 | 758 |
Oxide skin remove rate (
 | 2,703 | 4,092 | 4,117 |
Nitride layer remove rate (
 | 49 | 903 | 408 |
| Selectivity | 55 | 4.5 | 10.1 |
As above shown in the table 3, use molecular weight to be higher than 20,000 anionoid polymerization ionogen (comparative example 3 and 4) and cause the polishing selectivity reduction.
Therefore; Can find out from result shown in last table 1～3; Compare with each CMP slurry according to comparative example 1～4, according to CMP slurry of the present invention (embodiment 4～10) demonstrate identical or improved average agglomerated particles size, oxide skin removes rate and nitride layer is removed rate.Especially CMP slurry according to the present invention can provide excellent polishing selectivity.
Industrial applicibility
As stated; Be applied to the method that positively charged ion charged materials and negatively charged ion charged materials are polished simultaneously according to the auxiliary of the CMP of being used for slurry of the present invention, it comprises polyelectrolyte salt, and this polyelectrolyte salt comprises weight-average molecular weight and controls to 1; 000～20,000 graft type polyelectrolyte.Among the present invention, said polyelectrolyte salt forms adsorption layer on the structure of positively charged ion charged materials, with the polishing selectivity of the structure that increases the negatively charged ion charged materials, and the reunion of abrasive particle is minimized.
Though combined to think at present the most practical with preferred embodiment invention has been described, should be appreciated that, the invention is not restricted to disclosed embodiment and accompanying drawing.On the contrary, its plan covers the essence of accompanying claims and multiple modification and the variation in the scope.
Claims (16)
1. one kind is used for the auxiliary that positively charged ion charged materials and negatively charged ion charged materials are polished simultaneously; It forms adsorption layer on the positively charged ion charged materials; To increase the polishing selectivity of negatively charged ion charged materials, wherein said auxiliary comprises polyelectrolyte salt, and this polyelectrolyte salt comprises:
(a) weight-average molecular weight is 1,000～20,000 and comprises the charged graft type polyelectrolyte of negatively charged ion of main chain and side chain; And
(b) base material,
Wherein, it is 500～2,000 length that said side chain has corresponding to molecular weight, and said main chain to have corresponding to molecular weight be 500～15,000 length, and the pH of said polyelectrolyte salt is 4.5～8.8.
2. auxiliary that is used for chemical mechanical polishing slurry, it comprises polyelectrolyte salt, and this polyelectrolyte salt comprises:
(a) weight-average molecular weight is 1,000～20,000 and comprises the charged graft type polyelectrolyte of negatively charged ion of main chain and side chain; And
(b) base material,
Wherein, it is 500～2,000 length that said side chain has corresponding to molecular weight, and said main chain to have corresponding to molecular weight be 500～15,000 length, and the pH of said polyelectrolyte salt is 4.5～8.8.
3. auxiliary according to claim 1 and 2, wherein, said graft type polyelectrolyte comprises:
By comprising at least a ethylenically unsaturated monomers polymerization that is selected from hydroxyl, carboxyl and sulfonic functional group or copolymerization and the deutero-big unit, as side chain; And
By the ethylenically unsaturated monomers deutero-unit that comprises carboxyl, as main chain.
4. auxiliary according to claim 1 and 2, it obtains through the method that comprises the steps:
(i) at least a inferior monomer of polymerization forms the big monomer of the side chain of graft type polymkeric substance with acquisition; And
(ii) make the monomer copolymerizable of the main chain of said big monomer and formation graft type polymkeric substance.
5. auxiliary according to claim 4, wherein, said graft type polyelectrolyte obtains through the method that comprises the steps:
(i) make and comprise at least a ethylenically unsaturated monomers that is selected from the functional group that comprises hydroxyl, carboxyl and sulfonic group and carry out radical polymerization, to obtain big monomer; And
(ii) make said big monomer and the ethylenically unsaturated monomers copolymerization that comprises carboxyl.
6. auxiliary according to claim 5, wherein, the said ethylenically unsaturated monomers that comprises hydroxyl is C1～C12 hydroxyalkyl methacrylate.
7. auxiliary according to claim 3, wherein, said big unit obtains with the copolymerization that comprises the ethylenically unsaturated monomers of carboxyl through comprising at least a ethylenically unsaturated monomers that is selected from the functional group that comprises hydroxyl and sulfonic group.
8. auxiliary according to claim 7; Wherein, Comprise at least a gross weight that is selected from the ethylenically unsaturated monomers of the functional group that comprises hydroxyl and sulfonic group based on said, use the said ethylenically unsaturated monomers that comprises carboxyl with the amount of 30 weight parts at the most.
9. auxiliary according to claim 3 wherein, is present in the ethylenically unsaturated monomers institute deutero-unit by comprising carboxyl on the said graft type polyelectrolyte main chain and is derived by methylacrylic acid or vinylformic acid and obtain.
10. auxiliary according to claim 3, wherein, based on the gross weight of said main chain, with the amount of 65～100 weight parts use said be present on the graft type polyelectrolyte main chain by the ethylenically unsaturated monomers deutero-unit that comprises carboxyl.
11. auxiliary according to claim 5, wherein, the monomer that the said ethylenically unsaturated monomers that comprises carboxyl and polymerisable comprises vinyl is united use in step in (ii).
12. auxiliary according to claim 11, wherein, the said polymerisable monomer that comprises vinyl is (methyl) acrylate monomer.
13. auxiliary according to claim 1 and 2, wherein, said base material (b) is selected from volatile caustic, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and the tetrabutylammonium hydroxide.
14. a chemical mechanical polishing slurry, based on the gross weight of the said slurry of 100wt%, it comprises:
(a) 0.1～10wt%'s like each described auxiliary in the claim 1～13;
(b) abrasive particle of 0.1～10wt%; And
(c) water of surplus.
15. shallow-trench isolation method of using chemical mechanical polishing slurry as claimed in claim 14.
16. one kind is suppressed the polished method of positively charged ion charged materials in polishing process; It uses polyelectrolyte salt; This polyelectrolyte salt comprises (a) weight-average molecular weight to be 1,000～20,000 and to comprise the charged graft type polyelectrolyte of negatively charged ion of main chain and side chain; And (b) base material,
Wherein, it is 500～2,000 length that said side chain has corresponding to molecular weight, and said main chain to have corresponding to molecular weight be 500～15,000 length, and the pH of said polyelectrolyte salt is 4.5～8.8.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2004-0114824 | 2004-12-29 | ||
| KR1020040114824 | 2004-12-29 | ||
| KR20040114824 | 2004-12-29 | ||
| KR10-2005-0113758 | 2005-11-25 | ||
| KR1020050113758A KR100786950B1 (en) | 2004-12-29 | 2005-11-25 | Supplement agent for chemical mechanical polishing slurry |
| KR1020050113758 | 2005-11-25 | ||
| PCT/KR2005/004592 WO2006071063A1 (en) | 2004-12-29 | 2005-12-28 | Adjuvant for chemical mechanical polishing slurry |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101068901A CN101068901A (en) | 2007-11-07 |
| CN101068901B true CN101068901B (en) | 2012-05-09 |
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|---|---|---|---|
| CN2005800410698A Active CN101068901B (en) | 2004-12-29 | 2005-12-28 | Adjuvant for chemical mechanical polishing slurry |
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| Country | Link |
|---|---|
| JP (1) | JP4712813B2 (en) |
| KR (1) | KR100786950B1 (en) |
| CN (1) | CN101068901B (en) |
| TW (1) | TWI320055B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100786948B1 (en) * | 2005-12-08 | 2007-12-17 | 주식회사 엘지화학 | Adjuvant capable of controlling a polishing selectivity and chemical mechanical polishing slurry comprising the same |
| KR100786949B1 (en) * | 2005-12-08 | 2007-12-17 | 주식회사 엘지화학 | Adjuvant capable of controlling a polishing selectivity and chemical mechanical polishing slurry comprising the same |
| KR100832993B1 (en) * | 2006-04-14 | 2008-05-27 | 주식회사 엘지화학 | Adjuvant for chemical mechanical polishing slurry |
| CN101946309A (en) * | 2008-02-18 | 2011-01-12 | Jsr株式会社 | Aqueous dispersion for chemical mechanical polishing and chemical mechanical polishing method |
| US8822339B2 (en) | 2009-10-13 | 2014-09-02 | Lg Chem, Ltd. | Slurry composition for CMP, and polishing method |
| JP5637500B2 (en) * | 2011-02-01 | 2014-12-10 | 三菱レイヨン株式会社 | Method for producing vinyl polymer and vinyl polymer |
| EP2826827B1 (en) * | 2013-07-18 | 2019-06-12 | Basf Se | CMP composition comprising abrasive particles containing ceria |
| KR101353315B1 (en) * | 2013-08-07 | 2014-01-21 | 소문식 | Composition for cutting wheel and cutting wheel comprising the same |
| KR102475282B1 (en) | 2017-03-29 | 2022-12-07 | 삼성전자주식회사 | Slurry composition for chemical mechanical polishing |
| CN111378973A (en) * | 2018-12-28 | 2020-07-07 | 安集微电子科技（上海）股份有限公司 | Chemical mechanical polishing solution and application thereof |
| CN112872916B (en) * | 2020-12-28 | 2023-03-10 | 富联裕展科技(深圳)有限公司 | Polishing system and polishing method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1289811A (en) * | 1999-09-27 | 2001-04-04 | 不二见美国股份有限公司 | Polishing compositions |
| US6776810B1 (en) * | 2002-02-11 | 2004-08-17 | Cabot Microelectronics Corporation | Anionic abrasive particles treated with positively charged polyelectrolytes for CMP |
| US6824579B2 (en) * | 2000-05-24 | 2004-11-30 | International Business Machines Corporation | Selective polishing with slurries containing polyelectrolytes |
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| JP4744656B2 (en) * | 1998-10-08 | 2011-08-10 | 日立化成工業株式会社 | CMP polishing agent and substrate polishing method |
| JP4555936B2 (en) * | 1999-07-21 | 2010-10-06 | 日立化成工業株式会社 | CMP polishing liquid |
| KR100539983B1 (en) * | 2003-05-15 | 2006-01-10 | 학교법인 한양학원 | Ceria Abrasives for CMP and Methods of Fabricating the Same |
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2005
- 2005-11-25 KR KR1020050113758A patent/KR100786950B1/en active IP Right Grant
- 2005-12-27 TW TW094146707A patent/TWI320055B/en active
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1289811A (en) * | 1999-09-27 | 2001-04-04 | 不二见美国股份有限公司 | Polishing compositions |
| US6824579B2 (en) * | 2000-05-24 | 2004-11-30 | International Business Machines Corporation | Selective polishing with slurries containing polyelectrolytes |
| US6776810B1 (en) * | 2002-02-11 | 2004-08-17 | Cabot Microelectronics Corporation | Anionic abrasive particles treated with positively charged polyelectrolytes for CMP |
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| KR100786950B1 (en) | 2007-12-17 |
| CN101068901A (en) | 2007-11-07 |
| TWI320055B (en) | 2010-02-01 |
| TW200704760A (en) | 2007-02-01 |
| KR20060076190A (en) | 2006-07-04 |
| JP2008521242A (en) | 2008-06-19 |
| JP4712813B2 (en) | 2011-06-29 |
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