CN100336881C - Chemical methanical grinding paste composition and its use method - Google Patents
Chemical methanical grinding paste composition and its use method Download PDFInfo
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- CN100336881C CN100336881C CNB021459894A CN02145989A CN100336881C CN 100336881 C CN100336881 C CN 100336881C CN B021459894 A CNB021459894 A CN B021459894A CN 02145989 A CN02145989 A CN 02145989A CN 100336881 C CN100336881 C CN 100336881C
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- 239000000203 mixture Substances 0.000 title claims abstract description 65
- 238000000227 grinding Methods 0.000 title claims abstract description 38
- 239000000126 substance Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004065 semiconductor Substances 0.000 claims abstract description 10
- 238000005260 corrosion Methods 0.000 claims abstract description 6
- 230000007797 corrosion Effects 0.000 claims abstract description 6
- 239000003112 inhibitor Substances 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 63
- 239000002253 acid Substances 0.000 claims description 20
- 238000005498 polishing Methods 0.000 claims description 20
- 239000006061 abrasive grain Substances 0.000 claims description 18
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 18
- 239000012964 benzotriazole Substances 0.000 claims description 18
- 235000012431 wafers Nutrition 0.000 claims description 14
- 239000012530 fluid Substances 0.000 claims description 10
- 239000012736 aqueous medium Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- JOFWLTCLBGQGBO-UHFFFAOYSA-N triazolam Chemical compound C12=CC(Cl)=CC=C2N2C(C)=NN=C2CN=C1C1=CC=CC=C1Cl JOFWLTCLBGQGBO-UHFFFAOYSA-N 0.000 claims description 4
- 229960003386 triazolam Drugs 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- -1 diol compound Chemical class 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 5
- 210000004911 serous fluid Anatomy 0.000 abstract 2
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 239000002002 slurry Substances 0.000 description 26
- 239000010949 copper Substances 0.000 description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 19
- 229910052802 copper Inorganic materials 0.000 description 19
- 238000012360 testing method Methods 0.000 description 16
- 239000008267 milk Substances 0.000 description 14
- 210000004080 milk Anatomy 0.000 description 14
- 235000013336 milk Nutrition 0.000 description 14
- 239000003292 glue Substances 0.000 description 13
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 13
- 235000012239 silicon dioxide Nutrition 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 235000013772 propylene glycol Nutrition 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- AFENDNXGAFYKQO-VKHMYHEASA-N (S)-2-hydroxybutyric acid Chemical compound CC[C@H](O)C(O)=O AFENDNXGAFYKQO-VKHMYHEASA-N 0.000 description 1
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 1
- JVXHQHGWBAHSSF-UHFFFAOYSA-L 2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;hydron;iron(2+) Chemical compound [H+].[H+].[Fe+2].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O JVXHQHGWBAHSSF-UHFFFAOYSA-L 0.000 description 1
- GUOVBFFLXKJFEE-UHFFFAOYSA-N 2h-benzotriazole-5-carboxylic acid Chemical compound C1=C(C(=O)O)C=CC2=NNN=C21 GUOVBFFLXKJFEE-UHFFFAOYSA-N 0.000 description 1
- RDIMQHBOTMWMJA-UHFFFAOYSA-N 4-amino-3-hydrazinyl-1h-1,2,4-triazole-5-thione Chemical compound NNC1=NNC(=S)N1N RDIMQHBOTMWMJA-UHFFFAOYSA-N 0.000 description 1
- KUEFXPHXHHANKS-UHFFFAOYSA-N 5-nitro-1h-1,2,4-triazole Chemical compound [O-][N+](=O)C1=NC=NN1 KUEFXPHXHHANKS-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 241001646579 Coryphaenoides cinereus Species 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 240000004859 Gamochaeta purpurea Species 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 101100107923 Vitis labrusca AMAT gene Proteins 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M chlorate Inorganic materials [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 1
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 description 1
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- NHDHVHZZCFYRSB-UHFFFAOYSA-N pyriproxyfen Chemical compound C=1C=CC=NC=1OC(C)COC(C=C1)=CC=C1OC1=CC=CC=C1 NHDHVHZZCFYRSB-UHFFFAOYSA-N 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
The present invention provides a composition of a chemically machinery grinding serous fluid for the production of semiconductors, which contains 70 to 99.5 wt. % of water nature medium, 0.1 to 25 wt. % of grinding particle, 0.01 to 1 wt. % of chemical substance selected from corrosion inhibitor, 0.01 to 1% wt. % of diol compound, 2-hydroxy carboxylate and a mixture of the diol compound and the 2-hydroxy carboxylate. According to requirements, the composition of the chemically machinery grinding serous fluid can further contain an oxidizing agent. The present invention also relates to a method for grinding the surface of the semiconductor crystal by the composition.
Description
Technical field
The present invention relates to a kind of chemical and mechanical grinding fluid composition.Abrasive composition of the present invention can effectively be applied to the grinding of semiconductor wafer surface.
Background technology
Send out cmp technology (Chemical Mechanical Polishing is called for short CMP) and be when solving unicircuit (IC) and make the planarization that the difficulty that causes focusing on little shadow preparation process because of plated film height difference develops.The cmp technology at first is applied in the manufacturing of 0.5 micron assembly on a small quantity, and along with dwindling of size, the number of plies that cmp is used is also more and more.To 0.25 micron generation, cmp has become main flow and has been necessary planarization.Generally speaking, being used to make the Ginding process of metallic circuit, is that semiconductor crystal wafer is placed on the spin finishing platform of being furnished with grinding head, uses the grinding milk that comprises polishing particles and oxygenant in crystal column surface, grinds effect to promote.
United States Patent (USP) the 5th, 225 discloses a kind of chemical and mechanical grinding fluid No. 034, and it comprises AgNO
3, the solid abrasive material, be selected from H
2O
2, HOCl, KOCl, KMgO
4Or CH
3The oxygenant of COOOH.This grinding milk is used for the copper layer on the polishing semiconductor wafers, to make the copper cash on the wafer.
United States Patent (USP) the 5th, 209, a kind of chemical and mechanical grinding fluid that uses of No. 816 announcements will be will contain the method for Al or Ti metal level polishing, and its grinding milk still comprises the H of about 0.1-20 volume % except that comprising the solid abrasive material
3PO
4H with about 1-30 volume %
2O
2
United States Patent (USP) the 4th, 959 relates to a kind of method that makes the use abrasive composition with the surface, burnished metal No. 113.This water-based abrasive composition comprises water, abrasive (CeO for example
2, Al
2O
3, ZrO
2, TiO
2, SiO
2, SiC, SnO
2And TiC), with a kind of salt, the negatively charged ion of the metallic cation of this salt containing element periodictable IIA, IIIA, IVA or IVB family and chlorion, bromide anion, iodide ion, nitrate radical, sulfate radical, phosphate radical or mistake chlorate anions.This United States Patent (USP) also teaching uses hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid so that its water-based abrasive composition is deployed into pH=1-6.
United States Patent (USP) the 5th, 391 discloses a kind of abrasive composition that is used to polish the mixture of siliceous, silica or silicate for No. 258, and it still comprises hydrogen peroxide and potassium acid phthalate (potassium hydrogen phthalate) except that comprising abrasive grains.
United States Patent (USP) the 5th, 114, relate to a kind of polishing composition that is used for the polished aluminum base material for No. 437, it comprises average particle size particle size between the aluminum oxide polishing agent of 0.2 to 5 μ m and be selected from the polishing promotor of chromium nitrate (III), lanthanum nitrate, cerous nitrate (III) ammonium or neodymium nitrate.
United States Patent (USP) the 5th, 084 relates to a kind of chemical machinery polishing slurries that use for No. 071 with the method with the polishing of electronic package base material, and its employed polishing slurries comprise aluminum oxide, abrasive grains (for example, the SiO less than 1 weight %
2, CeO
2, SiC, Si
3N
4Or Fe
2O
3), as the transition metal chelating salt (for example, EDTA iron ammonium) of mill efficiency promotor, and for the solvent of this salt use.
United States Patent (USP) the 5th, 336 discloses a kind of polishing composition No. 542, and it comprises alumina abrasive particles, and a sequestrant that is selected from polyamines yl carboxylic acid (for example EDTA) or its sodium or sylvite.This polishing composition can further comprise boehmite (boehmite) or aluminium salt.
United States Patent (USP) the 5th, 340 discloses a kind of slurries that are used for the chemical machinery polishing of tungsten for example or tungsten nitride film for No. 370, and it comprises hydroferricyanic acid potassium oxygenant, abrasive and water for the film use, and wherein these slurries have 2 to 4 pH value.
United States Patent (USP) the 5th, 516 discloses a kind of slurries that are used for chemical machinery polishing titanium film No. 346, and it comprises concentration and is enough to Potassium monofluoride and abrasive (for example silicon oxide) with this titanium film misfit, and wherein these slurries have and are lower than 8 pH value.
WO 96/16436 discloses a kind of chemical machinery polishing slurries, and it comprises the abrasive grains that has less than footpath in 0.400 micron, molysite oxygenant, and the water-based interfacial agent suspension of propylene glycol and methyl p-hydroxybenzoate.
Generally be used for promoting the salt of grinding rate to contain iron ion (Fe (NO for example
3)
3Or K
3Fe (CN)
6) or potassium ion (KIO for example
3), yet, these metal ions meeting polluting wafer and CMP equipment, the workload that increases the back segment cleaning also reduces the time limit of service that CMP prepares equipment.In addition, potassium ion has suitable mobility, penetrates dielectric layer easily, reduces the reliability of IC.
In the IC preparation process, Ta or TaN film often are used to promote the tackyness of copper to insulating layer of silicon oxide.In addition, Ta or TaN film also are used as the metal of barrier film.In theory, Ta or TaN remove speed should with Cu to remove speed close, but the Ta metal is the metal with high resistance chemical, because it is difficult for oxidation, is equipped with in the process in copper, the grinding of Ta metal is to be difficult to the person of overcoming in the skill most always.Simultaneously, because that barrier film is difficult to is worn, often cause the problem of copper cash depression.
In addition, be equipped with in the process in this copper, the copper film can pass through that tempering (annealing) is handled and the cupric oxide that is easy to produce on the copper film one deck densification.And because the homogeneity question that the CMP preparation process exists, worn and when beginning to produce depression when the copper of wafer upper part, on the wafer of being everlasting, also unwanted copper can residually be arranged.Therefore, how to remove the copper residue fast and cave in, and the acceleration production capacity is the big problem that the CMP preparation process utmost point need overcome to reduce copper cash.
In sum, in the semiconductor fabrication process, still urgently seek more economical, have more usefulness and can reduce the Chemicomechanically grinding composition of above-mentioned shortcoming.
Summary of the invention
The invention provides a kind of chemical and mechanical grinding fluid composition that is used for the semiconductor fabrication process, it comprises the aqueous medium of 70-99.5 weight %; 0.1-25 the abrasive grains of weight %; 0.01-1 the chemical that is selected from two alcoholate, 2-hydroxycarboxylic acid thing and composition thereof of the corrosion inhibitor of weight % and 0.01-1% weight.Chemical and mechanical grinding fluid composition of the present invention can further comprise oxygenant.The present invention also relates to the method that said composition is used for the polishing semiconductor wafers surface.
Chemical and mechanical grinding fluid composition of the present invention comprises 70-99.5 weight %, the aqueous medium of preferable 80-99.5 weight %; 0.1-25 weight % is preferably 0.5-10 weight %, and is more preferred from the abrasive grains of 0.5-5 weight %; 0.01-1.0 weight % is more preferred from 0.01-0.5 weight %, and the best is the corrosion inhibitor of 0.05-0.2 weight %; And the chemical that is selected from two alcoholate and 2-hydroxycarboxylic acid thing and composition thereof of 0.01-1.0 weight %.Chemicomechanically grinding composition of the present invention can further comprise the oxygenant of 0.1-5 weight %.
Learn by embodiments of the invention, in ground slurry, add the generation that two alcoholate or 2-hydroxycarboxylic acid thing can prevent copper depression.
According to the present invention, the employed abrasive grains of grinding milk composition can be general commercially available person, for example SiO
2, Al
2O
3, ZrO
2, CeO
2, SiC, Fe
2O
3, TiO
2, Si
3N
4Or its mixture.These abrasive grains have higher degree, high-specific surface area, and advantage such as narrow size distribution, therefore are applicable in the abrasive composition as abrasive grains.
Selecting for use of the aqueous medium of grinding milk composition of the present invention for those who familiarize themselves with the technology, is conspicuous, for example in preparation process, can make water, is preferably to use deionized water so that abrasive composition is the slurries shape.
According to the present invention, the employed corrosion inhibitor of grinding milk composition is the triazolam thing, can be selected from benzotriazole, tricyanic acid (1,3,5-triazine-2,4, the 6-triol (1,3,5-triazine-2,4,6-triol)), 1,2,3-triazole, 3-amido-1,2,4-triazole, 3-nitro-1,2,4-triazole, Popeye get (purpald
), benzotriazole-5-carboxylic acid, 3-amido-1,2,4-triazole-5-carboxylic acid, I-hydroxybenzotriazole and nitrobenzene and triazolam; Be preferably the use benzotriazole.
According to the present invention, the compound that employed two alcoholate of grinding milk composition are the following structural formulas of tool:
Wherein, R
1And R
2Be to be selected from H or C respectively
1-C
6Alkyl.Be applicable to that two alcoholate among the present invention for example can be ethylene glycol, α-propylene glycol, 1,2-butyleneglycol or 2, the 3-butyleneglycol is preferably ethylene glycol or α-propylene glycol, and the best is an ethylene glycol.According to preferred embodiment of the present invention, the present composition is to comprise 0.01-1.0 weight %, is preferably 0.01-0.5 weight %, and is more preferred from the ethylene glycol of 0.1-0.4 weight %.
According to the present invention, the employed 2-hydroxycarboxylic acid of grinding milk composition thing is the compound of the following structural formula of tool:
Wherein, R is H or C
1-C
6Alkyl.Be applicable to that the 2-hydroxycarboxylic acid thing among the present invention for example can be 2-oxyacetic acid, 2 hydroxy propanoic acid or 2-hydroxybutyric acid, be preferably 2-oxyacetic acid or 2 hydroxy propanoic acid, the best is the 2-oxyacetic acid.According to preferred embodiment of the present invention, the present composition can comprise 0.01-1.0 weight %, is preferably 0.01-0.5 weight %, and is more preferred from the 2-oxyacetic acid of 0.1-0.4 weight %.
According to the present invention, the employed oxygenant of grinding milk composition is a composition known in the cmp field, its optional free H
2O
2, Fe (NO
3)
3, KIO
3, CH
3COOOH and KMnO
4Constitute group; Be preferably and use H
2O
2
According to the present invention, when deionized water was 80-99.5 weight %, the solids content of slurries was 0.5-15 weight %, was preferably 0.5-10 weight %, and was more preferred from 0.5-5 weight %.Then each component as indicated above is imported in the high purity slurries of gained, add again acid or alkali with the pH value of control slurries between required scope.
The present invention is also about the method on a kind of polishing semiconductor wafers surface, and it is included in uses on the crystal column surface according to chemical and mechanical grinding fluid composition of the present invention.
Following examples will the present invention is further illustrated, and only non-in order to limit the scope of the invention, modification and change that any personage who has the knack of this skill can reach easily all are covered by in the scope of the present invention.
Embodiment
Grind test
A. instrument: AMAT/Mirra
B. condition: mould (Membrane Pressure): 2psi
Interior pipe (Inner Tube): Vent
Keep ring compression (Retaining Ring): 2.6psi
Grinding plate rotating speed (Platen Speed): 93rpm
Carrier rotating speed (Carrier Speed): 87rpm
Temperature: 25 ℃
Grinding pad base pattern: IC1000, k-xy.
Slurry flow rate: 150 ml/min
C. chip: the pattern wafer, available from Semitech, model: 0.25 μ m live width 854CMP017 wafer.
D. slurries: the slurries and the 30%H that get the example gained
2O
2Evenly test after the stirring with 9: 1 volume ratios.
Grind testing process:
The present invention grinds with the Mirra grinder station of Applied Materials company, and the signal that process of lapping produces with End Point System is as the judgement of terminal point (EP2) signal.During grinding, be ground to EP2 with the slurries in the example respectively after, carry out 20% excessive polishing (over-polishing) again.After grind finishing, carry out the cleaning of wafer, clean the back that finishes with nitrogen (N with the Evergreen Model 10X type cleaning machine of solid-state instrument company (Solid State EquipmentCorporation)
2) wafer is dried up.Measure copper depression degree (Dishing) with KLA-Tencor P-11 SurfaceProfiler contact-type surface profiler again, copper cash with 100 microns of live widths (μ m) during mensuration is a gauge point, measures itself and the relative depression situation of barrier layer (Barrier Layer).
Example 1
(colloidal silica) prepares slurries as abrasive grains with silicic acid glue.Slurries are composed as follows, and it is as shown in table 1 that it grinds test result.
Silicic acid glue content: 2.0 weight %; Benzotriazole (BTA): 0.1 weight %;
All the other are for adjusting ammoniacal liquor or the nitric acid and the deionized water of pH value.
Example 2
With same way as described in example 1 and composition preparation slurries, but additionally add formic acid 0.2 weight %, it is as shown in table 1 that it grinds test result.
Example 3
With same way as described in example 1 and composition preparation slurries, but additionally add hexanodioic acid 0.2 weight %, it is as shown in table 1 that it grinds test result.
Example 4
With same way as described in example 1 and composition preparation slurries, but additionally add glycine 0.2 weight %, it is as shown in table 1 that it grinds test result.
Example 5
With same way as described in example 2 and composition preparation slurries, but additionally add ethylene glycol 0.2 weight %, it is as shown in table 1 that it grinds test result.
Example 6
With same way as described in example 3 and composition preparation slurries, but additionally add ethylene glycol 0.2 weight %, it is as shown in table 1 that it grinds test result.
Example 7
With same way as described in example 4 and composition preparation slurries, but additionally add ethylene glycol 0.2 weight %, it is as shown in table 1 that it grinds test result.
Example 8
Identical with example 7, only the pH value changes between the 5-6, and it is as shown in table 1 that it grinds test result.
Example 9
With same way as described in example 3 and composition preparation slurries, but additionally add ethylene glycol 0.4 weight %, it is as shown in table 1 that it grinds test result.
Example 10
Identical with example 6, only changing with the aluminum oxide is abrasive grains, and it is as shown in table 1 that it grinds test result.
Example 11
Identical with example 3, only changing with the aluminum oxide is abrasive grains, and it is as shown in table 1 that it grinds test result.
Example 12
Prepare slurries with same way as described in example 3 and composition, but additionally add the 2-oxyacetic acid of 0.2 weight %, it is as shown in table 1 that it grinds test result.
Example 13
Identical with example 12, only changing with the aluminum oxide is abrasive grains, and it is as shown in table 1 that it grinds test result.
Table 1
| Example | The abrasive grains kind | Solid content (%) | The chemical and the content (weight %) thereof that add | The pH value | Depression (/100 micron Cu live width) |
| 1 | Silicic acid glue | 2 | Benzotriazole (0.1%) | 3-4 | 1213 |
| 2 | Silicic acid glue | 2 | Benzotriazole (0.1%) formic acid (0.2%) | 3-4 | 1617 |
| 3 | Silicic acid glue | 2 | Benzotriazole (0.1%) hexanodioic acid (0.2%) | 3-4 | 1530 |
| 4 | Silicic acid glue | 2 | Benzotriazole (0.1%) Padil (0.2%) | 3-4 | 1593 |
| 5 | Silicic acid glue | 2 | Benzotriazole (0.1%) formic acid (0.2%) ethylene glycol (0.2%) | 3-4 | 659 |
| 6 | Silicic acid glue | 2 | Benzotriazole (0.1%) hexanodioic acid (0.2%) ethylene glycol (0.2%) | 3-4 | 544 |
| 7 | Silicic acid glue | 2 | Benzotriazole (0.1%) Padil (0.2%) ethylene glycol (0.2%) | 3-4 | 631 |
| 8 | Silicic acid glue | 2 | Benzotriazole (0.1%) hexanodioic acid (0.2%) ethylene glycol (0.2%) | 5-6 | 537 |
| 9 | Silicic acid glue | 2 | Benzotriazole (0.1%) hexanodioic acid (0.2%) ethylene glycol (0.4%) | 3-4 | 553 |
| 10 | Aluminum oxide | 2 | Benzotriazole (0.1%) hexanodioic acid (0.2%) ethylene glycol (0.2%) | 3-4 | 1139 |
| 11 | Aluminum oxide | 2 | Benzotriazole (0.1%) hexanodioic acid (0.2%) | 3-4 | 1802 |
| 12 | Silicic acid glue | 2 | Benzotriazole (0.1%) hexanodioic acid (0.2%) 2-oxyacetic acid (0.2%) | 3-4 | 613 |
| 13 | Aluminum oxide | 2 | Benzotriazole (0.1%) hexanodioic acid (0.2%) 2-alcohol radical-acetate (0.2%) | 3-4 | 1187 |
The result of comparative example 1 to 7 can prevent copper depression behind the grinding milk interpolation ethylene glycol as can be known.
Comparative example 6 and 8 result add ethylene glycol and all can prevent copper depression as can be known in the grinding milk of different pH values.
Comparative example 6 and 9 result as can be known, the ethylene glycol that adds different concns in grinding milk all can prevent copper depression.
Comparative example 3 and 6 and the result of example 10 and 11 as can be known, the interpolation of ethylene glycol is applicable to that all with silicic acid glue and aluminum oxide be the grinding milk of abrasive grains, and all can reach the effect that prevents copper depression.
Comparative example 3 and 12 and 11 and 13 result as can be known, grinding milk also can prevent copper depression after adding 2-alcohol radical-acetate.
Claims (17)
1. chemical and mechanical grinding fluid composition, it comprises the aqueous medium of 80-99.5 weight %; 0.1-25 the abrasive grains of weight %; 0.01-1 the corrosion inhibitor of weight %; And the chemical that is selected from two alcoholate and 2-hydroxycarboxylic acid thing and composition thereof of 0.01-1 weight %, wherein this two alcoholate has following structural formula:
Wherein, R
1And R
2Be selected from H or C respectively
1-C
6Alkyl, and wherein this 2-hydroxycarboxylic acid thing has following structural formula:
Wherein, R is H or C
1-C
6Alkyl, and said composition pH value is 3-4 or 5-6.
2. composition as claimed in claim 1, wherein abrasive grains is selected from SiO
2, Al
2O
3, ZrO
2, CeO
2, SiC, Fe
2O
3, TiO
2, Si
3N
4And composition thereof.
3. composition as claimed in claim 1, it comprises the abrasive grains of 0.5-10 weight %.
4. composition as claimed in claim 3, it comprises the abrasive grains of 0.5-5.0 weight %.
5. composition as claimed in claim 1, wherein this two alcoholate is an ethylene glycol.
6. composition as claimed in claim 5, it comprises the ethylene glycol of 0.01-0.5 weight %.
7. as the composition of claim 5, it is the ethylene glycol that comprises 0.1-0.4 weight %.
8. as the composition of claim 1, wherein this 2-hydroxycarboxylic acid thing is the 2-oxyacetic acid.
9. as the composition of claim 8, it comprises the 2-oxyacetic acid of 0.01-0.5 weight %.
10. as the composition of claim 8, it comprises the 2-oxyacetic acid of 0.1-0.4 weight %.
11. as the composition of claim 1, wherein this corrosion inhibitor is the triazolam thing.
12. as the composition of claim 11, wherein this triazolam thing is a benzotriazole.
13. composition as claimed in claim 1, it further comprises the oxygenant of 0.1-5 weight %.
14. as the composition of claim 13, wherein this oxygenant is selected from H
2O
2, Fe (NO
3)
3, KIO
3, CH
3COOOH and KMnO
4
15. as the composition of claim 14, wherein this oxygenant is H
2O
2
16. composition as claimed in claim 1, wherein this aqueous medium is a deionized water.
17. a method that is used for the polishing semiconductor wafers surface, it is included in uses on the crystal column surface as each chemical and mechanical grinding fluid composition of claim 1 to 16.
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|---|---|---|---|
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|---|---|---|---|
| CNB021459894A CN100336881C (en) | 2002-10-31 | 2002-10-31 | Chemical methanical grinding paste composition and its use method |
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| CN100336881C true CN100336881C (en) | 2007-09-12 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5217416A (en) * | 1992-04-17 | 1993-06-08 | Dana Corporation | Lock up/limited slip differential |
| EP0846742A2 (en) * | 1996-12-09 | 1998-06-10 | Cabot Corporation | Chemical mechanical polishing slurry useful for copper substrates |
| CN1249367A (en) * | 1998-09-25 | 2000-04-05 | 李伟明 | Non-corrosion pulsively electrochemical polishing solution and process |
| CN1270507A (en) * | 1997-09-15 | 2000-10-18 | 亨克尔两合股份公司 | Cleaning agent for dental use comprising a combination of polishing agents based on a silicic acid and aluminium oxide |
| CN1369530A (en) * | 2001-01-31 | 2002-09-18 | 不二见株式会社 | Polishing compsns. and polishing method using same |
-
2002
- 2002-10-31 CN CNB021459894A patent/CN100336881C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5217416A (en) * | 1992-04-17 | 1993-06-08 | Dana Corporation | Lock up/limited slip differential |
| EP0846742A2 (en) * | 1996-12-09 | 1998-06-10 | Cabot Corporation | Chemical mechanical polishing slurry useful for copper substrates |
| CN1270507A (en) * | 1997-09-15 | 2000-10-18 | 亨克尔两合股份公司 | Cleaning agent for dental use comprising a combination of polishing agents based on a silicic acid and aluminium oxide |
| CN1249367A (en) * | 1998-09-25 | 2000-04-05 | 李伟明 | Non-corrosion pulsively electrochemical polishing solution and process |
| CN1369530A (en) * | 2001-01-31 | 2002-09-18 | 不二见株式会社 | Polishing compsns. and polishing method using same |
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