CN1162498C - chemical mechanical polishing slurry composition and method of use thereof - Google Patents
chemical mechanical polishing slurry composition and method of use thereof Download PDFInfo
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- CN1162498C CN1162498C CNB011227915A CN01122791A CN1162498C CN 1162498 C CN1162498 C CN 1162498C CN B011227915 A CNB011227915 A CN B011227915A CN 01122791 A CN01122791 A CN 01122791A CN 1162498 C CN1162498 C CN 1162498C
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- grinding fluid
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- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 239000000126 substance Substances 0.000 title claims abstract description 29
- 238000005498 polishing Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000002002 slurry Substances 0.000 title abstract description 33
- 238000000227 grinding Methods 0.000 claims abstract description 70
- 239000004065 semiconductor Substances 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000012736 aqueous medium Substances 0.000 claims abstract description 6
- 238000005260 corrosion Methods 0.000 claims abstract description 5
- 230000007797 corrosion Effects 0.000 claims abstract description 5
- 239000003112 inhibitor Substances 0.000 claims abstract description 5
- 239000012530 fluid Substances 0.000 claims description 21
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 19
- 239000012964 benzotriazole Substances 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000006061 abrasive grain Substances 0.000 claims description 16
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 15
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 15
- 235000012431 wafers Nutrition 0.000 claims description 15
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 8
- 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 7
- 229960003386 triazolam Drugs 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 4
- XHFGWHUWQXTGAT-UHFFFAOYSA-N dimethylamine hydrochloride Natural products CNC(C)C XHFGWHUWQXTGAT-UHFFFAOYSA-N 0.000 claims description 4
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 claims description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 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
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 150000000177 1,2,3-triazoles Chemical class 0.000 claims description 2
- GUOVBFFLXKJFEE-UHFFFAOYSA-N 2h-benzotriazole-5-carboxylic acid Chemical compound C1=C(C(=O)O)C=CC2=NNN=C21 GUOVBFFLXKJFEE-UHFFFAOYSA-N 0.000 claims description 2
- KUEFXPHXHHANKS-UHFFFAOYSA-N 5-nitro-1h-1,2,4-triazole Chemical compound [O-][N+](=O)C1=NC=NN1 KUEFXPHXHHANKS-UHFFFAOYSA-N 0.000 claims description 2
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 claims description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 2
- 239000010949 copper Substances 0.000 abstract description 24
- 229910052802 copper Inorganic materials 0.000 abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 22
- 239000002245 particle Substances 0.000 abstract description 5
- 239000000460 chlorine Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 229910052801 chlorine Inorganic materials 0.000 abstract description 2
- 238000005496 tempering Methods 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 37
- 239000008267 milk Substances 0.000 description 24
- 210000004080 milk Anatomy 0.000 description 24
- 235000013336 milk Nutrition 0.000 description 24
- 239000000377 silicon dioxide Substances 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 241000370738 Chlorion Species 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- -1 sulfate radical Chemical class 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-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
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate 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
- 238000004140 cleaning Methods 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-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
- 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
- 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
- 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
- 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
- 230000001133 acceleration Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect 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
- 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
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 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
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds 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
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 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
- 239000007788 liquid Substances 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
- 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
- 238000007517 polishing process Methods 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
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-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
- 239000000523 sample Substances 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 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
- 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)
Abstract
The present invention provides a chemical mechanical polishing slurry composition for use in semiconductor processing comprising 70 to 99.5 wt% of an aqueous medium; 0.1 to 25 weight percent abrasive particles; 0.01 to 1% by weight of a triazolate as corrosion inhibitor; and 0.001 to 1% by weight of a water-soluble chlorine source. The aqueous solution chloride ions contained in the grinding slurry composition can grind through a compact layer generated on the surface of a copper film due to tempering treatment in the grinding process, and reduce the residual amount of copper after grinding. The chemical mechanical polishing slurry composition of the present invention may further comprise an oxidizing agent. The invention also relates to a method for polishing the surface of a semiconductor wafer by using the composition.
Description
Invention field
The present invention relates to a kind of chemical and mechanical grinding fluid composition.Grinding milk composition of the present invention can effectively be applied to the grinding of semiconductor wafer surface.
Background technology
Cmp technology (be called for short CMP) is the planarization that the difficulty that causes photomicrography processing to be gone up focusing on because of plated film height difference when solving unicircuit and make develops.The cmp technology at first is applied in the manufacturing of 0.5 micron element 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 epoch, 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 the copper layer that is used on the polishing semiconductor wafers, to make the copper cash on the wafer.
United States Patent (USP) the 5th, 209 discloses a kind of chemical and mechanical grinding fluid that uses for No. 816 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 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 component 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 of mill efficiency promotor sting close salt (for example, EDTA iron ammonium), 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 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 for No. 346, and it comprises concentration and is enough to Potassium monofluoride and abrasive (for example silicon oxide) with this titanium film complexing, and wherein these slurries have and are lower than 8 pH value.
WO96/16436 discloses a kind of chemical machinery polishing slurries, and it comprises abrasive grains, the molysite oxygenant that has less than 0.400 micron median size, the water-based interfacial agent suspension that reaches 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 can polluting wafer and CMP processing unitss, increase the workload of follow-up cleaning and reduce the time limit of service of CMP processing units.In addition, potassium ion has suitable mobility, penetrates dielectric layer easily, reduces the reliability of unicircuit.
In unicircuit processing, Ta or TaN film often are used to promote the tackiness of copper to insulating layer of silicon oxide, and in addition, Ta or TaN film also are used as membranous metal.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, in copper processing, the grinding of Ta metal is to be difficult to the person of overcoming in the skill most always, simultaneously, because it is worn that barrier film is difficult to, often cause the problem of copper cash depression.
In addition, in the processing of this copper, the copper film can pass through that tempering (annealing) is handled and the cupric oxide that is easy to generation one deck densification on the copper film.And because the homogeneity question that CMP processing 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 processing utmost point need overcome to reduce copper cash.
In sum, in the semiconductor machining skill, still urgently seek more economical, have more usefulness and can reduce the Chemicomechanically grinding composition of above-mentioned shortcoming.
Summary of the invention
The present invention provides a kind of chemical and mechanical grinding fluid composition that is used for semiconductor machining, and it comprises the aqueous medium of 70 to 99.5 weight %; 0.1 abrasive grains to 25 weight %; 0.01 to the triazolam thing of 1 weight % as corrosion inhibitor; And the soluble chloride ion source of 0.001 to 1 weight %.Institute's aqueous solution chlorion in the grinding milk composition of the present invention can be in process of lapping, the worn out tight zone that is produced in the copper film surface because of temper, and reduce copper residual quantity after grinding.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.
Embodiment
Chemical and mechanical grinding fluid composition of the present invention comprises the aqueous medium of 70 to 99.5 weight % and preferred 80 to 99.5 weight %; 0.1 to 25 weight %, preferred 0.5 to 15 weight %, more preferably 0.5 to 10 weight % reaches the most preferably abrasive grains of 0.5 to 5 weight %; 0.01 to 1.0 weight %, preferred 0.01 to 0.5 weight % reaches the more preferably corrosion inhibitor of 0.05 to 0.2 weight %; And 0.001 to 1 weight %, preferred 0.01 to 0.5 weight %, more preferably the soluble chloride ion source of 0.02 to 0.1 weight %.Chemical and mechanical grinding fluid composition of the present invention can further comprise the oxygenant of 0.1 to 5 weight %.
By hereinafter learning, in the grinding milk composition, add the tight zone that chlorion can worn out copper surface and reduce the copper residual quantity according to embodiments of the invention.Any chlorine-containing compound that can in aqueous medium, dissociate chlorion, all can be used in the grinding milk composition of the present invention as the soluble chloride ion source, for example hydrogenchloride, ammonium chloride, dimethyl amine hydrochloride, Tetramethylammonium chloride and hydrochlorinate are partly blocked hydrazine etc.
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, preferably uses deionized water so that abrasive composition is the slurries shape.
According to the present invention, the employed corrosion inhibitor of grinding milk composition is to be the triazolam thing, can be selected from benzotriazole, tricyanic acid, 1,2,3-triazoles, 3-amido-1,2,4-triazole, 3-nitro-1,2,4-triazole, 4-amido-3-diazanyl-5-thiol group-1,2, (Popeye gets (purpald to the 4-triazole
)), benzotriazole-5-carboxylic acid, 3-amido-1,2,4-triazole-5-carboxylic acid, I-hydroxybenzotriazole and nitrobenzene and triazolam; Preferably use benzotriazole.
According to the present invention, the employed oxygenant of grinding milk composition is a composition known in the cmp skill, and it can be selected from H
2O
2, Fe (NO
3)
3, KIO
3, CH
3COOOH and KMnO
4Preferably use H
2O
2
According to an advantageous embodiment of the invention, when deionized water was 80 to 99.5 weight %, the solids content of slurries was 0.5 to 15 weight %, was preferably 0.5 to 10 weight %, reached 0.5 to 5 weight % more preferably.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 also relates to the method on a kind of polishing semiconductor wafers surface, and it is to be included in to use 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, but not in order to limit the scope of the invention, modification and change that any personage who has the knack of this technology can reach easily all are covered by in the scope of the present invention.
Grind test
A. instrument: IPEC/Westech 472
B. condition: pressure: 2psi
Back pressure: 0.5psi
Temperature: 25 ℃
The speed of mainshaft: 93rpm
Platen rotating speed: 87rpm
Base pattern: IC1000, k-grv.
Slurry flow rate: 250 ml/min
C. wafer: the copper film, available from Silicon Valley Microelectonics.lnc., it is the thermal oxide of deposit 1000 silicon oxide on 8 inches Silicon Wafers, the PVD-Ta of 300 and the PVD copper film of 10000 ± 5%.
And place 100 ℃ baking oven to make temper this copper wafer.
D slurries: the slurries and the 30%H that get the embodiment gained
2O
2Evenly test after the stirring with 9: 1 volume ratios.
Grind testing process: before and after grinding, must measure the thickness of film with elcometer.Metallic membrane measures the sheet resistance of film with four-point probe, convert through following formula the thickness of film: T * R=specific resistance
Wherein T is that film thickness () and R are sheet resistance (Q/cm
2), for various metallic films, (Ω/cm) is a constant to specific resistance.
The present invention adopts the RS 75 type machines of KLA-Tencor company to measure the thickness of metal level.The measuring method of polishing speed is to record metal level thickness T with above-mentioned RS 75 type machines earlier
1, so that the grinding of gained slurries is after 1 minute among the embodiment, the Evergreen Mode1 10X type machine cleaning wafer with solid-state instrument company (Solid StateEquipment Corporation) afterwards, dries up wafer respectively.Measure the thickness T of metal level again with RS 75 type machines
2With T
1-T
2Be the polishing speed of metal level.
Embodiment 1
Prepare slurries with colloided silica as abrasive grains.
Slurries are composed as follows:
Colloided silica: 2.0 weight %;
Benzotriazole (BTA): 0.1 weight %;
All the other content are for adjusting ammoniacal liquor or the nitric acid and the deionized water of pH value.
The grinding rate of gained grinding milk and worn out tight zone time are as shown in table 1.
Embodiment 2
The preparation and the slurries of embodiment 1 described same composition, but additionally add the nitric acid of 0.2 weight %.
The grinding rate of gained grinding milk and worn out tight zone time are as shown in table 1.
Embodiment 3
The preparation and the slurries of embodiment 1 described same composition, but additionally add the phosphoric acid of 0.2 weight %.
The grinding rate of gained grinding milk and worn out tight zone time are as shown in table 1.
Embodiment 4
The preparation and the slurries of embodiment 1 described same composition, but additionally add the sulfuric acid of 0.2 weight %.
The grinding rate of gained grinding milk and worn out tight zone time are as shown in table 1.
Embodiment 5
The preparation and the slurries of embodiment 1 described same composition, but additionally add the hydrogenchloride of 0.2 weight %.
The grinding rate of gained grinding milk and worn out tight zone time are as shown in table 1.
Embodiment 6
The preparation and the slurries of embodiment 1 described same composition, but additionally add the ammonium chloride of 0.2 weight %.
The grinding rate of gained grinding milk and worn out tight zone time are as shown in table 1.
Embodiment 7
The slurries of preparation and embodiment 5 described same compositions just replace colloided silica as abrasive grains with aluminum oxide.
The grinding rate of gained grinding milk and worn out tight zone time are as shown in table 1.
Embodiment 8
The slurries of preparation and embodiment 5 described same compositions just are adjusted into the pH value between 5 to 6.
The grinding rate of gained grinding milk and worn out tight zone time are as shown in table 1.
Embodiment 9
The slurries of preparation and embodiment 5 described same compositions just are adjusted into the pH value between 2 to 3.
The grinding rate of gained grinding milk and worn out tight zone time are as shown in table 1.
Embodiment 10
The slurries of preparation and embodiment 5 described same compositions, just the consumption with hydrogenchloride changes 0.05 weight % into.
The grinding rate of gained grinding milk and worn out tight zone time are as shown in table 1.
Embodiment 11
The slurries of preparation and embodiment 5 described same compositions, just the dimethyl amine hydrochloride with 0.1 weight % replaces hydrogenchloride.
The grinding rate of gained grinding milk and worn out tight zone time are as shown in table 1.
Embodiment 12
The slurries of preparation and embodiment 5 described same compositions, just the Tetramethylammonium chloride with 0.1 weight % replaces hydrogenchloride.
The grinding rate of gained grinding milk and worn out tight zone time are as shown in table 1.
Embodiment 13
The slurries of preparation and embodiment 5 described same compositions just partly block hydrazine with the hydrochlorinate of 0.1 weight % and replace hydrogenchloride.
The grinding rate of gained grinding milk and worn out tight zone time are as shown in table 1.
Table 1
| Embodiment | The abrasive grains kind | Solid content (weight %) | Additive and content thereof (weight %) | The pH value | The worn out tight zone time (second) | The copper grinding rate (/minute) |
| 1 | Colloided silica | 2 | Benzotriazole (0.1%) | 3-4 | Can't be worn out | 0 |
| 2 | Colloided silica | 2 | Benzotriazole (0.1%) HNO 3(0.2％) | 3-4 | Can't be worn out | 0 |
| 3 | Colloided silica | 2 | Benzotriazole (0.1%) H 3PO 4(0.2％) | 3-4 | Can't be worn out | 0 |
| 4 | Colloided silica | 2 | Benzotriazole (0.1%) H 2SO 4(0.2％) | 3-4 | Can't be worn out | 0 |
| 5 | Colloided silica | 2 | Benzotriazole (0.1%) HCl (0.2%) | 3-4 | 15 | 2730 |
| 6 | Colloided silica | 2 | Benzotriazole (0.1%) NH 4Cl(0.2％) | 3-4 | 25 | 1693 |
| 7 | Aluminum oxide | 2 | Benzotriazole (0.1%) HCl (0.2%) | 3-4 | 10 | 4270 |
| 8 | Colloided silica | 2 | Benzotriazole (0.1%) HCl (0.2%) | 5-6 | 20 | 1872 |
| 9 | Colloided silica | 2 | Benzotriazole (0.1%) HCl (0.2%) | 2-3 | 10 | 5325 |
| 10 | Colloided silica | 2 | Benzotriazole (0.1%) HCl (0.05%) | 3-4 | 15 | 4022 |
| 11 | Colloided silica | 2 | Benzotriazole (0.1%) dimethyl amine hydrochloride HN (CH 3) 2-HCl(0.1％) | 3-4 | 20 | 1677 |
| 12 | Colloided silica | 2 | Benzotriazole (0.1%) Tetramethylammonium chloride N (CH 3) 4 +Cl -(0.1％) | 3-4 | 25 | 1260 |
| 13 | Colloided silica | 2 | Benzotriazole (0.1%) hydrochlorinate is partly blocked hydrazine N 2NNH-C(＝O)NH 2·HCl (0.1％) | 3-4 | 25 | 1932 |
Annotate: (1) is known by embodiment 1-5, gets final product the tight zone of worn out copper crystal column surface behind the interpolation hydrogenchloride.
Know by embodiment 5-6 that (2) what play an important role is chlorion.
Know by embodiment 5 and 7 that (3) interpolation of chlorion all is applicable to colloided silica and the aluminum oxide lapping liquid as abrasive grains.
Know by embodiment 7-13 that (4) chlorion is the main material of worn out copper surface compact layer.
Claims (12)
1, a kind of chemical and mechanical grinding fluid composition, it comprises the aqueous medium of 70-99.5 weight %; 0.1-25 the abrasive grains of weight %; 0.01-1.0 weight % is as the triazolam thing of corrosion inhibitor; 0.001-1.0 the soluble chloride ion source of weight %, and the oxygenant of 0.1-5 weight %.
2, according to the chemical and mechanical grinding fluid composition of 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
4, or its mixture.
3, according to the chemical and mechanical grinding fluid composition of claim 1, it comprises the abrasive grains of 0.5-15 weight %.
4, according to the chemical and mechanical grinding fluid composition of claim 3, it comprises the abrasive grains of 0.5-10.0 weight %.
5, according to the chemical and mechanical grinding fluid composition of claim 1, it comprises the soluble chloride ion source of 0.01-0.5 weight %.
6, according to the chemical and mechanical grinding fluid composition of claim 5, it comprises the soluble chloride ion source of 0.02-0.1 weight %.
7, according to the chemical and mechanical grinding fluid composition of claim 1, wherein said triazolam thing is selected from benzotriazole, tricyanic acid, 1,2,3-triazoles, 3-amido-1,2,4-triazole, 3-nitro-1,2,4-triazole, 4-amido-3-diazanyl-5-thiol group-1,2,4-triazole, benzotriazole-5-carboxylic acid, 3-amido-1,2,4-triazole-5-carboxylic acid, I-hydroxybenzotriazole and nitrobenzene and triazolam.
8, according to the chemical and mechanical grinding fluid composition of claim 7, wherein said triazolam thing is a benzotriazole.
9, according to the chemical and mechanical grinding fluid composition of claim 1, wherein said oxygenant is to be selected from H
2O
2, Fe (NO
3)
3, KIO
3, CH
3COOOH and KMnO
4
10, according to the chemical and mechanical grinding fluid composition of claim 9, wherein said oxygenant is H
2O
2
11, according to the chemical and mechanical grinding fluid composition of claim 1, wherein said soluble chloride ion source is selected from hydrogenchloride, ammonium chloride, dimethyl amine hydrochloride, Tetramethylammonium chloride and hydrochlorinate and partly blocks hydrazine.
12, a kind of method that is used for the polishing semiconductor wafers surface, it is included in uses on the crystal column surface as the chemical and mechanical grinding fluid composition of claim 1 to 11 in each.
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011227915A CN1162498C (en) | 2001-07-25 | 2001-07-25 | chemical mechanical polishing slurry composition and method of use thereof |
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| KR101091501B1 (en) * | 2006-03-31 | 2011-12-08 | 캐보트 마이크로일렉트로닉스 코포레이션 | Polymeric inhibitors for enhanced planarization |
| CN101684392B (en) * | 2008-09-26 | 2015-01-28 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution |
| CN101724347A (en) * | 2008-10-10 | 2010-06-09 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution |
| KR20140019401A (en) * | 2011-03-22 | 2014-02-14 | 바스프 에스이 | A chemical mechanical polishing (cmp) composition comprising a polymeric polyamine |
| CN106916536B (en) * | 2015-12-25 | 2021-04-20 | 安集微电子（上海）有限公司 | An alkaline chemical mechanical polishing solution |
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