WO2013189168A1 - Chemical mechanical polishing solution for silicon through-hole planarization - Google Patents
Chemical mechanical polishing solution for silicon through-hole planarization Download PDFInfo
- Publication number
- WO2013189168A1 WO2013189168A1 PCT/CN2013/000573 CN2013000573W WO2013189168A1 WO 2013189168 A1 WO2013189168 A1 WO 2013189168A1 CN 2013000573 W CN2013000573 W CN 2013000573W WO 2013189168 A1 WO2013189168 A1 WO 2013189168A1
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- WO
- WIPO (PCT)
- Prior art keywords
- polishing liquid
- chemical mechanical
- mechanical polishing
- liquid according
- acid
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims abstract description 99
- 239000000126 substance Substances 0.000 title claims abstract description 31
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 13
- 239000010703 silicon Substances 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- -1 azole compound Chemical class 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 21
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 16
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 14
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 59
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000844 anti-bacterial effect Effects 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims description 2
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical compound OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 claims description 2
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 claims description 2
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 2
- WWBXZKQQXUFSED-UHFFFAOYSA-N [Na].O=C.C1=CC=C2C(S(=O)(=O)OC)=CC=CC2=C1 Chemical compound [Na].O=C.C1=CC=C2C(S(=O)(=O)OC)=CC=CC2=C1 WWBXZKQQXUFSED-UHFFFAOYSA-N 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 claims description 2
- LCRMGUFGEDUSOG-UHFFFAOYSA-N naphthalen-1-ylsulfonyloxymethyl naphthalene-1-sulfonate;sodium Chemical group [Na].C1=CC=C2C(S(=O)(OCOS(=O)(=O)C=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 LCRMGUFGEDUSOG-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 150000002978 peroxides Chemical group 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 2
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 239000001384 succinic acid Substances 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims 1
- NTEGNZLJUGYVTC-UHFFFAOYSA-N N(CCO)CCO.P(=O)(OS)(O)O Chemical group N(CCO)CCO.P(=O)(OS)(O)O NTEGNZLJUGYVTC-UHFFFAOYSA-N 0.000 claims 1
- 235000019400 benzoyl peroxide Nutrition 0.000 claims 1
- 229910052581 Si3N4 Inorganic materials 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052802 copper Inorganic materials 0.000 abstract description 11
- 239000010949 copper Substances 0.000 abstract description 11
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 7
- 238000012937 correction Methods 0.000 abstract description 4
- 230000000903 blocking effect Effects 0.000 abstract 1
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 230000003628 erosive effect Effects 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000012876 topography Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 235000019256 formaldehyde Nutrition 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 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 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FHHPEPGEFKOMOF-UHFFFAOYSA-N 2-hydroxy-1,3,2lambda5-dioxaphosphetane 2-oxide Chemical compound OP1(=O)OCO1 FHHPEPGEFKOMOF-UHFFFAOYSA-N 0.000 description 1
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- LMIZORQOLSLQRY-UHFFFAOYSA-N benzene;naphthalene Chemical compound C1=CC=CC=C1.C1=CC=CC2=CC=CC=C21 LMIZORQOLSLQRY-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
Classifications
-
- 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
- C09K3/1472—Non-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
- H01L21/31—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]
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76898—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics formed through a semiconductor substrate
Definitions
- the present invention relates to a chemical mechanical polishing liquid, and more particularly to a chemical mechanical polishing liquid for planarizing silicon through holes.
- CMOS process development With the development of CMOS process development, the feature size of the device is gradually reduced, the circuit density is more complicated, and the design and manufacturing are becoming more and more difficult. The signal congestion in the interconnection process is further aggravated, miniaturization and super High integration is approaching its physical limits. In order to extend Moore's Law, solve the copper interconnect delay problem, and meet the performance, bandwidth and power requirements, 3D IC integration technology has gradually developed.
- the through silicon via (TSV) technology shown in the following figure is mainly divided into several steps: 1. Rapid etching to form via holes. 2: The process of through hole filling includes the deposition of an oxide layer, a metal adhesion layer/barrier layer/seed layer, and ECP metal copper. Metal copper is removed using CMP technology. Flattening is achieved, and the metal is turned on.
- TSV through silicon via
- TSV production needs to open different layers of materials, including silicon materials, various insulating or conductive thin film layers in ICs.
- materials including silicon materials, various insulating or conductive thin film layers in ICs.
- the thickness of various film layers is also relatively high, in order to improve the economics of the three-dimensional integration technology, it is necessary to have a higher CMP process.
- the removal rate and the appropriate polishing selectivity ratio can achieve the maximum correction of the precursor defects, and stop at the silicon nitride layer, and at the same time can not produce metal corrosion and defects, the surface particles are controlled within the scope of the process requirements. This puts higher demands on the CMP of the through-silicon via barrier layer.
- the current research on dedicated CMP polishing fluids for TSV technology is very active, but there have been no commercial product reports, especially the TSV barrier polishing fluid. Summary of invention
- the present invention provides a chemical mechanical polishing liquid, which satisfies the process requirement of high selection rate of silicon dioxide for silicon nitride in the planarization process of through silicon via holes, and the future
- the defect value has a good correction effect, and prevents corrosion generated during the metal polishing process, and the wafer surface defects and contaminants are less after polishing.
- the chemical mechanical polishing liquid for planarizing silicon through holes of the present invention comprises: abrasive particles, an acid, an anionic surfactant, an oxidizing agent and an azole compound and a derivative thereof.
- the abrasive particles are silica sols, and the abrasive particles have a particle diameter of 20 to 200 nm. Preferably, the abrasive particles have a particle diameter of 40 to 120 nm.
- the abrasive particles have a concentration of 10 to 50% by weight.
- the azole compound and its derivative are triazole compounds and derivatives thereof.
- the triazole compound and its derivative are one or more selected from the group consisting of benzotriazole, methylbenzotriazole, hydroxybenzotriazole and carboxybenzotriazole.
- the concentration of the azole compound is 0.01 to 0.5% by weight, preferably, the concentration of the azole compound is 0.05 to 0.2% by weight.
- the acid is an inorganic acid or an organic acid, and preferably, the inorganic or organic acid is selected from the group consisting of hydrochloric acid, nitric acid, oxalic acid, malonic acid, succinic acid and sulfosalicylic acid. One or more.
- the concentration of the acid is 0.01 to 1% by weight, and preferably, the concentration of the acid is 0.01 to 0.2% by weight.
- the anionic surfactant is at least two anionic surfactants.
- the anionic surfactant is a mixture of a naphthalene sulfonate surfactant and a phosphate salt surfactant. Things.
- the naphthalenesulfonate surfactant is sodium methylene dinaphthalenesulfonate and/or sodium methylnaphthalenesulfonate formaldehyde condensate;
- the phosphate ester surfactant is ruthenium Phosphate diethanolamine salt, ROP0 3 H 2 (NH(CH2CH20H) 2 ) 2 , wherein R is -C m H 2m+1 , 8 m 12, and/or alcohol ether phosphate monoester, RO (CH 2 CH 2 0) b PO(OH) 2 , where R is - C n H 2n+1 , 12 ⁇ n ⁇ 14, 1
- the mixed anionic surfactant has a concentration of 50 to 2000 ppm.
- the oxidizing agent is a peroxide or a persulfide.
- the oxidizing agent is selected from the group consisting of hydrogen peroxide, sodium peroxide, potassium peroxide, sodium persulfate, ammonium persulfate, peroxidation.
- One or more of benzoyl One or more of benzoyl.
- the polishing liquid further contains an additive and/or a bactericidal mold inhibitor.
- the additive is an organic solvent
- the bactericidal mold inhibitor is a quaternary ammonium salt active agent
- the organic solvent is glycerin.
- the polishing liquid has a pH of 1 to 4, and preferably, the polishing liquid has a pH of 2 to 3.
- the polishing liquid of the present invention has a higher silica removal rate and a lower silicon nitride removal rate, and a higher removal ratio of silicon dioxide to silicon nitride is obtained;
- the polishing liquid of the invention has high defect correction ability, and does not cause metal corrosion, thereby improving product yield;
- the wafer After polishing with the polishing liquid of the present invention, the wafer has a good surface topography and low surface contaminant residue. Turn over
- 1A is a schematic view showing a polishing surface of a TSV through silicon via barrier layer before polishing
- Figure 1B is a schematic view of a polished surface of a TSV through-silicon via barrier layer after polishing copper;
- 1C is a schematic view showing a polishing surface of a TSV through-silicon via barrier polishing layer
- Figure 2 shows the surface topography of the Semtech 854 graphics test wafer after polishing the polishing solution.
- Example 3 is an SEM image of the surface morphology of the Semtech 854 pattern test wafer after polishing of the polishing solution of Example 3;
- Table 1 shows the formulation of the comparative polishing liquid and the polishing liquid 1 ⁇ 10 of the present invention. According to the formula in the table, the components are simply and uniformly mixed, and the balance is water, and then adjusted to a suitable amount by using potassium hydroxide, ammonia water and nitric acid. At each pH, the polishing liquid of each example can be obtained. Table 1 Comparative polishing liquid and polishing liquid of the present invention 1-10
- polishing conditions Copper, tantalum, silicon dioxide (TEOS) and silicon nitride (Si 3 N 4 ) were polished using a comparative polishing liquid and the polishing liquids 1 to 10 of the present invention under the following conditions.
- Table 2 Comparison of polishing liquid and polishing liquid of the present invention 1 to 10 pairs of copper, tantalum, silicon dioxide (TEOS) and silicon nitride (Si 3 N 4 )
- the polishing liquid of the present invention has a higher enthalpy than the comparative polishing liquid.
- the removal rate of silica after adding a certain amount of naphthalenesulfonate anionic surfactant, the removal rate of silicon nitride is effectively inhibited without affecting the removal of silica, and the surface activity of the alcohol ether phosphate anion is added.
- the removal rate of silicon nitride is further reduced, and the selection ratio of silicon dioxide to silicon nitride removal rate is further improved. It can be seen from the polishing results of the polishing liquid 3 to 5 for copper that the removal rate of the metallic copper can be adjusted according to the concentration of the oxidizing agent and has appropriate sensitivity. Effect Example 2
- Fig. 1 and Fig. 2 are SEM images of the surface topography of the Semtech 854 pattern test wafer after polishing with polishing liquid 1 and polishing liquid 3, respectively.
- Figure 3 and Figure 4 are SEM images of the surface topography of the Semtech 854 pattern test wafer after 10 minutes of immersion with polishing solution 1 and polishing solution 3, respectively.
- the polishing liquid in the present invention effectively inhibits metal corrosion by adding an alcohol ether phosphate anionic surfactant, and the surface of the pattern sheet after being impregnated with the polishing liquid is still sharp and sharp, and no metal is found. Corrosion phenomenon.
- the azole compound binds to the alcohol ether phosphate anionic surfactant to protect the metallic copper well. Effect Example 3
- the TSV pattern test wafer was polished using the comparative polishing liquid 1 and the polishing liquid 1 to 2 in accordance with the following conditions.
- the polishing results are shown in Table 3. Compared with the comparative polishing liquid, the polishing liquid of the present invention can better correct the dish-shaped depression generated on the wafer by the prode, and obtain a better crystal circular appearance.
- wt% of the present invention refers to the mass percentage.
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Abstract
Disclosed is a chemical mechanical polishing solution for silicon through-holes, comprising at least a grinding particle, an azole compound, an acid, one or more anionic surfactants, and an oxidant. The polishing solution has a high silicon dioxide removal rate and a low silicon nitride removal rate, is capable of perform high-efficiency planarization on a silicon through-hole blocking layer, does not generate metal erosion at the same time, can linearly adjust a metallic copper removal rate, and has a high defect correction capability and a low surface pollutant index.
Description
一种用于硅通孔平坦化的化学机械抛光液 Chemical mechanical polishing liquid for planarizing silicon through holes
技术领域 Technical field
本发明涉及一种化学机械抛光液， 更具体地说， 本发明涉及一种用于硅 通孔平坦化的化学机械抛光液。 技术背景 The present invention relates to a chemical mechanical polishing liquid, and more particularly to a chemical mechanical polishing liquid for planarizing silicon through holes. technical background
随着 CMOS工艺开发的发展， 器件的特征尺寸逐渐缩小， 电路密度的 变的更加复杂， 由此带来的设计和制造变得愈加困难， 互连过程中的信号拥 堵进一步加剧，小型化和超高集成越加逼近其物理极限，为了延续摩尔定律， 解决铜互连的延迟问题， 满足性能， 频宽和功耗的要求， 3D IC集成技术逐 渐发展起来。 With the development of CMOS process development, the feature size of the device is gradually reduced, the circuit density is more complicated, and the design and manufacturing are becoming more and more difficult. The signal congestion in the interconnection process is further aggravated, miniaturization and super High integration is approaching its physical limits. In order to extend Moore's Law, solve the copper interconnect delay problem, and meet the performance, bandwidth and power requirements, 3D IC integration technology has gradually developed.
即在垂直方向将芯片叠层， 穿过有源电路直接实现高效互连， 由于大大 缩短了互联线的长度， 不仅提高了电路性能， 还进一步降低了功耗。 如下图 所示硅通孔 （TSV) 技术主要分为几个步骤 1 : 快速刻蚀形成通孔。 2: 通 孔填注的过程包括氧化层的淀积、金属粘附层 /阻挡层 /种子层、 ECP金属铜。 采用 CMP技术去除金属铜。 实现平坦化， 形现金属导通。 That is, the chips are stacked in the vertical direction, and the high-efficiency interconnection is directly realized through the active circuit. Since the length of the interconnection line is greatly shortened, not only the circuit performance is improved, but also the power consumption is further reduced. The through silicon via (TSV) technology shown in the following figure is mainly divided into several steps: 1. Rapid etching to form via holes. 2: The process of through hole filling includes the deposition of an oxide layer, a metal adhesion layer/barrier layer/seed layer, and ECP metal copper. Metal copper is removed using CMP technology. Flattening is achieved, and the metal is turned on.
TSV制程的集成方式非常多， 但都面临一个共同的难题， 即 TSV制作 都需要打通不同材料层， 包括硅材料、 IC中各种绝缘或导电的薄膜层。例如 金属铜， 阻挡层金属钽， 二氧化硅绝缘层以及氮化硅停止层等， 各种膜层的 厚度也比较高， 为了提高三维集成技术的经济性， 就需要在 CMP过程中具 有较高的去除速率和合适的抛光选择比， 才能实现对前程缺陷的最大矫正， 并停止在氮化硅层， 同时不能产生金属的腐蚀和缺陷， 表面颗粒物控制在工 艺要求的范围。这对硅通孔阻挡层的 CMP提出了更高的要求。目前针对 TSV 技术的专用 CMP抛光液研究非常活跃， 但至今还没有商业化的产品报道， 尤其是 TSV阻挡层的抛光液。
发明概要 There are many ways to integrate TSV processes, but they all face a common problem. TSV production needs to open different layers of materials, including silicon materials, various insulating or conductive thin film layers in ICs. For example, metal copper, barrier metal ruthenium, silicon dioxide insulating layer and silicon nitride stop layer, etc., the thickness of various film layers is also relatively high, in order to improve the economics of the three-dimensional integration technology, it is necessary to have a higher CMP process. The removal rate and the appropriate polishing selectivity ratio can achieve the maximum correction of the precursor defects, and stop at the silicon nitride layer, and at the same time can not produce metal corrosion and defects, the surface particles are controlled within the scope of the process requirements. This puts higher demands on the CMP of the through-silicon via barrier layer. The current research on dedicated CMP polishing fluids for TSV technology is very active, but there have been no commercial product reports, especially the TSV barrier polishing fluid. Summary of invention
本发明为解决上述现有技术存在的问题， 提供了一种化学机械抛光液， 满足了硅通孔平坦化过程中二氧化硅对氮化硅的去除速率选择比较高的工 艺要求， 并对前程的缺陷值具有较好的矫正作用， 且防止了金属抛光过程中 产生的腐蚀， 抛光后晶圆表面缺陷和污染物少。 In order to solve the above problems in the prior art, the present invention provides a chemical mechanical polishing liquid, which satisfies the process requirement of high selection rate of silicon dioxide for silicon nitride in the planarization process of through silicon via holes, and the future The defect value has a good correction effect, and prevents corrosion generated during the metal polishing process, and the wafer surface defects and contaminants are less after polishing.
本发明的用于硅通孔平坦化的化学机械抛光液， 包含： 研磨颗粒， 酸， 阴离子表面活性剂， 氧化剂和唑类化合物及其衍生物。 The chemical mechanical polishing liquid for planarizing silicon through holes of the present invention comprises: abrasive particles, an acid, an anionic surfactant, an oxidizing agent and an azole compound and a derivative thereof.
在本发明中， 所述的研磨颗粒为二氧化硅溶胶， 所述的研磨颗粒的粒径 为 20-200nm， 优选地， 所述的研磨颗粒的粒径为 40-120nm。 In the present invention, the abrasive particles are silica sols, and the abrasive particles have a particle diameter of 20 to 200 nm. Preferably, the abrasive particles have a particle diameter of 40 to 120 nm.
在本发明中， 所述的研磨颗粒的浓度为 10-50wt%。 In the present invention, the abrasive particles have a concentration of 10 to 50% by weight.
在本发明中， 所述的唑类化合物及其衍生物为三唑类化合物及其衍生 物。 优选地， 所述三唑类化合物及其衍生物选自苯并三氮唑， 甲基苯并三氮 唑， 羟基苯并三氮唑和羧基苯并三氮唑中的一种或多种。 In the present invention, the azole compound and its derivative are triazole compounds and derivatives thereof. Preferably, the triazole compound and its derivative are one or more selected from the group consisting of benzotriazole, methylbenzotriazole, hydroxybenzotriazole and carboxybenzotriazole.
在本发明中， 所述的唑类化合物浓度为 0.01-0.5wt%， 优选地， 所述的 唑类化合物浓度为 0.05-0.2wt%。 In the present invention, the concentration of the azole compound is 0.01 to 0.5% by weight, preferably, the concentration of the azole compound is 0.05 to 0.2% by weight.
在本发明中， 所述的酸为无机酸或有机酸， 优选地， 所述的无机酸或有 机酸选自盐酸， 硝酸， 草酸， 丙二酸， 丁二酸和磺基水杨酸中的一种或多种。 In the present invention, the acid is an inorganic acid or an organic acid, and preferably, the inorganic or organic acid is selected from the group consisting of hydrochloric acid, nitric acid, oxalic acid, malonic acid, succinic acid and sulfosalicylic acid. One or more.
在本发明中， 所述的酸的浓度为 0.01— 1wt%， 优选地， 所述的酸的浓 度为 0.01-0.2wt%。 In the present invention, the concentration of the acid is 0.01 to 1% by weight, and preferably, the concentration of the acid is 0.01 to 0.2% by weight.
在本发明中， 所述的阴离子表面活性剂为至少两种阴离子表面活性剂， 优选地，所述的阴离子表面活性剂为萘磺酸盐类表面活性剂和磷酸酯盐类表 面活性剂的混和物。 In the present invention, the anionic surfactant is at least two anionic surfactants. Preferably, the anionic surfactant is a mixture of a naphthalene sulfonate surfactant and a phosphate salt surfactant. Things.
在本发明中，所述的萘磺酸盐类表面活性剂为亚甲基二萘磺酸钠和 /或甲 基萘磺酸钠甲醛缩合物； 所述的磷酸酯盐类表面活性剂为垸基磷酸酯二乙醇 胺盐， ROP03H2(NH(CH2CH20H)2)2，其中 R为 -CmH2m+1， 8 m 12，和 /或 醇醚磷酸单酯， RO(CH2CH20)bPO(OH)2，其中 R为- CnH2n+1， 12^n^14, 1
在本发明中， 所述的混合阴离子表面活性剂的浓度为 50-2000ppm。 在本发明中， 所述的氧化剂为过氧化物或过硫化物， 优选地， 所述的氧 化剂为选自过氧化氢， 过氧化钠， 过氧化钾， 过硫酸钠， 过硫酸铵， 过氧化 苯甲酰中的一种或多种。 In the present invention, the naphthalenesulfonate surfactant is sodium methylene dinaphthalenesulfonate and/or sodium methylnaphthalenesulfonate formaldehyde condensate; the phosphate ester surfactant is ruthenium Phosphate diethanolamine salt, ROP0 3 H 2 (NH(CH2CH20H) 2 ) 2 , wherein R is -C m H 2m+1 , 8 m 12, and/or alcohol ether phosphate monoester, RO (CH 2 CH 2 0) b PO(OH) 2 , where R is - C n H 2n+1 , 12^n^14, 1 In the present invention, the mixed anionic surfactant has a concentration of 50 to 2000 ppm. In the present invention, the oxidizing agent is a peroxide or a persulfide. Preferably, the oxidizing agent is selected from the group consisting of hydrogen peroxide, sodium peroxide, potassium peroxide, sodium persulfate, ammonium persulfate, peroxidation. One or more of benzoyl.
在本发明中， 所述的抛光液还包含添加剂和 /或杀菌防霉变剂。 优选地， 所述添加剂为有机溶剂， 所述杀菌防霉变剂为季铵盐活性剂， 更优选地， 所 述有机溶剂为甘油。 In the present invention, the polishing liquid further contains an additive and/or a bactericidal mold inhibitor. Preferably, the additive is an organic solvent, the bactericidal mold inhibitor is a quaternary ammonium salt active agent, and more preferably, the organic solvent is glycerin.
在本发明中， 所述的抛光液的 pH值为 1~4， 优选地， 所述的抛光液的 pH值为 2~3。 In the present invention, the polishing liquid has a pH of 1 to 4, and preferably, the polishing liquid has a pH of 2 to 3.
本发明突出的技术效果在于： The outstanding technical effects of the present invention are:
1.本发明的抛光液具有较高的二氧化硅去除速率和较低的氮化硅去除 速率， 获得较高的二氧化硅对氮化硅的去除速率选择比； 1. The polishing liquid of the present invention has a higher silica removal rate and a lower silicon nitride removal rate, and a higher removal ratio of silicon dioxide to silicon nitride is obtained;
2.本发明的抛光液具有较高的缺陷校正能力， 同时不产生金属腐蚀， 提 高产品良率； 2. The polishing liquid of the invention has high defect correction ability, and does not cause metal corrosion, thereby improving product yield;
3.采用本发明的抛光液拋光后， 晶圆具有完好的表面形貌和较低的表面 污染物残留。 隨翻 3. After polishing with the polishing liquid of the present invention, the wafer has a good surface topography and low surface contaminant residue. Turn over
图 1A为 TSV硅通孔阻挡层抛光前的抛面示意图； 1A is a schematic view showing a polishing surface of a TSV through silicon via barrier layer before polishing;
图 1 B为 TSV硅通孔阻挡层抛光铜后的抛面示意图； Figure 1B is a schematic view of a polished surface of a TSV through-silicon via barrier layer after polishing copper;
图 1C为 TSV硅通孔阻挡层抛光阻挡层后的抛面示意图； 1C is a schematic view showing a polishing surface of a TSV through-silicon via barrier polishing layer;
图 2 为对比抛光液抛光后 Semtech 854 图形测试晶圆的表面形貌的 Figure 2 shows the surface topography of the Semtech 854 graphics test wafer after polishing the polishing solution.
SEM图； SEM image;
图 3为实施例 3的抛光液抛光后 Semtech 854图形测试晶圆的表面形 貌的 SEM图； 3 is an SEM image of the surface morphology of the Semtech 854 pattern test wafer after polishing of the polishing solution of Example 3;
图 4为对比抛光液浸渍 10min后 Semtech 854图形测试晶圆的表面形 貌的 SEM图；
图 5为实施例 3的抛光液浸渍 10min后 Semtech 854图形测试晶圆的 表面形貌的 SEM图。 发明内容 Figure 4 is an SEM image of the surface topography of the Semtech 854 pattern test wafer after 10 minutes of immersion in the polishing solution; 5 is an SEM image of the surface topography of the Semtech 854 pattern test wafer after immersion of the polishing solution of Example 3 for 10 minutes. Summary of the invention
下面通过具体实施方式来进一步阐述本发明的优势。 Advantages of the present invention are further illustrated by the following detailed description.
表 1给出了对比抛光液和本发明的抛光液 1~10的配方， 按表中配方， 将各成分简单均匀混合， 余量为水， 之后采用氢氧化钾、 氨水和硝酸调节至 合适的 pH值， 即可制得各实施例抛光液。 表 1对比抛光液和本发明的抛光液 1-10 Table 1 shows the formulation of the comparative polishing liquid and the polishing liquid 1~10 of the present invention. According to the formula in the table, the components are simply and uniformly mixed, and the balance is water, and then adjusted to a suitable amount by using potassium hydroxide, ammonia water and nitric acid. At each pH, the polishing liquid of each example can be obtained. Table 1 Comparative polishing liquid and polishing liquid of the present invention 1-10
Si02 苯 醇聚 Si0 2 phenyl alcohol
亚甲 过 Asian
并 氧乙 Oxygen B
草 氧 Grass oxygen
20 0.1 0.02 0.01 烯 (3) 0.005 0.1 2.5 20 0.1 0.02 0.01 ene (3) 0.005 0.1 2.5
酸 萘磺 化 Acid naphthalene sulfonate
(80nm) 酸磷 (80nm) acid phosphorus
酸钠 Sodium
唑 酸单 Azole acid
酯 Ester
十二 Twelve
Si02 苯 醇聚 Si0 2 phenyl alcohol
亚甲 过 Asian
并 氧乙 Oxygen B
草 氧 Grass oxygen
20 0.1 0.02 0.01 烯 (1) 0.005 0.2 2.5 20 0.1 0.02 0.01 olefin (1) 0.005 0.2 2.5
酸 萘磺 化 Acid naphthalene sulfonate
(80nm) 醚磷 (80nm) ether phosphorus
酸钠 氢 Sodium hydrogen
唑 酸单 Azole acid
酯 Ester
甲 A
Si02 甲基 十烷 Si0 2 methyl decane
萘磺 基磷 过 Naphthylsulfophosphate
苯 丙 Benzene
酸钠 酸酯 硫 Sodium sulphate
40 并 0.05 0.5 0.15 0.05 0.2 3 40 and 0.05 0.5 0.15 0.05 0.2 3
甲醛 二乙 酸 Formaldehyde
(40nm) 酸 (40nm) acid
縮合 醇胺 铰 Condensation alcohol amine hinge
氮 Nitrogen
物 盐 Salt
唑 Azole
甲基 十二 Methyl 12
Si02 苯 Si0 2 benzene
萘磺 烧基 过 Naphthalene sulfonate
并 丁 And
酸钠 磷酸 氧 Sodium phosphate
15 0.2 1 0.01 0.1 0.1 2 15 0.2 1 0.01 0.1 0.1 2
甲醛 酯二 化 Formaldehyde ester dimerization
(120nm) 酸 (120nm) acid
缩合 乙醇 钠 Condensation
唑 Azole
物 胺盐 Amine salt
Si02 羟 Si0 2 hydroxy
十烷 Decane
磺 Sulfur
亚甲 基磷 过 Methylene phosphate
苯 Benzene
酸酯 氧 Acid ester
50 并 0.01 水 0.05 0.05 0.15 0.5 4 50 and 0.01 water 0.05 0.05 0.15 0.5 4
萘磺 二乙 化 Naphthalene sulfonate
(20nm) 杨 (20nm) Yang
酸钠 醇胺 钾 Sodium alkoxide
酸 Acid
盐 Salt
Si02 Si0 2
羧 十四 Carboxy fourteen
过 Over
醇聚 Alcohol polymerization
亚甲 氧 Methylene oxide
苯 氧乙 Benzophenone
化 Chemical
10 并 0.5 0.2 0 烯 (2) 0.001 0.01 甘油 2 1 10 and 0.5 0.2 0 ene (2) 0.001 0.01 glycerol 2 1
萘磺 苯 Naphthalene benzene
(200nm) 醚磷 (200nm) ether phosphorus
酸钠 甲 Sodium
酸单 Acid sheet
酰 Acyl
唑 酯 十二 Oxazide
Si02 甲基 十二 Si0 2 methyl 12
苯 醇聚 Benzene alcohol
萘磺 过 院基 Naphthalene sulfonate
并 氧乙 Oxygen B
硝 酸钠 氧 二甲 Sodium nitric oxide
15 0.1 0.01 0.1 烯 (2) 0.1 0.2 0.005 3 ϊ 酸 甲醛 化 基苄 15 0.1 0.01 0.1 ene (2) 0.1 0.2 0.005 3 ϊ acid formaldehyde benzyl
(100nm) 醚磷 (100nm) ether phosphorus
缩合 氢 基氯 Condensation hydrogen chloride
唑 酸单 Azole acid
物 化铵 Ammonium
酯
效果实施例 1 Ester Effect Example 1
采用对比抛光液和本发明的抛光液 1 ~10按照下述条件对铜、 钽、 二氧 化硅 （TEOS) 和氮化硅 （Si3N4) 进行抛光。 抛光条件： 抛光垫为 IC pad, 下压力为 3.0psi， 转速为抛光盘 /抛光头 =70/90rpm， 抛光液流速为 100ml/min, 抛光时间为 1 min。 表 2 对比抛光液和本发明抛光液 1~10对铜、 钽、 二氧化硅 （TEOS) 和氮化硅 （Si3N4) Copper, tantalum, silicon dioxide (TEOS) and silicon nitride (Si 3 N 4 ) were polished using a comparative polishing liquid and the polishing liquids 1 to 10 of the present invention under the following conditions. Polishing conditions: The polishing pad is an IC pad with a downforce of 3.0 psi, a rotating disk/buffing head = 70/90 rpm, a polishing fluid flow rate of 100 ml/min, and a polishing time of 1 min. Table 2 Comparison of polishing liquid and polishing liquid of the present invention 1 to 10 pairs of copper, tantalum, silicon dioxide (TEOS) and silicon nitride (Si 3 N 4 )
的去除速率以及二氧化硅对氮化硅的去除速率的选择比 Removal rate and selectivity ratio of silicon dioxide to silicon nitride removal rate
采用抛光液 1和抛光液 3按照下述条件对 Semtech 854图形测试晶圆 进行抛光。 抛光条件： 抛光垫为 IC pad，下压力为 3.0psi， 转速为抛光盘 /抛 光头 =70/90rpm， 抛光液流速为 100ml/min， 抛光时间为 1 min。 The Semtech 854 pattern test wafer was polished using the polishing liquid 1 and the polishing liquid 3 under the following conditions. Polishing conditions: The polishing pad is IC pad, the downforce is 3.0 psi, the rotation speed is polishing disc / polishing head = 70/90 rpm, the polishing fluid flow rate is 100 ml/min, and the polishing time is 1 min.
图 1和图 2分别采用抛光液 1和抛光液 3拋光后 Semtech 854图形测 试晶圆的表面形貌的 SEM图。 Fig. 1 and Fig. 2 are SEM images of the surface topography of the Semtech 854 pattern test wafer after polishing with polishing liquid 1 and polishing liquid 3, respectively.
图 3和图 4分别采用抛光液 1和抛光液 3浸渍 10min后 Semtech 854 图形测试晶圆的表面形貌的 SEM图。 Figure 3 and Figure 4 are SEM images of the surface topography of the Semtech 854 pattern test wafer after 10 minutes of immersion with polishing solution 1 and polishing solution 3, respectively.
由图 3和图 4可以看出，本发明中的抛光液添加了醇醚磷酸酯类阴离子 表面活性剂后有效抑制了金属腐蚀， 图形片经过抛光液浸渍后的表面仍然清 晰锐利， 未发现金属腐蚀现象。 唑类化合物结合醇醚磷酸酯类阴离子表面活 性剂很好的保护了金属铜。 效果实施例 3 It can be seen from FIG. 3 and FIG. 4 that the polishing liquid in the present invention effectively inhibits metal corrosion by adding an alcohol ether phosphate anionic surfactant, and the surface of the pattern sheet after being impregnated with the polishing liquid is still sharp and sharp, and no metal is found. Corrosion phenomenon. The azole compound binds to the alcohol ether phosphate anionic surfactant to protect the metallic copper well. Effect Example 3
采用对比抛光液 1和抛光液 1〜2按照下述条件对 TSV图形测试晶圆进 行抛光。 抛光条件： 抛光垫为 IC pad,下压力为 3.0psi， 转速为抛光盘 /抛光 头 =70/90rpm， 抛光液流速为 100ml/min， 抛光时间为 1 min。
对比抛光液和本发明抛光液 1~2对前程的缺陷值的矫正能力 The TSV pattern test wafer was polished using the comparative polishing liquid 1 and the polishing liquid 1 to 2 in accordance with the following conditions. Polishing conditions: The polishing pad is an IC pad with a downforce of 3.0 psi, a rotating disk/buffing head = 70/90 rpm, a polishing solution flow rate of 100 ml/min, and a polishing time of 1 min. Comparing the polishing liquid and the polishing solution of the present invention 1~2 to correct the defect value of the future
应当理解的是， 本发明所述 wt%均指的是质量百分含量。 It should be understood that the wt% of the present invention refers to the mass percentage.
以上对本发明的具体实施例进行了详细描述， 但其只是作为范例， 本发 明并不限制于以上描述的具体实施例。 对于本领域技术人员而言， 任何对本 发明进行的等同修改和替代也都在本发明的范畴之中。 因此， 在不脱离本发 明的精神和范围下所作的均等变换和修改， 都应涵盖在本发明的范围内。
The specific embodiments of the present invention have been described in detail above, but by way of example only, the invention is not limited to the specific embodiments described above. Any equivalent modifications and substitutions of the present invention are also within the scope of the invention. Accordingly, equivalent changes and modifications may be made without departing from the spirit and scope of the invention.
Claims
1. 一种用于硅通孔平坦化的化学机械抛光液， 包含： 研磨颗粒， 酸， 阴离子 表面活性剂， 氧化剂和唑类化合物及其衍生物。 A chemical mechanical polishing fluid for planarizing silicon vias, comprising: abrasive particles, an acid, an anionic surfactant, an oxidizing agent, and an azole compound and a derivative thereof.
2. 根据权利要求 1所述的化学机械抛光液， 其特征在于： 所述的研磨颗粒为 二氧化硅溶胶， 所述的研磨颗粒的粒径为 20-200nm。 The chemical mechanical polishing liquid according to claim 1, wherein the abrasive particles are silica sols, and the abrasive particles have a particle diameter of 20 to 200 nm.
3. 根据权利要求 2所述的化学机械抛光液， 其特征在于： 所述的研磨颗粒的 粒径为 40-120nm。 The chemical mechanical polishing liquid according to claim 2, wherein the abrasive particles have a particle diameter of 40 to 120 nm.
4. 根据权利要求 1所述的化学机械抛光液， 其特征在于： 所述的研磨颗粒的 浓度为 10-50wt%。 The chemical mechanical polishing liquid according to claim 1, wherein the abrasive particles have a concentration of 10 to 50% by weight.
5. 根据权利要求 1所述的化学机械抛光液， 其特征在于： 所述的唑类化合物 及其衍生物为三唑类化合物及其衍生物。 The chemical mechanical polishing liquid according to claim 1, wherein the azole compound and the derivative thereof are a triazole compound and a derivative thereof.
6. 根据权利要求 5所述的化学机械抛光液， 其特征在于： 所述三唑类化合物 及其衍生物选自苯并三氮唑， 甲基苯并三氮唑， 羟基苯并三氮唑和羧基苯 并三氮唑中的一种或多种。 The chemical mechanical polishing liquid according to claim 5, wherein the triazole compound and a derivative thereof are selected from the group consisting of benzotriazole, methylbenzotriazole, and hydroxybenzotriazole. And one or more of carboxybenzotriazole.
7. 根据权利要求 1所述的化学机械抛光液， 其特征在于： 所述的唑类化合物 浓度为 0.01-0.5wt%。 The chemical mechanical polishing liquid according to claim 1, wherein the azole compound has a concentration of 0.01 to 0.5% by weight.
8. 根据权利要求 7所述的化学机械拋光液， 其特征在于： 所述的唑类化合物 浓度为 0.05-0.2wt%。 The chemical mechanical polishing liquid according to claim 7, wherein the azole compound has a concentration of 0.05 to 0.2% by weight.
9. 根据权利要求 1所述的化学机械抛光液， 其特征在于： 所述的酸为无机酸 或有机酸。 The chemical mechanical polishing liquid according to claim 1, wherein the acid is an inorganic acid or an organic acid.
10.根据权利要求 1所述的化学机械抛光液， 其特征在于： 所述的无机酸或有 机酸选自盐酸， 硝酸， 草酸， 丙二酸， 丁二酸和磺基水杨酸中的一种或多
种。 The chemical mechanical polishing liquid according to claim 1, wherein the inorganic acid or organic acid is one selected from the group consisting of hydrochloric acid, nitric acid, oxalic acid, malonic acid, succinic acid and sulfosalicylic acid. Kind or more Kind.
根据权利要求 1所述的化学机械抛光液， 其特征在于： 所述的酸的浓度为 0.01— lwt%。 The chemical mechanical polishing liquid according to claim 1, wherein the acid has a concentration of 0.01 to 1% by weight.
根据权利要求 11所述的化学机械抛光液， 其特征在于： 所述的酸的浓度为 0.01-0.2wt%。 The chemical mechanical polishing liquid according to claim 11, wherein the acid concentration is 0.01 to 0.2% by weight.
根据权利要求 1所述的化学机械抛光液， 其特征在于： 所述的阴离子表面 活性剂为至少两种阴离子表面活性剂。 The chemical mechanical polishing liquid according to claim 1, wherein the anionic surfactant is at least two anionic surfactants.
根据权利要求 13所述的化学机械抛光液， 其特征在于： 所述的阴离子表面 活性剂为萘磺酸盐类表面活性剂和磷酸酯盐类表面活性剂的混和物。 The chemical mechanical polishing liquid according to claim 13, wherein the anionic surfactant is a mixture of a naphthalenesulfonate surfactant and a phosphate salt surfactant.
根据权利要求 14所述的化学机械抛光液， 其特征在于： 所述的萘磺酸盐类 表面活性剂为亚甲基二萘磺酸钠和 /或甲基萘磺酸钠甲醛缩合物； 所述的磷 酸 酯 盐 类 表 面 活 性 剂 为 垸 基 磷 酸 酯 二 乙 醇 胺 盐 ， ROP03H2(NH(CH2CH2OH)2)2，其中 R为 -CmH2m+1， 8 m 12，和 /或醇醚磷酸 单酯， ！^^！！^！！^^^^！^，其中！^为-^！^+！， ^！！ ：^， l b 9。 根据权利要求 14所述的化学机械抛光液， 其特征在于： 所述的混合阴离子 表面活性剂的浓度为 50-2000ppm。 The chemical mechanical polishing liquid according to claim 14, wherein the naphthalene sulfonate surfactant is sodium methylene dinaphthalene sulfonate and/or sodium methyl naphthalene sulfonate formaldehyde condensate; The phosphate ester surfactant is a mercapto phosphate diethanolamine salt, ROP0 3 H 2 (NH(CH 2 CH 2 OH) 2 ) 2 , wherein R is -C m H 2m+1 , 8 m 12 , And / or alcohol ether phosphate monoester, ! ^^! ! ^! ! ^^^^! ^, where! ^为-^! ^+! , ^! ! :^, lb 9. The chemical mechanical polishing liquid according to claim 14, wherein the mixed anionic surfactant has a concentration of 50 to 2000 ppm.
根据权利要求 1所述的化学机械抛光液， 其特征在于： 所述的氧化剂为过 氧化物或过硫化物。 The chemical mechanical polishing liquid according to claim 1, wherein the oxidizing agent is a peroxide or a persulfide.
根据权利要求 17所述的化学机械抛光液， 其特征在于： 所述的氧化剂为选 自过氧化氢， 过氧化钠， 过氧化钾， 过硫酸钠， 过硫酸铵， 过氧化苯甲酰 中的一种或多种。 The chemical mechanical polishing liquid according to claim 17, wherein: said oxidizing agent is selected from the group consisting of hydrogen peroxide, sodium peroxide, potassium peroxide, sodium persulfate, ammonium persulfate and benzoyl peroxide. One or more.
根据权利要求 1所述的化学机械抛光液， 其特征在于： 所述的抛光液还包
含添加剂和 /或杀菌防霉变剂。 The chemical mechanical polishing liquid according to claim 1, wherein: said polishing liquid is further included Contains additives and / or bactericidal mildew inhibitors.
根据权利要求 19所述的化学机械抛光液， 其特征在于： 所述添加剂为有机 溶剂， 所述杀菌防霉变剂为季铵盐活性剂。 The chemical mechanical polishing liquid according to claim 19, wherein the additive is an organic solvent, and the bactericidal mildew inhibitor is a quaternary ammonium salt active agent.
根据权利要求 20所述的化学机械抛光液， 其特征在于： 所述有机溶剂为甘 油。 The chemical mechanical polishing liquid according to claim 20, wherein the organic solvent is glycerin.
根据权利要求 1所述的化学机械抛光液，其特征在于：所述的抛光液的 pH 值为 1~4。 The chemical mechanical polishing liquid according to claim 1, wherein said polishing liquid has a pH of from 1 to 4.
根据权利要求 22所述的化学机械拋光液，其特征在于:所述的抛光液的 pH 值为 2〜3。
The chemical mechanical polishing liquid according to claim 22, wherein said polishing liquid has a pH of 2 to 3.
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| CN103865400A (en) * | 2012-12-10 | 2014-06-18 | 安集微电子（上海）有限公司 | Application of organic phosphate surfactant in self-stopping polishing |
| CN108117840B (en) * | 2016-11-29 | 2021-09-21 | 安集微电子科技（上海）股份有限公司 | Silicon nitride chemical mechanical polishing solution |
| CN109971353B (en) * | 2017-12-27 | 2021-12-07 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution |
| US20200102475A1 (en) * | 2018-09-28 | 2020-04-02 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Chemical mecahnical polishing composition and method of polishing silcon dioxide over silicon nitiride |
| JP7041714B2 (en) * | 2019-06-26 | 2022-03-24 | 花王株式会社 | Abrasive liquid composition for silicon oxide film |
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| US20100178768A1 (en) * | 2007-06-15 | 2010-07-15 | Basf Se | Controlling passivating film properties using colloidal particles, polyelectrolytes, and ionic additives for copper chemical mechanical planarization |
| CN102051128A (en) * | 2009-11-06 | 2011-05-11 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution |
| CN102453439A (en) * | 2010-10-22 | 2012-05-16 | 安集微电子（上海）有限公司 | Chemical mechanical polishing liquid |
| CN102453440A (en) * | 2010-10-22 | 2012-05-16 | 安集微电子（上海）有限公司 | Chemical mechanical polishing liquid |
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| CN102051128A (en) * | 2009-11-06 | 2011-05-11 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution |
| CN102453439A (en) * | 2010-10-22 | 2012-05-16 | 安集微电子（上海）有限公司 | Chemical mechanical polishing liquid |
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