CN104745086A - Chemical mechanical polishing solution for barrier layer planarization, and use method thereof - Google Patents
Chemical mechanical polishing solution for barrier layer planarization, and use method thereof Download PDFInfo
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- 238000005498 polishing Methods 0.000 title claims abstract description 126
- 239000000126 substance Substances 0.000 title claims abstract description 40
- 230000004888 barrier function Effects 0.000 title abstract description 10
- 238000000034 method Methods 0.000 title description 12
- 239000010949 copper Substances 0.000 claims abstract description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 claims abstract description 26
- 230000007797 corrosion Effects 0.000 claims abstract description 21
- 238000005260 corrosion Methods 0.000 claims abstract description 21
- 239000003112 inhibitor Substances 0.000 claims abstract description 14
- 239000011814 protection agent Substances 0.000 claims abstract description 11
- 239000008139 complexing agent Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 5
- 239000012530 fluid Substances 0.000 claims description 47
- 239000007788 liquid Substances 0.000 claims description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000006061 abrasive grain Substances 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 230000000903 blocking effect Effects 0.000 claims description 9
- 229960001866 silicon dioxide Drugs 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-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
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- -1 aphthotriazoles Chemical compound 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical class NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 3
- 150000003852 triazoles Chemical class 0.000 claims description 3
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 claims description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- 229940054266 2-mercaptobenzothiazole Drugs 0.000 claims description 2
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- 229940120146 EDTMP Drugs 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- BVWCKYAYMBDPIP-UHFFFAOYSA-N NC=1C=C(C=C(C1)N)C=CC1=CC=CC=C1 Chemical compound NC=1C=C(C=C(C1)N)C=CC1=CC=CC=C1 BVWCKYAYMBDPIP-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 2
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- 239000011324 bead Substances 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
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 230000021523 carboxylation Effects 0.000 claims description 2
- 238000006473 carboxylation reaction Methods 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 2
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 238000007517 polishing process Methods 0.000 abstract description 5
- 239000007800 oxidant agent Substances 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- 239000002736 nonionic surfactant Substances 0.000 abstract 1
- 239000003989 dielectric material Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 238000012876 topography Methods 0.000 description 6
- 230000003628 erosive effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002002 slurry Substances 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
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 244000132059 Carica parviflora Species 0.000 description 1
- 235000014653 Carica parviflora Nutrition 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000019994 cava Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- 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
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
-
- 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]
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
The invention discloses a chemical mechanical polishing solution for barrier layer planarization. The polishing solution contains grinding particles, a corrosion inhibitor, a copper surface protection agent, a complexing agent, a nonionic surfactant and an oxidant. The chemical mechanical polishing solution can meet requirements of the polishing rates and the selectivity ratios of all materials in a barrier layer polishing process, has very strong rectification ability on defects of the surface of a semiconductor device to rapidly realize planarization, can prevent local and integral corrosion generated in the metal polishing process, improves the work efficiency, and reduces the production cost.
Description
Technical field
The present invention relates to a kind of chemical mechanical polishing liquid for blocking layer planarization and using method thereof.
Background technology
In integrated circuit fabrication, the standard of interconnection technique is in improve, along with the interconnection increase of the number of plies and reducing of technology feature size, also more and more higher to the requirement of silicon chip surface planeness, if there is no the ability of planarization, it is very limited for creating complicated and intensive structure on a semiconductor wafer, and cmp method CMP is exactly the most effective means that can realize whole silicon chip planarization.
CMP is exactly use a kind of mixture containing abrasive material and polishing pad polishing integrated circuit surface.In typical cmp method, substrate is directly contacted with rotating polishing pad, applies pressure with a loads at substrate back.During polishing, pad and operator's console rotate, the power simultaneously kept down at substrate back, is applied on pad by abrasive material and chemically reactive solution (being commonly referred to polishing fluid or polishing slurries), this polishing fluid with just start to carry out polishing process at the film generation chemical reaction of polishing.
Along with integrated circuit technique is to sub-micro (32, 28nm) future development, the performance affecting circuit that the stray capacitance caused because characteristic dimension reduces is further serious, for reducing this impact, ultra-low dielectric materials (ULK) just must be adopted to reduce stray capacitance between adjacent wires, current more employing ultra-low dielectric materials is Coral, except wanting strict control surface pollutent index and stopping except metallic corrosion in CMP process, also to have lower butterfly depression and polishing homogeneity guarantee electrical property more reliably, need to remove barrier metal fast under shorter time and lower pressure in the planarization process on particularly blocking layer, capping oxide compound also can well stop at ultra-low dielectric materials surface, form interconnection line, and it is insensitive to small size figure.This just proposes higher challenge to CMP, because ultra-low dielectric materials is the silicon oxide mixing carbon usually, to silicon-dioxide, there is similar superficiality, the residual thickness of stop-layer be controlled, the ability of regulation and control of very strong Selection radio will be had, also will have the features such as very high stability and easy cleaning.This patent aims to provide a kind of barrier polishing solution be suitable in ULK-copper-connection processing procedure, there is the technique stop performance at high barrier removal rates and ultra-low dielectric materials interface under relatively mild condition, and well can control butterfly depression, metallic corrosion and surface contaminant index.
CN1400266 discloses a kind of alkali barrier polishing fluid, and this polishing fluid comprises abrasive silica, aminated compounds and nonionogenic tenside, but the polishing fluid in this patent can produce corrosion to copper.CN101372089A discloses a kind of alkali barrier polishing fluid, and this polishing fluid comprises abrasive silica, corrosion inhibitor, oxygenant, non-ion fluorin surfactant, aromatic sulfonic acid oxidant compound, but the polishing speed of the polishing fluid in this patent to blocking layer is lower, and productive rate is lower.CN101012356A discloses a kind of blocked acidic layer polishing fluid, and this polishing fluid comprises oxygenant, the silica dioxide granule that part is covered by aluminium, inhibitor and complexing agent, but this acid polishing slurry exists the defect serious to copper corrosion.
Summary of the invention
The invention provides a kind of chemical mechanical polishing liquid being applied to blocking layer planarization, this polishing fluid comprises abrasive grains, corrosion inhibitor, copper surface protection agent, complexing agent, nonionogenic tenside and oxygenant.
Wherein abrasive grains can be this area and commonly uses abrasive grains, as the silicon-dioxide of silicon-dioxide, aluminium sesquioxide, cerium dioxide, adulterated al, and/or polymer beads etc.; The mass percent concentration of abrasive grains is preferably 1 ~ 20%, and better is 2 ~ 10%; The particle diameter of abrasive grains is preferably 20 ~ 150nm, and that better is 30 ~ 120nm.
Wherein corrosion inhibitor be preferably selected from following in one or more: benzotriazole, methyl benzotriazazole, 5-phenyl tetrazole, mercaptophenyl tetrazole, benzoglyoxaline, aphthotriazoles, and/or 2-Mercapto-benzothiazole.The mass percent concentration of described corrosion inhibitor is preferably 0.001 ~ 1%, and better is 0.01 ~ 0.5%.
Wherein copper surface protection agent be preferably selected from following in one or more: amino-1,2,4 triazoles of amino-1,2,4 triazoles of 5-aminotetrazole, 1,2,4-triazole, 3-, 4-, and/or 3,5-diaminostilbene, 2,4 triazoles.The mass percent concentration of described copper surface protection agent is preferably 0.001 ~ 1%, and better is 0.01 ~ 0.5%.
Its complexing agent be selected from organic acid, organic phosphoric acid and ammonia carboxylation compound one or more.Preferably be selected from following in one or more: acetic acid, propionic acid, oxalic acid, propanedioic acid, succinic acid, citric acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, Amino Trimethylene Phosphonic Acid, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, ethylene diamine tetra methylene phosphonic acid, and/or glycine.The concentration of the mass percent of described complexing agent is preferably 0.001 ~ 2%, and better is 0.01 ~ 1%.
Wherein nonionogenic tenside be preferably selected from following in one or more: C
10 ~ 18aliphatic alcohol polyethenoxy (n) ether (n=7 ~ 30), C
8 ~ 9alkylphenol-polyethenoxy (n) ether (n=8 ~ 200), C
12 ~ 18the TritonCF-10 of aliphatic amine polyoxyethylene (n) ether (n=10 ~ 60), Dow Chemical, the TritonCF-21 of Dow Chemical, the TritonDF-12 of Dow Chemical, the TritonDF-16 of Dow Chemical, and/or the TritonDF-18 of Dow Chemical.The mass percent concentration of described nonionogenic tenside is preferably: 0.001 ~ 0.5%, and better is 0.01 ~ 0.2%.
Wherein oxygenant be preferably selected from following in one or more: hydrogen peroxide, Peracetic Acid, Potassium Persulphate, and/or ammonium persulphate.The mass percent concentration of described oxygenant is preferably 0.01 ~ 5%, and better is 0.1 ~ 2%.
Wherein the pH value of chemical mechanical polishing liquid is 8.0 ~ 12.0, and better is 9.0 ~ 11.0.
Chemical mechanical polishing liquid of the present invention can also comprise other this area additives such as pH adjusting agent and sterilant.
Chemical mechanical polishing liquid of the present invention can be prepared as follows: mix in proportion, other components except oxygenant by pH adjusting agent (as KOH or HNO
3) be adjusted to required pH value, use front oxidizer, mix.
Agents useful for same of the present invention and raw material are all commercially.
Positive progressive effect of the present invention is:
Use polishing fluid of the present invention, the polishing speed on high blocking layer (TaN/Ta) can be reached, and meet in barrier polishing technique the removal speed of silicon-dioxide (Teos), copper and ultra-low dielectric materials (ULK) and the requirement of removing rate selection ratio, and have very strong rectification ability to the defect of semiconductor device surface, pollutent is residual few, the polishing fluid that stability is high.The present invention, by combinationally using corrosion inhibitor and copper surface protection agent, solves chip when polishing machine platform is out of order in polishing process and produces the problem of corrosion
Accompanying drawing explanation
Fig. 1 is that the SEM of the surface topography of Semtech854 graphics test wafer after adopting the polishing of contrast polishing fluid 2 schemes;
Fig. 2 is that the SEM of the surface topography of Semtech854 graphics test wafer after adopting polishing fluid 1 polishing schemes;
Fig. 3 is the SEM figure adopting contrast polishing fluid 2 to flood the surface topography of Semtech854 graphics test wafer after 30 minutes;
Fig. 4 is the SEM figure adopting polishing fluid 1 to flood the surface topography of Semtech854 graphics test wafer after 30 minutes.
Embodiment
Set forth advantage of the present invention further below by specific embodiment, but protection scope of the present invention is not only confined to following embodiment.
Table 1 gives contrast polishing fluid 1 ~ 4 of the present invention and polishing fluid of the present invention 1 ~ 15, by the formula given in table, other components except oxygenant is mixed, is adjusted to required pH value with KOH or HNO3.Use front oxidizer, mix.Water is surplus.
Table 1 contrasts polishing fluid 1 ~ 4 and polishing fluid of the present invention 1 ~ 15
Effect example 1
Contrast polishing fluid 1 ~ 4 and polishing fluid of the present invention 1 ~ 9 is adopted to carry out polishing according to following condition to copper (Cu), tantalum (Ta), silicon-dioxide (TEOS) and ultra-low dielectric materials (ULK).Polishing condition: polishing machine platform is 8 ' ' Mirra board, polishing pad is Fujibo pad, and overdraft is 1.5psi, and rotating speed is polishing disk/rubbing head=93/87rpm, and polishing fluid flow velocity is 150ml/min, and polishing time is 1min.
Table 2 contrasts polishing fluid 1 ~ 4 and polishing fluid of the present invention 1 ~ 9 pair of copper (Cu), tantalum (Ta), silicon-dioxide (TEOS) and the removal speed of ultra-low dielectric materials (ULK) and the static etch rate of copper (Cu)
From table 2, compared with contrast polishing fluid 1, polishing fluid of the present invention can obtain the removal speed of higher blocking layer Ta and silicon-dioxide (TEOS), obtain the removal speed of lower ultra-low dielectric materials ULK simultaneously, in polishing process, the surface of ultra-low dielectric materials ULK can be stopped at preferably.As can be seen from the polish results of contrast polishing fluid 1 ~ 4; the use of corrosion inhibitor reduces the erosion rate of copper; but the extra-inhibitory polishing speed of copper; even if regulate the consumption of corrosion inhibitor can not regulate the polishing speed of copper; and add copper surface protection agent; effectively the polishing speed of copper can be adjusted to suitable level, also protect the surface of copper simultaneously well.
Effect example 2
Contrast polishing fluid 1 ~ 2 and polishing fluid of the present invention 1 ~ 3 is adopted to carry out polishing according to following condition to Semtech854 graphics test wafer.Polishing condition: polishing machine platform is 8 ' ' Mirra board, polishing pad is Fujibo pad, and overdraft is 1.5psi, and rotating speed is polishing disk/rubbing head=93/87rpm, and polishing fluid flow velocity is 150ml/min, and polishing time is 1min.
Table 3 contrasts polishing fluid 1 ~ 2 and polishing fluid of the present invention 1 ~ 3 contrasts the rectification ability after the figuratum copper wafer polishing of band
Wherein, the butterfly before Dishing refers to barrier polishing in table 3 on metal gasket caves in (dust), and Erosion refers to the erosion (dust) of blocking layer in fine line region (50%line),
refer to the rectification ability value after polishing.
As can be seen from Table 3, contrast polishing fluid 2 due to the polishing speed of copper too low, and then correct excessively, create the protrusion phenomenon of copper, and compared with contrast polishing fluid, polishing fluid of the present invention can revise the saucerization and erosion that future produces on wafer preferably, obtain good wafer pattern.
Effect example 3
Adopt contrast polishing fluid 2 and polishing fluid 1? according to following condition, polishing is carried out to Semtech854 graphics test wafer.Polishing condition: polishing machine platform is 8 ' ' Mirra board, polishing pad is Fujibo pad, and overdraft is 1.5psi, and rotating speed is polishing disk/rubbing head=93/87rpm, and polishing fluid flow velocity is 150ml/min, and polishing time is 1min.
After Fig. 1 and Fig. 2 adopts contrast polishing fluid 2 and polishing fluid 1 polishing respectively, the SEM of the surface topography of Semtech854 graphics test wafer schemes.Fig. 3 and Fig. 4 adopts contrast polishing fluid 2 and polishing fluid 1 to flood the SEM figure of the surface topography of Semtech854 graphics test wafer after 30 minutes respectively.Contrast can be found out; polishing fluid of the present invention adopts the combination of corrosion inhibitor and copper surface protection agent effectively to inhibit metallic corrosion; particularly there is good protection to copper cash region; pattern piece is after polishing fluid polishing of the present invention and after dipping; surface is still clear sharp keen; do not find metallic corrosion phenomenon, and non-polluting particle remains.
Should be understood that, wt% of the present invention all refers to mass percentage.
Be described in detail specific embodiments of the invention above, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and substituting also all among category of the present invention.Therefore, equalization conversion done without departing from the spirit and scope of the invention and amendment, all should contain within the scope of the invention.
Claims (24)
1., for a chemical mechanical polishing liquid for blocking layer planarization, this polishing fluid comprises abrasive grains, corrosion inhibitor, copper surface protection agent, complexing agent, nonionogenic tenside and oxygenant.
2. chemical mechanical polishing liquid as claimed in claim 1, is characterized in that, described abrasive grains be selected from silicon-dioxide, aluminium sesquioxide, cerium dioxide, the silicon-dioxide of adulterated al and polymer beads one or more.
3. chemical mechanical polishing liquid as claimed in claim 1, it is characterized in that, the concentration of described abrasive grains is mass percent concentration 1 ~ 20%.
4. chemical mechanical polishing liquid as claimed in claim 3, it is characterized in that, the concentration of described abrasive grains is mass percent concentration 2 ~ 10%.
5. chemical mechanical polishing liquid as claimed in claim 1, it is characterized in that, described abrasive grains particle diameter is 20 ~ 150nm.
6. chemical mechanical polishing liquid as claimed in claim 5, it is characterized in that, described abrasive grains particle diameter is 30 ~ 120nm.
7. chemical mechanical polishing liquid as claimed in claim 1, it is characterized in that, described corrosion inhibitor be selected from following in one or more: benzotriazole, methyl benzotriazazole, 5-phenyl tetrazole, mercaptophenyl tetrazole, benzoglyoxaline, aphthotriazoles, and/or 2-Mercapto-benzothiazole.
8. chemical mechanical polishing liquid as claimed in claim 1, it is characterized in that, the concentration of described corrosion inhibitor is mass percent 0.001 ~ 1%.
9. chemical mechanical polishing liquid as claimed in claim 8, it is characterized in that, the concentration of described corrosion inhibitor is mass percent 0.01 ~ 0.5%.
10. chemical mechanical polishing liquid as claimed in claim 1, is characterized in that, described copper surface protection agent be selected from following in one or more: 5-aminotetrazole, 1; 2; amino-1,2,4 triazoles of 4-triazole, 3-, 4-amino-1; 2; 4 triazoles, and/or 3,5-diaminostilbene; 2,4 triazoles.
11. chemical mechanical polishing liquids as claimed in claim 1, is characterized in that, the concentration of described copper surface protection agent is mass percent 0.001 ~ 1%.
12. chemical mechanical polishing liquids as claimed in claim 11, is characterized in that, the concentration of described copper surface protection agent is mass percent 0.01 ~ 0.5%.
13. chemical mechanical polishing liquids as claimed in claim 1, is characterized in that, described complexing agent be selected from organic acid, organic phosphoric acid and ammonia carboxylation compound one or more.
14. chemical mechanical polishing liquids as claimed in claim 13, it is characterized in that, described complexing agent be selected from following in one or more: acetic acid, propionic acid, oxalic acid, propanedioic acid, succinic acid, citric acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, Amino Trimethylene Phosphonic Acid, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, ethylene diamine tetra methylene phosphonic acid, and/or glycine.
15. chemical mechanical polishing liquids as claimed in claim 1, is characterized in that, the concentration of described complexing agent is mass percent 0.001 ~ 2%.
16. chemical mechanical polishing liquids as claimed in claim 15, is characterized in that, the concentration of described complexing agent is mass percent 0.01 ~ 1%.
17. chemical mechanical polishing liquids as claimed in claim 1, is characterized in that, described nonionogenic tenside be selected from following in one or more: C
10~
18aliphatic alcohol polyethenoxy (n) ether (n=7 ~ 30), C
8 ~ 9alkylphenol-polyethenoxy (n) ether (n=8 ~ 200), C
12 ~ 18aliphatic amine polyoxyethylene (n) ether (n=10 ~ 60), TritonCF-10, TritonCF-21, TritonDF-12, TritonDF-16, and/or TritonDF-18.
18. chemical mechanical polishing liquids as claimed in claim 1, is characterized in that, the concentration of described nonionogenic tenside is mass percent 0.001 ~ 0.5%.
19. chemical mechanical polishing liquids as claimed in claim 18, is characterized in that, the concentration of described nonionogenic tenside is mass percent 0.01 ~ 0.2%.
20. chemical mechanical polishing liquids as claimed in claim 1, is characterized in that, described oxygenant be selected from following in one or more: hydrogen peroxide, Peracetic Acid, Potassium Persulphate, and/or ammonium persulphate.
21. chemical mechanical polishing liquids as claimed in claim 1, is characterized in that, the concentration of described oxygenant is mass percent 0.01 ~ 5%.
22. chemical mechanical polishing liquids as claimed in claim 21, is characterized in that, the concentration of described oxygenant is mass percent 0.1 ~ 2%.
23. chemical mechanical polishing liquids as claimed in claim 1, is characterized in that, the pH value of described chemical mechanical polishing liquid is 8.0 ~ 12.0.
24. chemical mechanical polishing liquids as claimed in claim 23, is characterized in that, the pH value of described chemical mechanical polishing liquid is 9.0 ~ 11.0.
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