CN104745088B - A kind of chemical mechanical polishing liquid and its application method for barrier layer planarization - Google Patents
A kind of chemical mechanical polishing liquid and its application method for barrier layer planarization Download PDFInfo
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- CN104745088B CN104745088B CN201310727947.8A CN201310727947A CN104745088B CN 104745088 B CN104745088 B CN 104745088B CN 201310727947 A CN201310727947 A CN 201310727947A CN 104745088 B CN104745088 B CN 104745088B
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- chemical mechanical
- mechanical polishing
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- 238000005498 polishing Methods 0.000 title claims abstract description 108
- 239000000126 substance Substances 0.000 title claims abstract description 28
- 239000007788 liquid Substances 0.000 title claims abstract description 26
- 230000004888 barrier function Effects 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title description 15
- 239000010949 copper Substances 0.000 claims abstract description 28
- 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 25
- 230000007797 corrosion Effects 0.000 claims abstract description 19
- 238000005260 corrosion Methods 0.000 claims abstract description 19
- 239000003112 inhibitor Substances 0.000 claims abstract description 14
- 239000007800 oxidant agent Substances 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 239000006061 abrasive grain Substances 0.000 claims abstract description 11
- 239000008139 complexing agent Substances 0.000 claims abstract description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 9
- 239000011814 protection agent Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012530 fluid Substances 0.000 claims description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-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
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 4
- -1 4- amino, 3, 5- diaminostilbene Chemical compound 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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 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
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical class OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 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
- 229940120146 EDTMP Drugs 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
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 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
- 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
- 150000007524 organic acids Chemical group 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
- 150000003852 triazoles Chemical class 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims 2
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims 1
- 150000001413 amino acids Chemical class 0.000 claims 1
- 230000021523 carboxylation Effects 0.000 claims 1
- 238000006473 carboxylation reaction Methods 0.000 claims 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims 1
- 238000012937 correction Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- 239000003989 dielectric material Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 230000003628 erosive effect Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000012876 topography Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000007517 polishing process Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-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
- 239000003513 alkali Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 230000003071 parasitic effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012545 processing Methods 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
- FMCUPJKTGNBGEC-UHFFFAOYSA-N 1,2,4-triazol-4-amine Chemical class NN1C=NN=C1 FMCUPJKTGNBGEC-UHFFFAOYSA-N 0.000 description 1
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical class NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 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
- 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 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
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000009466 transformation 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
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
The invention discloses a kind of chemical mechanical polishing liquid for barrier layer planarization, which contains abrasive grains, corrosion inhibitor, copper surface protection agent, complexing agent, polyvinylpyrrolidone, oxidant and water.Chemical mechanical polishing liquid of the invention requires the polishing speed and selection ratio of a variety of materials during can satisfy barrier polishing, there is very strong correction ability to the defect of semiconductor device surface, fast implement planarization, and the part generated during medal polish and general corrosion can be prevented, working efficiency is improved, production cost is reduced.
Description
Technical field
The present invention relates to a kind of chemical mechanical polishing liquids and its application method for barrier layer planarization.
Background technique
In integrated circuit fabrication, the standard of interconnection technique is improving, increase and technology characteristics ruler with the interconnection number of plies
Very little diminution, the requirement to silicon chip surface flatness is also higher and higher, if the ability not planarized, on a semiconductor wafer
Creation is complicated and intensive structure be it is very limited, cmp method CMP is exactly that entire silicon wafer planarization can be achieved
Most efficient method.
CMP process is exactly using a kind of mixture containing abrasive material and polishing pad polishing integrated circuit surface.Typically changing
It learns in mechanical polishing method, substrate is directly contacted with rotating polishing pad, apply pressure in substrate back with a loads.It is throwing
Between photophase, gasket and station rotation, while the power to keep down in substrate back, abrasive material and chemical activity solution is (usual
Referred to as polishing fluid or polishing slurries) it is applied on gasket, which occurs chemical reaction with the film polished and starts to carry out
Polishing process.
As integrated circuit technique develops to sub-micro (32,28nm) direction, caused by reducing because of characteristic size
The further serious performance for affecting circuit of parasitic capacitance must just use ultra-low dielectric materials (ULK) to reduce this influence
The parasitic capacitance between adjacent wires is reduced, at present relatively mostly using ultra-low dielectric materials is Coral, is removed during CMP
It wants strict control surface contaminant index and prevents outside metal erosion, also there is lower butterfly to be recessed and polish uniform
Property, which just can guarantee, to be needed in the planarization process on relatively reliable electrical property, especially barrier layer in shorter time and lower
Barrier metal is quickly removed under pressure, cover oxide and can stop at ultra-low dielectric materials surface well, forms interconnection
Line, and it is insensitive to small size figure.This just proposes higher challenge to CMP, because usually ultra-low dielectric materials are ginseng
The silica of miscellaneous carbon has similar superficiality with silica, to control the residual thickness of stop-layer it is necessary to there is very strong choosing
The ability of regulation and control of ratio is selected, also there are the features such as very high stability and easy cleaning.This patent is intended to provide one kind and is suitable for ULK-
Barrier polishing solution in copper-connection processing procedure has high barrier removal rates and ultralow dielectric material under the conditions of relatively mild
Expect the technique stop performance at interface, and butterfly recess, metal erosion and surface contaminant index can be controlled well.
CN1400266 discloses a kind of alkali barrier polishing fluid, which includes abrasive silica, amine chemical combination
Object and nonionic surfactant, but the polishing fluid in the patent can generate corrosion to copper.CN101372089A discloses one
Kind alkali barrier polishing fluid, the polishing fluid include abrasive silica, and corrosion inhibitor, oxidant, non-ion fluorin surface is lived
Property agent, aromatic sulfonic acid oxidant compound, but the polishing fluid in the patent is lower to the polishing speed on barrier layer, yield compared with
It is low.CN101012356A discloses a kind of blocked acidic layer polishing fluid, which includes oxidant, two partially covered by aluminium
Silicon oxide particle, inhibitor and complexing agent, but the acid polishing slurry exists to the serious defect of copper corrosion.
Summary of the invention
The problem to be solved by the invention is to provide a kind of barrier polishings being suitable in ULK- copper-connection processing procedure, have
The polishing speed on high barrier layer (TaN/Ta), and meet in barrier polishing technique to silica (Teos), copper and ultralow
The requirement of removal rate and removal rate the selection ratio of dielectric material (ULK), and have to the defect of semiconductor device surface very strong
Correction ability, pollutant residual is few, the high polishing fluid of stability.By the way that corrosion inhibitor and copper surface protection is applied in combination
Agent solves the problems, such as that chip generates corrosion when polishing machine platform is out of order during the polishing process.
The present invention provides a kind of chemical mechanical polishing liquid applied to barrier layer planarization, which includes grinding
Grain, corrosion inhibitor, copper surface protection agent, complexing agent, polyvinylpyrrolidone, oxidant and water.
Wherein abrasive grains can be abrasive grains commonly used in the art, such as silica, aluminum oxide, ceria, mix
Silica and/or polymer beads of miscellaneous aluminium etc.；The mass percent concentration of abrasive grains is preferably 1~20%, more preferably
It is 2~10%；The partial size of abrasive grains is preferably 20~150nm, more preferably 30~120nm.
Wherein corrosion inhibitor is preferably selected from one of the following or a variety of: benzotriazole, methyl benzotriazazole,
5- phenyl tetrazole, mercaptophenyl tetrazole, benzimidazole, aphthotriazoles and/or 2- Mercapto-benzothiazole.Corrosion inhibitor
Mass percent concentration be preferably 0.001~1%, more preferably 0.01~0.5%.
Wherein copper surface protection agent is preferably selected from one of the following or a variety of: 5- aminotetrazole, tri- nitrogen of 1,2,4-
Azoles, 3- amino -1,2,4 triazoles, 4- amino -1,2,4 triazoles and/or 3,5- diaminostilbene, 2,4 triazoles.Copper surface is protected
The mass percent concentration for protecting agent is preferably 0.001~1%, and more preferably 0.01~0.5%.
Wherein complexing agent is one of organic acid, organic phosphoric acid and ammonia carboxylic compound or a variety of.Preferably selected from following
One of or it is a variety of: acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, citric acid, 2- phosphonobutane -1,2,4- tricarboxylic acids, ammonia
Three methylenephosphonic acid of base, 1-hydroxy ethylidene-1,1-diphosphonic acid, ethylene diamine tetra methylene phosphonic acid and/or glycine.The mass percent of complexing agent
Concentration is preferably 0.001~2%, and more preferably 0.01~1%.
Wherein the molecular weight of polyvinylpyrrolidone is preferably 1000~1000000, and more preferably 1000~500000.
The mass percent concentration of polyvinylpyrrolidone is preferably: 0.001~2.0%, more preferably 0.01~1.0%.
Wherein oxidant is preferably selected from one of the following or a variety of: hydrogen peroxide, Peracetic acid, potassium peroxydisulfate, and/
Or ammonium persulfate.The mass percent concentration of oxidant is preferably 0.01~5%, and more preferably 0.1~2%.
Wherein the pH value of chemical mechanical polishing liquid is 8.0~12.0, more preferably 9.0~11.0.
Chemical mechanical polishing liquid of the invention can also include other this field additives such as pH adjusting agent and fungicide.
In polishing fluid of the invention, in addition to the above components, surplus is water.
Chemical mechanical polishing liquid of the invention can be prepared as follows: in proportion by the other components in addition to oxidant
It is uniformly mixed, with pH adjusting agent (such as KOH or HNO3) adjust and arrive required pH value, using preceding oxidizer, it is uniformly mixed i.e.
It can.
Agents useful for same and raw material of the present invention are commercially available.
The positive effect of the present invention is that: the application by the way that corrosion inhibitor and copper surface protection agent is applied in combination,
Solve the problems, such as that chip generates corrosion when polishing machine platform is out of order during the polishing process.
Detailed description of the invention
Fig. 1 is the SEM figure of the surface topography of Semtech854 graphics test wafer after being polished using comparison polishing fluid 2；
Fig. 2 is that the SEM of the surface topography of Semtech854 graphics test wafer after being polished using polishing fluid 1 is schemed；
Fig. 3 is the SEM of the surface topography of Semtech854 graphics test wafer after being impregnated 30 minutes using comparison polishing fluid 2
Figure；
Fig. 4 is that the SEM of the surface topography of Semtech854 graphics test wafer after being impregnated 30 minutes using polishing fluid 1 is schemed.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but the reality is not limited the present invention to this
It applies among a range.
Embodiment
Table 1 gives comparison polishing fluid 1~4 and polishing fluid 1~13 of the invention, by formula given in table, by deoxygenation
Other components other than agent are uniformly mixed, with KOH or HNO3Adjust required pH value.Use preceding oxidizer, mixing
Uniformly.Water is surplus.
Table 1 compares polishing fluid 1~4 and polishing fluid 1~13 of the invention
Effect example 1
Using comparison polishing fluid 1~4 and polishing fluid 1~9 of the invention according to following conditions to copper (Cu), tantalum (Ta), two
Silica (TEOS) and ultra-low dielectric materials (ULK) are polished.Polishing condition: polishing machine platform 8 ' ' Mirra board, polishing
Pad is Fujibo pad, and lower pressure is 1.5psi, and revolving speed is polishing disk/rubbing head=93/87rpm, and polishing flow velocity is 150ml/
Min, polishing time 1min.
Table 2 compares polishing fluid 1~4 and 1~9 pair of copper (Cu) of polishing fluid of the present invention, tantalum (Ta), silica (TEOS) and surpasses
Dielectric materials (ULK)
The static etch rate of removal rate and copper (Cu)
As can be seen from Table 2, polishing fluid of the invention can obtain higher barrier layer Ta and two compared with comparing polishing fluid 1
The removal rate of silica (TEOS), while the removal rate of lower ultra-low dielectric materials ULK is obtained, it can be during the polishing process
Preferably stop at the surface of ultra-low dielectric materials ULK.Corrode it can be seen from the polish results of comparison polishing fluid 1~4 and inhibits
The use of agent reduces the corrosion rate of copper, but the extra-inhibitory polishing speed of copper, even if adjust the use of corrosion inhibitor
Amount can not adjust the polishing speed of copper, and joined copper surfactant, can effectively be adjusted to the polishing speed of copper
Level appropriate, while the surface of copper is also protected well.
Effect example 2
Semtech854 figure is surveyed according to following conditions using comparison polishing fluid 1~2 and polishing fluid 1~3 of the invention
Examination wafer is polished.Polishing condition: polishing machine platform 8 ' ' Mirra board, polishing pad are Fujibo pad, and lower pressure is
1.5psi, revolving speed are polishing disk/rubbing head=93/87rpm, and polishing flow velocity is 150ml/min, polishing time 1min.
Table 3 compares polishing fluid 1~2 and rectifying after 1~3 pair of Semtech854 graphics test polishing wafer of polishing fluid of the present invention
Positive ability comparison
Wherein, Dishing refers to the butterfly recess (angstrom) before barrier polishing on metal gasket in upper table, and Erosion is
Refer to erosion (angstrom) of the barrier layer on fine line region (50%line),Correction ability value after referring to polishing.
As can be seen from Table 3, polishing fluid 2 is compared since the polishing speed of copper is too low, and then is corrected excessively, and copper is produced
Protrusion phenomenon, and compared with comparing polishing fluid, polishing fluid of the invention can preferably correct the dish that future generates on wafer
Recess and erosion, obtain preferable wafer pattern.
Effect example 3
Semtech854 graphics test wafer is polished according to following conditions using comparison polishing fluid 2 and polishing fluid 1.
Polishing condition: polishing machine platform 8 ' ' Mirra board, polishing pad are Fujibo pad, and lower pressure is 1.5psi, and revolving speed is polishing
Disk/rubbing head=93/87rpm, polishing flow velocity are 150ml/min, polishing time 1min.
The table of Semtech854 graphics test wafer after comparison polishing fluid 2 and the polishing of polishing fluid 1 is respectively adopted in Fig. 1 and Fig. 2
The SEM of face pattern schemes.
Fig. 3 and Fig. 4 is respectively adopted comparison polishing fluid 2 and polishing fluid 1 impregnate 30 minutes after Semtech854 graphics test it is brilliant
The SEM of round surface topography schemes.
Polishing fluid of the invention uses the combination of corrosion inhibitor and copper surface protection agent it can be seen from the comparison of Fig. 1~4
Metal erosion is effectively inhibited, especially has good protection to copper wire region, pattern piece is thrown by polishing fluid of the invention
After light and after dipping, surface is still clear sharp keen, does not find metal erosion phenomenon, and non-polluting particle remains.
It should be understood that wt% of the present invention refers to mass percentage.
Specific embodiments of the present invention are described in detail above, but it is merely an example, the present invention is simultaneously unlimited
It is formed on particular embodiments described above.To those skilled in the art, any couple of present invention carries out equivalent modifications and
Substitution is also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by equal transformation and
Modification, all should be contained within the scope of the invention.
Claims (16)
1. a kind of chemical mechanical polishing liquid for barrier layer planarization, the polishing fluid contain abrasive grains, corrosion inhibitor, copper
Surface protectant, complexing agent, polyvinylpyrrolidone, oxidant and water, wherein the copper surface protection agent is in following
It is one or more: 5- aminotetrazole, 1,2,4- triazole, -1,2,4 triazole of 3- amino, -1,2,4 triazole of 4- amino, 3,
5- diaminostilbene, 2,4 triazoles, the corrosion inhibitor are selected from one of the following or a variety of: benzotriazole, methyl benzo
Triazole, 5- phenyl tetrazole, mercaptophenyl tetrazole, benzimidazole, aphthotriazoles, 2- Mercapto-benzothiazole, the chemistry
The pH value of machine polishing liquor is 8.0~12.0, and the concentration of the abrasive grains is mass percent concentration 1~20%, the corruption
The concentration of corrosion inhibitor is mass percent 0.001~1%, and the concentration of the copper surface protection agent is mass percent 0.001
~1%, the concentration of the complexing agent is mass percent 0.001~2%, and the concentration of the polyvinylpyrrolidone is quality hundred
Divide ratio 0.001~2.0%, the concentration of the oxidant is mass percent 0.01~5%.
2. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the abrasive grains are selected from silica, three
One of Al 2 O, ceria, the silica of adulterated al and polymer beads are a variety of.
3. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the concentration of the abrasive grains is quality percentage
Specific concentration 2~10%.
4. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the abrasive grains partial size is 20~150nm.
5. chemical mechanical polishing liquid as claimed in claim 4, which is characterized in that the abrasive grains partial size is 30~120nm.
6. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the concentration of the corrosion inhibitor is quality hundred
Divide ratio 0.01~0.5%.
7. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the concentration of the copper surface protection agent is quality
Percentage 0.01~0.5%.
8. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the complexing agent is selected from organic acid and ammonia carboxylation
Close one of object or a variety of.
9. chemical mechanical polishing liquid as claimed in claim 8, which is characterized in that the complexing agent be selected from one of the following or
It is a variety of: acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, citric acid, 2- phosphonobutane -1,2,4- tricarboxylic acids, three methene phosphine of amino
Acid, 1-hydroxy ethylidene-1,1-diphosphonic acid, ethylene diamine tetra methylene phosphonic acid, glycine.
10. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the concentration of the complexing agent is quality percentage
Than 0.01~1%.
11. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the molecular weight of the polyvinylpyrrolidone
It is 1000~1000000.
12. chemical mechanical polishing liquid as claimed in claim 11, which is characterized in that the molecular weight of the polyvinylpyrrolidone
It is 1000~500000.
13. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the concentration of the polyvinylpyrrolidone is
Mass percent 0.01~1.0%.
14. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the oxidant is selected from one of the following
It is or a variety of: hydrogen peroxide, Peracetic acid, potassium peroxydisulfate, ammonium persulfate.
15. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the concentration of the oxidant is quality percentage
Than 0.1~2%.
16. chemical mechanical polishing liquid as described in claim 1, which is characterized in that the pH value of the chemical mechanical polishing liquid is
9.0~11.0.
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| CN108250973A (en) * | 2016-12-28 | 2018-07-06 | 安集微电子科技（上海）股份有限公司 | A kind of chemical mechanical polishing liquid for barrier layer planarization |
| CN109943237A (en) * | 2019-04-16 | 2019-06-28 | 江苏艾佳达新材料有限公司 | A kind of polishing fluid |
| CN110205034A (en) * | 2019-06-24 | 2019-09-06 | 苏州大学 | Gallium nitride chemical mechanical polishing liquid and preparation method thereof |
| CN114591686B (en) * | 2022-03-11 | 2023-05-26 | 万华化学集团电子材料有限公司 | Copper barrier layer chemical mechanical polishing solution and application thereof |
| CN115058712B (en) * | 2022-03-21 | 2024-02-27 | 万华化学集团电子材料有限公司 | Copper barrier layer chemical mechanical polishing composition and application thereof |
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|---|---|---|---|---|
| TW200802578A (en) * | 2006-04-14 | 2008-01-01 | Fujifilm Corp | Chemical mechanical polishing method |
| CN101358109A (en) * | 2007-08-03 | 2009-02-04 | 罗门哈斯电子材料Cmp控股股份有限公司 | Polymeric barrier removal polishing slurry |
| CN101407699A (en) * | 2007-10-12 | 2009-04-15 | 安集微电子（上海）有限公司 | Polishing solution for polishing low dielectric material |
| CN103965788A (en) * | 2013-01-24 | 2014-08-06 | 安集微电子（上海）有限公司 | Alkaline polishing solution and polishing method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200802578A (en) * | 2006-04-14 | 2008-01-01 | Fujifilm Corp | Chemical mechanical polishing method |
| CN101358109A (en) * | 2007-08-03 | 2009-02-04 | 罗门哈斯电子材料Cmp控股股份有限公司 | Polymeric barrier removal polishing slurry |
| CN101407699A (en) * | 2007-10-12 | 2009-04-15 | 安集微电子（上海）有限公司 | Polishing solution for polishing low dielectric material |
| CN103965788A (en) * | 2013-01-24 | 2014-08-06 | 安集微电子（上海）有限公司 | Alkaline polishing solution and polishing method |
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