WO2007009366A1 - Composition de polissage chimique et mecanique et ses utilisations - Google Patents
Composition de polissage chimique et mecanique et ses utilisations Download PDFInfo
- Publication number
- WO2007009366A1 WO2007009366A1 PCT/CN2006/001703 CN2006001703W WO2007009366A1 WO 2007009366 A1 WO2007009366 A1 WO 2007009366A1 CN 2006001703 W CN2006001703 W CN 2006001703W WO 2007009366 A1 WO2007009366 A1 WO 2007009366A1
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- WO
- WIPO (PCT)
- Prior art keywords
- mechanical polishing
- chemical mechanical
- polishing liquid
- metal
- liquid according
- 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 59
- 239000000203 mixture Substances 0.000 title abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 41
- 239000003112 inhibitor Substances 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims description 53
- 230000007797 corrosion Effects 0.000 claims description 21
- 238000005260 corrosion Methods 0.000 claims description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- -1 inorganic acid salt Chemical class 0.000 claims description 11
- 239000007800 oxidant agent Substances 0.000 claims description 9
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 7
- 239000011609 ammonium molybdate Substances 0.000 claims description 7
- 229940010552 ammonium molybdate Drugs 0.000 claims description 7
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000008139 complexing agent Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical group [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 239000011964 heteropoly acid Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 235000010755 mineral Nutrition 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 7
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000012964 benzotriazole Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 5
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- VYTBPJNGNGMRFH-UHFFFAOYSA-N acetic acid;azane Chemical compound N.N.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O VYTBPJNGNGMRFH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229940024548 aluminum oxide Drugs 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N hydroxylamine group Chemical group NO AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- CMDGQTVYVAKDNA-UHFFFAOYSA-N propane-1,2,3-triol;hydrate Chemical compound O.OCC(O)CO CMDGQTVYVAKDNA-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-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
- H01L21/3205—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]
Definitions
- the invention relates to a chemical mechanical polishing liquid and its use.
- BACKGROUND OF THE INVENTION With the development of microelectronic technology, the integration of very large integrated circuit chips has reached several billion components, and the feature size has entered the nanometer level, which requires nearly one hundred processes in the microelectronic process, especially multilayer wiring. , the substrate, the medium must be chemically mechanically planarized, and chemical mechanical polishing
- the polished surface of the substrate is directly in contact with the rotating polishing pad while applying pressure on the back surface of the substrate.
- the polishing pad rotates with the stage while maintaining a downward force on the back side of the substrate, and a liquid composed of an abrasive and a chemically active solution (commonly referred to as a chemical mechanical polishing liquid) is applied to the polishing pad.
- a liquid composed of an abrasive and a chemically active solution commonly referred to as a chemical mechanical polishing liquid
- the chemical reaction and mechanical action of the film being polished start the polishing process. Polishing paste is an important factor in CMP, and the polishing performance can be changed by selecting a suitable polishing slurry according to the needs of the process.
- the defect level is usually high, especially the problems of pitting, edge etching, corrosion, etc.
- the polishing rate is also high, and the damage to the metal surface is large, which is easy to produce scratches, such as scratches. , rough surface and other issues.
- the present invention is to solve the problems of corrosion and defects in the prior art, thereby improving the metal surface quality. It is an object of the present invention to provide a chemical mechanical polishing liquid.
- the object of the present invention is achieved by the following technical solution:
- the chemical mechanical polishing liquid of the present invention comprises at least one abrasive particle and a carrier; and further comprising at least one metal corrosion inhibitor.
- the metal corrosion inhibitor can react with the metal surface, and the reaction product covers the metal surface to form a protective film, which can prevent corrosion and pitting of the metal surface in an acidic environment. Therefore, the metal corrosion inhibitor can reduce the metal removal rate, reduce the defect rate, and improve the surface quality.
- the chemical mechanical polishing liquid of the present invention does not contain an oxidizing agent, and a typical chemical mechanical polishing liquid for polishing a metal contains an oxidizing agent.
- the polishing performance of the chemical mechanical polishing liquid containing no oxidizing agent of the present invention can also achieve the polishing performance of a typical chemical mechanical polishing liquid containing an oxidizing agent.
- the chemical mechanical polishing liquid of the present invention may also contain an oxidizing agent such as an adjustment for the polishing rate of a metal other than aluminum, such as copper.
- the metal corrosion inhibitor is preferably a mineral acid salt
- the inorganic acid salt may be an oxidizing and/or non-oxidizing inorganic acid salt
- the inorganic acid salt is preferably a molybdate, a chromate or a permanganic acid. Salts, silicates, tungstates and/or heteropolyacid salts, more preferably molybdates, said molybdates being ammonium molybdate.
- the metal corrosion inhibitor can form a protective film on the surface of the metal.
- the abrasive particles can be any abrasive particles of the prior art, preferably silica, alumina, ceria, titania and/or high molecular weight abrasive particles.
- the carrier is preferably an inorganic carrier such as water, or a mixture of an inorganic carrier and an organic carrier, such as a mixture of water and a polyol, preferably a glycerol.
- the mass concentration of the abrasive particles in the chemical mechanical polishing liquid of the present invention is preferably from 1 to 10%, the mass concentration of the metal corrosion inhibitor is preferably from 0.01 to 10%, and the carrier is the balance.
- the chemical mechanical polishing liquid of the present invention preferably includes one or more of a film forming agent, an oxidizing agent, a complexing agent and a pH adjusting agent, and may further include a surfactant to further enhance the surface of the polished substrate. quality.
- the mass concentration of the complexing agent is preferably 0.01 to 10%, the mass concentration of the oxidizing agent is preferably 0 to 10%, and the mass concentration of the surfactant is higher.
- the good land is 0.001 ⁇ 10 ⁇ / ⁇ .
- the film former is benzotriazole, pyrazole and/or imidazole, preferably benzotriazole.
- the complexing agent is preferably a compound containing a hydroxyl group, a carboxyl group, a sulfate group, a sulfonic acid group, a phosphoric acid group, a hydroxylamine group, an amine salt and/or an amine group, more preferably succinic acid, oxalic acid, citric acid or cyclohexane.
- the pH adjusting agent is preferably potassium hydroxide, ammonium hydroxide, sulfuric acid or nitric acid.
- the oxidizing agent is preferably hydrogen peroxide, iron nitrate, an organic peroxide and/or an inorganic peroxide.
- the surfactant is preferably a cationic, an anionic, a nonionic surfactant and/or a quinone molecular surfactant, more preferably a fatty alcohol polyoxyethylene ether, a polyvinyl alcohol, a polyoxyethylene alkylamine and/or an alkyl alcohol amide.
- Another object of the present invention is to provide the use of the chemical mechanical polishing liquid of the present invention in polishing a metal, wherein the metal is aluminum, copper, tantalum, tantalum nitride, titanium, titanium nitride, silver or gold, and the like. , preferably aluminum.
- the positive progress of the present invention is that the chemical mechanical polishing liquid of the present invention can suppress pitting corrosion and corrosion of metals, reduce metal removal rate, and improve metal surface quality.
- 1A is a bright field diagram of an optical microscope for pitting corrosion of an aluminum metal surface after polishing by the chemical mechanical polishing liquid of the present invention
- Fig. 1B is an optical microscope bright field diagram of pitting of an aluminum metal surface after polishing of a chemical mechanical polishing liquid without adding a metal corrosion inhibitor, wherein the black dots in the figure are pitting corrosion.
- Example 1 Chemical mechanical polishing liquid 1: 5 wt% silica particles, 0.1 wt% benzotriazole, 0.5% succinic acid, 0.01 wl% ammonium molybdate and others were water, pH 4.25.
- Example 2 'Chemical mechanical polishing liquid 2 5 wt% silica particles, 0.1 wt% benzotriazole, 0.5% succinic acid, 0.1 wt% ammonium molybdate, others water, pH 4.25.
- Chemical mechanical polishing liquid 3 5 wt% silica particles, 0.5% succinic acid, 0.5 wt% ammonium molybdate, other water, pH 4.25.
- Chemical mechanical polishing liquid 4 lwt% cerium oxide particles, 10wt% potassium permanganate, 10wt% peroxy hydrogen peroxide, 0.001wt% polyvinyl alcohol, 10wt% succinic acid, 5wt% glycerol, water for the balance , pH is 3.
- Chemical mechanical polishing liquid 5 10wt% alumina particles, lwt% sodium silicate, lwt% iron nitrate, 10wt% fatty alcohol polyoxyethylene ether, 0.1wt% ethylenediaminetetraacetic acid, water balance, pH Is 5.
- Chemical mechanical polishing liquid 7 5wt% silica particles, 1%% ammonium molybdate, water for the balance, pH 7.
- the above chemical mechanical polishing liquids 1 ', 1 to 3 were used to polish a metal aluminum film on a wafer.
- the parameters for polishing are: 2 psi downforce, 102 rpm for the polishing disc, 110 rpm for the polishing head, and 100 ml/min for the polishing slurry.
- the experimental results are shown in Table 1. Table 1
- Chemical mechanical polishing liquid 3 127 The results show that the chemical mechanical polishing liquid containing metal corrosion inhibitor of the invention can reduce the removal rate of aluminum, which is lower than 200 A/min ; the polished metal surface has no defects, thereby greatly improving the metal surface. quality. Effect Example 2
- the above chemical mechanical polishing liquids 1' and 1 were used to polish a metal aluminum film on a wafer.
- the parameters for polishing are the downforce: 2 psi, polishing disc speed: 102 rpm, polishing head speed: 110 rpm, polishing slurry flow rate: 100 ml/min.
- the experimental results are shown in Figures 1A and 1B.
- the experimental results show that the chemical mechanical polishing liquid polishing containing the metal corrosion inhibitor of the present invention is used.
- the surface of the aluminum metal behind the light is free of pitting (Fig. 1A), while the surface of the aluminum metal polished with a chemical mechanical polishing liquid containing no metal corrosion inhibitor has a large amount of pitting (Fig. 1B). Therefore, the use of the chemical mechanical polishing liquid containing the metal corrosion inhibitor of the present invention can greatly improve the surface quality of the aluminum metal.
- the above chemical mechanical polishing liquids 1 ', 1 to 3 were respectively polished with a pattern of a pattern composed of aluminum and silicon dioxide.
- the parameters for polishing were: 2 psi downforce, 102 rpm for the polishing disc, 110 rpm for the polishing head, and 100 ml/min for the polishing slurry.
- the experimental results are shown in Table 2.
- the above chemical mechanical polishing liquid 8 is subjected to polishing of a copper film on a wafer.
- the parameters for polishing are the lower pressure: 2 psi, the speed of the polishing disc: 102 rpm, the speed of the polishing head: 110 rpm, the flow rate of the polishing paddle: 100 ml/min.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (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)
- Mechanical Treatment Of Semiconductor (AREA)
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Description
化学机械抛光液及其用途 技术领域
本发明涉及一种化学机械抛光液及其用途。 背景技术 随着微电子技术的发展,甚大规模集成电路芯片集成度已高达几十亿个 元器件, 特征尺寸已进入纳米级, 这就要求微电子工艺中的近百道工艺, 尤 其是多层布线、 衬底、 介质必须进行化学机械全局平整化, 而化学机械抛光
(CMP) 已被证明是最好的平整化方法。
在化学机械抛光方法中, 将基底的被抛光表面直接与旋转抛光垫接触, 同时在基底背面施加压力。 在抛光期间, 抛光垫随操作台旋转, 同时在基底 背面保持向下的力, 将磨料和化学活性溶液组成的液体(通常称为化学机械 抛光液)涂布于抛光垫片上, 该抛光浆料与正在抛光的薄膜发生化学反应和 机械作用开始进行抛光过程。 抛光浆料在 CMP中是一种重要的因素, 而可 根据制程的需要来选取合适的抛光浆料的来改变抛光性能。
在典型的金属化学机械抛光中, 缺陷水平通常较高, 尤其是存在点蚀、 边蚀、 腐蚀等问题; 而且, 抛光速率也很高, 对金属表面的损伤程度较大, 易产生如划伤、 表面粗糙等问题。 如现有技术中的专利 US5209816、 US603989K US5897375, US6749488和 US6520840。 发明概要
本发明是为了解决现有技术中的腐蚀和缺陷问题,从而提高金属表面质
本发明的目的是提供一种化学机械抛光液。
本发明的目的是通过下列技术方案来实现的:本发明的化学机械抛光液 包括至少一种研磨颗粒和一种载体;其中,还包括至少一种金属腐蚀抑制剂。 所述的金属腐蚀抑制剂可以与金属表面发生反应,反应产物覆盖在金属表面 上形成一层保护膜,在酸性环境下该保护膜可以阻止金属表面发生腐蚀和点 蚀。 因此, 所述的金属腐蚀抑制剂可以降低金属除去速率, 降低缺陷率, 改 善表面质量。
本发明的化学机械抛光液不含有氧化剂,而典型的用于抛光金属的化学 机械抛光液中均含有氧化剂。但是本发明的不含有氧化剂的化学机械抛光液 的抛光性能也能达到典型的含有氧化剂的化学机械抛光液的抛光性能。 当 然, 本发明的化学机械抛光液也可以含有氧化剂, 如用于对除铝之外的其它 金属, 如铜的抛光速率的调节。
其中, 该金属腐蚀抑制剂较佳地为无机酸盐, 该无机酸盐可为氧化性和 /或非氧化性的无机酸盐, 该无机酸盐优选钼酸盐、铬酸盐、高锰酸盐、硅酸 盐、钨酸盐和 /或杂多酸盐, 更优选钼酸盐, 所述的钼酸盐较佳为钼酸铵。所 述的金属腐蚀抑制剂都可以在金属表面形成一层保护膜。
该研磨颗粒可为现有技术中的任何研磨颗粒, 较佳地为二氧化硅、氧化 铝、 二氧化铈、 二氧化钛和 /或高分子聚合物研磨颗粒。
该载体较佳地为无机载体, 如水, 也可以为无机载体和有机载体的混合 物, 如水和多元醇的混合物, 所述的多元醇较佳地为丙三醇。
本发明的化学机械抛光液中的研磨颗粒的质量浓度较佳地为 1〜10%、 金属腐蚀抑制剂的质量浓度较佳地为 0.01〜10%、 载体为余量。
本发明的化学机械抛光液较佳地包括成膜剂、 氧化剂、 络合剂和 pH调 节剂中的一种或几种, 也还可以包括表面活性剂, 以进一步提高抛光后的衬 底的表面质量。
在本发明的化学机械抛光液中, 所述的络合剂的质量浓度较佳地为 0.01〜10%、氧化剂的质量浓度较佳地为 0〜10%、表面活性剂的质量浓度较
佳地为 0.001〜10ο/ο。
所述的成膜剂为苯并三唑、 吡唑和 /或咪唑, 优选苯并三唑。
该络合剂较佳地为含羟基、 羧基、 硫酸基、 磺酸基、 磷酸基、 羟胺基、 胺盐和 /或胺基的化合物,更佳地为琥珀酸、草酸、柠檬酸、环己二胺四乙酸、 二乙三胺五乙酸、 乙二胺四乙酸和 /或丹宁酸。
所述的 ρΗ调节剂较佳地为氢氧化钾、 氢氧化氨、 硫酸或硝酸。
该氧化剂较佳地为过氧化氢、硝酸铁、有机过氧化物和 /或无机过氧化物。 该表面活性剂优选阳离子、阴离子、非离子表面活性剂和 /或髙分子表面 活性剂, 更优选脂肪醇聚氧乙烯醚、聚乙烯醇、聚氧乙烯烷基胺和 /或烷基醇 酰胺。
本发明的另一目的是提供本发明的化学机械抛光液在抛光金属中的用 途, 其中, 所述的金属为铝、 铜、 钽、 氮化钽、 钛、 氮化钛、 银或金等等, 优选铝。
本发明的积极进步效果在于:本发明的化学机械抛光液可以抑制金属的 点蚀和腐蚀, 降低金属除去速率, 改善金属表面质量。 附图说明 '
图 1A为经本发明的化学机械抛光液抛光后, 铝金属表面点蚀的光学显 微镜明场图;
图 1B为未添加金属腐蚀抑制剂的化学机械抛光液抛光后, 铝金属表面 点蚀的光学显微镜明场图, 其中, 图中的黑点为点蚀。 发明内容 下面给出本发明的较佳实施例, 以详细说明本发明的技术方案, 但并不 限制本发明。
实施例 1
化学机械抛光液 1 : 5wt%二氧化硅颗粒、 0.1wt%苯并三唑、 0.5\^%琥 珀酸、 0.01wl%钼酸铵和其它为水, pH为 4.25。
实施例 2 ' 化学机械抛光液 2: 5wt%二氧化硅颗粒、 0.1wt%苯并三唑、 0.5^%琥 珀酸、 0.1wt%钼酸铵、 其它为水, pH为 4.25。
实施例 3
化学机械抛光液 3: 5wt%二氧化硅颗粒、 0.5^%琥珀酸、 0.5wt%钼酸胺 铵、 其它为水, pH为 4.25。
实施例 4
化学机械抛光液 4: lwt%二氧化铈颗粒、 10wt%高锰酸钾、 10wt%过氧 · 化氢、 0.001wt%聚乙烯醇、 10wt%琥珀酸、 5wt%丙三醇、 水为余量, pH为 3。
实施例 5
化学机械抛光液 5: 10wt%氧化铝颗粒、 lwt%硅酸钠、 lwt%的硝酸铁、, 10wt%的脂肪醇聚氧乙烯醚、 0.1wt%乙二胺四乙酸、 水为余量, pH为 5。
实施例 6
化学机械抛光液 6: 2wt%=氧化钛颗粒、 5^%络酸钾、 0.5wt%过氧化 氢、 0.05wt%的烷基醇酰胺、 0.5wt%的柠檬酸、 10\^%丙三醇、 水为余量, pH为 6。
实施例 Ί
化学机械抛光液 7: 5wt%二氧化硅颗粒、 1^%钼酸铵、 水为余量, pH 为 7。
实施例 8
化学机械抛光液 8: 5wt%二氧化硅颗粒、 0.1wt%苯并三唑、 0.5%乙二 胺四乙酸、 0.1wt%钼酸铵、 lwt%过氧化氢、 其它为水, pH为 3。 对比实施例 1 化学机械抛光液 1 ' : 5wt%=氧化硅颗粒、 0.1wt%苯并三唑、 0.5wt% 琥珀酸和其它为水, pH为 4.25。 效果实施例 1
将上述化学机械抛光液 1 ' 、 1〜3用于抛光晶片上的金属铝薄膜。抛光 时的参数为: 下压力 2 psi、 抛光盘的转速 102 rpm、 抛光头转速 110 rpm、 抛光浆料流速 100 ml/min。 实验结果见表 1。 表 1
A1抛光速率 (A/min) ~
.化学机械抛光液 1 ' 362
化学机械抛光液 1 Π6
化学机械抛光液 2 152
化学机械抛光液 3 127 结果表明:本发明的含有金属腐蚀抑制剂的化学机械抛光液可以降低铝 的除去速率, 均低于 200A/min; 抛光后的金属表面无缺陷, 从而大大提高 了金属表面质量。 效果实施例 2 将上述化学机械抛光液 1 ' 和 1用于抛光晶片上的金属铝薄膜。 抛光时 的参数为下压力: 2 psi、 抛光盘的转速: 102 rpm、 抛光头转速: 110 rpm、 抛光浆料流速: 100 ml/min。 实验结果见图 1A和图 1B。 实验结果表明:使用本发明的含有金属腐蚀抑制剂的化学机械抛光液抛
光后的铝金属表面没有点蚀(图 1A), 而使用不含有金属腐蚀抑制剂的化学 机械抛光液抛光后的铝金属表面有大量的点蚀(图 1B)。 所以, 使用本发明 的含有金属腐蚀抑制剂的化学机械抛光液可以大大提高铝金属表面质量。
效果实施例 3
将上述化学机械抛光液 1 ' 、 1〜3分别抛光由铝和二氧化硅组成的图案 的晶片。 抛光时的参数为: 下压力 2 psi、 抛光盘的转速 102 rpm、 抛光头转 速 110 rpm、 抛光浆料流速 100 ml/min。 实验结果见表 2。
表 2
二氧化硅抛光 铝抛光速率 二氧化硅抛光速 速率 (A/min) (A/min) 率 /铝抛光速率 化学机械抛光液 1 ' 275 362 076 化学机械抛光液 1 269 , 176 1.53 化学机械抛光液 2 281 152 1.85 化学机械抛光液 3 302 127 2.36 实验结果表明: 本发明的化学机械抛光液不但可以抛光金属晶片, 而且 还可以抛光含有图案的晶片, 如铝、 铜或钽与二氧化硅组成的图案的晶片。 效果实施例 4
将上述化学机械抛光液 8进行抛光晶片上铜薄膜。抛光时的参数为下压 力: 2 psi、 抛光盘的转速: 102 rpm、 抛光头转速: 110 rpm、 抛光桨料流速: 100 ml/min。
以上实施例中所用到的原料国内均有销售。
Claims
1、 一种化学机械抛光液, 包括至少一种研磨颗粒和一种载体, 其特征 在于: 还包括至少一种金属腐蚀抑制剂。
2、 根据权利要求 1所述的化学机械抛光液, 其特征在于: 该金属腐蚀 抑制剂为无机酸盐。
3、 根据权利要求 2所述的化学机械抛光液, 其特征在于: 该无机酸盐 为氧化性和 /或非氧化性的无机酸盐。
4、 根据权利要求 2所述的化学机械抛光液, 其特征在于: 该无机酸盐 为钼酸盐、 铬酸盐、 高锰酸盐、 硅酸盐、 钨酸盐和 /或杂多酸盐。
5、 根据权利要求 4所述的化学机械抛光液, 其特征在于: 该钼酸盐为 钼酸铵。
6、根据权利要求 1所述的化学机械抛光液, 其特征在于: 该载体为水。
7、 根据权利要求 1所述的化学机械抛光液, 其特征在于: 该载体为水 和多元醇。
8、 根据权利要求 1所述的化学机械抛光液, 其特征在于: 研磨颗粒的 质量浓度为 1〜10%、 金属腐蚀抑制剂的质量浓度为 0.01〜10%、 载体为余
9、 根据权利要求 1所述的化学机械抛光液, 其特征在于: 还包括成膜 剂、 络合剂、 氧化剂和 pH调节剂中的一种或几种。
10、如权利要求 1所述的化学机械抛光液在抛光金属中的用途, 其特征 在于: 所述的金属为铝、 铜、 钜、 氮化钽、 钛、 氮化钛、 银或金。
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US20130045599A1 (en) * | 2011-08-15 | 2013-02-21 | Rohm and Electronic Materials CMP Holdings, Inc. | Method for chemical mechanical polishing copper |
CN104745084B (zh) * | 2013-12-25 | 2018-09-14 | 安集微电子(上海)有限公司 | 一种用于铝的化学机械抛光液及使用方法 |
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