WO2012051787A1 - Chemical mechanical polishing liquid - Google Patents
Chemical mechanical polishing liquid Download PDFInfo
- Publication number
- WO2012051787A1 WO2012051787A1 PCT/CN2011/001454 CN2011001454W WO2012051787A1 WO 2012051787 A1 WO2012051787 A1 WO 2012051787A1 CN 2011001454 W CN2011001454 W CN 2011001454W WO 2012051787 A1 WO2012051787 A1 WO 2012051787A1
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- WO
- WIPO (PCT)
- Prior art keywords
- chemical mechanical
- mechanical polishing
- polishing liquid
- liquid according
- acid
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims abstract description 71
- 239000007788 liquid Substances 0.000 title claims abstract description 39
- 239000000126 substance Substances 0.000 title claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 239000002738 chelating agent Substances 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- -1 azole compound Chemical class 0.000 claims description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 16
- 239000012964 benzotriazole Substances 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 229920002125 Sokalan® Polymers 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 239000004584 polyacrylic acid Substances 0.000 claims description 14
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 13
- 238000005260 corrosion Methods 0.000 claims description 12
- 230000007797 corrosion Effects 0.000 claims description 11
- 239000012459 cleaning agent Substances 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 7
- 229920003169 water-soluble polymer Polymers 0.000 claims description 7
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-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
- 230000004888 barrier function Effects 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- 150000002978 peroxides Chemical group 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-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
- 229920006243 acrylic copolymer Polymers 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
- QSLLXQPOVJSDAY-UHFFFAOYSA-L dipotassium;tetradecyl phosphate Chemical compound [K+].[K+].CCCCCCCCCCCCCCOP([O-])([O-])=O QSLLXQPOVJSDAY-UHFFFAOYSA-L 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- LMHAGAHDHRQIMB-UHFFFAOYSA-N 1,2-dichloro-1,2,3,3,4,4-hexafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(Cl)C1(F)Cl LMHAGAHDHRQIMB-UHFFFAOYSA-N 0.000 claims 1
- JKTORXLUQLQJCM-UHFFFAOYSA-N 4-phosphonobutylphosphonic acid Chemical compound OP(O)(=O)CCCCP(O)(O)=O JKTORXLUQLQJCM-UHFFFAOYSA-N 0.000 claims 1
- CRJWKIKXDLWJQP-UHFFFAOYSA-N N(CCO)(CCO)CCO.P(=O)(OS)(O)O Chemical class N(CCO)(CCO)CCO.P(=O)(OS)(O)O CRJWKIKXDLWJQP-UHFFFAOYSA-N 0.000 claims 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims 1
- JEVIDAVEYPPBFQ-UHFFFAOYSA-N decyl dodecyl hydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(=O)OCCCCCCCCCC JEVIDAVEYPPBFQ-UHFFFAOYSA-N 0.000 claims 1
- GWTCIAGIKURVBJ-UHFFFAOYSA-L dipotassium;dodecyl phosphate Chemical compound [K+].[K+].CCCCCCCCCCCCOP([O-])([O-])=O GWTCIAGIKURVBJ-UHFFFAOYSA-L 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 238000004140 cleaning Methods 0.000 abstract description 6
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 150000002736 metal compounds Chemical group 0.000 abstract description 2
- 230000000903 blocking effect Effects 0.000 abstract 2
- 239000000470 constituent Substances 0.000 abstract 1
- 235000012431 wafers Nutrition 0.000 abstract 1
- 229910019142 PO4 Inorganic materials 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000010452 phosphate Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 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 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000003989 dielectric material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- HZVIGSHUIQEAAI-UHFFFAOYSA-N C(CCCCCCCCC)[P] Chemical compound C(CCCCCCCCC)[P] HZVIGSHUIQEAAI-UHFFFAOYSA-N 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 101150033824 PAA1 gene Proteins 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- SCIGVHCNNXTQDB-UHFFFAOYSA-N decyl dihydrogen phosphate Chemical compound CCCCCCCCCCOP(O)(O)=O SCIGVHCNNXTQDB-UHFFFAOYSA-N 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- WZPRPGQIPUCXQE-UHFFFAOYSA-L dipotassium;decyl phosphate Chemical compound [K+].[K+].CCCCCCCCCCOP([O-])([O-])=O WZPRPGQIPUCXQE-UHFFFAOYSA-L 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- FPYMUXNASDOMBA-UHFFFAOYSA-N phosphoric acid;hydrate Chemical compound O.OP(O)(O)=O.OP(O)(O)=O FPYMUXNASDOMBA-UHFFFAOYSA-N 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- HXCSDCIKZNWBDT-UHFFFAOYSA-M potassium dihydrogen phosphate phosphoric acid hydrate Chemical compound O.P(=O)([O-])(O)O.P(=O)(O)(O)O.[K+] HXCSDCIKZNWBDT-UHFFFAOYSA-M 0.000 description 1
- RMGVATURDVPNOZ-UHFFFAOYSA-M potassium;hexadecyl hydrogen phosphate Chemical compound [K+].CCCCCCCCCCCCCCCCOP(O)([O-])=O RMGVATURDVPNOZ-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 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 present invention relates to a chemical mechanical polishing liquid.
- the purpose of the planarization of the barrier layer is to remove the barrier metal and dielectric material on the surface of the wafer and to control the thickness of the metal copper and the interlayer dielectric within the scope of the process to form an interconnection.
- One-stage polishing directly determines the electrical performance and reliability of the device, especially the efficiency of planarization after entering the 45-nanometer process, the removal rate of various materials, the amount of surface contaminants, the size of residual particles, and surface defects.
- the degree of adsorption and surface adsorption characteristics have higher requirements, especially for metal corrosion and surface contaminant control has reached new height and precision.
- the mechanical strength is weak in the 45nm process.
- Low dielectric material and covered with a silicon dioxide layer to protect the dielectric layer from damage during polishing, and the thickness of the barrier layer is further reduced.
- the residual of surface particles is also reduced to below 100 or even lower.
- the polishing uniformity at the wafer level and the slice level is as low as possible ( ⁇ 3%), and it is absolutely forbidden to produce various forms of corrosion on the metal. Phenomenon.
- the surface roughness and morphology of copper metal should meet the requirements.
- the comprehensive use cost of CMP slurry should be reduced to a certain level to ensure polishing performance. After reaching the standard, the concentration of the slurry can further reduce the cost.
- the object of the present invention is to provide a barrier polishing liquid having a high polishing rate, an adjustable selection ratio, a surface contamination index meeting requirements, and a low cost in the above background.
- the invention provides a chemical mechanical polishing liquid for flattening a metal copper interconnection barrier layer, which comprises:
- the abrasive particles are silica sol or a fumed silica aqueous dispersion having a particle size of from 20 to 250 nm, most preferably from 30 to 150 nm.
- the content of the abrasive grains is 2 to 30% by weight, preferably 5 to 20% by weight.
- the metal chelating agent is a mono- or polybasic organic acid or an organic phosphine such as HEDP (hydroxyethylidene diphosphonic acid), PBTCA (2-phosphonobutane-1, 2,4-tricarboxylic acid), HPAA (2) - hydroxyphosphonoacetic acid), oxalic acid, malonic acid, succinic acid, citric acid, tartaric acid, and the like.
- concentration of the metal chelating agent is from 0.01 to 1% by weight, most preferably from 0.1 to 0.5% by weight.
- the oxidizing agent is a peroxide or a persulfide.
- concentration of the oxidizing agent is 0.01 to 1% by weight.
- the combined metal corrosion inhibitor is: an azole compound such as BTA (benzotriazole) or a derivative of BTA; and a water-soluble polymer such as polyacrylic acid or an acrylic copolymer.
- BTA benzotriazole
- the concentration of BTA and its derivatives is 0.01-0.5 wt%, and the optimum is 0.1-0.2%; the concentration of the water-soluble polymer is 0.01%-0.5 wt%, and the optimum is 0.05-0.2%.
- the silica polishing accelerator is a quaternary ammonium salt or a quaternary ammonium base, specifically tetramethylammonium halide, tetraethylammonium halide, tetrapropylammonium halide, tetrabutylammonium halide, tetramethylhydrogenated ammonium , tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylhydrogen peroxide: ammonium, and the like.
- tetrabutylammonium fluoride tetrapropylammonium bromide
- tetramethylammonium hydroxide tetrabutylammonium hydroxide.
- concentration of the silica polishing accelerator is from 10 ppm by mass to 0.5% by mass, preferably from 100 ppm to 0.2% by mass.
- the present invention also includes an auxiliary cleaning agent, specifically one or more anthracene phosphate ester anionic surfactants, for example: alkyl phosphate diethanolamine salt, alkyl phosphate triethanolamine salt, phosphoric acid Ammonium decyl phosphatidyl ammonium salt, potassium decyl phosphate, potassium tetradecyl phosphate, potassium cetyl phosphate, and the like.
- the auxiliary cleaning agent is contained in an amount of from 0.005 to 0.2% by weight, preferably from 0.01 to 0.1% by weight.
- the polishing liquid of the present invention has a pH of from 2 to 5, preferably from 2.5 to 3.5.
- Abrasive particles are a source of mechanical force for the slurry and are primarily used to remove residual metal oxides and dielectric materials.
- the beneficial effects of the present invention are as follows:
- the present invention comprises a metal chelating agent capable of sequestering oxidized metal copper ions to form a water-soluble substance, which is discharged with the polishing liquid to prevent metal compounds from remaining on the polishing pad and the wafer surface;
- the oxidizing agent can oxidize Metallic copper to ionic state, easy to be removed by abrasive mechanical force;
- metal corrosion inhibitor system can protect metal copper surface, avoid corrosion, protect metal metal copper of recess from oxidation, ensure no defects and material erosion on the entire wafer surface
- silica polishing accelerator can improve the removal rate of silica, adjust the polishing selectivity ratio of oxide to metal;
- auxiliary cleaning component can ensure the polished wafer Easy to clean and reduce the amount of particulate residue.
- Figure 1 shows the surface of a wafer without the addition of an auxiliary cleaning alkyl phosphate
- Figure 2 is a wafer surface after adding a surfactant alkyl phosphate
- Figure 3 shows the effect of the amount of water-soluble polymer added on the removal rate of copper;
- Figure 4 shows the sensitivity of Cu to the change of hydrogen peroxide concentration in the presence of water-soluble polymer.
- Polishing head speed 90 rpm
- Polishing plate speed 70 rpm
- Polishing fluid flow rate 100 ml / min
- Polished sheet PETEOS, metal crucible, metallic copper, BD1, etc.
- the prior art polishing liquid causes a large range of particle residue and metal residue after polishing, and the present inventions 1 to 12 have excellent problems in the prior art. solve.
- the metal copper removal rate is more sensitive to the oxidant concentration, so that the adjustment of the process parameters can be used to adjust the thickness of the copper on-line.
- the invention adopts a composite anti-corrosion inhibitor to effectively protect the metal from corrosion during the polishing process, and can correct the surface defects of the front process to achieve the planarization effect, and the organic solvent is used to change the slurry and the polishing pad and the wafer. The adsorption behavior between the two to reduce the level of metal residues on the polishing pad, further improve the life of the polishing pad and increase productivity.
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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)
Abstract
Disclosed is a chemical mechanical polishing liquid for the planarization of a blocking layer, which comprises at least one kind of abrasive particle, a metal chelating agent, a silicon dioxide polishing promoter, a composite metal anticorrosive, an auxiliary cleaning constituent and an oxidant. During polishing of the blocking layer, the polishing liquid can effectively remove particle residues on the surface of wafers and metal compound residues on polishing pads, and has relatively good stability.
Description
一种化学机械抛光液 Chemical mechanical polishing liquid
技术领域 Technical field
本发明涉及一种化学机械抛光液。 The present invention relates to a chemical mechanical polishing liquid.
技术背景 technical background
在铜制程的大马氏工艺中, 阻挡层的平坦化目的是清除晶圆表面的阻挡 层金属和介质材料并将金属铜和层间介质的厚度控制在工艺要求的范围,形 成互连,这一阶段的抛光直接决定着器件的电性能和可靠性,尤其是进入 45 纳米制程后, 对平坦化的效率, 各种材^"的去除速率, 表面污染物数量, 残 留颗粒物的尺寸, 表面缺陷的程度以及表面的吸附特征都有了更高的要求, 尤其是对金属的腐蚀和表面污染物控制已经达到新的高度和精度。一般来讲 在 45纳米制程中现已采用机械强度较弱的低介电材料, 并与其上覆盖二氧 化硅层以保护介质层在抛光中受损, 阻挡层的厚度也进一步降低, 在 100多 埃左右, 表面颗粒物的残留也降低至 100以下甚至更低, 此外对晶圆级和切 片级的抛光均一性都尽可能的低 (<3%), 绝对禁止金属上产生各种形式的 腐蚀现象。铜金属的表面粗糙度和形貌均要达到要求。 另外随着全球半导体 行业降低成本的要求越来越高, 对 CMP浆料的综合使用成本也要降低到一 定的水平, 保证抛光性能达标后, 浆料的浓缩又可以进一步降低成本。 In the copper process of the Damascene process, the purpose of the planarization of the barrier layer is to remove the barrier metal and dielectric material on the surface of the wafer and to control the thickness of the metal copper and the interlayer dielectric within the scope of the process to form an interconnection. One-stage polishing directly determines the electrical performance and reliability of the device, especially the efficiency of planarization after entering the 45-nanometer process, the removal rate of various materials, the amount of surface contaminants, the size of residual particles, and surface defects. The degree of adsorption and surface adsorption characteristics have higher requirements, especially for metal corrosion and surface contaminant control has reached new height and precision. Generally speaking, the mechanical strength is weak in the 45nm process. Low dielectric material, and covered with a silicon dioxide layer to protect the dielectric layer from damage during polishing, and the thickness of the barrier layer is further reduced. At about 100 angstroms, the residual of surface particles is also reduced to below 100 or even lower. In addition, the polishing uniformity at the wafer level and the slice level is as low as possible (<3%), and it is absolutely forbidden to produce various forms of corrosion on the metal. Phenomenon. The surface roughness and morphology of copper metal should meet the requirements. In addition, as the global semiconductor industry lowers the cost requirements, the comprehensive use cost of CMP slurry should be reduced to a certain level to ensure polishing performance. After reaching the standard, the concentration of the slurry can further reduce the cost.
发明概要 Summary of invention
本发明的目的是在上述的背景下, 提供一种抛光速率高, 选择比可调, 表面污染物指标满足要求, 成本低的阻挡层抛光液。
本发明的提供一种用于金属铜互连阻挡层平坦化的化学机械抛光液, 它 包括: SUMMARY OF THE INVENTION The object of the present invention is to provide a barrier polishing liquid having a high polishing rate, an adjustable selection ratio, a surface contamination index meeting requirements, and a low cost in the above background. The invention provides a chemical mechanical polishing liquid for flattening a metal copper interconnection barrier layer, which comprises:
a: 一种磨料颗粒, a: an abrasive granule,
b : 一种金属螯合剂, b : a metal chelating agent,
c: , 一种二氧化硅抛光促进剂。 c: , a silica polishing accelerator.
d : 组合金属防腐蚀剂, d : combination metal corrosion inhibitor,
e: 一种辅助清洗剂 e: an auxiliary cleaning agent
f: 一种氧化剂 f: an oxidant
其中, 磨料颗粒是二氧化硅溶胶, 或者发烟二氧化硅水分散体, 颗粒的 粒径为 20-250nm, 最优的为 30-150nm。 磨料颗粒的含量为 2-30wt%, 最好 的是 5-20wt%。 Wherein the abrasive particles are silica sol or a fumed silica aqueous dispersion having a particle size of from 20 to 250 nm, most preferably from 30 to 150 nm. The content of the abrasive grains is 2 to 30% by weight, preferably 5 to 20% by weight.
其中, 金属螯合剂是一元或多元有机酸或者有机膦例如 HEDP (羟基亚 乙基二膦酸)、 PBTCA ( 2-膦酸基丁烷 -1, 2, 4-三羧酸)、 HPAA (2-羟基膦 酰基乙酸)、 草酸、 丙二酸、 丁二酸、 柠檬酸, 酒石酸等。 金属螯合剂的浓 度是在 0.01-lwt%, 最好的是在 0.1-0.5wt%。 Wherein, the metal chelating agent is a mono- or polybasic organic acid or an organic phosphine such as HEDP (hydroxyethylidene diphosphonic acid), PBTCA (2-phosphonobutane-1, 2,4-tricarboxylic acid), HPAA (2) - hydroxyphosphonoacetic acid), oxalic acid, malonic acid, succinic acid, citric acid, tartaric acid, and the like. The concentration of the metal chelating agent is from 0.01 to 1% by weight, most preferably from 0.1 to 0.5% by weight.
其中, 氧化剂为过氧化物或者过硫化物。 氧化剂的浓度为 0.01-lwt%。 其中, 组合金属防腐蚀剂为: 唑类化合物例如 BTA (苯骈三氮唑)或者 BTA的衍生物; 以及, 水溶性聚合物例如聚炳烯酸或者丙烯酸共聚物。其中 BTA及其衍生物的浓度为 0.01-0.5wt%, 最优的为 0.1-0.2%; 水溶性聚合物 的浓度为 0.01%-0.5wt%, 最优的为 0.05-0.2%。 Wherein the oxidizing agent is a peroxide or a persulfide. The concentration of the oxidizing agent is 0.01 to 1% by weight. Wherein, the combined metal corrosion inhibitor is: an azole compound such as BTA (benzotriazole) or a derivative of BTA; and a water-soluble polymer such as polyacrylic acid or an acrylic copolymer. The concentration of BTA and its derivatives is 0.01-0.5 wt%, and the optimum is 0.1-0.2%; the concentration of the water-soluble polymer is 0.01%-0.5 wt%, and the optimum is 0.05-0.2%.
其中, 二氧化硅抛光促进剂为季铵盐或季铵碱, 具体为四甲基卤化铵, 四乙基卤化铵, 四丙基卤化铵, 四丁基卤化铵, 四甲基氢 ft化铵, 四乙基氢 氧化铵, 四丙基氢氧化铵, 四丁基氢氧^:铵等。 优选的为四丁基氟化氨, 四 丙基溴化铵, 四甲基氢氧化铵、 四丁基氢氧化铵。 二氧化硅抛光促进剂的浓 度为质量百分比 lOppm到 0.5%, 优选的为质量百分比 lOOppm到 0.2%。 Wherein, the silica polishing accelerator is a quaternary ammonium salt or a quaternary ammonium base, specifically tetramethylammonium halide, tetraethylammonium halide, tetrapropylammonium halide, tetrabutylammonium halide, tetramethylhydrogenated ammonium , tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylhydrogen peroxide: ammonium, and the like. Preferred are tetrabutylammonium fluoride, tetrapropylammonium bromide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide. The concentration of the silica polishing accelerator is from 10 ppm by mass to 0.5% by mass, preferably from 100 ppm to 0.2% by mass.
本发明还包括辅助清洗剂,具体为一种或多种为垸基磷酸酯盐类阴离子 表面活性剂, 例如: 烷基磷酸酯二乙醇胺盐, 烷基磷酸酯三乙醇胺盐, 磷酸
垸基十二垸基磷酸酯铵盐, 十二垸基磷酸酯钾盐, 十四垸基磷酸酯钾盐, 十 六烷基磷酸酯钾盐等。 该辅助清洗剂的含量为 0.005-0.2wt%, 优选的为 0.01-0.1 wt %。 The present invention also includes an auxiliary cleaning agent, specifically one or more anthracene phosphate ester anionic surfactants, for example: alkyl phosphate diethanolamine salt, alkyl phosphate triethanolamine salt, phosphoric acid Ammonium decyl phosphatidyl ammonium salt, potassium decyl phosphate, potassium tetradecyl phosphate, potassium cetyl phosphate, and the like. The auxiliary cleaning agent is contained in an amount of from 0.005 to 0.2% by weight, preferably from 0.01 to 0.1% by weight.
本发明抛光液的 pH值在 2-5, 最好的为 2.5-3.5。 The polishing liquid of the present invention has a pH of from 2 to 5, preferably from 2.5 to 3.5.
磨料颗粒是浆料机械力的来源,它主要是用于去餘金属氧化物和介质材 料。 Abrasive particles are a source of mechanical force for the slurry and are primarily used to remove residual metal oxides and dielectric materials.
本发明的有益效果如下: 本发明包括金属螯合剂, 能够是螯合被氧化的金属铜离子, 形成水溶性 物质, 随抛光液排放, 避免金属化合物残留在抛光垫和晶圆表面; 氧化剂能 够氧化金属铜至离子状态, 易于被磨料机械力移除; 金属腐蚀抑制剂体系能 够保护金属铜表面, 避免产生腐蚀, 保护凹处的金属铜不被氧化, 保证整个 晶圆表面不产生缺陷和材料侵蚀, 另外还能够调节铜的去除对双氧水的敏感 程度; 二氧化硅抛光促进剂能够提高二氧化硅的去除速率, 调整氧化物与金 属的抛光选择比; 辅助清洗组分能够保证抛光后的晶圆容易清洗, 降低颗粒 物残留数量。 The beneficial effects of the present invention are as follows: The present invention comprises a metal chelating agent capable of sequestering oxidized metal copper ions to form a water-soluble substance, which is discharged with the polishing liquid to prevent metal compounds from remaining on the polishing pad and the wafer surface; the oxidizing agent can oxidize Metallic copper to ionic state, easy to be removed by abrasive mechanical force; metal corrosion inhibitor system can protect metal copper surface, avoid corrosion, protect metal metal copper of recess from oxidation, ensure no defects and material erosion on the entire wafer surface In addition, it can adjust the sensitivity of copper removal to hydrogen peroxide; silica polishing accelerator can improve the removal rate of silica, adjust the polishing selectivity ratio of oxide to metal; auxiliary cleaning component can ensure the polished wafer Easy to clean and reduce the amount of particulate residue.
附图说明 DRAWINGS
图 1为未添加辅助清洗剂烷基磷酸酯的晶圆表面; Figure 1 shows the surface of a wafer without the addition of an auxiliary cleaning alkyl phosphate;
图 2为添加表面活性剂烷基磷酸酯后的晶圆表面; Figure 2 is a wafer surface after adding a surfactant alkyl phosphate;
图 3为水溶性聚合物的添加量对铜去除速率的影响; 图 4为水溶性聚合物存在下 Cu对双氧水浓度变化的敏感程度。 Figure 3 shows the effect of the amount of water-soluble polymer added on the removal rate of copper; Figure 4 shows the sensitivity of Cu to the change of hydrogen peroxide concentration in the presence of water-soluble polymer.
发明内容 Summary of the invention
下面通过具体实施方式来进一步阐述本发明
化学机械抛光条件: Logteek PM50抛光机台 The invention is further illustrated by the following specific embodiments. Chemical mechanical polishing conditions: Logteek PM50 polishing machine
下压力: 1.5psi Downforce: 1.5psi
抛光头转速: 90转 /分 Polishing head speed: 90 rpm
抛光盘转速: 70转 /分 Polishing plate speed: 70 rpm
抛光液流量: 100毫升 /分 Polishing fluid flow rate: 100 ml / min
抛光时间: 2分钟 Polishing time: 2 minutes
抛光片: PETEOS, 金属钽, 金属铜, BD1 , 等 Polished sheet: PETEOS, metal crucible, metallic copper, BD1, etc.
表 1 实施例 1-12 实施 二氧化硅抛 Table 1 Example 1-12 Implementation Silica polishing
磨料 组合腐蚀抑制剂 络合剂 氧化剂 清洗助剂 PH 例 光促进剂 Abrasive combined corrosion inhibitor complexing agent oxidant cleaning aid PH example light accelerator
水溶性聚 Water soluble poly
唑类缓蚀剂 Azole corrosion inhibitor
合物 Compound
参比 Reference
抛光 3 液 Polishing 3 liquid
0.2%双 0.2% double
1 10%SiO2 0.2%BTA 0.2%柠檬酸 3 氧水 1 10% SiO 2 0.2% BTA 0.2% citric acid 3 oxygen water
0.2%双 0.2% double
. 2 10%SiO2 0.2%BTA 0.2%柠檬酸 0.]%TBAH 3 氧水 . 2 10% SiO 2 0.2% BTA 0.2% citric acid 0.]%TBAH 3 Oxygen water
0.2%双 0.2% double
3 10%SiO2 0.2%BTA 0.1%PAA 0.2%柠檬酸 0.1%TBAH 3 氧水 3 10% SiO 2 0.2% BTA 0.1% PAA 0.2% citric acid 0.1% TBAH 3 Oxygen water
0.2%双 0.05%十二垸 0.2% double 0.05% twelve
4 10%SiO2 0.2%BTA 0.1%PAA 0.2%柠檬酸 0.]%TBAH 3 氧水 基磷酸酯铵盐4 10% SiO 2 0.2% BTA 0.1% PAA 0.2% citric acid 0.]% TBAH 3 Oxygen phosphate phosphate ammonium salt
0.01%柠檬 0.2%双 0.05%十二垸 0.01% lemon 0.2% double 0.05% twelve 垸
5 30%SiO2 0.5%BTA 0.01%PAA 0.1%TBAH 5 5 30% SiO 2 0.5% BTA 0.01% PAA 0.1% TBAH 5
. 氧水 基磷酸酯铰盐 Oxygen phosphate phosphate hinge salt
0.05%垸基磷 0.05% decyl phosphorus
0.2%双 0.2% double
6 2%Si02 0.01%BTA 0.5%PAA 0.5%柠檬酸 0.5%ΤΒΑΉ 酸酯三乙醇铰 2 6 2%Si0 2 0.01%BTA 0.5%PAA 0.5% citric acid 0.5% bismuth ester triethanol hinge 2
±卜 ±卜
0.2%双 0.05%十六烷 0.2% double 0.05% hexadecane
1 10%SiO2 0.2%%BTA 0.1%PAA 0.5%HEDP 0.1%TBAH 3 氧水 . 基磷酸酯铰盐1 10% SiO 2 0.2%% BTA 0.1% PAA 0.5% HEDP 0.1% TBAH 3 Oxygen water. Phosphate hinge salt
0.2%双 0.05%十二垸0.2% double 0.05% twelve
8 10%SiO2 0.2%BTA 0.1%PAA 0.5%PBTCA 0.1 %TBAH 3 氧水 基磷酸酯钾盐 8 10% SiO 2 0.2% BTA 0.1% PAA 0.5% PBTCA 0.1 % TBAH 3 Oxygen phosphate phosphate potassium salt
0.005%十四 0.005% fourteen
0.2%双 0.2% double
9 2%Si02 0.5%BTA 0.01%PAA 1%丙二酸 0.5%TMAH 烷基磷酸酯 2 氧水 9 2%SiO 2 0.5% BTA 0.01% PAA 1% malonic acid 0.5% TMAH alkyl phosphate 2 oxygen water
钾盐 Potassium salt
0.2%十六烷 0.2% hexadecane
0.01%丙二 0.2%双 0.01% C2 0.2% Double
10 30%SiO2 0.01%BTA 0.5%PAA 0.01%TBAF 基磷酸酯钾 5 酸 氧水 : t卜
0.]%磷酸烷10 30% SiO2 0.01% BTA 0.5% PAA 0.01% TBAF Potassium Phosphate Potassium 5 Acid Oxygen Water: t Bu 0.]% phosphate
30%发烟 0.01%丁二 0.2%双 30% smoke 0.01% Ding 0.2% double
11 0.1%BTA 0.1%PAA Ο.ΟΓ/oTPABr 5 硅粉 酸 氧水 11 0.1%BTA 0.1%PAA Ο.ΟΓ/oTPABr 5 Silica powder Acid Oxygen water
磷酸酯 盐 Phosphate salt
0.1%丙烯 0.05%磷酸烷0.1% propylene 0.05% phosphate
2%发烟 2% smoke
12 0.2%BTA 酸马来酸 1%酒石酸 0.1%TBAH 0.2% 基十二焼基 2 硅粉 12 0.2% BTA acid maleic acid 1% tartaric acid 0.1% TBAH 0.2% base 12 fluorenyl 2 silicon powder
共聚物 磷酸酯铰盐 Copolymer phosphate hinge
表 2 实施例 1~12与现有技术的效果对比 Table 2 Comparison of the effects of the embodiments 1~12 with the prior art
从表 2中可以看出,现有技术的抛光液会造成抛光后有大范围的颗粒残 留物以及金属残留物, 而本发明实施例 1〜12 已将现有技术中存在的问题很 好的解决。 As can be seen from Table 2, the prior art polishing liquid causes a large range of particle residue and metal residue after polishing, and the present inventions 1 to 12 have excellent problems in the prior art. solve.
下面结合附图进一步阐述本发明的有益效果: The beneficial effects of the present invention are further explained below with reference to the accompanying drawings:
参见图 1, 为添加辅助清洗剂垸基磷酸酯活性剂, 抛光清洗后, 晶圆表
面有雾状附着物, SEM分析后发现未大片颗粒物残留。 参见图 2, 在添加垸基磷酸酯后, 晶圆表面的雾状物质消失, 未发现颗 粒物质残留, 表明阴离子活性剂烷基磷酸酯盐, 能够改变颗粒物表面电性, 使得在清洗过程中更加容易被清洗 ¾J移除, 提高晶圆洁净度。 See Figure 1, for the addition of the auxiliary cleaning agent guanyl phosphate ester active agent, after polishing and cleaning, wafer table There were foggy deposits on the surface. After SEM analysis, no large particles remained. Referring to Figure 2, after the addition of decyl phosphate, the misty substance on the surface of the wafer disappeared, and no residual particulate matter was found, indicating that the anionic active agent alkyl phosphate salt can change the surface electrical properties of the particles, making the cleaning process more Easy to be cleaned 3⁄4J removed, improving wafer cleanliness.
参见图 3, 添加 PAA (聚丙烯酸)后, 铜的去除速率得到不同程度的抑 制, 可以调整在图形晶圆上, 对蝶形凹陷的矫正能力。 Referring to Figure 3, after the addition of PAA (polyacrylic acid), the removal rate of copper is suppressed to varying degrees, and the ability to correct the butterfly depression on the graphic wafer can be adjusted.
参见图 4, 在 PAA (聚丙烯酸)存在下, 金属铜的去除速率对氧化剂浓 度的敏感程度有了较大程度的降低,这样可以采用工艺参数的调整来在线调 节铜的厚度。 综上, 本发明采用复合防腐蚀抑制剂, 有效保护金属在抛光过程中免受 腐蚀, 并能校正前程的表面缺陷, 达到平坦化的效果, 采用有机溶剂来改变 浆料与抛光垫和晶片之间的吸附行为, 来降低抛光垫上金属残留物的水平, 进一步提高抛光垫寿命, 提高产能。
Referring to Figure 4, in the presence of PAA (polyacrylic acid), the metal copper removal rate is more sensitive to the oxidant concentration, so that the adjustment of the process parameters can be used to adjust the thickness of the copper on-line. In summary, the invention adopts a composite anti-corrosion inhibitor to effectively protect the metal from corrosion during the polishing process, and can correct the surface defects of the front process to achieve the planarization effect, and the organic solvent is used to change the slurry and the polishing pad and the wafer. The adsorption behavior between the two to reduce the level of metal residues on the polishing pad, further improve the life of the polishing pad and increase productivity.
Claims
1、 一种用于铜互连阻挡层化学机械抛光的抛光液, 包括: 一种磨料颗 粒、 一种金属螯合剂、 一种二氧化硅抛光促进剂、 组合金属防腐蚀剂、 一种 辅助清洗剂以及一种氧化剂。 A polishing liquid for chemical mechanical polishing of a copper interconnect barrier layer, comprising: an abrasive particle, a metal chelating agent, a silica polishing accelerator, a combined metal corrosion inhibitor, and an auxiliary cleaning agent And an oxidizing agent.
2、 如权利要求 1所述的化学机械抛光液, 其特征在于, 所述磨料颗粒 是二氧化硅溶胶和 /或发烟二氧化硅水分散体。 The chemical mechanical polishing liquid according to claim 1, wherein the abrasive particles are silica sol and/or fumed silica aqueous dispersion.
3、 如权利要求 1所述的化学机械抛光液, 其特征在于, 所述磨料颗粒 的粒径为 20-250nm。 The chemical mechanical polishing liquid according to claim 1, wherein the abrasive particles have a particle diameter of 20 to 250 nm.
4、 如权利要求 3所述的化学机械抛光液, 其特征在于, 所述磨料颗粒 的粒径为 30-150nm。 The chemical mechanical polishing liquid according to claim 3, wherein the abrasive particles have a particle diameter of 30 to 150 nm.
5、 如权利要求 1所述的化学机械抛光液, 其特征在于, 所述磨料颗粒 的含量为 2-30wt%。 The chemical mechanical polishing liquid according to claim 1, wherein the abrasive particles are contained in an amount of 2 to 30% by weight.
6、 如权利要求 5所述的化学机械抛光液, 其特征在于, 所述磨料颗粒 的含量为 5-20wt%。 The chemical mechanical polishing liquid according to claim 5, wherein the abrasive particles are contained in an amount of 5 to 20% by weight.
7、 如权利要求 1所述的化学机械抛光液, 其特征在于, 所述金属螯合 剂为有机羧酸和 /或有机膦。 The chemical mechanical polishing liquid according to claim 1, wherein the metal chelating agent is an organic carboxylic acid and/or an organic phosphine.
8、 如权利要求 1所述的化学机械抛光液, 其特征在于, 所述金属螯合 剂为选自: 羟基亚乙基二膦酸、 2-膦酸基丁烷- 1, 2, 4-三羧酸、 2-羟基膦酰 基乙酸、 草酸、 丙二酸、 丁二酸、 柠檬酸和酒石酸中的一种或多种。 The chemical mechanical polishing liquid according to claim 1, wherein the metal chelating agent is selected from the group consisting of: hydroxyethylidene diphosphonic acid, 2-phosphonic acid butane-1, 2, 4-three One or more of a carboxylic acid, 2-hydroxyphosphonoacetic acid, oxalic acid, malonic acid, succinic acid, citric acid, and tartaric acid.
9、 如权利要求 1所述的化学机械抛光液, 其特征在于, 所述金属螯合 剂的浓度为 0.01-lwt%。 The chemical mechanical polishing liquid according to claim 1, wherein the metal chelating agent has a concentration of 0.01 to 1% by weight.
10、 如权利要求 9所述的化学机械抛光液, 其特征在于, 所述金属螯合 剂的浓度为 0.1-0.5wt%。 The chemical mechanical polishing liquid according to claim 9, wherein the metal chelating agent has a concentration of 0.1 to 0.5% by weight.
11、 如权利要求 1所述的化学机械抛光液, 其特征在于, 所述氧化剂为 过氧化物和 /或过硫化物。 The chemical mechanical polishing liquid according to claim 1, wherein the oxidizing agent is a peroxide and/or a persulfide.
12、 如权利要求 1所述的化学机械抛光液, 其特征在于, 所述氧化剂的 浓度为 0.01-lwt%。 The chemical mechanical polishing liquid according to claim 1, wherein the oxidizing agent The concentration is 0.01-lwt%.
13、 如权利要求 1所述的化学机械抛光液, 其特征在于, 所述组合金属 防腐蚀剂包括: 唑类化合物和水溶性聚合物。 The chemical mechanical polishing liquid according to claim 1, wherein the combined metal corrosion inhibitor comprises: an azole compound and a water-soluble polymer.
14、 如权利要求 13所述的化学机械抛光液, 其特征在于, 所述唑类化 合物为苯骈三氮唑或其衍生物;所述水溶性聚合物为聚丙烯酸及其盐或者丙 烯酸共聚物。 The chemical mechanical polishing liquid according to claim 13, wherein the azole compound is benzotriazole or a derivative thereof; and the water-soluble polymer is polyacrylic acid and a salt thereof or an acrylic copolymer. .
15、 如权利要求 13所述的化学机械抛光液, 其特征在于, 所述唑类化 合物的浓度为 0.01-0.5wt%。 The chemical mechanical polishing liquid according to claim 13, wherein the concentration of the azole compound is from 0.01 to 0.5% by weight.
16、 如权利要求 13所述的化学机械抛光液, 其特征在于, 所述水溶性 聚合物的浓度为 0.05-0.5wt%。 The chemical mechanical polishing liquid according to claim 13, wherein the water-soluble polymer has a concentration of 0.05 to 0.5% by weight.
17、 如权利要求 1所述的化学机械抛光液, 其特征在于, 所述二氧化硅 抛光促进剂为选自四申基卤化铵, 四乙基卤化铵, 四丙基卤化铵, 四丁基卤 化铵, 四甲基氢氧化铵, 四乙基氢氧化铵, 四丙基氢氧化铵和四丁基氢氧化 铵中的一种或多种。 The chemical mechanical polishing liquid according to claim 1, wherein the silica polishing accelerator is selected from the group consisting of tetra-sodium halide, tetraethylammonium halide, tetrapropylammonium halide, tetrabutyl. One or more of ammonium halide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide.
18、 如权利要求 17所述的化学机械抛光液, 其特征在于, 所述二氧化 硅抛光促进剂为选自四丁基氟化氨, 四丙基溴化铵和四丁基氢氧化铵中的一 种或多种。 The chemical mechanical polishing liquid according to claim 17, wherein the silica polishing accelerator is one selected from the group consisting of tetrabutylammonium fluoride, tetrapropylammonium bromide and tetrabutylammonium hydroxide. Kind or more.
19、 如权利要求.1所述的化学机械抛光液, 其特征在于, 所述二氧化硅 抛光促进剂的浓度为质量百分比 lOppm到 0.5%。 The chemical mechanical polishing liquid according to claim 1, wherein the silica polishing accelerator has a concentration of from 10 ppm by mass to 0.5% by mass.
20、 如权利荽求 19所述的化学机械抛光液, 其特征在于, 所述二氧化 硅抛光促进剂的浓度为质量百分比 lOOppm到 0.2%。 The chemical mechanical polishing liquid according to claim 19, wherein the concentration of the silica polishing accelerator is from 10,000 ppm to 0.2% by mass.
2 如权利要求 1所述的化学机械抛光液, 其特征在于, 所述辅助清洗 剂为: 阴离子表面活性剂。 The chemical mechanical polishing liquid according to claim 1, wherein the auxiliary cleaning agent is an anionic surfactant.
22、 如权利要求 21所述的化学机械抛光液, 其特征在于, 所述阴离子 表面活性剂为选自烷基磷酸酯二乙醇胺盐, 垸基磷酸酯三乙醇胺盐, 磷酸垸 基十二烷基磷酸酯铵盐, 十二垸基磷酸酯钾盐, 十四垸基磷酸酯钾盐和十六 The chemical mechanical polishing liquid according to claim 21, wherein the anionic surfactant is selected from the group consisting of alkyl phosphate diethanolamine salts, mercapto phosphate triethanolamine salts, and decyl dodecyl phosphate. Phosphate ammonium salt, potassium dodecyl phosphate, potassium tetradecyl phosphate and sixteen
23、 如权利要求 1所述的化学机械抛光液, 其特征在于, 所述的辅助清 洗剂的含量为 0.005-0.2wt%。 The chemical mechanical polishing liquid according to claim 1, wherein the auxiliary cleaning agent is contained in an amount of 0.005 to 0.2% by weight.
24、 如权利要求 23所述的化学机械抛光液, 其特征在于, 所述的辅助 清洗剂的含量为 0.01-0.1wt %。 The chemical mechanical polishing liquid according to claim 23, wherein the auxiliary cleaning agent is contained in an amount of from 0.01 to 0.1% by weight.
25、 如权利要求 1所述的化学机械抛光液, 其特征在于, 所述化学机械 抛光液 pH值为 2-5。 The chemical mechanical polishing liquid according to claim 1, wherein the chemical mechanical polishing liquid has a pH of from 2 to 5.
26、 如权利要求 25所述的化学机械抛光液, 其特征在于, 所述化学机 械抛光液 pH值为 2.5-3.5。 The chemical mechanical polishing liquid according to claim 25, wherein the chemical mechanical polishing liquid has a pH of 2.5 to 3.5.
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CN103160207A (en) * | 2011-12-16 | 2013-06-19 | 安集微电子(上海)有限公司 | Metal chemico-mechanical polishing sizing agent and application thereof |
CN103173127B (en) * | 2011-12-23 | 2016-11-23 | 安集微电子(上海)有限公司 | A kind of chemical mechanical polishing liquid for the planarization of silicon through-hole blocking layer |
CN103509468B (en) * | 2012-06-21 | 2017-08-11 | 安集微电子(上海)有限公司 | A kind of chemical mechanical polishing liquid planarized for silicon hole |
CN103866326A (en) * | 2012-12-10 | 2014-06-18 | 安集微电子(上海)有限公司 | Chemo-mechanical polishing slurry for metal, and its application |
CN103865402A (en) * | 2012-12-17 | 2014-06-18 | 安集微电子(上海)有限公司 | Chemically mechanical polishing liquid |
CN103898512B (en) * | 2012-12-28 | 2018-10-26 | 安集微电子(上海)有限公司 | A kind of chemical mechanical polishing liquid and technique for copper-connection |
CN103965788B (en) * | 2013-01-24 | 2017-10-13 | 安集微电子(上海)有限公司 | A kind of alkalescence polishing liquid and polishing method |
CN105802509B (en) * | 2014-12-29 | 2018-10-26 | 安集微电子(上海)有限公司 | A kind of application of composition in barrier polishing |
CN104592896A (en) * | 2014-12-31 | 2015-05-06 | 上海新安纳电子科技有限公司 | Chemical mechanical polishing solution |
CN111486744B (en) * | 2020-04-14 | 2022-07-22 | 重庆兴勇实业有限公司 | Firearm decoppering agent and preparation method thereof |
CN115785820A (en) * | 2022-11-17 | 2023-03-14 | 万华化学集团电子材料有限公司 | Silicon polishing composition and application thereof |
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CN1398939A (en) * | 2001-07-23 | 2003-02-26 | 不二见株式会社 | Polishing composition and its polishing method |
CN101410956A (en) * | 2006-04-03 | 2009-04-15 | Jsr株式会社 | Aqueous dispersion for chemical mechanical polishing, chemical mechanical polishing method, and kit for preparing aqueous dispersion for chemical mechanical polishing |
CN101541913A (en) * | 2006-12-22 | 2009-09-23 | 韩国泰科诺赛美材料株式会社 | Chemical mechanical polishing composition for copper comprising zeolite |
WO2010098278A1 (en) * | 2009-02-24 | 2010-09-02 | ニッタ・ハース株式会社 | Composition for metal film polishing |
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CN1398939A (en) * | 2001-07-23 | 2003-02-26 | 不二见株式会社 | Polishing composition and its polishing method |
CN101410956A (en) * | 2006-04-03 | 2009-04-15 | Jsr株式会社 | Aqueous dispersion for chemical mechanical polishing, chemical mechanical polishing method, and kit for preparing aqueous dispersion for chemical mechanical polishing |
CN101541913A (en) * | 2006-12-22 | 2009-09-23 | 韩国泰科诺赛美材料株式会社 | Chemical mechanical polishing composition for copper comprising zeolite |
WO2010098278A1 (en) * | 2009-02-24 | 2010-09-02 | ニッタ・ハース株式会社 | Composition for metal film polishing |
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