TW200907037A - Polymeric barrier removal polishing slurry - Google Patents
Polymeric barrier removal polishing slurry Download PDFInfo
- Publication number
- TW200907037A TW200907037A TW097128747A TW97128747A TW200907037A TW 200907037 A TW200907037 A TW 200907037A TW 097128747 A TW097128747 A TW 097128747A TW 97128747 A TW97128747 A TW 97128747A TW 200907037 A TW200907037 A TW 200907037A
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- TW
- Taiwan
- Prior art keywords
- weight
- weight percent
- hydrophilic portion
- copper
- aqueous slurry
- Prior art date
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- 239000002002 slurry Substances 0.000 title claims abstract description 47
- 238000005498 polishing Methods 0.000 title claims abstract description 21
- 230000004888 barrier function Effects 0.000 title description 16
- 239000004094 surface-active agent Substances 0.000 claims abstract description 44
- 239000010949 copper Substances 0.000 claims abstract description 39
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 claims abstract description 36
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 20
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 20
- 239000007800 oxidant agent Substances 0.000 claims abstract description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 14
- 239000011574 phosphorus Substances 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004065 semiconductor Substances 0.000 claims abstract description 11
- 239000003112 inhibitor Substances 0.000 claims abstract description 10
- 125000000129 anionic group Chemical group 0.000 claims abstract description 9
- 239000008139 complexing agent Substances 0.000 claims abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 16
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 14
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 14
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
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- 235000019289 ammonium phosphates Nutrition 0.000 claims description 4
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 4
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- 239000012964 benzotriazole Substances 0.000 description 9
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- 239000003139 biocide Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Chemical class [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- HAPISMNDDAHZJT-UHFFFAOYSA-N carbamodithioic acid;sodium Chemical compound [Na].NC(S)=S HAPISMNDDAHZJT-UHFFFAOYSA-N 0.000 description 1
- CVXBEEMKQHEXEN-UHFFFAOYSA-N carbaryl Chemical compound C1=CC=C2C(OC(=O)NC)=CC=CC2=C1 CVXBEEMKQHEXEN-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- HDFRDWFLWVCOGP-UHFFFAOYSA-N carbonothioic O,S-acid Chemical compound OC(S)=O HDFRDWFLWVCOGP-UHFFFAOYSA-N 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical compound CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 239000007931 coated granule Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- AXFZAZQUMXZWJV-UHFFFAOYSA-N diazanium;phosphono phosphate Chemical compound [NH4+].[NH4+].OP(O)(=O)OP([O-])([O-])=O AXFZAZQUMXZWJV-UHFFFAOYSA-N 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000000572 ellipsometry Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- SEOVTRFCIGRIMH-UHFFFAOYSA-N indole-3-acetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CNC2=C1 SEOVTRFCIGRIMH-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000462 iron(III) oxide hydroxide Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical compound [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 description 1
- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- VXTFGYMINLXJPW-UHFFFAOYSA-N phosphinane Chemical class C1CCPCC1 VXTFGYMINLXJPW-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 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
- 150000003112 potassium compounds Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 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 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- CBXWGGFGZDVPNV-UHFFFAOYSA-N so4-so4 Chemical compound OS(O)(=O)=O.OS(O)(=O)=O CBXWGGFGZDVPNV-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical class [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- OKQKDCXVLPGWPO-UHFFFAOYSA-N sulfanylidenephosphane Chemical compound S=P OKQKDCXVLPGWPO-UHFFFAOYSA-N 0.000 description 1
- WSANLGASBHUYGD-UHFFFAOYSA-N sulfidophosphanium Chemical class S=[PH3] WSANLGASBHUYGD-UHFFFAOYSA-N 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- VKFFEYLSKIYTSJ-UHFFFAOYSA-N tetraazanium;phosphonato phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])([O-])=O VKFFEYLSKIYTSJ-UHFFFAOYSA-N 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- CZPRKINNVBONSF-UHFFFAOYSA-M zinc;dioxido(oxo)phosphanium Chemical compound [Zn+2].[O-][P+]([O-])=O CZPRKINNVBONSF-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/04—Aqueous dispersions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
- C09K3/1463—Aqueous liquid suspensions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Description
200907037 六、發明說明: 【發明所屬之技術領域】 本發明係關於一種適用於化學機械研磨具有銅互聯的 半導體基材的聚合物阻障移除研磨聚液。 【先前技術】 當超大型積體電路(ULSI, ultra-large-scale-integrated circuit)技術朝越小的 線寬度邁進時,其對習知化學機械研磨(CMp)製程之整合係 為新的挑戰。另外’低k(l〇w k)及超低k(ult:ra-low k) 介電膜之導入則必須使用更溫和的CMP製程,這是因為談 膜的機械強度低及對鄰層的附著性弱。又,持續緊縮的缺 陷度規格(ever-tightening defectivity specifications) 也對用於低k膜的研磨漿液賦予額外要求。 將不同低k膜整合至USLI亦需要眾多外加步驟及新技 術之引入,如超臨界清洗技術、介電性及金屬帽、阻障及 銅之共形沈積(conformal deposition)、以低度向下力量 及不含研磨料之漿液進行化學機械平坦作用。在該等技術 選擇之外,ULSI業者必須考慮及滿足相對於製程複雜性之 產率、可靠度、機械強度及效能,亦即來自電阻-電容(RC, resistance-capacitance)延遲之功率耗散。 實施低k材料的週邊複雜性已對阻障CMP製程引入更 大的挑戰’將使得對控制複雜的輸入變因及達成穩定高產 率之能力變成必要條件。調整製程變因對於降低低k膜的 研磨變異有助益。但最為所欲的阻障CMP漿液將引入具有 94413 3 200907037 可°周整製程效能之調整力的低k介電特異性的表面活性 劑。例如’ Ye等人於美國專利案第6, 916, 742號揭露一種 "周整聚乙稀°比洛烷酮的量以控制氮化鈕及碳摻雜氧化物 的移除速率之漿液。調整聚乙烯吡咯烷酮及氧化矽的 控制以該漿液達成的氮化鈕(阻障)對CD0(超低k介電 有、尚移除速率的比例。不幸的是,該等漿液於一些應用將具 、度刮傷以及不適切的TaN移除速率。 介電鸹求可達到具有降低C0D移除速率之阻障對超低让 需求:之的核組移除(m〇dular rem〇Val)之研磨漿液。又, r欲'移除阻障並降低刮痕(scratching)之研磨漿液。 L發明内容】 研磨且明—面向中’本發明包含—種適用於化學機械 計,α、有銅互聯的半導體基材的水性漿液,包括,以重量 研磨重!百分比的氧化劑、0,1至50重量百分比的 咖至5重量百分比的聚乙料錢嗣、 10重胃至5重置百分比的多成分界面活性劑、〇.〇〇1至 至5 ^分比之用以降低銅互聯之靜電钕刻的抑制劑、0 物,合 以及餘晷p .UUi主1U重1百分比的錯合劑, 子性親水:部界面活性劑具有疏水性尾端、非離 有6至3fu 子性親水性部分,該疏水性尾端具 0個碳原子及該非離子性 個碳原子。 f親夂陡邛v刀具有10至3〇〇 ‘種適用於化學名 在本發明另一面向中,本發明包含 94413 4 200907037 械研磨具有銅互聯的半導體基材的水性漿液,包括,以重 量計,0.01至15重量百分比的氧化劑、0.1至40重量百 分比的氧化石夕研磨料顆粒、0. 0 0 2至3重量百分比的聚乙 稀°比11各院酮、0. 0 0 0 0 5至2重量百分比的多成分界面活性 劑、0. 0 0 2至5重量百分比的σ坐類抑制劑以降低銅互聯之 靜電蝕刻、0至3重量百分比之用以增加銅互聯的移除率 的含磷化合物,於研磨期間形成的0. 01至5重量百分比的 有機酸錯合劑,以及餘量水;其中該多成分界面活性劑具 有疏水性尾端、非離子性親水性部分及陰離子性親水性部 分,該疏水性尾端具有8至20個碳原子及該非離子性親水 性部分具有20至200個碳原子,且該水性漿液具有pH為 8 至 12。 在本發明另一面向中,本發明包含一種適用於化學機 械研磨具有銅互聯的半導體基材的水性漿液,包括,以重 量計,0.1至10重量百分比的氧化劑、0.25至35重量百 分比的氧化矽研磨料顆粒、0. 01至2重量百分比的聚乙烯 σ比咯烧酮、0. 0 0 01至1重量百分比的多成分界面活性劑、 0.005至2重量百分比之用以降低銅互聯之靜電蝕刻的苯 并三唑抑制劑、0. 001至2重量百分比之用以增加銅互聯的 移除率的含磷化合物、於研磨期間形成的0.01至5重量百 分比的有機酸錯合劑,以及餘量水;其中該多成分界面活 性劑具有疏水性尾端、非離子性親水性部分及陰離子性親 水性部分,該疏水性尾端具有12至16個碳原子及該非離 子性親水性部分具有25至150個碳原子,且該水性漿液具 5 94413 200907037 有pH為9至11. 5。 【實施方式】 、已發現聚乙稀鱗烧a同及多成分界面活 增進氮化㈣除速率,且對於半 2、σ β 移除速率沒有不利影響。針對:::== ::::::綱互聯及藉由絕緣層一可產 電性材料的晶圓。又,該等漿液出乎 Γ圓的缺陷度。最後,該等漿液(有助於阻障對 低除速率之優異選擇性)在⑽製程後提供穩定的膜。
為了具有低k介電膜的選擇性移除速 該衆液包含〇·至5重量百分比的聚乙雄鱗3除除 非另有指示,本說明書之所有濃度係指重量百分比。較佳 該聚液包含〇. 〇〇2至3重量百分比的聚乙烯鱗院嗣。 最佳地,該漿液包含U1至2重量百分比的聚乙烯料烧 ,。對於要求具中等之低k移除速率之阻障移除之應用而 言,該漿液較佳包含低於0.4重量百分比的聚乙烯吡咯烷 酮。對於要求以低等的低k移除速率之阻障移除之應用而 言’該漿液較佳包含至少〇·4重量百分比的聚乙烯吡咯烷 酬。此非離子性聚合物促進低k及超低k介電膜(典型地, 疏水性)及硬遮罩覆蓋層臈之研磨。 該聚乙烯吡咯烷酮較佳具有1,000至1,〇〇〇, 〇〇〇之重 量平均分子量。對於本說明書之目的來說,重量平均分子 量係指以膠體滲透性色層分析測量之分子量。該漿液更佳 具有1,000至500,000之分子量,且最佳具有2, 500至 6 94413 200907037 50, 000之分子量。例如,已證實具有分子量範圍為7, 〇〇〇 至25, 000的聚乙烯吡咯烷酮具有特別功效。 如同用於本說明書之表面活性劑或界面活性劑,其意指 一種當其存在時’具有吸附至該晶圓基材之表面或界面、或 改變該晶圓基材之表面或界面之表面自由能(free energy) 之特性的物質。術語『界面(interface)』係為在任何兩種 非互溶相之間的界面。術語『表面(surface)』意指其中一 相為氣體(通常是空氣)之界面。界面活性劑通常作用來降低 界面自由能。若干界面活性劑,如脂肪醇聚乙二醇醚硫酸酯 (fatty alcohol P〇lyglycol ether suHate),可抑制 c㈧ 速率,但該等界面活性劑會增加晶圓缺陷數。 已發現多成分界面活性劑與聚乙婦吼洛烧綱之虹人 降低CD0移除速率’且不伴隨無法接受的晶圓缺陷度的增 加。該多成分界面活性劑含有第—結構部分H = 小的水吸引力之分子結構,已知為疏水性尾端;第二 (部分,其為具有水吸引力的非離子性親水性部分;2 強水吸引力的陰離子性親水性基團-當於溶液中離心匕 時,該陰離子性親水性基團具有負離子價。 該疏水性基團通常為具有適於水溶解性的長度的長鍊 煙、氟化碳或石夕烧鍊。特別是,該疏水性基團具有输數 6至30健原子。較佳地,該疏水性基團具有、、= 碳原子,且最佳地,其具有12 Λ 別们 β以至W個碳原子。該疏水性 科可為直鍊、支鍊或環鍊其—。該疏水性部分 鍊、不飽和鍊或含有芳香基團。一特定實例係為街^自^ 94413 7 200907037 肪醇之直鍊聚合物。 該非離子性親水性部分係包含10至300個碳原子。較 佳地,該非離子性親水性部分係包含20至200個碳原子。 最佳地,該非離子性親水性部分係包含25至150個碳原 子。該非離子性親水性部分可為直鍊、支鍊或環鍊。該非 離子性親水性部分可為飽和鍊、不餘和鍊或含有芳香基 團。適當的非離子性親水性部分之特定實例係為聚氧乙烯 (polyethylene oxide)之直鍊。 例示陰離子性部分包含了含有至少一種缓酸、續酸、 硫酸、膦酸、及其鹽類或其混合物之陰離子性部分。較佳 的陰離子性部分包含至少一種選自下列各者之化學基團:. 羧酸根(羧酸鹽)、磺酸根(磺酸鹽)、硫酸根(硫酸鹽)、或 磷酸根(磷酸及聚磷酸酯)。該界面活性劑之親水性部分可 包含一個或多個氮原子或一個或多個氧原子或其混合物, 但其較佳係包含至少一個可離子化基團(ionizable group),以提供溶解性及對帶負荷表面(如氧化矽表面)之 排斥力。 典型地,可藉由添加0. 00002至5重量百分比的多成 分界面活性劑達到高選擇性。除非另有指示,本說明書之 所有濃度係指重量百分比。又,所揭露之範圍包含範圍之 組合或範圍之部分組合及落在範圍之限制内。較佳地,該 界面活性劑係為0. 00005至2 wt% ;且最佳地,該界面活 性劑係為0. 0001至1 wt°/〇。 典型地,該等界面活性劑係以銨鹽、鉀鹽、四級銨或 8 94413 200907037 鈉鹽而添加。最佳地,該界面活性劑係以銨鹽形式添加以 得到尚純度配方。 較佳地,該多成分界面活性劑係以相較於其抑制阻障 膜(如钽(Ta)或氮化組(TaN))之移除速率來得更大之差異 速率來抑制碳摻雜氧化物(CD0)之移除速率(以每分鐘埃 (angstroms per minute)測量)。若我們定義一膜X之移除
速率之相對抑制度(ΔΧ)為ΔΧ =(Χ〇-Χ)/Χ〇,其中,X〇及X f代表在添加界面活性劑之前及之後之X膜之移除速率,以 埃/每分鐘測量,揭露於本發明之界面活性劑較佳係滿足至 少一個下列方程式(以TaN為例):△((:!)〇)> A(TaN),利用 以13. 8 kPa(2 psi)之垂直於晶圓所測得的微孔性聚胺酷研 磨墊壓力及實施例之條件下測量。例如,當於13.8 壓力及以Hi浮凸的p〇iitex™吝 ' -r ΓυΐΐτΘΧ多孔性凝結之聚胺酯 (Pomex係為羅門哈斯公司或其子.公司之商標)研磨塾之 貫施例之條件,以不含界面活性劑之組成 L供對照組研磨速率(X〇) :對碳摻雜氧化物為每分鐘5〇(^ 及對氮化组為每分鐘500埃。接著 刀鐘埃 多成分界面活性劑係降低該研磨速率至二:件下加入該 分鐘300埃,且對灿之移除速率,摻雜氧化物每 滿足上述選擇率方程式。 ;母分鐘300埃以 該漿液視需要包含0至5重量百分 針對本說明書之目的,『含磷』化合物係勺含磷化合物。 之化合物。較佳地,該裝液包含Q至3、·'、',何包含磷原子 化合物。更佳地,該襞液包含Q 1 百刀比的含辱ί • 至2重量百分比的含 94413 9 200907037 磷化合物。例如,含磷化合物包含磷酸鹽、焦磷酸鹽、聚 罐酸鹽、膦酸鹽、氧化膦(phosphine oxides)、硫化膦 (phosphine sulphides)、氧雜填雜環院類 (phosphorinanes)、膦酸鹽、亞鱗酸鹽(phosphites)、亞 膦酸鹽(phosphinates),包含它們的酸、鹽、混合的酸式 鹽、酯、部分酯、混合酯、及其混合物,例如,磷酸。特 別是,該研磨漿液可包含如下特定含磷化合物:磷酸鋅、 焦構酸鋅、聚填酸鋅、膦酸鋅(zinc phosphonate)、構酸 銨、焦鱗酸銨、聚罐酸銨、膦酸銨(ammonium phosphonate)、 磷酸二銨、焦磷酸二銨、聚磷酸二銨、膦酸二胺、磷酸鉀、 填酸二鉀、磷酸胍、焦填酸胍、聚磷酸胍、膦酸胍(guanidine phosphonate)、鱗酸鐵、焦填酸鐵、聚構酸鐵、膦酸鐵(iron phosphonate)、鱗酸錦、焦填酸#、聚鱗酸鈽、膦酸鋅 (cerium phosphonate)、乙二胺鱗酸鹽、鱗酸σ底哄、焦填 酸哌畊、膦酸哌畊、三聚氰胺磷酸鹽(melamine , phosphate)、二-三聚氰胺填酸鹽、三聚氰胺焦磷酸鹽、三 聚氰胺聚磷酸鹽、三聚氰胺膦酸鹽、蜜白胺磷酸鹽(melam —p品spfiaYey、蜜白胺焦麟酸鹽—、一變百胺—聚磷麗鹽厂、一蜜_百胺一 膦酸鹽、蜜勒胺磷酸鹽(melem phosphate)、蜜勒胺焦磷酸 鹽、蜜勒胺聚磷酸鹽、蜜勒胺膦酸鹽、二氰二胺磷酸鹽 (dicyanodi amide phosphate)、展素鱗酸鹽,包含它們的酸、 鹽、混合之酸式鹽、酯、部分酯、混合酯、及其混合物。 該含磷化合物較佳係包含磷酸銨及磷酸。然而’過量 的磷酸銨會導入過量的游離銨至溶液中。且過量的游離銨 10 94413 200907037 會侵害銅,造成粗糙的金屬表面。所添加之磷酸會與游離 鹼金屬(如鉀)於原位反應,以形成磷酸鉀鹽及磷酸二鉀 鹽,其係為特別有效。 該鉀化合物亦提供形成保護膜之益處,保護膜係於侵 蝕性的後CMP清理溶液中保護鋼。例如,後CMp晶圓的^ 具有足夠的完整性以在具有侵蝕性銅錯合劑(如氫氧化四 曱胺、乙醇胺及抗壞血酸)的pH 12的溶液中保護晶圓。 視而要地’含量為〇至25重量百分比的氧化劑亦促進 P且障層的移除’如艇、氮化组、欽、及氛化欽。較佳地, 該漿液包含〇· 01至15重量百分比的氧化劑。更佳地,該 漿液包含0· 1至1〇重量百分比的氧化劑。適當的氧化劑包 3例如過氧化虱、單過硫酸鹽(monopersulfates)、碟 酸鹽、過笨二曱酸鎂(magnesium perphthalate)、過乙酸 及其他過酸類、過硫酸鹽類、溴酸鹽、過碘酸鹽、硝酸鹽、 鐵鹽、鈽鹽、錳鹽(Mn(III)、Mn(IV)、Mn(VI))、銀鹽、鋼 鹽、鉻鹽、鈷鹽、齒素、次氯酸鹽、或包舍至少一種上述 氧化劑之組合。較佳的氧化劑係為過氧化氫。須注意氧化 劑係典型地於使用前才添加於研磨組成物中,且於該等例 中氧化劑係含於分開的包裝中,並於使用處混合。此對於 不穩定氧化劑如過氧化氫特別適用。 5周整氧化劑(如過氧化物)的量亦可控制金屬互聯移除 速率。例如’増加過氧化物濃度會增加銅的移除速率。然 而’過ΐ增加氧化劑對於研磨速率有不利的影響。 該阻障金屬研磨組成物包含氧化矽研磨料,以『機械 11 94413 200907037 性』移除該阻障材料。該研磨料較佳為膠體研磨料。研磨 料之實例包含下列:無機氧化物、金屬蝴化物、金屬碳化 物、金屬氫氧化物、金屬氮化物、或包含至少一種上述研 磨料之組合。適當的無機氧化物包含,例如,氧化矽 (Si〇2)、氧化蝴2〇3)、氧化錯⑽2)、氧化鈽㈣)、氧 化鍾(_2),衫混合物。可獲得之氧化財許多型式, 斤《氧化is r氧化銘、占一氧化銘及非晶形(非結晶狀) 化紹。其他適當的氧化銘之實例係為柏買Μα_Η), 粒及其混合物。如有需要,該等無機氧化物經 、之i式m合物塗佈之無機氧化物顆粒亦可使 用欲適,金屬碳化物1化物及氮化物包含,例如,碳 赛夕、氮化石夕、碳氮化妙(_、碳化蝴、碳化鶴、碳化 碳化组、碳化鈦及包含至少-種上述金屬碳 = 騎化物线合物。㈣需要,鑽 乍研磨料。其他研磨料亦包含聚合性顆粒及經塗 ν佈之υ顆粒。較佳的研磨料為氧化石夕。 在該研磨組成物的水相中具有0.1至50重量百分比的 研磨料濃度。對於不含研磨料之㈣/重里百刀比的 =阻ρ早層之移除。較佳地,該研磨料之濃度為01至4〇 =百分比。且最佳地,該研磨料之濃度為㈣至奶重 =比。典型地’增加研磨料濃度係增加介電材料之移 換且其特別增加W介電材料之移除速率,諸如碳 移匕物。例如’若半導體業者期望增加的低k介電質 乐麵,則增加該研輯含量可將介電f的移除速率增 94413 12 200907037 加至所欲程度。 、。研磨料較佳具有彳、於咖⑽之平均顆粒尺寸以防止 過度金屬欠碟化及介電腐餘。對於本說明書之目的來說, 顆粒尺寸意指該膠體氧化石夕的平均顆粒尺寸。更佳地,該 氧化石夕具有小於log nm之平均顆粒尺寸以進—步降低金屬 乂碟化及"電腐餘。特別是,小於75 nm之研磨料平均顆 粒尺寸會以可接受的速率移除該阻障金屬’且不會有介電 材料的過度移除。例如’最少的介電腐#及金屬淺碟化發 生於使用具有20至75 nm之平均顆粒尺寸的膠體氧化矽。 降低該谬體氧化矽的尺寸有助於改善該溶液的選擇性;但 也易於降低阻障移除速率。另外’較佳的膠體氧化矽可包 含添加劑’如分散劑以改善氧化矽在酸性pH範圍中的穩定 度。該等研磨料之一為膠體氧化矽,可購自AZElectronic Materials France S. A. S.,於 Puteaux,France·。 除了抑制劑外,0至10重量百分比的錯合劑視需要地 防止非鐵金屬沈澱。最佳地,該漿液包含0.01至5重量百 %, 分比的錯合劑。較佳地,該錯合劑係為有機酸。例示錯合 劑包含下列:乙酸、檸檬酸、乙醯乙酸乙酯、乙醇酸、乳 酸、蘋果酸、草酸、水楊酸、二硫代胺基曱酸二乙基酯鈉、 琥珀酸、酒石酸、魏乙酸(thioglycolic acid)、甘胺酸、 丙胺酸、天門冬胺酸、乙二胺、三曱基二胺、丙二酸、戊二 酸、3-羥基丁酸、丙酸、苯二曱酸、間苯二甲酸、3-羥基水 揚酸、3, 5-二羥基水楊酸、沒食子酸(gallic acid)、葡萄 糖酸、鄰苯二盼(pyrocatechol)、五倍子齡(pyr〇gall〇l)、 13 94413 200907037 丹寧酸、及其鹽類。較佳地, °次错合劑传 檬酸、乙醯乙酸乙酯、乙醇酸、 ⑦碡自由乙酸、檸 • 孔酸> jte ™ 成之群組。最佳地,該錯合劑你 ’果®文、草酸所組 节马檸檬酸。 添加0.001至10總重量百分比 之移除速率及保護銅免於靜電餘叫 彳係降低銅互聯 的’銅互聯意指以具有偶發性雜質之3對於本申請案之目 金所形成的互聯。調整抑制劑之濃户2或以銅為基礎之合 靜電蝕刻而調整該銅互聯移除迷率I糸藉由保護金屬免於 〇· 002至5重量百分比的抑制劑。1佳地該裝液較佳係包含 至2重量百分比的抑制劑。該抑制劑可由 所組成。唑類抑制劑對銅互聯特別 剜之此s物 劑包含苯并三唑(BTA)、縣笨并噻唑抑制 嗅及^坐。BTA係對於銅互聯為特別有 ^开二 可增加銅移除速率。 、、彳且味唾 該研磨組成物之pH可為酸性及鹼性’並| 、較佳地,該pH係介於8及12之間,且最佳係介 2間。另外,該溶液最佳仙去離子水補足體積以限制偶 發性雜質。鱗子源,如氨、氫氧化納或氫氧化鉀,於驗 性區間調整pH。最佳地,該經離子來源係為氯氧化卸。 該漿OTf 平劑(如氯化物’或特別是氯化 錢)、缓衝溶液、分散劑及界面活性劑。例如,該衆液視需 要包含0. 0001至0. 1重量百分比的氣化錢。氯化銨提供表 面外觀之改善,且其可藉由增加鋼移除速率而促進銅移除。 該研磨組成物亦可視需要包含緩衝劑,諸如不同的有 94413 14 200907037
機鹼及無機鹼或其彼等之具有Ph為大於8至12之pH範 圍中之鹽類。該研磨組成物可視需要復包含消泡劑,如非 , 離子性界面活性劑包含酯類、環氧乙烷類、醇類、乙氧化 物類(ethoxylate)、矽化合物、氟化合物、醚類、糖苷及 其衍生物等。該消泡劑亦可為兩性的界面活性劑。該研磨 組成物可視需要包含殺菌劑(biocides),如KordexTM MLX(9. 5至9. 9%甲基-4-異嗔唾淋-3-酮、89. 1至89. 5% 水及S 1· 0%相關反應產物)或包含活性成分:2-甲基-4-異噻唑啉-3-酮及5-氯-2-甲基-4-異噻唑啉-3-酮之 KathonTM ICP ΠΓ ’各由羅門哈斯公司製造(Kath〇n及K〇rdex 係為羅門哈斯公司之商標)。 較佳地,該漿液係藉由將漿液施用至半導體基材,並 於研磨墊施加21 kPa或更少的向下力量而研磨半導體基 材。該向下力量表示該研磨墊抵頂該半導體基材的力量。 該研磨墊可為圓形、帶狀或網狀構形。此低度向下力量係 (特別適用於平坦化該半導體基材,以自該半導體基材移除 阻障材料。最佳地,該研磨之發生係以少於15 kPa的向下 力量。 實施例 一系列與餘量去離子水混合的漿液(比較例漿液A至η 與實施例漿液1至8)如下表丨所示。 15 94413 200907037 表1 漿液 CA Cwt°/o) PVP (wt%) 添加物 (wt%) BTA (wt%) H3PO4 (wt%) pH 氧化矽 (wt%) H202 (wt%) A 0.3 0.4* 0.02 0.1 10.50 ]4* 0.4 B 0.3 _0.0I多成分界面活性劑 0.02 0.1 10.50 14* 0.4 C 0.3 0.05多成分界面活性劑 0.02 0.1 10.50 14* 0.4 D 0.2 0.1** 0.1聚丙嬌酸* 0.02 10 14** 0.1 E 0.2 0.1** 0.1聚丙嬌醅** 0.02 10 14** 0.1 F 0.2 0.1 ** 0.1 CMC* 0.02 10 ]4♦冰 0.1 G 0.2 0.1** 0.1 CMC** 0.02 10 0.1 Η 0.3 0.4* 0.02 10.50 14* 0.4 1 0.3 1 0.4* 0.01多成分界面活性剤 0.02 0.1 10.50 14* 0.4 2 0.3 0.4* 0.05多成分界面活性劑 0.02 10.50 14* 0.4 3 0.3 0.4* 0.05多成分界面活性劑 0.06 10.50 14* 0.4 4 0.3 0.4*** 0.05多成分界面活性劑 0.02 10.50 14* 0.4 5 0.3 0.4*** 0_05乡成分界面活性劑 0.06 10.50 14* 0.4 6 0.3 0.4* 0.01多成分界面活性劑 0.02 10.50 14* 0.4 7 0.3 0.4* 0.03多成分界面活性劑 0.02 10.50 10* 0.4 8 0.3 0.4* 0.05’多成分界面活性劑 0.02 10.50 10* 0.4 CA=檸檬酸;PVP*=10K聚乙烯吡咯烷酮;PVP**=15K聚乙烯 ί 吡咯烷酮;PVP***=55K聚乙烯吡咯烷酮;多成分界面活性 劑=Disponi 1™ FES 界面活性劑,由 Cognis Chemical Group 製造;NH4C1=0. Olwt% ;聚丙烯酸*=Sokalon 30 與 0. 5 wt% 礙酸胍;聚丙烯酸**=Sokalon 250與0.5 wt%碳酸胍; CMC*=Blanos 7L1C1叛曱基纖維素與0.5 wt%碳酸胍; CMC**=Blanos 7ULC1羧曱基纖維素與〇. 5 wt%碳酸胍;BTA= 苯并三唑;殺菌劑=0.005 wt°/〇 Kordex™ MLX ,由羅門哈 斯公司製造(9. 5至9. 9%曱基-4-異噻唑啉-3-酮、89. 1至 89. 5%水及S1. 0%相關反應產物);氧化矽*=1501-50,購 16 94413 200907037 自 AZ Electronic Materials FranceS. A. S.,於 Puteaux, France的50nm氧化矽;氧化矽**=1501-35,購自AZ Electronic Materials France S. A. S.,於 Puteaux,France 的35nm氧化矽,且以KOH調整pH值。 實施例1 研磨測試係使用購自Novellus System, Inc.的 CoralTM碳摻雜氧化物(CD0)之200 mm晶圓片、TE0S介電 質、氮化組、及電鍍銅。形貌(topographical)資料係得自 / ' 研磨羅門哈斯電子材料CMP科技公司購得的IC1010TM晶圓 片及浮凸的PolitexTMW磨塾。 以ΜIRRA旋轉型研磨平台研磨晶圓片。第一步驛之銅 研磨使用Eternal漿液EPL2360與環狀溝槽的聚胺酯研磨 墊在平台1及2(使用Kinik AD3CG-181060網格鑽石調理 盤)研磨銅。用於平台1的研磨條件為平-台速度93 rpm、 載體速度21 rpm及向下力量4 psi(27. 6 kPa),及用於平 ( 台2的研磨條件為平台速度33 rpm、載體速度61 rpm及 向下力量3 psi(20. 7 kPa)。用於平台3的研磨條件為向 下力量1.5 psi (10.3 kPa)、平台速度93 rpm、載體速度 87卬1〇及漿液流速20〇1!11/分,並使用舡浮凸的?〇1衍6又^ 凝集聚胺酯研磨墊。 自研磨前及研磨後的膜厚度計算移除速率。使用 Tencor SM300橢偏法測量裝置(對銅設定於170χ1(Γ6ω及, 對氮化钽設於28,〇〇〇χ1(Γ6Ω)測量所有光學透明膜。使用
Dektak Veeco V200SL探針式輪摩儀(stylus profilometer) 17 94413 200907037 收集晶圓形貌數據。移除速率均以A /分鐘之單位報導。缺 陷數據係於藉ATMI供給之ESC 784清理後,得自〇rb〇t激光 散射缺陷度測量工具及AFM表面粗縫度測量。 表2係提供自研磨添加劑系列之研磨_選結果。 表2 漿液 TE0S (A/分鐘) Cu (人/分鐘) TaN (A/分鐘) CD0 (A/分鐘) 刮痕 (數目) PVP 10K (wt %) Disponil FES 界面活性劑 (wt%) A 1139 872 1331 543 90 0. 40 B 1217 1214 1320 ----- 538 546 0.01 C 1230 1664 1407 292 392 0.05 D 677 1367 957 635 E 814 1429 1093 -------- 753 F 823 1886 1122 709 G 811 1685 1091 ------- 789 1 . 1133 923 1236 367 108 0.40 0.01 刮痕=濾光以檢測來自該漿液之刮痕。 表2係說明Disponip fes界面活性劑及聚乙烯吡咯 烷酮之組合係提供絕佳的TaN移除速率及低CD0或碳摻雜 氧化物移除速率之纟且合。特別是,該漿液移除TaN之速率 係為CD0移除速率之至少兩倍。另外,如刮痕測試所示, 該漿液提供低度的晶圓缺陷。 實施例2 18 94413 200907037 表3係提供對於一系列BTA濃度及聚乙烯吡咯烷酮分 子量之在此實施例之條件下操作之移除與刮痕結果。 表 3 漿液 TE0S (A/雜) Cu TaN (A觸) CDO (A/雜) 刮痕 (數目) 基礎 (數目) PVP 10K PVP 55K BTA 2 1120 408 990 310 54 207 0.4 0.02 3 1208 233 1148 298 49 169 0.4 0.06 4 1108 421 939 312 39 141 0.4 0. 02 5 1168 221 1055 306 22 123 0.4 0.06 基礎=缺陷之總數;刮痕=濾光以檢測來自該漿液之刮痕。 該系列係說明ΒΤΑ提供低刮痕且對銅移除速率提供了 絕佳的控制。另外,該低分子量聚乙烯吡咯烷酮係對TaN 移除速率提供最高的增加。 實施例3 表4係以1. 5 psi (10. 3 kPa)向下力量、93 rpm平台 速度、87 rpm載體速度、200 ml/分襞液流速及其他此實 施例之條件操作運作。表4係提供研磨購自羅門哈斯電子 材料CMP科技公司的鑄模VisionPadTM3100及3500聚胺酯 研磨塾之結果(VisionPad為羅門哈斯公司或其子公司之 商標)。 19 94413 200907037 表4 漿液 墊 TE0S (人/分鐘) Cu (人/分鐘) TaN (A/分鐘) CDO (人/分鐘) Disponil FES 界面活性劑 (wt%) Η VP3100 775 692 1027 666 Η VP3500 905 830 1159 572 6 VP3100 676 520 927 418 0.01 6 VP3500 870 380 1076 422 0.01 7 VP3100 319 264 608 69 0. 03 7 VP3500 508 300 612 151 0.03 8 VP3100 308 307 557 50 0. 05 8 VP3500 481 311 569 119 0. 05 表4係說明該鑄模聚胺酯研磨墊傾向於增加TaN相對 於CD0移除速率之選擇性。但此選擇性之增加,會犧牲整 體TaN移除速率。 【圖式簡單說明】 無 【主要元件符號說明】 無 20 94413
Claims (1)
- 200907037 七、申請專利範圍: 1. 一種適用於化學機械研磨具有銅互聯的半導體基材的 水性漿液,包括,以重量百分比計,0至2 5重量百分 比的氧化劑、0. 1至50重量百分比的研磨料顆粒、0. 001 至5重量百分比的聚乙烯吡咯烷酮、0. 00002至5重量 百分比的多成分界面活性劑、0. 0 01至10重量百分比 之用以降低該銅互聯之靜電蝕刻的抑制劑、0至5重量 , 百分比之用以增加該銅互聯的移除率的含磷化合物、於 研磨期間形成的0. 001至10重量百分比的錯合劑,以 及餘量水,其中該多成分界面活性劑具有疏水性尾端、 非離子性親水性部分及陰離子性親水性部分,該疏水性 尾端具有6至30個碳原子及該非離子性親水性部分具 有10至300個碳原子。 2. 如申請專利範圍第1項之水性漿液,其中,該聚乙烯吡 , 咯烷酮具有1,000至1, 000, 000之重量平均分子量。 V. . 3. 如申請專利範圍第1項之水性漿液,其中,該漿液包含 氧化矽研磨料顆粒。 4. 一種適用於化學機械研磨具有銅互聯的半導體基材的 水性漿液,包括,以重量百分比計,0. 01至15重量百 分比的氧化劑、0. 1至40重量百分比的氧化石夕研磨料 顆粒、0.002至3重量百分比的聚乙烯吡咯烷酮、 0. 0 0 0 0 5至2重量百分比的多成分界面活性劑、0. 0 0 2 21 94413 200907037 , 至5重量百分比之用以降彻 牛低該銅互聯之靜電蝕刻的唑 —類抑制劑、G至3重量百分比之用以增加該鋼互聯 除率的含齡合物、於期間形成的㈣至 百分比的有機酸錯合劑,以洛从θ ^ 乂及餘量水;其中該多成分界 面活性劑具有疏水性尾端、韭 崦非離子性親水性部分及降論 子性親水性部分,該疏水性屋 士 = 具有8至20個碳原子 及該非離子性親水性部分具有20至20〇個碳原子’,、且 該水性漿液具有pH為8至12。 5. 如申請專利範圍第4項之水性漿液,其中,該聚乙埽吡 p各院酮具有1,000至500, 〇〇〇之重量平均分子量。 6. 如申請專利範圍第4項之水性漿液,其中,該裝液包人 具有平均顆粒尺寸小於100 nm之氧化矽研磨料顆粒。 7. 如申請專利範圍第4項之水性漿液,其中,該漿液包人 選自磷酸銨、磷酸鉀及磷酸二鉀之含磷化合物。 % 8· ~種適用於化學機械研磨具有銅互聯的半導體基材的 水性漿液,包括,以重量百分比計,〇· 1至〇 里ΐ百 为比的氧化劑、〇· 25至35重量百分比的氧化矽研磨料 '顆粒、〇·〇1至2重量百分比的聚乙烯吼咯烷酮、〇〇⑽工 至1重量百分比的多成分界面活性劑、〇· 至2备θ ^室夏 百分比之用以降低該銅互聯之靜電蝕刻的苯并=唾私 制劑、〇· 001至2重量百分比之用以增加該銅互聯的2 除率的含磷化合物、於研磨期間形成的〇 〇1至5 直董 94413 22 200907037 百分比的有機酸錯合劑,以及餘量水;其中該多成分界 面活性劑具有疏水性尾端、非離子性親水性部分及陰離 子性親水性部分,該疏水性尾端具有12至16個碳原子 及該非離子性親水性部分具有25至150個碳原子,且 該水性漿液具有pH為9至11.5。 9. 如申請專利範圍第8項之水性漿液,其中,該錯合劑係 為檸檬酸。 10. 如申請專利範圍第8項之水性漿液,其中,該含磷化合 物係選自磷酸銨、磷酸鉀及磷酸二鉀。 23 94413 200907037 四、指定代表圖:本案無圖式 (一) 本案指定代表圖為:第( )圖。 (二) 本代表圖之元件符號簡單說明: 五、本案若有化學式時,請揭示最能顯示發明特徵的化學式: 本案無代表化學式 2 94413
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2007
- 2007-08-03 US US11/890,182 patent/US20090031636A1/en not_active Abandoned
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2008
- 2008-07-30 TW TW097128747A patent/TW200907037A/zh unknown
- 2008-07-30 JP JP2008196224A patent/JP2009049402A/ja active Pending
- 2008-08-01 KR KR1020080075484A patent/KR20090014109A/ko not_active Application Discontinuation
- 2008-08-04 CN CN2008101312912A patent/CN101358109B/zh not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JP2009049402A (ja) | 2009-03-05 |
CN101358109A (zh) | 2009-02-04 |
CN101358109B (zh) | 2012-01-11 |
US20090031636A1 (en) | 2009-02-05 |
KR20090014109A (ko) | 2009-02-06 |
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