TWI487760B - 含銅之圖案化晶圓之研磨 - Google Patents
含銅之圖案化晶圓之研磨 Download PDFInfo
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- TWI487760B TWI487760B TW098102429A TW98102429A TWI487760B TW I487760 B TWI487760 B TW I487760B TW 098102429 A TW098102429 A TW 098102429A TW 98102429 A TW98102429 A TW 98102429A TW I487760 B TWI487760 B TW I487760B
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- Prior art keywords
- acid
- copper
- bta
- weight percent
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- 239000010949 copper Substances 0.000 title claims description 63
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 40
- 229910052802 copper Inorganic materials 0.000 title claims description 40
- 238000005498 polishing Methods 0.000 title claims description 27
- 235000012431 wafers Nutrition 0.000 title description 18
- 229910052751 metal Inorganic materials 0.000 claims description 41
- 239000002184 metal Substances 0.000 claims description 41
- 239000002244 precipitate Substances 0.000 claims description 30
- 239000002002 slurry Substances 0.000 claims description 22
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 18
- 239000012964 benzotriazole Substances 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 18
- 239000003112 inhibitor Substances 0.000 claims description 15
- 150000002500 ions Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 claims description 10
- 239000004065 semiconductor Substances 0.000 claims description 10
- 150000002466 imines Chemical class 0.000 claims description 9
- 239000008346 aqueous phase Substances 0.000 claims description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910001431 copper ion Inorganic materials 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 claims description 2
- 238000007517 polishing process Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 55
- 150000001875 compounds Chemical class 0.000 description 19
- 239000002245 particle Substances 0.000 description 14
- 229910052698 phosphorus Inorganic materials 0.000 description 13
- 239000011574 phosphorus Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 238000009472 formulation Methods 0.000 description 11
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 10
- 239000001630 malic acid Substances 0.000 description 10
- 235000011090 malic acid Nutrition 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 9
- 229920000388 Polyphosphate Polymers 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
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- 239000001205 polyphosphate Substances 0.000 description 9
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- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 8
- 150000001720 carbohydrates Chemical class 0.000 description 8
- 229920002678 cellulose Polymers 0.000 description 8
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- 239000008139 complexing agent Substances 0.000 description 8
- 239000007800 oxidant agent Substances 0.000 description 8
- 229920003169 water-soluble polymer Polymers 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 7
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- 229910052799 carbon Chemical group 0.000 description 7
- 239000001913 cellulose Substances 0.000 description 7
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 7
- 238000003801 milling Methods 0.000 description 7
- 235000021317 phosphate Nutrition 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000004254 Ammonium phosphate Substances 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 6
- 235000019289 ammonium phosphates Nutrition 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 description 6
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
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- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 description 5
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 5
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- -1 monopersulfate Chemical compound 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
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- YZEZMSPGIPTEBA-UHFFFAOYSA-N 2-n-(4,6-diamino-1,3,5-triazin-2-yl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NC=2N=C(N)N=C(N)N=2)=N1 YZEZMSPGIPTEBA-UHFFFAOYSA-N 0.000 description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- 125000000129 anionic group Chemical group 0.000 description 3
- 239000003989 dielectric material Substances 0.000 description 3
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- 150000002576 ketones Chemical class 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
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- 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 compound C1CCPCC1 VXTFGYMINLXJPW-UHFFFAOYSA-N 0.000 description 1
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- 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
- MWFNQNPDUTULBC-UHFFFAOYSA-N phosphono dihydrogen phosphate;piperazine Chemical compound C1CNCCN1.OP(O)(=O)OP(O)(O)=O MWFNQNPDUTULBC-UHFFFAOYSA-N 0.000 description 1
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- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 1
- QVJYHZQHDMNONA-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1 QVJYHZQHDMNONA-UHFFFAOYSA-N 0.000 description 1
- NQQWFVUVBGSGQN-UHFFFAOYSA-N phosphoric acid;piperazine Chemical compound OP(O)(O)=O.C1CNCCN1 NQQWFVUVBGSGQN-UHFFFAOYSA-N 0.000 description 1
- SWXKOPASTUVMMT-UHFFFAOYSA-N phosphoric acid;urea Chemical compound NC(N)=O.NC(N)=O.OP(O)(O)=O SWXKOPASTUVMMT-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229960001954 piperazine phosphate Drugs 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000012064 sodium phosphate buffer Substances 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- WSANLGASBHUYGD-UHFFFAOYSA-N sulfidophosphanium Chemical class S=[PH3] WSANLGASBHUYGD-UHFFFAOYSA-N 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
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 229910003468 tantalcarbide Inorganic materials 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
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- 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
- 238000009966 trimming Methods 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- OMSYGYSPFZQFFP-UHFFFAOYSA-J zinc pyrophosphate Chemical compound [Zn+2].[Zn+2].[O-]P([O-])(=O)OP([O-])([O-])=O OMSYGYSPFZQFFP-UHFFFAOYSA-J 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 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
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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]
-
- 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
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
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- C—CHEMISTRY; METALLURGY
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Description
本發明係有關於一種半導體晶圓材料之化學機械研磨(CMP),且特別是有關於在具有電介質或阻障材料之半導體晶圓上研磨金屬內連線之CMP方法以及CMP組合物。
傳統上,半導體晶圓係具有介電層之矽晶圓,且此介電層中包括呈圖案化排列之多個溝槽以作為內連接電路之用。此圖案排列中通常具有金屬鑲嵌結構或雙重金屬鑲嵌結構。阻障層係覆蓋圖案化介電層且金屬層係覆蓋阻障層。此金屬層具有至少足夠在圖案化溝槽中填滿金屬而形成電路內連線之厚度。
CMP流程通常包含多重研磨步驟。例如,第一步驟以初始高速率移除過量的內連線金屬,如銅。在第一步驟移除過量的內連線金屬之後,第二步驟可研磨移除殘留在金屬內連線外面之阻障層上的金屬。後續的研磨步驟可自半導體晶圓之下方介電層移除阻障層,藉以使得介電層與金屬內連線具有平坦之研磨後表面。
位於半導體基材之溝槽或溝渠(through)中的金屬係用來提供金屬線以形成金屬電路。其中之一個需要克服的問題在於研磨操作常會從每個溝槽或溝渠中移除金屬,而造成金屬產生凹陷。此種凹陷會造成金屬電路之臨界尺寸(critical dimension)產生改變,因此這種凹陷是不受歡迎。為了減少凹陷,所以需要在較低的研磨壓力下進行研磨。然而,只降低研磨壓力,卻需要延長研磨一段時間。但是,延長研磨一段時間之後,仍會產生凹陷,因此對於效能之改善並無多大幫助。
美國專利案第7,086,935號(Wang)係揭示在圖案化晶圓上使用不含研磨劑(abrasive-free)之銅配方,此配方包含甲基纖維素(methyl cellulose)、丙烯酸/甲基丙烯酸共聚物(acrylic acid/methacrylic acid copolymer)、苯并三唑(benzotriazole;BTA)與可溶混之溶劑。此配方能夠移除與潔淨銅且具有少量凹陷之銅,但是在快速研磨中,此配方卻會在研磨墊與晶圓上沉澱綠色Cu-BTA化合物。因此,這些沉澱物需要對研磨墊進行研磨後潔淨以避免這些膠狀沉澱物降低了研磨移除速率,並且它們需要對晶圓進行研磨後潔淨步驟以避免產生缺陷。這些潔淨步驟需要大量且昂貴的潔淨溶液,並會使得晶圓處理速度變慢,而增加整體成本。
因此,需要提供能夠使得潔淨後之銅具有低缺陷率、低凹陷、低腐蝕且均不會產生Cu-BTA沉澱物之研磨組合物。再者,需要提供具有上述研磨特性之低刮傷配方。
本發明之目的在於提供一種以研磨墊研磨具有銅內連線金屬之圖案化半導體晶圓之方法,包括下列步驟:提供水相研磨液,此研磨液包括苯并三唑(BTA)抑制劑以及具有下列化學式之錯合物:
其中,R為氫或含碳化合物,此錯合物可錯合銅離子與水;以銅溶解成Cu+1
離子,且Cu+1
離子與BTA抑制劑之濃度為[BTA]*[Cu+1
]>當水相研磨液中不含錯合物時Cu-BTA沉澱物之Ksp之方式,以水相研磨液與研磨墊研磨圖案化晶圓;以及將至少部份之Cu+1
離子氧化成Cu+2
離子以避免Cu-BTA沉澱物在研磨時沉澱在圖案化晶圓與研磨墊上。
當以研磨組合物對半導體晶圓進行CMP處裡時,此組合物與方法可提供良好的金屬移除速率且可潔淨金屬以及可使得金屬內連線具有低凹陷(lowdishing),其中此研磨組合物包括錯合物組合水溶性改性纖維素、非醣類水溶性聚合物、氧化劑、抑制劑與餘量水。添加錯合物之額外好處在於可降低Cu-BTA(Cu+1
)沉澱物所造成之綠色污物。從研磨經驗中可知,當Cu離子(+1)
與BTA之濃度乘積大於其操作或研磨溫度下之Ksp時,則會形成不可溶之Cu-BTA沉澱物。在本說明書中,Cu-BTA沉澱物包括非液體,例如固體、膠體或聚合物,且可包括Cu+2
離子、尖晶石沉澱物、似尖晶石沉澱物以及雜質;以及Ksp代表在其操作或研磨溫度下之溶解度乘積(solubility product)。在研磨液中,係
依據下列平衡式(1)而產生Cu-BTA沉澱物:(1)BTAH+Cu+
←(慢) (快)
→Cu-BTA+H+
雖然某些胺類能夠有效地從晶圓與研磨墊上溶解綠色"黏泥狀"沉澱物,然而特殊的錯合物則可降低或消除Cu-BTA沉澱物之有害數量。尤其是具有下列之化學式之錯合物:
其中,R為氫或含碳化合物。此錯合物能夠錯合單價(+1)與雙價(+2)之銅離子。在研磨時,錯合劑係用來錯合足量之銅離子以降低Cu-BTA沉澱物之生成並且控制下列式(2)之Cu+2
離子之形成速率。
(2)2Cu+
→Cu0
+Cu+2
此流程以銅溶解成Cu+1
離子,且Cu+1
離子與BTA抑制劑之濃度為[BTA]*[Cu+1
]>當水相研磨液中不含錯合物時Cu-BTA沉澱物之Ksp之方式而有助於以水相研磨液與研磨墊研磨圖案化晶圓。添加酸化合物使得研磨方法從會產生Cu-BTA沉澱物轉變成能夠避免產生Cu-BTA沉澱物問題。此流程將至少部份之Cu+1
離子氧化成Cu+2
離子以避免研磨時在圖案化晶圓與研磨墊上沉澱Cu-BTA沉澱物。此流程亦可在其他銅錯合劑存在的情況下進行。例如,第一酸錯合劑可與第二錯合劑,如有機酸,一同使用,以降低或消除
研磨液產生Cu-BTA沉澱物之傾向。濃度為0.05至20重量百分比之錯合物可降低Cu-BTA沉澱物之生成。例如,濃度範圍為0.1至10重量百分比之錯合物可減少Cu-BTA沉澱物。其優點在於,此配方中具有濃度至少為0.4重量百分比的酸化合物,如0.4至5重量百分比之錯合物,藉以控制Cu-BTA沉澱物之產生。當錯合物濃度大於約0.4重量百分比時,增加錯合物之濃度可增加或加速銅的移除速率;以及當錯合物濃度介於0至約0.4重量百分比時,增加錯合物之濃度可減少銅的移除速率。尤其,亞胺二乙酸(iminodiacetic acid,IDA或diglycine)與乙二胺四乙酸(ethylenediaminetetraacetic acid;EDTA)中的至少一者提供有效地降低Cu-BTA沉澱物之手段。IDA似乎是能夠最有效降低Cu-BTA沉澱物的錯合劑。本發明之方法包括以純化水溶液潔淨該研磨墊之額外步驟。
本發明之組合物係使用0.001至15重量百分比之羧酸官能基改性之水溶性纖維素與可溶混於水之有機溶劑,例如醇與酮。此組合物較佳為包括0.005至5重量百分比之水溶性纖維素。此組合物最佳為包括0.01至3重量百分比之水溶性纖維素。改性纖維素的例子係陰離子膠(例如瓊膠(agar gum)、阿拉伯樹膠(arabic gum)、印度樹膠(ghatti gum)、梧桐膠(karaya gum)、瓜耳膠(guar gum)、果膠(pectin)、刺槐豆膠(locust bean gum)、西黃蓍膠(tragacanth gum)、羅望子膠(tamarind gum)、鹿角菜膠(carrageenan gum)與黃原膠(xanthan gum)之至少一者);改性澱粉;藻酸(alginic acid);甘露糖醛酸(mannuronic acid);古羅糖醛酸(guluronic acid)及其衍生物與共聚物。較佳之水溶性纖維素(羧甲基纖維素(CMC))之取代度為0.1至3.0且重量平均分子量為1K至1000K。在本說明書中,分子量係指纖維素之重量平均分子量。更佳者為CMC之取代度為0.7至1.2且重量平均分子量為40K至250K。CMC之取代度係指在纖維素分子之每個葡萄糖殘基(anhydroglucose unit)上之乙酸鹽醚化羥基(acetate etherified hydroxyl group)的平均數量。CMC之取代度可被視為CMC之羧基之“密度”之度量單位。
本發明之非醣類水溶性聚合物包括利用丙烯酸單體或甲基丙烯酸單體合成之丙烯酸聚合物、甲基丙烯酸聚合物與共聚物。在本發明中,非醣類水溶性聚合物亦包括各種分子量之聚合物與低分子量之寡聚物。共聚物包括由丙烯酸與甲基丙烯酸組合而形成之共聚物,而且尤其是,由丙烯酸與甲基丙烯酸之莫耳比範圍為1:30至30:1,較佳為1:9至9:1之範圍,最佳為約2:3所形成之共聚物。此共聚物之較佳重量平均分子量範圍為1K至1000K,更佳之範圍為I0K至500K。
另一種可作為替代之非醣類水溶性聚合物則為兩親聚合物(amphiphilic polymer),如由丙烯酸或甲基丙烯酸形成之共聚物。在本說明書中,兩親聚合物係指由疏水性鏈段與親水性鏈段組成之嵌段共聚物。疏水性鏈段可為碳數於2至250變化之聚合物鏈。在本說明書中,碳數代表在疏水性鏈段中碳原子之數量。較佳之碳數為5至100,且最佳之碳數為5至50。親水性鏈段係離子性的。親水性鏈段之單體單元之較佳數量範圍為1至100。較佳的組合物包括0.005至5重量百分比之非醣類水溶性聚合物。更佳的組合物包括0.01至3重量百分比之非醣類水溶性聚合物。最佳的組合物則包括0.02至2重量百分比之非醣類水溶性聚合物。
兩親聚合物之較佳數量平均分子量為50至5000,本說明書提到兩親聚合物時是指其數量平均分子量且明確來說係指使用串聯之TSK-GEL pn/08025 GMPWx與TSK-GEL pn/08020 G2500PWx柱以及折射率偵測器(refractive index detector)與磷酸鈉緩衝液沖提劑(eluent)之水性凝膠滲透色譜法(aqueous gel permeation chromatography)測得者。更佳之數量平均分子量為介於50至4000,且最佳之數量平均分子量為介於100至3000。離子性鏈段包括陽離子性、陰離子性與兩性離子(聚兩性電解質與聚甜菜鹼)。較佳之親水性鏈段為陰離子性的,例如聚丙烯酸或聚甲基丙烯酸。親水性鏈段較佳包括聚丙烯酸、聚甲基丙烯酸或丙烯酸與甲基丙烯酸之共聚物。將這些鏈段組合成共聚物時會產生性質不同於其各自均聚物之分子,因此有助於進行潔淨且不會造成金屬內連線產生過量之凹陷。聚合物之疏水性端可包括碳氫鏈或烷基硫醇(alkylmercaptan)。最佳地,疏水性鏈段與親水性鏈段組合成嵌段共聚物形式。
此溶液包括氧化劑。較佳之溶液為包括0.5至25重量百分比之氧化劑。更佳為氧化劑之重量百分比範圍為1至10。在低pH範圍時,此氧化劑對於幫助溶液移除銅特別有效。此氧化劑可為多種氧化化合物之至少一者,例如為過氧化氫(H2
O2
)、單過硫酸鹽、碘酸鹽、過鄰苯二甲酸鎂、過乙酸與其他過酸、過硫酸鹽、溴酸鹽、過碘酸鹽、硝酸鹽、鐵鹽、鈰鹽、Mn(III)鹽、Mn(IV)鹽、與Mn(VI)鹽、銀鹽、銅鹽、鉻鹽、鈷鹽、鹵素、次氯酸鹽及其混合物。再者,使用氧化劑化合物之混合物通常是有好處的。當研磨漿包括不穩定之氧化劑如過氧化氫時,則通常是最有利的情況是在使用當時才將氧化劑混入組合物中。
另外,此溶液包括抑制劑,以控制利用靜態蝕刻或其他移除機制之銅內連線之移除速率。調整抑制劑之濃度時,可藉由在保護金屬免於靜態蝕刻,而調整內連線金屬之移除速率。較佳之溶液為包括0.01至15重量百分比之抑制劑。最佳之溶液為包括0.2至1.0重量百分比之抑制劑。此抑制劑可由唑類(azole)抑制劑之混合物所組成。苯并三唑抑制劑對於如純銅或銅合金之銅內連線金屬特別有效。實驗測試指出增加抑制劑之濃度可增加研磨時的移除速率。但是增加唑類之濃度卻有造成研磨液傾向沉澱Cu-BTA化合物之缺點。
除了抑制劑之外,組合物可選擇性地包括第二錯合劑,以用於銅內連線金屬。此錯合劑,如0至15重量百分比之錯合劑,有助於金屬膜,如銅,之移除速率。較佳之組合物包括0.01至15重量百分比之第二銅錯合劑。最佳之組合物包括0.1至1重量百分比之第二銅錯合劑。第二銅錯合劑之例子包括乙酸(acetic acid)、檸檬酸(citric acid)、乙醯乙酸乙酯(ethyl acetoacetate)、乙醇酸(glycolic acid)、乳酸(lactic acid)、蘋果酸(malic acid)、草酸(oxalic acid)、水楊酸(salicylic acid)、二硫代胺甲酸二乙酯鈉(sodium diethyl dithiocarbamate)、琥珀酸(succinic acid)、酒石酸(tartaric acid)、硫代乙醇酸(thioglycolic acid)、甘胺酸(glycine)、丙胺酸(alanine)、天門冬胺酸(aspartic acid)、乙二胺(ethylene diamine)、三甲基二胺(trimethyl diamine)、丙二酸(malonic acid)、戊二酸(glutaric acid)、3-羥基丁酸(3-hydroxybutyric acid)、丙酸(propionic acid)、鄰苯二甲酸(phthalic acid)、間苯二甲酸(isophthalic acid)、3-羥基水楊酸(3-hydroxy salicylic acid)、3,5-二羥基水楊酸(3,5-dihydroxy salicylic acid)、沒食子酸(gallic acid)、葡萄糖酸(gluconic acid)、兒茶酚(pyrocatechol)、五倍子酚(pyrogallol)、單寧酸(tannic acid),包括其鹽類及其混合物。較佳之第二銅錯合劑係選自乙酸、檸檬酸、乙醯乙酸乙酯、乙醇酸、乳酸、蘋果酸、草酸及其混合物所組成之族群。最佳之第二銅錯合劑係蘋果酸。蘋果酸所提供之額外優點在於可改善平坦性。
組合物可選擇性地包括0至15含磷化合物(文中有稱為磷化合物的情形)。在本說明書中,“含磷化合物”係任何含有磷原子之化合物。較佳之含磷化合物例如為磷酸鹽(phosphate)、焦磷酸鹽(pyrophosphate)、聚磷酸鹽(polyphosphate)、膦酸鹽(phosphonate),包括彼等之酸類、鹽類、混合之酸式鹽類、酯類、部分酯類、混合之酯類及其混合物,例如磷酸。尤其,較佳之水相研磨組合物之配製可使用,例如,下列之含磷化合物:磷酸鋅(zincphosphate)、焦磷酸鋅(zinc pyrophosphate)、聚磷酸鋅(zinc polyphosphate)、膦酸鋅(zinc phosphonate)、磷酸銨(ammonium phosphate)、焦磷酸銨(ammonium pyrophosphate)、聚磷酸銨(ammonium polyphosphate)、膦酸銨(ammonium phosphonate)、磷酸氫二銨(diammonium phosphate)、焦磷酸氫二銨(diammonium pyrophosphate)、聚磷酸氫二銨(diammonium polyphosphate)、膦酸氫二銨(diammonium phosphonate)、磷酸胍(guanidinephosphate)、焦磷酸胍(guanidine pyrophosphate)、聚磷酸胍(guanidine polyphosphate)、膦酸胍(guanidine phosphonate)、磷酸鐵(iron phosphate)、焦磷酸鐵(iron pyrophosphate)、聚磷酸鐵(iron polyphosphate)、膦酸鐵(iron phosphonate)、磷酸鈰(cerium phosphate)、焦磷酸鈰(cerium pyrophosphate)、聚磷酸鈰(cerium polyphosphate)、膦酸鈰(cerium phosphonate)、乙二胺磷酸鹽(etbylene-diamine phosphate)、哌磷酸鹽(piperazine phosphate)、哌焦磷酸鹽(piperazine pyrophosphate)、哌膦酸鹽(piperazine phosphonate)、三聚氰胺磷酸鹽(melamine phosphate)、雙三聚氰胺磷酸鹽(dimelamine phosphate)、三聚氰胺焦磷酸鹽(melamine pyrophosphate)、三聚氰胺聚磷酸鹽(melamine polyphosphate)、三聚氰胺膦酸鹽(melamine phosphonate)、蜜白胺磷酸鹽(melam phosphate)、蜜白胺焦磷酸鹽(melam pyrophosphate)、蜜白胺聚磷酸鹽(melam polyphosphate)、蜜白胺膦酸鹽(melam phosphonate)、蜜勒胺磷酸鹽(melem phosphate)、蜜勒胺焦磷酸鹽(melem pyrophosphate)、蜜勒胺聚磷酸鹽(melem polyphosphate)、蜜勒胺膦酸鹽(melem phosphonate)、二氰二胺磷酸鹽(dicyanodiamide phosphate)、尿素磷酸鹽(urea phosphate),包括彼等之酸類、鹽類、混合之酸式鹽類、酯類、部分酯類、混合酯類及其混合物。同樣,亦可使用膦氧化物(phosphine oxide)、膦硫化物(phosphine sulphide)與磷雜環己烷(phosphorinane)及其膦酸鹽、亞磷酸鹽(phosphites)與次膦酸鹽(phosphinates),包括彼等之酸類、鹽類、混合之酸式鹽類、酯類、部分酯類與混合酯類。較佳之含磷化合物為磷酸銨。
其優點在於,本發明之研磨組合物中含有有效數量之含磷化合物以增加於低的下壓力時的研磨速率。據信,即使研磨組合物中僅有微量的含磷化合物亦能夠有效地研磨銅。當研磨組合物中具有約0.05至約10重量百分比之含磷化合物時,即可在可接受之研磨下壓力下獲得令人滿意的研磨速率。含磷化合物之較佳範圍為佔研磨組合物之約0.1至約5重量百分比。含磷化合物之最佳範圍為佔研磨組合物之約0.3至約2重量百分比。
在含有餘量水的溶液中,此化合物之效力可及於很廣之pH值範圍。此溶液之有用pH值範圍係從至少2延伸至12。有利地,此溶液具有酸性pH值,如pH2至約7,如低於7。此外,此溶液較佳為依賴去離子水作為餘量水以限制偶而產生之雜質。本發明之研磨漿的較佳pH值為2至6且更佳之pH值為2.5至5.5。在本發明中,用來調整組合物之pH值之酸類例如為硝酸、硫酸、鹽酸與磷酸等。而用來調整本發明組合物之pH值之鹼的例子,則例如為氫氧化銨(ammonium hydroxide)與氫氧化鉀(potassium hydroxide)。
選擇性地出現在改性纖維素化合物之醇或酮係提供可接受之金屬移除速率且潔淨銅時為少凹陷。此組合物可包括非醣類水溶性聚合物且選擇性包括磷化合物。典型來說,這種可溶混於水之有機溶劑為醇或酮,例如為甲醇(methanol)、乙醇(ethanol)、1-丙醇(1-propanol)、2-丙醇(2-propanol)、乙二醇(ethylene glycol)、1,2-丙二醇(1,2-propanediol)、丙三醇(glycerol)、丙酮(acetone)與甲基乙基酮(methyl ethyl ketone)之至少一者。其優點在於,組合物包括0.005至10重量百分比之這些有機溶劑,在本說明書中所提到的所有成份範圍均為重量百分比。較佳的組合物為包括0.01至7.5重量百分比之這些有機溶劑。最佳的組合物為包括0.02至5重量百分比之這些有機溶劑。
另外,研磨組合物可選擇性包括研磨劑,如0至3重量百分比之研磨劑,以幫助移除金屬層。在此範圍中,研磨劑之數量須少於或等於1重量百分比。最佳之研磨組合物不含研磨劑。
研磨劑之平均粒子尺寸為少於或等於500奈米(nm)以避免產生過多的金屬凹陷、電介質腐蝕並藉以改善平坦性。在本說明書中,粒子尺寸係指研磨劑之平均粒子尺寸。較佳係使用平均粒子尺寸少於或等於100nm之膠狀研磨劑。另外,當膠狀二氧化矽之平均粒子尺寸少於或等於70nm時,即可減少電介質腐蝕與金屬凹陷。另外,較佳之膠狀研磨劑可包括添加物,如分散劑、表面活性劑、緩衝劑與抗微生物劑,藉以改善膠狀研磨劑之穩定性。一種這類的膠狀研磨劑係取自法國(France)普托市(Puteaux)之克萊昂公司(Clariant S. A.)之膠狀二氧化矽。同樣地,也可使用其他的研磨劑,包括使用氣相式(fumed)、經過沉澱與凝聚等之研磨劑。
研磨組合物可包括機械性移除金屬內連線層之研磨劑。這些研磨劑之例子包括無機氧化物、無機氫氧化物、無機氫氧化氧化物、金屬硼化物、金屬碳化物、金屬氮化物、聚合物粒子與包括至少上述之一者之混合物。適合之無機氧化物包括例如,二氧化矽(SiO2
)、氧化鋁(Al2
O3
)、氧化鋯(ZrO2
)、氧化鈰(CeO2
)、氧化錳(MnO2
)、氧化鈦(TiO2
)或包括至少上述氧化物之一者之組合。適合之無機氫氧化氧化物,例如,包括水鋁土(Boehmite)。這些無機氧化物之改性形式例如為塗覆有機聚合物之無機氧化物粒子,且假使有需要的話也可以使用經無機塗覆之粒子。適合之金屬碳化物、金屬硼化物與金屬氮化物包括例如,碳化矽(silicon carbide)、氮化矽(silicon nitride)、碳氮化矽(silicon carbonitride;SiCN)、碳化硼(boron carbide)、碳化鎢(tungsten carbide)、碳化鋯(zirconium carbide)、硼化鋁(aluminum boride)、碳化鉭(tantalum carbide)、碳化鈦(titanium carbide)或包括上述之金屬碳化物、金屬硼化物與金屬氮化物之至少一者的組合。假使有需要的話,鑽石也可以作為研磨劑。其他可作為替代之研磨劑同樣包括聚合物粒子、有塗覆之聚合物粒子與經表面活性劑穩定之粒子。在使用時,較佳之研磨劑為二氧化矽。
本發明之組合物係適用於任何包括如純銅或銅合金之銅內連線金屬之半導體晶圓。在本說明書中,介電質這個名詞係指具介電常數k之半導體材料,包括低k值與超低k值之介電材料。此組合物與方法可非常有效地避免多重晶圓構件之腐蝕,此晶圓構件例如為多孔性與非多孔性低k電介質、有機與無機低k電介質、有機矽酸鹽玻璃(OSG)、氟矽酸鹽玻璃(FSG)、摻雜碳之氧化物(CDO)、四乙基正矽酸鹽(TEOS)與TEOS之二氧化矽衍生物。本發明之組合物可同樣被用於電化學機械研磨(electrochemical mechanical polishing;ECMP)。
在此範例中,所有之組合物包括0.32重量百分比之羧甲基纖維素(CMC)、0.1重量百分比之丙烯酸/甲基丙烯酸共聚物(比例為2:3,分子量為23K)以及9.00重量百分比之過氧化氫,並且以硝酸調整pH值,與餘量蒸餾水。
應用材料公司(Applied Material,Inc.)之Mirra 200毫米(mm)研磨機配備有ISRM偵測系統並使用IC1010TM
聚胺酯研磨墊(羅門哈斯電子材料CMP公司:Rohm and Hass Electronic Materials CMP Inc.),其中下壓力條件為約1.5磅每平方吋(psi)(10.3千帕(kPa))、研磨液流速為200立方厘米(cc)/分(min)、平台轉速為93RPM以及平坦化Cu晶圓之載體轉速為87RPM。使用Kinik鑽石研磨盤修整研磨墊。在範例1至範例6中所測試之特定研磨漿與溶液包含如下之基本配方:
0.5wt%苯并三唑(BTA)
0.22wt%蘋果酸
0.32wt%羧甲基纖維素(分子量為200K)
0.1wt%丙烯酸/甲基丙烯酸共聚物(比例為2:3,分子量為23K)
9wt% H2
O2
(研磨時加入)
以硝酸調整至pH 3.5(加入H2
O2
前)
餘量去離子水
注意事項:在這些範例中,數字代表本發明之例子且字母代表比較例。
此範例篩選用以降低與在大量BTA存在下以高速銅研磨相關之潛力銅錯合劑。
檸檬酸、EDTA、氮基三乙酸與亞胺二乙酸均可消除研磨墊上之污物。但僅有亞胺二乙酸與EDTA可同時避免產生污物並提供足夠之銅移除速率。
此範例係說明在基本配方具有0.44重量百分比之磷酸鹽的情況下,亞胺二乙酸對於移除速率與綠色污物形成之影響。
範例3至10均與銅錯合以降低Cu-BTA沉澱物之形成。然而,研磨液6至10可提供最佳之銅移除速率與消除綠色污物之組合。增加研磨液之流速或調整研磨液之pH值可使得研磨液3至5從會產生綠色沉澱物轉變成不會產生綠色銅-BTA沉澱物。
此範例係說明磷酸銨與pH值對於銅凹陷與移除速率效能之影響。
增加磷酸銨濃度會增加銅移除速率。此外,增加pH值會減少銅凹陷,但也減少銅移除速率。
此漿液評估基本配方經修改而包括研磨劑粒子與0.44重量百分比之磷酸銨後之數據。
此範例說明此配方係適用於納入研磨劑粒子。尤其,二氧化矽與氧化鋁粒子均可增加銅移除速率。
此範例係說明蘋果酸對於具有或不含亞胺二乙酸之基本配方之影響。
此範例係說明蘋果酸、亞胺二乙酸以及蘋果酸與亞胺二乙酸之組合,可增加銅移除速率。此外,進一步之測試說明蘋果酸可改善研磨液之平坦化能力。
下列之測試係組合1.5重量百分比之磷酸銨下變化亞胺二乙酸之濃度。
表六係說明當pH值為4.1時,在很廣之亞胺二乙酸之濃度範圍中,研磨液可提供有效的污物控制與低凹陷。
此範例係說明流程參數所能產生的進一步好處。
這些數據係說明原位修整可進一步減少研磨墊留下有害之銅-BTA沉澱物之能力。這些流程參數可降低亞胺二乙酸有效控制銅-BTA沉澱物之所需含量。一個有效配方的具體例子係如下所示:0.3wt%BTA、0.22wt%蘋果酸、0.32wt%CMC、0.1wt%丙烯酸/甲基丙烯酸共聚物(比例為2:3,分子量為23K)、1wt%亞胺二乙酸、1.5wt%磷酸二氫銨(NH4
H2
PO4
)以及9wt%H2
O2
(研磨前立即加入),其中在加入H2
O2
之前,量測到的pH值為4.1。
Claims (4)
- 一種以研磨墊研磨具有銅內連線金屬之圖案化半導體晶圓之方法,包括下列步驟:a.提供水相研磨液,該研磨液含>0.2至1.0重量百分比之苯并三唑(BTA)抑制劑以及0.4至5重量百分比之選自亞胺二乙酸、乙二胺四乙酸及其組合之錯合物,該錯合物可錯合銅離子與水;b.以銅溶解成Cu+1 離子,且該Cu+1 離子與該BTA抑制劑之濃度為[BTA]*[Cu+1 ]>當該水相研磨液中不含該錯合物時Cu-BTA沉澱物之Ksp之方式,以該水相研磨液與該研磨墊研磨該圖案化晶圓;以及c.將至少部份之該Cu+1 離子氧化成Cu+2 離子以避免該Cu-BTA沉澱物在研磨時沉澱在該圖案化晶圓與該研磨墊上。
- 如申請專利範圍第1項所述之方法,更包括以純化水溶液潔淨該研磨墊之步驟。
- 如申請專利範圍第1項所述之方法,其中該研磨液不含研磨劑。
- 如申請專利範圍第1項所述之方法,其中增加該錯合物之濃度會加速銅移除速率。
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KR20230093321A (ko) * | 2020-10-29 | 2023-06-27 | 후지필름 일렉트로닉 머티리얼스 유.에스.에이., 아이엔씨. | 연마 조성물 및 이를 사용하는 방법 |
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- 2009-02-20 JP JP2009037541A patent/JP5514449B2/ja active Active
- 2009-02-20 KR KR1020090014260A patent/KR101560648B1/ko active IP Right Grant
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JP5514449B2 (ja) | 2014-06-04 |
KR20090091056A (ko) | 2009-08-26 |
CN101515546A (zh) | 2009-08-26 |
TW200946619A (en) | 2009-11-16 |
US20090215266A1 (en) | 2009-08-27 |
KR101560648B1 (ko) | 2015-10-16 |
EP2093789A3 (en) | 2010-01-27 |
CN101515546B (zh) | 2012-06-27 |
EP2093789A2 (en) | 2009-08-26 |
JP2009200496A (ja) | 2009-09-03 |
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