TW200907038A - Selective barrier polishing slurry - Google Patents
Selective barrier polishing slurry Download PDFInfo
- Publication number
- TW200907038A TW200907038A TW097128748A TW97128748A TW200907038A TW 200907038 A TW200907038 A TW 200907038A TW 097128748 A TW097128748 A TW 097128748A TW 97128748 A TW97128748 A TW 97128748A TW 200907038 A TW200907038 A TW 200907038A
- Authority
- TW
- Taiwan
- Prior art keywords
- acid
- benzene
- weight percent
- weight
- hydrophilic portion
- Prior art date
Links
- 239000002002 slurry Substances 0.000 title claims abstract description 48
- 238000005498 polishing Methods 0.000 title claims abstract description 15
- 230000004888 barrier function Effects 0.000 title description 19
- 239000010949 copper Substances 0.000 claims abstract description 37
- 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
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000004094 surface-active agent Substances 0.000 claims abstract description 32
- 239000007800 oxidant agent Substances 0.000 claims abstract description 21
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 15
- 239000003112 inhibitor Substances 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 239000004065 semiconductor Substances 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 11
- 125000000129 anionic group Chemical group 0.000 claims abstract description 10
- 239000008139 complexing agent Substances 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000003068 static effect Effects 0.000 claims abstract 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 26
- -1 4-dicarboxylic acid Chemical compound 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 18
- 239000005711 Benzoic acid Substances 0.000 claims description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 11
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 11
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 claims description 8
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 7
- 239000012964 benzotriazole Substances 0.000 claims description 7
- 239000004575 stone Substances 0.000 claims description 7
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- QNSOHXTZPUMONC-UHFFFAOYSA-N benzene-1,2,3,4,5-pentacarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O QNSOHXTZPUMONC-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims 3
- OIJMIQIDIZASII-UHFFFAOYSA-N benzene;benzoic acid Chemical group C1=CC=CC=C1.OC(=O)C1=CC=CC=C1 OIJMIQIDIZASII-UHFFFAOYSA-N 0.000 claims 2
- WWTBZEKOSBFBEM-SPWPXUSOSA-N (2s)-2-[[2-benzyl-3-[hydroxy-[(1r)-2-phenyl-1-(phenylmethoxycarbonylamino)ethyl]phosphoryl]propanoyl]amino]-3-(1h-indol-3-yl)propanoic acid Chemical compound N([C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)O)C(=O)C(CP(O)(=O)[C@H](CC=1C=CC=CC=1)NC(=O)OCC=1C=CC=CC=1)CC1=CC=CC=C1 WWTBZEKOSBFBEM-SPWPXUSOSA-N 0.000 claims 1
- DXBHBZVCASKNBY-UHFFFAOYSA-N 1,2-Benz(a)anthracene Chemical compound C1=CC=C2C3=CC4=CC=CC=C4C=C3C=CC2=C1 DXBHBZVCASKNBY-UHFFFAOYSA-N 0.000 claims 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 229940126208 compound 22 Drugs 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 238000003801 milling Methods 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims 1
- 230000003247 decreasing effect Effects 0.000 abstract description 2
- 229960004365 benzoic acid Drugs 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 13
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 229920000388 Polyphosphate Polymers 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 150000004767 nitrides Chemical class 0.000 description 6
- 239000001205 polyphosphate Substances 0.000 description 6
- 235000011176 polyphosphates Nutrition 0.000 description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- NHDLVKOYPQPGNT-UHFFFAOYSA-N benzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1 NHDLVKOYPQPGNT-UHFFFAOYSA-N 0.000 description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 4
- 235000011180 diphosphates Nutrition 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 description 4
- 229910052742 iron 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
- 238000005121 nitriding Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
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- 229920002125 Sokalan® Polymers 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000003082 abrasive agent Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000003636 chemical group Chemical group 0.000 description 3
- 239000003989 dielectric material Substances 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
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- 239000002023 wood Substances 0.000 description 3
- 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 2
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- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
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- 125000003118 aryl group Chemical group 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
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- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
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- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 description 2
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- 239000012776 electronic material Substances 0.000 description 2
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- 239000005696 Diammonium phosphate Substances 0.000 description 1
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- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-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
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- 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
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- PNYYBUOBTVHFDN-UHFFFAOYSA-N sodium bismuthate Chemical compound [Na+].[O-][Bi](=O)=O PNYYBUOBTVHFDN-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 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
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- WSANLGASBHUYGD-UHFFFAOYSA-N sulfidophosphanium Chemical class S=[PH3] WSANLGASBHUYGD-UHFFFAOYSA-N 0.000 description 1
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- 239000013589 supplement Substances 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
- 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
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000011850 water-based material Substances 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-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
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
- 239000011686 zinc sulphate Substances 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
- 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
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
-
- 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)
- General Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Description
200907038 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 . 半導體基材的選擇性阻障研磨漿。 【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(low k)及超低k(ultra-low k) 介電膜之導入則必須使用更溫和的CMP製程,這是因為該 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USL.I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 94412 3 200907038 可調整製程效能之調整力的低k介電特異性的表面活性 背J °例如’ Biari於美國專利公開號2006/0131275揭露的 一種聚液’其包含具有疏水性尾端、非離子性親水性部分 -及陰離子性親水性部分之界面活性劑,以降低低k移除速 率,例如碳摻雜氧化物(CD0)。 現需求可達到具有降低C0D移除速率之阻障對超低k ”電貝之的模、組移除(modular removal)之研磨漿液。又, 需求以高選擇性之阻障對介電質移除速率來移除阻障之研 磨漿液。 【發明内容】 在本發明一面向中,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 计,0至25重量百分比的氧化劑、ο ι至3〇重量百分比的 研磨料顆粒、0.001至5.重量百分比的苯甲酸 (benzenecarboxylic acid)、0. 00002 至 5 重量百分比的
多成分界面活性劑(muiti-component 、〇,卯] 至10重量百分比之用以降低銅互聯之靜電蝕刻的抑制 齊J 〇至5重里百分比之用以增加銅互聯的移除率的含嶙 化合物、於研磨期間形成之〇至1〇重量百分比的錯合气, 以及餘量水,其中該多成分界面活性劑具有疏水性尾^、’ =離子性親水性部分及陰離子性親水性部分,該疏水性尸 端具有6至30個碳原子及該非離子性親水性部分具^ 至300個碳原子。 種適用於化學機 在本發明另一面向中,本發明包含一 94412 4 200907038 導體基材的水性漿液,包括,以重 _至15重罝百分比的氧化劑、〇. i至 分比的氧切研磨料齡、Q()l至 里百 酸、至2重量百分比的多成分界面:刀:的苯甲 至5重量百分比之用以降低銅互聯之靜電蝕列:· °〇2 劑、0至3番曰m P〈静電蝕刻的唑類抑制 二至3重!百分比之用以增加銅 化合物,於研磨期間形成之0 ()1至5移,革的各磷 錯合劑,以;5丛!丨 ^ 刀比的有機酸 ^麵子性親水性部分及陰離子性親水性部分 ,L水性尾端具有8至20個碳原子,且該非籬 〜 分具有別至200碳原子;且該水性裝 為卒=部 _ =明另—面向中,本發明包含-=二: =磨具有鋼互聯的半導體基材的水性漿括,= 以,G.1至10重量百分比的氧化劑、〇25至二, 分比的氧化石夕研磨料顆粒、〇. 〇2至2. 5 =百 酸、0.0001至i重量百分比的多成分 1刀比的本甲 至2重量百分比之用以降低銅互聯之靜^=并〇篇 抑制劑、〇.〇〇1 i 2重量百分比之用以^刻的本并三唾 率的含填化合物、於研磨期間形成之移除 的有機酸錯合劑’以及餘量水;其 成== :r^::r--------- 二個碳原子及該非離子性
為7至115。 反原子,且該水性漿液具有PH 94412 5 200907038 【實施方式】 已發現苯曱酸及多成分界面活性劑之組合可增進氮化 鈕移除速率,且對於半導體基材之低k及超低k移除速率 • 沒有不利影響。針對本說明書之目的,半導體基材係包含 具有金屬導體互聯及藉由絕緣層以可產生特定電訊號之方 式隔開之介電材料的晶圓。又,該等漿液出乎意料地改善 晶圓的缺陷度。最後,該等漿液(有助於阻障對低k移除速 率之優異選擇性)在CMP製程後提供穩定的膜。 該漿液包含0. 001至5重量百分比的苯曱酸以加速阻 障移除速率,如TaN移除速率。較佳地,該漿液包含0. 01 至3重量百分比的苯曱酸。最佳地,該漿液包含0. 02至 2.5重量百分比的苯曱酸。苯甲酸之實例包含至少下列其 一:對苯二甲酸、苯-1,3-二羧酸、苯-1,2, 4-三羧酸、苯 -1,3, 5-三羧酸、苯-1, 2, 3-三羧酸、苯-1,2, 3, 4-四羧酸、 苯-1,2, 4, 5-四羧酸、苯-1,2, 3, 5-四羧酸及苯-1,2, 3, 4, 5-五羧酸。每個苯環具有至少兩個羧酸基團的苯甲酸提供氮 化鈕移除速率之最大增加。舉例言之,該漿液可包含選自 下列至少其中之一者的苯曱酸:苯-1,3-二羧酸、苯-1, 2, 4-三羧酸、苯-1,3, 5-三羧酸、苯-1,2, 3-三羧酸、苯-1,2, 3, 4-四羧酸、苯-1,2, 4, 5-四羧酸、苯-1,2, 3, 5-四羧酸及苯 -1,2, 3, 4, 5-五羧酸其。較佳地,該苯甲酸於每個苯環上具 有兩個至四個羧酸基團。例如,每個苯環具有三個羧酸基 團之苯-1,2,4-三羧酸對於TaN移除速率提供了良好的增 進0 6 94412 200907038 如同用於本說明書之表面活性劑或界面活性劑,係意 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)之特性之物質。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 一醇鲢硫^^酉曰(fatty alcohol polyglycol ether sulfate),可抑制CDO速率,但該等界面活性劑會增加晶 圓缺陷數。 已見本曱酉欠與多成分界面活性劑之組合可降低Qq 移除速率,衫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,其具有非常小的水吸 引力之分子結構,已知為疏水性尾端;第二結構部分,复 為具有水料力的非離子性親水性部分;及具有強水吸弓j 力的陰離子性親水性基團―當於溶液中離子化時,該 子性親水性基團具有負離子價。 絲纽基騎常^有適於水溶解性喊度的長鍊 rV 切烧鍊。特別是’該疏水性基®具有總數為 絲子。較佳地,該疏水性基團具有8至2= 佳地’其具有12至16個碳原子。該疏水性 二刀=直鍊、支鍊或環鍊其-。該疏水性部分可為飽和 鍊、不飽和鍊或含有芳香基團一縣實例係 肪醇之直鍊聚合物。 94412 7 200907038 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、不飽和鍊或含有芳香基 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叛酸、項酸、 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)之。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(i on i zab 1 e 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%。 典型地,該等界面活性劑係以銨鹽、鉀鹽、四級銨或 鈉鹽的形式添加。最佳地,該界面活性劑係以銨鹽形式添 8 94412 200907038 加以得到高純度配方。 較佳地,該多成分界面活性劑係以相較於其抑制阻障 膜(如鈕(Ta)或氮化鈕(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(M)為ΑΧ =(χ〇_χ)/χ〇,其中,χ〇及X 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/母分鐘測量’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):A(CD0)>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酯 研磨墊壓力及實施例之條件下測量。例如,當於13 8 kpa 之壓力及以Hi浮凸的p〇iitexTM多孔性凝結之聚胺酉 (Politex係為關哈斯公以其子公之商標)之實施々 之條件,以不含界面活性劑之組成物研磨時,係提供對只 組研磨速率(X。):對雜氧化物為每分鐘5⑽埃及; 化包為每分鐘5GG埃。接著,在相同條件下加人該多^ 界面活性劑麵低該研磨速率至對碳摻雜氧化物每八^ 300埃,且對TaN之移除速率必大於每分鐘埃以= 上述選擇率方程式。 、 該漿液視需要包含G至5重量百分比的含鱗化合物 針對本說明書之目的,『含鱗』化合物係為任何包含碟原 之化合物。較佳地’該漿液包含〇至3重量百分比的知 化合物。更佳地,該漿液包含〇· 001至2重量百分比的2 磷化合物。例如,含磷化合物包含磷酸鹽、焦磷酸鹽、^ 94412 9 200907038 磷酸鹽、膦酸鹽、氧化膦(phosphine oxides)、硫化膦 (phosphine sulphides)、氧雜磷雜環烧類 (phosphorinanes)、膦酸鹽、亞磷酸鹽(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、 焦破酸鋅、聚鱗酸鋅、膦酸鋅(zinc phosphonate)、構酸 錢、焦麟酸銨、聚磷酸銨、膦酸銨(ammonium phosphonate)、磷酸二銨、焦鱗酸二銨、聚碟酸二銨、膦 酸二胺、磷酸鉀、磷酸二鉀、磷酸胍、焦磷酸胍、聚磷酸 胍、膦酸胍(guanidine phosphonate)、填酸鐵、焦填酸鐵、 聚鱗酸鐵、膦酸鐵(iron phosphonate)、填酸錦、焦麟酸 錦、聚磷酸錦、膦酸飾(cerium phosphonate)、乙二胺填 酸鹽、磷酸哌畊、焦磷酸哌畊、膦酸哌啡、三聚氰胺磷酸 鹽(melamine phosphate)、二-三聚氰胺鱗酸鹽、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 碟酸鹽(melamphosphate)、蜜白胺焦鱗酸鹽、蜜白胺聚鱗 酸鹽、蜜白胺膦酸鹽、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 二胺填酸鹽(dicyanodiamide phosphate)、尿素磷酸鹽, 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。 該含填化合物較佳係包含鱗酸鏔及磷酸。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 94412 200907038 會$告銅,造成粗糙的金屬表面。所添加之磷酸會與游離 鹼孟屬(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 姓性的後CMP清理溶液中保護銅。例如,後CMp晶圓的膜 八有足夠的元整性以在具有侵钱性銅錯合劑(如氫氧化四 曱胺乙醇胺及抗壞血酸)的pn 12的溶液中保護晶圓。 立視而要地,含量為〇至25重量百分比的氧化劑也促進 阻P早層的移除,如叙、氮化叙、鈦、及氮化欽。較佳地, =水液包含〇. 〇1至15重量百分比的氧化劑。更佳地,該 2液包含0· 1至10重量百分比的氧化劑。適當的氧化劑包 3例如過氧化氫、單過硫酸鹽(monopersulfates)、埃 夂|過本一甲酸鎂(magnesium perphthalate)、過乙酸 及八他過§欠類、過硫酸鹽類、溴酸鹽、過碰酸鹽、破酸鹽、 鐵孤鈽鹽、錳鹽(Mn(皿)、Mn(IV)、Mn(VI))、銀鹽、銅 鹽、絡鹽、㈣、自素、次氯酸鹽、或包含至少—種上述 =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。 '以5周整氧化劑(如過氧化物)的量亦可控制金屬互聯移除 ' ' 幻如增加過氧化物濃度會增加銅的移除速率。然 而,過1增加氧化劑對於研磨速率有不利的影響。 該阻卩羊金屬研磨組成物包含氧化矽研磨料,以『機械 94412 11 200907038 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,氧化石夕 (Si0〇、氧化鋁(AhO3)、氧化錯(Zr〇2)、氧化鈽(ce〇2)、氧 化鐘(Mn〇2),及其混合物。可獲得之氧化銘有許多型式, 如α-氧化鋁、r-氧化鋁、5_氧化鋁及非晶形(非結晶狀) 氧化鋁。其他適當的氧化鋁之實例係為柏買石 ((AIO(OH),boehmite)顆粒及其混合物。如有需要,該等 無機氧化物經改質之型式,如經聚合物塗傅之無機氧化物 顆粒亦可使用。適當的金屬碳化物、爛化物及氮化物包含, 例如’碳化石夕、氮化石夕、碳氮化石夕(SiCN)、碳化蝴、碳化 鎢、碳化錯、硼化鋁、碳化鈕、碳化鈦及包含至少一種上 2金屬碳化物、金相化物及金屬氮化.物之混合物。如有 j ’鑽;S亦可用作研純。替代性研磨料亦包含聚合性 '立及、攻龛佈之聚合性顆粒。較佳的研磨料為氧化矽。 百八該研磨料在該研磨組成物的水相中具有01至50重量 該於不含研磨料之溶液,固定的研磨料墊有助於 量百八θ移除。較佳地,該研磨料之濃度為1 1至40重 为比。且最佳地,該研磨料之濃度為〇. 25至35重 迷^且,型地,增加研磨料濃度係增加介電材料之移除 雜氧化物寺別增加低U電材料之移除速率,諸如碳摻 除 例如,若半導體業者期望增加的低k介電質移 ' J增加該研磨料含量可將介電質的移除速率增加 94412 12 200907038 至所欲程度。 該研磨料較佳具有小於25〇卿之平均顯教尺寸 過度金屬淺碟化及介電輕。對於本㈣ 顆粒尺寸意指該膠體氧化料平均顆粒尺寸。更=說 = =1°°1110之平均顆粒尺寸以進-步降低金; 欠碟化及;丨電賴。特別是,小於75 nm <研磨料平均顆 粒尺寸會以可接受的速率移除該阻障金孱,而不會過度移 除介電材料。例如,最少的介電腐蝕及金屬淺碟:發:於 使用具有20至75 mn之平均顆粒尺寸的膠體氧化矽。降低 該膠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AZ_Electronic
Materials France S. A. S·,於 Puiieaux,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、顏 果酸、草酸、水揚酸、二硫代胺基曱酸二乙基i旨納、琥站酸、 酒石酸、酼乙酸(thioglycolic acid)、甘胺酸、丙胺酸、 天門冬胺酸、乙二胺、三甲基二胺、丙二酸、戊二酸、3-羥 基丁酸、丙酸、苯二曱酸、間苯二甲酸、3-羥基水楊酸、3,5-二羥基水揚酸、沒食子酸(galHe acid)、葡萄糖酸、鄰苯 二酚(pyrocatechol)、五倍子酚(Pyr〇Sall〇1)、丹寧酸、及 13 94412 200907038 其鹽類。較佳地,該錯合劑係選自由乙酸、檸檬酸、乙醯 乙酸乙酯、乙醇酸、乳酸、蘋果酸、草酸所組成之群組。 最佳地,該錯合劑係為擰檬酸。 添加0. 001至10總重量百分比的抑制劑係降低銅互聯 之移除速率及保護銅免於靜電蝕刻。對於本申請案之目 的,銅互聯意指以具有偶發性雜質之銅或以銅為基礎之合 金所形成的互聯。調整抑制劑之濃度係藉由保護金屬免於 靜電蝕刻而調整該銅互聯移除速率。該漿液較佳係包含 0. 0 0 2至5重量百分比的抑制劑。更佳地,該溶液包含0. 0 0 5 至2重量百分比的抑制劑。該抑制劑可由抑制劑之混合物 所組成。唑類抑制劑對銅互聯特別有效。典型的唑類抑制 劑包含苯并三唑(BTA)、巯基苯并噻唑(MBT)、曱基苯并三 唑及咪唑。BTA係對於銅互聯為特別有效的抑制劑且咪唑 可增加銅移除速率。 為了以低k介電膜之選擇性移除速率來移除阻障,該 漿液視需要亦包含0至5重量百分比的聚乙烯吡咯烷酮。 除非另有指示,否則本說明書以重量百分比表示所有濃 度。視需要地,該漿液包含0. 002至3重量百分比的聚乙 烯吼咯烷酮。視需要地,該漿液包含0· 01至2重量百分比 的聚乙烯吡咯烷酮。針對要求以中等的低k移除速率移除 阻障之應用而言,該漿液較佳係包含少於0.4重量百分比 的聚乙烯吡咯烷酮。針對要求以低等的低k移除速率移除 阻障之應用而言,該漿液較佳係包含至少0.4重量百分比 的聚乙烯吡咯烷酮。此種非離子性聚合物促進低k及超低 14 94412 200907038 k介電膜(典型地,疏水性)及硬遮罩帽層(hard mask capping layer)膜之研磨。 該聚乙炸°比略院_較佳具有重量平均分子量為1,〇〇〇 至1,000, 000。針對本說明書之目的,重量平均分子量意 指以膠體滲透層析法測定之分子量。該漿液更佳係具有分 子量為1,000至500,000,且最佳分子量為2,500至 50, 000 例如,具有分子量為範圍自7, 〇〇〇至25, 000之聚 乙烯吡咯烷酮已被證實特別有效。 該研磨組成物之pH可為酸性及驗性,並具有餘量水。 較佳地,該pH係介於6及12之間,且最佳係介於7及η 5 之間。另外,該溶液最佳係以去離子水補足體積以限制偶 發性雜質。羥離子源,如氨、氳氧化鈉或氫氧化鉀,於鹼 性區間調整pH。最佳地,該羥離子來源係為氳氧化鉀。 該衆液可視需要包含整平劑(如氯.化物,或特別是氯化 銨)、缓衝溶液、分散劑及界面活性劑。例如 菘漿液視需 ‘要包含0.0001 S 0.1重量百分比的氯化銨。氯化錢提供表 面外觀之改善’且其可藉由增加銅移除速率而促進銅移除 該研磨組成㈣可視需要包錢_ 同^ ° 機鹼及無機驗或其彼等之具有pKa為大於8 5 1。 、 句八化0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, 離子性界面活性劑包含酯類、環氣乙烷類、醇類、乙氧化 物類(ethoxylate)、矽化合物、氟化合物、峽類、糖= 其衍生物等。該消泡劑亦可為兩性的界面活性劑。該 組成物可視需要包含殺菌劑(biocides) ’ : κ:^χΤΜ 94412 15 200907038 MLX(9. 5至9. 9%曱基-4-異噻唑啉-3-酮、89. 1至89. 5% 水及$1.0%相關反應產物)或包含活性成分:2-曱基-4-異°塞σ坐琳-3-酮及5-氯-2-曱基-4-異°塞α坐淋-3-酮之 KathonTM ICP ΠΙ,皆由羅門哈斯公司製造(Kathon及Kordex 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 於研磨墊上施加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塾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·的苯曱酸之漿液(比較例 漿液A至J與實施例漿液1至7)如下表1所示。 16 94412 200907038 表 1 漿液 添加物 (wt%) 多成分界面活性劑 (wt%) BTA (wt%) pH 氧化矽 (wt%) A 0 0.10 10 10 B 0.2 苯-1,2, 4, 5-四羧酸 0.10 10 10 C 0.3 苯-1, 2, 4, 5-四羧酸 0.10 10 10 D 0.4 苯-1, 2, 4, 5-四羧酸 0.10 10 10 E 0.6 苯-1,2, 4, 5-四羧酸 0.10 10 10 F 0.2 苯-1,2, 4-三羧酸 0.10 10 10 G 0.2 1,2, 3, 4, 5, 6-環己烷 六羧酸 0.10 10 10 H 0.2 聚丙烯酸 (M.W. :1800) 0.10 10 10 I 0.2 聚丙烯酸 (M.W. :5000) 0.10 10 10 J 0.2 聚丙烯酸 (M.W. :10000) 0.10 10 10 K 0.2 0.10 10 10 17 94412 200907038 苯甲酸 J 0.2 對苯二甲酸 0.10 10 10 1 0.2 苯-1,2,4-三羧酸 0.005 0. 10 8 10 2 0.2 苯-1,2,4-三羧酸 0.007 0. 10 8 10 3 0.2 苯-1,2,4-三羧酸 0.01 0.10 8 10 4 0.2 苯-1,2, 4-三羧酸 0.015 0. 10 8 10 5 0.2 苯-1,2, 4-三羧酸 0.03 0.10 9 8木 6 0.4 苯-1,2, 4-三羧酸 0.03 0.10 9 8木 7 0.8 苯-1,2, 4-三羧酸 0.03 0.10 9 8木 多成分界面活性劑=DiSp〇nil™ FES界面活性劑,由Cognis
Chemical Group 製造;NH4C1=0. Olwt% ; BTA=苯并三唑;殺 菌劑=0. 005 wt°/。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S 1. 0 /相關反應產物)’氧化發=jQebasol II,購自AZ
Electronic Materials France S. A. S.,於 Puteaux,France 的50 nm乳化石夕’及氧化石夕*=i5〇1 _5〇,購自az Electronic
Materials France S. A.S.,於 puteaux,France 的 50nm 氧化石夕;所有敷液包含〇.2〇 wt% H2〇2。 18 94412 200907038 實施例1 研磨測試係使用購自Noyellus System,Inc.的
TM C〇ral碳推雜氧化物(CD0)之200 mm晶圓片、TE0S介電 貝氮化紐、及電鑛銅。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κ1〇1〇τΜ晶圓 片及浮凸的PolitexTMw磨塾。 以MIRRATM旋轉型研磨平台研磨晶圓片。第一步驟之銅 研磨使用Eternal裝液EPL2360以具環狀漠槽的聚胺醋研 磨塾在平台1及2(使用Kinik AD3CG_181〇6〇網格鑽石調 理盤)研磨銅。用於平台1的研磨條件為平台速度93·、 載體速度21 rpm及向下力量4灿(27 6㈣,及用於平 台2的,磨條件為平台速度33 rpm、載體速度61_及 向下力里3 psi(20· 7 kPa)。用於平台3的研磨條件為向 下力量1.5 psiU.0.3 kPa)、平台速度93 rpm、載體速度 87聊及裝液流速200 ml/分,並使用&浮凸的p〇mexTM 卜 凝集聚胺酯研磨墊。 自研磨則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17〇χ1〇-6Ω及, 對氮化链設於28,000x10、)測量所有光學透明膜。使用 DektakVe⑽ V2GGSL 探針式輪雜(stylusprQfilQmeter) 收集晶圓形貌數據。移除速率均以人/分鐘之單位報導。 表2係提供自研磨添加劑系列之研磨篩遽結果。 19 94412 200907038 表2 漿液 TaN (A/分) TEOS (A/分) CDO (A/分) Cu (A/分) A 354 292 447 399 B 610 447 689 248 C 840 539 869 164 D 864 584 999 211 E 915 612 1168 219 F 771 529 840 206 G 502 399 579 177 Η 334 265 421 193 I 330 239 410 221 J 385 299 452 202 K 432 371 469 154 L 563 417 582 183 1 774 501 149 146 2 699 475 207 191 3 620 417 126 141 4 537 384 105 70 表2係說明苯曱酸增加TaN移除速率,且並未對碳摻 雜氧化物移除速率有不利的增加。特別是,苯多羧酸係提 供TaN移除速率最大的增加。另外,包含多成分界面活性 20 94412 200907038 ηί苯甲馱之組合之漿液係提供絕佳的TaN移除速率及低 碳摻雜氧化物移除速率之組合。 表3 ° 多成分 漿液|界面活性劑
苯-1,2,4-三羧酸 | TE0S I Cu I TaN
(Wt%) (wt%) I (A/分)(A/分)I (A/分) A ------ 292 399 354 447 U- 0. 03 0.2 315 92 I 358 ρπ Η 0. 03 0. 4 —_441 668 73 1 7 Λ·' 0.03 1 0.8 428 103 1 685
Cognis Chemical Group 所製造 表3係說明具有每環三個賴的苯2,4—三緩酸,血 編性劑之組合可提供TaN移除速率相對 於石厌摻雜氧化物移除速率之高選擇率。另外,㈣ 移除速率之伽可因增加㈣之濃度至t = 0.4重量百分比而減少。 辰度至呵於 【圖式簡單說明】 益 【主要元件符號說明】
Ml 94412 21
Claims (1)
- 200907038 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30重量百分比的研磨料顆粒、0. 001 至5重量百分比的苯曱酸、0.00002至5重量百分比的 多成分界面活性劑、0. 001至10重量百分比之用以降 低該銅互聯之靜電#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 形成之0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,該苯曱酸之 苯環係包含至少兩個羧酸基。 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、0.01至3重量百分比的苯甲酸、0.00005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 之用以降低該銅互聯之靜電蝕刻的唑類抑制劑、0至3 重量百分比之用以增加該銅互聯的移除率的含鱗化合 22 94412 200907038 物、於研磨期間形成之o.G1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㈣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2〇個碳原子及該非離子性 親水性部分具有2〇至2GQ個碳原子,且該水性聚液具 有pH為6至12。 5.=請專利範圍第4項之水性裝液,其中,該苯甲酸之 苯環係包含二至四個羧酸基。 6·如申請專利範圍第4項之水㈣液,其中,該漿液包含 具有平均雜尺寸小於1GG nm之氧切研磨料顆粒。 7. 如申請專利範圍第4項之水性漿液,其中,該苯甲酸係 選自苯-1,3-二羧酸、苯-1,2-二羧酸、苯_丨,4_二羧酸、 苯-1,2,4-三羧酸、苯-l,3,5-三羧酸、笨_丨,2,3_三鲮 酸、苯-1,2,3,4-四羧酸、苯-i,2,4,5__四羧酸苯 -1’ 2, 3, 5-四羧酸及苯-1,2, 3, 4, 5-五羧酸之至少一種。 8. 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,〇1至ι〇重量百 分比的氧化劑' 〇. 25至35重量百分比的氧化矽研磨料 顆粒、0.02至2.5重量百分比的苯甲酸、〇 〇〇〇1至2 重羞百分比的多成分界面活性劑、0.005至2重量百分 比之用以降低該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該銅互聯的移除 率的含磷化合物、於研磨期間形成之〇 〇1至5重量百 分比的有機酸錯合劑,以及及餘量水;其中該多成分界 94412 23 200907038 面活性劑具有疏水性尾端、非離子性親水性部分 子性親水性部分,該疏水性尾端具有12至16個碳;子 及該非離子性親水性部分具有25至150碳原子,且該 水性浆液具有pH為7至11. 5。 9. ^申請專·圍第8項之水絲液,其中,該苯甲酸係 j自苯-1,3-二羧酸、苯—丨,2_二羧酸、苯-^―二羧酸、 f — 1’2’4-三羧酸、苯-1,3, 5-三羧酸、苯-1,2, 3-三羧 酸、苯-1,2,3,4-四羧酸、苯_1,2,4,5-四羧酸、苯 ―1,2’ 3, 5-四羧酸及苯-1,2, 3, 4, 5-五羧酸之至少一種。 1 Π I 1 慕王 •、曱請專利範圍第8項之水性漿液,其中,該苯甲酸係 為笨~1,2, 4-三羧酸。 94412 24 200907038 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 94412
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CN101712907A (zh) * | 2009-08-26 | 2010-05-26 | 辽阳科隆化学品有限公司 | 一种水溶性硅料切削液的组成和应用组合 |
US8492277B2 (en) * | 2010-03-16 | 2013-07-23 | Rohm And Haas Electronic Materials Cmp Holdings, Inc | Method of polishing a substrate comprising polysilicon and at least one of silicon oxide and silicon nitride |
CN102477258B (zh) * | 2010-11-26 | 2015-05-27 | 安集微电子(上海)有限公司 | 一种化学机械抛光液 |
CN102559061A (zh) * | 2010-12-28 | 2012-07-11 | 安集微电子(上海)有限公司 | 含有机酸的硅和铜化学机械平坦化浆料 |
US8440097B2 (en) * | 2011-03-03 | 2013-05-14 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Stable, concentratable, water soluble cellulose free chemical mechanical polishing composition |
EP2502969A1 (en) * | 2011-03-22 | 2012-09-26 | Basf Se | A chemical mechanical polishing (cmp) composition comprising two types of corrosion inhibitors |
CN102199400A (zh) * | 2011-03-25 | 2011-09-28 | 江南大学 | 适用于精细雾化cmp的铜抛光液 |
JP2013138053A (ja) * | 2011-12-28 | 2013-07-11 | Fujimi Inc | 研磨用組成物 |
US20140011362A1 (en) * | 2012-07-06 | 2014-01-09 | Basf Se | Chemical mechanical polishing (cmp) composition comprising a non-ionic surfactant and an aromatic compound comprising at least one acid group |
JP6101444B2 (ja) * | 2012-08-01 | 2017-03-22 | 株式会社フジミインコーポレーテッド | 研磨用組成物及びそれを用いた磁気ディスク用基板の製造方法 |
CN104726028A (zh) * | 2013-12-18 | 2015-06-24 | 安集微电子(上海)有限公司 | 一种化学机械抛光液及其使用方法 |
CN105177578B (zh) * | 2015-10-19 | 2018-06-08 | 江苏理工学院 | 用于铜基钯镍合金镀层退镀的退镀液及退镀方法 |
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JP2004231748A (ja) * | 2003-01-29 | 2004-08-19 | Fuji Photo Film Co Ltd | 金属用研磨液及び研磨方法 |
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JP2007194593A (ja) * | 2005-12-20 | 2007-08-02 | Fujifilm Corp | 金属用研磨液及びそれを用いた研磨方法 |
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- 2008-08-01 KR KR1020080075502A patent/KR20090014110A/ko not_active Application Discontinuation
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