TWI396731B - 多成分之阻障研磨溶液 - Google Patents
多成分之阻障研磨溶液 Download PDFInfo
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- TWI396731B TWI396731B TW096101385A TW96101385A TWI396731B TW I396731 B TWI396731 B TW I396731B TW 096101385 A TW096101385 A TW 096101385A TW 96101385 A TW96101385 A TW 96101385A TW I396731 B TWI396731 B TW I396731B
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- Prior art keywords
- acid
- weight percent
- solution
- salts
- anionic surfactant
- Prior art date
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- 230000004888 barrier function Effects 0.000 title claims description 45
- 238000005498 polishing Methods 0.000 title claims description 26
- 239000000203 mixture Substances 0.000 claims description 45
- 229910052751 metal Inorganic materials 0.000 claims description 44
- 239000002184 metal Substances 0.000 claims description 44
- 238000000227 grinding Methods 0.000 claims description 38
- 239000003945 anionic surfactant Substances 0.000 claims description 37
- 239000010949 copper Substances 0.000 claims description 37
- 229910052802 copper Inorganic materials 0.000 claims description 35
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 34
- 125000004432 carbon atom Chemical group C* 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 30
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 25
- -1 ester salt Chemical class 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 239000007800 oxidant agent Substances 0.000 claims description 17
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 15
- 239000003112 inhibitor Substances 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 15
- 150000003863 ammonium salts Chemical class 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000004065 semiconductor Substances 0.000 claims description 9
- 230000003628 erosive effect Effects 0.000 claims description 8
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical class CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000007517 polishing process Methods 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 6
- 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
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical class C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 claims description 5
- 235000015165 citric acid Nutrition 0.000 claims description 5
- 239000008139 complexing agent Substances 0.000 claims description 5
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 claims description 4
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QSRFYFHZPSGRQX-UHFFFAOYSA-N benzyl(tributyl)azanium Chemical class CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 QSRFYFHZPSGRQX-UHFFFAOYSA-N 0.000 claims description 4
- VBQDSLGFSUGBBE-UHFFFAOYSA-N benzyl(triethyl)azanium Chemical class CC[N+](CC)(CC)CC1=CC=CC=C1 VBQDSLGFSUGBBE-UHFFFAOYSA-N 0.000 claims description 4
- 150000001721 carbon Chemical group 0.000 claims description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 4
- 235000004515 gallic acid Nutrition 0.000 claims description 4
- 229940074391 gallic acid Drugs 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- 235000021317 phosphate Nutrition 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- TYTGWHZODQKWEF-UHFFFAOYSA-N 1-o-dodecyl 4-o-sulfo butanedioate Chemical compound CCCCCCCCCCCCOC(=O)CCC(=O)OS(O)(=O)=O TYTGWHZODQKWEF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- CSMFSDCPJHNZRY-UHFFFAOYSA-M decyl sulfate Chemical compound CCCCCCCCCCOS([O-])(=O)=O CSMFSDCPJHNZRY-UHFFFAOYSA-M 0.000 claims description 3
- 150000002430 hydrocarbons Chemical group 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 229940071180 lauryl sulfosuccinate Drugs 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- UZZYXUGECOQHPU-UHFFFAOYSA-M n-octyl sulfate Chemical compound CCCCCCCCOS([O-])(=O)=O UZZYXUGECOQHPU-UHFFFAOYSA-M 0.000 claims description 3
- 229940067739 octyl sulfate Drugs 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 3
- CSMFSDCPJHNZRY-UHFFFAOYSA-N sulfuric acid monodecyl ester Natural products CCCCCCCCCCOS(O)(=O)=O CSMFSDCPJHNZRY-UHFFFAOYSA-N 0.000 claims description 3
- UZZYXUGECOQHPU-UHFFFAOYSA-N sulfuric acid monooctyl ester Natural products CCCCCCCCOS(O)(=O)=O UZZYXUGECOQHPU-UHFFFAOYSA-N 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- JOELYYRJYYLNRR-UHFFFAOYSA-N 2,3,5-trihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC(O)=C1O JOELYYRJYYLNRR-UHFFFAOYSA-N 0.000 claims description 2
- GLDQAMYCGOIJDV-UHFFFAOYSA-N 2,3-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1O GLDQAMYCGOIJDV-UHFFFAOYSA-N 0.000 claims description 2
- XNSPQPOQXWCGKC-UHFFFAOYSA-N C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.[N] Chemical compound C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.[N] XNSPQPOQXWCGKC-UHFFFAOYSA-N 0.000 claims description 2
- WHTXMUJUOQCOQT-UHFFFAOYSA-K F[C+3].P(=O)([O-])([O-])[O-] Chemical compound F[C+3].P(=O)([O-])([O-])[O-] WHTXMUJUOQCOQT-UHFFFAOYSA-K 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 2
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 2
- 235000004279 alanine Nutrition 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 235000003704 aspartic acid Nutrition 0.000 claims description 2
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 235000019439 ethyl acetate Nutrition 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 150000003871 sulfonates Chemical class 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims 2
- WLGDAKIJYPIYLR-UHFFFAOYSA-N octane-1-sulfonic acid Chemical compound CCCCCCCCS(O)(=O)=O WLGDAKIJYPIYLR-UHFFFAOYSA-N 0.000 claims 2
- RLPALQSCQZLDHX-UHFFFAOYSA-N C[N+](CCCC)(CCCC)CCCC.C1=CC=CC=C1 Chemical class C[N+](CCCC)(CCCC)CCCC.C1=CC=CC=C1 RLPALQSCQZLDHX-UHFFFAOYSA-N 0.000 claims 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims 1
- 229910052581 Si3N4 Inorganic materials 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- FMQNKVGDYIXYDI-UHFFFAOYSA-N [Na].C=C.C=C Chemical compound [Na].C=C.C=C FMQNKVGDYIXYDI-UHFFFAOYSA-N 0.000 claims 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims 1
- 229910000416 bismuth oxide Inorganic materials 0.000 claims 1
- 229910002090 carbon oxide Inorganic materials 0.000 claims 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims 1
- 239000008103 glucose Substances 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 235000019260 propionic acid Nutrition 0.000 claims 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 claims 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 51
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 28
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 23
- 239000002245 particle Substances 0.000 description 22
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 13
- 239000012964 benzotriazole Substances 0.000 description 13
- 229910000420 cerium oxide Inorganic materials 0.000 description 12
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 12
- 229920003169 water-soluble polymer Polymers 0.000 description 12
- 239000002002 slurry Substances 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 230000002378 acidificating effect Effects 0.000 description 10
- 239000003989 dielectric material Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000002411 adverse Effects 0.000 description 7
- 230000007547 defect Effects 0.000 description 6
- 239000010432 diamond Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003002 pH adjusting agent Substances 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
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- 238000003801 milling Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 4
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- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
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- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 4
- 229910003460 diamond Inorganic materials 0.000 description 4
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- 125000000524 functional group Chemical group 0.000 description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
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- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000003082 abrasive agent Substances 0.000 description 3
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 2
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 2
- LGCBVEQNSDSLIH-UHFFFAOYSA-N 4-pyridin-3-ylbutanal Chemical compound O=CCCCC1=CC=CN=C1 LGCBVEQNSDSLIH-UHFFFAOYSA-N 0.000 description 2
- 244000132059 Carica parviflora Species 0.000 description 2
- 235000014653 Carica parviflora Nutrition 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000003139 biocide Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- RHDUVDHGVHBHCL-UHFFFAOYSA-N niobium tantalum Chemical compound [Nb].[Ta] RHDUVDHGVHBHCL-UHFFFAOYSA-N 0.000 description 2
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- LLYCMZGLHLKPPU-UHFFFAOYSA-M perbromate Chemical compound [O-]Br(=O)(=O)=O LLYCMZGLHLKPPU-UHFFFAOYSA-M 0.000 description 2
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- HRQDCDQDOPSGBR-UHFFFAOYSA-M sodium;octane-1-sulfonate Chemical compound [Na+].CCCCCCCCS([O-])(=O)=O HRQDCDQDOPSGBR-UHFFFAOYSA-M 0.000 description 2
- WFRKJMRGXGWHBM-UHFFFAOYSA-M sodium;octyl sulfate Chemical group [Na+].CCCCCCCCOS([O-])(=O)=O WFRKJMRGXGWHBM-UHFFFAOYSA-M 0.000 description 2
- 229910003468 tantalcarbide Inorganic materials 0.000 description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 2
- NMJKIRUDPFBRHW-UHFFFAOYSA-N titanium Chemical compound [Ti].[Ti] NMJKIRUDPFBRHW-UHFFFAOYSA-N 0.000 description 2
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- LLNAMUJRIZIXHF-CLFYSBASSA-N (z)-2-methyl-3-phenylprop-2-en-1-ol Chemical compound OCC(/C)=C\C1=CC=CC=C1 LLNAMUJRIZIXHF-CLFYSBASSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- 229940100555 2-methyl-4-isothiazolin-3-one Drugs 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- 229940100484 5-chloro-2-methyl-4-isothiazolin-3-one Drugs 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910017089 AlO(OH) Inorganic materials 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 229910026551 ZrC Inorganic materials 0.000 description 1
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 1
- JXOOCQBAIRXOGG-UHFFFAOYSA-N [B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[Al] Chemical compound [B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[B].[Al] JXOOCQBAIRXOGG-UHFFFAOYSA-N 0.000 description 1
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 1
- DZZDTRZOOBJSSG-UHFFFAOYSA-N [Ta].[W] Chemical compound [Ta].[W] DZZDTRZOOBJSSG-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- ZWXYEWJNBYQXLK-UHFFFAOYSA-N azanium;4-dodecoxy-4-oxo-3-sulfobutanoate Chemical compound [NH4+].CCCCCCCCCCCCOC(=O)C(S(O)(=O)=O)CC([O-])=O ZWXYEWJNBYQXLK-UHFFFAOYSA-N 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Chemical class [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical compound CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- IOMDIVZAGXCCAC-UHFFFAOYSA-M diethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](CC)(CC)CC=C IOMDIVZAGXCCAC-UHFFFAOYSA-M 0.000 description 1
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 1
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical compound C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 description 1
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229950004394 ditiocarb Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 238000005227 gel permeation chromatography 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
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000138 intercalating agent Substances 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- APLYTANMTDCWTA-UHFFFAOYSA-L magnesium;phthalate Chemical compound [Mg+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O APLYTANMTDCWTA-UHFFFAOYSA-L 0.000 description 1
- 150000004701 malic acid derivatives Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229930003658 monoterpene Natural products 0.000 description 1
- 235000002577 monoterpenes Nutrition 0.000 description 1
- RJSRQTFBFAJJIL-UHFFFAOYSA-N niobium titanium Chemical compound [Ti].[Nb] RJSRQTFBFAJJIL-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 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
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940067741 sodium octyl sulfate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- KZOJQMWTKJDSQJ-UHFFFAOYSA-M sodium;2,3-dibutylnaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(CCCC)C(CCCC)=CC2=C1 KZOJQMWTKJDSQJ-UHFFFAOYSA-M 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
- 230000035882 stress Effects 0.000 description 1
- VSSLEOGOUUKTNN-UHFFFAOYSA-N tantalum titanium Chemical compound [Ti].[Ta] VSSLEOGOUUKTNN-UHFFFAOYSA-N 0.000 description 1
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- USFMMZYROHDWPJ-UHFFFAOYSA-N trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium Chemical compound CC(=C)C(=O)OCC[N+](C)(C)C USFMMZYROHDWPJ-UHFFFAOYSA-N 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
- GXQFALJDHPPWKR-UHFFFAOYSA-L trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;sulfate Chemical compound [O-]S([O-])(=O)=O.CC(=C)C(=O)OCC[N+](C)(C)C.CC(=C)C(=O)OCC[N+](C)(C)C GXQFALJDHPPWKR-UHFFFAOYSA-L 0.000 description 1
- VZTGWJFIMGVKSN-UHFFFAOYSA-O trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium Chemical compound CC(=C)C(=O)NCCC[N+](C)(C)C VZTGWJFIMGVKSN-UHFFFAOYSA-O 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 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]
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Description
本發明係有關用於移除阻障金屬之化學機械平坦化(CMP)配方,且具體而言,本發明係有關在積體電路裝置中於互連結構存在下用於選擇性移除阻障金屬之研磨組成物。
近年來,半導體工業於形成積體電路漸漸地依賴銅電性連接。這些銅連接具有低電阻率及高電遷移阻力。由於銅在很多介電材料(例如二氧化矽和低-K或二氧化矽的摻雜形式)中高度可溶,因而需要擴散阻障層來防止銅擴散到下方介電材料。典型的阻障材料包含鉭、氮化鉭、鉭-氮化矽、鈦、氮化鈦、鈦-氮化矽、鈦-氮化鈦、鈦-鎢、鎢、氮化鎢及鎢-氮化矽。
為因應對高密度積體電路逐漸增加之需求,半導體製造商目前製造包含複數層金屬互連結構覆蓋層之積體電路。當製造積體電路裝置時,係將每一互連層平坦化以改善封裝密度、製程一致性、產品品質,且最重要地是能夠製造複數層積體電路。半導體製造商仰賴化學機械平坦化(CMP)作為製造平坦基材表面之成本有效性方法。該CMP製程典型以兩步驟順序進行。首先,該研磨製程使用特別設計用來快速移除銅之“第一步驟”漿料。
於初始的銅移除後,使“第二步驟”漿料移除該硬質阻障材料。典型地,第二步驟漿料需要絕佳的選擇性以移除該阻障材料而不會對該互連結構的物理結構或電學特性有不良影響。因為高導電性互連金屬,例如銅,相較於典型的阻障材料(如氮化鉭和氮化鈦)係較為軟,故習知銅主體(bulk)移除漿料無法用於阻障應用。酸性阻障漿料藉由導入足夠的苯并三唑到漿料中以降低銅移除速率而達到選擇性。
銅及介電質(例如TEOS)速率之可調性(tunability)於阻障研磨步驟是重要的。為達到本說明書之目的,TEOS表示由原矽酸四乙酯(trtraethylorthosilicates)製造的介電質。例如,Liu等人於美國專利公開案第2005/0031789號揭露使用四級銨鹽來增加TEOS移除速率之酸性阻障漿料。此漿料提供優異的阻障移除速率及具有低銅速率和控制的TEOS移除速率等優點。進一步地,該過氧化氫濃度提供用以控制銅移除速率之有效觸發(toggle)。不幸地,這些漿料缺乏對低-K介電質的控制,該低K介電質為例如摻雜碳之氧化物(carbon-doped oxide;CDO)。
因為不同IC製造者使用之整合方式(integration schemes)各異,故於阻障CMP步驟中研磨各種薄膜所需的速率選擇性也就不同。某些薄膜堆疊需要較高的銅、TEOS和CDO速率以供形貌修正;但在其他時候,則使用低的銅、TEOS和CDO速率。可修正銅、TEOS和CDO外貌之阻障移除漿料將有助於進一步減小線寬(line width)。
有鑑於上述者,此時係存在於提供第二步驟漿料之需求,該漿料具有:阻障材料之高移除速率,對互連金屬之極佳選擇性,受控制的TEOS、CDO及銅移除速率。
本發明提供具有有限的介電質侵蝕之研磨溶液,其係用於在至少一種非鐵互連金屬的存在下移除阻障材料,該研磨溶液包括0至20重量百分比之氧化劑;至少0.001重量百分比之抑制劑,其係用於降低該非鐵互連金屬之移除速率;1ppm至4重量百分比之由下式形成的含有機銨陽離子鹽(organic-containing ammonium cationic salt):
式中,R1
、R2
、R3
及R4
為基圍,R1
具有2至25個碳原子之碳鏈長度;1 ppm至4重量百分比之陰離子界面活性劑,該陰離子界面活性劑具有4至25個碳原子,且該銨陽離子鹽加上該陰離子界面活性劑之全部碳原子為6至40個碳原子;0至50重量百分比之研磨劑;以及餘量水(balance water),且該溶液之pH值小於7。
於另一態樣,本發明提供具有有限的介電質侵蝕之研磨溶液,其係用於在至少一種非鐵互連金屬的存在下移除阻障材料,該研磨溶液包括0.001至15重量百分比之氧化劑;至少0.001重量百分比之抑制劑,其係用於降低該非鐵互連金屬之移除速率;1ppm至4重量百分比之由下式形成的含有機銨陽離子鹽:
式中,R1
、R2
、R3
及R4
為基團,R1
具有2至10個碳原子之碳鏈長度,該含有機銨陽離子鹽具有5至25個碳原子;1ppm至4重量百分比之陰離子界面活性劑,該陰離子界面活性劑具有5至20個碳原子,且該銨陽離子鹽加上該陰離子界面活性劑之全部碳原子為10至35個;0至50重量百分比之研磨劑;以及餘量水,且該溶液pH值小於5。
於另一態樣,本發明提供研磨半導體基材之方法,該方法包含以研磨漿溶液及研磨墊研磨半導體基材的步驟,該研磨溶液具有有限的介電質侵蝕,係用於在至少一種非鐵互連金屬的存在下移除阻障材料溶液,其包括:0至20重量百分比之氧化劑;至少0.001重量百分比之抑制劑,其係用於降低該非鐵互連金屬之移除速率;1ppm至4重量百分比之由下式形成的含有機銨陽離子鹽:
式中,R1
、R2
、R3
及R4
為基團,R1
具有2至25個碳原子之碳鏈長度;1ppm至4重量百分比之陰離子界面活性劑,該陰離子界面活性劑具有4至25個碳原子,且該銨陽離子鹽加上該陰離子界面活性劑之全部碳原子為6至40個碳原子;0至50重量百分比之研磨劑;以及餘量水,且該溶液之pH值小於7。
已發現陰離子界面活性劑可於銨陽離子鹽的存在下作用,以於酸性pH值下增加摻雜碳的氧化物之移除速率。該陰離子界面活性劑可以一種不會對鉭、氮化鉭、銅或TEOS之移除速率有不良影響的方式作用。為達本說明書之目的,研磨溶液係指水溶性研磨溶液,該溶液可包括或可不包括研磨劑。若研磨溶液包括研磨劑,那麼該研磨溶液也是研磨漿料。該研磨溶液也可視需要包括界面活性劑、pH緩衝液、消泡劑及除生物劑。
對研磨低-k和極低-k介電材料而言,維持低壓力以降低這些材料的剝離與斷裂是很重要的。然而,低壓產生低阻障材料(Ta/TaN)移除速率,其對於晶圓產量而言為非所欲的。幸運地,已證明於低壓操作時酸性研磨溶液比習知鹼性阻障漿料更具有高阻障移除速率。該阻障材料可包含下列:鉭、氮化鉭、鉭-氮化矽、鈦、氮化鈦、鈦-氮化矽、鈦-氮化鈦、鈦-鎢、鎢、氮化鎢及鎢-氮化矽。
添加銨鹽有助於控制含氧化矽層(例如於酸性pH值之TEOS層)之移除速率,且因此其允許控制含氧化矽材料的移除速率。該銨鹽為由包含下式結構化合物形成之有機銨鹽:
R1
、R2
、R3
及R4
為基團,且可為相同或不同者。該組成物係於酸性pH值操作,於該酸性pH值下銨化合物變為離子化。陰離子的例子包括,硝酸鹽、硫酸鹽、鹵化物(例如溴化物、氯化物、氟化物和碘化物)、檸檬酸鹽、磷酸鹽、草酸鹽、蘋果酸鹽、葡萄糖酸鹽、氫氧化物、醋酸鹽、硼酸鹽、乳酸鹽、硫氰酸鹽、氰酸鹽、磺酸鹽、矽酸鹽、全鹵化物(per-halides)(例如過溴酸鹽、過氯酸鹽及過碘酸鹽)、鉻酸鹽、及其混合物。可直接將該鹽加入組成物中或是在原位形成該鹽。例如,將氫氧化四丁基銨(TBAH)加入至pH值為2.5的硝酸溶液形成該硝酸四丁基銨。
較佳的銨鹽組合是由氫氧化四丁基銨與氫氟酸反應所形成者。這組合是於低pH值下反應形成氟化四丁基銨鹽。雖然確切的機制不是很清楚(該氟化物鹽解離以在溶液中提供氟化物離子),但是在溶液中具有有機氟化銨鹽進一步加速了該TEOS移除速率。
R1
是具有2至25個碳原子之碳鏈長度的有機基團。更佳地,R1
具有2至10個碳原子之碳鏈長度。最佳地,R1
具有2至5個碳原子之碳鏈長度。該R1之有機基團可為經取代或未經取代之芳基、烷基、芳烷基、或烷芳基。
較佳地,R2
、R3
及R4
為有機化合物,例如經取代或未經取代之芳基、烷基、芳烷基、或烷芳基;或氫。若R2
、R3
及R4
為有機化合物,那麼該有機化合物較佳具有2至20個碳原子之碳鏈長度;更佳地,其具有2至10個碳原子之碳鏈長度;且最佳地,其具有2至5個碳原子之碳鏈長度。該四級陽離子銨鹽之碳原子總數較佳為5至25個。一般而言,碳原子數的增加會增加有效性,但卻會降低化合物的溶解度。較佳地,該碳原子總數為介於10至20個碳原子之間。
適合形成銨鹽之化合物包括四乙基銨、四丁基銨、苯甲基三丁基銨、苯甲基三甲基銨、苯甲基三乙基銨、二烯丙基二甲基銨、甲基丙烯酸二乙基胺基乙酯、甲基丙烯酸二甲基胺基乙酯、甲基丙烯醯氧基乙基三甲基銨、3-(甲基丙烯醯胺基)丙基三甲基銨、三伸乙基四胺、四甲基胍、己胺及其混合物。具體銨鹽包括硝酸四乙基銨、氟化四丁基銨、硝酸四乙基銨、氟化四乙基銨、氯化苯甲基三丁基銨、氯化苯甲基三甲基銨、氯化苯甲基三乙基銨、氯化二烯丙基二甲基銨、氯化二烯丙基二乙基銨、甲基丙烯酸二乙胺基乙酯、甲基丙烯酸二甲胺基乙酯、硫酸甲基丙烯醯氧基乙基三甲基銨、氯化甲基丙烯醯氧基乙基三甲基銨、氯化3-(甲基丙烯醯胺基)丙基三甲基銨、三伸乙基四胺、四甲基胍、己胺及包括前述至少一者的混合物。較佳的銨鹽為四乙基銨鹽、四丁基銨鹽、苯甲基三丁基銨鹽、苯甲基三甲基銨鹽、苯甲基三乙基銨鹽及其混合物。
該銨鹽以1ppm至4重量百分比之量存在。為達到本說明書之目的,除非特別地指明,否則所有組成物均以重量百分比表示。較佳地,該銨鹽以10ppm至2重量百分比之量存在。最佳地,該銨鹽為25ppm至1重量百分比。
已發現陰離子界面活性劑會與該銨鹽組合作用以加速摻雜碳之氧化物(例如購自Novellus Systems,Inc之CoralTM
低k介電質)之移除速率。該陰離子界面活性劑具有4至25個的碳原子總數。較佳地,該陰離子界面活性劑具有5至20個且最佳為6至12個碳原子。陰離子鹽類之例子包括選自磺酸鹽、硫酸鹽、磷酸鹽及羧酸鹽之至少一者。此外,烴和氟碳化合物(fluorocarbon)陰離子界面活性劑二者皆特別有效。具體的界面活性劑型式包含磺基琥珀酸十二酯鹽(lauryl sulfosuccinate)、磺酸辛酯鹽(capryl sulfonate)、硫酸癸酯鹽、硫酸辛酯鹽及磷酸酯鹽氟碳化合物之至少一者。
該陰離子界面活性劑以1ppm至4重量百分比之量存在。較佳地,該陰離子界面活性劑以10ppm至2重量百分比之量存在。最佳地,該陰離子界面活性劑為25ppm至1重量百分比。
此外,由於該陰離子界面活性劑可與該陽離子銨鹽結合並自水溶液沉澱,因此限制該銨陽離子鹽與該陰離子界面活性劑的碳原子總數是很重要的。6至40個碳原子總數對控制TEOS及CDO速率係特別有效的且無不良的沉澱影響。較佳地,該銨陽離子鹽與該陰離子界面活性劑的碳原子總數為10至35個碳原子。最佳地,該銨陽離子鹽與該陰離子界面活性劑的碳原子總數為15至30個碳原子。
該溶液視需要包含0.0005至5重量百分比的至少一種非鐵加速劑,該非鐵加速劑係選自用於錯合該非鐵金屬之錯合劑與含有丙烯酸官能基之水溶性聚合物之群組。除非
特別地指明,否則本說明書係以重量百分比定義所有溶液成分。較佳地,該溶液包含0.001至3重量百分比的至少一種非鐵加速劑,該非鐵加速劑係選自用於錯合該非鐵金屬之錯合劑與含有丙烯酸官能基之水溶性聚合物之群組。最佳地,該溶液包含0.002至2重量百分比的至少一種非鐵加速劑,該非鐵加速劑係選自用於錯合該非鐵金屬之錯合劑與含有丙烯酸官能基之水溶性聚合物之群組。
該溶液視需要包含0.02至2重量百分比之非鐵金屬之錯合劑。最佳地,該溶液包含0.05至1重量百分比之非鐵金屬之錯合劑。典型的錯合劑包含至少一種的羧酸、多元羧酸(multi-carboxylic acid)、胺基羧酸、多胺(multi-amine)化合物、及其混合物。具體的錯合劑包含下列:乙酸、丙胺酸、天冬胺酸、乙醯乙酸乙酯、乙二胺、三亞甲基二胺、乙二胺四乙酸(EDTA)、檸檬酸、乳酸、蘋果酸、順丁烯二酸、丙二酸、草酸、三亞乙基四胺、二伸乙基三胺、甘胺酸、羥乙酸、戊二酸、水楊酸、氮基三乙酸、乙二胺、N-羥基乙基乙二胺三乙酸(HEDTA)、羥基喹啉、酒石酸、二乙二硫胺甲酸鈉、丁二酸、磺柳酸、三羥乙酸、硫代羥乙酸、3-羥基丁酸、丙酸、苯二甲酸、間苯二甲酸、3-羥基水楊酸、3,5-二羥基水楊酸、五倍子酸、葡萄糖酸、兒茶酚、五倍子酚、五倍子酸、鞣酸、其鹽類及其混合物。一些有機酸(例如檸檬酸)可同時作為錯合劑與pH調節劑。該錯合劑也提供在老化處理(aging)期間控制研磨溶液變色的優點。添加錯合劑加速銅移除,但過量的錯合劑卻
會對研磨速率有不好的影響。
10億分之10(10ppb)至4重量百分比之錯合劑可控制研磨溶液變色。不足的錯合劑會導致不穩定的研磨漿料(研磨漿料於很短的時間週期內產生顏色的改變);而過量的錯合劑會對研磨速率有不良影響。
該溶液視需要包含具有丙烯酸官能基之水溶性聚合物以增加該非鐵互連金屬之移除速率。例如,聚丙烯酸、聚甲基丙烯酸、其共聚物及其混合物對於逐漸增加銅移除速率是特別有效的。例如,加入0.0005至5重量百分比之水溶性聚合物可增加該非鐵互連金屬速率至可接受程度。較佳地,該溶液包含0.001至3重量百分比之水溶性聚合物。最佳地,該溶液包含0.002至3重量百分比之水溶性聚合物。該水溶性聚合物的數量平均分子量係介於100至1,000,000之間。本說明書藉由凝膠滲透層析法測量分子量,並以數量平均分子量的型式定義所有分子量。較佳地,該水溶性聚合物的數量平均分子量係介於100至750,000之間。最佳地,該水溶性聚合物的數量平均分子量係介於100至500,000之間。在此等範圍內,共聚物在該等範圍的最高點作用得最好。
此外,該水溶性聚合物較佳包含胺基官能基,例如聚(丙烯醯胺-共-丙烯酸)(poly(acrylamide-co-acrylic acid))以限制對TEOS移除速率的影響。當該溶液包含銨鹽時,該胺基官能基尤其重要。如果該水溶性聚合物不是共聚物,那麼低分子量聚合物為較佳的。例如,數量平均分子量為100至50,000的聚丙烯酸、聚甲基丙烯酸及其混合物對逐漸增加銅移除速率尤其有效且對TEOS移除速率無實質上的影響。較佳地,該聚丙烯酸、聚甲基丙烯酸或其混合物的數量平均分子量為100至20,000。最佳地,該聚丙烯酸、聚甲基丙烯酸或其混合物的數量平均分子量為100至10,000。
該阻障金屬研磨組成物視需要包含研磨劑以用於阻障材料之「機械性」移除。該CMP組成物包含研磨劑以用於阻障層之「機械性」移除。該研磨劑較佳為膠狀(colloidal)研磨劑。研磨劑的例子包含下列:無機氧化物、金屬硼化物、金屬碳化物、金屬氫氧化物、金屬氮化物、或包含前述研磨劑之至少一者的組合。適合的無機氧化物包含:例如,二氧化矽(SiO2
)、氧化鋁(Al2
O3
)、氧化鋯(ZrO2
)、二氧化鈰(CeO2
)、二氧化錳(MnO2
)、及其混合物。氧化鋁係以許多種形式取得,例如α-氧化鋁、γ-氧化鋁、δ-氧化鋁、及非晶形(非晶體)氧化鋁。其他適合的氧化鋁例子為水鋁礦(boehmite)(AlO(OH))粒子及其混合物。必要時,也可使用這些無機氧化物的改質形式,如經聚合物塗佈的無機氧化物粒子。適合的金屬碳化物、硼化物及氮化物包括,例如,碳化矽、氮化矽、碳氮化矽(SiCN)、碳化硼、碳化鎢、碳化鋯、硼化鋁、碳化鉭、碳化鈦、及包含前述金屬碳化物、硼化物及氮化物之至少一者之混合物。必要時,也可使用鑽石作為研磨劑。其他研磨劑還包含聚合物粒子及經塗佈的聚合物粒子。較佳的研磨劑為二氧化矽。
該研磨劑於研磨組成物水相之濃度為0至50重量百分比。就無研磨劑之溶液來說,固定的研磨墊有助於該阻障層的移除。較佳地,該研磨劑濃度為0.1至40重量百分比。且最佳地,該研磨劑濃度為0.25至35重量百分比。典型地,增加研磨劑濃度亦增加該介電材料的移除速率;且尤其係增加低-k介電材料的移除速率,該低k介電材料為例如摻雜碳的氧化物。例如,如果半導體製造商期望增加低-k介電材料的移除速率,那麼增加該研磨劑含量即可增加該介電質之移除速率到該期望值。
該研磨劑較佳具有小於250nm之平均粒子尺寸以防止過度金屬碟形化(dishing)及介電質侵蝕。為達本說明書之目的,粒子尺寸係指該膠狀氧化矽的平均粒子尺寸。最佳地,該二氧化矽具有小於100nm之平均粒子尺寸以進一步降低金屬碟形化及介電質侵蝕。尤其小於15nm之平均研磨劑粒子尺寸係於可接受速率移除阻障金屬,且不會過度移除介電材料。例如最小的介電質侵蝕與金屬碟形化係發生在膠狀二氧化矽具有2至15nm之平均粒子尺寸。減小該膠狀二氧化矽尺寸有助於改善該溶液的選擇性;但也易於降低該阻障移除速率。此外,該較佳的膠狀二氧化矽可包含添加劑,例如分散劑,以改良二氧化矽在酸性pH值範圍之穩定性。一種此類研磨劑為購自AZ Electronic Materials,of Puteaux,France之膠狀二氧化矽。
此外,高純度二氧化矽粒子也可降低研磨溶液之老化或黃化速率。例如,維持過渡金屬總濃度至小於百萬分之1(1ppm),進一步增加該溶液的穩定以減少黄化。再者,將鉀和鈉限制在小於1ppm以減少此等有害成分逆向擴散進入介電質層。
視需要地,該阻障層(例如,鉭、氮化鉭、鈦和氮化鈦)的移除速率較佳係藉由使用氧化劑進行最佳化。適合的氧化劑包括,例如過氧化氫、單過硫酸鹽、碘酸鹽、過鄰苯二甲酸鎂、過乙酸及其他過酸(peracid)、過硫酸鹽、溴酸鹽、過碘酸鹽、硝酸鹽、鐵鹽、鈰鹽、錳(Mn)(III)鹽、Mn(IV)鹽、及Mn(VI)鹽、銀鹽、銅鹽、鉻鹽、鈷鹽、鹵素、次氯酸鹽、或包含前述氧化劑之至少一者的組合。較佳的氧化劑為過氧化氫。須注意的是該氧化劑典型係在使用前加入該研磨組成物,且在該等情況中該氧化劑包含於獨立包裝內。
一般期望使用的氧化劑量為0至20重量百分比。較佳地,該氧化劑為0.001至15重量百分比。最佳地,該組成物包含0.05至10重量百分比的氧化劑。調整該氧化劑(例如過氧化物)的用量,也可控制該金屬互連移除速率。例如增加該過氧化物濃度以增加銅移除速率。然而,氧化劑之過度增加會對研磨速率產生不良影響。
此外,該溶液包含至少0.001重量百分比的抑制劑以藉由靜態蝕刻或其他移除機制控制非鐵互連移除速率。調整該抑制劑濃度以藉由保護該金屬免於靜態蝕刻而來調整該非鐵互連金屬移除速率。較佳地,該溶液包含0.001至10重量百分比的抑制劑以用於抑制非鐵金屬(例如銅互連)之靜態蝕刻。最佳地,該溶液包含0.05至2重量百分比的抑制劑。該抑制劑可由抑制劑的混合物組成。唑抑制劑對於銅和銀互連尤其有效。典型的唑抑制劑包括苯并三唑(BTA)、氫硫基苯并噻唑(MBT)、甲苯基三唑及咪唑。BTA對於銅和銀互連是尤其有效的抑制劑。
該研磨組成物具有小於7的pH值及餘量水。較佳地,該pH值小於或等於5。視需要,該研磨組成物包含無機的pH調節劑以降低該研磨組成物的pH值至具有餘量水的小於7之酸性pH值。較佳地,該pH調節劑僅包含雜質程度濃度的金屬離子。此外,該溶液最佳藉由餘量去離子水以限制伴隨的雜質。該pH調節劑可為有機酸或無機酸。有機酸之實例包含乙酸、檸檬酸、蘋果酸、順丁烯二酸、羥乙酸、鄰苯二甲酸、草酸、丙二酸、乳酸、丁二酸、酒石酸、及其混合物的至少一種。較佳地,該pH調節劑為無機酸,例如硝酸、硫酸、氫氯酸、氫氟酸及磷酸。最有利的pH調節劑為硝酸(HNO3
)。典型地,該溶液的pH值為1.5至5。最佳地,該pH值為2至4。
在pH值低於5時,研磨組成物可提供高阻障金屬移除速率,即使具有相對低的研磨劑濃度。此低的研磨劑濃度可藉由降低研磨劑所導致之不期望的缺陷(例如刮痕)來改良該CMP製程的研磨效能。此外,在pH值低於4時,該研磨組成物可與具有相對較小粒子尺寸的研磨劑顆粒配製。例如,小如約10nm的粒子尺寸仍提供可接受的Ta/TaN移除速率。藉由利用具有相對較小粒子尺寸的研磨劑及在低研磨劑濃度下配製酸性研磨組成物,則研磨缺陷係減至極佳程度。
該溶液使得該CMP裝置能在低CMP墊壓力下操作,例如7.5至25 kPa,且在某些情況下甚至低於7.5 kPa。該低CMP墊壓力係藉由降低刮痕及其他不期望的研磨缺陷來改善研磨效能並減少脆性材料之損害。例如若暴露於高壓應力時,則低介電常數材料會破裂與分層。再者,由酸性研磨溶液獲得之高阻障金屬移除速率能使用低研磨劑濃度及小粒子尺寸來達成有效的阻障金屬研磨。
為達本說明書之目的,用於在非鐵互連金屬存在下優先移除阻障材料係指以每分鐘埃(Angstrom)表示,移除該阻障材料之速率高於移除該互連金屬之速率。典型地,在具有垂直於晶圓測量之研磨墊壓力小於15 kPa時測得該研磨溶液係具有至少1比1的氮化鉭比銅選擇率。較佳地,在具有垂直於晶圓測量之研磨墊壓力小於15 kPa時測得該研磨溶液係具有至少1.5比1的氮化鉭比銅選擇率。最佳地,該研磨溶液具有至少2比1的氮化鉭比銅選擇率。測試該選擇率的具體實施例為實施例1的條件,其包含聚胺甲酸酯研磨墊。此高度選擇率允許晶片製造商移除阻障材料而不會移除過量介電質或互連材料。
為達本說明書之目的,有限的介電質侵蝕是指化學機械研磨製程研磨後,該介電質具有足夠的厚度以作用在其所期望的目標,例如作為半導體、光罩或阻障材料。此外,該研磨溶液提供彈性的氮化鉭比介電質或CDO選擇率。例如,在具有垂直於晶圓測量之研磨墊壓力小於15 kPa時測得研磨溶液具有1比2至高如10比1的氮化鉭比TEOS或CDO選擇率。測試該選擇率的具體實施例為實施例1的條件,其包含該聚胺甲酸酯研磨墊。
該研磨組成物亦可視需要包含緩衝劑,例如各種有機酸及無機酸,及具有pKa在pH值範圍為1.5至小於4之胺基酸或其鹽類。該研磨組成物可進一步視需要地包含消泡劑,例如非離子性界面活性劑,其包含酯類、環氧乙烷類、醇類、乙氧基化合物類、矽化合物類、氟化合物類、醚類、配糖體及其衍生物等。該消泡劑亦可為兩性界面活性劑。該研磨組成物可視需要包含除生物劑,例如KathonICP Ⅲ,其包含2-甲基-4-異噻唑啉-3-酮及5-氯-2-甲基-4-異噻唑啉-3-酮之活性成分(Kathon為羅門哈斯公司(Rohm and Hass Company)註冊之商標)。
製備表1至5所顯示之溶液組成物列表以評估在各種濃度值下各種陰離子界面活性劑的效能。該組成物的製備中,將顯示的所有所需化學品之需要量(除了過氧化氫與研磨劑外)添加至容器中的去離子水。攪拌該容器中的溶液直到所有成分均溶解於水。接著將研磨劑加入該容器。然後藉由添加硝酸來將該溶液之pH值調整至目標pH值。接著,將過氧化氫加至該容器以用作為研磨組成物。為達本說明書之目的,英文字母表示比較例而數字表示本發明之實施例。
研磨係使用應材(Applied Materials)公司所製造的Mirra模型研磨工具進行。研磨墊為Rohm and Haas Electronic Materials CMP Technilogies供應之PolitexTM
High E多孔聚胺甲酸酯墊。該研磨墊在每一輪操作之前先以鑽石研磨平板處理,該平板是由Kinik製造並具有180 μ m的鑽石。於10.33kPa(1.5psi)之薄膜壓力、每分鐘93轉(rpm)之工作檯轉速及87rpm之載具速度下進行研磨製程。使用購自ATDF公司之200mm空白晶圓,該研磨組成物之供應速率為200 ml/min。Cu及TaN的移除速率是由四點探針量側儀(Four-Point Probe CDE Resmap)所測量。銅、TaN、TEOS及Coral摻雜碳的氧化物(CDO)薄膜移除速率則由Therma Wave Optiprobe2600量測機台測量且使用應材公司(Applied Material)之OrbotTM
WF-720測量缺陷。下表1至4提供研磨結果。
表1至4說明陰離子烴界面活性劑與TBAH組合對增加摻雜碳的氧化物之移除速率是有效的。尤其,該陰離子界面活性劑在酸性阻障漿料中增加CDO移除速率但對氮化鉭、TEOS或銅移除速率則沒有顯著的不利影響。在CDO與TEOS移除速率性質,該Bioterge PAS-8S、Polystep B25、Polystep B29界面活性劑提供有效的與四級銨鹽組合之例子。這些界面活性劑促進合適的TEOS及CDO移除速率以由該鉭移除步驟改善平坦性。
使用Strasbaugh模型6EC研磨機進行研磨。該研磨墊是羅門哈斯電子材料CMP科技公司(Rohm and Haas Electronic Materials CMP Technilogies)提供之PolitexTM
多孔聚胺甲酸酯墊。該研磨墊在每一輪運作之前先以鑽石研磨平板處理,該平板是由Kinik製造並具有180 μ m的鑽石。於10.33kPa(1.5psi)之薄膜壓力、每分鐘93轉(rpm)之工作檯轉速及87rpm之載具速度進行研磨製程。使用ATDF公司之200mm空白晶圓,該研磨組成物之供應速率為200 ml/min。Cu及TaN的移除速率是由四點探針量側儀(Four-Point Probe CDE Resmap)所測量。銅、TaN、TEOS及Coral摻雜碳的氧化物(CDO)薄膜移除速率則由Therma Wave Optiprobe2600量測機台測量且使用應材公司(Applied Material)之OrbotTM
WF-720測量缺陷。下表5提供研磨結果。
該Zonyl FSP界面活性劑之結構如下:(Rf
CH2
CH2
O)x
P(O)(ONH4
)y
其中Rf
=F(CF2
CF2
)z
x=1或2 y=2或1 x+y=3 z=1至約7
當x=1 y=2 z=4時,此分子具有大約10個碳原子。
表5說明陰離子氟碳化合物界面活性劑與TBAH組合對增加摻雜碳的氧化物之移除速率是有效的。尤其,該陰離子界面活性劑在酸性阻障漿料增加CDO移除速率但對氮化鉭、TEOS或銅移除速率則沒有顯著的不利影響。這些界面活性劑促進合適的TEOS及CDO移除速率以由該鉭移除步驟改善平坦性。
綜上所述,該組合提供低pH值研磨溶液,其具有優異的鉭阻障移除速率,受控制的銅、TEOS及CDO移除速率。進一步地,其能快速的移除阻障材料、及對互連金屬有優異的選擇性、優異的晶圓缺陷率。視需要地,研磨劑粒子可增加低-k介電質移除速率且該錯合劑與丙烯酸聚合物控制銅移除速率以提供適合各種整合方式的(integration schemes)的研磨溶液。
Claims (13)
- 一種具有有限的介電質侵蝕之研磨溶液,係用於在至少一種非鐵互連金屬的存在下移除阻障材料,該研磨溶液包括:0.001至15重量百分比之氧化劑;至少0.001重量百分比之抑制劑,其係用於降低該非鐵互連金屬之移除速率;1ppm至4重量百分比之至少一種選自由下列各者所組成群組之含有機銨陽離子鹽(organic-containing ammonium cationic salt):四丁基銨鹽類、苯甲基三丁基銨鹽類、苯甲基三甲基銨鹽類、苯甲基三乙基銨鹽類以及其混合物;1ppm至4重量百分比之用於增加摻雜碳之氧化物之移除速率之陰離子界面活性劑,該陰離子界面活性劑具有4至25個碳原子,且該含有機銨陽離子鹽加上該陰離子界面活性劑之全部碳原子為6至40個碳原子;0至50重量百分比之研磨劑;以及餘量水,且該溶液之pH值小於5,而且在具有垂直於晶圓之研磨墊壓力小於15 kPa時以每分鐘埃表示測得之至少1比1的氮化鉭比銅選擇率,以及在具有垂直於該晶圓之該研磨墊壓力小於15 kPa時以每分鐘埃表示測得之1比2至10比1之的氮化鉭比摻雜碳之氧化物選擇率。
- 如申請專利範圍第1項之研磨溶液,其中,該陰離子界 面活性劑包含選自磺酸鹽、硫酸鹽、磷酸鹽及羧酸鹽之至少一者。
- 如申請專利範圍第2項之研磨溶液,其中,該陰離子界面活性劑為烴或氟碳化合物。
- 如申請專利範圍第3項之研磨溶液,其中,該陰離子界面活性劑係選自磺基琥珀酸十二酯鹽(lauryl sulfosuccinate)、磺酸辛酯鹽、硫酸癸酯鹽、硫酸辛酯鹽及磷酸酯鹽氟碳化合物之至少一者。
- 如申請專利範圍第1項之研磨溶液,其中,該含有機銨陽離子鹽是四丁基銨鹽類。
- 一種具有有限的介電質侵蝕之研磨溶液,係用於在至少一種非鐵互連金屬的存在下移除阻障材料,該研磨溶液包括:0.001至15重量百分比之氧化劑;至少0.001重量百分比之抑制劑,其係用於降低該非鐵互連金屬之移除速率;1ppm至4重量百分比之至少一種選自由下列各者所組成群組之含有機銨陽離子鹽:四丁基銨鹽類、苯甲基三丁基銨鹽類、苯甲基三甲基銨鹽類、苯甲基三乙基銨鹽類以及其混合物;1ppm至4重量百分比之用於增加摻雜碳之氧化物之移除速率之陰離子界面活性劑,該陰離子界面活性劑具有5至20個碳原子,且該含有機銨陽離子鹽加上該陰離子界面活性劑之全部碳原子為10至35個; 0至50重量百分比之研磨劑;以及餘量水,且該溶液之pH值小於5,而且在具有垂直於晶圓之研磨墊壓力小於15 kPa時以每分鐘埃表示測得之至少1比1的氮化鉭比銅選擇率,以及在具有垂直於該晶圓之該研磨墊壓力小於15 kPa時以每分鐘埃表示測得之1比2至10比1之的氮化鉭比摻雜碳之氧化物選擇率。
- 如申請專利範圍第6項之研磨溶液,其中,該陰離子界面活性劑包含選自磺酸鹽、硫酸鹽、磷酸鹽及羧酸鹽之至少一者。
- 如申請專利範圍第7項之研磨溶液,其中,該陰離子界面活性劑為烴或氟碳化合物。
- 如申請專利範圍第8項之研磨溶液,其中,該陰離子界面活性劑係選自磺基琥珀酸十二酯鹽(lauryl sulfosuccinate)、磺酸辛酯鹽、硫酸癸酯鹽、硫酸辛酯鹽、及磷酸酯氟碳化合物之至少一者。
- 如申請專利範圍第9項之研磨溶液,其中,該溶液包含錯合劑,該錯合劑包括選自下列所組成群之至少一者:乙酸、丙胺酸、天冬胺酸、乙醯乙酸乙酯、乙二胺、三亞甲基二胺、乙二胺四乙酸(EDTA)、檸檬酸、乳酸、蘋果酸、順丁烯二酸、丙二酸、草酸、三伸乙基四胺、二伸乙基三胺、甘胺酸、羥乙酸、戊二酸、水楊酸、氮基三乙酸、乙二胺、N-羥基乙基乙二胺三乙酸(HEDTA)、羥基喹啉、酒石酸、二乙二硫胺甲酸鈉、丁二酸、磺柳 酸、三羥乙酸、硫代羥乙酸、3-羥基丁酸、丙酸、苯二甲酸、間苯二甲酸、3-羥基水楊酸、3,5-二羥基水楊酸、五倍子酸、葡萄糖酸、兒茶酚、五倍子酚、五倍子酸、鞣酸、其鹽類及其混合物。
- 如申請專利範圍第6項之研磨溶液,其中,該含有機銨陽離子鹽是四丁基銨鹽類。
- 一種研磨半導體基材之方法,包含下述步驟:以研磨溶液及研磨墊研磨該半導體基材,於該研磨溶液具有有限的介電質侵蝕,係用於在至少一種非鐵互連金屬的存在下移除阻障材料,該研磨溶液包括:0.001至15重量百分比之氧化劑;至少0.001重量百分比之抑制劑,其係用於降低該非鐵互連金屬之移除速率;1ppm至4重量百分比之至少一種選自由下列各者所組成群組之含有機銨陽離子鹽:四丁基銨鹽類、苯甲基三丁基銨鹽類、苯甲基三甲基銨鹽類、苯甲基三乙基銨鹽類以及其混合物;1ppm至4重量百分比之用於增加摻雜碳之氧化物之移除速率之陰離子界面活性劑,該陰離子界面活性劑具有4至25個碳原子,且該含有機銨陽離子鹽加上該陰離子界面活性劑之全部碳原子為6至40個碳原子;0至50重量百分比之研磨劑;以及餘量水,且該溶液之pH值小於5,而且在具有垂 直於晶圓之研磨墊壓力小於15 kPa時以每分鐘埃表示測得之至少1比1的氮化鉭比銅選擇率,以及在具有垂直於該晶圓之該研磨墊壓力小於15 kPa時以每分鐘埃表示測得之1比2至10比1之的氮化鉭比摻雜碳之氧化物選擇率。
- 如申請專利範圍第12項之方法,其中,該有機銨陽離子鹽是四丁基銨鹽類。
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