TW202248413A - 清潔組合物 - Google Patents
清潔組合物 Download PDFInfo
- Publication number
- TW202248413A TW202248413A TW111114354A TW111114354A TW202248413A TW 202248413 A TW202248413 A TW 202248413A TW 111114354 A TW111114354 A TW 111114354A TW 111114354 A TW111114354 A TW 111114354A TW 202248413 A TW202248413 A TW 202248413A
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- Prior art keywords
- acid
- composition
- ether
- hydroxide
- ammonium
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 154
- 238000004140 cleaning Methods 0.000 title abstract description 48
- 238000004377 microelectronic Methods 0.000 claims abstract description 45
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 17
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 16
- 239000010941 cobalt Substances 0.000 claims abstract description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 15
- -1 alkali metal cation Chemical class 0.000 claims description 144
- 239000000356 contaminant Substances 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 30
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 21
- 239000003638 chemical reducing agent Substances 0.000 claims description 18
- 238000005260 corrosion Methods 0.000 claims description 17
- 230000007797 corrosion Effects 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000003112 inhibitor Substances 0.000 claims description 15
- SVMUEEINWGBIPD-UHFFFAOYSA-N dodecylphosphonic acid Chemical compound CCCCCCCCCCCCP(O)(O)=O SVMUEEINWGBIPD-UHFFFAOYSA-N 0.000 claims description 14
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical group [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 14
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- NJGCRMAPOWGWMW-UHFFFAOYSA-N octylphosphonic acid Chemical compound CCCCCCCCP(O)(O)=O NJGCRMAPOWGWMW-UHFFFAOYSA-N 0.000 claims description 10
- 235000010323 ascorbic acid Nutrition 0.000 claims description 9
- 239000011668 ascorbic acid Substances 0.000 claims description 9
- 229960005070 ascorbic acid Drugs 0.000 claims description 9
- FTMKAMVLFVRZQX-UHFFFAOYSA-N octadecylphosphonic acid Chemical compound CCCCCCCCCCCCCCCCCCP(O)(O)=O FTMKAMVLFVRZQX-UHFFFAOYSA-N 0.000 claims description 9
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- HMBHAQMOBKLWRX-UHFFFAOYSA-N 2,3-dihydro-1,4-benzodioxine-3-carboxylic acid Chemical compound C1=CC=C2OC(C(=O)O)COC2=C1 HMBHAQMOBKLWRX-UHFFFAOYSA-N 0.000 claims description 7
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 7
- 229940075419 choline hydroxide Drugs 0.000 claims description 7
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical group C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 235000000346 sugar Nutrition 0.000 claims description 6
- AYQDAYSTSMCOCJ-UHFFFAOYSA-N 10-phosphonodecylphosphonic acid Chemical compound OP(O)(=O)CCCCCCCCCCP(O)(O)=O AYQDAYSTSMCOCJ-UHFFFAOYSA-N 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 5
- IPUAADANTWKVJD-UHFFFAOYSA-N 2-[1-di(propan-2-yloxy)phosphorylethenyl-propan-2-yloxyphosphoryl]oxypropane Chemical compound CC(C)OP(=O)(OC(C)C)C(=C)P(=O)(OC(C)C)OC(C)C IPUAADANTWKVJD-UHFFFAOYSA-N 0.000 claims description 5
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 5
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 5
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 5
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 claims description 5
- GATNOFPXSDHULC-UHFFFAOYSA-N ethylphosphonic acid Chemical compound CCP(O)(O)=O GATNOFPXSDHULC-UHFFFAOYSA-N 0.000 claims description 5
- GJWAEWLHSDGBGG-UHFFFAOYSA-N hexylphosphonic acid Chemical compound CCCCCCP(O)(O)=O GJWAEWLHSDGBGG-UHFFFAOYSA-N 0.000 claims description 5
- MBKDYNNUVRNNRF-UHFFFAOYSA-N medronic acid Chemical compound OP(O)(=O)CP(O)(O)=O MBKDYNNUVRNNRF-UHFFFAOYSA-N 0.000 claims description 5
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 5
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 5
- CIWBSHSKHKDKBQ-SZSCBOSDSA-N 2-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxy-2h-furan-5-one Chemical compound OC[C@H](O)C1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-SZSCBOSDSA-N 0.000 claims description 4
- MNWHEINDSPXJFN-UHFFFAOYSA-N C(C1=CC=CC=C1)N.CN(C1=CC=CC=C1)C Chemical compound C(C1=CC=CC=C1)N.CN(C1=CC=CC=C1)C MNWHEINDSPXJFN-UHFFFAOYSA-N 0.000 claims description 4
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-araboascorbic acid Natural products OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 claims description 4
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002211 L-ascorbic acid Substances 0.000 claims description 4
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 4
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 4
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 4
- 235000010350 erythorbic acid Nutrition 0.000 claims description 4
- 229930182830 galactose Natural products 0.000 claims description 4
- 150000002443 hydroxylamines Chemical class 0.000 claims description 4
- 229940026239 isoascorbic acid Drugs 0.000 claims description 4
- 239000000467 phytic acid Substances 0.000 claims description 4
- 235000002949 phytic acid Nutrition 0.000 claims description 4
- 229940068041 phytic acid Drugs 0.000 claims description 4
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 claims description 4
- 229940043349 potassium metabisulfite Drugs 0.000 claims description 4
- 235000010263 potassium metabisulphite Nutrition 0.000 claims description 4
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 3
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 3
- 229930091371 Fructose Natural products 0.000 claims description 3
- 239000005715 Fructose Substances 0.000 claims description 3
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 3
- 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 description 3
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 3
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 claims description 3
- 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 description 3
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 3
- PCAXGMRPPOMODZ-UHFFFAOYSA-N disulfurous acid, diammonium salt Chemical compound [NH4+].[NH4+].[O-]S(=O)S([O-])(=O)=O PCAXGMRPPOMODZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004318 erythorbic acid Substances 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 239000008101 lactose Substances 0.000 claims description 3
- VMESOKCXSYNAKD-UHFFFAOYSA-N n,n-dimethylhydroxylamine Chemical compound CN(C)O VMESOKCXSYNAKD-UHFFFAOYSA-N 0.000 claims description 3
- 229940093932 potassium hydroxide Drugs 0.000 claims description 3
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 3
- 235000011009 potassium phosphates Nutrition 0.000 claims description 3
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 3
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 3
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229940024545 aluminum hydroxide Drugs 0.000 claims description 2
- 238000011109 contamination Methods 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 19
- 229910052751 metal Inorganic materials 0.000 abstract description 14
- 239000002184 metal Substances 0.000 abstract description 14
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 4
- 150000004706 metal oxides Chemical class 0.000 abstract description 4
- HEUUBWQOIYCBCI-UHFFFAOYSA-N 2h-benzotriazole;copper Chemical class [Cu].C1=CC=CC2=NNN=C21 HEUUBWQOIYCBCI-UHFFFAOYSA-N 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 description 36
- 239000000463 material Substances 0.000 description 25
- 239000002585 base Substances 0.000 description 22
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 12
- 229960003237 betaine Drugs 0.000 description 12
- 229920001223 polyethylene glycol Polymers 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical class CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 238000005498 polishing Methods 0.000 description 9
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- 230000008569 process Effects 0.000 description 9
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
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- 239000000654 additive Substances 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 8
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- 239000003002 pH adjusting agent Substances 0.000 description 8
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- 239000002202 Polyethylene glycol Substances 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 description 7
- 239000003989 dielectric material Substances 0.000 description 7
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- 238000004519 manufacturing process Methods 0.000 description 7
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
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- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
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- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 5
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 5
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 description 5
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- 125000006577 C1-C6 hydroxyalkyl group Chemical group 0.000 description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 5
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 229960001950 benzethonium chloride Drugs 0.000 description 5
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 description 5
- 229920001400 block copolymer Polymers 0.000 description 5
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- 235000014113 dietary fatty acids Nutrition 0.000 description 5
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- 239000000194 fatty acid Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
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- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical class COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 5
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 4
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- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 1
- JKVUQLWTIZFTMF-UHFFFAOYSA-M potassium;2-oxopropanoate Chemical compound [K+].CC(=O)C([O-])=O JKVUQLWTIZFTMF-UHFFFAOYSA-M 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- ZQZJKHIIQFPZCS-UHFFFAOYSA-N propylurea Chemical compound CCCNC(N)=O ZQZJKHIIQFPZCS-UHFFFAOYSA-N 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- HBROZNQEVUILML-UHFFFAOYSA-N salicylhydroxamic acid Chemical compound ONC(=O)C1=CC=CC=C1O HBROZNQEVUILML-UHFFFAOYSA-N 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229940043230 sarcosine Drugs 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 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
- 235000012239 silicon dioxide Nutrition 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
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 1
- 239000004324 sodium propionate Substances 0.000 description 1
- 235000010334 sodium propionate Nutrition 0.000 description 1
- 229960003212 sodium propionate Drugs 0.000 description 1
- 229940054269 sodium pyruvate Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- UELAIMNOXLAYRW-UHFFFAOYSA-M sodium;1,4-dicyclohexyloxy-1,4-dioxobutane-2-sulfonate Chemical compound [Na+].C1CCCCC1OC(=O)C(S(=O)(=O)[O-])CC(=O)OC1CCCCC1 UELAIMNOXLAYRW-UHFFFAOYSA-M 0.000 description 1
- 229940063675 spermine Drugs 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000011885 synergistic combination Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- FBWNMEQMRUMQSO-UHFFFAOYSA-N tergitol NP-9 Polymers CCCCCCCCCC1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 FBWNMEQMRUMQSO-UHFFFAOYSA-N 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- YNJQKNVVBBIPBA-UHFFFAOYSA-M tetrabutylazanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCC[N+](CCCC)(CCCC)CCCC YNJQKNVVBBIPBA-UHFFFAOYSA-M 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- ZOMVKCHODRHQEV-UHFFFAOYSA-M tetraethylphosphanium;hydroxide Chemical compound [OH-].CC[P+](CC)(CC)CC ZOMVKCHODRHQEV-UHFFFAOYSA-M 0.000 description 1
- CRUVUWATNULHFA-UHFFFAOYSA-M tetramethylphosphanium;hydroxide Chemical compound [OH-].C[P+](C)(C)C CRUVUWATNULHFA-UHFFFAOYSA-M 0.000 description 1
- OORMKVJAUGZYKP-UHFFFAOYSA-M tetrapropylphosphanium;hydroxide Chemical compound [OH-].CCC[P+](CCC)(CCC)CCC OORMKVJAUGZYKP-UHFFFAOYSA-M 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- WBWDWFZTSDZAIG-UHFFFAOYSA-M thonzonium bromide Chemical compound [Br-].N=1C=CC=NC=1N(CC[N+](C)(C)CCCCCCCCCCCCCCCC)CC1=CC=C(OC)C=C1 WBWDWFZTSDZAIG-UHFFFAOYSA-M 0.000 description 1
- 229940051002 thonzonium bromide Drugs 0.000 description 1
- 229940113082 thymine Drugs 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- LDGFRUUNCRYSQK-UHFFFAOYSA-N triazin-4-ylmethanediamine Chemical compound NC(N)C1=CC=NN=N1 LDGFRUUNCRYSQK-UHFFFAOYSA-N 0.000 description 1
- MPSUGQWRVNRJEE-UHFFFAOYSA-N triazol-1-amine Chemical compound NN1C=CN=N1 MPSUGQWRVNRJEE-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- HJHUXWBTVVFLQI-UHFFFAOYSA-N tributyl(methyl)azanium Chemical compound CCCC[N+](C)(CCCC)CCCC HJHUXWBTVVFLQI-UHFFFAOYSA-N 0.000 description 1
- XDUVTZGINNGNAG-UHFFFAOYSA-M tridodecyl(methyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(CCCCCCCCCCCC)CCCCCCCCCCCC XDUVTZGINNGNAG-UHFFFAOYSA-M 0.000 description 1
- GPQCSCQDQNXQSV-UHFFFAOYSA-N tridodecylazanium;chloride Chemical compound Cl.CCCCCCCCCCCCN(CCCCCCCCCCCC)CCCCCCCCCCCC GPQCSCQDQNXQSV-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 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
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
- H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
-
- 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
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
- H01L21/02065—Cleaning during device manufacture during, before or after processing of insulating layers the processing being a planarization of insulating layers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/34—Derivatives of acids of phosphorus
- C11D1/342—Phosphonates; Phosphinates or phosphonites
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0042—Reducing agents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/042—Acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/044—Hydroxides or bases
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
- C11D3/361—Phosphonates, phosphinates or phosphonites
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
- C11D3/362—Phosphates or phosphites
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3218—Alkanolamines or alkanolimines
-
- 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
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
- H01L21/02074—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a planarization of conductive layers
-
- C11D2111/22—
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/36—Organic compounds containing phosphorus
Abstract
本發明提供可用於清潔微電子裝置結構之組合物。殘留物可包含CMP後、蝕刻後、灰化後殘留物、墊及刷碎屑、金屬及金屬氧化物粒子及沉澱之金屬有機錯合物(諸如銅-苯并三唑錯合物)。有利地,如本文中所述之組合物顯示改良之鋁、鈷及銅相容性。
Description
本發明大體上係關於微電子裝置製造之領域。特定言之,其係關於CMP後清潔組合物。
微電子裝置晶圓係用於形成積體電路及包含基板,諸如矽,該基板中區域經圖案化以供沉積具有絕緣、導電或半導電性質之不同材料用。
為獲得正確圖案化,必須將用於在該基板上形成層之過量材料移除。此外,為製造功能及可靠電路,在後續加工之前準備好平坦或平面微電子晶圓表面係重要的。因此,將微電子裝置晶圓之某些表面移除及/或拋光係必要的。
化學機械拋光或平面化(「CMP」)為一種製程,其中將材料自微電子裝置晶圓之表面移除,及將該表面藉由耦接物理製程(諸如研磨)與化學製程(諸如氧化或螯合)經拋光(更特定言之,平面化)。根本地,CMP涉及將漿液(諸如磨料含於含有活性化學品之水性溶液中之組合)施覆至拋光墊,其將微電子裝置晶圓之表面擦拭以達成移除、平面化及拋光製程。物理及化學作用之協同組合達成快速均勻移除。於製造積體電路中,CMP漿液亦應能優先移除包含金屬及其他材料之複合層之膜使得可產生高度平面表面用於後續光蝕刻法或圖案化、蝕刻及薄膜加工。於拋光後獲得跨晶圓表面之良好均勻性之關鍵為使用針對所存在之材料各者具有恰當移除選擇性之CMP漿液。
大多數製程操作,包括晶圓基板表面製備、沉積、電鍍、蝕刻及化學機械拋光,需要清潔操作以確保微電子裝置產品不含原本有害影響產品功能或甚至致使其預期功能成無用之污染物。通常,此等污染物之粒子小於0.3 µm。若不移除,則此等殘留物可造成對(例如)銅線之損壞,或使銅金屬化嚴重糙化,以及造成裝置基板上之CMP後施覆層之差的黏附。
工業中持續需求提供自基板有效且選擇性移除各種殘留物(諸如CMP後殘留物、蝕刻後殘留物及灰化後殘留物)之組合物及方法,特定言之對改良之裝置性能及減少之裝置尺寸及減少之裝置特徵尺寸的需求增加。該等組合物及方法應消除粒子及其他污染物以及不明顯腐蝕或以其他方式損壞組件(諸如鋁、鈷及銅)。
鋁連同諸如銅、鈷、釕、錳、鉬、錸、氮化鈦、氮化鉭、氮化鎢、二氧化矽、氮化矽、碳化矽、碳氮化矽、低k介電質、多晶矽及矽倍半氧化物-或矽氧烷基介電質之材料用作後段製程互連(BEOL)。
總之,本發明係關於用於自微電子裝置清潔殘留物及/或污染物之組合物及方法,該等微電子裝置上具有該等殘留物及污染物。該等殘留物可包含CMP後、蝕刻後、灰化後殘留物、墊及刷碎屑、金屬及金屬氧化物粒子及沉澱之金屬有機錯合物(諸如銅-苯并三唑錯合物)。
有利地,如本文中所述之組合物顯示與某些金屬(諸如鋁、鈷及銅)之改良之相容性。
於一個態樣中,本發明提供組合物,其包含水、蝕刻劑化合物、pH調節劑及選自某些含磷化合物之腐蝕抑制劑。
如本說明書及隨附申請專利範圍中所用,除非上下文另有明確指定,否則單數形式「一(a/an)」及「該」包含複數個提及物。如本說明書及隨附申請專利範圍中所用,除非上下文另有明確指定,否則術語「或」一般以其包含「及/或」之含義採用。
術語「約」一般係指考慮等效於所詳述值(例如,具有相同功能或結果)之數字範圍。於許多實例中,術語「約」可包含圓整至最近有效數字之數字。
使用端點表述之數值範圍包含歸入該範圍內之所有數字(例如,1至5包含1、1.5、2、2.75、3、3.80、4及5)。
本發明大體上係關於可用於自微電子裝置基板移除殘留物及污染物之組合物,該微電子裝置基板上具有此(等)材料。該等組合物特別可用於自含鋁基板移除CMP後、蝕刻後或灰化後殘留物而不明顯損壞其上之主體鋁。
術語「微電子裝置」對應於半導體基板、平面顯示器、相變記憶裝置、太陽能板及用於微電子積體電路或電腦晶片應用製造之其他產品(包括太陽能基板、光伏打及微電機系統(MEMS))。太陽能基板包括(但不限於)矽、非晶型矽、多晶矽、單晶矽、CdTe、硒化銅銦、硫化銅銦及砷化鎵載鎵。太陽能基板可經摻雜或未經摻雜。應瞭解,術語「微電子裝置」不意欲以任何方式限制及包括最終變成微電子裝置或微電子總成之任何基板。
如本文中所用,「殘留物」對應於在微電子裝置之製造,包括(但不限於)電漿蝕刻、灰化、化學機械拋光、濕法蝕刻及其組合期間產生之粒子。
如本文中所用,「污染物」對應於CMP漿液中存在之化學品、拋光漿液之反應副產物、濕法蝕刻組合物中存在之化學品、濕法蝕刻組合物之反應副產物、及為CMP製程、濕法蝕刻、電漿蝕刻或電漿灰化製程之副產物之任何其他材料,諸如墊及刷碎屑、金屬及金屬氧化物粒子及沉澱之金屬有機錯合物(諸如銅-苯并三唑錯合物)。
如本文中所用,「蝕刻後殘留物」對應於於氣相電漿蝕刻製程(例如,BEOL雙鑲嵌加工)或濕法蝕刻製程後殘留之材料。蝕刻後殘留物本質上可係有機、有機金屬、有機矽或無機,例如,含矽材料、碳基有機材料、及蝕刻氣體殘留物(諸如氧氣及氟)。
如本文中所用,「灰化後殘留物」對應於於氧化或還原電漿灰化以移除硬化光阻劑及/或底部抗反射塗層(BARC)材料後殘留之材料。灰化後殘留物本質上可係有機、有機金屬、有機矽或無機。
如本文中所用,「CMP後殘留物」對應於來自拋光漿液之粒子(例如,含二氧化矽之粒子)、存在於漿液中之化學品、拋光漿液之反應副產物、富碳粒子、拋光墊粒子、刷塗減載粒子、設備構建材料粒子、金屬、金屬氧化物、有機殘留物、障壁層殘留物、及為CMP製程之副產物之任何其他材料。如本文中所定義,通常被拋光之「金屬」包括銅、鋁及鈷。
如本文中所用,術語「低k介電材料」對應於於層狀微電子裝置中用作介電材料之任何材料,其中該材料具有小於約3.5之介電常數。於某些實施例中,該等低k介電材料包括低極性材料,諸如含矽有機聚合物、含矽雜化有機/無機材料、有機矽酸鹽玻璃(OSG)、TEOS、氟化矽酸鹽玻璃(FSG)、二氧化矽及碳摻雜之氧化物(CDO)玻璃。應瞭解,該等低k介電材料可具有變化密度及變化孔隙度。
如本文中所用,術語「障壁材料」對應於此項技術中用於密封金屬線(例如,銅互連)以最小化該金屬(例如,銅)擴散至介電材料之任何材料。障壁層材料包括鉭、鈦、釕、鉿、鎢、鈷及上述金屬中之任一者之氮化物、碳化物及矽化物。
如本文中所用,「反應或降解產物」包括(但不限於)由於表面處之催化、氧化、還原、與組成組分之反應或以其他方式聚合形成之產物或副產物;由於變化或轉變形成之產物或副產物,該(等)變化或轉變中物質或材料(例如,分子、化合物等)與其他物質或材料組合,與其他物質或材料互換成分,分解、重排或以其他方式化學及/或物理地改變,包含上述任一者或上述反應、變化及/或轉變之任何組合之中間產物或副產物。
如本文中所用,「錯合劑」包含由熟習此項技術者理解為錯合劑、螯合劑及/或隔離劑之彼等化合物。錯合劑將與待使用本文中所述組合物移除之金屬原子及/或金屬離子化學組合、與之配位或物理固持之。
如本文中所用,「含氟化物化合物」對應於包含離子鍵結至另一原子之氟離子(F-)之鹽或酸化合物。
「實質上避免」於本文中經定義為小於2重量%、小於1重量%、小於0.5重量%或小於0.1重量%。於一個實施例中,「實質上避免」對應於0%,指示該組合物不含特定組分。
如本文中所用,自其上具有殘留物及污染物之微電子裝置清潔該等殘留物及污染物之「適宜性」對應於自微電子裝置至少部分移除該等殘留物/污染物。清潔功效藉由微電子裝置上之物體之減少來評級。例如,可使用原子力顯微鏡進行清潔前及清潔後分析。可將樣品上之粒子登記為像素範圍。可應用直方圖(例如,Sigma Scan Pro)以過濾某個強度(例如,231至235)之像素,及將粒子數目計數。可使用以下計算粒子減少:
清潔功效=
( 清潔前物體數目 - 清潔後物體數目 )x 100
清潔前物體數目
應注意,清潔功效之測定方法僅針對實例提供且不意欲受限於實例。或者,可認為清潔功效為總表面之由微粒物質覆蓋之百分比。例如,可將原子力顯微鏡裝置程式化以進行z-平面掃描以識別高於某個高度臨限值之所關注之地形區域及然後計算總表面之由所關注之該等區域覆蓋之面積。熟習此項技術者將容易瞭解,清潔後由所關注之該等區域覆蓋之面積越小,清潔組合物之效率越高。於某些實施例中,使用本文中所述組合物自微電子裝置移除至少75%、至少90%、至少95%或至少99%之殘留物/污染物。
本文中所述組合物可於廣泛各種特定調配物中實施,如下文中更充分描述。
於某些實施例中,本發明之組合物實質上避免或避免含氟化物來源、磨料材料、氫氧化四甲銨(TMAH)及其組合,之後用於自微電子裝置移除殘留材料。
本發明之組合物包含水、還原劑、蝕刻劑化合物、及選自某些含磷化合物之鋁、銅及/或鈷腐蝕抑制劑,由其組成或基本上由其組成。有利地,該等組合物增加微電子裝置上之暴露之含鋁表面上殘留之污染物及殘留物(例如,苯并三唑、漿液粒子及其他CMP後殘留物)的移除,同時降低暴露之鋁、銅或鈷表面之腐蝕速率。
於第一態樣中,本發明提供組合物,該組合物包含以下:
a)水;
b)蝕刻劑化合物;
c)還原劑;及
d)選自具有下式之化合物之鋁、鈷或銅腐蝕抑制劑
(I);或
(II);
其中各x獨立地為0或1,R為芳基或伸芳基或單價或二價C
1-C
20烴基,且M選自氫、C
1-C
6烷基、銨或鹼金屬陽離子,
且其中該組合物之pH大於約8。
如本文中所用,術語「C
1-C
20烴基」係指具有1至20個碳或聚合物碳主鏈之烷基、伸烷基、烯基、亞烷基、芳基或伸芳基,其視情況經選自C
1-C
6烷基、C
1-C
6烷氧基、C
2-C
6烯基、C
3-C
8環烷基、C
1-C
6羧基、C
1-C
6烷氧羰基、C
1-C
6烷醯氧基、羥基、鹵基、氰基、芳基及雜芳基之一或多個基團取代。特定實例包括直鏈、分支鏈或環狀烷基或伸烷基以及苯基或伸苯基。另外,該(等)式(I)及(II)化合物可呈兩種或更多種式(I)及/或(II)化合物之混合物存在。
於一個實施例中,式(I)及(II)化合物選自:
苯基膦酸;
植酸;
(12-膦醯基十二烷基)膦酸;
正十二烷基膦酸;
6-膦醯基己酸;
1,4-伸苯基雙(膦酸);
聚(乙烯基膦酸);
辛基膦酸;
亞乙烯基二膦酸四異丙酯;
二-第三丁基磷酸鉀;
乙基膦酸;
亞甲基二膦酸;
1,10-癸基二膦酸;
辛基膦酸;
己基膦酸;
十八基膦酸;
正十二烷基膦酸;及
磷酸單-N-十二烷酯。
於該等組合物中,據信,蝕刻劑化合物(或「蝕刻劑」)功能為錯合劑。於一些實施例中,該組合物可包含包含複數種蝕刻劑之蝕刻劑組分。說明性蝕刻劑可包括具有通式NR
1R
2R
3之物質,其中R
1、R
2及R
3可彼此相同或不同及選自氫、直鏈或分支鏈C
1-C
6烷基(例如,甲基、乙基、丙基、丁基、戊基及己基)、直鏈或分支鏈C
1-C
6羥烷基(例如,羥甲基、羥乙基、羥丙基、羥丁基、羥戊基及羥己基)、及如上所定義之直鏈或分支鏈C
1-C
6羥烷基之C
1-C
6烷基醚。於某些實施例中,R
1、R
2及R
3中之至少一者為直鏈或分支鏈C
1-C
6羥烷基。實例包括(不限於)烷醇胺,諸如胺基乙基乙醇胺、N-甲胺基乙醇、胺基乙氧基乙醇、二甲胺基乙氧基乙醇、二乙醇胺、N-甲基二乙醇胺、單乙醇胺(MEA)、三乙醇胺(TEA)、異丙醇胺、二異丙醇胺、胺基丙基二乙醇胺、N,N-二甲基丙醇胺、N-甲基丙醇胺、1-胺基-2-丙醇、2-胺基-1-丁醇、3-胺基-4-辛醇、異丁醇胺、三乙二胺、二甘醇胺、其他C
1-C
8烷醇胺、及環氧乙烷或環氧丙烷基聚合物吉夫胺(Jeffamine)及其組合。當胺包含烷基醚組分時,可認為該胺為烷氧基胺,例如,1-甲氧基-2-胺基乙烷。
或者,或除了NR
1R
2R
3胺以外,蝕刻劑化合物劑可為多官能胺,包括(但不限於) 4-(2-羥乙基)嗎啉(HEM)、1,2-環己烷二胺-N,N,N',N'-四乙酸(CDTA)、乙二胺四乙酸(EDTA)、間二甲苯二胺(MXDA)、亞胺基二乙酸(IDA)、2-(羥乙基)亞胺基二乙酸(HIDA)、氮基三乙酸、硫脲、1,1,3,3-四甲基脲、脲、脲衍生物、尿酸、丙胺酸、精胺酸、天冬醯胺、天冬胺酸、半胱胺酸、麩胺酸、麩胺醯胺、組胺酸、異白胺酸、白胺酸、離胺酸、甲硫胺酸、苯丙胺酸、脯胺酸、絲胺酸、蘇胺酸、色胺酸、酪胺酸、纈胺酸及其組合。
或者,或除了上述蝕刻劑以外,另外蝕刻劑化合物可包括1,5,9-三氮雜環十二烷-N,N',N''-參(亞甲基膦酸) (DOTRP)、1,4,7,10-四氮雜環十二烷-N,N',N'',N'''-肆(亞甲基膦酸) (DOTP)、氮基參(亞甲基)三膦酸、二伸乙基三胺五(亞甲基膦酸(DETAP)、胺基三(亞甲基膦酸)、雙(六亞甲基)三胺五亞甲基膦酸、1,4,7-三氮雜環壬烷-N,N',N''-參(亞甲基膦酸) (NOTP)、羥乙基二膦酸酯、氮基參(亞甲基)膦酸、2-膦醯基-丁烷-1,2,3,4-四甲酸、羧乙基膦酸、胺基乙基膦酸、草甘膦、乙二胺肆(亞甲基膦酸)苯基膦酸、其鹽及其衍生物及/或羧酸(例如,草酸、琥珀酸、馬來酸、蘋果酸、丙二酸、肥酸、酞酸、檸檬酸、檸檬酸鈉、檸檬酸鉀、檸檬酸銨、均丙三甲酸、二羥甲基丙酸、三羥甲基丙酸、酒石酸、乙醯基丙酮、麩胺酸、肥酸、胺基參(亞甲基膦酸);硫脲、1,1,3,3-四甲基脲、脲、脲衍生物、尿酸、丙胺酸、精胺酸、牛磺酸及其組合;葡萄糖醛酸、2-羧基吡啶)及/或磺酸,諸如4,5-二羥基-1,3-苯二磺酸二鈉鹽。於一個實施例中,該蝕刻劑可選自單乙醇胺、三乙醇胺、硫酸、檸檬酸及其組合。
於一個實施例中,組合物中之蝕刻劑化合物之量係於基於清潔組合物之總重量計約0.005重量%至約20重量%之範圍內。於另一實施例中,該蝕刻劑以基於清潔組合物之總重量計約0.01重量%至約10重量%之量存在,及於另一實施例中,以約0.01重量%至約25重量%之量存在。
該等組合物包含一或多種還原劑。說明性還原劑包括(但不限於)抗壞血酸、L(+)-抗壞血酸、異抗壞血酸、抗壞血酸衍生物、磷酸氫酸(H
3PO
2)、羥胺(諸如DEHA (二乙基羥胺))、還原糖(例如,半乳糖)、木糖、山梨醇、亞硫酸、亞硫酸銨、亞硫酸鉀、亞硫酸鈉、多巴胺HCl、亞磷酸、次亞膦酸、磷酸氫酸、偏亞硫酸氫鉀、偏亞硫酸氫鈉、偏亞硫酸氫銨、丙酮酸鉀、丙酮酸鈉、丙酮酸銨、甲酸、甲酸鈉、甲酸鉀、甲酸銨、多巴胺、二氧化硫溶液及其任何組合。例如,該還原劑可包含至少一種亞硫酸根離子及至少一種其他列舉之還原劑,例如,亞硫酸、亞硫酸鉀、亞硫酸銨、次亞膦酸、雷瑣酚(即,1,1-二羥基苯、1,3-二羥基苯及1,4-二羥基苯)及其任何組合。當存在亞硫酸銨時,該亞硫酸銨可原位產生,其中特定組分之組合導致亞硫酸銨之形成以幫助移除殘留物,例如,磨料粒子,諸如二氧化矽粒子及該(等)其他CMP後殘留物。
於另一實施例中,當存在時,該還原劑選自N-胺基嗎啉、N-胺基哌嗪、氫醌、兒茶酚、四氫富瓦烯、N,N-二甲基苯胺苄胺、羥胺及其他硫基還原劑。
於另一實施例中,該還原劑選自亞磷氫酸、亞磷酸、亞硫酸、偏亞硫酸氫鈉、偏亞硫酸氫銨、偏亞硫酸氫鉀、抗壞血酸、L(+)-抗壞血酸、異抗壞血酸、羥胺、羥胺鹽、二甲基羥胺、二乙基羥胺、還原糖(選自半乳糖、木糖、葡萄糖、果糖、乳糖及麥芽糖)、氫醌、兒茶酚、四氫富瓦烯、N,N-二甲基苯胺苄胺及其組合。
於各種實施例中,該組合物中之還原劑之量係於基於該組合物之總重量計約0.0001重量%至約20重量%之範圍內。於另一實施例中,該還原劑以基於該組合物之總重量計約0.0001重量%至約10重量%之量存在,及於又其他實施例中,以0.01重量%至6重量%或0.005重量%至5重量%之量存在。於一個實施例中,該還原劑為抗壞血酸。於各種實施例中,該清潔組合物不含有還原劑。
如上所指定,該組合物之pH大於約8。於另一實施例中,該pH小於約14。於另一實施例中,該pH為約8.5至約12。於另一實施例中,組分d)為鋁腐蝕抑制劑及該pH為約8至11。於另一實施例中,組分d)為鈷腐蝕抑制劑及該pH為約8至約13.5。為達到所需目標pH,該組合物可進一步包含一或多種pH調節劑。於一個實施例中,該pH調節劑為鹼及用於升高清潔組合物之pH。說明性鹼包括(但不限於)鹼金屬氫氧化物(例如,LiOH、KOH、RbOH、CsOH)、鹼土金屬氫氧化物(例如,Be(OH)
2、Mg(OH)
2、Ca(OH)
2、Sr(OH)
2、Ba(OH)
2)、氫氧化銨(即,氨)及具有式NR
1R
2R
3R
4OH之氫氧化四烷基銨化合物,其中R
1、R
2、R
3及R
4可彼此相同或不同及選自由以下組成之群:氫、直鏈或分支鏈C
1-C
6烷基(例如,甲基、乙基、丙基、丁基、戊基及己基)、C
1-C
6羥烷基(例如,羥甲基、羥乙基、羥丙基、羥丁基、羥戊基及羥己基)及經取代或未經取代之C
6-C
10芳基(例如,苄基)。可使用市售之氫氧化四烷基銨包括氫氧化四甲銨(TMAH)、氫氧化四乙銨(TEAH)、氫氧化四丙銨(TPAH)、氫氧化四丁銨(TBAH)、氫氧化三丁基甲基銨(TBMAH)、氫氧化苄基三甲基銨(BTMAH)、氫氧化膽鹼、氫氧化乙基三甲基銨、氫氧化參(2-羥乙基)甲基銨、氫氧化二乙基二甲基銨及其組合。
或者或此外,該pH調節劑可為具有式(PR
1R
2R
3R
4)OH之四級鹼,其中R
1、R
2、R
3及R
4可彼此相同或不同及選自氫、直鏈C
1-C
6烷基(例如,甲基、乙基、丙基、丁基、戊基及己基)、分支鏈C
1-C
6烷基、C
1-C
6羥烷基(例如,羥甲基、羥乙基、羥丙基、羥丁基、羥戊基及羥己基)、經取代之C
6-C
10芳基、未經取代之C
6-C
10芳基(例如,苄基)及其任何組合,諸如氫氧化四丁基鏻(TBPH)、氫氧化四甲基鏻、氫氧化四乙基鏻、氫氧化四丙基鏻、氫氧化苄基三苯基鏻、氫氧化甲基三苯基鏻、氫氧化乙基三苯基鏻、氫氧化N-丙基三苯基鏻。
於一個實施例中,該pH調節劑選自TMAH、TEAH、氫氧化膽鹼、氫氧化銨及氫氧化鉀。
添加之pH調整化合物之量係取決於所需pH,如本文中所揭示及如由熟習此項技術者所瞭解。例如,該pH調整劑可以基於清潔組合物之總重量計約0.1重量%至約10重量%之量存在,或以約1重量%至約5重量%之量存在。
於某些實施例中,該組合物可進一步包含選自溶劑、水溶性聚合物及/或表面活性劑之某些清潔添加劑組分。
說明性清潔添加劑包括(但不限於)溶劑,諸如2-吡咯啶酮、1-(2-羥乙基)-2-吡咯啶酮(HEP)、甲醇、乙醇、異丙醇、丁醇、及高碳數醇(諸如C
2-C
4二醇及C
2-C
4三醇)、四氫呋喃醇(THFA)、鹵化醇(諸如3-氯-1,2-丙二醇、3-氯-1-丙硫醇、1-氯-2-丙醇、2-氯-1-丙醇、3-氯-1-丙醇、3-溴-1,2-丙二醇、1-溴-2-丙醇、3-溴-1-丙醇、3-碘-1-丙醇、4-氯-1-丁醇、2-氯乙醇)、二氯甲烷、氯仿、甘油、1,4-丁二醇、四亞甲基碸(環丁碸)、二甲基碸、乙二醇、丙二醇、二丙二醇、四甘醇二甲醚、二甘醇二甲醚、甲基異丁基酮、甲基乙基酮、丙酮、異丙醇、辛醇、乙醇、丁醇、甲醇、異佛爾酮、二乙二醇單甲醚、三乙二醇單甲醚、二乙二醇單乙醚、三乙二醇單乙醚、乙二醇單丙醚、乙二醇單丁醚、二乙二醇單丁醚(DEGBE)、三乙二醇單丁醚(TEGBE)、乙二醇單己醚(EGHE)、二乙二醇單己醚(DEGHE)、乙二醇苯醚、二乙二醇苯醚、六乙二醇單苯醚、丙二醇甲醚、二丙二醇甲醚(DPGME)、三丙二醇甲醚(TPGME)、二異丙醇二甲醚、二丙二醇乙醚、丙二醇正丙醚、二丙二醇正丙醚(DPGPE)、三丙二醇正丙醚、丙二醇正丁醚(諸如DOWANOL PnB)、二丙二醇正丁醚、三丙二醇正丁醚、二丙二醇苯醚、丙二醇苯醚(PPh,諸如DOWANOL™ PPh)、4-甲基-2-戊酮、2,4-二甲基-3-戊酮、環己酮、5-甲基-3-庚酮、3-戊酮、5-羥基-2-戊酮、2,5-己二酮、4-羥基-4-甲基-2-戊酮、丙酮、丁酮、2-甲基-2-丁酮、3,3-二甲基-2-丁酮、4-羥基-2-丁酮、環戊酮、2-戊酮、3-戊酮、1-苯乙酮、乙醯苯、苯甲酮、2-己酮、3-己酮、2-庚酮、3-庚酮、4-庚酮、2,6-二甲基-4-庚酮、2-辛酮、3-辛酮、4-辛酮、二環己酮、2,6-二甲基環己酮、2-乙醯基環己酮、2,4-戊二酮、甲酮、二甲亞碸(DMSO)、二甲基甲醯胺(DMF)、N-甲基吡咯啶酮(NMP)、伸丙基脲、N, N’-二甲基伸丙基脲、環己基吡咯啶酮、N-辛基吡咯啶酮、N-苯基吡咯啶酮、碳酸乙二酯、碳酸丙二酯、昔蘭尼(cyrene)、二甲基伸乙脲、苯丙酮、乳酸乙酯、乙酸乙酯、苯甲酸乙酯、乙腈、丙酮、乙二醇、丙二醇(PG)、1,3-丙二醇、二噁烷、丁醯內酯、碳酸丁二酯、碳酸乙二酯、碳酸丙二酯、二丙二醇、二乙二醇單甲醚、三乙二醇單甲醚、二乙二醇單乙醚、三乙二醇單乙醚、乙二醇單丙醚、乙二醇單丁醚、二乙二醇單丁醚(即,丁基卡必醇)、三乙二醇單丁醚、乙二醇單己醚、二乙二醇單己醚、乙二醇苯醚、丙二醇甲醚、二丙二醇甲醚(DPGME)、三丙二醇甲醚(TPGME)、二丙二醇二甲醚、二丙二醇乙醚、丙二醇正丙醚、二丙二醇正丙醚(DPGPE)、三丙二醇正丙醚、丙二醇正丁醚、二丙二醇正丁醚、三丙二醇正丁醚、丙二醇苯醚、乙二醇單苯醚、二乙二醇單苯醚、六乙二醇單苯醚、二丙二醇甲醚乙酸酯、四乙二醇二甲醚(TEGDE)、二元酯、碳酸甘油酯、N-甲醯基嗎啉、磷酸三乙酯、及其組合。
或者,或此外,該清潔添加劑可包括水溶性聚合物,包括(例如)丙烯酸或甲基丙烯酸均聚物及與(例如)丙烯醯胺基甲基丙磺酸及馬來酸及其鹽之共聚物;馬來酸/乙烯基醚共聚物;聚(乙烯基吡咯啶酮)/乙酸乙烯酯;均聚物,諸如磷酸化之聚乙二醇低聚物、聚(丙烯酸) (PAA)、聚(丙烯醯胺)、聚(乙酸乙烯酯)、聚(乙二醇) (PEG)、聚(丙二醇) (PPG)、聚(苯乙烯磺酸)、聚(乙烯基磺酸)、聚(乙烯基膦酸)、聚(乙烯基膦酸)、聚(乙烯亞胺)、聚(丙烯亞胺)、聚烯丙胺、聚環氧乙烷(PEO)、聚乙烯基吡咯啶酮(PVP)、聚(乙烯醇)、親水性水溶性或可分散聚胺基甲酸酯、聚(丙烯酸乙二醇酯)、聚(甲基丙烯酸乙二醇酯)、PPG-PEG-PPG嵌段共聚物、PEG-PPG-PEG嵌段共聚物及其組合。
或者,或此外,當存在時,該清潔添加劑可為表面活性劑,包括(但不限於)陰離子、非離子、陽離子及/或兩性離子表面活性劑。
此等表面活性劑之實例包括藻酸及其鹽;羥基或羧烷基纖維素;硫酸葡聚糖及其鹽;聚(半乳糖醛酸)及其鹽;(甲基)丙烯酸及其鹽、馬來酸、馬來酸酐、苯乙烯磺酸及其鹽、乙烯基磺酸及其鹽、烯丙基磺酸及其鹽、丙烯醯胺基丙基磺酸及其鹽之均聚物;(甲基)丙烯酸及其鹽、馬來酸、馬來酸酐、苯乙烯磺酸及其鹽、乙烯基磺酸及其鹽、烯丙基磺酸及其鹽、丙烯醯胺基丙基磺酸及其鹽之共聚物;殼聚糖;陽離子澱粉;聚離胺酸及其鹽;氯化二烯丙基二甲基銨(DADMAC)、溴化二烯丙基二甲基銨、二烯丙基二甲基硫酸銨、二烯丙基二甲基磷酸銨、氯化二甲基烯丙基二甲基銨、氯化二乙基烯丙基二甲基銨、氯化二烯丙基二(β-羥乙基)銨、氯化二烯丙基二(β-乙氧基乙基)銨、(甲基)丙烯酸二甲胺基乙酯酸加成鹽及季鹽、(甲基)丙烯酸二乙胺基乙酯酸加成鹽及季鹽、(甲基)丙烯酸7-胺基-3,7-二甲基辛酯酸加成鹽及季鹽、N,N'-二甲胺基丙基丙烯醯胺酸加成鹽及季鹽、烯丙胺、二烯丙胺、乙烯胺、乙烯基吡啶之均聚物;及氯化二烯丙基二甲基銨(DADMAC)、溴化二烯丙基二甲基銨、二烯丙基二甲基硫酸銨、二烯丙基二甲基磷酸銨、氯化二甲基烯丙基二甲基銨、氯化二乙基烯丙基二甲基銨、氯化二烯丙基二(β-羥乙基)銨、氯化二烯丙基二(β-乙氧基乙基)銨、(甲基)丙烯酸二甲胺基乙酯酸加成鹽及季鹽、(甲基)丙烯酸二乙胺基乙酯酸加成鹽及季鹽之共聚物;椰油基二甲基羧甲基甜菜鹼;月桂基二甲基羧甲基甜菜鹼;月桂基二甲基-α-羧乙基甜菜鹼;鯨蠟基二甲基羧甲基甜菜鹼;月桂基-雙-(2-羥乙基)羧甲基甜菜鹼;硬脂醯基-雙-(2-羥丙基)羧甲基甜菜鹼;油烯基二甲基-γ-羧丙基甜菜鹼;月桂基-雙-(2-羥丙基)α-羧乙基甜菜鹼;椰油基二甲基磺丙基甜菜鹼;硬脂醯基二甲基磺丙基甜菜鹼;月桂基-雙-(2-羥乙基)磺丙基甜菜鹼;十二烷基硫酸鈉(SDS);Surfynol 104,磺基琥珀酸二辛酯鈉鹽;月桂基醚硫酸鈉;聚乙二醇分枝之壬基苯基醚硫酸銨鹽;2-十二烷基-3-(2-磺酸根苯氧基)二鈉;PEG25-PABA;聚乙二醇單C
10-16-烷基醚硫酸鈉鹽;(2-N-丁氧乙氧基)乙酸;六癸基苯磺酸;氫氧化鯨蠟基三甲基銨;氫氧化十二烷基三甲基銨;氯化十二烷基三甲基銨;氯化鯨蠟基三甲基銨;氯化N-烷基-N-苄基-N,N-二甲基銨;十二烷胺;聚氧乙烯月桂基醚;十二烯基琥珀酸單二乙醇醯胺;乙二胺肆(乙氧基化物-嵌段-丙氧基化物);PolyFox PF-159 (OMNOVA溶液),聚乙二醇) (「PEG」)、聚(丙二醇) (「PPG」)、環氧乙烷/環氧丙烷嵌段共聚物(諸如普朗尼克(Pluronic) F-127 (BASF))、聚山梨醇酯聚氧乙烯(20)脫水山梨糖醇單油酸酯(Tween 80)、聚氧乙烯(20)脫水山梨糖醇單硬脂酸酯(Tween 60)、聚氧乙烯(20)脫水山梨糖醇單棕櫚酸酯(Tween 40)、聚氧乙烯(20)脫水山梨糖醇單月桂酸酯(Tween 20)、聚氧丙烯/聚氧乙烯嵌段共聚物(例如,普朗尼克L31、普朗尼克31R1、普朗尼克25R2及普朗尼克25R4)、癸基膦酸、十二烷基膦酸(DDPA)、十四基膦酸、十六基膦酸、雙(2-乙基己基)膦酸酯、十八基膦酸、全氟庚酸、全氟癸酸、三氟甲磺酸、膦醯基乙酸、十二烷基苯磺酸(DDBSA)、其他R
1苯磺酸或其鹽(其中R
1為直鏈或分支鏈C
8至C
18烷基)、膦酸氫二十八酯、膦酸二氫十八酯、十二烷胺、十二烯基琥珀酸單二乙醇醯胺、月桂酸、棕櫚酸、油酸、檜酸、12-羥基硬脂酸、十八基膦酸(ODPA)、磷酸十二烷酯。
示例性非離子表面活性劑包括(但不限於)乙氧基化疏水性醇,諸如C
8至C
20烷基醚,諸如聚氧乙烯月桂基醚、單二乙醇醯胺、乙二胺肆(乙氧基化物-嵌段-丙氧基化物)四醇、聚乙二醇、聚丙二醇、聚乙二醇或聚丙二醇醚、基於環氧乙烷及環氧丙烷之嵌段共聚物、聚氧丙烯蔗糖醚、第三辛基苯氧基聚乙氧基乙醇、10-乙氧基-9,9-二甲基癸-1-胺、分支鏈聚氧乙烯(9)壬基苯基醚、分支鏈聚氧乙烯(40)壬基苯基醚、二壬基苯基聚氧乙烯、壬基苯酚烷氧基化物、聚氧乙烯山梨醇六油酸酯、聚氧乙烯山梨醇四油酸酯、聚乙二醇脫水山梨糖醇單油酸酯、脫水山梨糖醇單油酸酯、醇烷氧基化物、烷基-聚葡萄糖苷、全氟丁酸乙酯、1,1,3,3,5,5-六甲基-1,5-雙[2-(5-降冰片烯-2-基)乙基]三矽氧烷、單體十八基矽烷衍生物、經矽氧烷改性之聚矽氮烷、聚矽氧-聚醚共聚物、及乙氧基化氟表面活性劑。
考慮之陽離子表面活性劑包括(但不限於)溴化鯨蠟基三甲基銨(CTAB)、十七烷氟辛磺酸、四乙基銨、氯化硬脂醯基三甲基銨、4-(4-二乙胺基苯基偶氮基)-1-(4-硝基苄基)溴化吡啶鎓、鯨蠟基氯化吡啶鎓單水合物、苯紮氯銨、苄索氯銨氯化苄基二甲基十二烷基銨、氯化苄基二甲基十六烷基銨、十六溴化烷基三甲基銨、氯化二甲基二十八烷基銨、氯化十二烷基三甲基銨、十六烷基三甲基對甲苯磺酸銨、溴化二十二烷基二甲基銨、氯化二(氫化牛脂)二甲基銨、溴化四庚銨、溴化肆(癸基)銨、及奧芬溴銨、胍鹽酸鹽(C(NH
2)
3Cl)或三氟甲磺酸鹽,諸如四丁基三氟甲磺酸銨、氯化二甲基二十八基銨、溴化二甲基二十六基銨、氯化二(氫化牛脂)二甲基銨、及聚氧乙烯(16)牛脂乙基硫酸乙基鎓。
考慮之陰離子表面活性劑包括(但不限於)聚(丙烯酸鈉鹽)、聚丙烯酸銨、聚氧乙烯月桂基醚鈉、二己基磺基琥珀酸鈉、十二烷基硫酸鈉、二辛基磺基琥珀酸鹽、2-磺基琥珀酸鹽、2,3-二巰基-1-丙磺酸鹽、二環己基磺基琥珀酸鈉鹽、7-乙基-2-甲基-4-十一基硫酸鈉、磷酸鹽氟表面活性劑、氟表面活性劑及聚丙烯酸酯。
兩性離子表面活性劑包括(但不限於)炔二醇或經改性之炔二醇、環氧乙烷烷基胺、N,N-二甲基十二烷胺N-氧化物、椰油胺丙酸鈉、3-(N,N-二甲基肉豆蔻基胺基)丙磺酸酯及(3-(4-庚基)苯基-3-羥丙基)二甲胺基丙磺酸酯、癸基膦酸、十二烷基膦酸(DDPA)、十四烷基膦酸、十六烷基膦酸、雙(2-乙基己基)膦酸酯、十八烷基膦酸、全氟庚酸、全氟癸酸、三氟甲磺酸、及膦醯基乙酸。
於另一實施例中,清潔添加劑選自乙二醇單丁醚、二乙二醇單丁醚、丙二醇單丁醚、二丙二醇單丁醚、乙二醇單己醚、二乙二醇單己醚、三乙二醇單丁醚、乙二醇單苯醚、二乙二醇單苯醚、丙二醇單苯醚、二甲亞碸、環丁碸、聚(苯乙烯磺酸)或其鹽、聚(乙烯基吡咯啶酮)、聚(乙烯醇)、聚(丙烯酸)及其鹽、聚丙烯酸共聚物及其鹽、聚(乙二醇)、聚乙二醇-共-聚丙二醇、羥乙基纖維素、聚(2-丙烯醯胺基-2-甲基-1-丙磺酸)及其共聚物、聚氯化二烯丙基二甲基銨、聚(二甲胺基乙基甲基丙烯酸酯)及其共聚物、聚(三甲胺基乙基甲基丙烯酸酯)鹽及其共聚物、乙氧基化醇或苯酚、乙氧基化脂肪酸糖、十二烷基苯磺酸、月桂基磺酸、辛酸、壬酸、癸酸、十一酸、十二酸、氯化苄基二甲基十二烷基銨、氫氧化苄基二甲基十二烷基銨、及氯化三甲基十二烷基銨。
當存在時,於一個實施例中,該組合物中之清潔化合物之量係於基於該組合物之總重量計約0.001重量%至約20重量%之範圍內。於另一實施例中,該清潔添加劑係以基於該組合物之總重量計約0.1重量%至約10重量%之量存在,及於另一實施例中,以約0.5重量%至約5重量%之量存在。
於另一實施例中,該組合物進一步包含不同於本文中組分d)之另外腐蝕抑制劑。此(等)視情況可選的另外腐蝕抑制劑選自5-胺基四唑、5-苯基-苯并三唑、1H-四唑-5-乙酸、1-苯基-2-四唑啉-5-硫酮、苯并咪唑、甲基四唑、鉍試劑(Bismuthiol) I、胞嘧啶、鳥嘌呤、胸腺嘧啶、吡唑、亞胺基二乙酸(IDA)、丙硫醇、苯甲羥肟酸、檸檬酸、抗壞血酸、5-胺基-1,3,4-噻二唑-2-硫醇(ATDT)、苯并三唑(BTA)、1,2,4-三唑(TAZ)、甲苯基三唑、5-甲基-苯并三唑(mBTA)、5-苯基-苯并三唑、5-硝基-苯并三唑、苯并三唑甲酸、3-胺基-5-巰基-1,2,4-三唑、1-胺基-1,2,4-三唑、羥基苯并三唑、2-(5-胺基-戊基)-苯并三唑、1-胺基-1,2,3-三唑、1-胺基-5-甲基-1,2,3-三唑、3-胺基-1,2,4-三唑(3-ATA)、3-巰基-1,2,4-三唑、3-異丙基-1,2,4-三唑、5-苯基硫醇-苯并三唑、鹵基-苯并三唑(鹵基=F、Cl、Br或I)、萘并三唑、2-巰基苯并咪唑(MBI)、2-巰基苯并噻唑、4-甲基-2-苯基咪唑、2-巰基噻唑啉、5-胺基-1,2,4-三唑(5-ATA)、十二烷基硫酸鈉(SDS)、ATA-SDS、3-胺基-5-巰基-1,2,4-三唑、戊四唑、5-戊基-1H-四唑、5-苄基-1H-四唑、Ablumine O、2-苄基吡啶、琥珀醯亞胺、2,4-二胺基-6-甲基-1,3,5-三嗪、噻唑、三嗪、甲基四唑、1,3-二甲基-2-咪唑啶酮、1,5-環戊烷四唑、1-苯基-5-巰基四唑、二胺基甲基三嗪、咪唑啉硫酮、4-甲基-4H-1,2,4-三唑-3-硫醇、4-胺基-4H-1,2,4-三唑、3-胺基-5-甲硫基-1H-1,2,4-三唑、苯并噻唑、咪唑、吲唑、腺嘌呤、琥珀醯亞胺、腺苷、咔唑、糖精、尿酸、苯偶姻肟、陽離子季鹽(例如,苯紮氯銨、氯化苄基二甲基十二烷基銨、溴化肉豆蔻基三甲基銨、十二溴化烷基三甲基銨、十六烷基氯化吡啶鎓、Aliquat 336 (Cognis)、氯化苄基二甲基苯基銨、Crodaquat TES (Croda. Inc.)、Rewoquat CPEM (Witco)、十六烷基三甲基對甲苯磺酸銨、氫氧化十六烷基三甲基銨、二氯化1-甲基-1'-十四烷基-4,4'-聯吡啶鎓、溴化烷基三甲基銨、鹽酸胺丙啉(amprolium)、苄索氫氧化銨、苄索氯銨、氯化苄基二甲基十六烷基銨、氯化苄基二甲基十四烷基銨、溴化苄基十二烷基二甲基銨、氯化苄基十二烷基二甲基銨、鯨蠟基氯化吡啶鎓、膽鹼對甲苯磺酸鹽、溴化二甲基二十八烷基銨、溴化十二烷基乙基二甲基銨、氯化十二烷基三甲基銨、氯化癸基三甲基銨(DTAC)、溴化乙基十六烷基二甲基銨、格氏(Girard's)試劑、十六烷基(2-羥乙基)二甲基磷酸二氫銨、十六烷基溴化吡啶鎓、溴化十六烷基三甲基銨、氯化十六烷基三甲基銨、甲基苄索氯銨、Hyamine® 1622、Luviquat™、N,N',N'-聚氧乙烯(10)-N-牛脂-1,3-二胺基丙烷液體、奧芬溴銨(oxyphenonium bromide)、溴化四庚銨、溴化肆(癸基)銨、通佐溴銨(thonzonium bromide)、氯化三十二烷基銨、溴化三甲基十八烷基銨、1-甲基-3-n-辛基咪唑鎓四氟硼酸鹽、1-癸基-3-甲基咪唑鎓四氟硼酸鹽、1-癸基-3-甲基氯化咪唑鎓、溴化三十二烷基甲基銨、氯化二甲基二硬脂醯基銨、溴化鯨蠟基三甲基銨、溴化肉豆蔻基三甲基銨、及氯化六羥季銨及其組合、十六烷基三甲基對甲苯磺酸銨、氫氧化十六烷基三甲基銨、二氯化1-甲基-1'-十四烷基-4,4'-聯吡啶鎓、溴化烷基三甲基銨、鹽酸胺丙啉、苄索氫氧化銨、苄索氯銨、氯化苄基二甲基十六烷基銨、氯化苄基二甲基十四烷基銨、溴化苄基十二烷基二甲基銨、氯化苄基十二烷基二甲基銨、鯨蠟基氯化吡啶鎓、膽鹼對甲苯磺酸鹽、溴化二甲基二十八烷基銨、溴化十二烷基乙基二甲基銨、氯化十二烷基三甲基銨、溴化乙基十六烷基二甲基銨、格氏試劑、十六烷基(2-羥乙基)二甲基磷酸二氫銨、十六烷基溴化吡啶鎓、溴化十六烷基三甲基銨、氯化十六烷基三甲基銨、甲基苄索氯銨、Hyamine® 1622、Luviquat™、N,N',N'-聚氧乙烯(10)-N-牛脂-1,3-二胺基丙烷液體、奧芬溴銨、溴化四庚銨、溴化肆(癸基)銨、通佐溴銨、氯化三十二烷基銨、溴化三甲基十八烷基銨、四氟硼酸1-甲基-3-n-辛基咪唑鎓、四氟硼酸1-癸基-3-甲基咪唑鎓、1-癸基-3-甲基氯化咪唑鎓、溴化三十二烷基甲基銨、氯化二甲基二硬脂醯基銨、溴化鯨蠟基三甲基銨、溴化肉豆蔻基三甲基銨、及氯化六羥季銨)、陰離子表面活性劑(例如,十二烷基苯磺酸、十二烷基苯磺酸鈉、十二烷基膦酸(DDPA))、乙酸、丙酮肟、丙烯酸、肥酸、丙胺酸、精胺酸、天冬醯胺、天冬胺酸、甜菜鹼、二甲基乙二肟、甲酸、富馬酸、葡糖酸、麩胺酸、麩胺醯胺、戊二酸、甘油酸、甘油、乙醇酸、乙醛酸、組胺酸、亞胺基二乙酸、異酞酸、衣康酸、乳酸、白胺酸、離胺酸、馬來酸、馬來酸酐、蘋果酸、丙二酸、扁桃酸、2,4-戊二酮、苯基乙酸、苯丙胺酸、酞酸、脯胺酸、丙酸、焦兒茶酚、均苯四酸、奎寧酸、絲胺酸、山梨醇、琥珀酸、酒石酸、對苯二甲酸、偏苯三酸、均苯三酸、酪胺酸、纈胺酸、木糖醇、草酸、吡啶甲酸、1,3-環戊二酮、兒茶酚、焦棓酸、雷瑣酚、氫醌、三聚氰酸、巴比妥酸、1,2-二甲基巴比妥酸、丙酮酸、丙硫醇、苯甲羥肟酸、2,5-二羧基吡啶、4-(2-羥乙基)嗎啉(HEM)、N-胺基乙基哌嗪(N-AEP)、乙二胺四乙酸(EDTA)、1,2-環己二胺-N,N,N',N'-四乙酸(CDTA)、N-(羥乙基)-乙二胺三乙酸(HEdTA)、亞胺基二乙酸(IDA)、2-(羥乙基)亞胺基二乙酸(HIDA)、氮基三乙酸、硫脲、1,1,3,3-四甲基脲、脲、脲衍生物、甘胺酸、半胱胺酸、麩胺酸、異白胺酸、甲硫胺酸、哌啶、N-(2-胺基乙基)哌啶、吡咯啶、蘇胺酸、色胺酸、水楊酸、對甲苯磺酸、水楊基異羥肟、5-磺基水楊酸、三唑、胺基三唑、二甲基炔丙醇、月桂醯基肌胺酸、硬脂醯基肌胺酸、糖精、硼酸、3-羥基-2-萘甲酸、丙二酸、亞胺基二乙酸、五硼酸銨、脲、甲基三乙氧基矽烷、4-甲基吡唑、吡唑、2-胺基-噻唑、腺苷、2-胺基-1,3,4-噻二唑、5-胺基-1H-四唑、腺嘌呤、喋呤、嘧啶、吡嗪、胞嘧啶、嗒嗪、1H-吡唑-3-甲酸、1H-吡唑-4-甲酸、3-胺基-5-羥基-1H-吡唑、3-胺基-5-甲基-1H-吡唑、3-胺基-5-第三丁基-1H-吡唑、2-胺基-甲基噻唑、2-巰基噻唑、2,5-二巰基-1,3,4-噻二唑、2-巰基-5-甲基-1,3,4-噻二唑、2-胺基噻唑-5-甲腈、2-胺基噻唑-5-甲醛、2-胺基噻唑-4-甲酸乙酯、1,2,3-三唑、1,2,4-三唑、咪唑、3-胺基-1,2,4-三唑衍生物及其組合。
於另一實施例中,該組合物進一步包含殺生物劑,諸如異噻唑啉酮。
於另一實施例中,該組合物實質上不含氧化劑及氟化物。
本文中所述組分之重量百分比比率之範圍將覆蓋組合物之所有可能濃縮或稀釋實施例。為達成該目的,於一個實施例中,提供濃縮之移除組合物,其可經稀釋以用作清潔溶液。濃縮組合物或「濃縮物」有利地允許使用者(例如,CMP製程工程師)將濃縮物稀釋至在使用時之所需強度及pH。濃縮水性移除組合物之稀釋可係於約1:1至約2500:1,或約5:1至約200:1,或約20:1至約120:1之範圍內,其中該水性移除組合物在併與溶劑(例如,去離子水)使用時或剛好之前經稀釋。熟習此項技術者應瞭解,於稀釋後,本文中所揭示之組分之重量百分比比率之範圍應保持不變。
因此,本文中所述組合物可用於包括(但不限於)蝕刻後殘留物移除、灰化後殘留物移除表面準備、電鍍後清潔及CMP後殘留物移除之應用中。除了清潔含鋁組分外,於一些實施例中,本文中所述之清潔組合物可用於清潔及保護其他金屬(例如,含銅及含鈷)微電子裝置結構。
該等清潔組合物容易藉由簡單添加各自成分及混合成均勻狀態來調配。此外,該等組合物可容易調配成單包裝調配物或在使用時或之前混合之多部分調配物,例如,可將多部分調配物之個別部分在工具處或於CMP工具之儲存罐上游中混合。各自成分之濃度可以組合物之特定倍數廣泛變化,即,更稀釋或更濃縮,及應瞭解,本文中所述組合物可不同地且替代地包含與本文中揭示內容一致之成分之任何組合,由其組成或基本上由其組成。
因此,另一態樣係關於套組,其包含於一或多個容器中經調適以形成本文中所述清潔組合物之一或多種組分。該套組可於一或多個容器中包含水、蝕刻劑化合物、pH調節劑及如本文中所闡述之一或多種式(I)或(II)化合物以供在工廠或使用時與另外溶劑(例如,水)合併用。當然,該套組可進一步包含以上詳述之視情況可選成分中之一或多者。套組之容器必須適於儲存及運送組合物及可為(例如) NOWPak®容器(Entegris, Inc., Billerica, Mass., USA)。
含有水性清潔組合物之組分之一或多個容器較佳地包括將該等組分帶入以流體連通之該一或多個容器中供摻合及分配用之構件。例如,提及NOWPak®容器,可將氣壓施加至該一或多個容器之內襯外部以引起內襯之內容物之至少一部分被排出及因此使能流體連通供摻合及分配用。或者,可將氣壓施加至習知可加壓容器之頂部空間或可使用泵以使能流體連通。此外,系統較佳地包括分配埠供將經摻合之移除組合物分配至製程工具用。
如應用於微電子製造操作,本文中所述之清潔組合物有效地用以自微電子裝置之表面移除殘留物及污染物,包括粒子、CMP後殘留物、灰化後殘留物、及蝕刻後殘留物。有利地,本文中所述之所揭示之清潔組合物相對於此項技術中先前所述之替代清潔組合物顯示改良的鈷相容性。因此,本發明進一步關於一種使用本文中所述之清潔組合物自其上具有殘留物及污染物之微電子裝置移除該等殘留物及污染物之方法。
該方法包括使微電子裝置與所揭示之清潔組合物接觸達足以自微電子裝置至少部分清潔殘留物及污染物之時間。在使用中,該組合物通常與裝置在約20℃至約90℃,較佳地約20℃至約50℃之範圍內之溫度下接觸達約5秒至約10分鐘,較佳地約1秒至20分鐘,較佳地約15秒至約5分鐘之時間。此等接觸時間及溫度係說明性,及可採用於該方法之廣泛實務內有效自裝置至少部分移除殘留物及污染物之任何其他適宜時間及溫度。因此,於另一態樣中,本發明提供一種自其上具有殘留物及污染物之微電子裝置基板移除該等殘留物及污染物之方法,該方法包括使該微電子裝置基板與如上所闡述之第一態樣之組合物接觸達足以自微電子裝置基板至少部分清潔殘留物及污染物之時間。
「至少部分清潔」及「實質上移除」均對應於移除至少85%之在粒子移除之前存在於裝置上之二氧化矽粒子,較佳地至少90%,甚至更佳地至少95%,及最佳地至少99%。
於接觸裝置及移除目標所需殘留物及/或污染物後,該清潔組合物可容易自先前施覆其之裝置移除,如可於本文中所述組合物之給定最終用途應用中所需且有效。例如,可使用沖洗溶液,其中該沖洗溶液包含去離子水。此後,可將裝置使用氮氣或旋乾循環乾燥,如此項技術中已知。
本發明之另一態樣係關於根據本文中所述方法製備之改良之微電子裝置及含有此等微電子裝置之產品。另一態樣係關於再循環之組合物,其中該組合物可再循環直至粒子及/或污染物負載達到該組合物可容納之最大量,如由熟習此項技術者容易測定。因而,本文中所揭示之組合物可包含殘留物及/或污染物。可將殘留物及污染物溶解於組合物中。或者,可將殘留物及污染物懸浮於組合物中。於某些實施例中,該殘留物包括CMP後殘留物、蝕刻後殘留物、灰化後殘留物、污染物或其組合。仍另一態樣係關於製造包含微電子裝置之物品之方法,該方法包括使微電子裝置與本發明之組合物接觸達足以自微電子裝置移除殘留物及/或污染物之時間及將經清潔之微電子裝置併入物品中。另一態樣係關於藉由此方法生產之物品。
如上所指定,本發明之組合物可用於CMP後清潔操作中。以下實例及圖式說明。亦發現該等組合物在模擬微電子裝置基板暴露於CMP後清潔之條件下具有對鋁、銅及鈷表面之標稱蝕刻效應。
實例
基礎組合物:製備如表1中所闡述之基礎組合物:
表1
基礎組合物之一般程 序
摻合順序 | 組分 | 溶劑 (若於溶液中) | 組分分析重量% | 添加之重量% |
1 | 去離子水 | N/A | 100 | 55.42 |
2 | 三乙醇胺 | N/A | 100 | 20.56 |
3 | 抗壞血酸 | N/A | 100 | 11.21 |
4 | 氫氧化膽鹼 | DIW | 46.7 | 12.81 |
向50克去離子水中添加20.56克三乙醇胺。向此溶液中添加11.21克抗壞血酸,接著添加氫氧化膽鹼,以調整pH至約9。
然後將此基礎組合物與下列鋁腐蝕抑制劑組合,以形成組合物1至14。
組合物1——基礎組合物加上苯基膦酸(CAS號1571-33-1)
組合物2——基礎組合物加上植酸(CAS號83-86-3)
組合物3——基礎組合物加上辛基膦酸(CAS號4724-48-5)
組合物4——基礎組合物加上亞乙烯基二膦酸四異丙酯(CAS號48074-47-1)
組合物5——基礎組合物加上二第三丁基膦酸鉀(CAS號33494-80-3)
組合物6——基礎組合物加上胡敏酸(CAS號1415-93-6)
組合物7——基礎組合物加上乙基膦酸(CAS號6779-09-5)
組合物8——基礎組合物加上亞甲基二膦酸(CAS號1984-15-2)
組合物9——基礎組合物加上1,10-癸基二膦酸(CAS號5943-21-5)
組合物10——基礎組合物加上辛基膦酸(CAS號4724-48-5)
組合物11——基礎組合物加上己基膦酸(CAS號4721-24-8)
組合物12——基礎組合物加上十八烷基膦酸(CAS號4724-47-4)
組合物13——基礎組合物加上正十二烷基膦酸(CAS號5137-70-2)
組合物14——基礎組合物加上磷酸單-N-十二烷酯(CAS號2627-35-2)
測試所有組合物之AlCu蝕刻速率作為在pH = 9下在將表面暴露於以上組合物1至14後自該表面移除之AlCu金屬之量的量度。針對此等實驗,AlCu晶圓為99.5% Al及0.5% Cu合金。在30℃及500 rpm攪動下在15分鐘清潔製程之前及之後,藉由使用X-射線螢光(XRF)量測AlCu金屬膜厚度。如下表2中所示,如與基礎組合物相比,本發明之組合物提供AlCu材料之更低蝕刻速率。
表2
組合物編號 | AlCu蝕刻速率(Å/分鐘) | Co蝕刻速率(Å/分鐘) | Cu蝕刻速率(Å/分鐘) |
基礎組合物 | 16.18 | 5.45 | 0.89 |
1 | 8.98 | ||
2 | 0.50 | 9.13 | 1.20 |
3 | 8.86 | ||
4 | 11.86 | ||
5 | 7.38 | ||
6 | 4.55 | ||
7 | 0.12 | 15.68 | 4.91 |
8 | 0.09 | 3.04 | 0.90 |
9 | 4.30 | 2.85 | 0.96 |
10 | 5.82 | ||
11 | 1.70 | ||
12 | 0.22 | ||
13 | -0.06 | ||
14 | 0.22 |
組合物1至14顯示AlCu表面在pH = 12及14下無腐蝕抑制。
於第一態樣中,本發明提供組合物,其包含:
a)水;
b)蝕刻劑化合物;
c)還原劑;及
d)選自具有下式之化合物之鋁、鈷或銅腐蝕抑制劑
(I);或
(II);
其中各x獨立地為0或1,R為芳基或伸芳基或單價或二價C
1-C
20烴基,且M選自氫、C
1-C
6烷基、銨或鹼金屬陽離子,且其中該組合物之pH大於約8。
於第二態樣中,本發明提供第一態樣之組合物,其中該C
1-C
20烴基選自直鏈或分支鏈烷基或伸烷基。
於第三態樣中,本發明提供第一態樣之組合物,其中該C
1-C
20烴基選自環烷基、伸環烷基、苯基或伸苯基。
於第四態樣中,本發明提供第一態樣之組合物,其中該等式(I)及(II)化合物選自
苯基膦酸;
植酸;
(12-膦醯基十二烷基)膦酸;
正十二烷基膦酸;
6-膦醯基己酸;
1,4-伸苯基雙(膦酸);
聚(乙烯基膦酸);
辛基膦酸;
亞乙烯基二膦酸四異丙酯;
二-第三丁基磷酸鉀;
乙基膦酸;
亞甲基二膦酸;
1,10-癸基二膦酸;
辛基膦酸;
己基膦酸;
十八基膦酸;
正十二烷基膦酸;及
磷酸單-N-十二烷酯。
於第五態樣中,本發明提供前四個態樣中之任一者之組合物,其中該蝕刻劑化合物選自單乙醇胺、三乙醇胺、硫酸、檸檬酸及其組合。
於第六態樣中,本發明提供前四個態樣中之任一者之組合物,其中該蝕刻劑化合物為三乙醇胺。
於第七態樣中,本發明提供前五個態樣中之任一者之組合物,其進一步包含一或多種pH調節劑。
於第八態樣中,本發明提供第七態樣之組合物,其中該pH調節劑選自氫氧化四甲銨、氫氧化四乙銨、氫氧化膽鹼、氫氧化鋁及氫氧化鉀。
於第九態樣中,本發明提供第七或第八態樣之組合物,其中該pH調節劑為氫氧化膽鹼。
於第十態樣中,本發明提供前九個態樣中之任一者之組合物,其中該pH小於約14。
於第十一態樣中,本發明提供第一態樣之組合物,其中該pH為約8.5至約12。
於第十二態樣中,本發明提供第一態樣之組合物,其中組分d)為鋁腐蝕抑制劑且該pH為約8至約11。
於第十三態樣中,本發明提供第一態樣之組合物,其中組分d)為鈷腐蝕抑制劑且該pH為約8至約13.5。
於第十四態樣中,本發明提供前十三個態樣中任一者之組合物,其進一步包含一或多種清潔添加劑。
於第十五態樣中,本發明提供前十四個態樣中任一者之組合物,其進一步包含第二腐蝕抑制劑。
於第十六態樣中,本發明提供前十五個態樣中任一者之組合物,其中該還原劑選自亞磷氫酸、亞磷酸、亞硫酸、偏亞硫酸氫鈉、偏亞硫酸氫銨、偏亞硫酸氫鉀、抗壞血酸、L(+)-抗壞血酸、異抗壞血酸、羥胺、羥胺鹽、二甲基羥胺、二乙基羥胺、選自半乳糖、木糖、葡萄糖、果糖、乳糖及麥芽糖之還原糖、氫醌、兒茶酚、四氫富瓦烯、N,N-二甲基苯胺苄胺及其組合。
於第十七態樣中,本發明提供前十六個態樣中任一者之組合物,其中該還原劑為抗壞血酸。
於第十八態樣中,本發明提供第十四態樣之組合物,其中該清潔添加劑選自乙二醇單丁醚、二乙二醇單丁醚、丙二醇單丁醚、二丙二醇單丁醚、乙二醇單己醚、二乙二醇單己醚、三乙二醇單丁醚、乙二醇單苯醚、二乙二醇單苯醚、丙二醇單苯醚、二甲亞碸、環丁碸、聚(苯乙烯磺酸)或其鹽、聚(乙烯基吡咯啶酮)、聚(乙烯醇)、聚(丙烯酸)及其鹽、聚丙烯酸共聚物及其鹽、聚(乙二醇)、聚乙二醇-共-聚丙二醇、羥乙基纖維素、聚(2-丙烯醯胺基-2-甲基-1-丙磺酸)及其共聚物、聚氯化二烯丙基二甲基銨、聚(二甲胺基乙基甲基丙烯酸酯)及其共聚物、聚(三甲胺基乙基甲基丙烯酸酯)鹽及其共聚物、乙氧基化醇或苯酚、乙氧基化脂肪酸糖、十二烷基苯磺酸、月桂基磺酸、辛酸、壬酸、癸酸、十一酸、十二酸、氯化苄基二甲基十二烷基銨、氫氧化苄基二甲基十二烷基銨、及氯化三甲基十二烷基銨。
於第十九態樣中,本發明提供一種自其上具有殘留物及污染物之微電子裝置基板移除該等殘留物及污染物之方法,該方法包括使該微電子裝置基板與第一至第十七態樣中之任一者之組合物接觸達足以自該微電子裝置基板至少部分清潔殘留物及污染物之時間。
於第二十態樣中,本發明提供套組,其包含前十八個態樣中之任一者之組分a)、b)、c)及d)中之兩者或更多者於兩個或更多個容器中。
因此已描述本發明之若干說明性實施例,熟習此項技術者應容易瞭解,可在附接於此之申請專利範圍之範圍內作出及使用又其他實施例。已於上述描述中闡述由本檔案覆蓋之本發明之許多優點。然而,應瞭解,本發明於許多態樣中僅係說明性。本發明之範圍當然以表述隨附申請專利範圍之語言限定。
Claims (10)
- 如請求項1之組合物,其中該等式(I)及(II)化合物選自 苯基膦酸; 植酸; (12-膦醯基十二烷基)膦酸; 正十二烷基膦酸; 6-膦醯基己酸; 1,4-伸苯基雙(膦酸); 聚(乙烯基膦酸); 辛基膦酸; 亞乙烯基二膦酸四異丙酯; 二-第三丁基磷酸鉀; 乙基膦酸; 亞甲基二膦酸; 1,10-癸基二膦酸; 辛基膦酸; 己基膦酸; 十八基膦酸; 正十二烷基膦酸;及 磷酸單-N-十二烷酯。
- 如請求項1之組合物,其中該蝕刻劑化合物選自單乙醇胺、三乙醇胺、硫酸、檸檬酸及其組合。
- 如請求項1之組合物,其進一步包含一或多種pH調節劑。
- 如請求項4之組合物,其中該pH調節劑選自氫氧化四甲銨、氫氧化四乙銨、氫氧化膽鹼、氫氧化鋁及氫氧化鉀。
- 如請求項1之組合物,其中該pH小於約14。
- 如請求項1之組合物,其中組分d)為鋁腐蝕抑制劑且該pH為約8至約11。
- 如請求項1之組合物,其中組分d)為鈷腐蝕抑制劑且該pH為約8至約13.5。
- 如請求項1之組合物,其中該還原劑選自亞磷氫酸、亞磷酸、亞硫酸、偏亞硫酸氫鈉、偏亞硫酸氫銨、偏亞硫酸氫鉀、抗壞血酸、L(+)-抗壞血酸、異抗壞血酸、羥胺、羥胺鹽、二甲基羥胺、二乙基羥胺、還原糖(選自半乳糖、木糖、葡萄糖、果糖、乳糖及麥芽糖)、氫醌、兒茶酚、四氫富瓦烯、N,N-二甲基苯胺苄胺及其組合。
- 一種用於自微電子裝置基板移除殘留物及污染物之方法,該微電子裝置基板上具有該殘留物及污染物,該方法包括使該微電子裝置基板與如請求項1之組合物接觸達足以至少部分清潔來自該微電子裝置基板之該殘留物及污染物之時間。
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