CN102061228A - 包含氧化剂和有机溶剂的微电子清洁组合物 - Google Patents
包含氧化剂和有机溶剂的微电子清洁组合物 Download PDFInfo
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- CN102061228A CN102061228A CN2011100064160A CN201110006416A CN102061228A CN 102061228 A CN102061228 A CN 102061228A CN 2011100064160 A CN2011100064160 A CN 2011100064160A CN 201110006416 A CN201110006416 A CN 201110006416A CN 102061228 A CN102061228 A CN 102061228A
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- 239000000203 mixture Substances 0.000 title claims abstract description 100
- 238000004140 cleaning Methods 0.000 title claims abstract description 82
- 238000004377 microelectronic Methods 0.000 title claims abstract description 19
- 239000003960 organic solvent Substances 0.000 title description 9
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- 239000010949 copper Substances 0.000 claims abstract description 17
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 10
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
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- 238000005260 corrosion Methods 0.000 claims description 20
- 230000007797 corrosion Effects 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 13
- 239000003112 inhibitor Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
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- 239000006184 cosolvent Substances 0.000 claims description 10
- 238000001465 metallisation Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 239000003352 sequestering agent Substances 0.000 claims description 7
- 230000005764 inhibitory process Effects 0.000 claims description 6
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- 239000013543 active substance Substances 0.000 claims description 5
- 239000002738 chelating agent Substances 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 238000001020 plasma etching Methods 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011358 absorbing material Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001298 alcohols Chemical class 0.000 abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 5
- 238000000637 aluminium metallisation Methods 0.000 abstract description 3
- 150000001408 amides Chemical class 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- MBDNRNMVTZADMQ-UHFFFAOYSA-N sulfolene Chemical class O=S1(=O)CC=CC1 MBDNRNMVTZADMQ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003989 dielectric material Substances 0.000 abstract description 2
- 150000003457 sulfones Chemical class 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 229920006395 saturated elastomer Polymers 0.000 abstract 1
- 150000003966 selones Chemical class 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- FCKYPQBAHLOOJQ-UHFFFAOYSA-N Cyclohexane-1,2-diaminetetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)C1CCCCC1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UHFFFAOYSA-N 0.000 description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 12
- BZORFPDSXLZWJF-UHFFFAOYSA-N N,N-dimethyl-1,4-phenylenediamine Chemical compound CN(C)C1=CC=C(N)C=C1 BZORFPDSXLZWJF-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 10
- 239000011888 foil Substances 0.000 description 10
- GTDKXDWWMOMSFL-UHFFFAOYSA-M tetramethylazanium;fluoride Chemical compound [F-].C[N+](C)(C)C GTDKXDWWMOMSFL-UHFFFAOYSA-M 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
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- 229910052710 silicon Inorganic materials 0.000 description 4
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- 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 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004380 ashing Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229940075419 choline hydroxide Drugs 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 150000008053 sultones Chemical class 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- WDQFELCEOPFLCZ-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrolidin-2-one Chemical compound OCCN1CCCC1=O WDQFELCEOPFLCZ-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 206010016825 Flushing Diseases 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
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- 150000004965 peroxy acids Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- GYSDUVRPSWKYDJ-UHFFFAOYSA-N selinone Chemical compound C1=CC(OCC=C(C)C)=CC=C1C1OC2=CC(O)=CC(O)=C2C(=O)C1 GYSDUVRPSWKYDJ-UHFFFAOYSA-N 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- GPRYKVSEZCQIHD-UHFFFAOYSA-N 1-(4-aminophenyl)ethanone Chemical compound CC(=O)C1=CC=C(N)C=C1 GPRYKVSEZCQIHD-UHFFFAOYSA-N 0.000 description 1
- JEXYCADTAFPULN-UHFFFAOYSA-N 1-propylsulfonylpropane Chemical compound CCCS(=O)(=O)CCC JEXYCADTAFPULN-UHFFFAOYSA-N 0.000 description 1
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- HPNFIBSFPLJOQC-UHFFFAOYSA-N 2-trihydroxysilyloxyethanol Chemical compound OCCO[Si](O)(O)O HPNFIBSFPLJOQC-UHFFFAOYSA-N 0.000 description 1
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 1
- CMJLMPKFQPJDKP-UHFFFAOYSA-N 3-methylthiolane 1,1-dioxide Chemical compound CC1CCS(=O)(=O)C1 CMJLMPKFQPJDKP-UHFFFAOYSA-N 0.000 description 1
- AGGCEDYMGLPKNS-UHFFFAOYSA-N 5,5,6-trimethylundec-3-yne-2,2-diol Chemical class CCCCCC(C)C(C)(C)C#CC(C)(O)O AGGCEDYMGLPKNS-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical class F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 1
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- MLRKYSNODSLPAB-UHFFFAOYSA-N hex-1-yn-1-ol Chemical class CCCCC#CO MLRKYSNODSLPAB-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- LYTNHSCLZRMKON-UHFFFAOYSA-L oxygen(2-);zirconium(4+);diacetate Chemical compound [O-2].[Zr+4].CC([O-])=O.CC([O-])=O LYTNHSCLZRMKON-UHFFFAOYSA-L 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- 150000004977 peroxyborates 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
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- 125000005402 stannate group Chemical group 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- IXZDIALLLMRYOU-UHFFFAOYSA-N tert-butyl hypochlorite Chemical compound CC(C)(C)OCl IXZDIALLLMRYOU-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
- C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
- C23G1/061—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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Abstract
适用于清洁具有二氧化硅、低κ或高κ电介质和铜或铝金属化的微电子结构的清洁组合物包含氧化剂和选自酰胺、砜、环丁烯砜、硒代砜和饱和醇的极性有机溶剂,及任选的其它组分。
Description
此案是申请日为2003年5月27日、中国申请号为03813035.1(国际申请号为PCT/US03/16828)、发明名称为“包含氧化剂和有机溶剂的微电子清洁组合物”的分案申请。
技术领域
本发明涉及用于清洁微电子基底的方法和清洁组合物,以及具体涉及对以二氧化硅、敏感的低κ或高κ电介质和铜金属化(copper metallization)为特征的微电子基底以及Al或Al(Cu)金属化的基底有用并具有改进相容性的清洁组合物。本发明也涉及该清洁组合物用于剥离光致抗蚀剂(photoresist)、清洁来自等离子过程生成的有机化合物、有机金属化合物和无机化合物的残留物、清洁从如化学机械抛光的平整过程(planarization process)中产生的残留物,以及在平整浆料残留物中用作添加剂的用途。
背景技术
在微电子领域中,已经建议使用许多光致抗蚀剂剥离剂和残留物去除剂作为生产线下游或后端(back end)的清洁剂。在制造过程中光致抗蚀剂薄膜沉积在晶片基底上,然后在薄膜上成像电路图案。烘焙后,未聚合的抗蚀剂用光致抗蚀剂展开剂(developer)除去。然后通过反应性等离子体蚀刻气体或化学蚀刻剂溶液将所得到的图像转印至底层材料,该材料通常是电介质或金属。蚀刻气体或化学蚀刻剂溶液选择性蚀刻基底上未被光致抗蚀剂保护的区域。
另外,在蚀刻步骤终止后,抗蚀剂掩膜(mask)必须从晶片的保护区除去,从而可以进行最终的抛光操作。这可以在等离子体灰化步骤中通过采用合适的等离子体灰化(ashing)气体或湿法化学剥离剂完成。然而,寻找用于除去该抗蚀剂掩膜材料而对金属电路没有如腐蚀、溶解或钝化等负面影响的合适清洁组合物,已证实是有问题的。
随着微电子制造集成水平的提高以及图案化微电子器件尺寸的减小,在本领域中使用铜金属化、低κ和高κ电介质变得越来越普遍。这些材料对寻找可接受的清洁剂组合物提出了另外的挑战。先前开发的用于“传统”或“常规”半导体器件(含有Al/SiO2或Al(Cu)SiO2结构)的许多工艺技术组合物不能用于铜金属化的低κ或高κ电介质结构。例如,羟胺类剥离剂或残留物除去剂组合物成功地用于清洁由铝金属化的器件,但对那些由铜金属化的器件实际上不合适。同样,如果不在组合物中作出重大调整,许多铜金属化的/低κ剥离剂不适合铝金属化的器件。
已经证实在等离子蚀刻和/或灰化过程后这些蚀刻和/或灰化残留物的去除是有问题的,特别对具有低κ电介质材料的基底和由铜金属化的那些基底。无法完全除去或抵消这些残留物会导致湿气的吸收和对金属结构引起腐蚀的不希望物质的形成。电路材料被这些不希望的物质腐蚀,并在电路线路(circuitry wiring)中产生不连续性以及不希望地增加电阻。
迄今为止,氧化剂使用在主要为水溶液形式的清洁组合物中。已知氧化剂如普通使用的过氧化氢和过酸容易发生反应或易于分解,特别是在有机溶剂基质(通常应用在剥离剂组合物中)中。在这些例子中,氧化剂被消耗,对所期望的应用变得无法得到。另外,含有氧化剂的微电子清洁组合物经常显示出差的产品稳定性,特别在存在大量的(10重量%或更多的)有机溶剂,以及在较高的pH范围内和高的处理温度下。而且,在许多组合物中,稳定剂和溶剂的使用经常会妨碍氧化剂,导致在清洁过程中进行有效氧化/还原反应的能力降低。
发明内容
因此,需要适合后端清洁操作的微电子清洁组合物,其中该组合物是有效的清洁剂,且能用于剥离光致抗蚀剂和清洁来自等离子过程生成的有机化合物、有机金属化合物和无机化合物的残留物,清洁如CMP的平整过程产生的残留物,和在平整浆料/液中用作添加剂,以及该组合物可用于采用铜金属化,和多孔或无孔低κ(即κ值为3或更小)或高κ(即κ值为20或更大)的电介质的高级互连材料(advanced interconnect materials),以及适用于清洁常规器件,例如那些含有二氧化硅、低κ或高κ电介质的铝或铝(同)金属化的器件。本发明涉及包含氧化剂的清洁组合物,该组合物是用于清洁所有这些器件的有效清洁剂。
已经发现以下配制剂能提供普遍可接受的清洁组合物,该配制剂包含氧化剂和与氧化剂发生最小程度的反应或不发生反应的某些极性有机溶剂,以及特别是能帮助稳定该氧化剂的那些溶剂。还已发现具有良好氢键键合能力的溶剂可提供包含这些氧化剂的配制剂。本发明的清洁组合物通常具有大约0.1-30wt%氧化剂和大约1-99.9wt%具有良好氢键键合能力的极性有机溶剂。本发明的清洁组合物也可任选包含水和/或相容的酸或碱(alkaline base)、螯合剂、共溶剂、氧化剂稳定剂、金属腐蚀抑制剂抑制剂(metal corrosion inhibitor)、表面活性剂和氟化物。尽管在本发明的清洁组合物中碱是任选的组分,但优选存在碱,这是因为尽管不是必需的,但清洁组合物具有碱性pH是优选的。碱存在的量为0至大约30重量%,优选存在的量为大约0.1-10重量%。在本说明书中提供的重量百分数基于清洁组合物的总重量。
具体实施方式
本发明的新型后端清洁组合物将包含一种或多种任意的氧化剂和极性有机溶剂。该清洁组合物可配制为高含水性、半含水性或有机溶剂类的配制剂。清洁组合物可以只和其它溶剂单独使用,或与酸和碱结合使用。本发明的清洁组合物可用于大范围的pH和温度的加工/操作条件,及可用于有效除去光致抗蚀剂、后等离子体(post plasma)蚀刻/灰化残留物、牺牲(sacrificial)光吸收材料和防反射涂层(ARC)。另外,发现用本发明的清洁组合物容易清洁难以清洁的样品,例如高度交联或硬化的光致抗蚀剂和含有含钛物质(如钛、氧化钛和氮化钛)或含钽物质(如钽、氧化钽和氮化钽)的结构。
本发明的组合物可以含有适合用于微电子清洁组合物的任何氧化剂。这些氧化剂的例子,可提及例如,过氧化物,特别是过氧化氢,来自过氧化氢和含氧酸、乙酸氧锆和偶氮化合物的过氧水合物(peroxyhydrates)的分子加合物,例如过碳酸钠、高硼酸钠,以及高碘酸盐(IO4 -)、高硼酸盐、高锰酸盐(MnO4 -)、过硫酸氢盐(hydrogen persulfates)、过硫酸盐和烷氧基卤化物如t-BuOCl。也可以采用从H2O2和有机分子的取代反应得到的其它过氧化合物,但较不优选。实例包括烷基过氧化物、过氧酸、二酰基过氧化物和酮过氧化物。也可以采用H2O2和无机分子的相似取代产物如过氧硫酸。在本发明的清洁组合物中使用的氧化剂的量为大约0.1-30重量%,优选为大约0.1-5重量%,更优选为大约1-5重量%。优选的氧化剂是过氧化氢(H2O2),优选采用3-30%的水溶液。
所述有机溶剂是具有氢键键合能力以及与氧化剂发生最小程度的反应或不发生反应的极性有机溶剂。该有机溶剂包括酰胺、砜、环丁烯砜(sulfolene)、硒代砜(selenone)和饱和醇。在优选的溶剂中,可提及环丁砜(四氢噻吩-1,1-二氧化物)、3-甲基环丁砜、正丙基砜、正丁基砜;环丁烯砜(2,5-二氢噻吩-1,1-二氧化物)、3-甲基环丁烯砜;酰胺如1-(2-羟乙基)-2-吡咯烷酮(HEP)、二甲基哌啶酮(DMPD)、N-甲基吡咯烷酮(NMP)、二甲基乙酰胺(DMAc)、二甲基甲酰胺;和饱和醇如乙醇、丙醇、丁醇、己醇、乙二醇、丙二醇、丙三醇和六氟异丙醇。有机溶剂组分可以包括一种或多种该溶剂,并且在组合物中存在的量通常为大约1-99.9重量%,优选为大约10-90重量%,最优选为大约30-80重量%。这些溶剂对酸性和碱性条件具有抵抗力并且不会和氧化剂结合得太牢固。另外,通过相互作用如氢键键合形成稳定的络合物它们能够稳定氧化剂,如过氧化氢。
水可存在于清洁组合物中,并且水存在时,存在的量为大约0.1-98重量%,优选为大约10-60重量%,最优选为大约15-50重量%。水可作为其它组分的水性部分和/或作为另外添加的水而存在。
碱是作为本发明清洁组合物的任选但通常是优选的组分而存在的。碱存在的量可以为0至大约30重量%,优选为大约0.1-10重量%,最优选为大约0.1-5重量%。在清洁组合物中可以使用任何合适的碱。该碱优选为氢氧化铵或氨或非氨衍生碱(non-ammonia derived base)。正如下文公开的,当组合物是打算用来清洁铜金属化结构时,碱优选为非氨衍生碱,而当组合物是打算用来清洁含铝结构时,该碱优选为氢氧化铵、氨或与腐蚀抑制共溶剂(corrosion-inhibiting co-solvent)和/或腐蚀抑制剂(corrosion-inhibiting agent)结合的非氨衍生碱。作为合适的非氨衍生碱的例子,可提及氢氧化四烷基铵,例如分子式为R4N+OH-的那些,其中每个R独立为取代的或未取代的烷基,该烷基优选具有1-22个碳原子,且更优选具有1-4个碳原子。在适用于组合物的非氨衍生碱中,可提及例如,氢氧化四甲基铵、氢氧化四丁基铵、胆碱氢氧化物(choline hydroxide)等。无机碱如氢氧化钾、氢氧化钠等也可以用作所述碱。
如前面提到的,本发明的清洁组合物也可以在酸性pH条件下应用,并且可以使用必需量的任何合适的酸组分(例如HCI或HF)以足够给予组合物酸性pH。
清洁组合物也可以任选包括一种或多种腐蚀抑制共溶剂。在本发明的组合物中使用的优选腐蚀抑制共溶剂具有下述通式:
W-[CR1R2]n-Y
其中R1和R2各自独立选自H、烷基,优选具有1-6个碳原子的烷基、芳基,优选具有3-14个碳原子的芳基、OR3和SO2R4;n为2-6的数,优选2或3;W和Y各自独立选自OR3和SO2R4;及R3和R4各自独立选自H、烷基,优选具有1-6个碳原子的烷基、芳基,优选具有3-14个碳原子的芳基。作为该腐蚀抑制共溶剂的例子,可提及例如,乙二醇、丙二醇和丙三醇等。如果清洁组合物所要求的极性有机溶剂不是上述通式内的饱和醇,则此饱和醇可作为共溶剂存在。组合物中存在的共溶剂的量为0至大约80重量%,优选为大约1-50重量%,最优选为大约1-30重量%。
本发明的组合物也可以包含其它腐蚀抑制剂,优选为包含与芳香环直接键合的两个或多个OH、OR6和/或SO2R6R7基团的芳基化合物,其中R6、R7和R8各自独立为烷基,优选具有1-6个碳原子的烷基,或芳基,优选具有6-14个碳原子的芳基。这些优选的腐蚀抑制剂的例子,可提及邻苯二酚、焦酚、没食子酸、间苯二酚等。其它腐蚀抑制剂存在的量为0至大约15重量%,优选为大约0.1-10重量%,最优选为大约0.5-5重量%。
有机或无机螯合剂或者金属络合剂不是必需的,但它们能提供实质的益处,例如提高的产品稳定性。合适的螯合剂或络合剂的例子包括但不限于反-1,2-环己烷二胺四乙酸(CyDTA)、乙二胺四乙酸(EDTA)、锡酸盐、焦膦酸盐、亚烷基-二膦酸衍生物(如乙烷-1-羟基-1,1-二膦酸盐)、包含乙二胺、二亚乙基三胺或三亚乙基四胺官能部分的膦酸盐[如乙二胺四(亚甲基膦酸)(EDTMP)、二亚乙基三胺五(亚甲基膦酸)、三亚乙基四胺六(亚甲基膦酸)]。组合物中螯合剂的量为0至大约5重量%,优选为大约0.1-2重量%。各种膦酸盐的金属螯合剂或络合剂如乙二胺四(亚甲基膦酸)(EDTMP)对在酸性或碱性条件下含氧化剂的本发明清洁组合物提供了更加改进的稳定性,因而通常是优选的。
需要时,用于氧化剂的其它稳定剂也可以用在本发明的清洁组合物中。这些稳定剂可以使用的量是0至大约10重量%,优选大约0.1-5重量%。这些稳定剂的例子包括但不限于,N-乙酰苯胺和硅酸酯,优选为不含金属离子的硅酸酯如硅酸四烷基铵(包括羟烷基和烷氧烷基),其中烷基优选包含1-4个碳原子。在这些硅酸酯中有原硅酸四乙酯、四(2-羟乙基)原硅酸酯等。
任选的:可以使用其它金属腐蚀抑制剂,如苯并三唑,其含量为0至大约5重量%,优选为大约0.1-2重量%。
清洁组合物也可以任选包含表面活性剂,例如二甲基己炔醇(Surfynol-61)、乙氧化四甲基癸炔二醇(Surfynol-465)、聚四氟亚乙基十六烷氧基丙基甜菜碱(Zonyl FSK),Zonyl FSH等。表面活性剂存在的量通常为0至大约5重量%,优选大约0.1-3重量%。
清洁组合物也可以在清洁组合物中任选包含氟化物,例如,氟化四甲基铵、氟化四丁基铵和氟化铵。其它合适的氟化物包括,例如氟硼酸盐、氟硼酸四丁基铵、六氟化铝、氟化锑等。氟化物组分存在的量为0至大约10重量%,优选为大约0.1-5重量%。
在下表1-9中列出了本发明的清洁组合物的例子。
在下表中所用的缩写词如下。
HEP=1-(2-羟乙基)-2-吡咯烷酮
TMAH=氢氧化四甲基铵
TMAF=氟化四甲基铵
ACA=N-乙酰苯胺
CyDTA=反-1,2-环己烷二胺四乙酸
TEOS=原硅酸四乙酯
DMPD=二甲基哌啶酮
SFL=环丁砜
TMAS=硅酸四甲基胺
EG=乙二醇
CAT=邻苯二酚
EHDP=乙烷-1-羟基-1,1-二膦酸盐
EDTMP=乙二胺四(亚甲基膦酸)
1N HCI=1当量浓度盐酸
NH4OH=氢氧化铵
CH=胆碱氢氧化物
水=来自组分水溶液的水之外加入的水
在下表中,组合物XM-188、XM-188A和XM-191也指下列组合物,其中括号内表示的是列出组分的重量份数。
XM-188=SFL(300),水(75),25%TMAH(25),CyDTA(2.3)
XM-188A=SFL(150),水(60),25%TMAH(17.5),EDTMP(1.8)
XM-191=SFL(150),水(60),25%TMAH(17.5),EDTMP(1.8),EG(30)
表1
组合物/重量份数
组分 | A | B | C | D | E | F | G |
HEP | 30 | 30 | 30 | 30 | 60 | ||
25%TMAH | 2 | 2.6 | 2 | 2 | 2 | 5 | 5 |
ACA | 0.2 | 0.2 | |||||
CyDTA | 0.2 | 0.4 | 0.4 | ||||
TEOS | 1 | ||||||
DMPD | 30 | 60 | |||||
SFL | |||||||
EG | |||||||
CAT | |||||||
60%EHDP | |||||||
EDTMP | |||||||
TMAF |
10%TMAS | |||||||
29%NH4OH | |||||||
30%H2O2 | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 | 5 | 5 |
水 | 15 | 15 | 15 | 15 | 15 | 30 | 30 |
XM-188 | |||||||
XM-188A | |||||||
XM-191 | |||||||
1N HCI | |||||||
20%CH |
表2
组合物/重量份数
组分 | H | I | J | K | L | M | N |
HEP | 30 | ||||||
25%TMAH | 1 | 10 | 8.8 | 4 | 3 | 4.9 | |
ACA | |||||||
CyDTA | 0.92 | 0.35 | 0.24 | ||||
TEOS | |||||||
DMPD | |||||||
SFL | 120 | 50 | 30 | 37 | |||
EG | 10 | ||||||
CAT |
60%EHDP | 0.24 | 0.29 | |||||
EDTMP | |||||||
TMAF | |||||||
10%TMAS | 1 | ||||||
29%NH4OH | |||||||
30%H2O2 | 2 | 10 | 8.8 | 2.5 | 4.2 | 2.5 | 4 |
水 | 15 | 60 | 9 | ||||
XM-188 | 40 | 40 | |||||
XM-188A | |||||||
XM-191 | |||||||
1N HCI | |||||||
20%CH |
表3
组合物/重量份数
组分 | O | P | Q | R | S | T | U |
HEP | |||||||
25%TMAH | 5 | 20 | 4.4 | 7.8 | |||
ACA | |||||||
CyDTA | |||||||
TEOS | |||||||
DMPD | |||||||
SFL | 200 | 37.5 | 42.5 |
EG | 10.3 | 15 | |||||
CAT | |||||||
60%EHDP | 1.5 | 2.6 | |||||
EDTMP | 0.68 | ||||||
TMAF | 2 | ||||||
10%TMAS | |||||||
29%NH4OH | |||||||
30%H2O2 | 19.2 | 18.7 | 4.8 | 5 | 4.3 | 5 | |
水 | 20 | 70 | 22.5 | 10.6 | 3.5 | ||
XM-188 | 200 | 40 | |||||
XM-188A | 57.4 | 40 | |||||
XM-191 | |||||||
1N HCI | |||||||
20%CH |
表4
组合物/重量份数
组分 | V | W | X | Y | Z | AA | BB |
HEP | |||||||
25%TMAH | |||||||
ACA | |||||||
CyDTA | 0.39 | 0.39 | |||||
TEOS | |||||||
DMPD |
SFL | 50 | 50 | 50 | 50 | 40 | ||
EG | 15 | 15 | |||||
CAT | 3 | 3.5 | 3.5 | 1.5 | |||
60%EHDP | |||||||
EDTMP | 0.6 | 0.6 | 0.6 | ||||
TMAF | |||||||
10%TMAS | |||||||
29%NH4OH | 1.4 | 1.9 | 1.4 | 1.9 | 2 | ||
30%H2O2 | 6.4 | 5.8 | 5.5 | 7.2 | 6.7 | 6.7 | 7.6 |
水 | 12.5 | 20 | 12.5 | 20 | 30 | ||
XM-188 | 40 | 40 | |||||
XM-188A | |||||||
XM-191 | |||||||
1N HCI | |||||||
20%CH |
表5
组合物/重量份数
组分 | CC | DD | EE | FF | GG | HH | II |
HEP | |||||||
25%TMAH | 2 | ||||||
ACA | |||||||
CyDTA | 0.39 |
TEOS | |||||||
DMPD | |||||||
SFL | 50 | 50 | 60 | 60 | |||
EG | 50 | ||||||
CAT | |||||||
60%EHDP | |||||||
EDTMP | 0.6 | ||||||
TMAF | |||||||
10%TMAS | |||||||
29%NH4OH | 1.7 | 2.2 | |||||
30%H2O2 | 7 | 7.3 | 5 | 5 | 5 | 6.2 | 2.5 |
水 | 12.5 | 20 | |||||
XM-188 | 40 | ||||||
XM-188A | 57 | ||||||
XM-191 | |||||||
1N HCI | 1 | ||||||
20%CH |
表6
组合物/重量份数
组分 | JJ | KK | LL | MM | NN | OO |
HEP |
25%TMAH | 5 | 5 | 6 | 5 | 6 | |
ACA | ||||||
CyDTA | ||||||
TEOS | ||||||
DMPD | ||||||
SFL | ||||||
EG | ||||||
CAT | ||||||
60%EHDP | ||||||
EDTMP | ||||||
TMAF | ||||||
10%TMAS | ||||||
29%NH4OH | ||||||
30%H2O2 | 7 | 7.5 | 6 | 2.5 | 7 | 6 |
水 | 5 | |||||
XM-188 | 80 | 40 | 80 | |||
XM-188A | ||||||
XM-191 | 62.5 | 64.5 | 62.5 | |||
1N HCI | 1 | |||||
20%CH |
表7
组合物/重量份数
组分 | PP | RR | SS | TT | UU | W | |
HEP | |||||||
25%TMAH | 25 | 25 | 20 | 25 | 17.5 | 17.5 | 2.5 |
ACA | |||||||
CyDTA | 3 | 3 | 2.5 | 1.5 | 0.23 | ||
TEOS | |||||||
DMPD | |||||||
SFL | 300 | 300 | 300 | 300 | 150 | 150 | 30 |
EG | 5 | 40 | 20 | 15 | |||
CAT | 3 | ||||||
60%EHDP | |||||||
EDTMP | 1.8 | 1.8 | |||||
TMAF | |||||||
10%TMAS | |||||||
29%NH4OH | |||||||
30%H2O2 | 36.8 | 37.3 | 36.7 | 37.2 | 26 | 24 | 5.8 |
水 | 35 | 45 | 45 | 45 | 50 | 50 | 7.5 |
XM-188 | |||||||
XM-188A | |||||||
XM-191 | |||||||
1N HCI | |||||||
20%CH |
表8
组合物/重量份数
组分 | WW | XX | YY | ZZ | AAA | BBB | CCC |
HEP | |||||||
25%TMAH | 3.1 | 7.5 | |||||
ACA | |||||||
CyDTA | 0.39 | 0.39 | 0.28 | 1.2 | 0.8 | ||
TEOS | |||||||
DMPD | 7.5 | ||||||
SFL | 50 | 50 | 50 | 50 | 74 | 75 | |
EG | |||||||
CAT | 3.5 | 3.5 | |||||
60%EHDP | |||||||
EDTMP | 0.6 | 0.6 | |||||
TMAF | |||||||
10%TMAS | |||||||
29%NH4OH | 1.4 | 1.9 | 1.4 | 1.9 | |||
30%H2O2 | 6.8 | 7.6 | 6.4 | 7.25 | 14.7 | 13.6 | 14 |
水 | 12.5 | 20 | 12.5 | 20 | 40 | 25 | 25 |
XM-188 | |||||||
XM-188A | |||||||
XM-191 | |||||||
1N HCI | |||||||
20%CH | 12 |
表9
组合物/重量份数
组分 | DDD | EEE |
HEP | 75 | |
25%TMAH | 6.25 | 7.5 |
ACA | ||
CyDTA | 0.6 | 1.2 |
TEOS | ||
DMPD | ||
SFL | ||
EG | 75 | |
CAT | ||
60%EHDP | ||
EDTMP | ||
TMAF | ||
10%TMAS | ||
29%NH4OH | ||
30%H2O2 | 13.4 | 13.6 |
水 | 25 | 25 |
XM-188 | ||
XM-188A | ||
XM-191 |
1N HCI |
通过下表10中的蚀刻速率数据说明本发明清洁组合物对铜和铝的蚀刻速率。使用下述测试程序确定蚀刻速率。
采用大约13×50mm的铝箔或铜箔的薄片。测量箔片厚度。在用2-丙醇、蒸馏水和丙酮清洁箔片后,将箔片放入干燥箱干燥。然后将清洁和干燥过的箔片放入盖子松开的瓶中,瓶中有预热过的本发明清洁组合物,并将其置于指定温度的真空箱中2到4个小时。在进行处理和从箱和瓶中取出后,用大量的蒸馏水冲洗清洁过的箔片,并放入干燥箱中干燥大约1小时,然后使其冷却至室温,再根据重量损失或重量变化来确定蚀刻速率。
表10
通过下面的测试程序评估本发明的组合物JJ和NN(表6)对各种电介质的层间电介质(ILD)蚀刻速率。
采用Rudolph干涉仪测量晶片的膜厚度。在指定温度下将晶片(硅晶片上沉积有ILD材料)浸入指定的清洁组合物中30分钟,接着用去离子水冲洗并在氮气流动/气流下干燥。然后在处理之后再次测量厚度,并根据膜厚的变化计算指定处理方法产生的蚀刻速率。
下列是组合物JJ(表11)、组合物NN(表12)、组合物HH(表13)、组合物FF(表14)和组合物GG(表15)的IDL蚀刻速率。
表11
表12
表13
表14
表15
本发明的组合物的清洁能力也可以通过下面的测试进行说明,其中将包含下列结构的晶片,即光致抗蚀机/掺杂碳的氧化物/氮化硅/铜(被氮化硅穿通以露出铜)的晶片的微电子结构放入指定温度的清洁溶液中浸泡指定时间,然后用水冲洗、干燥,并通过SEM检查测定清洁度。结果列于表16中。
表16
本发明的组合物的清洁能力也可以通过下面的测试进行说明,其中将包含下列结构(即TiN/AI/TiN/Ti/Si)的铝晶片的微电子结构放入指定温度的清洁溶液中浸泡指定时间,然后用水冲洗、干燥,并通过SEM检查测定清洁度。结果列于表17中。
表17
本发明的清洁组合物的铝蚀刻速率也可用下表18中的蚀刻速率数据进行说明。该蚀刻速率利用下列的测试程序进行测定。
采用大约13×50mm的铝箔或铜箔的薄片。测量箔片厚度。在用2-丙醇、蒸馏水和丙酮清洁箔片后,将箔片放入干燥箱干燥。然后将清洁和干燥过的箔片放入盖子松开的瓶中,瓶中有预热过的本发明清洁组合物,并将其置于指定温度的真空箱中2到4个小时。在进行处理和从箱和瓶中取出后,用大量的蒸馏水冲洗清洁过的箔片,并放入干燥箱中干燥大约1小时,然后使其冷却至室温,再根据重量损失或重量变化来确定蚀刻速率。
表18
尽管已经参考本发明的具体实施方式描述了本发明,但应理解在不偏离在此公开的创造性概念的实质和范围内,可以进行变化、修改和变更。因此,旨在包含落入所附权利要求书的范围和实质内的所有变化、修改和变更。
Claims (9)
1.清洁组合物,其能够从铜金属化且具有低κ或高κ电介质的微电子基底清洁高度交联或硬化的光致抗蚀剂的残留物、后等离子体蚀刻/灰化残留物、牺牲光吸收材料、防反射涂层、和含有钛或钽的结构,所述清洁组合物基本上由以下组成:
约0.1至约30重量%的过氧化氢;
约1至约99.9重量%的环丁砜作为具有氢键键合能力以及与所述氧化剂发生最小程度的反应或不发生反应的极性有机溶剂;
大于0至约30重量%的氢氧化四烷基铵作为碱;
0.1至5重量%的螯合剂或金属络合剂,其选自反-1,2-环己烷二胺四乙酸和乙二胺四(亚甲基膦酸);和
约0.1至约98重量%的水,
其中该清洁组合物中各成分含量百分比的总和不超过100%。
2.权利要求1所述的清洁组合物,其中所述极性有机溶剂在组合物中存在的量为约10至约90重量%。
3.权利要求2所述的清洁组合物,其基本上由以下组成:环丁砜、氢氧化四甲基铵、反-1,2-环己烷二胺四乙酸、过氧化氢和水。
4.权利要求2所述的清洁组合物,其基本上由以下组成:环丁砜、氢氧化四甲基铵、乙二胺四(亚甲基膦酸)、过氧化氢和水。
5.权利要求1所述的清洁组合物,所述清洁组合物仅由所述组分组成。
6.权利要求5所述的清洁组合物,其由以下组成:环丁砜、反-1,2-环己烷二胺四乙酸、氢氧化四甲基铵、过氧化氢和水。
7.一种用于从铜金属化且具有低κ或高κ电介质的微电子基底清洁高度交联或硬化的光致抗蚀剂的残留物、后等离子体蚀刻/灰化残留物、牺牲光吸收材料、防反射涂层、和含有钛或钽的结构的方法,所述方法包含将基底与清洁组合物接触足够的时间以从微电子基底清洁光致抗蚀剂和残留物,其中所述清洁组合物包含权利要求1至6任一项的组合物。
8.用于从微电子基底清洁光致抗蚀剂和残留物的清洁组合物,所述清洁组合物基本上由以下组成:
约0.1至约30重量%的氧化剂;
约1至约99.9重量%的极性有机溶剂;
大于0至约30重量%的碱以向组合物提供碱性pH;
以及任选以下组分的一种或多种:
腐蚀抑制共溶剂;
螯合剂或金属络合剂;
氧化剂稳定剂;
腐蚀抑制剂;
金属腐蚀抑制剂;
氟化物化合物;
表面活性剂;和
水,
其中该清洁组合物中各成分含量百分比的总和不超过100%。
9.用于从微电子基底清洁光致抗蚀剂和残留物的清洁组合物,所述清洁组合物基本上由以下组成:
约0.1至约30重量%的氧化剂;
约1至约99.9重量%的极性有机溶剂;
必需量的合适的酸组分以足够给予组合物酸性pH,如HCl或HF;
以及任选以下组分的一种或多种:
腐蚀抑制共溶剂;
螯合剂或金属络合剂;
氧化剂稳定剂;
腐蚀抑制剂;
金属腐蚀抑制剂;
氟化物化合物;
表面活性剂;和
水,
其中该清洁组合物中各成分含量百分比的总和不超过100%。
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Cited By (6)
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---|---|---|---|---|
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US11079677B2 (en) | 2017-02-20 | 2021-08-03 | Fujifilm Corporation | Chemical liquid, chemical liquid storage body, and pattern forming method |
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Families Citing this family (50)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MY143399A (en) * | 2001-07-09 | 2011-05-13 | Avantor Performance Mat Inc | Microelectronic cleaning compositons containing ammonia-free fluoride salts for selective photoresist stripping and plasma ash residue cleaning |
US7399365B2 (en) * | 2003-04-18 | 2008-07-15 | Ekc Technology, Inc. | Aqueous fluoride compositions for cleaning semiconductor devices |
CN1954267B (zh) * | 2004-02-11 | 2010-12-08 | 马林克罗特贝克公司 | 含有卤素含氧酸、其盐及其衍生物的微电子清洗组合物 |
EP1847880A3 (en) | 2004-02-11 | 2010-02-17 | Mallinckrodt Baker, Inc. | Composition for cleaning microelectronic substrates containing halogen oxygen acids and derivatives thereof |
SG150509A1 (en) * | 2004-03-01 | 2009-03-30 | Mallinckrodt Baker Inc | Nanoelectronic and microelectronic cleaning compositions |
JP4524744B2 (ja) * | 2004-04-14 | 2010-08-18 | 日本電気株式会社 | 有機マスクの形成方法及び該有機マスクを利用したパターン形成方法 |
US7867779B2 (en) | 2005-02-03 | 2011-01-11 | Air Products And Chemicals, Inc. | System and method comprising same for measurement and/or analysis of particles in gas stream |
US8044009B2 (en) * | 2005-04-04 | 2011-10-25 | Avantor Performance Materials, Inc. | Compositions for cleaning ion implanted photoresist in front end of line applications |
CN101171551B (zh) * | 2005-05-06 | 2012-12-26 | 安万托特性材料股份有限公司 | 用于清除蚀刻后和灰化的光致抗蚀剂残余物及大部分光致抗蚀剂的组合物 |
CN1862392B (zh) * | 2005-05-13 | 2011-08-03 | 安集微电子(上海)有限公司 | 一种去除光阻层的组合物及其使用方法 |
CN1862391B (zh) * | 2005-05-13 | 2013-07-10 | 安集微电子(上海)有限公司 | 除光阻层的组合物及其使用方法 |
JP2008546214A (ja) * | 2005-06-06 | 2008-12-18 | アドバンスド テクノロジー マテリアルズ,インコーポレイテッド | 集積された化学機械研磨組成物および単一プラテン処理のためのプロセス |
KR101477455B1 (ko) * | 2005-06-07 | 2014-12-29 | 어드밴스드 테크놀러지 머티리얼즈, 인코포레이티드 | 금속 및 유전체 상용성 희생 반사 방지 코팅 세정 및 제거 조성물 |
KR101221560B1 (ko) * | 2005-09-02 | 2013-01-14 | 주식회사 동진쎄미켐 | 변성된 포토레지스트 제거를 위한 반도체 소자용 박리액조성물 |
JP2009512194A (ja) | 2005-10-05 | 2009-03-19 | アドバンスド テクノロジー マテリアルズ,インコーポレイテッド | ポストエッチング残渣を除去するための酸化性水性洗浄剤 |
WO2007111694A2 (en) * | 2005-11-09 | 2007-10-04 | Advanced Technology Materials, Inc. | Composition and method for recycling semiconductor wafers having low-k dielectric materials thereon |
KR101319113B1 (ko) * | 2006-04-13 | 2013-10-17 | 동우 화인켐 주식회사 | 금속용 세정제 |
KR101636996B1 (ko) * | 2006-12-21 | 2016-07-07 | 엔테그리스, 아이엔씨. | 에칭 후 잔류물의 제거를 위한 액체 세정제 |
WO2008114616A1 (ja) * | 2007-03-16 | 2008-09-25 | Mitsubishi Gas Chemical Company, Inc. | 洗浄用組成物、半導体素子の製造方法 |
JP4952375B2 (ja) * | 2007-05-23 | 2012-06-13 | 株式会社明電舎 | レジスト除去方法及びその装置 |
US8110508B2 (en) * | 2007-11-22 | 2012-02-07 | Samsung Electronics Co., Ltd. | Method of forming a bump structure using an etching composition for an under bump metallurgy layer |
US20100320457A1 (en) * | 2007-11-22 | 2010-12-23 | Masahito Matsubara | Etching solution composition |
CN101889330B (zh) | 2007-12-04 | 2012-11-14 | 株式会社明电舍 | 除去抗蚀剂的方法和用于它的装置 |
CN101359189B (zh) * | 2008-09-17 | 2011-04-27 | 电子科技大学 | 正性光敏聚酰亚胺光刻胶用显影液 |
US20100178887A1 (en) | 2009-01-13 | 2010-07-15 | Millam Michael J | Blast shield for use in wireless transmission system |
WO2010098899A1 (en) * | 2009-02-25 | 2010-09-02 | Mallinckrodt Baker, Inc. | Multipurpose acidic, organic solvent based microelectronic cleaning composition |
EP2401352B1 (en) * | 2009-02-25 | 2013-06-12 | Avantor Performance Materials, Inc. | Stripping compositions for cleaning ion implanted photoresist from semiconductor device wafers |
US8754021B2 (en) | 2009-02-27 | 2014-06-17 | Advanced Technology Materials, Inc. | Non-amine post-CMP composition and method of use |
WO2010150135A2 (en) * | 2009-06-25 | 2010-12-29 | Lam Research Ag | Method for treating a semiconductor wafer |
KR20120092501A (ko) * | 2009-06-25 | 2012-08-21 | 램 리서치 아게 | 반도체 웨이퍼의 처리 방법 |
SI2348142T1 (sl) | 2010-01-25 | 2019-03-29 | Westinghouse Electric Company Llc | Postopek in pripravek za odstranjevanje usedlin vodnega kamna s kovinskih površin v generatorju pare |
CA3075329C (en) | 2010-01-26 | 2022-11-01 | Dominion Engineering, Inc. | Method and composition for removing deposits |
CN101908503A (zh) * | 2010-07-21 | 2010-12-08 | 河北工业大学 | 超大规模集成电路多层铜布线化学机械抛光后的洁净方法 |
US8921295B2 (en) | 2010-07-23 | 2014-12-30 | American Sterilizer Company | Biodegradable concentrated neutral detergent composition |
CN101968610A (zh) * | 2010-08-12 | 2011-02-09 | 武汉华灿光电有限公司 | 一种全湿刻蚀后去胶的方法 |
CN105869997A (zh) * | 2011-10-21 | 2016-08-17 | 安格斯公司 | 无胺cmp后组合物及其使用方法 |
JP6066552B2 (ja) * | 2011-12-06 | 2017-01-25 | 関東化學株式会社 | 電子デバイス用洗浄液組成物 |
CN104508072A (zh) | 2012-02-15 | 2015-04-08 | 安格斯公司 | 用于cmp后去除的组合物及使用方法 |
KR101827756B1 (ko) * | 2012-12-03 | 2018-02-12 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | 반도체소자용 세정액 및 이를 이용한 세정방법 |
JP2015108041A (ja) * | 2013-12-03 | 2015-06-11 | ダイキン工業株式会社 | 洗浄用組成物 |
WO2015119925A1 (en) * | 2014-02-05 | 2015-08-13 | Advanced Technology Materials, Inc. | Non-amine post-cmp compositions and method of use |
CN103955123A (zh) * | 2014-04-11 | 2014-07-30 | 武汉高芯科技有限公司 | 一种离子注入后晶片的湿法去胶液及光刻胶去除方法 |
US9908821B2 (en) | 2015-09-29 | 2018-03-06 | Winfield Solutions, Llc | Micronutrient compositions and systems and methods of using same |
US9938201B1 (en) | 2016-02-25 | 2018-04-10 | Winfield Solutions, Llc | Micronutrient compositions containing zinc and systems and methods of using same |
CN114706271A (zh) | 2016-03-31 | 2022-07-05 | 富士胶片株式会社 | 半导体制造用处理液及图案形成方法 |
AT519943A1 (de) * | 2017-04-29 | 2018-11-15 | Thonhauser Gmbh | Zusammensetzung |
CN113287187A (zh) | 2019-01-11 | 2021-08-20 | 弗萨姆材料美国有限责任公司 | 氧化铪腐蚀抑制剂 |
JP7271993B2 (ja) * | 2019-02-19 | 2023-05-12 | 三菱ケミカル株式会社 | セリウム化合物除去用洗浄液、洗浄方法及び半導体ウェハの製造方法 |
TWI824299B (zh) * | 2020-09-22 | 2023-12-01 | 美商恩特葛瑞斯股份有限公司 | 蝕刻劑組合物 |
US20230033363A1 (en) * | 2021-07-23 | 2023-02-02 | Ascend Performance Materials Operations Llc | Aqueous solutions containing amino carboxylic acid chelators |
Family Cites Families (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3673099A (en) * | 1970-10-19 | 1972-06-27 | Bell Telephone Labor Inc | Process and composition for stripping cured resins from substrates |
BE789090A (fr) * | 1971-09-22 | 1973-01-15 | Western Electric Co | Procede et solution d'attaque de semi-conducteurs |
US4096243A (en) * | 1976-02-09 | 1978-06-20 | Clairol Incorporated | Composition for lightening hair containing an oxidizing agent and certain quaternary amines |
FR2372904A1 (fr) * | 1976-11-19 | 1978-06-30 | Ibm | Composition de decapage du silicium polycristallin contenant de l'hydroxyde de tetramethylammonium et procede d'application |
JPS60203944A (ja) * | 1984-03-28 | 1985-10-15 | Mitsubishi Gas Chem Co Inc | ポジ型フオトレジストの除去法 |
US4744834A (en) * | 1986-04-30 | 1988-05-17 | Noor Haq | Photoresist stripper comprising a pyrrolidinone, a diethylene glycol ether, a polyglycol and a quaternary ammonium hydroxide |
US5037724A (en) * | 1988-02-25 | 1991-08-06 | Hoya Corporation | Peeling solution for photo- or electron beam-sensitive resin |
US5002687A (en) * | 1989-04-13 | 1991-03-26 | Lever Brothers Company, Division Of Conopco, Inc. | Fabric washing compositions |
DE69027774T2 (de) * | 1990-10-22 | 1997-02-20 | Procter & Gamble | Stabile, flüssige Reinigungsmittel enthaltend ein Bleichmittel |
TW263531B (zh) * | 1992-03-11 | 1995-11-21 | Mitsubishi Gas Chemical Co | |
JP3183310B2 (ja) * | 1992-09-25 | 2001-07-09 | 三菱瓦斯化学株式会社 | 半導体基板の洗浄液 |
US5308745A (en) * | 1992-11-06 | 1994-05-03 | J. T. Baker Inc. | Alkaline-containing photoresist stripping compositions producing reduced metal corrosion with cross-linked or hardened resist resins |
US5498293A (en) * | 1994-06-23 | 1996-03-12 | Mallinckrodt Baker, Inc. | Cleaning wafer substrates of metal contamination while maintaining wafer smoothness |
DE69636618T2 (de) * | 1995-07-27 | 2007-08-30 | Mitsubishi Chemical Corp. | Verfahren zur behandlung einer substratoberfläche und behandlungsmittel hierfür |
US5911836A (en) * | 1996-02-05 | 1999-06-15 | Mitsubishi Gas Chemical Company, Inc. | Method of producing semiconductor device and rinse for cleaning semiconductor device |
US6096138A (en) * | 1997-04-30 | 2000-08-01 | Bausch & Lomb Incorporated | Method for inhibiting the deposition of protein on contact lens |
US5989353A (en) * | 1996-10-11 | 1999-11-23 | Mallinckrodt Baker, Inc. | Cleaning wafer substrates of metal contamination while maintaining wafer smoothness |
US5993685A (en) * | 1997-04-02 | 1999-11-30 | Advanced Technology Materials | Planarization composition for removing metal films |
JPH11121418A (ja) * | 1997-10-14 | 1999-04-30 | Kao Corp | 洗浄剤組成物及び洗浄方法 |
IL139546A (en) * | 1998-05-18 | 2005-08-31 | Mallinckrodt Inc | Silicate-containing alkaline compositions for cleaning microelectronic substrates |
JP2000056478A (ja) * | 1998-08-04 | 2000-02-25 | Showa Denko Kk | サイドウォール除去液 |
JP2000202617A (ja) * | 1999-01-06 | 2000-07-25 | Nippon Steel Corp | 溶融金属容器の調心・傾転装置 |
EP1039518A1 (en) * | 1999-03-24 | 2000-09-27 | Interuniversitair Micro-Elektronica Centrum Vzw | Chemical solution and method for reducing the metal contamination on the surface of a semiconductor substrate |
JP4224652B2 (ja) * | 1999-03-08 | 2009-02-18 | 三菱瓦斯化学株式会社 | レジスト剥離液およびそれを用いたレジストの剥離方法 |
JP2002113431A (ja) * | 2000-10-10 | 2002-04-16 | Tokyo Electron Ltd | 洗浄方法 |
US6599370B2 (en) * | 2000-10-16 | 2003-07-29 | Mallinckrodt Inc. | Stabilized alkaline compositions for cleaning microelectronic substrates |
EP1211563B1 (en) * | 2000-11-30 | 2011-12-21 | Tosoh Corporation | Resist stripper composition |
JP2003005383A (ja) * | 2000-11-30 | 2003-01-08 | Tosoh Corp | レジスト剥離剤 |
JP4267359B2 (ja) * | 2002-04-26 | 2009-05-27 | 花王株式会社 | レジスト用剥離剤組成物 |
-
2003
- 2003-05-27 JP JP2004511910A patent/JP4304154B2/ja not_active Expired - Fee Related
- 2003-05-27 KR KR1020047019578A patent/KR100958069B1/ko active IP Right Grant
- 2003-05-27 RS YUP-1062/04A patent/RS50930B/sr unknown
- 2003-05-27 CN CN2011100064160A patent/CN102061228B/zh not_active Expired - Lifetime
- 2003-05-27 CA CA002488735A patent/CA2488735A1/en not_active Abandoned
- 2003-05-27 AU AU2003238773A patent/AU2003238773A1/en not_active Abandoned
- 2003-05-27 US US10/515,392 patent/US7419945B2/en not_active Expired - Lifetime
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- 2003-05-27 EP EP08075596A patent/EP2034365A3/en not_active Withdrawn
- 2003-05-27 CN CN038130351A patent/CN1659481A/zh active Pending
- 2003-05-27 WO PCT/US2003/016828 patent/WO2003104900A2/en active Application Filing
- 2003-05-27 BR BR0311827-4A patent/BR0311827A/pt not_active IP Right Cessation
- 2003-05-27 EP EP03734237A patent/EP1520211A2/en not_active Withdrawn
- 2003-06-03 TW TW092115125A patent/TWI322827B/zh not_active IP Right Cessation
- 2003-06-06 MY MYPI20032125A patent/MY139208A/en unknown
-
2004
- 2004-11-29 ZA ZA200409621A patent/ZA200409621B/en unknown
- 2004-12-06 IL IL165580A patent/IL165580A/en unknown
- 2004-12-07 IN IN2761CH2004 patent/IN2004CH02761A/en unknown
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2005
- 2005-01-06 NO NO20050076A patent/NO20050076L/no not_active Application Discontinuation
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105378901A (zh) * | 2013-07-05 | 2016-03-02 | 和光纯药工业株式会社 | 蚀刻剂、蚀刻方法和蚀刻剂制备液 |
CN105017973A (zh) * | 2014-04-25 | 2015-11-04 | 台湾积体电路制造股份有限公司 | 用于硬化的流体材料的cmp浆料溶液 |
CN105017973B (zh) * | 2014-04-25 | 2018-10-23 | 台湾积体电路制造股份有限公司 | 用于硬化的流体材料的cmp浆料溶液 |
US11079677B2 (en) | 2017-02-20 | 2021-08-03 | Fujifilm Corporation | Chemical liquid, chemical liquid storage body, and pattern forming method |
TWI742246B (zh) * | 2017-02-20 | 2021-10-11 | 日商富士軟片股份有限公司 | 藥液、藥液收容體及圖案形成方法 |
CN107338126A (zh) * | 2017-06-23 | 2017-11-10 | 昆山欣谷微电子材料有限公司 | 一种水基微电子剥离和清洗液组合物 |
US11549086B2 (en) | 2017-07-25 | 2023-01-10 | Shanghai Sinyang Semiconductor Materials Co., Ltd. | Cleaning agent and preparation method and use thereof |
CN112430508A (zh) * | 2020-12-09 | 2021-03-02 | 淄博鑫欧瑞环保科技有限公司 | 一种消毒粉雾化装置清洁剂、应用及其清洁方法 |
Also Published As
Publication number | Publication date |
---|---|
KR20050019103A (ko) | 2005-02-28 |
AU2003238773A1 (en) | 2003-12-22 |
KR100958069B1 (ko) | 2010-05-17 |
CN102061228B (zh) | 2013-02-13 |
BR0311827A (pt) | 2005-03-29 |
WO2003104900A3 (en) | 2004-02-19 |
IL165580A (en) | 2009-05-04 |
RS50930B (sr) | 2010-08-31 |
ZA200409621B (en) | 2006-07-26 |
NO20050076L (no) | 2005-01-06 |
US20050239673A1 (en) | 2005-10-27 |
EP1520211A2 (en) | 2005-04-06 |
US7419945B2 (en) | 2008-09-02 |
JP2005529487A (ja) | 2005-09-29 |
CN1659481A (zh) | 2005-08-24 |
TWI322827B (en) | 2010-04-01 |
IN2004CH02761A (zh) | 2006-02-10 |
PL208299B1 (pl) | 2011-04-29 |
PL373809A1 (en) | 2005-09-19 |
JP4304154B2 (ja) | 2009-07-29 |
EP2034365A2 (en) | 2009-03-11 |
MY139208A (en) | 2009-08-28 |
TW200407419A (en) | 2004-05-16 |
RS106204A (en) | 2007-02-05 |
IL165580A0 (en) | 2006-01-15 |
CA2488735A1 (en) | 2003-12-18 |
WO2003104900A2 (en) | 2003-12-18 |
EP2034365A3 (en) | 2009-11-11 |
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