TWI292437B - Ammonia-free alkaline microelectronic cleaning compositions with improved substrate compatibility - Google Patents
Ammonia-free alkaline microelectronic cleaning compositions with improved substrate compatibility Download PDFInfo
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- TWI292437B TWI292437B TW091115168A TW91115168A TWI292437B TW I292437 B TWI292437 B TW I292437B TW 091115168 A TW091115168 A TW 091115168A TW 91115168 A TW91115168 A TW 91115168A TW I292437 B TWI292437 B TW I292437B
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- cleaning composition
- cleaning
- water
- ammonia
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- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 238000004140 cleaning Methods 0.000 title claims abstract description 61
- 239000000758 substrate Substances 0.000 title claims abstract description 15
- 238000004377 microelectronic Methods 0.000 title claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000003989 dielectric material Substances 0.000 claims abstract description 18
- 238000001465 metallisation Methods 0.000 claims abstract description 15
- 230000000269 nucleophilic effect Effects 0.000 claims abstract description 9
- 150000002500 ions Chemical class 0.000 claims abstract 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 35
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 29
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910021529 ammonia Inorganic materials 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- RJLKIAGOYBARJG-UHFFFAOYSA-N 1,3-dimethylpiperidin-2-one Chemical compound CC1CCCN(C)C1=O RJLKIAGOYBARJG-UHFFFAOYSA-N 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- 239000002738 chelating agent Substances 0.000 claims description 7
- 238000005260 corrosion Methods 0.000 claims description 7
- 230000007797 corrosion Effects 0.000 claims description 7
- -1 salt anion Chemical class 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000006184 cosolvent Substances 0.000 claims description 5
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 150000002222 fluorine compounds Chemical class 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 2
- 150000001621 bismuth Chemical class 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 4
- 150000005622 tetraalkylammonium hydroxides Chemical group 0.000 claims 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 2
- PCTMTFRHKVHKIS-BMFZQQSSSA-N (1s,3r,4e,6e,8e,10e,12e,14e,16e,18s,19r,20r,21s,25r,27r,30r,31r,33s,35r,37s,38r)-3-[(2r,3s,4s,5s,6r)-4-amino-3,5-dihydroxy-6-methyloxan-2-yl]oxy-19,25,27,30,31,33,35,37-octahydroxy-18,20,21-trimethyl-23-oxo-22,39-dioxabicyclo[33.3.1]nonatriaconta-4,6,8,10 Chemical compound C1C=C2C[C@@H](OS(O)(=O)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2.O[C@H]1[C@@H](N)[C@H](O)[C@@H](C)O[C@H]1O[C@H]1/C=C/C=C/C=C/C=C/C=C/C=C/C=C/[C@H](C)[C@@H](O)[C@@H](C)[C@H](C)OC(=O)C[C@H](O)C[C@H](O)CC[C@@H](O)[C@H](O)C[C@H](O)C[C@](O)(C[C@H](O)[C@H]2C(O)=O)O[C@H]2C1 PCTMTFRHKVHKIS-BMFZQQSSSA-N 0.000 claims 1
- DHBZRQXIRAEMRO-UHFFFAOYSA-N 1,1,2,2-tetramethylhydrazine Chemical compound CN(C)N(C)C DHBZRQXIRAEMRO-UHFFFAOYSA-N 0.000 claims 1
- FCKYPQBAHLOOJQ-UWVGGRQHSA-N 2-[[(1s,2s)-2-[bis(carboxymethyl)amino]cyclohexyl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)[C@H]1CCCC[C@@H]1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UWVGGRQHSA-N 0.000 claims 1
- LTACQVCHVAUOKN-UHFFFAOYSA-N 3-(diethylamino)propane-1,2-diol Chemical compound CCN(CC)CC(O)CO LTACQVCHVAUOKN-UHFFFAOYSA-N 0.000 claims 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 claims 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims 1
- 240000006394 Sorghum bicolor Species 0.000 claims 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 claims 1
- 150000001622 bismuth compounds Chemical class 0.000 claims 1
- HQFQTTNMBUPQAY-UHFFFAOYSA-N cyclobutylhydrazine Chemical compound NNC1CCC1 HQFQTTNMBUPQAY-UHFFFAOYSA-N 0.000 claims 1
- JGGQWILNAAODRS-UHFFFAOYSA-N n-methyl-4-[4-(methylamino)phenyl]aniline Chemical compound C1=CC(NC)=CC=C1C1=CC=C(NC)C=C1 JGGQWILNAAODRS-UHFFFAOYSA-N 0.000 claims 1
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 13
- 239000002904 solvent Substances 0.000 abstract description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 2
- 150000001408 amides Chemical class 0.000 abstract description 2
- 150000002484 inorganic compounds Chemical class 0.000 abstract description 2
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 150000002902 organometallic compounds Chemical class 0.000 abstract description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000006117 anti-reflective coating Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 4
- 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 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 229940120146 EDTMP Drugs 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 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
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 239000012038 nucleophile Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 2
- WYMDDFRYORANCC-UHFFFAOYSA-N 2-[[3-[bis(carboxymethyl)amino]-2-hydroxypropyl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)CN(CC(O)=O)CC(O)=O WYMDDFRYORANCC-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- 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 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229960004106 citric acid Drugs 0.000 description 2
- 230000009918 complex formation Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940074391 gallic acid Drugs 0.000 description 2
- 235000004515 gallic acid Nutrition 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- DVUVKWLUHXXIHK-UHFFFAOYSA-N tetraazanium;tetrahydroxide Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[OH-].[OH-].[OH-].[OH-] DVUVKWLUHXXIHK-UHFFFAOYSA-N 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- 239000010455 vermiculite Substances 0.000 description 2
- 229910052902 vermiculite Inorganic materials 0.000 description 2
- 235000019354 vermiculite Nutrition 0.000 description 2
- AMLFJZRZIOZGPW-NSCUHMNNSA-N (e)-prop-1-en-1-amine Chemical compound C\C=C\N AMLFJZRZIOZGPW-NSCUHMNNSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 1
- FQERLIOIVXPZKH-UHFFFAOYSA-N 1,2,4-trioxane Chemical compound C1COOCO1 FQERLIOIVXPZKH-UHFFFAOYSA-N 0.000 description 1
- WDQFELCEOPFLCZ-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrolidin-2-one Chemical compound OCCN1CCCC1=O WDQFELCEOPFLCZ-UHFFFAOYSA-N 0.000 description 1
- GGYVTHJIUNGKFZ-UHFFFAOYSA-N 1-methylpiperidin-2-one Chemical compound CN1CCCCC1=O GGYVTHJIUNGKFZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RAEOEMDZDMCHJA-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-[2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]ethyl]amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CCN(CC(O)=O)CC(O)=O)CC(O)=O RAEOEMDZDMCHJA-UHFFFAOYSA-N 0.000 description 1
- ZIMXAFGAUMQPMG-UHFFFAOYSA-N 2-[4-[bis(carboxymethyl)amino]butyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCCCN(CC(O)=O)CC(O)=O ZIMXAFGAUMQPMG-UHFFFAOYSA-N 0.000 description 1
- XWSGEVNYFYKXCP-UHFFFAOYSA-N 2-[carboxymethyl(methyl)amino]acetic acid Chemical compound OC(=O)CN(C)CC(O)=O XWSGEVNYFYKXCP-UHFFFAOYSA-N 0.000 description 1
- KKMOSYLWYLMHAL-UHFFFAOYSA-N 2-bromo-6-nitroaniline Chemical compound NC1=C(Br)C=CC=C1[N+]([O-])=O KKMOSYLWYLMHAL-UHFFFAOYSA-N 0.000 description 1
- VYQMXBMNWDFBHM-UHFFFAOYSA-K 2-hydroxypropane-1,2,3-tricarboxylate tetramethylazanium Chemical group C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.OC(CC([O-])=O)(CC([O-])=O)C([O-])=O VYQMXBMNWDFBHM-UHFFFAOYSA-K 0.000 description 1
- WIBQNXUVQNMAOI-UHFFFAOYSA-N 3-(dimethylamino)propane-1,1-diol Chemical compound CN(C)CCC(O)O WIBQNXUVQNMAOI-UHFFFAOYSA-N 0.000 description 1
- KWYJDIUEHHCHCZ-UHFFFAOYSA-N 3-[2-[bis(2-carboxyethyl)amino]ethyl-(2-carboxyethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CCC(O)=O)CCN(CCC(O)=O)CCC(O)=O KWYJDIUEHHCHCZ-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
- VCUVETGKTILCLC-UHFFFAOYSA-N 5,5-dimethyl-1-pyrroline N-oxide Chemical compound CC1(C)CCC=[N+]1[O-] VCUVETGKTILCLC-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 1
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- 241000283153 Cetacea Species 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
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- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 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 1
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- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
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- VYTBPJNGNGMRFH-UHFFFAOYSA-N acetic acid;azane Chemical compound N.N.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O VYTBPJNGNGMRFH-UHFFFAOYSA-N 0.000 description 1
- RUSUZAGBORAKPY-UHFFFAOYSA-N acetic acid;n'-[2-(2-aminoethylamino)ethyl]ethane-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCNCCN RUSUZAGBORAKPY-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical class [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000005588 carbonic acid salt group Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229940075419 choline hydroxide Drugs 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- 229960002433 cysteine Drugs 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 235000021312 gluten Nutrition 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 229960000448 lactic acid Drugs 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 229940098895 maleic acid Drugs 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- IWYDHOAUDWTVEP-UHFFFAOYSA-N mandelic acid Chemical compound OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 1
- 229960002510 mandelic acid Drugs 0.000 description 1
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000011824 nuclear material Substances 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229940116315 oxalic acid Drugs 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229960003540 oxyquinoline Drugs 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- NAYYNDKKHOIIOD-UHFFFAOYSA-N phthalamide Chemical compound NC(=O)C1=CC=CC=C1C(N)=O NAYYNDKKHOIIOD-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- WJZPIORVERXPPR-UHFFFAOYSA-L tetramethylazanium;carbonate Chemical compound [O-]C([O-])=O.C[N+](C)(C)C.C[N+](C)(C)C WJZPIORVERXPPR-UHFFFAOYSA-L 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- 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
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
-
- 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
- C11D3/16—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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic 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
- C11D3/43—Solvents
-
- 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
- C11D7/3209—Amines or imines with one to four nitrogen atoms; 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
- 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
-
- 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
- C11D7/3263—Amides or imides
-
- 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
- C11D7/3281—Heterocyclic compounds
-
- 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
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5013—Organic solvents containing nitrogen
-
- 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
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
-
- 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
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/426—Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides
-
- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
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- 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
- C11D7/34—Organic compounds containing sulfur
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Detergent Compositions (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Description
1292437 A7
-4- 發明範疇 發^係關於用以清潔微電子基板之不含氨之清潔組合 物特疋3 <,係關於有效且對微電子基板具有增進相容 :之此類清潔組合物,纟中之微電子基板特徵為:靈敏之 夕3、低K和问κ介電材料及銅金屬化。本發明亦關於使用 此頜巧潔、、且5物來剝離光阻劑,清除自電漿產生之有機、 有機金屬和無機化合物之殘渣,及清除來自平坦化過程例 如化予機械研磨法(CMp)之殘渣,以及清除平坦化漿體殘 渣中之添加劑。 發明背景 業已建議許多光阻劑剝除劑和殘渣移除劑供使用於微電 子頃域中作為生產線清潔者的下游或後端。在製造過程中 將光阻劑之薄膜沉積在晶圓基板上,然後將電路設計成 像在薄膜上。接著烘焙後,將未聚合之阻體使用光阻劑顯 影劑移去。然後將所得之像經由反應性電漿蝕刻氣體或化 學蝕刻液轉移至下層材料(通常其為介電質或金屬)上。蝕 刻劑氣體或化學蝕刻液選擇性侵蝕基板上未受光阻劑保護 <區域。電漿蝕刻程序之結果,光阻劑,蝕刻氣體和經蝕 刻之材料副產物沉積成為殘渣,其環繞在基板上經蝕刻之 開口的側壁或在其上。 另外,接著蝕刻步驟終止後,必須將光罩自晶圓的受保 護區域上移去以便可進行最後完工操作。此可以電漿砂磨 步驟,經由使用適當電漿砂磨氣體成濕化學汽提劑而達成 。尋找用於移除此光罩材料之適當清潔組合物而不致不利 78900-950519.doc 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐)
裝 訂
1292437 A7 -------- B7 五、發明説明(2 ) 影響(例如腐#、溶解或減弱)金屬電路亦是_問題。 由於微電子製造’積體層次增加及圖型形成之微電子元 件尺寸縮小,目此,該項技藝中已變成且漸普遍採用銅金 屬化、,多孔,低K和高K介電材料。此等材料對於尋求合格 之β潔組合物王現另外之難題。先前為了含有或 Al(Cu)/Si〇2結構之"傳統”或”習用,,半導體元件所發展之許 多製2組合物不能用於銅金屬化之似或高時電結構。舉 例而言,以羥胺為主之剥離劑或殘渣移除劑組合物成功地 使用於清潔具有A1金屬化之元件但是其實際上不適合於具 有銅金屬化之元件。相似地,除非顯著調整組成,否則, 許多銅金屬化/低κ剝離劑不適合於八〖金屬化之元件。 接著蝕刻及/或砂磨程序後,移除此等蝕劑及/或砂磨殘 渣證明是一困難。不能完全移除或中和此等殘渣可導致水 刀之及收並形成可對金屬結構造成腐蚀之所不欲物質。電 路組件材料由該等所不欲之物質所腐蝕並在電路組件配線 中產生斷續性及所不欲之電阻增加。 現行後端清潔劑顯示與某些靈敏介電材料和金屬化之廣 大範圍的相容性,範圍自完全不合格之少許令人滿意。= 多現行剥離劑或殘渣清除劑不合格用於先進之互連材料例 如低K與高K介電材料和銅金屬化。另外,所採用之一般鹼 性清潔溶液對於低K和高κ介電材料及/或銅金屬化過度侵 蝕。而且,許多的此等鹼性清潔組合物含有有機溶劑以致 顯示不良之產物穩定性,尤其在較高pH範圍及在較高之處 理溫度時。 78900-950519.doc -5- 1292437
-6 - 本發明之概要 因此,須要適合於後端清潔操作之微電子清潔組合物。 此類組合物是有效之清潔劑而可應用於剝離光阻劑,清潔 自電漿過程所產生之有機,有機金屬和無機物質之殘渣, 及清除來自平坦化過程例如化學機械研磨法及類似者之殘 渣。本發明係關於剝離光阻劑,製備/清潔半導體表面及具 有與先進之互連材料和銅金屬化良好相容性之結構而有效 之組合物。 頃發現之氨(NH3)和氨衍生之鹼例如氫氧化銨和其他鹽 類(NhX ’ X=〇H,碳酸鹽等)能通過錯合物形成而溶解腐 蝕金屬’例如銅。因此,當需要與多孔、低κ和高κ介電材 料和銅金屬化之相容性時,不選擇使用氨和氨衍生之鹼在 半導體清潔調配物中。此等化合物通過平衡程序可產生氨 。氨與各種金屬例如銅可形成錯合物而導致金屬腐蝕/溶解 如下列方程式中所特舉出。 NH4XeNH3 + ΗΧ (方程式 1)
Cu+2 NH3— [Cn(NH3)2]+4 [Cu(NH3)2]2+ (方程式 2) 因此,氫氧化銨和銨鹽通過方程式1中所述之平衡程序可 產生親核和金屬螫合之氨(nh3),尤其需添加其鹼例如胺類 和烷醇胺時。在氧氣之存在下,金屬例如銅可通過與氨之 錯合物成形而被溶解/腐蚀如方程式2中所述。此錯合物成 形可更進一步移動平衡(方程式1)向右而產生更多的氨,導 致較高之金屬溶解/腐蝕。 通常,靈敏之低κ介電材料在強鹼條件下顯著降解。氨和 78900-950519.doc 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐)
裝 訂
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-7 - (HS〇f:驗亦顯示與靈敏之介電材料例如,三氧切燒 ,和甲基梦倍半氧燒(MSQ)不良相容性。又,彼等= 解風及/或其他親核物而因此導致靈敏介電材料的反應/降 頃發現二無氨製造強鹼鹼性清潔調配物(其中含有非親核 ^正電荷之抗衡離子(例如四烷基銨)在位阻醯胺溶劑中) 拎二與噩敏之多孔,低κ和高κ介電材料和銅金屬化之大為 C相谷性。由於空間阻礙效應及/或低或無親核反應之反 怎性(關於親核物,例如氫氧化物離子),較佳之溶劑基體 鹼狀況。由於所不欲之親核物不存在於組合物中,可 4刀獲得改良之介電材料相容性。與銅金屬化之良好相容 f生係由選擇使用某些.與鋼可相容之位阻醯胺溶劑而獲得。 可將此等組份調配成半含水至實際上無水(以有機溶劑為 基底)清潔溶液或漿體。 發明之詳細敘述 本發明之新穎後端清潔組合物可包括一或數種任何適當 播氨製造之強驗其中含有非親核性,正電荷之抗衡離子及 在強驗狀況下穩疋之一或數種的任何適當位阻酿胺溶劑。 在適當無氨製造強鹼(其中含有適合供使用於本發明之清 潔組合物中之非親核性,正電荷之抗衡離子)中,可述及卞 式的氫氧化四燒(基)铵: [(R)4N+]p[xrq 其中每一個R獨立是一種經取代或未經取代之烷基,較隹 具有自1至22個碳原子(更佳自1至6個碳原子)之燒基或羧 78900-950519.doc 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐)
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A7 B7 1292431 G91115168號專利申請案 中文說明書替換頁(95年12月) 五、發明説明(5 ) -:~~' 燒基(R矣H);而X係0H或一個適當鹽陰離子,例如碳酸鹽 及類似者;而p和q相等而是1至3之整數。適當強鹼亦包括 KOH和NaOH。含有無氨製造之強驗(其中含有非親核性, 正電荷之抗衡離子)之清潔組合物顯示與低κ介電材料和銅 金屬化大為增進之相容性。不含氨之氫氧化四烷銨(TAAH) 是極強鹼,尚發現彼等提供與具有氫氧化銨之清潔組合物 比較,出人意料以外增進之低κ相容性。特佳者是氫氧化四 甲銨、氫氧化四丁銨,膽鹼氫氧化物及碳酸四甲銨。 雖然控制或抑制金屬腐蝕之先前嘗試包括以<2重量%的 相當低濃度仔細控制pH值及/或使用抑制腐蝕之化合物例 如苯并三唑(BT),但是頃發現:當採用一或數種位阻醯胺 溶劑時,可將控制銅金屬腐蚀之出人意料外,顯著改進提 供至本發明之清潔組合物。可採用任何適當之位阻醯胺溶 劑在本發明之清潔組合物中。較佳作為此類位阻醯胺溶劑 者是具有下列各式的受阻無環及受阻環狀醯胺。 R1CONR2R3 及 ^(CFliRs)^-----> ^CReR/CONRe 其中η是1至22之數字,較佳1至6 ;而l,R2,R3,R4, 78900-951204.doc -8- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 1292437 A7 B7 五、發明説明(6 ) " R5,R0,R7和每一者獨立係選自Η,烷基(經取代或未經 取代)’較佳具有自1至6個碳原子之烷基,及芳基(經取代 或未經取代),較佳具有自3至14個碳原子之芳基),其附帶 條件為:Ri ’ R2和R3之至少一者及R4,r5,R6,心和心之 至少一者不是氫。 此類位阻醯胺無環溶劑的某些適當實例,舉例而言包括 乙醯胺、二曱基甲醯胺(DMF)、N,N,-二甲基乙醯胺(DMAc) ,苯醯胺及其類似物。位阻環狀醯胺的某些適當實例,舉 例而言,包括N-甲基-2_吡咯啶酮(NMp)、ι,5-二甲基-2-吡 咯哫酮、1,3-二甲基-2-哌啶酮、1_(2_羥乙基)2_吡咯啶酮, 1二甲基-2-旅淀酮及其類似物。 可含有操歲製造之強驗之本發明清潔組合物調配成為 含水、半含水或含有機溶劑之組合物。可將含有非親核性 ’正電荷抗衡離子之無氨製造強鹼單獨連同位阻醯胺溶劑 而使用或與其他穩定溶劑較佳係耐強鹼之一或數種極性有 機落劑併用且此類極性有機溶劑不含未受阻之親核化合物 ,例如二甲亞颯(DMS0)、環丁砜(SFL)、二甲基哌啶酮、 二乙醇胺、三乙醇胺、2-(甲胺基)乙醇、3-(二甲胺基) 丙二醇及其類似物。該清潔組合物亦可視需要含有有機或 供機紅(較佳是弱有機或無機酸),受阻胺、受阻燒醇胺、 受阻羥胺及其他腐蝕抑制劑,例如苯并三唑、鄰苯二酚、 甘油、乙二醇及其類似物。該等清潔組合物亦可含有任何 適當界面活性劑舉例而言,例如二甲基己块醇(Surfyn〇1_61) ,羥乙基化之四甲基癸炔二醇(Surfyn〇i_465),聚四氟乙埽 78900-950519.doc _ 9 _ 本紙張尺度適用中@國家料(CNS) Μ規格(21GX 297公爱) ---- 1292437 A7 B7 五、發明説明(7 ) ,鯨虫鼠氧基丙基甜菜驗(Zonyl FSK),(Zonyl FSH)及其類似物 。因此,可使用廣大範圍的加工/操作pH值和溫度來有效移 除和清潔光阻劑,電聚姓刻/砂磨後之殘澄,犧牲性吸收光 之物負及抗反射塗層(ARC)。亦經發現:某些的此型調配 物用來清潔其結構中含有鈕(例如鉍(Ta)或氮化鈕障壁和 鈕氧化物)之極困難樣品特別有效。 可將任何適當不含金屬離子之矽酸鹽使用於本發明的組 合物中。矽酸鹽較佳是第四銨矽酸鹽,例如矽酸四燒(基) 铵(包括通常·具有1至4個碳原子在燒基或燒氧基基團中之 含有羥基和烷氧基之烷基基團)。最佳不含金屬離子之♦酸 鹽組份是矽酸四甲銨^適合本發明之其他適當不含金屬離 子之矽酸鹽來源可經由溶解任何一或數種的下列物質在高 鹼性清潔劑中而就地產生。使用於清潔劑中產生珍酸鹽之 適當不含金屬離子之物質是固體碎晶圓、碎酸,膠體珍石 ,烟薰矽石或任何其他適當形成的矽或矽石。可使用金屬 矽酸鹽例如偏矽酸鈉但是由於金屬污染積體電路的不利效 果,並不推薦使用、矽酸鹽可在組合物中之數量可能是自 約0至10重量%,較佳自約0·1至約5重量%。 本發明的組合物亦可調配以適當金屬係螯合劑來增加保 持金屬在溶液中之調配能力及加強溶解晶圓基板上之金屬 殘造。螯合劑通常在組合物中之數量自約〇至5重量%,較 佳自約0 · 1至2重量%之數量。為了此目的而使用之螯合劑的 一般實例是下列有機酸及其異構物和鹽類:(乙二氮基四醋 酸(EDTA),丁二胺四醋酸,(1,2_環己二氮基)四醋酸 -10- 78900-950519.doc 本紙張尺度適用中國國家標準(CNS) Α4規格(210 X 297公嫠> A7 B7 1292437 五、發明説明(8 ) (CyDTA),二乙三胺五醋酸(DETPA),乙二胺四丙酸,(羥 乙基)乙二胺三醋酸(HEDTA)、N,N,N’,N’-乙二胺四(亞甲基 膦)酸(EDTMP)、三乙四胺六醋酸(TTHA)、1,3-二胺基-2_ 羥丙烷-N,N,N’,N’-四醋酸(DHPTA)、甲基亞胺基二醋酸、 丙二胺四醋酸、氮基三醋酸(NTA)、檬檬酸、酒石酸、葡 糖酸、糖二酸、甘油酸、草酸、酞酸、馬來酸、苯乙醇酸 、乳酸、水楊酸、鄰苯二驗、五倍子酸、五倍子酸丙酿、 連苯三酚、8-羥基喹啉和半胱胺酸。較佳之螯合劑是胺基 羧酸例如 EDTA、CyDTA和 EDTMP。 此等清潔組合物亦可視需要含有氟化合物在清潔組合物 中,舉例而言,例如氟化四甲銨,氟化四丁銨及氟化銨。 其他適當氟化物包括,舉例而言,氟硼酸鹽、氟硼酸四丁 铵、六氟化銘、氟化鍊及其類似物。氟組份之數量自0至10 重量%,較佳自約0.1至5重量%。 本發明的清潔組合物通常可包括自約0.05至約30重量% 之無氨製造之強鹼;自約5至約99.95重量%之位阻醯胺溶劑 組份;自約0至約95重量%水或其他有機共溶劑,自約0至 40重量%位阻胺或烷醇胺;約0至40重量%有機或無機酸; 約0至40重量%金屬腐蝕抑制劑化合物例如苯并三唑、鄰苯 二酚、甘油、乙二醇及其類似物;自約0至5重量%界面活 性劑,自約0至10重量%不含金屬離子之矽酸鹽;自約0至5 重量%金屬螯合劑自約0至1〇重量%氟化合物。 各型的調配物的實例在下表1中特舉出。 78900-950519.doc - 11 - 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公董) A7 B7 1292437 五、發明説明(9 ) 表1 以重量計,組成份表 組份 A B C D E F G H DMPO 32 16 16 20 50 16 η2ο 32 32 32 32 ΤΜΑΗ 16 16 16 10 10 10 10 16 TEA 16 15 CyDTA 0.2 SFL 16 30 HEP 50 NMP 50 EDTMP 0.4 DMPD =二甲基旅淀酮 TMAH = 25%氫氧化四甲銨 TEA =三乙醇胺
CyDTA:反式1,2_環己(燒)二胺四醋酸 S F L =環丁 >5風 HEP=l-(2-J^乙基)-2_p比洛淀酮 NMP=N-甲基p比嘻淀酮 EDTMP=乙二胺四(亞甲基膦酸) 表1的清潔組合物D、E、F、G和Η之銅蝕刻速率經由下 表2與3中之蝕刻速率數據予以顯示。蝕刻速率係利用下列 試驗步驟予以測定。 78900-950519.doc - 12- 本紙張尺度適用中國國家標準(CNS) Α4規格(210 X 297公釐) A7 B7 1292437 五、發明説明(10 ) 採用大概13 X 50 mm的銅箔片。量測箔片的厚度。在使 用2-丙醇、蒸餾水和丙酮將箔片清潔後,將箔片在乾燥烘 箱中乾燥。然後將經清潔、乾燥之箔片置入本發明經預熱 之清潔組合物的鬆弛加蓋之瓶中並在所指示溫度下置入真 空烘箱中歷自2至4小時期間。接著處理並自烘箱和瓶中移 出後,將經清潔之箔使大量的蒸餾水沖洗並在乾燥烘箱中 乾燥歷約1小時,然後容許冷卻至室溫,然後蝕刻速率以重 量損失或重量改變為基準而測定。 結果在表2與3中特舉出。 表2 組合物 在70-75°C下,Cu姓刻速率(A/小時) (24小時試驗) D <10 E <10 F <10 G <10 表3 組合物 在65°C下,Cu蚀刻速率(Α/小時) (24小時試驗) Η 1 本發明的組合物之清潔能力在下列試驗中舉例說明,其 中將一種微電子結構(其包含具有下列結構之晶圓即: PR/ARC/CDO/SiN/Cu Dual Damascene(溝道蝕刻後)(其中 78900-950519.doc -13- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公董) 1292437 A7 · B7 五、發明説明(11 ) PR是光阻劑而ARC是抗反射塗層)浸沒入清潔溶液中歷所 指示之溫度和時間,然後用水沖洗,乾燥,然後清潔經由 SEM檢驗而測定。結果特舉出於表4中。 表4 組合物及程序條件 清潔性能 基數相容性 組合物Η 75°C,20分鐘 100%清潔,移除所有 PR、ARC和殘渣 與Cu及CDO可相容 關於本發明之前述,熟諳此藝者應了解:只要不脫離本 發明之要旨和範圍可對於本發明作成修正。因此,不希望 :本發明的範圍受限為所舉例說明和所述之特定具體實施 例0 78900-950519.doc - 14- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐)
Claims (1)
- Α8 Β8 C8 D8 Ι292435ϊιΐ5ΐ68號專利申請案 中文申請專利範圍替換本(95年12月) 六寸鱗莉, 1· 一種能夠清潔來自微電子基板之殘渣之清潔組合物,其 中該基板上具有(1)至少一種多孔介電材料、低κ介電材 料或高Κ介電材料及(2)銅金屬化,該清潔組合物包括: 約0.0 5重量%至3 0重量%的含有非親核性,正電荷抗衡 離子之一或數種無氨產生之強驗; 約5至約99.95重量%之二甲基哌啶酮; 約0至約95重量%水或其他有機共溶劑; 約0至40重量%位阻胺或烷醇胺; 約0至40重量%有機或無機酸; 約0至4 0重量%的其他金屬腐蚀抑制劑化合物; 約0至5重量%之界面活性劑; 約0至10重量%之不含金屬離子之矽酸鹽化合物; 約0至5重量%之金屬螯合劑;及 約0至10重量%之氟化合物。 2·如申請專利範圍第1項之清潔組合物,其中該無氨產生之 強鹼是氫氧化四烷基銨或其鹽類。 3.如申請專利範圍第2項之清潔組合物,其中該氫氧化四燒 基銨或鹽是具有下式之化合物: [(R)4N 十]p[X]-q 其中每一個R是經取代或未經取代之烷基基團,而χ是 0H或鹽陰離子;而p和q相等且是1至3之整數。 4·如申請專利範圍第3項之清潔組合物,其中r是含有1至 22個碳原子之烷基而X是0H或碳酸鹽。 5·如申請專利範圍第4項之清潔組合物,其中r是1至6個碳 78900-951204.doc , 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公爱). 1292437 A8 B8 C8 D8 六、申請專利範圍 原子之燒基基團。 6·如申請專利範圍第1項之清潔組合物,包括水或由下列各 化合物組成之群中選出之至少一種其他有機共溶劑:二 甲亞砜、環丁颯、二乙醇胺、三乙醇胺、2-(甲胺基)乙 醇及3-(二乙胺基)_1,2_丙二醇。 7·如申請專利範圍第1項之清潔組合物,包括氫氧化四甲銨 、二甲基哌啶酮、三乙醇胺、反式-1,2-環己烷二胺四醋 酸和水。 8·如申請專利範圍第1項之清潔組合物,包括氫氧化四甲銨 、二甲基旅啶酮和水。 9·如申請專利範圍第1項之清潔組合物,包括氫氧化四甲按 、二甲基哌啶酮、三乙醇胺、乙二胺四(亞甲基膦酸)和 水0 10·—種用於清潔具有(1)至少一種多孔介電材料、低κ令電 材料或高κ介電材料及(2)銅金屬化之微電子基板之方法 ,該方法包括使該基板與清潔組合物接觸歷足以清潔該 基板之一段時間,其中該清潔組合物包括: 約0.05重量%至30重量%的含有非親核性,正電荷抗衡 離子之一或數種無氨產生之強鹼; 約5至約99.95重量%之的二甲基哌啶酮; 約0至約95重量%水或其他有機共溶劑; 約0至40重量%位阻胺或烷醇胺; 約0至40重量%有機或無機酸; 約〇至40重量%的其他金屬腐姓抑制劑化合物; 78900-951204.doc -2 - 1292437 as B8 C8 ------------D8 六、申請專利範圍 約0至5重量%之界面活性劑; 約〇至10重量%之不含金屬離子之矽酸鹽; 約〇至5重量%之金屬螯合劑;及 約〇至10重量%之氟化合物。 1 ^如申叫專利範圍第1 〇項之方法,其中該無氨產生之強鹼 是氫氧化四烷基銨或其鹽類。 12.如申請專利範圍第丨丨項之方法,其中該氫氧化四烷基銨 或鹽是具有下式之化合物: [(R)4N+]p[xrq 其中每一個R是經取代或未經取代之燒基基團,而X是 OH或一種鹽陰離子;而p*q相等且是自1至3之整數。 13·如申請專利範圍第12項之方法,其中r是含有1至22個碳 原子之燒基而X是OH或碳酸鹽。 14·如申請專利範圍第13項之方法,其中R是具有1至6個碳 原子之烷基基團。 15·如申凊專利範圍第1 0項之方法,其中該清潔組合物包括 水或由下列各化合物缸成之群中選出之至少一種其他共 溶劑··二甲亞砜、環丁颯、二乙醇胺、三乙醇胺、2•(曱 胺基)乙醇及3-(二乙胺基)-1,2-丙二醇。 16·如申請專利範圍第1〇項之方法,其中該清潔組合物包括 氫氧化四甲銨、二甲基旅淀酮、三乙醇胺、反式 己烷二胺四醋酸及水。 17.如申請專利範圍第1〇項之方法,其中該清潔·組合物包括 氫氧化四甲銨、二甲基哌啶酮及水。 78900-951204.doc ·3_ 本紙張尺度適財®國家標準(CNS) Α4規格(210X297公②) 8 8 8 8 ABCD 1292437 々、申請專利範圍 18.如申請專利範圍第10項之方法,其中該清潔組合物包括 氫氧化四甲銨、二甲基哌啶酮、三乙醇胺、乙二胺四( 亞甲基膦酸)及水。 78900-951204.doc -4- 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐)·
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EP1664935B1 (en) | 2003-08-19 | 2007-10-17 | Mallinckrodt Baker, Inc. | Stripping and cleaning compositions for microelectronics |
WO2006081406A1 (en) * | 2005-01-27 | 2006-08-03 | Advanced Technology Materials, Inc. | Compositions for processing of semiconductor substrates |
US7632796B2 (en) | 2005-10-28 | 2009-12-15 | Dynaloy, Llc | Dynamic multi-purpose composition for the removal of photoresists and method for its use |
US9329486B2 (en) | 2005-10-28 | 2016-05-03 | Dynaloy, Llc | Dynamic multi-purpose composition for the removal of photoresists and method for its use |
US8263539B2 (en) | 2005-10-28 | 2012-09-11 | Dynaloy, Llc | Dynamic multi-purpose composition for the removal of photoresists and methods for its use |
DE602008002819D1 (de) | 2007-02-14 | 2010-11-11 | Mallinckrodt Baker Inc | Peroxid-aktivierte formulierungen auf oxometalat-basis zur entfernung von ätzungsresten |
CA2740027A1 (en) | 2008-10-09 | 2010-04-15 | Avantor Performance Materials, Inc. | Aqueous acidic formulations for copper oxide etch residue removal and prevention of copper electrodeposition |
US8298751B2 (en) | 2009-11-02 | 2012-10-30 | International Business Machines Corporation | Alkaline rinse agents for use in lithographic patterning |
WO2012161790A1 (en) * | 2011-02-24 | 2012-11-29 | John Moore | Concentrated chemical composition and method for removing photoresist during microelectric fabrication |
US9158202B2 (en) * | 2012-11-21 | 2015-10-13 | Dynaloy, Llc | Process and composition for removing substances from substrates |
US10072237B2 (en) * | 2015-08-05 | 2018-09-11 | Versum Materials Us, Llc | Photoresist cleaning composition used in photolithography and a method for treating substrate therewith |
US20220326620A1 (en) * | 2019-08-30 | 2022-10-13 | Dow Global Technologies Llc | Photoresist stripping composition |
CN111519190B (zh) * | 2020-05-27 | 2022-03-18 | 湖北兴福电子材料有限公司 | 一种铜制程面板中稳定蚀刻锥角的蚀刻液及稳定方法 |
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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 |
EP0301044A4 (en) * | 1987-02-05 | 1989-03-29 | Macdermid Inc | ETCHING COMPOSITION FOR PHOTORESERVE. |
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