KR102608367B1 - Etching solution composition and method of etching using the same - Google Patents
Etching solution composition and method of etching using the same Download PDFInfo
- Publication number
- KR102608367B1 KR102608367B1 KR1020160170344A KR20160170344A KR102608367B1 KR 102608367 B1 KR102608367 B1 KR 102608367B1 KR 1020160170344 A KR1020160170344 A KR 1020160170344A KR 20160170344 A KR20160170344 A KR 20160170344A KR 102608367 B1 KR102608367 B1 KR 102608367B1
- Authority
- KR
- South Korea
- Prior art keywords
- acid
- sulfate
- etchant composition
- phosphate
- weight
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 69
- 238000005530 etching Methods 0.000 title claims description 53
- 238000000034 method Methods 0.000 title claims description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 65
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 52
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 31
- 239000010452 phosphate Substances 0.000 claims abstract description 31
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 26
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 22
- 239000002738 chelating agent Substances 0.000 claims abstract description 13
- 230000007797 corrosion Effects 0.000 claims abstract description 13
- 238000005260 corrosion Methods 0.000 claims abstract description 13
- 239000011737 fluorine Substances 0.000 claims abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 13
- 239000003112 inhibitor Substances 0.000 claims abstract description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims description 45
- 239000002184 metal Substances 0.000 claims description 45
- 239000010949 copper Substances 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 13
- -1 phosphate compound Chemical class 0.000 claims description 9
- 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 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 5
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical group OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 5
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 4
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- HIMXGTXNXJYFGB-UHFFFAOYSA-N alloxan Chemical compound O=C1NC(=O)C(=O)C(=O)N1 HIMXGTXNXJYFGB-UHFFFAOYSA-N 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 4
- 235000011151 potassium sulphates Nutrition 0.000 claims description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 4
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 3
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 235000013922 glutamic acid Nutrition 0.000 claims description 3
- 239000004220 glutamic acid Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 claims description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 claims description 2
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 claims description 2
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 claims description 2
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 2
- ASZZHBXPMOVHCU-UHFFFAOYSA-N 3,9-diazaspiro[5.5]undecane-2,4-dione Chemical compound C1C(=O)NC(=O)CC11CCNCC1 ASZZHBXPMOVHCU-UHFFFAOYSA-N 0.000 claims description 2
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 claims description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 2
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 2
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 2
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 2
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 235000004279 alanine Nutrition 0.000 claims description 2
- 229940124277 aminobutyric acid Drugs 0.000 claims description 2
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 claims description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 claims description 2
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 2
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims description 2
- 150000003536 tetrazoles Chemical class 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 229910001182 Mo alloy Inorganic materials 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 4
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 4
- 235000019799 monosodium phosphate Nutrition 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- QFKJQDAZSYZAOM-UHFFFAOYSA-N (1-oxidanyl-1-phosphono-ethyl)phosphonic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O.OP(=O)(O)C(O)(C)P(O)(O)=O QFKJQDAZSYZAOM-UHFFFAOYSA-N 0.000 description 1
- VRESBNUEIKZECD-UHFFFAOYSA-N 2-methyltetrazole Chemical compound CN1N=CN=N1 VRESBNUEIKZECD-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229940116349 dibasic ammonium phosphate Drugs 0.000 description 1
- 229940111685 dibasic potassium phosphate Drugs 0.000 description 1
- 229940061607 dibasic sodium phosphate Drugs 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229940111688 monobasic potassium phosphate Drugs 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/12—Oxygen-containing compounds
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/16—Sulfur-containing compounds
Abstract
본 발명은 과산화수소; 인산 또는 인산염계 화합물; 황산염계 화합물: 불소계 화합물; 킬레이트제; 및 부식방지제를 포함하는 식각액 조성물에 관한 것이다.The present invention relates to hydrogen peroxide; Phosphoric acid or phosphate-based compounds; Sulfate-based compounds: Fluorine-based compounds; Chelating agent; and an etchant composition containing a corrosion inhibitor.
Description
본 발명은 구리를 포함하는 단일막, 또는 다중막을 식각하기 위한 식각액 조성물 및 이를 이용한 식각 방법에 관한 것이다.The present invention relates to an etchant composition for etching a single layer or multilayer containing copper and an etching method using the same.
통상적으로 반도체 소자 제조 시 기판 위에 회로 패턴을 형성하는 과정은 스퍼터링 등에 의한 금속막 형성공정; 포토레지스트 도포, 노광 및 현상에 의한 선택적인 영역에서의 포토레지스트 형성공정; 및 식각공정을 포함한다. 상기 식각공정은 포토레지스트를 마스크로 하여 선택적인 영역에 금속막을 남기는 공정으로, 플라즈마 등을 이용한 건식식각 또는 식각액 조성물을 이용하는 습식식각이 사용된다.Typically, the process of forming a circuit pattern on a substrate when manufacturing a semiconductor device includes a metal film forming process by sputtering, etc.; Photoresist formation process in selective areas by photoresist application, exposure, and development; and an etching process. The etching process is a process of leaving a metal film in a selective area using a photoresist as a mask, and dry etching using plasma or the like or wet etching using an etchant composition is used.
상기 식각액 조성물과 관련하여 대한민국 공개특허 제2007-0055259호에는 과산화수소, 유기산, 인산염 화합물을 포함하는 구리 몰리브덴 합금막의 식각용액이 개시되어 있다. 그러나, 상기 식각용액은 구리계 금속막의 후막에 적용시킬 경우 인산염 화합물로 인해 테이퍼 각(taper angle)이 높아져 후속 공정 진행 시 불량이 발생하는 문제점이 있다.Regarding the etchant composition, Republic of Korea Patent Publication No. 2007-0055259 discloses an etching solution for a copper molybdenum alloy film containing hydrogen peroxide, an organic acid, and a phosphate compound. However, when the etching solution is applied to a thick copper-based metal film, the taper angle increases due to the phosphate compound, resulting in defects during subsequent processes.
이외에 과산화수소, 인산염 화합물, 황산염 화합물을 포함하는 식각액 조성물이 개시된 바 있다. 상기 식각액 조성물은 인산염 화합물과 황산염 화합물을 높은 함량(예를 들어, 1 중량% 이상)으로 포함함에 따라 개선된 식각속도를 나타낼 수 있다. 그러나 식각액을 일정 시간 정체시켰다가 다시 재사용할 때 식각액에 고농도의 금속이 잔류하여 테이퍼 각이 급격히 증가함에 따라 불량 발생율이 높아지기 때문에 이를 방지하기 위해서는 식각액 조성물의 교체를 자주 해주어야 하는(교체주기 단축) 문제점이 있다. 또한 식각액 조성물의 물성을 제어하기 위해 다른 첨가제의 함량도 증가되어 결과적으로 경제성이 떨어지는 문제점이 있다.In addition, an etchant composition containing hydrogen peroxide, a phosphate compound, and a sulfate compound has been disclosed. The etchant composition may exhibit an improved etching rate as it contains a high content of a phosphate compound and a sulfate compound (for example, 1% by weight or more). However, when the etchant is allowed to stagnate for a certain period of time and then reused, a high concentration of metal remains in the etchant and the taper angle increases rapidly, increasing the defect occurrence rate. To prevent this, the etchant composition must be frequently replaced (shortened replacement cycle). There is. In addition, in order to control the physical properties of the etchant composition, the content of other additives is also increased, resulting in lower economic efficiency.
따라서 식각속도, 식각 프로파일 등이 우수하면서 경제성을 확보할 수 있는 식각액 조성물이 요구되고 있다.Therefore, there is a need for an etchant composition that has excellent etching speed, etching profile, etc. and can secure economic feasibility.
본 발명은 식각속도, 식각 프로파일 등이 우수하면서 경제성을 확보할 수 있는 식각액 조성물을 제공하고자 한다.The present invention seeks to provide an etchant composition that has excellent etching speed, etching profile, etc. while ensuring economic feasibility.
또한, 본 발명은 상기 식각액 조성물을 이용한 식각 방법을 제공하고자 한다.Additionally, the present invention seeks to provide an etching method using the etchant composition.
상기 과제를 해결하기 위해 본 발명은, 과산화수소; 인산 또는 인산염계 화합물; 황산염계 화합물: 불소계 화합물; 킬레이트제; 및 부식방지제를 포함하는 식각액 조성물로서, 상기 식각액 조성물 100 중량부를 기준으로, 상기 인산 또는 인산염계 화합물이 0.05 내지 0.1 중량부로 포함되고, 상기 황산염계 화합물이 0.1 내지 0.4 중량부로 포함되는 식각액 조성물을 제공한다.In order to solve the above problems, the present invention includes hydrogen peroxide; Phosphoric acid or phosphate-based compounds; Sulfate-based compounds: Fluorine-based compounds; Chelating agent; And an etching solution composition comprising a corrosion inhibitor, wherein the phosphoric acid or phosphate-based compound is included in an amount of 0.05 to 0.1 parts by weight, and the sulfate-based compound is included in an amount of 0.1 to 0.4 parts by weight, based on 100 parts by weight of the etching solution composition. do.
또 본 발명은, 기판 위의 금속막을 상기 식각액 조성물로 식각하는 단계를 포함하는 식각 방법을 제공한다.The present invention also provides an etching method including the step of etching a metal film on a substrate with the etchant composition.
본 발명의 식각액 조성물은 인산 또는 인산염계 화합물과 황산염계 화합물을 최적 비율로 포함하기 때문에 이들이 저함량으로 포함되더라도 빠른 식각속도와 우수한 식각 프로파일(예를 들어, 테이퍼 각, CD bias 등)을 나타낼 수 있다. 또한 본 발명은 상기 인산 또는 인산염계 화합물과 상기 황산염계 화합물을 저함량으로 포함함에 따라 식각액 조성물의 경제성을 확보할 수 있다.Since the etchant composition of the present invention contains phosphoric acid or a phosphate-based compound and a sulfate-based compound in an optimal ratio, it can exhibit a fast etching speed and an excellent etching profile (e.g., taper angle, CD bias, etc.) even if it is included in a low content. . In addition, the present invention can ensure the economic efficiency of the etchant composition by containing the phosphoric acid or phosphate-based compound and the sulfate-based compound in low amounts.
도 1 및 도 2는 실시예 1 및 비교예 7에 따른 식각 특성을 나타낸 주사전자현미경 사진이다.Figures 1 and 2 are scanning electron microscope photographs showing etching characteristics according to Example 1 and Comparative Example 7.
이하 본 발명을 설명한다.The present invention will be described below.
1. One. 식각액etchant 조성물 composition
본 발명의 식각액 조성물은, 과산화수소, 인산 또는 인산염계 화합물, 황산염계 화합물, 불소계 화합물, 킬레이트제 및 부식방지제를 포함한다.The etchant composition of the present invention includes hydrogen peroxide, phosphoric acid or a phosphate-based compound, a sulfate-based compound, a fluorine-based compound, a chelating agent, and a corrosion inhibitor.
본 발명의 식각액 조성물에 포함되는 과산화수소는 금속막을 산화시키는 역할을 한다.Hydrogen peroxide included in the etchant composition of the present invention serves to oxidize the metal film.
이러한 과산화수소의 함량은 특별히 한정되지 않으나, 식각액 조성물 100 중량부를 기준으로 15 내지 25 중량부인 것이 바람직하다. 상기 과산화수소의 함량이 15 중량부 미만이면 금속막에 대한 산화력이 충분하지 않아 금속막의 식각이 충분히 이루어지지 않을 수 있고, 25 중량부를 초과하면 금속막의 식각속도가 과도하게 높아지거나 식각액 조성물의 안정성 저하로 인해 폭발 위험성이 높아질 수 있다.The content of hydrogen peroxide is not particularly limited, but is preferably 15 to 25 parts by weight based on 100 parts by weight of the etchant composition. If the content of hydrogen peroxide is less than 15 parts by weight, the oxidizing power of the metal film may not be sufficient and the metal film may not be sufficiently etched. If it exceeds 25 parts by weight, the etching rate of the metal film may increase excessively or the stability of the etchant composition may deteriorate. This may increase the risk of explosion.
본 발명의 식각액 조성물에 포함되는 인산 또는 인산염계 화합물은 금속막의 식각속도와 금속막의 테이퍼 각을 조절하는 역할을 한다.Phosphoric acid or a phosphate-based compound included in the etchant composition of the present invention serves to control the etching rate of the metal film and the taper angle of the metal film.
상기 인산염계 화합물은 특별히 한정되지 않으나, 제일인산나트륨(NaH2PO4), 제이인산나트륨(Na2HPO4), 제일인산칼륨(KH2PO4), 제이인산칼륨(K2HPO4), 제일인산암모늄((NH4)H2PO4) 및 제이인산암모늄((NH4)2HPO4)으로 이루어진 군에서 선택된 1종 이상인 것이 바람직하다.The phosphate-based compound is not particularly limited, but includes monobasic sodium phosphate (NaH 2 PO 4 ), dibasic sodium phosphate (Na 2 HPO 4 ), monobasic potassium phosphate (KH 2 PO 4 ), dibasic potassium phosphate (K 2 HPO 4 ), It is preferable that it is at least one selected from the group consisting of monobasic ammonium phosphate ((NH 4 )H 2 PO 4 ) and dibasic ammonium phosphate ((NH 4 ) 2 HPO 4 ).
이러한 인산 또는 인산염계 화합물의 함량은 식각액 조성물 100 중량부를 기준으로 0.05 내지 0.1 중량부이다. 상기 인산 또는 인산염계 화합물의 함량이 0.05 중량부 미만이면 금속막의 식각속도가 저하될 수 있다. 또한 0.1 중량부를 초과하면 금속막의 식각속도가 과도하게 높아지거나 금속막의 테이퍼 각이 너무 커질 수 있다. 또 과량의 인산 또는 인산염계 화합물이 사용됨에 따라 이를 제어하기 위한 첨가제의 함량이 증가하게 되어 식각액 조성물의 경제성이 저하될 수 있다.The content of such phosphoric acid or phosphate-based compound is 0.05 to 0.1 parts by weight based on 100 parts by weight of the etchant composition. If the content of the phosphoric acid or phosphate-based compound is less than 0.05 parts by weight, the etching rate of the metal film may decrease. Additionally, if it exceeds 0.1 part by weight, the etch rate of the metal film may become excessively high or the taper angle of the metal film may become too large. Additionally, as excessive amounts of phosphoric acid or phosphate-based compounds are used, the content of additives to control them increases, which may reduce the economic feasibility of the etchant composition.
본 발명의 식각액 조성물에 포함되는 황산염계 화합물은 금속막의 식각속도와 금속막의 테이퍼 각을 조절하는 역할을 한다. 상기 황산염계 화합물은 특별히 한정되지 않으나, 황산수소칼륨(KHSO4), 황산수소나트륨(NaHSO4), 황산수소암모늄((NH4)HSO4), 황산칼륨(K2SO4), 황산나트륨(Na2SO4) 및 황산암모늄((NH4)2SO4)으로 이루어진 군에서 선택된 1종 이상인 것이 바람직하다.The sulfate-based compound included in the etchant composition of the present invention plays a role in controlling the etching rate of the metal film and the taper angle of the metal film. The sulfate-based compound is not particularly limited, but includes potassium hydrogen sulfate (KHSO 4 ), sodium hydrogen sulfate (NaHSO 4 ), ammonium hydrogen sulfate ((NH 4 )HSO 4 ), potassium sulfate (K 2 SO 4 ), sodium sulfate (Na 2 SO 4 ) and ammonium sulfate ((NH 4 ) 2 SO 4 ). It is preferable that it is at least one selected from the group consisting of.
이러한 황산염계 화합물의 함량은 식각액 조성물 100 중량부를 기준으로 0.1 내지 0.4 중량부이다. 상기 황산염계 화합물의 함량이 0.1 중량부 미만이면 금속막의 식각속도가 저하되고 금속막의 테이퍼 각이 너무 커져 제조공정 상에 문제가 유발될 수 있고, 0.4 중량부를 초과하면 금속막의 식각속도가 과도하게 높아지고 금속의 농도가 증가함에 따라 CD bias가 과도하게 커질 수 있다. 또한 과량의 황산염계 화합물이 사용됨에 따라 이를 제어하기 위한 첨가제의 함량이 증가하게 되어 식각액 조성물의 경제성이 저하될 수 있다.The content of this sulfate-based compound is 0.1 to 0.4 parts by weight based on 100 parts by weight of the etchant composition. If the content of the sulfate-based compound is less than 0.1 part by weight, the etching rate of the metal film decreases and the taper angle of the metal film becomes too large, which may cause problems in the manufacturing process. If the content of the sulfate-based compound exceeds 0.4 part by weight, the etching rate of the metal film increases excessively. As the metal concentration increases, CD bias may become excessively large. Additionally, as excessive amounts of sulfate-based compounds are used, the content of additives to control them increases, which may reduce the economic feasibility of the etchant composition.
이와 같이 본 발명의 식각액 조성물은 상기 인산 또는 인산염계 화합물과 상기 황산염계 화합물을 특정 비율, 즉, 각각 0.05 내지 0.1 중량부와 0.1 내지 0.4 중량부로 포함함에 따라 인산 또는 인산염계 화합물과 황산염계 화합물이 비교적 저함량으로 포함되어 있더라도 식각속도가 빠르며 우수한 식각 프로파일을 나타낼 수 있다. 또한 상기 특정 비율로 인해 식각액 조성물을 일정 시간 정체한 후 재사용할 때 식각액 조성물에 금속 농도가 증가되어 있더라도 금속막의 테이퍼 각을 일정하게 유지할 수 있어, 식각액 조성물의 교체 주기를 늘릴 수 있으며, 이로 인해 경제성을 높일 수 있다.As such, the etchant composition of the present invention contains the phosphoric acid or phosphate-based compound and the sulfate-based compound in a specific ratio, that is, 0.05 to 0.1 parts by weight and 0.1 to 0.4 parts by weight, respectively, so that the phosphoric acid or phosphate-based compound and the sulfate-based compound Even if it is contained in a relatively low content, it has a fast etching rate and can exhibit an excellent etching profile. In addition, due to the above-mentioned specific ratio, when the etchant composition is reused after stagnant for a certain period of time, the taper angle of the metal film can be maintained constant even if the metal concentration in the etchant composition is increased, and the replacement cycle of the etchant composition can be increased, which makes it economical. can increase.
구체적으로, 본 발명의 식각액 조성물은 인산 또는 인산염계 화합물과 황산염계 화합물을 0.15 내지 0.5 중량부로 포함하고, 바람직하게는 0.2 내지 0.35 중량부로 포함할 수 있다. 상기 인산 또는 인산염계 화합물과 상기 황산염계 화합물의 총 함량이 0.15 내지 0.5 중량부임에 따라 본 발명의 식각액 조성물은 높은 식각속도와 더불어 테이터 각이 40 내지 60°범위이고, CD bias 변화가 0.2 ㎛ 이내이며, 기판 처리 누적 매수 7000 ppm까지 우수한 식각성을 나타낼 수 있다.Specifically, the etchant composition of the present invention may include 0.15 to 0.5 parts by weight, and preferably 0.2 to 0.35 parts by weight, of phosphoric acid or a phosphate-based compound and a sulfate-based compound. As the total content of the phosphoric acid or phosphate-based compound and the sulfate-based compound is 0.15 to 0.5 parts by weight, the etchant composition of the present invention has a high etching rate, a tater angle in the range of 40 to 60°, and a CD bias change within 0.2 ㎛. It can exhibit excellent etching properties up to 7000 ppm of cumulative substrate processing.
본 발명의 식각액 조성물에 포함되는 불소계 화합물은 금속막의 식각과정에서 발생할 수 있는 금속막의 잔사를 제거하는 역할을 한다. 상기 불소계 화합물은 특별히 한정되지 않으나, 불화수소(HF), 불화나트륨(NaF), 불화수소나트륨(NaHF2), 불화암모늄(NH4F), 산성불화암모늄(NH4HF2), 불화붕소산암모늄(NH4BF4), 불화칼륨(KF), 불화수소칼륨(KHF2) 및 불화알루미늄(AlF3)으로 이루어진 군에서 선택된 1종 이상인 것이 바람직하다.The fluorine-based compound included in the etchant composition of the present invention serves to remove residues of the metal film that may occur during the etching process of the metal film. The fluorine-based compound is not particularly limited, but includes hydrogen fluoride (HF), sodium fluoride (NaF), sodium hydrogen fluoride (NaHF 2 ), ammonium fluoride (NH 4 F), acidic ammonium fluoride (NH 4 HF 2 ), boronic acid. It is preferable that it is at least one selected from the group consisting of ammonium (NH 4 BF 4 ), potassium fluoride (KF), potassium hydrogen fluoride (KHF 2 ), and aluminum fluoride (AlF 3 ).
이러한 불소계 화합물의 함량은 특별히 한정되지 않으나, 식각액 조성물 100 중량부를 기준으로 0.01 내지 1 중량부인 것이 바람직하다. 상기 불소계 화합물의 함량이 0.01 중량부 미만이면 금속막의 잔사를 효과적으로 제거하기 어려울 수 있고, 1 중량부를 초과하면 금속막이 형성되어 있는 기판, 또는 절연막에 손상을 입힐 수 있다.The content of this fluorine-based compound is not particularly limited, but is preferably 0.01 to 1 part by weight based on 100 parts by weight of the etchant composition. If the content of the fluorine-based compound is less than 0.01 parts by weight, it may be difficult to effectively remove residues of the metal film, and if it exceeds 1 part by weight, it may damage the substrate on which the metal film is formed or the insulating film.
본 발명의 식각액 조성물에 포함되는 킬레이트제는 금속막의 식각과정에서 발생되는 금속 이온과 리간드 결합하여 금속 이온을 비활성화시킴으로써 식각액 조성물에 포함된 과산화수소의 분해 반응을 억제하는 역할을 한다.The chelating agent included in the etchant composition of the present invention serves to suppress the decomposition reaction of hydrogen peroxide contained in the etchant composition by binding to a ligand and deactivating the metal ion generated during the etching process of the metal film.
상기 킬레이트제는 특별히 한정되지 않으나, 이미노디아세트산(iminodiacetic acid), 디글리콜산(diglycolic acid), 티오글리콜산(thioglycolic acid), 니트릴로트리아세트산(nitrilotriacetic acid), 에틸렌디아민테트라아세트산(ethylenediaminetetraacetic acid), 디에틸렌트리니트릴펜타아세트산(diethylenetrinitrilacetic acid), 아미노트리스(메틸렌포스폰산)(aminotris(methylenephosphonic acid)), (1-히드록시에탄-1,1-디일)비스(포스폰산)((1-hydroxyethane-1,1-diyl)bis(phosphonic acid)), 에틸렌디아민테트라(메틸렌포스폰산)(ethylenediamine tetra(methylene phosphonic acid)), 디에틸렌트리아민 펜타(메틸렌포스폰산)(Diethylenetriamine penta(methylene phosphonic acid), 알라닌(alanine), 글루탐산(glutamic acid), 아미노부티르산(aminobutyric acid) 및 글리신(glycin)으로 이루어진 군에서 선택된 1종 이상인 것이 바람직하다.The chelating agent is not particularly limited, but includes iminodiacetic acid, diglycolic acid, thioglycolic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetrinitrilacetic acid, aminotris(methylenephosphonic acid), (1-hydroxyethane-1,1-diyl)bis(phosphonic acid) ((1-hydroxyethane- 1,1-diyl)bis(phosphonic acid)), ethylenediamine tetra(methylene phosphonic acid), Diethylenetriamine penta(methylene phosphonic acid), It is preferable that it is at least one selected from the group consisting of alanine, glutamic acid, aminobutyric acid, and glycin.
이러한 킬레이트제의 함량은 특별히 한정되지 않으나, 식각액 조성물 100 중량부를 기준으로 1 내지 5 중량부인 것이 바람직하다. 상기 킬레이트제의 함량이 1 중량부 미만이면 과산화수소의 분해 반응을 제어하기 어려울 수 있고, 5 중량부를 초과하면 식각액 조성물에 금속 이온의 농도가 증가함에 따라 CD bias가 커질 수 있다.The content of this chelating agent is not particularly limited, but is preferably 1 to 5 parts by weight based on 100 parts by weight of the etchant composition. If the content of the chelating agent is less than 1 part by weight, it may be difficult to control the decomposition reaction of hydrogen peroxide, and if it exceeds 5 parts by weight, CD bias may increase as the concentration of metal ions in the etchant composition increases.
본 발명의 식각액 조성물에 포함되는 부식방지제는 금속막의 식각속도를 조절하는 역할을 한다. 상기 부식방지제는 특별히 한정되지 않으나, 퓨란(furane), 티오펜(thiophene), 피롤(pyrrole), 옥사졸(oxazole), 이미다졸(imidazole), 메틸이미다졸(methylimidazole), 피라졸(pyrazole), 트리아졸(triazole), 아미노트리아졸(aminotriazole), 테트라졸(tetrazole), 5-아미노테트라졸(5-aminotetrazole), 메틸테트라졸(methyltetrazole), 피페라진(piperazine), 메틸피페라진(methylpiperazine), 히드록실에틸피페라진(hydroxyethylpiperazine), 피롤리딘(pyrrolidine), 알록산(alloxan), 벤조퓨란(benzofurane), 벤조티오펜(benzothiophene), 인돌(indole), 벤즈이미다졸(benzimidazole), 벤즈피라졸(benzpyrazole), 톨루트리아졸(tolutriazole), 히드로톨루트리아졸(hydrotolutriazole) 및 히드록시톨루트리아졸(hydroxytolutriazole)로 이루어진 군에서 선택된 1종 이상인 것이 바람직하다.The corrosion inhibitor included in the etchant composition of the present invention serves to control the etching rate of the metal film. The corrosion inhibitor is not particularly limited, but includes furan, thiophene, pyrrole, oxazole, imidazole, methylimidazole, and pyrazole. , triazole, aminotriazole, tetrazole, 5-aminotetrazole, methyltetrazole, piperazine, methylpiperazine , hydroxyethylpiperazine, pyrrolidine, alloxan, benzofurane, benzothiophene, indole, benzimidazole, benzpyra It is preferable that it is at least one selected from the group consisting of benzpyrazole, tolutriazole, hydrotolutriazole, and hydroxytolutriazole.
이러한 부식방지제의 함량은 특별히 한정되지 않으나, 식각액 조성물 100 중량부를 기준으로 0.01 내지 1 중량부인 것이 바람직하다. 상기 부식방지제의 함량이 0.01 중량부 미만이면 과도한 식각이 일어나거나 식각 프로파일(CD bias, 테이퍼 각)이 불량해질 수 있고, 1 중량부를 초과하면 식각속도의 저하로 인해 잔류물이 남아있거나 식각 공정의 시간이 길어질 수 있다.The content of this corrosion inhibitor is not particularly limited, but is preferably 0.01 to 1 part by weight based on 100 parts by weight of the etchant composition. If the content of the corrosion inhibitor is less than 0.01 part by weight, excessive etching may occur or the etching profile (CD bias, taper angle) may become poor, and if it exceeds 1 part by weight, residue may remain due to a decrease in the etching speed or damage to the etching process may occur. It may take a long time.
이외에도 본 발명의 식각액 조성물은 상기 성분들을 안정시키는 안정제를 더 포함할 수 있다. 구체적으로 상기 안정제는 반복적인 식각 과정에 의해 식각액 조성물에 금속 이온의 농도가 높아짐에 따라 일어날 수 있는 과산화수소의 분해 반응을 제어하는 역할을 한다. 이러한 안정제로는 알코올류, 글리콜류, 또는 아민류 등을 사용할 수 있고, 그 함량은 식각액 조성물 100 중량부를 기준으로 0.1 내지 5 중량부일 수 있다.In addition, the etchant composition of the present invention may further include a stabilizer to stabilize the above components. Specifically, the stabilizer serves to control the decomposition reaction of hydrogen peroxide that may occur as the concentration of metal ions in the etchant composition increases due to repeated etching processes. Alcohols, glycols, or amines may be used as such stabilizers, and the content may be 0.1 to 5 parts by weight based on 100 parts by weight of the etchant composition.
또한 본 발명의 식각액 조성물은 상기 성분들을 용해 또는 분산시키는 용매를 더 포함할 수 있다. 상기 용매는 특별히 한정되지 않으나, 물, 이온수, 순수, 또는 초순수일 수 있다.Additionally, the etchant composition of the present invention may further include a solvent that dissolves or disperses the components. The solvent is not particularly limited, but may be water, ionized water, pure water, or ultrapure water.
2. 2. 식각etching 방법 method
본 발명은 상술한 식각액 조성물을 이용하여 금속막을 식각하는 방법을 제공하는데, 이에 대해 구체적으로 설명하면 다음과 같다.The present invention provides a method of etching a metal film using the above-described etchant composition, which will be described in detail as follows.
a) 기판 준비a) Substrate preparation
먼저, 금속막이 형성된 기판을 준비한다. 상기 기판은 당 업계에 공지된 것이라면 특별히 한정되지 않으나, 유리 기판일 수 있다.First, prepare a substrate on which a metal film is formed. The substrate is not particularly limited as long as it is known in the art, but may be a glass substrate.
상기 기판에 금속막을 형성하는 방법은 당 업계에 공지된 것이라면 특별히 한정되지 않는다. 이때, 금속막은 구리막, 또는 구리 합금막일 수 있다. 구체적으로, 상기 금속막은 구리로 이루어진 단일막, 구리와 몰리브덴의 합금으로 이루어진 단일막, 구리와 몰리브덴으로 각각 이루어진 단일막이 적층된 다중막, 또는 구리와 몰리브덴의 합금으로 이루어진 단일막이 적층된 다중막일 수 있다.The method of forming a metal film on the substrate is not particularly limited as long as it is known in the art. At this time, the metal film may be a copper film or a copper alloy film. Specifically, the metal film may be a single film made of copper, a single film made of an alloy of copper and molybdenum, a multi-film in which single films made of copper and molybdenum are stacked, or a multi-film in which single films made of an alloy of copper and molybdenum are stacked. there is.
b) b) 식각etching
다음, 상술한 식각액 조성물과 금속막이 형성된 기판을 접촉시켜 금속막을 식각한다. 이때, 식각을 통해 금속막에 금속 회로 패턴을 형성하고자 할 때는 금속막 상에 포토레지스트 패턴을 형성하고, 이를 식각액 조성물과 접촉시킴으로써 금속 회로 패턴을 형성할 수 있다.Next, the metal film is etched by contacting the above-described etchant composition with the substrate on which the metal film is formed. At this time, when it is desired to form a metal circuit pattern on a metal film through etching, the metal circuit pattern can be formed by forming a photoresist pattern on the metal film and contacting it with an etchant composition.
이하 본 발명을 실시예를 통하여 상세히 설명하면 다음과 같다. 단, 하기 실시예는 본 발명을 예시하는 것일 뿐, 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail through examples. However, the following examples are merely illustrative of the present invention, and the present invention is not limited by the following examples.
[[ 실시예Example 1 내지 11] 1 to 11]
하기 표 1 및 표 2의 조성을 가지는 식각액 조성물을 각각 준비하였다. 각 함량의 단위는 중량%이고, 이온수로 100 중량%가 되도록 조절하였다.Etching solution compositions having the compositions shown in Tables 1 and 2 below were prepared. The unit of each content is weight%, and was adjusted to 100% by weight using ionized water.
[[ 비교예Comparative example 1 내지 7] 1 to 7]
하기 표 3의 조성을 가지는 식각액 조성물을 각각 준비하였다. 각 함량의 단위는 중량%이고, 이온수로 100 중량%가 되도록 조절하였다.Etching solution compositions having the compositions shown in Table 3 below were prepared. The unit of each content is weight%, and was adjusted to 100% by weight using ionized water.
[[ 실험예Experiment example 1] One]
유리 기판 상에 Cu/Mo 합금막(5000 Å/100 Å)을 증착한 후 포토리소그래피 공정을 진행하여 패턴을 형성시켜 시편을 제조하였다. 다음, 스프레이가 가능한 장비(Mini-etcher)를 이용하여 실시예 및 비교예에서 각각 제조된 식각액 조성물로 식각을 진행하였다. 식각 특성을 확인하기 위해서 누적 매수는 Cu 이온이 300 ppm 및 7000 ppm에서 총 식각 시간을 상기 기판에 대해서 EPD(End Point Detection)를 기준으로 하여 Over Etch를 100%로 주어 실시하였다. 측정된 결과는 하기 표 4에 나타내었다.A specimen was manufactured by depositing a Cu/Mo alloy film (5000 Å/100 Å) on a glass substrate and then performing a photolithography process to form a pattern. Next, etching was performed with the etchant compositions prepared in the Examples and Comparative Examples, respectively, using a sprayable equipment (mini-etcher). In order to check the etching characteristics, the cumulative number of Cu ions was measured at 300 ppm and 7000 ppm, and the total etching time was performed by setting Over Etch to 100% based on EPD (End Point Detection) for the substrate. The measured results are shown in Table 4 below.
1. 식각 속도: 금속막의 EPD를 초시계로 측정 후 식각 속도를 계산하였다(측정된 값이 140 내지 170 Å/s 범위 내인 경우: ○, 140 Å/s 미만이거나 170 Å/s를 초과하는 경우: ×).1. Etching rate: The EPD of the metal film was measured with a stopwatch and the etch rate was calculated (if the measured value is within the range of 140 to 170 Å/s: ○, if it is less than 140 Å/s or exceeds 170 Å/s: ×).
2. CD bias 변화: 주사전자 현미경(히다치사 제조, SU-8010)으로 관찰하여 CD bias 변화량을 분석하였다(측정된 값이 0.2 ㎛ 이하인 경우: ○, 0.2 ㎛를 초과하는 경우: ×).2. CD bias change: The amount of change in CD bias was analyzed by observing with a scanning electron microscope (SU-8010, manufactured by Hitachi) (if the measured value is less than 0.2 ㎛: ○, if it exceeds 0.2 ㎛: ×).
3. 테이퍼 각: 주사전자 현미경(히다치사 제조, SU-8010)으로 관찰하여 테이퍼 각을 분석하였다(측정된 값이 40 내지 60°범위 내인 경우: ○, 40°미만이거나 60°를 초과하는 경우: ×).3. Taper angle: The taper angle was analyzed by observing with a scanning electron microscope (SU-8010, manufactured by Hitachi) (if the measured value is within the range of 40 to 60°: ○, if it is less than 40° or exceeds 60°) :×).
상기 표 4를 참조하면, 본 발명의 식각액 조성물에 해당하는 실시예 1 내지 11의 경우, 식각 속도, CD bias 변화, 테이퍼각에 대한 평가결과가 모두 우수한 것을 확인할 수 있다.Referring to Table 4, it can be seen that in the case of Examples 1 to 11 corresponding to the etchant composition of the present invention, the evaluation results for etching speed, CD bias change, and taper angle were all excellent.
[[ 실험예Experiment example 2] 2]
식각액 조성물의 시간 경시 평가를 다음과 같은 과정을 거쳐 진행하였으며, 진행과정마다 CD bias 변화와 테이퍼 각을 측정하여 하기 표 5 및 도 1, 2에 나타내었다.The time-lapse evaluation of the etchant composition was conducted through the following process, and the CD bias change and taper angle were measured for each process and are shown in Table 5 and Figures 1 and 2 below.
1. 실시예 1 및 비교예 7의 식각액 조성물에 Cu 300ppm, Mo 21ppm, Ti 9ppm을 용해시키고 mini etcher에서 etch 평가1. Dissolve 300 ppm of Cu, 21 ppm of Mo, and 9 ppm of Ti in the etchant composition of Example 1 and Comparative Example 7 and perform etch evaluation in a mini etcher.
2. 다음, 금속 이온의 함량이 Cu 3000ppm, Mo 210ppm, Ti 90ppm이 되도록 금속 분말을 추가로 용해시키고 32 ℃의 항온조에서 유지 및 spray2. Next, additionally dissolve the metal powder so that the metal ion content is 3000ppm of Cu, 210ppm of Mo, and 90ppm of Ti, and maintained and sprayed in a constant temperature bath at 32℃.
3. 6 시간 후 etch 평가3. Etch evaluation after 6 hours
4. 그 다음, 금속 이온의 함량이 Cu 5000ppm, Mo 350ppm, Ti 150ppm이 되도록 금속 분말을 추가로 용해시키고 32 ℃의 항온조에서 유지 및 spray4. Next, additionally dissolve the metal powder so that the metal ion content is 5000ppm of Cu, 350ppm of Mo, and 150ppm of Ti, and maintained and sprayed in a constant temperature bath at 32°C.
5. 6 시간 후 etch 평가5. Etch evaluation after 6 hours
6. 마지막으로, 금속 이온의 함량이 Cu 7000ppm, Mo 490ppm, Ti 210ppm이 되도록 금속 분말을 추가로 용해시키고 32 ℃의 항온조에서 유지 및 spray6. Finally, additionally dissolve the metal powder so that the metal ion content is 7000ppm of Cu, 490ppm of Mo, and 210ppm of Ti, and then maintained and sprayed in a constant temperature bath at 32°C.
7. 6 시간 후 etch 평가7. Etch evaluation after 6 hours
상기 표 5를 참조하면, 본 발명의 식각액 조성물에 해당하는 실시예 1은 CD bias 및 테이퍼 각이 요구되는 범위로 나타나고 있으며, 그 변화도 작은 것을 확인할 수 있다. 이러한 점은 본 발명의 식각액 조성물을 LCD 또는 OLED Wet Etch 공정에 적용할 경우, 일정 시간이 정체된 후 다시 Etch 공정을 진행하더라도 식각액 조성물의 교체가 자주 필요하지 않다는 점을 뒷받침하는 것이며, 이로 인해 생산성 및 경제성을 확보할 수 있다.Referring to Table 5, it can be seen that Example 1, which corresponds to the etchant composition of the present invention, has CD bias and taper angle within the required range, and the change is small. This fact supports the fact that when the etchant composition of the present invention is applied to the LCD or OLED wet etch process, replacement of the etchant composition is not frequently necessary even if the etch process is performed again after a certain period of time has been stagnant, thereby increasing productivity. and economic feasibility can be secured.
Claims (9)
상기 인산염계 화합물이 제일인산염 화합물을 포함하고,
상기 식각액 조성물 100 중량부를 기준으로,
상기 과산화수소가 15 내지 25 중량부로 포함되고,
상기 인산 또는 인산염계 화합물이 0.05 내지 0.1 중량부로 포함되고,
상기 황산염계 화합물이 0.1 내지 0.4 중량부로 포함되고,
상기 불소계 화합물이 0.01 내지 1 중량부로 포함되고,
상기 킬레이트제가 1 내지 5 중량부로 포함되고,
상기 부식방지제가 0.01 내지 1 중량부로 포함되는 식각액 조성물.hydrogen peroxide; Phosphoric acid or phosphate-based compounds; Sulfate-based compounds: Fluorine-based compounds; Chelating agent; And an etchant composition containing a corrosion inhibitor,
The phosphate-based compound includes a monobasic phosphate compound,
Based on 100 parts by weight of the etchant composition,
Hydrogen peroxide is included in an amount of 15 to 25 parts by weight,
The phosphoric acid or phosphate-based compound is included in an amount of 0.05 to 0.1 parts by weight,
The sulfate-based compound is included in an amount of 0.1 to 0.4 parts by weight,
The fluorine-based compound is included in an amount of 0.01 to 1 part by weight,
The chelating agent is included in an amount of 1 to 5 parts by weight,
An etchant composition comprising 0.01 to 1 part by weight of the corrosion inhibitor.
상기 인산염계 화합물이 제일인산나트륨(NaH2PO4), 제일인산칼륨(KH2PO4) 및 제일인산암모늄((NH4)H2PO4)으로 이루어진 군에서 선택된 1종 이상인 것인 식각액 조성물.In claim 1,
An etchant composition wherein the phosphate-based compound is at least one selected from the group consisting of sodium phosphate monobasic (NaH 2 PO 4 ), potassium phosphate monobasic (KH 2 PO 4 ), and ammonium phosphate monobasic ((NH 4 )H 2 PO 4 ). .
상기 황산염계 화합물이 황산수소칼륨(KHSO4), 황산수소나트륨(NaHSO4), 황산수소암모늄((NH4)HSO4), 황산칼륨(K2SO4), 황산나트륨(Na2SO4) 및 황산암모늄((NH4)2SO4)으로 이루어진 군에서 선택된 1종 이상인 것인 식각액 조성물.In claim 1,
The sulfate-based compounds include potassium hydrogen sulfate (KHSO 4 ), sodium hydrogen sulfate (NaHSO 4 ), ammonium hydrogen sulfate ((NH 4 )HSO 4 ), potassium sulfate (K 2 SO 4 ), sodium sulfate (Na 2 SO 4 ), and An etchant composition comprising at least one selected from the group consisting of ammonium sulfate ((NH 4 ) 2 SO 4 ).
상기 불소계 화합물이 불화수소(HF), 불화나트륨(NaF), 불화수소나트륨(NaHF2), 불화암모늄(NH4F), 산성불화암모늄(NH4HF2), 불화붕소산암모늄(NH4BF4), 불화칼륨(KF), 불화수소칼륨(KHF2) 및 불화알루미늄(AlF3)으로 이루어진 군에서 선택된 1종 이상인 것인 식각액 조성물.In claim 1,
The fluorine-based compound is hydrogen fluoride (HF), sodium fluoride (NaF), sodium hydrogen fluoride (NaHF 2 ), ammonium fluoride (NH 4 F), acidic ammonium fluoride (NH 4 HF 2 ), and ammonium fluoroborate (NH 4 BF). 4 ), potassium fluoride (KF), potassium hydrogen fluoride (KHF 2 ), and aluminum fluoride (AlF 3 ).
상기 킬레이트제가 이미노디아세트산(iminodiacetic acid), 디글리콜산(diglycolic acid), 티오글리콜산(thioglycolic acid), 니트릴로트리아세트산(nitrilotriacetic acid), 에틸렌디아민테트라아세트산(ethylenediaminetetraacetic acid), 디에틸렌트리니트릴펜타아세트산(diethylenetrinitrilacetic acid), 아미노트리스(메틸렌포스폰산)(aminotris(methylenephosphonic acid)), (1-히드록시에탄-1,1-디일)비스(포스폰산)((1-hydroxyethane-1,1-diyl)bis(phosphonic acid)), 에틸렌디아민테트라(메틸렌포스폰산)(ethylenediamine tetra(methylene phosphonic acid)), 디에틸렌트리아민 펜타(메틸렌포스폰산)(Diethylenetriamine penta(methylene phosphonic acid), 알라닌(alanine), 글루탐산(glutamic acid), 아미노부티르산(aminobutyric acid) 및 글리신(glycin)으로 이루어진 군에서 선택된 1종 이상인 것인 식각액 조성물.In claim 1,
The chelating agent is iminodiacetic acid, diglycolic acid, thioglycolic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetrinitrile pentaacetic acid. (diethylenetrinitrilacetic acid), aminotris(methylenephosphonic acid), (1-hydroxyethane-1,1-diyl)bis(phosphonic acid)((1-hydroxyethane-1,1-diyl) bis(phosphonic acid)), ethylenediamine tetra(methylene phosphonic acid), Diethylenetriamine penta(methylene phosphonic acid), alanine, glutamic acid An etchant composition comprising at least one selected from the group consisting of glutamic acid, aminobutyric acid, and glycin.
상기 부식방지제가 퓨란(furane), 티오펜(thiophene), 피롤(pyrrole), 옥사졸(oxazole), 이미다졸(imidazole), 메틸이미다졸(methylimidazole), 피라졸(pyrazole), 트리아졸(triazole), 아미노트리아졸(aminotriazole), 테트라졸(tetrazole), 5-아미노테트라졸(5-aminotetrazole), 메틸테트라졸(methyltetrazole), 피페라진(piperazine), 메틸피페라진(methylpiperazine), 히드록실에틸피페라진(hydroxyethylpiperazine), 피롤리딘(pyrrolidine), 알록산(alloxan), 벤조퓨란(benzofurane), 벤조티오펜(benzothiophene), 인돌(indole), 벤즈이미다졸(benzimidazole), 벤즈피라졸(benzpyrazole), 톨루트리아졸(tolutriazole), 히드로톨루트리아졸(hydrotolutriazole) 및 히드록시톨루트리아졸(hydroxytolutriazole)로 이루어진 군에서 선택된 1종 이상인 것인 식각액 조성물.In claim 1,
The corrosion inhibitors include furan, thiophene, pyrrole, oxazole, imidazole, methylimidazole, pyrazole, and triazole. ), aminotriazole, tetrazole, 5-aminotetrazole, methyltetrazole, piperazine, methylpiperazine, hydroxylethyl pipe hydroxyethylpiperazine, pyrrolidine, alloxan, benzofurane, benzothiophene, indole, benzimidazole, benzpyrazole, An etchant composition comprising at least one selected from the group consisting of tolutriazole, hydrotolutriazole, and hydroxytolutriazole.
상기 인산 또는 인산염계 화합물과 상기 황산염계 화합물의 총 함량이 0.2 내지 0.35 중량부인 것인 식각액 조성물.In claim 1,
An etchant composition wherein the total content of the phosphoric acid or phosphate-based compound and the sulfate-based compound is 0.2 to 0.35 parts by weight.
상기 금속막은 구리막, 또는 구리 합금막인 것인 식각 방법.In claim 8,
An etching method wherein the metal film is a copper film or a copper alloy film.
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