KR20030079740A - Etchant composition for aluminum (or aluminum alloy) single layer and multi layers - Google Patents
Etchant composition for aluminum (or aluminum alloy) single layer and multi layers Download PDFInfo
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- KR20030079740A KR20030079740A KR1020030020425A KR20030020425A KR20030079740A KR 20030079740 A KR20030079740 A KR 20030079740A KR 1020030020425 A KR1020030020425 A KR 1020030020425A KR 20030020425 A KR20030020425 A KR 20030020425A KR 20030079740 A KR20030079740 A KR 20030079740A
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- Prior art keywords
- composition
- acid
- aluminum
- etching
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- 239000000203 mixture Substances 0.000 title claims abstract description 56
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 48
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 19
- 239000010410 layer Substances 0.000 title description 22
- 239000002356 single layer Substances 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 239000007800 oxidant agent Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 15
- 239000011737 fluorine Substances 0.000 claims abstract description 15
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 22
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 11
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 6
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000012425 OXONE® Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 claims description 5
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 claims description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- -1 diazole compound Chemical class 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-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
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910016569 AlF 3 Inorganic materials 0.000 claims description 2
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- OYLGLPVAKCEIKU-UHFFFAOYSA-N diazanium;sulfonato sulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OS([O-])(=O)=O OYLGLPVAKCEIKU-UHFFFAOYSA-N 0.000 claims description 2
- 239000007884 disintegrant Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-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
- 239000003112 inhibitor Substances 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 2
- 239000011593 sulfur Substances 0.000 claims 2
- 229910052717 sulfur Inorganic materials 0.000 claims 2
- SXFBQAMLJMDXOD-UHFFFAOYSA-N (+)-hydrogentartrate bitartrate salt Chemical compound OC(=O)C(O)C(O)C(O)=O.OC(=O)C(O)C(O)C(O)=O SXFBQAMLJMDXOD-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- NIFHFRBCEUSGEE-UHFFFAOYSA-N oxalic acid Chemical compound OC(=O)C(O)=O.OC(=O)C(O)=O NIFHFRBCEUSGEE-UHFFFAOYSA-N 0.000 claims 1
- HUPQYPMULVBQDL-UHFFFAOYSA-N pentanoic acid Chemical compound CCCCC(O)=O.CCCCC(O)=O HUPQYPMULVBQDL-UHFFFAOYSA-N 0.000 claims 1
- KAQHZJVQFBJKCK-UHFFFAOYSA-L potassium pyrosulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OS([O-])(=O)=O KAQHZJVQFBJKCK-UHFFFAOYSA-L 0.000 claims 1
- SXBRULKJHUOQCD-UHFFFAOYSA-N propanoic acid Chemical compound CCC(O)=O.CCC(O)=O SXBRULKJHUOQCD-UHFFFAOYSA-N 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 238000005530 etching Methods 0.000 abstract description 57
- 239000007788 liquid Substances 0.000 abstract description 7
- 239000010408 film Substances 0.000 description 34
- 229910052751 metal Inorganic materials 0.000 description 23
- 239000002184 metal Substances 0.000 description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000001039 wet etching Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001312 dry etching Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000010186 staining Methods 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RALRVIPTUXSBPO-UHFFFAOYSA-N 4-[4-chloro-3-(trifluoromethyl)phenyl]piperidin-4-ol Chemical compound C=1C=C(Cl)C(C(F)(F)F)=CC=1C1(O)CCNCC1 RALRVIPTUXSBPO-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-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
- 239000004159 Potassium persulphate Substances 0.000 description 1
- 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004148 unit process 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
- C23F1/20—Acidic compositions for etching aluminium or alloys thereof
-
- 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
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
Abstract
본 발명은 알루미늄(또는 알루미늄 합금)층을 함유한 다층막 및 단일막을 식각하기 위한 새로운 형태의 식각액 조성물에 관한 것으로, 전체 조성물 총중량에 대하여 1∼15 중량% 의 Fe3+, 3∼20 중량% 의 HNO3, 0.1∼5.0 중량% 의 함불소 화합물, 0.1∼5.0 중량% 의 산화제, 0∼5.0 중량% 의 식각 조절제, 및 전체 조성물 총중량이 100 중량% 가 되도록 하는 물을 함유하는 식각액 조성물은 제공한다. 본 발명에 의하면, 장비의 의존성이 전혀 없고, 알루미늄(또는 알루미늄 합금)층을 함유한 다층막 및 단일막은 경사각이 60 도 이하로 매우 양호한 식각 특성을 갖는 식각액을 제공할 수 있다.The present invention relates to a new type of etching liquid composition for etching a multilayer and a single film containing an aluminum (or aluminum alloy) layer, comprising 1 to 15% by weight of Fe 3+ , 3 to 20% by weight, based on the total weight of the total composition. An etchant composition comprising HNO 3 , 0.1-5.0 wt% fluorine-containing compound, 0.1-5.0 wt% oxidant, 0-5.0 wt% etch regulator, and water such that the total weight of the total composition is 100 wt% is provided. . According to the present invention, there is no dependence of equipment, and multilayer films and single films containing an aluminum (or aluminum alloy) layer can provide an etching liquid having very good etching characteristics with an inclination angle of 60 degrees or less.
Description
본 발명은 반도체 장치에서 금속막의 습식 식각용으로 사용되는 새로운 식각액 조성물에 관한 것으로, 보다 구체적으로 TFT-LCD 공정 중에 사용되는 알루미늄(Al) (또는 알루미늄 합금(Al 합금))층을 함유한 다층막 및 단일막을 식각하기 위한 새로운 형태의 식각액 조성물에 관한 것이다.The present invention relates to a novel etchant composition used for wet etching of a metal film in a semiconductor device, and more particularly, to a multilayer film containing an aluminum (Al) (or aluminum alloy (Al alloy)) layer used during a TFT-LCD process; A new type of etchant composition for etching a single membrane.
반도체 장치에서 기판 위에 금속 배선을 형성하는 과정은 통상적으로 스퍼터링에 의한 금속막 형성공정, 포토레지스트 도포, 노광 및 현상에 의한 선택적인 영역에서의 포토레지스트 형성공정, 및 식각 공정에 의한 단계로 구성되고, 개별적인 단위 공정 전후의 세정 공정 등을 포함한다. 이러한 식각 공정은 포토레지스트 마스크를 사용하여 선택적인 영역에 금속막을 남기는 공정을 의미하며, 통상적으로 플라즈마 등을 이용한 건식 식각 또는 식각 용액을 사용하는 습식 식각이 사용된다.The process of forming the metal wiring on the substrate in the semiconductor device is generally composed of a metal film forming process by sputtering, a photoresist forming process in a selective region by photoresist coating, exposure and development, and an etching process. And washing processes before and after individual unit processes. The etching process refers to a process of leaving a metal film in a selective region using a photoresist mask, and typically, a dry etching using a plasma or the like, or a wet etching using an etching solution is used.
이러한 반도체 장치에서, TFT-LCD (thin film transistor liquid crystal display) 의 배선재료로서 일반적으로 사용되는 금속은 알루미늄 또는 알루미늄 합금으로서, 순수한 알루미늄은 화학물질에 대한 내성이 약하고 후속 공정에서 배선 결합 문제를 야기할 수 있으므로 알루미늄 합금 형태로 사용되거나, 알루미늄 또는 알루미늄 합금층 위에 또 다른 금속층, 예컨대 몰리브덴, 크롬, 텅스텐, 주석 등의 금속층을 갖는 다층의 적층 구조가 적용될 수 있다.In such semiconductor devices, metals commonly used as wiring materials for thin film transistor liquid crystal displays (TFT-LCDs) are aluminum or aluminum alloys, and pure aluminum has low chemical resistance and causes wiring bonding problems in subsequent processes. As such, it may be used in the form of an aluminum alloy, or a multilayered laminated structure having another metal layer such as molybdenum, chromium, tungsten, tin, or the like on the aluminum or aluminum alloy layer may be applied.
예컨대, Mo/Al-Nd 이중막의 경우 통상 인산-주성분 알루미늄 식각액으로 식각할 수 있으나, 두 층간의 식각 속도 차이로 인하여 Mo 오버행(overhang)이 발생하므로 후속공정으로 이러한 오버행을 건식 식각하는 것으로 알려져 있다.For example, a Mo / Al-Nd double layer can be commonly etched with a phosphate-based aluminum etchant, but since the Mo overhang occurs due to the difference in etching rates between the two layers, it is known to dry etch such an overhang in a subsequent process. .
이와 같이, TFT-LCD 등의 반도체 장치의 배선을 형성하기 위한 금속막을 다중층 구조로 할 경우에는 습식 공정과 건식 공정을 함께 적용함으로서 서로의 단점을 보완하는 것이 일반적이다. 또한, 환경규제가 심해지는 지금 인산-주성분 알루미늄 식각액 이외에 대체 식각액의 필요성이 나타나고 있다.As described above, when the metal film for forming wiring of a semiconductor device such as a TFT-LCD has a multilayer structure, it is common to apply a wet process and a dry process together to compensate for the disadvantages of each other. In addition, there is a need for an alternative etchant in addition to the phosphoric acid-based aluminum etchant as environmental regulations become more severe.
Mo/Al-Nd 이중막을 종래 기술에 의한 알루미늄 식각액으로 습식 식각할 경우, 상부 Mo 층의 식각 속도가 알루미늄 합금층의 식각 속도보다 작기 때문에 상부 Mo 층이 하부 Al-Nd 층의 외부로 돌출되는 단면을 갖게 되는 불량한 프로파일을 나타낸다. 이러한 불량한 프로파일로 인해 후속 공정에서 단차 커버리지(coverage)가 불량하게 되고 상부층이 경사면에서 단선되든가 또는 상하부 금속이 단락될 확률이 커지게 된다. 이러한 경우, 1 차로 알루미늄 식각 용액으로 습식 식각하고, 2 차로 식각 속도의 차이로 인해 미처 식각되지 못하고 하부층 바깥으로 돌출된 상부층을 다시 건식 식각하는 2 단계 공정을 적용하는 것이 일반적이나, 공정이 복잡하여 생산성 및 비용적인 측면에서 불리하며, 제품 손상 등의 문제점이 존재한다.When wet etching Mo / Al-Nd bilayer with aluminum etching liquid according to the prior art, the cross section in which the upper Mo layer protrudes outward from the lower Al-Nd layer because the etching rate of the upper Mo layer is smaller than that of the aluminum alloy layer. Indicates a bad profile that has This poor profile results in poor step coverage in subsequent processes and increases the likelihood that the top layer is disconnected from the slope or the upper and lower metals are shorted. In this case, it is common to apply a two-step process of wet etching first with an aluminum etching solution and dry etching secondly with the upper layer protruding out of the lower layer due to the difference in etching rate. It is disadvantageous in terms of productivity and cost, and there are problems such as product damage.
이러한 종래 기술에 대응하여, 본 출원인에 의해 기 출원된 특허출원 제 1999-41119 호 (공개번호 제 2001-28729 호) 는 인산-주성분 식각액을 개시하고 있으며, 인산, 질산 및 아세트산의 조성비를 특정하게 변화시킴으로써, 상부 Mo 층이 하부 알루미늄 합금층의 외부로 돌출되는 단면을 갖게 되는 불량 프로파일이 없어지고, 추가의 건식 식각이 필요하지 않을 정도로 우수한 프로파일을 수득할 수 있으므로, 2 단계 공정의 종래 기술에 비해 매우 간단하고 경제적으로 식각을 행할 수 있었다.Corresponding to this prior art, Patent Application No. 1999-41119 (Publication No. 2001-28729), previously filed by the present applicant, discloses a phosphoric acid-main component etching solution, and specifically specifies the composition ratio of phosphoric acid, nitric acid and acetic acid. By changing, the defect profile that the upper Mo layer has a cross section protruding to the outside of the lower aluminum alloy layer is eliminated, and an excellent profile can be obtained so that no additional dry etching is required, so that the prior art of the two-step process In comparison, etching was very simple and economical.
그러나, 기판의 크기가 커짐에 따른 장비의 물리적인 특성이 매우 민감하게 작용하여 Mo 오버행이 부분적으로 발생한다거나, 경사각(taper angle)이 당 업계에서 요구되는 60 도가 아닌 여러 가지 각도가 나타나서 얼룩이 발생하는 문제점이 나타나, 결국 장비 의존성에 대한 문제점은 해결되지 못하였다.However, as the size of the substrate increases, the physical characteristics of the equipment are very sensitive, resulting in partial Mo overhang or staining due to various angles other than the 60 degrees required in the industry. The problem appeared, and eventually the problem of equipment dependency was not solved.
이에 본 발명자들은 이러한 문제점을 해결하고자 예의 노력한 결과, 종래의 알루미늄 식각액 즉, 인산, 질산, 초산을 기재로 한 식각액과는 달리, 새로운 조성을 갖는 식각액을 개발할 수 있었으며, 본 발명에 의한 새로운 형태의 식각액은 알루미늄(또는 알루미늄 합금)층을 함유한 다층막 및 단일막에 사용함으로써, 지금까지 장비의 조건에 따라 발생할 수 있는 상부나 하부 금속의 식각 불량 문제, 알루미늄 경사각의 불량, 얼룩문제 등의 장비 의존성, 첨가제로 들어간 계면 활성제가 만드는 문제 및 공정 중 식각 시간이 늘어나면 CD (critical dimension) 손실이 커지는 단점을 완전히 해결할 수 있음을 발견하고 본 발명을 완성하게 되었다.Accordingly, the present inventors have diligently tried to solve these problems. As a result, unlike the conventional aluminum etchant, that is, phosphoric acid, nitric acid, and acetic acid based etchant, the present inventors have been able to develop an etchant having a new composition. By using it for multi-layer and single film containing silver aluminum (or aluminum alloy) layer, equipment dependence such as etching problem of upper or lower metal, defect of aluminum inclination angle, stain problem, etc. The present invention has been found to completely solve the problems created by the surfactants added as additives and the disadvantage of increasing the critical dimension (CD) loss as the etching time increases during the process.
본 발명에 의하면, 경사각이 60 도 이하로 경사진 프로파일이 양호하고, 알루미늄 식각액인 인산-주성분 식각액이 갖는 단점인 얼룩, 상부나 하부 금속의 식각 불량 문제, 경사각의 불량 문제를 모두 해결될 수 있는 장점이 있다.According to the present invention, the inclined angle is less than 60 degrees, the profile is good, and the problem that the disadvantages of the phosphate-based component of the aluminum etchant, the etching problem of the upper or lower metal, the problem of the inclination angle can all be solved There is an advantage.
결국, 본 발명의 목적은, 알루미늄(또는 알루미늄 합금)층을 함유한 다층막 및 단일막을 식각하기 위한 새로운 형태의 식각액 조성물(이하, "알루미늄 식각액 조성물" 이라 함) 을 제공하는 것이다.After all, it is an object of the present invention to provide a new type of etching liquid composition (hereinafter referred to as "aluminum etching liquid composition") for etching a multilayer film and a single film containing an aluminum (or aluminum alloy) layer.
본 발명을 실현하기 위한 수단으로서, Fe3+, HNO3, 함불소 화합물, 산화제, 식각 조절제 및 물을 함유하는 알루미늄 식각액 조성물을 제공한다.As a means for realizing the present invention, there is provided an aluminum etchant composition containing Fe 3 + , HNO 3 , a fluorine-containing compound, an oxidizing agent, an etching control agent and water.
더욱 구체적으로, 본 발명은 전체 조성물 총중량에 대하여 1∼15 중량% 의 Fe3+, 3∼20 중량% 의 HNO3, 0.1∼5.0 중량% 의 함불소 화합물, 0.1∼5.0 중량% 의 산화제, 0∼5.0 중량% 의 식각 조절제, 및 전체 조성물 총중량이 100 중량% 가 되도록 하는 물을 함유하는 알루미늄 식각액 조성물을 제공한다.More specifically, the present invention relates to 1 to 15% by weight of Fe 3+ , 3 to 20% by weight of HNO 3 , 0.1 to 5.0% by weight of fluorine-containing compound, 0.1 to 5.0% by weight of oxidizing agent, 0 An aluminum etchant composition is provided comprising -5.0 wt% of an etchant, and water such that the total weight of the total composition is 100 wt%.
보다 바람직한 구현 예로서의 본 발명은 전체 조성물 총중량에 대하여 1∼10중량% 의 Fe3+, 5∼16 중량% 의 HNO3, 0.1∼3 중량% 의 함불소 화합물, 0.5∼4 중량% 의 산화제, 0∼4 중량% 의 식각 조절제, 및 전체 조성물 총중량이 100 중량% 가 되도록 하는 물을 함유하는 알루미늄 식각액 조성물을 제공한다.As a more preferred embodiment of the present invention, the present invention comprises 1 to 10% by weight of Fe 3+ , 5 to 16% by weight of HNO 3 , 0.1 to 3% by weight of fluorine-containing compound, 0.5 to 4% by weight of oxidizing agent, 0 An aluminum etchant composition is provided containing -4 wt% of an etchant, and water such that the total weight of the total composition is 100 wt%.
이하에서 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명에 의한 식각액 조성물은 알루미늄(또는 알루미늄 합금)층을 함유한 다층막 및 단일막을 식각하기 위한 식각액이다.The etchant composition according to the present invention is an etchant for etching a multilayer film and a single film containing an aluminum (or aluminum alloy) layer.
본 발명에서의 알루미늄(또는 알루미늄 합금) 다층막이란 알루미늄 막과 다른 금속 막질로 이루어진 다층막을 의미한다. 예를 들어 Mo/Al-Nd 이중막의 경우, Mo 막을 상부막으로 하고 Al-Nd 막을 하부막으로 하거나, 그의 역도 성립한다.The aluminum (or aluminum alloy) multilayer film in the present invention means a multilayer film made of an aluminum film and another metal film. For example, in the case of a Mo / Al-Nd double film, the Mo film is made an upper film and the Al-Nd film is made a lower film, or vice versa.
본 발명에서의 알루미늄(또는 알루미늄 합금) 단일막이란 알루미늄 막으로 이루어진 막을 의미한다. 이때 알루미늄 막은 알루미늄 단독 또는 알루미늄 을 주성분으로 하여 합금으로 된 금속막을 포함하며, 순수한 알루미늄 은 화학물질에 대한 내성이 약하고 후속 공정에서 배선 결합 문제를 야기할 수 있으므로 통상 알루미늄 합금의 형태로 제공되며, 특히 Nd 가 합금된 Al-Nd 막이 바람직하게 사용된다.In the present invention, the aluminum (or aluminum alloy) single film means a film made of an aluminum film. In this case, the aluminum film includes a metal film made of aluminum alone or an alloy composed mainly of aluminum, and pure aluminum is generally provided in the form of an aluminum alloy because it is weak in chemical resistance and may cause wiring bonding problems in subsequent processes. Al-Nd films alloyed with Nd are preferably used.
본 발명의 알루미늄 식각액 조성물에 사용되는 Fe3+은 Fe3+를 포함한 염의 형태로 제공되며, 그 종류는 특별히 한정되지는 않으나, 예컨대 FeCl3, Fe(NO3)3, Fe2(SO4)3, NH4Fe(SO4)2, Fe(ClO4)3, FePO4및 Fe(NH4)3(C2O4)3등을 들 수 있으며, 바람직하게는 FeCl3이다.Fe 3+ used in the aluminum etchant composition of the present invention is provided in the form of a salt containing Fe 3+ , and the type thereof is not particularly limited, but for example, FeCl 3 , Fe (NO 3 ) 3 , Fe 2 (SO 4 ) 3 , NH 4 Fe (SO 4 ) 2 , Fe (ClO 4 ) 3 , FePO 4 and Fe (NH 4 ) 3 (C 2 O 4 ) 3 , and the like, and preferably FeCl 3 .
본 발명의 알루미늄 식각액 조성물에 사용된 Fe3+의 함량은 이를 함유하는 염 중에서 Fe3+의 중량만을 고려하여 계산되었다.The content of Fe 3+ used in the aluminum etchant composition of the present invention was calculated by considering only the weight of Fe 3+ in the salt containing it.
본 발명의 알루미늄 식각액 조성물에 사용되는 함불소 화합물은 물에 해리되어 F-를 낼 수 있는 화합물의 형태로 제공되며, HF를 제외한 NaF, NaHF2, NH4F, NH4HF2, NH4BF4, NH4F HF, KF, KHF2, AlF3, 및 HBF4등이 사용될 수 있으며, 바람직하게는 NaF 또는 NH4F 이다.The fluorine-containing compound used in the aluminum etchant composition of the present invention is provided in the form of a compound capable of dissociating in water to give F − , except for HF, NaF, NaHF 2 , NH 4 F, NH 4 HF 2 , and NH 4 BF 4 , NH 4 F HF, KF, KHF 2 , AlF 3 , HBF 4 and the like can be used, preferably NaF or NH 4 F.
함불소 화합물로서 HF 를 사용하였을 경우, 유리 손상(glass attack) 등의 문제가 발생할 수 있으나, 본 발명에 의한 알루미늄 식각액은 HF를 사용하지 않음으로써 유리 손상 등의 문제는 전혀 발생하지 않는다는 장점이 있다.When HF is used as the fluorine-containing compound, problems such as glass attack may occur. However, the aluminum etchant according to the present invention does not use HF, so there is no problem such as glass damage. .
본 발명의 알루미늄 식각액 조성물에 사용되는 산화제의 종류는 특별히 한정되지는 않으나, 예컨대, 옥손(칼륨 모노퍼술페이트), CAN(세릭 암모늄 니트레이트), K2S2O8, Na2S2O8, (NH4)2S2O8, H2SO4, HClO4및 H2O2등의 강산화제가 사용될 수 있으며, 바람직하게는 옥손(칼륨 모노퍼술페이트) 또는 H2SO4이다.The type of oxidizing agent used in the aluminum etchant composition of the present invention is not particularly limited, but, for example, oxone (potassium monopersulfate), CAN (cerium ammonium nitrate), K 2 S 2 O 8 , Na 2 S 2 O 8 Strong oxidants such as, (NH 4 ) 2 S 2 O 8 , H 2 SO 4 , HClO 4 and H 2 O 2 may be used, preferably oxone (potassium monopersulfate) or H 2 SO 4 .
본 발명의 알루미늄 식각액 조성물에 사용되는 식각 조절제란 황산염 또는 디아졸계 화합물, 및 임의의 pH 조절제로 구성되어지며, 식각 속도를 조절하여 경사각이 60 도 이하인 양호한 프로파일을 나타내고, CD 손실을 줄여주어 공정상의마진을 높이는 역할을 한다.The etchant used in the aluminum etchant composition of the present invention is composed of a sulfate or a diazole-based compound, and an arbitrary pH adjuster, and exhibits a good profile having an inclination angle of 60 degrees or less by controlling the etching rate, and reducing the CD loss on the process. It increases the margin.
상기 황산염은 황산암모늄(ammonium sulfate), 과황산암모늄(ammonium disulfate), 황산나트륨(sodium sulfate), 과황산나트륨(sodium disulfate), 황산칼륨(potassium sulfate), 과황산칼륨(potassium disulfate) 과 같이 황산에서 수소가 암모늄이나 알칼리 금속 혹은 알칼리 토금속으로 치환된 염을 의미하며, 알루미늄의 상부 또는 하부의 금속막의 식각 속도를 높여주어 이 금속막이 식각되는 동안 알루미늄이 과하게 식각되어 계단형 테이프 프로파일을 만드는 현상을 막아주는 역할을 한다.The sulfate is hydrogen in sulfuric acid, such as ammonium sulfate, ammonium disulfate, sodium sulfate, sodium disulfate, potassium sulfate, potassium persulphate Is a salt substituted with ammonium, an alkali metal or an alkaline earth metal, and increases the etching rate of the metal film on the upper or lower portion of aluminum to prevent the aluminum from being excessively etched while the metal film is etched to form a stepped tape profile. Play a role.
상기 디아졸계 화합물의 구체적인 예로는 이미다졸 (imidazole), 아미노테트라졸 (aminotetrazole), 인돌 (indole), 푸린 (purine), 피라졸 (pyrazole), 피리딘 (pyridine), 피리미딘 (pyrimidine), 피롤 (pyrrole), 피롤리딘 (pyrrolidine), 피롤린 (pyrroline) 및 그 외 수용성 헤테로시클릭 아민 화합물 (heterocyclic amine compound) 등을 들 수 있으며, 몰리브덴막의 식각 속도를 조절하며 패턴의 CD 손실을 줄여주어 공정상의 마진을 높이는 역할을 한다. 그 중 이미다졸이 가장 바람직하게 사용된다.Specific examples of the diazole-based compound include imidazole, aminotetrazole, indole, purine, pyrazole, pyridine, pyrimidine, pyrrole ( pyrrole), pyrrolidine, pyrroline, and other water-soluble heterocyclic amine compounds.They can control the etching rate of the molybdenum film and reduce the CD loss of the pattern. It increases the margin of the award. Among them, imidazole is most preferably used.
상기 pH 조절제의 예로는 아세트산 (acetic acid), 부탄산 (butanoic acid), 시트르산 (citric acid), 포름산 (formic acid), 글리콜산 (glycolic acid), 말론산 (malonic acid), 옥살산 (oxalic acid), 펜탄산 (pentanoic acid), 프로피온산 (propionic acid), 타르타르산 (tartaric acid) 및 그 외 수용성 유기산을 들 수 있으며, 식각 용액의 pH 를 적당히 맞춰 주어 금속막이 식각될 수 있는 환경을 만들어 준다.Examples of the pH regulator include acetic acid, butanoic acid, citric acid, formic acid, glycolic acid, malonic acid, oxalic acid. , Pentanoic acid, propionic acid, tartaric acid, and other water-soluble organic acids. The pH of the etching solution is properly adjusted to create an environment where the metal film can be etched.
본 발명에 있어서 식각 조절제의 함량은 전체 조성물 총중량의 0∼5.0 중량%, 바람직하게는 0∼4.0 중량% 으로서, 식각 조절제를 함유하지 않은 경우를 포함하며, 식각 조절제를 제외한 Fe3+, HNO3, 함불소 화합물 및 산화제 각 성분의 농도가 비교적 낮은 경우 (실시예 1 내지 5), 식각 조절제를 함유하지 않고도 양호한 경사 프로파일을 나타내나, 각 성분의 농도가 비교적 높은 경우 (실시예 6 내지 10) 에는, 이에 따른 식각 속도 및 식각 경사에 영향이 커지므로 식각 조절제를 첨가할 필요가 있다.In the present invention, the content of the etch regulator is 0 to 5.0% by weight, preferably 0 to 4.0% by weight of the total weight of the total composition, and includes no case where the etch regulator is included, except for the Fe 3+ , HNO 3 , When the concentration of each component of the fluorine-containing compound and the oxidizing agent is relatively low (Examples 1 to 5), but exhibits a good inclination profile without containing an etching regulator, but when the concentration of each component is relatively high (Examples 6 to 10) In this case, it is necessary to add an etch regulator because the effect on the etching rate and the etching inclination is increased.
본 발명의 알루미늄 식각액 조성물은 전체 조성물의 총 중량이 100 중량% 가 되도록 물로 희석한다.The aluminum etchant composition of the present invention is diluted with water such that the total weight of the total composition is 100% by weight.
본 발명의 알루미늄 식각액 조성물은 대부분 물로 구성되며, 상기 Fe3+, HNO3, 함불소 화합물, 산화제 및 식각 조절제를 필수적으로 함유하며, 필요에 따라 계면활성제, 금속 이온 붕쇄제 및 부식 방지제 등의 첨가제를 추가로 함유할 수 있다.The aluminum etchant composition of the present invention is composed mostly of water, and the Fe 3 + , HNO 3 , a fluorine-containing compound, an oxidizing agent and an etching control agent are essential, and if necessary, additives such as surfactants, metal ion disintegrants and corrosion inhibitors. It may further contain.
본 발명의 알루미늄 식각액 조성물은 Fe3+, HNO3, 함불소 화합물, 산화제, 식각 조절제 및 물을 함유할 수 있으며, 물을 제외한 Fe3+/HNO3/함불소 화합물/산화제/식각 조절제의 조성비가 1∼15/3∼20/0.1∼5/0.1∼5/0∼5 (중량%)인 알루미늄 식각액 조성물을 알루미늄(또는 알루미늄 합금)층을 함유한 다층막 또는 단일막에 적용한 경우, 금속 식각 잔류물이 발생하지 않을 뿐 아니라, 경사각이 60 도 이하로 경사 프로파일이 매우 양호한 결과를 나타낼 수 있다. 이러한 결과는 본 발명의 실시예 1 내지 10 를 통해서도 알 수 있다.The aluminum etchant composition of the present invention may contain Fe 3+ , HNO 3 , a fluorine-containing compound, an oxidizing agent, an etching agent, and water, and a composition ratio of Fe 3+ / HNO 3 / fluorine-containing compound / oxidant / etching agent except water. When the aluminum etchant composition having a value of 1 to 15/3 to 20 / 0.1 to 5 / 0.1 to 5/0 to 5 (wt%) is applied to a multilayer film or a single film containing an aluminum (or aluminum alloy) layer, the metal etching residue Not only does water generate, but the inclination profile is 60 degrees or less, which can produce very good results. These results can also be seen through Examples 1 to 10 of the present invention.
한편, 식각액 조성물이 본 발명에서 제시한 함량 범위를 벗어난 경우, 예컨대 비교예 1 내지 4 에서 알 수 있듯이, 금속 식각 잔류물 발생, 얼룩 발생, 부분적인 식각 및 식각 프로파일이 불량하게 나타나게 된다. 이러한 결과는 금속에 대한 산화력의 부족 또는 알루미늄막의 식각 속도가 증대되고, 상대적으로 다른 금속층의 식각 속도의 증감 효과가 감쇄되기 때문에 발생되는 결과라 할 수 있다. 특히, 본 발명의 식각액 조성물에 함유된 산화제는 금속 산화를 도와 식각 잔류물을 제거하며, 균일한 식각이 일어나게 한다.On the other hand, when the etchant composition is out of the content range presented in the present invention, as can be seen in Comparative Examples 1 to 4, for example, metal etching residue generation, stain generation, partial etching and etching profiles appear poorly. This result can be said to be a result of the lack of the oxidation power to the metal or the etching rate of the aluminum film is increased, and the increase or decrease effect of the etching rate of the other metal layer is reduced. In particular, the oxidizing agent contained in the etchant composition of the present invention assists metal oxidation to remove the etching residues, and enables uniform etching.
이하, 실시예를 들어 본 발명을 상세히 설명하지만, 본 발명은 하기 실시예로만 한정되는 것은 아니다.Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited only to a following example.
실시예 1 내지 5Examples 1-5
Mo/Al-Nd 이중막 기판을 다이아몬드 칼을 이용하여 100 mm ×100 mm 로 잘라둔다. FeCl3, HNO3, NaF, 옥손(칼륨 모노퍼술페이트) 및 나머지 물을 표 1 에 기재된 전체 조성물의 총중량에 대한 조성비로 함유하는 식각액을 10 kg 이 되도록 제조한다. 분사식 식각 방식의 실험장비 (KDNS사 제조, 모델명: ETCHER(TFT)) 내에 제조된 식각액을 넣고 온도를 30 ℃ 로 셋팅하여 가온한 후, 온도가 30±0.5℃에 도달하면 식각 공정을 수행한다. 유리를 넣고 분사를 시작하여 식각이 다 되면 꺼내어 탈이온수로 세정한 후, 열풍(熱風)건조장치를 이용하여 건조하고, 포토 레지스트(PR) 박리기(stripper)를 이용하여 포토 레지스트를 제거한다. 세정 및 건조 후 전자주사현미경 (SEM ; HITACHI사 제조, 모델명: S-4200)을 이용하여 식각 프로파일을 경사각, CD (critical dimension) 손실, 식각 잔류물 등으로 평가한다. 그 결과를 표 1 에 나타낸다. 각 성분의 함량이 본 발명에 의한 알루미늄 식각액 조성물의 조성범위에 해당하므로, 금속 식각 잔류물이 발생하지 않을 뿐 아니라, 경사각이 60 도 이하로 경사 프로파일이 양호한 결과를 나타내었다.The Mo / Al-Nd bilayer substrate is cut into 100 mm x 100 mm using a diamond knife. An etchant containing FeCl 3 , HNO 3 , NaF, oxone (potassium monopersulfate) and the remaining water in a composition ratio to the total weight of the total composition described in Table 1 was prepared to be 10 kg. After inserting the prepared etching solution in the experimental equipment of the spray etching method (manufactured by KDNS, model name: ETCHER (TFT)) and set the temperature to 30 ℃ warmed, the etching process is performed when the temperature reaches 30 ± 0.5 ℃. After the glass is started and sprayed, the etching is completed, the glass is removed, washed with deionized water, dried using a hot air dryer, and removed using a photoresist stripper. After washing and drying, the etching profile is evaluated using an electron scanning microscope (SEM; manufactured by HITACHI, model name: S-4200) with an inclination angle, critical dimension (CD) loss, and etching residue. The results are shown in Table 1. Since the content of each component corresponds to the composition range of the aluminum etchant composition according to the present invention, not only the metal etching residue is generated, but the inclination angle is 60 degrees or less, indicating a good result.
실시예 6 내지 8Examples 6-8
FeCl3, HNO3, NH4F, H2SO4, 이미다졸 및 나머지 물을 표 1 에 기재된 조성비로 배합하여 제조된 식각액을 사용하는 것 이외에는 실시예 1 과 동일한 방법으로 실시한다. 그 결과를 표 1 에 나타낸다. 각 성분의 함량이 본 발명에 의한 알루미늄 식각액 조성물의 조성범위에 해당하므로, 경사각이 60 도 이하로 경사 프로파일이 양호한 결과를 나타내었다.FeCl 3 , HNO 3 , NH 4 F, H 2 SO 4 , imidazole and the remainder are carried out in the same manner as in Example 1 except using an etching solution prepared by combining the composition ratio shown in Table 1. The results are shown in Table 1. Since the content of each component corresponds to the composition range of the aluminum etchant composition according to the present invention, the inclination angle was 60 degrees or less, showing a good inclination profile.
실시예 9 및 10Examples 9 and 10
Mo/Al-Nd 이중막 기판 대신 Al/Cr 기판을 이용하고, FeCl3, HNO3, NH4F, H2SO4, 이미다졸 및 나머지 물을 표 1 에 기재된 조성비로 배합하여 제조된 식각액을 사용하는 것 이외에는 실시예 1 과 동일한 방법으로 실시한다. 그 결과를 표 1 에 나타낸다. 각 성분의 함량이 본 발명에 의한 알루미늄 식각액 조성물의 조성범위에 해당하므로, 경사각이 60 도 이하로 경사 프로파일이 양호한 결과를 나타내었다.An etchant prepared by using an Al / Cr substrate instead of a Mo / Al-Nd bilayer substrate and combining FeCl 3 , HNO 3 , NH 4 F, H 2 SO 4 , imidazole and the remaining water in the composition ratios shown in Table 1 Except for using, the same method as in Example 1 was carried out. The results are shown in Table 1. Since the content of each component corresponds to the composition range of the aluminum etchant composition according to the present invention, the inclination angle was 60 degrees or less, showing a good inclination profile.
비교예 1 내지 4Comparative Examples 1 to 4
FeCl3, HNO3, NaF, 옥손(칼륨 모노퍼술페이트) 및 나머지 물을 표 2 에 기재된 조성비로 배합하여 제조된 식각액을 사용하는 것 이외에는 실시예 1 과 동일한 방법으로 실시한다. 그 결과를 표 2 에 나타낸다. 식각액 조성물이 본 발명에서 제시한 함량 범위를 벗어난 경우에 해당하므로, 금속 식각 잔류물 발생, 얼룩 발생, 부분적인 식각 및 식각 프로파일이 불량하게 나타남을 알 수 있다.FeCl 3 , HNO 3 , NaF, oxone (potassium monopersulfate) and the remaining water was carried out in the same manner as in Example 1 except using an etching solution prepared by combining the composition ratio shown in Table 2. The results are shown in Table 2. Since the etchant composition is outside the content ranges set forth in the present invention, it can be seen that metal etching residue generation, stain generation, partial etching and etching profiles are poor.
본 발명에 의하면, 알루미늄(또는 알루미늄 합금)층을 함유한 다층막 및 단일막을 식각하기 위한 새로운 형태의 식각액 조성물에 관한 것으로, 장비의 의존성이 전혀 없고, 알루미늄을 함유한 다양한 종류의 기판을 식각 할 수 있으며, 경사각이 60 도 이하로 매우 양호한 식각 특성을 갖는 식각액을 제공할 수 있다.The present invention relates to a new type of etching liquid composition for etching a multilayer film and a single film containing an aluminum (or aluminum alloy) layer, and has no dependence on equipment and can etch various kinds of substrates containing aluminum. In addition, the inclination angle of 60 degrees or less can provide an etching liquid having very good etching characteristics.
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2003
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