KR20240098327A - Etchant composition for metal layer containing silver or indium oxide layer and preparation method thereof - Google Patents
Etchant composition for metal layer containing silver or indium oxide layer and preparation method thereof Download PDFInfo
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- KR20240098327A KR20240098327A KR1020220180007A KR20220180007A KR20240098327A KR 20240098327 A KR20240098327 A KR 20240098327A KR 1020220180007 A KR1020220180007 A KR 1020220180007A KR 20220180007 A KR20220180007 A KR 20220180007A KR 20240098327 A KR20240098327 A KR 20240098327A
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- South Korea
- Prior art keywords
- acid
- compound
- formula
- silver
- alkyl
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 48
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 44
- 239000002184 metal Substances 0.000 title claims abstract description 44
- 239000004332 silver Substances 0.000 title claims abstract description 44
- 229910003437 indium oxide Inorganic materials 0.000 title claims abstract description 25
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910001923 silver oxide Inorganic materials 0.000 title description 2
- 238000002360 preparation method Methods 0.000 title 1
- 229910052709 silver Inorganic materials 0.000 claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 33
- -1 sulfonic acid compound Chemical class 0.000 claims description 33
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 27
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 18
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 17
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 11
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 11
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 6
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 6
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 6
- 150000003460 sulfonic acids Chemical class 0.000 claims description 6
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 5
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 5
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 4
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 4
- XQCHMGAOAWZUPI-UHFFFAOYSA-M sodium;butane-1-sulfonate Chemical compound [Na+].CCCCS([O-])(=O)=O XQCHMGAOAWZUPI-UHFFFAOYSA-M 0.000 claims description 4
- 229960003080 taurine Drugs 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 3
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 claims description 3
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 3
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 claims description 3
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 claims description 3
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 claims description 3
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 3
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 3
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-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
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 235000004279 alanine Nutrition 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 229960004050 aminobenzoic acid Drugs 0.000 claims description 3
- 229940124277 aminobutyric acid Drugs 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 3
- BEHLMOQXOSLGHN-UHFFFAOYSA-N benzenamine sulfate Chemical compound OS(=O)(=O)NC1=CC=CC=C1 BEHLMOQXOSLGHN-UHFFFAOYSA-N 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 229960004365 benzoic acid Drugs 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 claims description 3
- 239000000174 gluconic acid Substances 0.000 claims description 3
- 235000012208 gluconic acid Nutrition 0.000 claims description 3
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 229960002446 octanoic acid Drugs 0.000 claims description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 3
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000343 potassium bisulfate Inorganic materials 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
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- 229940107700 pyruvic acid Drugs 0.000 claims description 3
- 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 claims description 3
- 159000000000 sodium salts Chemical group 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 235000013922 glutamic acid Nutrition 0.000 claims description 2
- 239000004220 glutamic acid Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 238000005530 etching Methods 0.000 abstract description 43
- 238000000034 method Methods 0.000 abstract description 8
- 239000002244 precipitate Substances 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 53
- 230000000052 comparative effect Effects 0.000 description 17
- 229910052738 indium Inorganic materials 0.000 description 9
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- 239000010409 thin film Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 238000011077 uniformity evaluation Methods 0.000 description 2
- ZMCHBSMFKQYNKA-UHFFFAOYSA-N 2-aminobenzenesulfonic acid Chemical compound NC1=CC=CC=C1S(O)(=O)=O ZMCHBSMFKQYNKA-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- DYVDGBSUUIURBC-UHFFFAOYSA-L C(CCC)S(=O)(=O)[O-].C(CCC)S(=O)(=O)[O-].[Na+].[Na+] Chemical compound C(CCC)S(=O)(=O)[O-].C(CCC)S(=O)(=O)[O-].[Na+].[Na+] DYVDGBSUUIURBC-UHFFFAOYSA-L 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229930195712 glutamate Natural products 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
-
- 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
- C23F1/30—Acidic compositions for etching other metallic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
Abstract
본 발명은 인듐산화막 또는 은 함유 금속막 식각액 조성물 및 그 제조방법에 관한 것으로, 본 발명에 따르면 하부막의 손상을 억제하고, 바이어스의 불량 및 잔사 또는 석출물의 발생을 최소화하여 우수한 식각 특성을 나타낼 수 있다.The present invention relates to an etchant composition for an indium oxide film or a silver-containing metal film and a method for manufacturing the same. According to the present invention, damage to the lower film can be suppressed, bias defects and generation of residues or precipitates can be minimized, and excellent etching characteristics can be exhibited. .
Description
본 발명은 인듐산화막 또는 은 함유 금속막을 선택적으로 식각하기 위한 조성물 및 그 제조 방법에 관한 것이다.The present invention relates to a composition for selectively etching an indium oxide film or a silver-containing metal film and a method for manufacturing the same.
디스플레이 반사판은 후면 빛을 전면으로 반사시켜 빛 손실을 줄이는 역할을 한다. 반사율이 높은 은(Ag)을 포함하는 얇은 막은 후면 빛을 전면으로 반사시키는 효율이 백색도료를 처리한 반사판 및 알루미늄 반사판보다 높아 조명도를 2배 가까이 높일 수 있다. 은 막을 사용하는 경우 빛 손실이 적고, 은(Ag)은 다른 금속에 비해 낮은 저항과 높은 휘도를 가지므로 반사판으로 은 막이 사용되고 있다. 또한, 디스플레이 장치의 고해상도 및 대형화에 따라 박막트랜지스터 기판의 배선에 있어서 일반적으로 사용되는 알루미늄 및 구리보다 높은 전도성을 가지는 은을 함유하는 배선이 사용되고 있다.The display reflector serves to reduce light loss by reflecting back light to the front. A thin film containing highly reflective silver (Ag) has a higher efficiency in reflecting back light to the front than a whitewashed reflector or an aluminum reflector, which can increase the illumination intensity by nearly two times. When using a silver film, light loss is small, and silver (Ag) has low resistance and high luminance compared to other metals, so the silver film is used as a reflector. In addition, as display devices become higher resolution and larger, wiring containing silver, which has higher conductivity than aluminum and copper, which are generally used, is being used in the wiring of thin film transistor substrates.
인듐(In)산화물 함유막은 전기 신호를 빛 신호로 변환하는 특성을 가지며 일반적으로 여러 평판 소자에 투명 전기전도성 막으로, 예를 들면 액정표시장치의 투명 전극으로 활용된다.Indium (In) oxide-containing films have the property of converting electrical signals into light signals and are generally used as transparent electrically conductive films in various flat panel devices, for example, as transparent electrodes in liquid crystal displays.
그러나, 종래의 질산, 인산, 황산 또는 초산을 포함하는 식각액을 사용하는 경우에는 은을 포함하는 일부 배선의 단락이 발생할 수 있고, 인듐산화막 또는 은 함유 금속막의 식각 처리 매수가 증가함에 따라 식각 편차가 크게 증가하는 등의 문제점이 발생할 수 있다. However, when using a conventional etchant containing nitric acid, phosphoric acid, sulfuric acid, or acetic acid, short-circuiting of some wiring containing silver may occur, and as the number of etched indium oxide films or silver-containing metal films increases, etching deviation increases. Problems such as a significant increase may occur.
따라서, 인듐산화막 또는 은을 함유하는 금속막을 선택적으로 식각하기 위한 조성물의 연구가 필요하다.Therefore, research on compositions for selectively etching an indium oxide film or a metal film containing silver is needed.
본 발명의 목적은 인듐(In)산화막 또는 은(Ag)을 함유하는 금속막을 균일하게 식각하고, 식각 공정에 따른 석출물의 발생을 방지하기 위한 조성물 및 그 제조방법을 제공하는 것이다.The purpose of the present invention is to provide a composition and a manufacturing method for uniformly etching an indium (In) oxide film or a metal film containing silver (Ag) and preventing the generation of precipitates during the etching process.
상기 과제를 해결하기 위하여 본 발명은,In order to solve the above problem, the present invention,
질소 화합물;nitrogen compounds;
황산염;sulfate;
술폰산 화합물; 및sulfonic acid compounds; and
카복실산을 포함하고,Contains carboxylic acids,
상기 술폰산 화합물이 화학식 1의 화합물 또는 이의 염; 및 화학식 2의 화합물 또는 이의 염을 포함하는 것인, 인듐산화막 또는 은 함유 금속막 식각액 조성물을 제공한다.The sulfonic acid compound is a compound of formula 1 or a salt thereof; and a compound of Formula 2 or a salt thereof.
[화학식 1][Formula 1]
상기 식에서,In the above equation,
R1 은 C1~10알킬이다;R 1 is C 1-10 alkyl;
[화학식 2][Formula 2]
상기 식에서,In the above equation,
R2는 (C1~10알킬)벤질, 벤질, 아미노(C1~10알킬), C1~10알킬 또는 아미노벤질이다.R 2 is (C 1-10 alkyl)benzyl, benzyl, amino(C 1-10 alkyl), C 1-10 alkyl, or aminobenzyl.
일 구현예에 따르면, 상기 화학식 1의 R1이 C1~6알킬이고, 상기 화학식 2의 R2가 (C1~6알킬)벤질, 벤질, 아미노(C1~6알킬), C1~6알킬 또는 아미노벤질일 수 있다.According to one embodiment, R 1 in Formula 1 is C 1~6 alkyl, and R 2 in Formula 2 is (C 1~6 alkyl)benzyl, benzyl, amino(C 1~6 alkyl), C 1~ 6 It can be alkyl or aminobenzyl.
일 구현예에 따르면, 상기 염은 나트륨 염 또는 칼륨 염일 수 있다.According to one embodiment, the salt may be a sodium salt or a potassium salt.
일 구현예에 따르면, 상기 질소 화합물은 질산을 포함할 수 있다.According to one embodiment, the nitrogen compound may include nitric acid.
일 구현예에 따르면, 상기 화학식 1의 화합물은 메탄술폰산을 포함할 수 있다.According to one embodiment, the compound of Formula 1 may include methanesulfonic acid.
일 구현예에 따르면, 상기 화학식 2의 화합물은 톨루엔술폰산, 벤젠술폰산, 타우린, 부탄술폰산 나트륨 및 아닐린술폰산 중 하나 이상을 포함할 수 있다.According to one embodiment, the compound of Formula 2 may include one or more of toluenesulfonic acid, benzenesulfonic acid, taurine, sodium butanesulfonate, and anilinesulfonic acid.
일 구현예에 따르면, 상기 술폰산 화합물의 총 함량은 조성물 100중량부에 대하여 5 내지 30중량부일 수 있다.According to one embodiment, the total content of the sulfonic acid compound may be 5 to 30 parts by weight based on 100 parts by weight of the composition.
일 구현예에 따르면, 상기 카복실산은 시트르산, 아세트산, 숙신산, 글루타르산, 아디프산, 피멜산, 수베르산, 말산, 타르타르산, 락트산, 프로피온산, 카프로산, 카프릴산, 페닐아세트산, 벤조산, 벤젠모노카르복실산, 니트로벤조산, 히드록시벤조산, 아미노벤조산, 디아세트산, 피루빈산, 글루콘산, 글리콜산, 이미노디아세트산, 니트릴로트리아세트산, 에틸렌디아민테트라아세트산, 알라닌, 글루탐산, 아미노부티르산, 글리신 및 이미노디숙신산 중 하나 이상을 포함할 수 있다.According to one embodiment, the carboxylic acid is citric acid, acetic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, malic acid, tartaric acid, Lactic acid, propionic acid, caproic acid, caprylic acid, phenylacetic acid, benzoic acid, benzene monocarboxylic acid, nitrobenzoic acid, hydroxybenzoic acid, aminobenzoic acid, diacetic acid, pyruvic acid, gluconic acid, glycolic acid, iminodiacetic acid, nitrile. It may include one or more of lotriacetic acid, ethylenediaminetetraacetic acid, alanine, glutamic acid, aminobutyric acid, glycine, and iminodisuccinic acid.
일 구현예에 따르면, 상기 황산염은 황산수소암모늄, 황산암모늄, 황산수소칼륨, 황산칼륨, 황산수소나트륨 및 황산나트륨 중 하나 이상을 포함할 수 있다.According to one embodiment, the sulfate may include one or more of ammonium hydrogen sulfate, ammonium sulfate, potassium hydrogen sulfate, potassium sulfate, sodium hydrogen sulfate, and sodium sulfate.
본 발명의 다른 구현예에 따르면,According to another embodiment of the present invention,
질소 화합물 1 내지 30중량부;1 to 30 parts by weight of a nitrogen compound;
황산염 5 내지 30중량부;5 to 30 parts by weight of sulfate;
술폰산 화합물 5 내지 30중량부;5 to 30 parts by weight of a sulfonic acid compound;
카복실산 20 내지 60중량부 및20 to 60 parts by weight of carboxylic acid and
조성물의 전체 중량이 100 중량부가 되도록 하는 잔량의 물을 혼합하는 단계를 포함하고,Comprising the step of mixing the remaining amount of water so that the total weight of the composition is 100 parts by weight,
상기 술폰산 화합물이 화학식 1의 화합물 또는 이의 염; 및 화학식 2의 화합물 또는 이의 염을 포함하는 것인, 인듐산화막 또는 은 함유 금속막 식각액 조성물의 제조방법을 제공한다.The sulfonic acid compound is a compound of formula 1 or a salt thereof; and a method for producing an indium oxide film or a silver-containing metal film etchant composition comprising the compound of Formula 2 or a salt thereof.
[화학식 1][Formula 1]
상기 식에서,In the above equation,
R1은 C1~10알킬이다;R 1 is C 1-10 alkyl;
[화학식 2][Formula 2]
상기 식에서,In the above equation,
R2는 (C1~10알킬)벤질, 벤질, 아미노(C1~10알킬), C1~10알킬 또는 아미노벤질이다.R 2 is (C 1-10 alkyl)benzyl, benzyl, amino(C 1-10 alkyl), C 1-10 alkyl, or aminobenzyl.
일 구현예에 따르면, 상기 술폰산 화합물은 화학식 1의 화합물 또는 이의 염; 및 화학식 2의 화합물 또는 이의 염을 1:0.1 내지 1:5의 중량비로 포함할 수 있다.According to one embodiment, the sulfonic acid compound is a compound of Formula 1 or a salt thereof; and a compound of Formula 2 or a salt thereof at a weight ratio of 1:0.1 to 1:5.
일 구현예에 따르면, 상기 술폰산 화합물과 상기 황산염은 1:0.3 내지 1:3의 중량비로 혼합되는 것일 수 있다.According to one embodiment, the sulfonic acid compound and the sulfate may be mixed at a weight ratio of 1:0.3 to 1:3.
기타 본 발명에 따른 구현예들의 구체적인 사항은 이하의 상세한 설명에 포함되어 있다.Specific details of other embodiments according to the present invention are included in the detailed description below.
본 발명에 따른 식각액 조성물은 인듐산화막 또는 은을 포함하는 금속막의 식각 속도를 향상시키고, 균일한 식각 특성을 가진다.The etchant composition according to the present invention improves the etching rate of an indium oxide film or a metal film containing silver and has uniform etching characteristics.
본 발명은 다양한 변환을 가할 수 있고 여러 가지 실시예를 가질 수 있는 바, 특정 실시예를 예시하고 상세하게 설명하고자 한다. 그러나, 이는 본 발명을 특정한 실시 형태에 대하여 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변환, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다. 본 발명을 설명함에 있어서 관련된 공지 기술에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우 그 상세한 설명을 생략한다.Since the present invention can be modified in various ways and have various embodiments, specific embodiments will be exemplified and described in detail. However, this is not intended to limit the present invention to specific embodiments, and should be understood to include all transformations, equivalents, and substitutes included in the spirit and technical scope of the present invention. In describing the present invention, if it is determined that a detailed description of related known technologies may obscure the gist of the present invention, the detailed description will be omitted.
본 명세서 내에서 특별한 언급이 없는 한, "내지"라는 표현은 해당 수치를 포함하는 표현으로 사용된다. 구체적으로 예를 들면, "1 내지 2"라는 표현은 1 및 2를 포함할 뿐만 아니라 1과 2 사이의 수치를 모두 포함하는 것을 의미한다. Unless otherwise specified within the specification, the expression “to” is used as an expression including the corresponding numerical value. Specifically, for example, the expression “1 to 2” means not only including 1 and 2, but also including all numerical values between 1 and 2.
반도체 기판의 식각 공정 중에는 하부 금속막이 손상되는 문제점이 발생할 수 있으며, 하부막은 구리, 알루미늄 등을 포함할 수 있다. 본 발명은 하부막의 종류에 관계없이 하부 금속막의 손상을 최소화하면서도, 상부막인 인듐산화막 및 은 함유 금속막 식각 특성을 향상시킬 수 있는 식각액 조성물을 제공하고자 한다.During the etching process of a semiconductor substrate, a problem may occur in which the lower metal layer is damaged, and the lower layer may include copper, aluminum, etc. The present invention seeks to provide an etchant composition that can improve the etching properties of the indium oxide film and silver-containing metal film, which are the upper film, while minimizing damage to the lower metal film regardless of the type of the lower film.
이하, 본 발명에 따른 인듐(In) 산화막 또는 은(Ag) 함유 금속막용 식각액 조성물에 대하여 상세히 설명한다.Hereinafter, the etchant composition for an indium (In) oxide film or a silver (Ag)-containing metal film according to the present invention will be described in detail.
본 발명의 일 실시형태에 따른 식각액 조성물은 표시장치의 투명전극 등으로 사용되는 인듐(In)산화물, 또는 반사판이나 박막트랜지스터(TFT, thin film transistor) 금속 배선으로 사용되는 은(Ag) 함유 금속막을 식각하기 위한 것으로, 상기 금속막은 합금막, 단일막 또는 다층막일 수 있다. 예를 들면, 다층막은 금속산화물을 포함하는 제 1층, 상기 제1층의 위에 배치되며, 은 또는 은합금을 포함하는 제 2층 및 상기 제2층의 상부에 배치되고, 금속산화물을 포함하는 제 3층을 포함할 수 있다. 구체적으로 예를 들면, 상기 다층막의 제 1층 및 제 3층은 인듐주석 산화물을 포함할 수 있다. 그러나, 본 발명의 실시예들은 상기 삼중막의 식각에 한정되지 않으며, 금속산화물막과 은 함유 막의 이중막 구조 등과 같은 다양한 다층 구조의 식각에 사용될 수 있다. 상기 금속산화물막은 금속, 예를 들면 인듐(In), 주석(Sn) 또는 이들 조합을 포함하는 산화막을 의미할 수 있다. 일 구현예에 따르면, 은합금은 은을 주성분으로 하여, Nd, Cu, Pb, Nb, Ni, Mo, Ni, Cr, Mg, W, Pa 내지 Ti 등 다른 금속을 포함하는 합금 형태와 은의 질화물, 규화물, 탄화물, 산화물 형태 등의 다양한 형태를 포함할 수 있다.The etchant composition according to one embodiment of the present invention contains indium (In) oxide used as a transparent electrode of a display device, or a silver (Ag)-containing metal film used as a reflector or a metal wiring of a thin film transistor (TFT). For etching, the metal film may be an alloy film, a single film, or a multilayer film. For example, the multilayer film includes a first layer containing a metal oxide, disposed on the first layer, a second layer containing silver or a silver alloy, and disposed on top of the second layer and containing a metal oxide. It may include a third layer. Specifically, for example, the first and third layers of the multilayer film may include indium tin oxide. However, embodiments of the present invention are not limited to the etching of the triple layer, and can be used for etching various multilayer structures, such as a double layer structure of a metal oxide layer and a silver-containing layer. The metal oxide film may refer to an oxide film containing a metal, for example, indium (In), tin (Sn), or a combination thereof. According to one embodiment, the silver alloy is an alloy containing silver as a main component and other metals such as Nd, Cu, Pb, Nb, Ni, Mo, Ni, Cr, Mg, W, Pa to Ti, and a nitride of silver, It may include various forms such as silicide, carbide, and oxide forms.
또한 예를 들면 인듐산화막은 구체적으로 인듐아연산화물(IZO), 인듐주석산화물(ITO) 또는 이들의 혼합물과 같은 산화인듐막으로 형성될 수 있고, 화상표시장치용 기판의 전극으로 사용될 수 있다.Also, for example, the indium oxide film may be specifically formed of an indium oxide film such as indium zinc oxide (IZO), indium tin oxide (ITO), or a mixture thereof, and may be used as an electrode for a substrate for an image display device.
구체적인 실시 양태에 따르면, 본 발명은 질소 화합물, 황산염, 술폰산 화합물 및 카복실산을 포함하는 인듐산화막 또는 은 함유 금속막 식각액 조성물을 제공한다.According to a specific embodiment, the present invention provides an etchant composition for an indium oxide film or a silver-containing metal film containing a nitrogen compound, a sulfate, a sulfonic acid compound, and a carboxylic acid.
이하에서는 본 발명의 일 실시형태에 따른 식각액 조성물의 구성성분들에 대해 보다 상세히 설명한다.Hereinafter, the components of the etchant composition according to an embodiment of the present invention will be described in more detail.
질소 화합물nitrogen compounds
본 발명의 일 실시형태에 따른 식각 조성물은 인듐(In) 산화막 또는 은(Ag) 함유 금속막의 표면을 산화시키는 주산화제로서 질소 화합물을 포함한다. 질소 화합물은 은(Ag) 및 산화인듐 등을 빠르게 산화하여 식각할 수 있도록 하며, 예를 들면, 질산을 포함할 수 있다. 구체적으로 예를 들면, 질산은 금속 표면 산화제로 사용할 수 있다.The etching composition according to an embodiment of the present invention includes a nitrogen compound as a main oxidizing agent that oxidizes the surface of an indium (In) oxide film or a silver (Ag) containing metal film. Nitrogen compounds can rapidly oxidize and etch silver (Ag) and indium oxide, and may include, for example, nitric acid. Specifically, for example, nitric acid can be used as a metal surface oxidizing agent.
일 구현예에 따르면, 질소 화합물은 식각액 조성물 100중량부를 기준으로 1 내지 30 중량부, 예를 들면 1 내지 25 중량부, 또는 1 내지 20 중량부, 또는 5 내지 20중량부, 또는 10 내지 20중량부, 또는 20 중량부 이하로 포함할 수 있다. 상기 범위를 만족할 때 은 및 산화인듐 등의 과침식을 방지하여 식각 속도를 조절할 수 있다는 점에서 유리하다.According to one embodiment, the nitrogen compound is 1 to 30 parts by weight, for example, 1 to 25 parts by weight, or 1 to 20 parts by weight, or 5 to 20 parts by weight, or 10 to 20 parts by weight, based on 100 parts by weight of the etchant composition. parts, or 20 parts by weight or less. When the above range is satisfied, it is advantageous in that the etching rate can be controlled by preventing over-erosion of silver and indium oxide.
황산염sulfate
본 발명의 일 실시형태에 따른 식각 조성물은 인듐(In) 산화막 또는 은(Ag) 함유 금속막을 식각하는 식각제로서 황산염을 포함한다. 황산염은 무기 황 화합물로서 후술하는 유기 황 화합물과 구분하여 함께 사용됨으로 인하여 금속을 효과적으로 식각할 수 있다.The etching composition according to an embodiment of the present invention includes sulfate as an etchant for etching an indium (In) oxide film or a silver (Ag)-containing metal film. Sulfate is an inorganic sulfur compound that can effectively etch metal when used separately from the organic sulfur compound described later.
황산염 화합물의 예로는, 황산수소암모늄(ammonium hydrogen sulfate, (NH4)HSO4), 황산암모늄(ammonium sulfate, (NH4)2SO4), 황산수소칼륨(potassium hydrogen sulfate, KHSO4), 황산칼륨(potassium sulfate, K2SO4), 황산수소나트륨(sodium hydrogen sulfate, NaHSO4) 및 황산나트륨(sodium sulfate, Na2SO4) 등을 들 수 있으며, 이들은 각각 단독으로 또는 조합으로 사용될 수 있다. 구체적으로 예를 들면, 황산염으로 황산수소나트륨 및 황산수소암모늄 중 하나 이상을 포함할 수 있다.Examples of sulfate compounds include ammonium hydrogen sulfate (NH 4 )HSO 4 ), ammonium sulfate (NH 4 ) 2 SO 4 ), potassium hydrogen sulfate (KHSO 4 ), and sulfuric acid. Examples include potassium sulfate (K 2 SO 4 ), sodium hydrogen sulfate (NaHSO 4 ), and sodium sulfate (Na 2 SO 4 ), which may be used alone or in combination. Specifically, for example, the sulfate may include one or more of sodium bisulfate and ammonium bisulfate.
일 구현예에 따르면, 황산염은 식각액 조성물 100중량부를 기준으로 5 내지 30중량부, 예를 들면 5 내지 20중량부, 또는 7 내지 15중량부, 또는 10 내지 15중량부 포함할 수 있다. 황산염의 함량이 지나치게 낮을 경우 금속막의 미식각으로 인한 잔사가 발생할 수 있고, 반대로 지나치게 과할 경우 금속막의 과식각에 의한 배선 유실 및 식각 편차 증가의 문제점이 발생할 수 있다.According to one embodiment, the sulfate may be included in an amount of 5 to 30 parts by weight, for example, 5 to 20 parts by weight, or 7 to 15 parts by weight, or 10 to 15 parts by weight, based on 100 parts by weight of the etchant composition. If the sulfate content is too low, residue may occur due to under-etching of the metal film, and conversely, if it is too excessive, problems such as loss of wiring and increased etching deviation due to over-etching of the metal film may occur.
술폰산 화합물sulfonic acid compounds
본 발명의 일 실시형태에 따른 식각 조성물은 인듐(In) 산화막 또는 은(Ag) 함유 금속막을 식각하는 식각제로서 술폰산 화합물을 포함한다. 술폰산 화합물은 유기 황 화합물로서 전술된 무기 황 화합물인 황산염과 구분하여 함께 사용됨으로써 금속을 효과적으로 식각할 수 있다.The etching composition according to an embodiment of the present invention includes a sulfonic acid compound as an etchant for etching an indium (In) oxide film or a silver (Ag)-containing metal film. The sulfonic acid compound is an organic sulfur compound that can effectively etch metal by being used separately from sulfate, which is the inorganic sulfur compound described above.
일 구현예에 따르면, 본 발명의 술폰산 화합물은 화학식 1의 화합물 또는 이의 염과 함께, 화학식 2의 화합물 또는 이의 염을 포함할 수 있다.According to one embodiment, the sulfonic acid compound of the present invention may include a compound of Formula 1 or a salt thereof, as well as a compound of Formula 2 or a salt thereof.
[화학식 1][Formula 1]
상기 식에서,In the above equation,
R1은 C1~10알킬이다;R 1 is C 1-10 alkyl;
[화학식 2][Formula 2]
상기 식에서,In the above equation,
R2는 (C1~10알킬)벤질, 벤질, 아미노(C1~10알킬), C1~10알킬 또는 아미노벤질이다.R 2 is (C 1-10 alkyl)benzyl, benzyl, amino(C 1-10 alkyl), C 1-10 alkyl, or aminobenzyl.
일 구현예에 따르면, 화학식 1의 R1은 C1~6알킬이고, 화학식 2의 R2는 (C1~6알킬)벤질, 벤질, 아미노(C1~6알킬), C1~6알킬 또는 아미노벤질일 수 있다. 구체적으로 예를 들면, 화학식 1의 R1은 메틸, 에틸, 프로필, 부틸, 펜틸 또는 헥실일 수 있다. 또한 화학식 2의 R2는 메틸벤질, 벤질, 아미노에틸, 부틸 또는 아미노벤질일 수 있다.According to one embodiment, R 1 in Formula 1 is C 1-6 alkyl, and R 2 in Formula 2 is (C 1-6 alkyl)benzyl, benzyl, amino(C 1-6 alkyl), C 1-6 alkyl. Or it may be aminobenzyl. Specifically, for example, R 1 in Formula 1 may be methyl, ethyl, propyl, butyl, pentyl, or hexyl. Additionally, R 2 in Formula 2 may be methylbenzyl, benzyl, aminoethyl, butyl, or aminobenzyl.
일 구현예에 따르면, 화학식 1 또는 2의 화합물의 염이 나트륨 염 또는 칼륨염일 수 있다. 구체적으로 예를 들면, 본 발명은 화학식 2의 화합물로 부탄술폰산 나트륨을 포함할 수 있으나, 이에 한정되는 것은 아니며 상기에 기재한 화학식 1 또는 화학식 2의 화합물을 염의 형태로 포함할 수 있다.According to one embodiment, the salt of the compound of Formula 1 or 2 may be a sodium salt or a potassium salt. Specifically, for example, the present invention may include sodium butanesulfonate as the compound of Formula 2, but is not limited thereto and may include the compound of Formula 1 or Formula 2 described above in the form of a salt.
본 명세서에 사용된 용어 “알킬”은 선형 또는 분지형의 포화된 탄화수소 라디칼 사슬을 의미하며, 그 예로는 메틸, 에틸, n-프로필, 아이소프로필, n-부틸, 아이소부틸, t-부틸, n-펜틸, 이소펜틸, 헥실 등을 포함할 수 있으나, 이에 한정되지는 않는다.As used herein, the term “alkyl” refers to a linear or branched saturated hydrocarbon radical chain, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n -May include pentyl, isopentyl, hexyl, etc., but is not limited thereto.
구체적으로 예를 들면, 화학식 1의 화합물은 메탄술폰산(methane sulfonic acid)을 포함할 수 있다. 또한, 화학식 2의 화합물은 톨루엔술폰산(toluene sulfonic acid), 벤젠술폰산(benzene sulfonic acid), 타우린(taurine), 부탄술폰산 나트륨(sodium butane sulfonate) 및 아닐린술폰산(aniline sulfonic acid) 중 하나 이상을 포함할 수 있다.For example, the compound of Formula 1 may include methanesulfonic acid. In addition, the compound of Formula 2 may include one or more of toluene sulfonic acid, benzene sulfonic acid, taurine, sodium butane sulfonate, and aniline sulfonic acid. You can.
일 구현예에 따르면, 본 발명은 상기 화학식 1의 화합물 및 화학식 2의 화합물을 1:0.1 내지 1:5, 예를 들면 1:0.1 내지 1:1, 또는 1:0.5 내지 1:1, 또는 1:1.5 내지 1:3, 또는 1:2 내지 3의 중량비로 포함할 수 있다.According to one embodiment, the present invention provides the compound of Formula 1 and the compound of Formula 2 in a ratio of 1:0.1 to 1:5, for example, 1:0.1 to 1:1, or 1:0.5 to 1:1, or 1. :1.5 to 1:3, or 1:2 to 3 by weight.
일 구현예에 따르면, 술폰산 화합물의 총 함량은 식각액 조성물 100중량부를 기준으로 5 내지 30중량부, 예를 들면 7 내지 25중량부, 또는 10 내지 20중량부, 또는 13 내지 20중량부 포함할 수 있다. 본 발명에서 술폰산 화합물의 총 함량은 화학식 1의 화합물 및 화학식 2의 화합물 함량의 합을 의미한다. According to one embodiment, the total content of the sulfonic acid compound may include 5 to 30 parts by weight, for example, 7 to 25 parts by weight, or 10 to 20 parts by weight, or 13 to 20 parts by weight, based on 100 parts by weight of the etchant composition. there is. In the present invention, the total content of sulfonic acid compounds refers to the sum of the contents of the compound of Formula 1 and the compound of Formula 2.
또한, 본 발명은 술폰산 화합물과 황산염을 구분하여 1:0.3 내지 1:3, 예를 들면 1:0.5 내지 1:1.5, 또는 1:0.5 내지 1:1, 또는 1:1 내지 1:2의 중량비로 포함할 수 있다.In addition, the present invention distinguishes between the sulfonic acid compound and the sulfate, and uses a weight ratio of 1:0.3 to 1:3, for example, 1:0.5 to 1:1.5, or 1:0.5 to 1:1, or 1:1 to 1:2. It can be included as .
술폰산 화합물의 함량이 지나치게 낮을 경우 금속막의 미식각으로 인한 잔사가 발생할 수 있고, 반대로 지나치게 과할 경우 금속막의 과식각에 의한 배선 유실 및 식각 편차 증가의 문제점이 발생할 수 있다.If the content of the sulfonic acid compound is too low, residue may occur due to under-etching of the metal film, and conversely, if it is too excessive, problems such as loss of wiring and increased etching deviation due to over-etching of the metal film may occur.
본 발명의 황산염 및 술폰산 화합물의 술폰산 작용기는 질산에 의해 산화된 금속 이온과 강하게 결합함으로써 안정된 식각이 가능하도록 한다. 술폰산 작용기로 인하여 산화된 금속의 재흡착이 방지되고 잔사 형성이 감소되며, 하부막에 대한 침투력이 약화될 수 있다. 이러한 작용으로 막과 막 사이의 식각액 침투를 억제하여 미세 배선 형성시에 바이어스(bias, 또는 skew 라고도 함)의 불량을 줄일 수 있으며, 배선 직진성을 개선할 수 있다.The sulfonic acid functional group of the sulfate and sulfonic acid compounds of the present invention binds strongly to metal ions oxidized by nitric acid, thereby enabling stable etching. Due to the sulfonic acid functional group, re-adsorption of oxidized metals is prevented, residue formation is reduced, and penetration into the underlying film can be weakened. This action suppresses the penetration of the etchant between the films, reduces defective bias (also called skew) when forming fine wiring, and improves the straightness of the wiring.
카복실산carboxylic acid
본 발명의 일 실시형태에 따른 식각 조성물은 버퍼 또는 킬레이트제로서 카복실산 화합물을 포함한다. 구체적으로는 식각 공정 중에 카복실산 화합물이 금속이온을 킬레이트화하여 식각 용액 내에 녹아 들어갈 수 있도록 안정화시키는 역할을 할 수 있으며, 이에 따라 금속이온이 기판에 환원되어 재흡착되는 것을 방지하는 역할을 할 수 있다. 즉, 식각 후 잔사의 발생을 줄이는 효과가 있다.The etching composition according to one embodiment of the present invention includes a carboxylic acid compound as a buffer or chelating agent. Specifically, during the etching process, carboxylic acid compounds can chelate metal ions and stabilize them so that they can be dissolved in the etching solution, thereby preventing metal ions from being reduced and re-adsorbed to the substrate. . In other words, it has the effect of reducing the generation of residues after etching.
카복실산으로는 예를 들면, 시트르산(citric acid), 아세트산(acetic acid), 숙신산(succinic acid), 글루타르산(glutaric acid), 아디프산(adipic acid), 피멜산(pimelic acid), 수베르산(suberic acid), 말산(malic acid), 타르타르산(tartaric acid), 락트산(lactic acid), 프로피온산(propionic acid), 카프로산(caproic acid), 카프릴산(caprylic acid), 페닐아세트산(phenylacetic acid), 벤조산(benzoic acid), 벤젠모노카르복실산 (benzene monocarboxylic acids), 니트로벤조산(nitrobenzoic acid), 히드록시벤조산(hydroxybenzoic acid), 아미노벤조산(aminobenzoic acid), 디아세트산(diacetic acid), 피루빈산(pyruvic acid), 글루콘산(gluconic acid), 글리콜산(glycolic acid), 이미노디아세트산(iminodiacetic acid), 니트릴로트리아세트산(nitrilotriacetic acid), 에틸렌디아민테트라아세트산(ethylenediaminetetraacetic acid), 알라닌(alanine), 글루탐산(glutamate), 아미노부티르산(aminobutyric acid), 글리신(glycine) 및 이미노디숙신산(iminodisuccinic acid) 중 하나 이상을 포함할 수 있다. 구체적으로 예를 들면, 킬레이트제로 시트르산을 포함함으로 인하여 금속 이온을 안정화하고, 버퍼용액으로 아세트산을 포함할 수 있다.Carboxylic acids include, for example, citric acid, acetic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, and suber. Suberic acid, malic acid, tartaric acid, Lactic acid, propionic acid, caproic acid, caprylic acid, phenylacetic acid, benzoic acid, benzene monocarboxylic acids , nitrobenzoic acid, hydroxybenzoic acid, aminobenzoic acid, diacetic acid, pyruvic acid, gluconic acid, glycolic acid. ), iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, alanine, glutamate, aminobutyric acid, glycine and It may contain one or more of iminodisuccinic acid. Specifically, for example, metal ions may be stabilized by including citric acid as a chelating agent, and acetic acid may be included as a buffer solution.
일 구현예에 따르면, 카복실산의 총 함량은 식각액 조성물 100중량부를 기준으로 20 내지 60중량부, 예를 들면 20 내지 50중량부, 또는 30 내지 50중량부 포함할 수 있다. 구체적인 일 양태에 따르면, 본 발명은 시트르산 10 내지 35중량부, 예를 들면 15 내지 30중량부, 또는 20 내지 30중량부 및 아세트산 10 내지 25중량부, 예를 들면 10 내지 20중량부를 포함할 수 있다.According to one embodiment, the total content of carboxylic acid may include 20 to 60 parts by weight, for example, 20 to 50 parts by weight, or 30 to 50 parts by weight, based on 100 parts by weight of the etchant composition. According to one specific aspect, the present invention may include 10 to 35 parts by weight, for example 15 to 30 parts by weight, or 20 to 30 parts by weight, and 10 to 25 parts by weight, for example, 10 to 20 parts by weight of acetic acid. there is.
물water
본 발명의 일 실시형태에 따른 식각액 조성물은 조성물의 전체 중량이 100 중량%가 되도록 잔량의 물을 포함할 수 있다. 본 발명에서, 상기 물은 특별히 한정하지 않으나, 탈이온수가 바람직하고, 물 속에 이온이 제거된 정도를 보여주는 물의 비저항값이 18㏁·cm 이상인 탈이온수가 보다 바람직하다.The etchant composition according to an embodiment of the present invention may include a residual amount of water so that the total weight of the composition is 100% by weight. In the present invention, the water is not particularly limited, but deionized water is preferable, and deionized water having a water resistivity value of 18 MΩ·cm or more, which shows the degree to which ions have been removed from the water, is more preferable.
상술한 바와 같은 본 발명에 따른 식각액 조성물은 화면표시장치의 투명전극 등으로 사용되는 인듐(In) 산화막 또는, 표시장치의 반사판 또는 배선으로 사용되는 은(Ag) 함유 금속막에 대해서 하부막의 손상을 억제하고, 미세 배선의 형성 시에 바이어스의 불량 및 잔사 또는 석출물의 발생을 최소화하여 우수한 식각 특성을 나타낼 수 있다.As described above, the etchant composition according to the present invention prevents damage to the lower layer of the indium (In) oxide film used as a transparent electrode of a screen display device, or a silver (Ag)-containing metal film used as a reflector or wiring of a display device. It is possible to exhibit excellent etching characteristics by suppressing bias defects and minimizing the generation of residues or precipitates when forming fine wiring.
이하, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 실시예에 대하여 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다.Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement it. However, the present invention may be implemented in many different forms and is not limited to the embodiments described herein.
실시예 및 비교예Examples and Comparative Examples
표 1에 따른 조성으로 인듐산화막 또는 은 함유 금속막용 식각액 조성물을 제조하였다. 함량의 단위는 중량%이다.An etchant composition for an indium oxide film or a silver-containing metal film was prepared with the composition according to Table 1. The unit of content is weight%.
NA: 질산(nitric acid)NA: nitric acid
SHS: 황산수소 나트륨(sodium hydrogen sulfate)SHS: sodium hydrogen sulfate
MSA: 메탄술폰산(methanesulfonic acid)MSA: methanesulfonic acid
CA: 시트르산(citric acid)CA: citric acid
AA: 아세트산(acetic acid)AA: acetic acid
PTSA: p-톨루엔술폰산(p-Toluenesulfonic acid)PTSA: p-Toluenesulfonic acid
BSA: 벤젠술폰산(benzenesulfonic acid)BSA: benzenesulfonic acid
TA: 타우린(taurine)TA: taurine
BSS: 부탄술폰산 나트륨(butane-1-sulfonic acid sodium salt)BSS: Sodium butane-1-sulfonic acid sodium salt
ASA: 아닐린술폰산(aniline-2-sulfonic acid)ASA: aniline-2-sulfonic acid
실험예 1: 식각 속도 평가Experimental Example 1: Etching rate evaluation
실시예 및 비교예의 식각액 조성물에 따른 식각 속도를 평가하기 위하여 시편으로서 기판 상에 ITO(indium tin oxide)/은(Ag)/ITO 삼중막을 형성한 뒤, 상기 삼중막 상에 포토레지스트를 패터닝하였다. 각각의 식각액 조성물을 이용하여 상기 기판에 대한 식각 공정을 수행하였다.In order to evaluate the etching speed according to the etchant composition of Examples and Comparative Examples, an indium tin oxide (ITO)/silver (Ag)/ITO triple layer was formed on a substrate as a specimen, and then photoresist was patterned on the triple layer. An etching process for the substrate was performed using each etchant composition.
식각액 조성물을 각각 10kg으로 wet etcher에 채운 후, 40℃ 온도로 설정하여 준비된 시편에 대한 식각 속도를 평가하였다.After filling the wet etcher with 10 kg of each etchant composition, the temperature was set to 40°C to evaluate the etching rate for the prepared specimen.
삼중막 시편의 전체 영역 중, 포토레지스트가 패터닝되지 않은 영역의 식각이 종료된 시점을 기준으로 식각 속도를 평가하고 표 2에 나타내었다.Among the entire areas of the triple layer specimen, the etch rate was evaluated based on the time when etching of the area where the photoresist was not patterned was completed and is shown in Table 2.
<식각속도 평가 기준><Etching speed evaluation criteria>
◎: 30초 미만◎: Less than 30 seconds
○: 30초 이상 40초 미만○: More than 30 seconds but less than 40 seconds
△: 40초 이상 50초 미만△: More than 40 seconds but less than 50 seconds
X: 50초 이상X: 50 seconds or more
실험예 2: 바이어스 평가Experimental Example 2: Bias Evaluation
실시예 및 비교예의 식각액 조성물을 각각 10kg으로 wet etcher에 채운 후, 40℃ 온도로 설정하여 준비된 시편을 식각 처리하였다. 식각 처리된 시편은 초순수를 이용하여 약 60초 동안 린스 처리 후 3.0kgf/cm2 압력으로 질소 건조 실시하였다.After filling the wet etcher with 10 kg of each of the etchant compositions of Examples and Comparative Examples, the temperature was set to 40°C and the prepared specimen was etched. The etched specimen was rinsed with ultrapure water for about 60 seconds and then dried with nitrogen at a pressure of 3.0 kgf/cm 2 .
포토레지스트의 끝단으로부터 삼중막 시편 중의 은 박막까지의 거리를 전자주사현미경(SEM; 모델명: SU-8010, HITACHI)을 이용하여 측정하고, 표 2에 나타내었다.The distance from the tip of the photoresist to the silver thin film in the triple layer specimen was measured using a scanning electron microscope (SEM; model name: SU-8010, HITACHI) and is shown in Table 2.
실험예 3: 잔사 평가Experimental Example 3: Residue Evaluation
실시예 및 비교예의 식각액 조성물에 따른 식각 후 잔사 정도를 평가하였다.The degree of residue after etching was evaluated according to the etchant compositions of Examples and Comparative Examples.
실험예 1의 결과에 따른 각각의 시편을 주사전자 현미경으로 관찰하여 ITO/Ag/ITO 배선 사이 영역의 잔류 금속막 면적을 관찰하였다.Each specimen according to the results of Experimental Example 1 was observed with a scanning electron microscope to observe the residual metal film area in the area between the ITO/Ag/ITO wiring.
하기의 기준으로 잔사 형성 여부를 판단하여 표 2에 나타내었다.The formation of residues was determined based on the following criteria and is shown in Table 2.
<잔사 평가 기준><Residue evaluation criteria>
◎: 잔사 미발생◎: No residue generated
○: 잔사 거의 없음○: Almost no residue
X: 잔사 발생X: Residue generation
실험예 4: 석출물 평가Experimental Example 4: Precipitate evaluation
실시예 및 비교예의 식각액 조성물에 따른 식각 공정 중의 석출물 형성 정도를 평가하기 위하여, 실험예 1의 결과에 따른 각각의 시편을 주사전자 현미경으로 관찰하였다.In order to evaluate the degree of precipitate formation during the etching process according to the etchant compositions of Examples and Comparative Examples, each specimen according to the results of Experimental Example 1 was observed with a scanning electron microscope.
Ti/Al/Ti 배선 상단에 발생한 은(Ag) 입자의 개수를 측정하고, 하기의 기준으로 평가하여, 표 2에 나타내었다.The number of silver (Ag) particles generated on the top of the Ti/Al/Ti wiring was measured, evaluated based on the following criteria, and shown in Table 2.
<석출물 평가 기준><Precipitate evaluation criteria>
◎: 5개 미만◎: Less than 5
○: 5개 이상 20개 미만○: 5 or more but less than 20
△: 20개 이상 50개 미만△: 20 or more but less than 50
X: 50개 이상X: 50 or more
실험예 5: 식각 균일도 평가Experimental Example 5: Etching uniformity evaluation
실시예 및 비교예의 식각액 조성물에 따른 식각 균일도를 평가하기 위하여, 실험예 및 비교예의 결과에 따른 각각의 시편을 주사전자 현미경으로 관찰하여 형성된 배선의 균일도를 측정하였다.In order to evaluate the etching uniformity according to the etchant composition of the Examples and Comparative Examples, each specimen according to the results of the Experimental Examples and Comparative Examples was observed with a scanning electron microscope to measure the uniformity of the formed wiring.
식각 후의 기판을 수산화 테트라메틸 암모늄(tetramethylammonium hydroxide, TMAH) 용액을 이용하여 상부 포토레지스트를 제거하였다. 전자주사현미경(SEM; 모델명: SU-8010, HITACHI)을 이용하여 삼중막 시편 중 은 박막의 패턴 균일도를 측정하고, 표 3에 나타내었다.The upper photoresist of the etched substrate was removed using a tetramethylammonium hydroxide (TMAH) solution. The pattern uniformity of the silver thin film among the triple layer specimens was measured using a scanning electron microscope (SEM; model name: SU-8010, HITACHI), and is shown in Table 3.
<식각 균일도 평가 기준><Etching uniformity evaluation criteria>
◎: 0.05um 미만◎: Less than 0.05um
○: 0.05이상 0.1um 미만○: More than 0.05 but less than 0.1um
△: 0.1um 이상 0.2um 미만△: More than 0.1um but less than 0.2um
X: 0.2um 이상X: 0.2um or more
이상으로 본 발명의 특정한 부분을 상세히 기술하는 바, 본 발명이 속한 기술분야에서 통상의 지식을 가진 자에게 있어서 이러한 구체적인 기술은 단지 바람직한 구현 예일 뿐이며, 이에 본 발명의 범위가 제한되는 것이 아님은 명백하다. 본 발명이 속한 기술분야에서 통상의 지식을 가진 자라면 상기 내용을 바탕으로 본 발명의 범주 내에서 다양한 응용 및 변형을 행하는 것이 가능할 것이다. 따라서, 본 발명의 실질적인 범위는 첨부된 특허청구범위와 그의 등가물에 의하여 정의된다고 할 것이다.As the specific parts of the present invention have been described in detail above, it is clear to those of ordinary skill in the technical field to which the present invention pertains that these specific techniques are merely preferred implementation examples and do not limit the scope of the present invention. do. Anyone skilled in the art to which the present invention pertains will be able to make various applications and modifications within the scope of the present invention based on the above contents. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.
Claims (12)
황산염;
술폰산 화합물; 및
카복실산을 포함하고,
상기 술폰산 화합물은 화학식 1의 화합물 또는 이의 염; 및 화학식 2의 화합물 또는 이의 염을 포함하는 것인, 인듐산화막 또는 은 함유 금속막 식각액 조성물:
[화학식 1]
상기 식에서,
R1은 C1~10알킬이다;
[화학식 2]
상기 식에서,
R2는 (C1~10알킬)벤질, 벤질, 아미노(C1~10알킬), C1~10알킬 또는 아미노벤질이다.nitrogen compounds;
sulfate;
sulfonic acid compounds; and
Contains carboxylic acids,
The sulfonic acid compound is a compound of formula 1 or a salt thereof; and an etchant composition for an indium oxide film or a silver-containing metal film, comprising a compound of Formula 2 or a salt thereof:
[Formula 1]
In the above equation,
R 1 is C 1-10 alkyl;
[Formula 2]
In the above equation,
R 2 is (C 1-10 alkyl)benzyl, benzyl, amino(C 1-10 alkyl), C 1-10 alkyl, or aminobenzyl.
상기 화학식 1의 R1이 C1~6알킬이고,
상기 화학식 2의 R2가 (C1~6알킬)벤질, 벤질, 아미노(C1~6알킬), C1~6알킬 또는 아미노벤질인 것인, 인듐산화막 또는 은 함유 금속막 식각액 조성물.According to paragraph 1,
R 1 of Formula 1 is C 1-6 alkyl,
An etchant composition for an indium oxide film or a silver-containing metal film, wherein R 2 of Formula 2 is (C 1-6 alkyl)benzyl, benzyl, amino (C 1-6 alkyl), C 1-6 alkyl, or aminobenzyl.
상기 염이 나트륨 염 또는 칼륨 염인 것인, 인듐산화막 또는 은 함유 금속막 식각액 조성물.According to paragraph 1,
An etchant composition for an indium oxide film or a silver-containing metal film, wherein the salt is a sodium salt or a potassium salt.
상기 질소 화합물이 질산을 포함하는 것인, 인듐산화막 또는 은 함유 금속막 식각액 조성물.According to paragraph 1,
An etchant composition for an indium oxide film or a silver-containing metal film, wherein the nitrogen compound includes nitric acid.
상기 화학식 1의 화합물이 메탄술폰산을 포함하는 것인, 인듐산화막 또는 은 함유 금속막 식각액 조성물.According to paragraph 1,
An etchant composition for an indium oxide film or a silver-containing metal film, wherein the compound of Formula 1 includes methanesulfonic acid.
상기 화학식 2의 화합물이 톨루엔술폰산, 벤젠술폰산, 타우린, 부탄술폰산 나트륨 및 아닐린술폰산 중 하나 이상을 포함하는 것인, 인듐산화막 또는 은 함유 금속막 식각액 조성물.According to paragraph 1,
An etchant composition for an indium oxide film or a silver-containing metal film, wherein the compound of Formula 2 includes one or more of toluenesulfonic acid, benzenesulfonic acid, taurine, sodium butanesulfonate, and anilinesulfonic acid.
상기 술폰산 화합물의 총 함량이 조성물 100중량부에 대하여 5 내지 30중량부인 것인, 인듐산화막 또는 은 함유 금속막 식각액 조성물.According to paragraph 1,
An etchant composition for an indium oxide film or a silver-containing metal film, wherein the total content of the sulfonic acid compound is 5 to 30 parts by weight based on 100 parts by weight of the composition.
상기 카복실산이 시트르산, 아세트산, 숙신산, 글루타르산, 아디프산, 피멜산, 수베르산, 말산, 타르타르산, 락트산, 프로피온산, 카프로산, 카프릴산, 페닐아세트산, 벤조산, 벤젠모노카르복실산, 니트로벤조산, 히드록시벤조산, 아미노벤조산, 디아세트산, 피루빈산, 글루콘산, 글리콜산, 이미노디아세트산, 니트릴로트리아세트산, 에틸렌디아민테트라아세트산, 알라닌, 글루탐산, 아미노부티르산, 글리신 및 이미노디숙신산 중 하나 이상을 포함하는 것인, 인듐산화막 또는 은 함유 금속막 식각액 조성물.According to paragraph 1,
The carboxylic acids include citric acid, acetic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, malic acid, tartaric acid, Lactic acid, propionic acid, caproic acid, caprylic acid, phenylacetic acid, benzoic acid, benzene monocarboxylic acid, nitrobenzoic acid, hydroxybenzoic acid, aminobenzoic acid, diacetic acid, pyruvic acid, gluconic acid, glycolic acid, iminodiacetic acid, nitrile. An etchant composition for an indium oxide film or a silver-containing metal film, comprising one or more of lotriacetic acid, ethylenediaminetetraacetic acid, alanine, glutamic acid, aminobutyric acid, glycine, and iminodisuccinic acid.
상기 황산염이 황산수소암모늄, 황산암모늄, 황산수소칼륨, 황산칼륨, 황산수소나트륨 및 황산나트륨 중 하나 이상을 포함하는 것인, 인듐산화막 또는 은 함유 금속막 식각액 조성물.According to paragraph 1,
An etchant composition for an indium oxide film or a silver-containing metal film, wherein the sulfate includes one or more of ammonium hydrogen sulfate, ammonium sulfate, potassium hydrogen sulfate, potassium sulfate, sodium hydrogen sulfate, and sodium sulfate.
황산염 5 내지 30중량부;
술폰산 화합물 5 내지 30중량부;
카복실산 20 내지 60중량부 및
조성물의 전체 중량이 100 중량부가 되도록 하는 잔량의 물을 혼합하는 단계를 포함하고,
상기 술폰산 화합물이 화학식 1의 화합물 또는 이의 염; 및 화학식 2의 화합물 또는 이의 염을 포함하는 것인, 인듐산화막 또는 은 함유 금속막 식각액 조성물의 제조방법:
[화학식 1]
상기 식에서,
R1은 C1~10알킬이다;
[화학식 2]
상기 식에서,
R2는 (C1~10알킬)벤질, 벤질, 아미노(C1~10알킬), C1~10알킬 또는 아미노벤질이다.1 to 30 parts by weight of a nitrogen compound;
5 to 30 parts by weight of sulfate;
5 to 30 parts by weight of a sulfonic acid compound;
20 to 60 parts by weight of carboxylic acid and
Comprising the step of mixing the remaining amount of water so that the total weight of the composition is 100 parts by weight,
The sulfonic acid compound is a compound of formula 1 or a salt thereof; A method for producing an indium oxide film or a silver-containing metal film etchant composition comprising a compound of Formula 2 or a salt thereof:
[Formula 1]
In the above equation,
R 1 is C 1-10 alkyl;
[Formula 2]
In the above equation,
R 2 is (C 1-10 alkyl)benzyl, benzyl, amino(C 1-10 alkyl), C 1-10 alkyl, or aminobenzyl.
상기 술폰산 화합물이 화학식 1의 화합물 또는 이의 염; 및 화학식 2의 화합물 또는 이의 염을 1:0.1 내지 1:5의 중량비로 포함하는 것인, 인듐산화막 또는 은 함유 금속막 식각액 조성물의 제조방법.According to clause 10,
The sulfonic acid compound is a compound of formula 1 or a salt thereof; and a compound of Formula 2 or a salt thereof at a weight ratio of 1:0.1 to 1:5.
상기 술폰산 화합물과 상기 황산염이 1:0.3 내지 1:3의 중량비로 혼합되는 것인, 인듐산화막 또는 은 함유 금속막 식각액 조성물의 제조방법.According to clause 10,
A method for producing an indium oxide film or a silver-containing metal film etchant composition, wherein the sulfonic acid compound and the sulfate are mixed at a weight ratio of 1:0.3 to 1:3.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20240098327A true KR20240098327A (en) | 2024-06-28 |
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