CN118223022A - Etching liquid composition for indium oxide film or silver-containing metal film and preparation method thereof - Google Patents
Etching liquid composition for indium oxide film or silver-containing metal film and preparation method thereof Download PDFInfo
- Publication number
- CN118223022A CN118223022A CN202311561273.9A CN202311561273A CN118223022A CN 118223022 A CN118223022 A CN 118223022A CN 202311561273 A CN202311561273 A CN 202311561273A CN 118223022 A CN118223022 A CN 118223022A
- Authority
- CN
- China
- Prior art keywords
- acid
- compound
- silver
- chemical formula
- indium oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000005530 etching Methods 0.000 title claims abstract description 81
- 239000000203 mixture Substances 0.000 title claims abstract description 51
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 48
- 239000004332 silver Substances 0.000 title claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 47
- 239000002184 metal Substances 0.000 title claims abstract description 47
- 229910003437 indium oxide Inorganic materials 0.000 title claims abstract description 34
- 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 34
- 239000007788 liquid Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title description 3
- 238000004519 manufacturing process Methods 0.000 claims abstract 3
- 239000000126 substance Substances 0.000 claims description 52
- -1 Sulfonic acid compound Chemical class 0.000 claims description 38
- 125000000217 alkyl group Chemical group 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 31
- 150000003839 salts Chemical class 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 12
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 12
- 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 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 9
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 8
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- XQCHMGAOAWZUPI-UHFFFAOYSA-M sodium;butane-1-sulfonate Chemical compound [Na+].CCCCS([O-])(=O)=O XQCHMGAOAWZUPI-UHFFFAOYSA-M 0.000 claims description 7
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 6
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 6
- 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 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- 239000004471 Glycine Substances 0.000 claims description 4
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 4
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-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
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 235000004279 alanine Nutrition 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000174 gluconic acid Substances 0.000 claims description 4
- 235000012208 gluconic acid Nutrition 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 4
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 4
- 235000011151 potassium sulphates Nutrition 0.000 claims description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 4
- 150000003460 sulfonic acids Chemical class 0.000 claims description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 4
- 229960003080 taurine Drugs 0.000 claims description 4
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 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 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
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 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
- 235000013922 glutamic acid Nutrition 0.000 claims description 3
- 239000004220 glutamic acid Substances 0.000 claims description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 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
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 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 2
- 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 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 2
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 claims description 2
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 claims description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 2
- 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 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 229960004050 aminobenzoic acid Drugs 0.000 claims description 2
- 229940124277 aminobutyric acid Drugs 0.000 claims description 2
- BEHLMOQXOSLGHN-UHFFFAOYSA-N benzenamine sulfate Chemical compound OS(=O)(=O)NC1=CC=CC=C1 BEHLMOQXOSLGHN-UHFFFAOYSA-N 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 229960004365 benzoic acid Drugs 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 claims description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- 229960002446 octanoic acid Drugs 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- 229940107700 pyruvic acid Drugs 0.000 claims description 2
- 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 2
- 159000000000 sodium salts Chemical group 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims 1
- 239000002244 precipitate Substances 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 70
- 239000010410 layer Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 229950006191 gluconic acid Drugs 0.000 description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 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
- 150000002739 metals Chemical class 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
- WWIWLTSSHDKOKO-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1.OS(=O)(=O)C1=CC=CC=C1 WWIWLTSSHDKOKO-UHFFFAOYSA-N 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- FZIPCQLKPTZZIM-UHFFFAOYSA-N 2-oxidanylpropane-1,2,3-tricarboxylic acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O.OC(=O)CC(O)(C(O)=O)CC(O)=O FZIPCQLKPTZZIM-UHFFFAOYSA-N 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 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
- YBCVMFKXIKNREZ-UHFFFAOYSA-N acoh acetic acid Chemical compound CC(O)=O.CC(O)=O YBCVMFKXIKNREZ-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- WXBLLCUINBKULX-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1 WXBLLCUINBKULX-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 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
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 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
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 2
- GXHMMDRXHUIUMN-UHFFFAOYSA-N methanesulfonic acid Chemical compound CS(O)(=O)=O.CS(O)(=O)=O GXHMMDRXHUIUMN-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- ACXGEQOZKSSXKV-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O.CCCCCCCC(O)=O ACXGEQOZKSSXKV-UHFFFAOYSA-N 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 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 description 1
- IOQLGFCIMRCCNA-UHFFFAOYSA-N 2-(carboxymethylamino)acetic acid Chemical compound OC(=O)CNCC(O)=O.OC(=O)CNCC(O)=O IOQLGFCIMRCCNA-UHFFFAOYSA-N 0.000 description 1
- GBIBYNIYVUFTIT-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O.OC(=O)CN(CC(O)=O)CC(O)=O GBIBYNIYVUFTIT-UHFFFAOYSA-N 0.000 description 1
- HKVPYOWRRPUFRE-UHFFFAOYSA-N 2-aminobenzenesulfonic acid phenylsulfamic acid Chemical compound NC1=C(C=CC=C1)S(=O)(=O)O.N(C1=CC=CC=C1)S(=O)(=O)O HKVPYOWRRPUFRE-UHFFFAOYSA-N 0.000 description 1
- WIFSDCDETBPLOR-UHFFFAOYSA-N 2-aminobenzoic acid Chemical compound NC1=CC=CC=C1C(O)=O.NC1=CC=CC=C1C(O)=O WIFSDCDETBPLOR-UHFFFAOYSA-N 0.000 description 1
- LPMKADABKPYRHE-UHFFFAOYSA-N 2-aminobutanoic acid Chemical compound CCC(N)C(O)=O.CCC(N)C(O)=O LPMKADABKPYRHE-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
- VHBSECWYEFJRNV-UHFFFAOYSA-N 2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1O.OC(=O)C1=CC=CC=C1O VHBSECWYEFJRNV-UHFFFAOYSA-N 0.000 description 1
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 1
- GYZVCMCORBRKLC-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O.OC(=O)C1=CC=CC=C1[N+]([O-])=O GYZVCMCORBRKLC-UHFFFAOYSA-N 0.000 description 1
- HWKRAUXFMLQKLS-UHFFFAOYSA-N 2-oxidanylidenepropanoic acid Chemical compound CC(=O)C(O)=O.CC(=O)C(O)=O HWKRAUXFMLQKLS-UHFFFAOYSA-N 0.000 description 1
- KVZLHPXEUGJPAH-UHFFFAOYSA-N 2-oxidanylpropanoic acid Chemical compound CC(O)C(O)=O.CC(O)C(O)=O KVZLHPXEUGJPAH-UHFFFAOYSA-N 0.000 description 1
- XTILJCALGBRMPR-UHFFFAOYSA-N 2-phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1.OC(=O)CC1=CC=CC=C1 XTILJCALGBRMPR-UHFFFAOYSA-N 0.000 description 1
- BNNMDMGPZUOOOE-UHFFFAOYSA-N 4-methylbenzenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1.CC1=CC=C(S(O)(=O)=O)C=C1 BNNMDMGPZUOOOE-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- ZPIOVRXYXHZCLY-UHFFFAOYSA-N C(C1=CC=CC=C1)S(=O)(=O)O.C(C1=CC=CC=C1)S(=O)(=O)O Chemical compound C(C1=CC=CC=C1)S(=O)(=O)O.C(C1=CC=CC=C1)S(=O)(=O)O ZPIOVRXYXHZCLY-UHFFFAOYSA-N 0.000 description 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 description 1
- HJMNHQWHKVNGNB-UHFFFAOYSA-N N(C(C(=O)O)CC(=O)O)C(C(=O)O)CC(=O)O.N(C(C(=O)O)CC(=O)O)C(C(=O)O)CC(=O)O Chemical compound N(C(C(=O)O)CC(=O)O)C(C(=O)O)CC(=O)O.N(C(C(=O)O)CC(=O)O)C(C(=O)O)CC(=O)O HJMNHQWHKVNGNB-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- RZIBGLKHMYKLPJ-UHFFFAOYSA-N S(=O)(=O)(O)NC1=CC=CC=C1.S(=O)(=O)(O)NC1=CC=CC=C1 Chemical compound S(=O)(=O)(O)NC1=CC=CC=C1.S(=O)(=O)(O)NC1=CC=CC=C1 RZIBGLKHMYKLPJ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- PKJKFLHTQJUUII-UHFFFAOYSA-N acetic acid;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;ethane-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCN.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O PKJKFLHTQJUUII-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- OVYQSRKFHNKIBM-UHFFFAOYSA-N butanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCC(O)=O OVYQSRKFHNKIBM-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960004275 glycolic acid Drugs 0.000 description 1
- XEUHNWODXVYLFD-UHFFFAOYSA-N heptanedioic acid Chemical compound OC(=O)CCCCCC(O)=O.OC(=O)CCCCCC(O)=O XEUHNWODXVYLFD-UHFFFAOYSA-N 0.000 description 1
- YVSCCMNRWFOKDU-UHFFFAOYSA-N hexanedioic acid Chemical compound OC(=O)CCCCC(O)=O.OC(=O)CCCCC(O)=O YVSCCMNRWFOKDU-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 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
- 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
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([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
- LFLZOWIFJOBEPN-UHFFFAOYSA-N nitrate, nitrate Chemical compound O[N+]([O-])=O.O[N+]([O-])=O LFLZOWIFJOBEPN-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- TWHMVKPVFOOAMY-UHFFFAOYSA-N octanedioic acid Chemical compound OC(=O)CCCCCCC(O)=O.OC(=O)CCCCCCC(O)=O TWHMVKPVFOOAMY-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- YKEKYBOBVREARV-UHFFFAOYSA-N pentanedioic acid Chemical compound OC(=O)CCCC(O)=O.OC(=O)CCCC(O)=O YKEKYBOBVREARV-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- SXBRULKJHUOQCD-UHFFFAOYSA-N propanoic acid Chemical compound CCC(O)=O.CCC(O)=O SXBRULKJHUOQCD-UHFFFAOYSA-N 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
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 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
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000011077 uniformity evaluation Methods 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
Abstract
The present invention relates to an etching liquid composition for an indium oxide film or a silver-containing metal film and a method for producing the same, and according to the present invention, excellent etching characteristics can be exhibited by suppressing damage to a lower film and minimizing occurrence of offset defects and residues or precipitates.
Description
Technical Field
The present invention relates to a composition for selectively etching an indium oxide film or a silver-containing metal film and a method for preparing the same.
Background
The display reflection plate functions to reduce light loss by reflecting the backlight to the front. The film containing silver (Ag) having high reflectance reflects backlight to the front more efficiently than the reflective plate and aluminum reflective plate treated with the white paint, and thus can increase illuminance by nearly two times. When a silver film is used, light loss is small, and silver (Ag) has low resistance and high brightness compared to other metals, so the silver film is used as a reflection plate. In addition, with the increase in resolution and size of the display device, silver-containing wirings having higher conductivity than aluminum and copper which are generally used are used in the wiring of the thin film transistor substrate.
Films containing indium (In) oxide have a property of converting an electric signal into an optical signal, and are generally used as transparent conductive films In various flat panel devices, for example, as transparent electrodes In liquid crystal display devices.
However, when a conventional etching solution containing nitric acid, phosphoric acid, sulfuric acid, or acetic acid is used, a short circuit of a part of wirings containing silver may occur, and as the number of etching treatments of an indium oxide film or a silver-containing metal film increases, there may be a problem that etching deviation greatly increases, or the like.
Therefore, a composition for selectively etching an indium oxide film or a silver-containing metal film needs to be studied.
Disclosure of Invention
Problems to be solved by the invention
The present invention is directed to a composition for uniformly etching an indium oxide (In) film or a silver (Ag) -containing metal film and preventing the generation of precipitates In an etching process, and a method for preparing the same.
Means for solving the problems
In order to solve the problems, the present invention provides an indium oxide film or silver-containing metal film etching liquid composition comprising: nitrogen compounds, sulfates, sulfonic acid compounds, and carboxylic acids; wherein the sulfonic acid compound comprises: a compound of formula 1 or a salt thereof; and a compound of chemical formula 2 or a salt thereof.
[ Chemical formula 1]
In the above-mentioned chemical formula, the chemical formula,
R 1 is a C 1～10 alkyl group,
[ Chemical formula 2]
In the above-mentioned chemical formula, the chemical formula,
R 2 is (C 1～10 alkyl) benzyl, amino (C 1～10 alkyl), C 1～10 alkyl or aminobenzyl.
According to one embodiment, R 1 of chemical formula 1 may be C 1～6 alkyl, and R 2 of chemical formula 2 may be (C 1～6 alkyl) benzyl, amino (C 1～6 alkyl), C 1～6 alkyl, or aminobenzyl.
According to one embodiment, the salt may be a sodium or potassium salt.
According to an embodiment, the nitrogen compound may comprise nitric acid.
According to one embodiment, the compound of formula 1 may comprise methanesulfonic acid.
According to an embodiment, the compound of chemical formula 2 may include one or more of toluene sulfonic acid, benzene sulfonic acid, taurine, sodium butane sulfonate, and aniline sulfonic acid.
According to an embodiment, the total content of the sulfonic acid compound may be 5 parts by weight to 30 parts by weight with respect to 100 parts by weight of the composition.
According to an embodiment, the carboxylic acid may include more than one of 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, nitrilotriacetic acid, ethylenediamine tetraacetic acid, alanine, glutamic acid, aminobutyric acid, glycine, and iminodisuccinic acid.
According to an embodiment, the sulfate may comprise more than one of ammonium bisulfate, ammonium sulfate, potassium bisulfate, potassium sulfate, sodium bisulfate, and sodium sulfate.
According to another embodiment of the present invention, there is provided a method for preparing an etching liquid composition for an indium oxide film or a silver-containing metal film, comprising the steps of mixing: 1 to 30 parts by weight of a nitrogen compound, 5 to 30 parts by weight of a sulfate, 5 to 30 parts by weight of a sulfonic acid compound, 20 to 60 parts by weight of a carboxylic acid, and the balance water in such a manner that the total weight of the composition is 100 parts by weight; the sulfonic acid compound comprises: a compound of formula 1 or a salt thereof; and a compound of chemical formula 2 or a salt thereof.
[ Chemical formula 1]
In the above-mentioned chemical formula, the chemical formula,
R 1 is a C 1～10 alkyl group,
[ Chemical formula 2]
In the above-mentioned chemical formula, the chemical formula,
R 2 is (C 1～10 alkyl) benzyl, amino (C 1～10 alkyl), C 1～10 alkyl or aminobenzyl.
According to an embodiment, the sulfonic acid compound may include a compound of chemical formula 1 or a salt thereof; and a compound of chemical formula 2 or a salt thereof in a weight ratio of 1:0.1 to 1:5.
According to one embodiment, the sulfonic acid compound and the sulfate may be mixed in an amount of 1:0.3 to 1:3 weight ratio.
Other details of embodiments of the invention are included in the following detailed description.
Effects of the invention
The etching liquid composition of the present invention has the property of improving the etching rate of an indium oxide film or a silver-containing metal film and uniformly etching.
Detailed Description
The invention is capable of many variations and has many embodiments, and thus specific embodiments will be illustrated and described in detail. It is not intended, however, to limit the invention to the particular embodiments, but is to be understood to include all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. In describing the present invention, when it is determined that a detailed description of known technologies related to the present invention may obscure the gist of the present invention, a detailed description thereof will be omitted.
The expression "to" is used as an expression including the corresponding numerical value unless specifically mentioned in the present specification. Specifically, for example, the expression "1 to 2" means to include not only 1 and 2 but also all values between 1 and 2.
In the etching process of the semiconductor substrate, a problem may occur in that the lower metal film is damaged, and the lower film may include copper, aluminum, or the like. The invention provides an etching liquid composition which can minimize damage to a lower metal film, is independent of the type of the lower film, and can improve etching characteristics of an indium oxide film and a silver-containing metal film as an upper film.
The etching liquid composition for an indium oxide (In) film or a silver (Ag) -containing metal film of the present invention will be described In detail below.
The etching solution composition according to an embodiment of the present invention is used for etching indium oxide (In) used as a transparent electrode or the like of a display device or a silver (Ag) containing metal film used as a reflective plate or a thin film transistor (thin film transistor, TFT) metal wiring, and the metal film may be an alloy film, a single-layer film, or a multilayer film. For example, the multilayer film may include: a first layer comprising a metal oxide; a second layer disposed on the first layer and comprising silver or a silver alloy; and a third layer disposed on the first layer and comprising a metal oxide. Specifically, for example, the first and third layers of the multilayer film may include indium tin oxide. However, the embodiment of the present invention is not limited to etching the three-layer film, and may be used to etch various multi-layer structures such as a double-layer film structure of a metal oxide film and a silver-containing film, and the like. The metal oxide film may refer to an oxide film including a metal, such as an oxide film including indium (In), tin (Sn), or a combination thereof. According to one embodiment, the silver alloy comprises silver as a main component, and may comprise an alloy form comprising Nd, cu, pb, nb, ni, mo, ni, cr, mg, W, pa to other metals such as Ti, and a plurality of forms comprising nitride, silicide, carbide, oxide forms, and the like of silver.
In addition, 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 of a substrate for an image display device.
According to an embodiment, the present invention provides an indium oxide film or silver-containing metal film etching liquid composition including a nitrogen compound, a sulfate, a sulfonic acid compound, and a carboxylic acid.
Hereinafter, the constituent components of the etching liquid composition according to an embodiment of the present invention will be described in more detail.
Nitrogen compound
The etching composition of an embodiment of the present invention contains a nitrogen compound as a main oxidizing agent for oxidizing the surface of an indium oxide (In) film or a silver (Ag) -containing metal film. The nitrogen compound may be silver (Ag) oxide, indium oxide, or the like, which is etched, for example, may include nitric acid. Specifically, nitric acid, for example, may be used as the metal surface oxidizing agent.
According to an embodiment, the nitrogen compound may include 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, or 20 parts by weight or less, based on 100 parts by weight of the etching solution composition. When the range is satisfied, it is advantageous that the etching rate can be adjusted by preventing excessive attack of silver, indium oxide, or the like.
Sulfate salt
The etching composition of an embodiment of the present invention contains sulfate as an etchant for etching an indium oxide (In) film or a silver (Ag) -containing metal film. As an inorganic sulfur compound, sulfate can be used separately from an organic sulfur compound described later to etch metals effectively.
Examples of the sulfate compound may include ammonium bisulfate (ammonium hydrogen sulfate, (NH 4)HSO4), ammonium sulfate (NH 4)2SO4), potassium bisulfate (potassium hydrogen sulfate, KHSO 4), potassium sulfate (potassium sulfate, K 2SO4), sodium bisulfate (sodium hydrogen sulfate, naHSO 4), sodium sulfate (Na 2SO4), and the like, and these may be used alone or in combination, respectively.
According to an embodiment, the sulfate may include 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 etching solution composition. When the sulfate content is too low, residues may be generated due to non-etching of the metal film, whereas when the sulfate content is too high, problems of wiring loss and increased etching deviation may be generated due to excessive etching of the metal film.
Sulfonic acid compound
The etching composition of an embodiment of the present invention includes a sulfonic acid compound as an etchant for etching indium oxide (In) or silver (Ag) -containing metal films. The sulfonic acid compound is used as an organic sulfur compound, and can be distinguished from and used together with the aforementioned inorganic sulfur compound, i.e., sulfate, to thereby effectively etch metals.
According to one embodiment, the sulfonic acid compound of the present invention may comprise: a compound of formula 1 or a salt thereof; and a compound of chemical formula 2 or a salt thereof.
[ Chemical formula 1]
In the above-mentioned chemical formula, the chemical formula,
R 1 is a C 1～10 alkyl group,
[ Chemical formula 2]
In the above-mentioned chemical formula, the chemical formula,
R 2 is (C 1～10 alkyl) benzyl, amino (C 1～10 alkyl), C 1～10 alkyl or aminobenzyl.
According to one embodiment, R 1 of formula 1 may be C 1～6 alkyl, and R 2 of formula 2 may be (C 1～6 alkyl) benzyl, amino (C 1～6 alkyl), C 1～6 alkyl, or aminobenzyl. Specifically, for example, R 1 of chemical formula 1 may be methyl, ethyl, propyl, butyl, pentyl, or hexyl. In addition, R 2 of chemical formula 2 may be methylbenzyl, benzyl, aminoethyl, butyl, or aminobenzyl.
According to an embodiment, the salt of the compound of chemical formula 1 or chemical formula 2 may be a sodium salt or a potassium salt. Specifically, for example, the present invention may include sodium butane sulfonate as the compound of chemical formula 2, but is not limited thereto, and may include the compound of chemical formula 1 or chemical formula 2 described above in a salt form.
The term "alkyl" as used in this specification refers to a straight or branched saturated hydrocarbon-based chain, for example, which may contain methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, hexyl, etc., but is not limited thereto.
Specifically, for example, the compound of chemical formula 1 may include methanesulfonic acid (methane sulfonic acid). In addition, the compound of chemical formula 2 may include one or more of toluene sulfonic acid (toluene sulfonic acid), benzene sulfonic acid (benzene sulfonic acid), taurine (taurines), sodium butane sulfonate (sodium butane sulfonate), and aniline sulfonic acid (aniline sulfonic acid).
According to one embodiment, the present invention may comprise the compound of formula 1 and the compound of formula 2 in a weight 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.
According to an 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 etching solution composition. In the present invention, the total content of the sulfonic acid compound means the sum of the contents of the compound of chemical formula 1 and the compound of chemical formula 2.
In addition, the present invention can distinguish between sulfonic acid compounds and sulfates and is described in terms 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.
When the content of the sulfonic acid compound is too low, residues may be generated due to non-etching of the metal film, whereas when the content of the sulfonic acid compound is too high, problems may occur such as loss of wiring and increase of etching deviation due to excessive etching of the metal film.
The sulfonic acid groups of the sulfate and sulfonic acid compounds of the present invention are firmly bonded to the metal ions oxidized by nitric acid, so that stable etching can be realized. Because of the sulfonic acid group, re-adsorption of oxidized metal can be prevented, the formation of residue is reduced, and the permeability to the lower film is impaired. By this action, penetration of the etching solution between films can be suppressed, so that a bias (or referred to as a bias) defect at the time of forming fine wiring is reduced, and wiring straightness can be improved.
Carboxylic acids
The etching composition of one embodiment of the present invention comprises a carboxylic acid compound as a buffer or chelating agent. Specifically, a stabilization function may be performed to enable the carboxylic acid compound to chelate and dissolve the metal ions in the etching solution during the etching process, and thus a function of preventing the metal ions from being reduced and re-adsorbed onto the substrate may be performed. That is, the effect of reducing the generation of residues after etching is obtained.
For example, as the carboxylic acid, one or more of citric acid (CITRIC ACID), acetic acid (ACETIC ACID), succinic acid (succinic acid), glutaric acid (glutaric acid), adipic acid (ADIPIC ACID), pimelic acid (PIMELIC ACID), suberic acid (suberic acid), malic acid (MALIC ACID), tartaric acid (TARTARIC ACID), lactic acid (LACTIC ACID), propionic acid (propionic acid), caproic acid (caproic acid), caprylic acid (CAPRYLIC ACID), phenylacetic acid (PHENYLACETIC ACID), benzoic acid (benzoic acid), benzene monocarboxylic acid (benzene monocarboxylic acids), nitrobenzoic acid (nitrobenzoic acid), hydroxybenzoic acid (hydroxybenzoic acid), aminobenzoic acid (aminobenzoic acid), diacetic acid (DIACETIC ACID), pyruvic acid (pyruvic acid), gluconic acid (gluconic acid), glycolic acid (glyconic acid), iminodiacetic acid (iminodiacetic acid), nitrilotriacetic acid (nitrilotriacetic acid), ethylenediamine tetraacetic acid (ETHYLENEDIAMINETETRAACETIC ACID), alanine (alanine), glutamic acid (glutarate), aminobutyric acid (aminobutyric acid), glycine (glycine), and iminodisuccinic acid (iminodisuccinic acid) may be included. Specifically, for example, citric acid may be contained as the chelating agent, thus stabilizing the metal ion, and acetic acid may be contained as the buffer solution.
According to an 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 etching solution composition. According to a specific aspect, the present invention may comprise 10 to 35 parts by weight of citric acid, for example, 15 to 30 parts by weight, or 20 to 30 parts by weight, and may comprise 10 to 25 parts by weight of acetic acid, for example, 10 to 20 parts by weight.
Water and its preparation method
The etching solution composition of an embodiment of the present invention may include the balance of water such that the total weight of the composition is 100 wt%. In the present invention, the water is not particularly limited, but is preferably deionized water, more preferably deionized water having a resistivity of 18mΩ/cm or more, which means the degree of ion removal from water.
As described above, the etchant composition of the present invention can exhibit excellent etching characteristics by suppressing damage to a lower film and minimizing occurrence of offset defects and residues or precipitates when forming fine wirings, for an indium (In) film used as a transparent electrode or the like of an image display device or a silver (Ag) -containing metal film used as a reflective plate or wiring of the display device.
Hereinafter, embodiments of the present invention will be described in detail so as to enable those skilled in the art to which the present invention pertains to easily practice the present invention. However, the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
Examples and comparative examples
Etching liquid compositions for indium oxide films or silver-containing metal films were prepared according to the compositions of table 1. The content unit is weight percent.
TABLE 1
NA: nitric acid (NITRIC ACID)
SHS: sodium bisulfate (sodium hydrogen sulfate)
MSA: methanesulfonic acid (methanesulfonic acid)
CA: citric acid (CITRIC ACID)
AA: acetic acid (ACETIC ACID)
PTSA: p-toluene sulfonic acid (p-Toluenesulfonic acid)
BSA: benzenesulfonic acid (benzenesulfonic acid)
TA: taurine (taurines)
BSS: sodium butanesulfonate (butane-1-sulfonic acid sodium salt)
ASA: aniline sulfonic acid (aniline-2-sulfonic acid)
Experimental example 1: evaluation of etching Rate
In order to evaluate the etching rates of the etching liquid compositions of examples and comparative examples, as test pieces, three films of Indium Tin Oxide (ITO)/silver (Ag)/Indium Tin Oxide (ITO) were formed on a substrate, and then a photoresist was patterned on the three films. The substrate is subjected to an etching process using each of the etching liquid compositions.
After 10kg of each etching solution composition was charged into a wet etching machine (WET ETCHER), the etching rate of the prepared test piece was evaluated by setting the temperature to 40 ℃.
The etching rate was evaluated based on the etching stop time of the resist unpatterned region in the entire region of the three-layer film coupon, and is shown in table 2.
< Etching Rate evaluation criterion >
And (3) the following materials: less than 30 seconds
O: 30 seconds or more and less than 40 seconds
Delta: 40 seconds or more and less than 50 seconds
X: for more than 50 seconds
Experimental example 2: deviation evaluation
After 10kg of each of the etching liquid compositions of examples and comparative examples was charged into a wet etching machine (WET ETCHER), the temperature was set to 40℃and the prepared test piece was subjected to etching treatment. After the etched test piece was rinsed with ultrapure water for about 60 seconds, nitrogen gas drying was performed under a pressure of 3.0kgf/cm 2.
The distance from the end of the photoresist to the silver thin film in the three-layer film coupon was measured using an electron scanning microscope (SEM; model: SU-8010, hitachi (Hitachi)) and is shown in Table 2.
Experimental example 3: evaluation of residue
The degree of residue after etching was evaluated based on the etching liquid compositions of examples and comparative examples.
Each test piece according to the result of experimental example 1 was observed with an electron scanning microscope to observe the residual metal film area in the region between Indium Tin Oxide (ITO)/silver (Ag)/Indium Tin Oxide (ITO) wirings.
Whether residue was formed or not was judged based on the following criteria, and is shown in table 2.
< Residue evaluation criterion >
And (3) the following materials: no residue is generated
O: almost no residue
X: generating residues
Experimental example 4: evaluation of precipitate
In order to evaluate the degree of formation of precipitates in the etching process of the etching liquid compositions of examples and comparative examples, each test piece according to the result of experimental example 1 was observed using an electron scanning microscope.
The amount of silver (Ag) particles generated at the upper end of the Ti/Al/Ti wiring was measured, evaluated on the basis of the following criteria, and shown in table 2.
< Precipitate evaluation criterion >
And (3) the following materials: less than 5
O: more than 5 and less than 20
Delta: more than 20 and less than 50
X: more than 50
Experimental example 5: etch uniformity evaluation
In order to evaluate the etching uniformity of the etching liquid compositions of examples and comparative examples, each test piece according to the results of experimental examples and comparative examples was observed using an electron scanning microscope to determine the uniformity of the formed wiring.
The photoresist on the etched substrate was removed using a tetramethylammonium hydroxide (tetramethylammonium hydroxide, TMAH) solution. The pattern uniformity of the silver thin film in the three-layer film test piece was measured using an electron scanning microscope (SEM; model: SU-8010, hitachi (Hitachi)) and is shown in Table 2.
< Evaluation criterion for etching uniformity >
And (3) the following materials: less than 0.05um
O: 0.05 or more and less than 0.1um
Delta: 0.1um or more and less than 0.2um
X: above 0.2um
TABLE 2
The specific portions of the present invention have been described in detail above, and it should be apparent that such detail is merely a preferred embodiment and does not limit the scope of the present invention to those of ordinary skill in the art to which the present invention pertains. Based on the above, a person skilled in the art to which the present invention pertains can apply and modify the present invention in various ways. Accordingly, the substantial scope of the present invention is defined by the appended claims and equivalents thereof.
Claims (12)
1. An etching liquid composition for an indium oxide film or a silver-containing metal film, wherein,
Comprising:
a nitrogen compound that contains at least one of the nitrogen compound,
A sulfate salt of the sulfuric acid,
Sulfonic acid compound, and
A carboxylic acid;
Wherein the sulfonic acid compound comprises:
a compound of formula 1 or a salt thereof, and
A compound of formula 2 or a salt thereof;
[ chemical formula 1]
In the chemical formula 1 described above, a compound having the formula,
R 1 is a C 1～10 alkyl group,
[ Chemical formula 2]
In the chemical formula 2 described above, the chemical formula,
R 2 is (C 1～10 alkyl) benzyl, amino (C 1～10 alkyl), C 1～10 alkyl or aminobenzyl.
2. The indium oxide film or silver-containing metal film etching liquid composition according to claim 1, wherein,
R 1 of the chemical formula 1 is C 1～6 alkyl,
R 2 of chemical formula 2 is (C 1～6 alkyl) benzyl, amino (C 1～6 alkyl), C 1～6 alkyl or aminobenzyl.
3. The indium oxide film or silver-containing metal film etching liquid composition according to claim 1, wherein,
The salt is sodium salt or potassium salt.
4. The indium oxide film or silver-containing metal film etching liquid composition according to claim 1, wherein,
The nitrogen compound comprises nitric acid.
5. The indium oxide film or silver-containing metal film etching liquid composition according to claim 1, wherein,
The compound of formula 1 comprises methanesulfonic acid.
6. The indium oxide film or silver-containing metal film etching liquid composition according to claim 1, wherein,
The compound of chemical formula 2 comprises more than one of toluene sulfonic acid, benzene sulfonic acid, taurine, sodium butane sulfonate and aniline sulfonic acid.
7. The indium oxide film or silver-containing metal film etching liquid composition according to claim 1, wherein,
The total content of the sulfonic acid compounds is 5 to 30 parts by weight with respect to 100 parts by weight of the composition.
8. The indium oxide film or silver-containing metal film etching liquid composition according to claim 1, wherein,
The carboxylic acid comprises one or more of 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, phenylmonocarboxylic acid, nitrobenzoic acid, hydroxybenzoic acid, aminobenzoic acid, diacetic acid, pyruvic acid, gluconic acid, glycolic acid, iminodiacetic acid, nitrilotriacetic acid, ethylenediamine tetraacetic acid, alanine, glutamic acid, aminobutyric acid, glycine, and iminodisuccinic acid.
9. The indium oxide film or silver-containing metal film etching liquid composition according to claim 1, wherein,
The sulfate comprises more than one of ammonium bisulfate, ammonium sulfate, potassium bisulfate, potassium sulfate, sodium bisulfate and sodium sulfate.
10. A method for preparing an etching solution composition of an indium oxide film or a silver-containing metal film, wherein,
Comprises the steps of mixing the following components:
1 to 30 parts by weight of a nitrogen compound,
5 To 30 parts by weight of a sulfate,
5 To 30 parts by weight of a sulfonic acid compound,
20 To 60 parts by weight of a carboxylic acid, and
Water in a balance of 100 parts by weight based on the total weight of the composition;
Wherein the sulfonic acid compound comprises:
a compound of formula 1 or a salt thereof, and
A compound of formula 2 or a salt thereof;
[ chemical formula 1]
In the chemical formula 1 described above, a compound having the formula,
R 1 is a C 1～10 alkyl group,
[ Chemical formula 2]
In the chemical formula 2 described above, the chemical formula,
R 2 is (C 1～10 alkyl) benzyl, amino (C 1～10 alkyl), C 1～10 alkyl or aminobenzyl.
11. The method for producing an indium oxide film or a silver-containing metal film etching liquid composition according to claim 10, wherein,
The sulfonic acid compound includes the compound of formula 1 or a salt thereof; and the compound of formula 2 or a salt thereof,
The weight ratio of the compound of chemical formula 1 or a salt thereof to the compound of chemical formula 2 or a salt thereof is 1:0.1 to 1:5.
12. The method for producing an indium oxide film or a silver-containing metal film etching liquid composition according to claim 10, wherein,
The sulfonic acid compound and the sulfate salt are mixed in a ratio of 1:0.3 to 1:3 weight ratio.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2022-0180007 | 2022-12-21 |
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| Publication Number | Publication Date |
|---|---|
| CN118223022A true CN118223022A (en) | 2024-06-21 |
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