CN116411278A - Etching solution and preparation method and application thereof - Google Patents
Etching solution and preparation method and application thereof Download PDFInfo
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- CN116411278A CN116411278A CN202310395606.9A CN202310395606A CN116411278A CN 116411278 A CN116411278 A CN 116411278A CN 202310395606 A CN202310395606 A CN 202310395606A CN 116411278 A CN116411278 A CN 116411278A
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- acid
- etching solution
- ito
- etching
- organic acid
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- 238000005530 etching Methods 0.000 title claims abstract description 134
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 150000007524 organic acids Chemical class 0.000 claims abstract description 66
- 150000004965 peroxy acids Chemical class 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims abstract description 14
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 12
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims abstract description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 8
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229940098779 methanesulfonic acid Drugs 0.000 claims abstract description 7
- 235000011054 acetic acid Nutrition 0.000 claims abstract description 6
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims abstract description 5
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001630 malic acid Substances 0.000 claims abstract description 5
- 235000011090 malic acid Nutrition 0.000 claims abstract description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 4
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims abstract description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims abstract description 4
- 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 abstract description 4
- 239000001361 adipic acid Substances 0.000 claims abstract description 4
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 4
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 4
- 235000019253 formic acid Nutrition 0.000 claims abstract description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 4
- 239000011976 maleic acid Substances 0.000 claims abstract description 4
- 229960002446 octanoic acid Drugs 0.000 claims abstract description 4
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 4
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 4
- 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 abstract description 4
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 4
- 239000011975 tartaric acid Substances 0.000 claims abstract description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 35
- 239000002184 metal Substances 0.000 claims description 35
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 27
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 7
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 claims description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-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
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 235000002639 sodium chloride Nutrition 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 239000011790 ferrous sulphate Substances 0.000 claims description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 4
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-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
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-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
- 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
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 235000011148 calcium chloride Nutrition 0.000 claims description 3
- 235000011132 calcium sulphate Nutrition 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 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
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 229940005605 valeric acid Drugs 0.000 claims description 3
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 2
- DAFQZPUISLXFBF-UHFFFAOYSA-N tetraoxathiolane 5,5-dioxide Chemical compound O=S1(=O)OOOO1 DAFQZPUISLXFBF-UHFFFAOYSA-N 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 32
- 229910052709 silver Inorganic materials 0.000 abstract description 31
- 239000004332 silver Substances 0.000 abstract description 31
- HKBLLJHFVVWMTK-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti].[Ti] HKBLLJHFVVWMTK-UHFFFAOYSA-N 0.000 abstract description 30
- 238000001179 sorption measurement Methods 0.000 abstract description 21
- 239000000758 substrate Substances 0.000 abstract description 21
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 16
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 37
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 29
- 230000006378 damage Effects 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 15
- 239000002253 acid Substances 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- -1 hydrogen ions Chemical class 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical compound OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000007373 indentation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012851 eutrophication Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000009103 reabsorption Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- 229910018575 Al—Ti Inorganic materials 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009528 severe injury Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003079 width control Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
-
- 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
- C23F1/02—Local etching
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/20—Acidic compositions for etching aluminium or alloys thereof
Abstract
The invention discloses an etching solution and a preparation method and application thereof, and belongs to the technical field of etchants. The etching solution comprises 2.00-15.00wt% of peroxyacid, 2.00-15.00wt% of organic acid A, 2.00-25.00wt% of organic acid B and the balance of water according to mass percentage; the organic acid A comprises at least one of formic acid, acetic acid, propionic acid, butyric acid, caprylic acid, adipic acid, oxalic acid, malonic acid and benzoic acid; the organic acid B comprises at least one of methanesulfonic acid, malic acid, citric acid, maleic acid and tartaric acid. The etching solution is used for etching the silver of the multilayer film formed by the silver and the ITO film, so that the problems that the titanium aluminum titanium layer in the substrate is damaged to a certain extent and is unfavorable for environmental protection due to the use of phosphoric acid are avoided, the ITO/Ag/ITO structure can be effectively removed, an excellent profile is formed, no silver and ITO residues exist, and no re-adsorption phenomenon of Ag occurs.
Description
Technical Field
The invention relates to the technical field of etchants, in particular to an etching solution and a preparation method and application thereof.
Background
With the development of technology, displays are widely used in mobile phones and tablets. The manufacturing process of the organic light emitting element (OLED) includes: a metal thin film is first formed on a substrate, then a protective film having a predetermined pattern is formed on the thin film, and then the metal thin film is etched using the protective film as a mask. Silver is widely used in anode wiring (ITO/Ag/ITO) structures as a metal having high conductivity and carrier mobility and high brightness.
The etching solution used in the prior art can not effectively remove the ITO/Ag/ITO parts, and has certain damage to the titanium aluminum titanium layers at other parts of the substrate.
For the same substrate (glass substrate), the surface of the substrate comprises both an ITO/Ag/ITO part and a titanium aluminum titanium part (for example, the left area corresponds to the ITO/Ag/ITO part and the right area corresponds to the titanium aluminum titanium part).
In view of this, the present invention has been made.
Disclosure of Invention
One of the purposes of the present invention is to provide an etching solution to solve the problem of damage to the titanium-aluminum-titanium layer in the prior art.
The second object of the present invention is to provide a method for preparing the etching solution.
It is a further object of the present invention to provide an application of the etching solution.
In a first aspect, the present invention provides an etching solution, which comprises 2.00wt% to 15.00wt% of peroxyacid, 2.00wt% to 15.00wt% of organic acid A, 2.00wt% to 25.00wt% of organic acid B, and the balance of water;
wherein the organic acid A comprises at least one of formic acid, acetic acid, propionic acid, butyric acid, caprylic acid, adipic acid, oxalic acid, malonic acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid, valeric acid, caproic acid and capric acid;
the organic acid B comprises at least one of methanesulfonic acid, malic acid, citric acid, maleic acid and tartaric acid.
The peroxy acid serves as a main oxidizing agent for etching reaction, and serves to oxidize silver and an ITO film to perform wet etching; the organic acid A is used as an auxiliary oxidant, the etching speed is reduced along with the reduction of the content of the main oxidant in the etching process, and the organic acid A can continuously provide hydrogen ions, so that the stability of the hydrogen ion concentration is ensured, and the etching speed is ensured; the organic acid B is mainly used for providing additional hydrogen ions to adjust the pH value of the etching solution, so that the oxidation reaction can be smoothly performed, and an excellent profile can be formed after etching.
The etching solution containing the peroxy acid, the organic acid A and the organic acid B in the proportion relation can avoid using phosphoric acid, can reduce the cost of the etching solution (including raw material cost, wastewater treatment cost and the like), can effectively avoid the problem that the titanium-aluminum-titanium layer at other parts of the surface of the substrate is damaged to a certain extent due to the use of the phosphoric acid, and can effectively remove the ITO/Ag/ITO structure.
In an alternative embodiment, the etching solution further comprises 10.00wt% to 30.00wt% of an inorganic salt.
The inorganic salt may reduce silver (Ag) re-adsorption of the ITO film by controlling pH of the etching solution component, and may adjust an etching rate to uniformly etch when removing the ITO film residue.
In an alternative embodiment, the etching solution further comprises 0.01wt% to 1.00wt% of a metal morphology improving agent.
The metal appearance improver can improve the appearance of silver and ITO film.
In an alternative embodiment, the etching solution includes 7.00-12.00wt% of peroxyacid, 10.00-15.00 wt% of organic acid A, 5.00-25.00 wt% of organic acid B, 15.00-25.00 wt% of inorganic salt, and 0.30-1.00 wt% of metal morphology improving agent, with the balance being water.
In an alternative embodiment, the etching solution includes 10.00wt% of peroxyacid, 15.00wt% of organic acid A, 15.00wt% of organic acid B, 25.00wt% of inorganic salt, and 1.00wt% of metal morphology improving agent, with the balance being water.
The etching solution corresponding to the preferred scheme not only can not damage the titanium aluminum titanium layer on the surface of the substrate, but also can remove the ITO/Ag/ITO structure more effectively to form a more excellent profile, and no silver and ITO residues or Ag re-adsorption phenomenon occurs.
In an alternative embodiment, the peroxyacid comprises at least one of peroxymonosulfuric acid, peroxydisulfuric acid, and peracetic acid.
The peroxy acid is weak acid, so that the titanium aluminum titanium layer can be effectively prevented from being damaged, and ITO and silver can be effectively oxidized together with other organic acids.
In alternative embodiments, the inorganic salt comprises at least one of sodium sulfate, potassium sulfate, calcium sulfate, iron sulfate, ferrous sulfate, sodium chloride, calcium chloride, potassium chloride, sodium bisulfate, potassium nitrate, ammonium nitrate, sodium nitrate, silver nitrate, calcium nitrate, sodium dihydrogen phosphate, and ammonium sulfate.
The inorganic salt can provide sufficient sulfate, nitrate and chloride ions, can be respectively combined with hydrogen ions in the solution to form sulfuric acid, nitric acid and hydrochloric acid, and the existence of the acid enables silver adsorbed on the surface of the substrate to be redissolved, so that silver (Ag) re-adsorption of the film is reduced, and the etching speed can be adjusted to uniformly etch when ITO is removed.
In an alternative embodiment, the metal morphology modifier comprises at least one of ferric nitrate, ferrous nitrate, ferric sulfate, and ferrous sulfate.
The metal appearance improver can effectively improve the appearance problems of Ag and ITO.
In a second aspect, the present invention provides a method for preparing an etching solution according to any one of the preceding embodiments, comprising the steps of: mixing the raw materials according to the proportion.
In an alternative embodiment, the inorganic salt and the metal morphology modifier are mixed with water for the first time, then mixed with the peroxy acid for the second time, and then mixed with the organic acid A and the organic acid B for the third time, so that the uniform mixing of the raw materials is facilitated.
In a third aspect, the present invention provides an etching solution according to any one of the above embodiments, which is useful for etching a multilayer film made of Ag and an ITO film, for example.
In an alternative embodiment, the multilayer film is an ITO/Ag/ITO composite film.
The beneficial effects of the invention include:
according to the etching solution, the specific components and the components are matched according to the specific proportion, so that phosphoric acid can be prevented from being used in the etching solution, the cost of the etching solution (including raw material cost, wastewater treatment cost and the like) can be reduced, and the problem that the titanium-aluminum-titanium layer on the surface of the substrate is damaged to a certain extent due to the use of phosphoric acid can be effectively avoided. Through practical application, the etching solution is proved to be capable of effectively removing the ITO/Ag/ITO structure, forming an excellent profile, having no Ag and ITO residues, having no Ag re-adsorption phenomenon and having no damage to the titanium aluminum titanium layer.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM sectional view of an etched ITO/Ag/ITO film layer for observing the profile of etched metal according to example 2 of the test example;
FIG. 2 is an SEM TOP diagram of an etched ITO/Ag/ITO film layer for observing metal residue on the surface of a etched substrate according to example 2;
FIG. 3 is an SEM TOP diagram of an etched ITO/Ag/ITO film layer for observing silver adsorption on the surface of an etched substrate according to example 2 of the test example;
FIG. 4 is an SEM TOP diagram of an etched ITO/Ag/ITO film layer for observing damage of an etched TiAlTiAlTilayer according to example 2;
fig. 5 is an SEM TOP view of an etched ITO/Ag/ITO film layer for observing damage of an etched titanium aluminum titanium layer corresponding to comparative example 1 in the test example.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The etching solution, the preparation method and the application thereof are specifically described below.
The inventors have suggested that the etching solution used in the prior art cannot effectively remove the ITO/Ag/ITO structure, and one of the reasons why the titanium aluminum titanium layer on the substrate surface is damaged to some extent is that the etching solution contains phosphoric acid.
The price of phosphoric acid is higher, and the titanium aluminum titanium layer of the substrate is damaged to a certain extent, and serious damage to titanium aluminum titanium is even caused, so that poor products are caused. In addition, the discharge of phosphorus content of wastewater is usually controlled within 0.50mg/L to avoid excessive algae propagation and subsequent water quality deterioration and ecological system degradation caused by water eutrophication, but the control within 0.50mg/L greatly increases the production cost of etching solution. The acid used in the application has no problem of eutrophication of water body caused by phosphorus, and the price of the acid is lower than that of phosphoric acid.
The application creatively provides the etching solution, which can avoid using phosphoric acid in the etching solution, can reduce the cost of the etching solution (including raw material cost, wastewater treatment cost and the like), and can effectively avoid the problem that the titanium-aluminum-titanium layer on the surface of the substrate is damaged to a certain extent due to the use of the phosphoric acid. Through practical application, the etching solution is proved to be capable of effectively removing the ITO/Ag/ITO structure, forming an excellent profile, having no Ag and ITO residues, having no Ag re-adsorption phenomenon, and having no damage to the titanium aluminum titanium layer.
For reference, the etching solution referred to herein may include 2.00wt% to 15.00wt% of the peroxyacid, 2.00wt% to 15.00wt% of the organic acid A, and 2.00wt% to 25.00wt% of the organic acid B, with the balance being water, in mass%.
Specifically, the amount of the peroxy acid may be 2.00wt%, 3.00wt%, 4.00wt%, 5.00wt%, 6.00wt%, 7.00wt%, 8.00wt%, 9.00wt%, 10.00wt%, 11.00wt%, 12.00wt%, 13.00wt%, 14.00wt% or 15.00wt%, etc., and may be any other value within a range of 2.00wt% to 15.00 wt%.
It should be noted that the amount of the peroxy acid is set to 2.00wt% to 15.00wt%, so that the ITO layer has a proper etching rate, and metal residues are reduced after etching. If the consumption of the peroxy acid in the etching solution is lower than 2.00wt%, the etching of the top layer ITO is difficult, the etching rate is too low, the top layer edge ITO collapses, and the etching section profile is poor; when the content is more than 15.00wt%, the reaction rate of silver tends to be too high due to the excessively high oxidizing property, and the line defect is caused by the excessively high etching amount at one side.
In the present application, the peroxy acid serves as a main oxidizing agent for the etching reaction, and serves to oxidize Ag and ITO to perform wet etching without damaging titanium aluminum titanium.
Illustratively, the peroxyacid may include at least one of peroxymonosulfuric acid and peroxydisulfuric acid. In addition, peracetic acid and the like may be included.
The peroxy acid is weak acid, so that the titanium aluminum titanium layer can be effectively prevented from being damaged, and ITO and silver can be effectively oxidized together with other organic acids.
In some preferred embodiments, the peroxyacid is selected from at least one of peroxymonosulfuric acid and peroxydisulfuric acid. The reasons for this include: the ITO film can be etched better than other peroxyacid by adopting the peroxymonosulfuric acid and/or the peroxydisulfuric acid, so that the metal residue is reduced.
The amount of the organic acid A may be 2.00wt%, 3.00wt%, 4.00wt%, 5.00wt%, 6.00wt%, 7.00wt%, 8.00wt%, 9.00wt%, 10.00wt%, 11.00wt%, 12.00wt%, 13.00wt%, 14.00wt% or 15.00wt%, etc., and may be any other value in the range of 2.00wt% to 15.00 wt%.
It should be noted that the amount of the organic acid A is set to 2.00wt% to 15.00wt%, and the reaction speed can be controlled within a reasonable range. If the using amount of the organic acid A in the etching solution is less than 2.00wt%, the ITO residue on the surface of the substrate is easy to be obvious; and more than 15.00wt% is easy to cause larger single-side etching amount, which is unfavorable for line width control.
In the application, the organic acid A is used as an auxiliary oxidant, the etching speed is reduced along with the reduction of the content of the main oxidant in the etching process, and the organic acid A can continuously provide hydrogen ions, so that the stability of the concentration of the hydrogen ions is ensured, and the etching speed is ensured. Illustratively, the organic acid a may include at least one of formic acid, acetic acid, propionic acid, butyric acid, caprylic acid, adipic acid, oxalic acid, malonic acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid, valeric acid, caproic acid, and capric acid.
The amount of the organic acid B may be 2.00wt%, 3.00wt%, 4.00wt%, 5.00wt%, 6.00wt%, 7.00wt%, 8.00wt%, 9.00wt%, 10.00wt%, 11.00wt%, 12.00wt%, 13.00wt%, 14.00wt%, 15.00wt%, 16.00wt%, 17.00wt%, 18.00wt%, 19.00wt%, 20.00wt%, 21.00wt%, 22.00wt%, 23.00wt%, 24.00wt% or 25.00wt%, etc., and may be any other value within a range of 2.00wt% to 25.00 wt%.
It should be noted that the amount of the organic acid B is set to 2.00-25.00wt%, because the etching speed of silver is extremely high, the addition of the organic acid B can obviously accelerate the etching speed of ITO, reduce the risk of collapse of the top ITO caused by too slow etching, reduce the adsorption quantity of the silver simple substance on the substrate, and improve the yield of etched products. If the amount of the organic acid B in the etching solution is less than 2.00wt%, the silver adsorption amount is easily increased; above 25.00wt%, the ITO etching rate tends to be too high, and the single-sided etching amount increases.
In the application, the organic acid B is mainly used for adjusting the pH value of the etching solution, so that the oxidation reaction can be smoothly performed, and an excellent profile can be formed after etching.
Illustratively, the organic acid B may include at least one of methanesulfonic acid, malic acid, citric acid, maleic acid, and tartaric acid.
Further, the etching solution according to the present application may further include 10.00wt% to 30.00wt% of an inorganic salt.
Specifically, the amount of the inorganic salt may be 10.00wt%, 11.00wt%, 12.00wt%, 13.00wt%, 14.00wt%, 15.00wt%, 16.00wt%, 17.00wt%, 18.00wt%, 19.00wt%, 20.00wt%, 21.00wt%, 22.00wt%, 23.00wt%, 24.00wt%, 25.00wt%, 26.00wt%, 27.00wt%, 28.00wt%, 29.00wt% or 30.00wt%, etc., or may be any other value within a range of 10.00wt% to 30.00 wt%.
The inorganic salt is used in an amount of 10.00wt% to 30.00wt%, so that the pH of the etching liquid component can be effectively controlled. If the amount of inorganic salt in the etching solution is less than 10.00wt%, the etching solution is easily insufficient in acidity, and ITO residues are generated; above 30.00wt%, inorganic salts are likely to precipitate in the production line, resulting in defects.
In the present application, the inorganic salt may reduce silver (Ag) re-adsorption of the thin film and may adjust an etching rate to uniformly etch when ITO is removed.
Illustratively, the inorganic salt may include at least one of sodium sulfate, potassium sulfate, calcium sulfate, sodium chloride, calcium chloride, potassium chloride, sodium bisulfate, potassium nitrate, ammonium nitrate, sodium nitrate, silver nitrate, calcium nitrate, sodium dihydrogen phosphate, and ammonium sulfate.
The inorganic salt can provide sufficient sulfate, nitrate and chloride ions, can be respectively combined with hydrogen ions in the solution to form sulfuric acid, nitric acid and hydrochloric acid, and the existence of the acid enables silver adsorbed on the surface of the substrate to be redissolved, so that silver (Ag) re-adsorption of the film is reduced, and the etching speed can be adjusted to uniformly etch when ITO is removed.
Further, the etching solution according to the application can further comprise 0.01-1.00 wt% of metal appearance improving agent.
Specifically, the metal morphology improver may be used in an amount of 0.01wt%, 0.02wt%, 0.05wt%, 0.08wt%, 0.10wt%, 0.20wt%, 0.30wt%, 0.40wt%, 0.50wt%, 0.60wt%, 0.70wt%, 0.80wt%, 0.90wt% or 1.00wt%, etc., or may be any other value within a range of 0.01wt% to 1.00 wt%.
The dosage of the metal appearance improver is set to be 0.01 to 1.00 weight percent, so that silver residue can be improved to a certain extent. If the dosage of the metal appearance improver in the etching solution is lower than 0.01 weight percent, the content is easily too low to achieve the effect of improving the appearance; above 1.00wt% it is easy to cause too high a concentration of metal ions in the solution, affecting the etching characteristics of the etching solution.
In the application, the metal morphology improver can improve the morphology of Ag and ITO.
Illustratively, the metal morphology improving agent may include at least one of ferric nitrate, ferrous nitrate, ferric sulfate, and ferrous sulfate.
The metal morphology residual improver is iron-containing metal salt, and plays a role in reducing the speed of the etching solution penetrating into the upper ITO pinholes through the metal salt of iron, so that the phenomenon of rat bite can be prevented, and the morphology after etching is obviously improved.
In some preferred embodiments, the etching solutions of the present application comprise 7.00-12.00wt% of peroxyacid, 10.00wt% to 15.00wt% of organic acid A, 5.00wt% to 25.00wt% of organic acid B, 15.00wt% to 25.00wt% of inorganic salt, and 0.30wt% to 1.00wt% of metal morphology improving agent, the balance being water.
In some preferred embodiments, the etchant comprises 10.00wt% peroxyacid, 15.00wt% organic acid A, 15.00wt% organic acid B, 25.00wt% inorganic salt, and 1.00wt% metal morphology improving agent, the balance being water.
The etching solution corresponding to the preferred embodiment not only can not damage the titanium aluminum titanium layer part on the surface of the substrate, but also can remove the ITO/Ag/ITO part on the surface of the substrate more effectively, so that an excellent profile is formed, no silver and ITO residues exist, and no silver re-adsorption phenomenon occurs.
Correspondingly, the invention also provides a preparation method of the etching solution, which comprises the following steps: mixing the raw materials according to the proportion.
In some alternative embodiments, the inorganic salt and the metal morphology improving agent may be mixed with water for the first time, then mixed with the peroxyacid for the second time, and then mixed with the organic acid a and the organic acid B for the third time, which is beneficial to uniformly mixing the raw materials.
In addition, the invention also provides application of the etching solution, for example, the etching solution can be used for etching a multilayer film formed by Ag and an ITO film.
For reference, the multilayer film may be an ITO/Ag/ITO composite film.
Through carrying out the sculpture to the multilayer film that silver and ITO membrane constitute with the etching solution that this application provided, can effectively get rid of ITO/Ag/ITO structure, form excellent profile, no silver and ITO residue, also no re-adsorption phenomenon of Ag takes place, does not have the damage to titanium aluminium titanium rete.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The present example provides an etching solution (10.00 kg) containing, in mass%, 5.00wt% of peroxodisulfuric acid (peroxoic acid), 10.00wt% of acetic acid (organic acid a), 25.00wt% of sodium bisulfate (inorganic salt), 15.00wt% of methanesulfonic acid (organic acid B), and 1.00wt% of ferric nitrate (metal morphology improver), with the balance being deionized water.
The etching solution is prepared according to the following method:
the deionized water, the inorganic salt, the metal appearance improver, the peroxy acid, the organic acid A and the organic acid B are respectively weighed according to the proportion, the inorganic salt, the metal appearance improver and the deionized water are stirred and dissolved, then the peroxy acid is added, the stirring is continued to be uniform, and then the organic acid A and the organic acid B are added, and the stirring (30 min) is uniform.
Examples 2 to 10 and comparative examples 1 to 9
The components of the etching solutions corresponding to examples 2 to 10 and comparative examples 1 to 9 are shown in Table 1, and the method of disposing the etching solutions was carried out with reference to example 1.
The total mass of the etching solutions corresponding to each example and comparative example was 10.00kg.
TABLE 1 composition of ingredients
Test examples
ITO/Ag/ITO was etched with the etching solutions (10 kg) of examples 1 to 10 and comparative examples 1 to 9, respectively, and etching characteristics, residual conditions, and titanium-aluminum-titanium damage conditions were observed.
Specifically, 10kg of etching solution is poured into the etching device respectively, and etching is performed after the temperature reaches 40+/-0.1 ℃, because the EPD (etching completion time) of the bottom ITO layer cannot be observed, only the etching completion time of the ITO/Ag two-layer film is observed, the total etching time is 1.5 times of the etching completion time of the ITO/Ag two-layer film EPD, deionized water is used for washing the etching completion time within 2 seconds, the surface moisture is dried, and a scanning electron microscope is used for observation after the etching completion time, and further the performance parameters after etching are evaluated.
The performance parameter evaluation criteria are as follows:
(1) the evaluation criteria for the single-sided etching amount (distance of the etched photoresist edge from the etched silver) are as follows:
o: excellent [ single side etching amount: 0.40-0.60 μm ];
delta: good [ single side etching amount: 0.30-0.40 μm ];
x: poor [ single side etching amount: 0.60 μm or more or 0.30 or less ].
(2) The evaluation criteria for silver re-adsorption (number of Ag particles adsorbed on the surface at SEM 20K magnification) were as follows:
o: excellent [ less than 10 ];
delta: good [10-30 ];
x: bad [30 or more ].
(3) The evaluation criteria for residues (number of Ag/ITO residual particles on the surface under SEM 20K magnification) were as follows:
o: excellent [ less than 10 ];
delta: good [10-30 ];
x: bad [30 or more ].
(4) The titanium aluminum titanium damage evaluation criteria were as follows:
o: excellent [ no damage at all (no indentation of Al) ];
delta: good [ micro damage (Al indentation less than 0.10 μm) ];
x: bad [ severe damage (Al indentation greater than 0.10 μm) ].
The evaluation results are shown in Table 2.
Table 2 evaluation results
As can be seen from table 2: when etching was performed using the etching solutions of examples 1 to 10, the problem of titanium aluminum titanium damage did not occur, and the index of single-side etching amount, residue, ag re-adsorption, and the like were all good or excellent. Specifically, example 1 may have a certain ITO residue due to the lower content of peroxodisulphuric acid compared with example 2, and comparison of example 2 with example 4 may find that the use of acetic acid, which is an organic acid a, is more advantageous for solving the silver adsorption problem than the use of terephthalic acid, and that the use of malic acid is an organic acid B of example 5, and that comparison of example 2 may find that methanesulfonic acid is more advantageous for solving the residue problem. In examples 6 and 7, if the content of methanesulfonic acid and inorganic salt was insufficient, a certain amount of residue was found, but good test results could be maintained. In example 10, peracetic acid is selected as the main oxidant, hydrogen ions provided by peracetic acid are smaller than peroxodisulfuric acid, and the reaction rate of the peracetic acid on metals is insufficient to cause residue generation.
In contrast, when etching was performed using the etching solutions of comparative examples 1 to 9, problems of Ag adsorption and titanium-aluminum-titanium damage occurred, probably because phosphoric acid corroded titanium-aluminum-titanium at a relatively high rate compared to organic acids. In comparative examples 1 to 3, in which the organic acid B was not added and phosphoric acid was adjusted in different amounts, compared with example 2, the problems of Ag reabsorption and titanium-aluminum-titanium damage were all occurred in comparative examples 1 to 3, and when the phosphoric acid content was low, the amount of residue was not very excellent, and in comparative example 5, the inorganic salt was added, and the residue was improved to some extent, but the problems of Ag reabsorption and titanium-aluminum-titanium damage were still not solved. Comparative examples 6 to 8 were compared with example 2 without adding organic acid A and with different amounts of phosphoric acid adjusted, and the problems of Ag re-adsorption and Ti-Al-Ti damage occurred in comparative examples 6 to 8. Comparative example 9 does not contain the organic acid a and the organic acid B, and the organic acid a and the organic acid B are replaced with phosphoric acid, and the results also show that Ag adsorption and titanium aluminum titanium damage problems occur.
Further, by taking example 2 and comparative example 1 as examples, etching result comparison was performed.
Fig. 1 is a SEM cross-sectional view of the etched ITO/Ag/ITO film layer corresponding to example 2, as can be seen from fig. 1: the etching solution provided in example 2 has very good etching effect on the ITO/Ag/ITO film.
Fig. 2 is a SEM TOP view of the etched ITO/Ag/ITO film layer corresponding to example 2, and it can be seen from fig. 2: the etching solution provided in example 2 did not leave any residue after etching the ITO/Ag/ITO film.
Fig. 3 is a SEM TOP view of the etched ITO/Ag/ITO film layer corresponding to example 2, and it can be seen from fig. 3: the etching solution provided in example 2 did not cause Ag adsorption after etching the ITO/Ag/ITO film.
Fig. 4 is a SEM TOP view of the etched ITO/Ag/ITO film layer corresponding to example 2, and it can be seen from fig. 4: the etching solution provided in example 2 did not damage the titanium aluminum titanium film.
Fig. 5 is a SEM TOP view of the etched ITO/Ag/ITO film layer corresponding to comparative example 1, and it can be seen from fig. 5: the etching solution provided in comparative example 1 had some damage to the titanium aluminum titanium film layer.
In summary, the etching solution provided by the application has lower cost, is mainly suitable for etching silver in the multilayer film formed by silver and the ITO film, not only avoids the problem that the titanium aluminum titanium layer on the surface of the substrate is damaged to a certain extent and is unfavorable for environmental protection due to the use of phosphoric acid, but also can effectively remove the ITO/Ag/ITO structure to form an excellent profile, and has no silver and ITO residues and no silver re-adsorption phenomenon.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The etching solution is characterized by comprising 2.00-15.00wt% of peroxyacid, 2.00-15.00wt% of organic acid A, 2.00-25.00wt% of organic acid B and the balance of water according to mass percent;
wherein the organic acid A comprises at least one of formic acid, acetic acid, propionic acid, butyric acid, caprylic acid, adipic acid, oxalic acid, malonic acid, benzoic acid, phenylacetic acid, phthalic acid, terephthalic acid, valeric acid, caproic acid and capric acid;
the organic acid B comprises at least one of methanesulfonic acid, malic acid, citric acid, maleic acid and tartaric acid.
2. The etching solution according to claim 1, further comprising 10.00wt% to 30.00wt% of an inorganic salt.
3. The etching solution according to claim 2, further comprising 0.01wt% to 1.00wt% of a metal morphology improver.
4. The etching solution according to claim 3, wherein the etching solution comprises 7.00 to 12.00wt% of the peroxyacid, 10.00 to 15.00wt% of the organic acid a, 5.00 to 25.00wt% of the organic acid B, 15.00 to 25.00wt% of the inorganic salt, and 0.30 to 1.00wt% of the metal morphology improving agent, the balance being water;
preferably, the etching solution comprises 10.00wt% of the peroxyacid, 15.00wt% of the organic acid A, 15.00wt% of the organic acid B, 25.00wt% of the inorganic salt, and 1.00wt% of the metal morphology improving agent, with the balance being water.
5. The etching solution according to any one of claims 1 to 4, wherein the peroxyacid comprises at least one of peroxomonosulfuric acid, peroxodisulfuric acid, and peracetic acid.
6. The etching solution according to any one of claims 2 to 4, wherein the inorganic salt comprises at least one of sodium sulfate, potassium sulfate, calcium sulfate, iron sulfate, ferrous sulfate, sodium chloride, calcium chloride, potassium chloride, sodium bisulfate, potassium nitrate, ammonium nitrate, sodium nitrate, silver nitrate, calcium nitrate, sodium dihydrogen phosphate, and ammonium sulfate.
7. The etching solution according to claim 3 or 4, wherein the metal morphology improving agent comprises at least one of ferric nitrate, ferrous nitrate, ferric sulfate, and ferrous sulfate.
8. The method for preparing an etching solution according to any one of claims 1 to 7, comprising the steps of: mixing the raw materials according to the proportion.
9. The method of claim 8, wherein the inorganic salt and the metal morphology improving agent are mixed with water for the first time, then mixed with the peroxyacid for the second time, and then mixed with the organic acid A and the organic acid B for the third time.
10. The use of the etching solution according to any one of claims 1 to 7, wherein the etching solution is used for etching a multilayer film composed of Ag and an ITO film;
preferably, the multilayer film is an ITO/Ag/ITO composite film.
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