CN114507859A - Etching solution, preparation method thereof and metal film material treatment method - Google Patents
Etching solution, preparation method thereof and metal film material treatment method Download PDFInfo
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- CN114507859A CN114507859A CN202111481164.7A CN202111481164A CN114507859A CN 114507859 A CN114507859 A CN 114507859A CN 202111481164 A CN202111481164 A CN 202111481164A CN 114507859 A CN114507859 A CN 114507859A
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- 238000005530 etching Methods 0.000 title claims abstract description 143
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 73
- 239000002184 metal Substances 0.000 title claims abstract description 73
- 239000000463 material Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 66
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 50
- 230000007797 corrosion Effects 0.000 claims abstract description 44
- 238000005260 corrosion Methods 0.000 claims abstract description 44
- 239000003112 inhibitor Substances 0.000 claims abstract description 38
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 37
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 37
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 32
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims abstract description 32
- 239000004094 surface-active agent Substances 0.000 claims abstract description 26
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 25
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 23
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims abstract description 18
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 phosphine carboxylic acid Chemical class 0.000 claims abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 16
- 235000011056 potassium acetate Nutrition 0.000 claims abstract description 16
- 229920001732 Lignosulfonate Polymers 0.000 claims abstract description 14
- 235000019357 lignosulphonate Nutrition 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 10
- ZXTFQUMXDQLMBY-UHFFFAOYSA-N alumane;molybdenum Chemical compound [AlH3].[Mo] ZXTFQUMXDQLMBY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 9
- DNAUJKZXPLKYLD-UHFFFAOYSA-N alumane;molybdenum Chemical compound [AlH3].[Mo].[Mo] DNAUJKZXPLKYLD-UHFFFAOYSA-N 0.000 claims abstract description 8
- IOJUPLGTWVMSFF-UHFFFAOYSA-N cyclobenzothiazole Natural products C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims abstract description 7
- UVWMBBFOJLHDEV-UHFFFAOYSA-N alumane;molybdenum Chemical compound [AlH3].[AlH3].[Mo] UVWMBBFOJLHDEV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 4
- 229910001182 Mo alloy Inorganic materials 0.000 claims abstract description 4
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims 2
- 239000011521 glass Substances 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 57
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 29
- 229910052750 molybdenum Inorganic materials 0.000 description 29
- 239000011733 molybdenum Substances 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 7
- 230000005764 inhibitory process Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- LOGBRYZYTBQBTB-UHFFFAOYSA-N butane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(C(O)=O)CC(O)=O LOGBRYZYTBQBTB-UHFFFAOYSA-N 0.000 description 4
- 238000003486 chemical etching Methods 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- ZJAOAACCNHFJAH-UHFFFAOYSA-N phosphonoformic acid Chemical class OC(=O)P(O)(O)=O ZJAOAACCNHFJAH-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- LMHAGAHDHRQIMB-UHFFFAOYSA-N 1,2-dichloro-1,2,3,3,4,4-hexafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(Cl)C1(F)Cl LMHAGAHDHRQIMB-UHFFFAOYSA-N 0.000 description 1
- ZCXGMSGCBDSEOY-UHFFFAOYSA-N 2-benzothiazolsulfonic acid Chemical compound C1=CC=C2SC(S(=O)(=O)O)=NC2=C1 ZCXGMSGCBDSEOY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- UNQHSZOIUSRWHT-UHFFFAOYSA-N aluminum molybdenum Chemical compound [Al].[Mo] UNQHSZOIUSRWHT-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229960005102 foscarnet Drugs 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- MEUIIHOXOWVKNP-UHFFFAOYSA-N phosphanylformic acid Chemical compound OC(P)=O MEUIIHOXOWVKNP-UHFFFAOYSA-N 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic 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
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/20—Acidic compositions for etching aluminium or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—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
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/12—Oxygen-containing compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The application provides an etching solution, a preparation method thereof and a treatment method of a metal film material. The etching solution comprises the following components in parts by weight: 50-80 parts of phosphoric acid, 1-10 parts of nitric acid, 10-30 parts of acetic acid, 0.01-1 part of metal corrosion inhibitor, 0.01-1 part of surfactant and the balance of water; the surfactant comprises nonylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether sulfate; the metal corrosion inhibitor comprises at least one of potassium acetate, sulfonated lignin, phosphine carboxylic acid and sulfenyl benzothiazole. The etching solution has strong controllability, good etching uniformity, smooth etching angle and high precision, can finish the etching of materials in a short time, the loss of the critical dimension of the etched metal film is less than 0.5 mu m, the etching angle is less than 60 degrees, and no residue exists on the surface of the glass panel. And can simultaneously meet the etching requirements of aluminum films, aluminum alloy films, molybdenum alloy films, and molybdenum-aluminum laminated films, aluminum-molybdenum-aluminum laminated films and molybdenum-aluminum-molybdenum laminated films which are superposed in different thicknesses.
Description
Technical Field
The application relates to the field of chemical etching, in particular to an etching solution, a preparation method thereof and a metal film material processing method.
Background
At present, a chemical etching method is usually used to etch a metal film layer containing aluminum or molybdenum to obtain a gate, a source, a drain, etc. of a thin display with a certain pattern. Due to the different chemical characteristics of aluminum and molybdenum, the etching rates of aluminum and molybdenum are different during the chemical etching process, so that the etching uniformity is poor, and the actual pattern is different from the preset pattern. In addition, the chemical etching is isotropic, and the etched film layer is easily subjected to side etching, so that the line width and angle of etching are difficult to control, the etching precision is poor, and the influence is also caused.
Disclosure of Invention
The mixed solution of phosphoric acid, nitric acid and acetic acid is commonly used to etch metal film materials containing aluminum, molybdenum or molybdenum-aluminum laminated film. In the etching process, the nitric acid respectively oxidizes the metal molybdenum and the metal aluminum into multivalent molybdenum oxide and Al2O3And phosphoric acid in the system can generate a complex with the oxide so as to dissolve the oxide, so as to achieve the aim of etching the molybdenum layer and/or the aluminum layer. Molybdenum is more susceptible to oxidation and the etch rate for molybdenum is much greater than the etch rate for aluminum, ultimately resulting in poor etch uniformity. On the other hand, the controllability of the etching solution is poor, and the stripe width loss of the molybdenum aluminum laminated film after etching is large, resulting in poor accuracy. In order to solve the technical problems, the application provides an etching solution, a preparation method thereof and a treatment method of a metal film material.
In a first aspect, specifically, the application provides an etching solution, which contains the following components in parts by weight: 50-80 parts of phosphoric acid, 1-10 parts of nitric acid, 10-30 parts of acetic acid, 0.01-1 part of metal corrosion inhibitor, 0.01-1 part of surfactant and the balance of water; the surfactant comprises nonylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether sulfate; the metal corrosion inhibitor comprises at least one of potassium acetate, sulfonated lignin, phosphine carboxylic acid and sulfenyl benzothiazole.
In the etching solution provided by the application, nitric acidCan respectively oxidize metal molybdenum and metal aluminum into multivalent molybdenum oxide and Al2O3In the presence of acetic acid, phosphoric acid can react with the above-mentioned oxides to form a complex to dissolve the oxides for the purpose of etching the molybdenum layer and/or the aluminum layer. On the basis of phosphoric acid, nitric acid and acetic acid, specific surfactants, namely nonylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether sulfate, and specific metal corrosion inhibitors (at least one of potassium acetate, sulfonated lignin, phosphinocarboxylic acid and thiobenzothiazole) are added, so that the etching rates of the etching solution to a molybdenum layer and an aluminum layer are basically kept consistent, and the etching precision is ensured. The nonylphenol polyoxyethylene ether has good permeability and dispersibility, is not easy to foam, has good oxidation and reduction resistance, can stably exist in the etching solution, and does not have side reaction with nitric acid in the etching solution; the nonylphenol polyoxyethylene ether and the fatty alcohol polyoxyethylene ether sulfate are jointly used as the surfactant, the infiltration speed of the etching solution on the surface of the aluminum film and the infiltration capacity of the etching solution on the aluminum film can be effectively improved, the etching rate of the etching solution on the aluminum film can be improved to a certain extent, and the etching speeds of aluminum and molybdenum tend to be consistent. In addition, the surfactant can increase the dispersion degree of the complex generated by the aluminum oxide and the phosphoric acid in the etching solution, so that the problem that the complex generated by the aluminum oxide and the phosphoric acid is gathered on the surface of a metal film to reduce the etching rate of the aluminum after reaching a certain concentration in the etching process can be effectively avoided, the etching uniformity can be improved, and the problem of side etching of the aluminum layer can be relieved.
On the other hand, the surfactant can be matched with a metal corrosion inhibitor to regulate the etching ratio of molybdenum and aluminum. The etching speed of the etching solution on molybdenum and aluminum can be effectively adjusted under the condition that the effectiveness of the etching solution is not influenced by potassium acetate, sulfonated lignin, phosphine carboxylic acid and sulfenyl benzothiazole. Wherein, potassium acetate can simultaneously realize corrosion inhibition on aluminum and molybdenum, but has better corrosion inhibition effect on metal molybdenum. The organic metal corrosion inhibitors such as sulfonated lignin, phosphine carboxylic acid and sulfobenzothiazole have better affinity to molybdenum than aluminum, and can be preferentially infiltrated and attached to the surface of metal molybdenum after being compounded with a surfactant, so that the etching of acid to the metal molybdenum is hindered, and the etching speed of the metal molybdenum is reduced. When the etching solution is used for treating an aluminum-molybdenum, molybdenum-aluminum-molybdenum or aluminum-molybdenum-aluminum laminated film, the difference of the corrosion inhibition effect of the metal corrosion inhibitor on aluminum and molybdenum can enable the etching speed of the whole etching solution on aluminum and molybdenum to be consistent, and further uniform etching on the molybdenum-aluminum laminated film is realized. Particularly, under the action of the metal corrosion inhibitor, the etching solution can also effectively relieve the side etching effect of the metal film material, and reduce the etching selection ratio on the side wall of the laminated film (namely, improve the verticality of the etched laminated film side wall), thereby improving the etching precision. In particular, the laminated film does not delaminate after etching, i.e., the etching solution does not affect the interfacial bonding force of the metal film layer. In conclusion, the surfactant and the metal corrosion inhibitor are compounded, so that the regulation and control capability of the metal corrosion inhibitor on the etching speed and angle can be further improved, the etching ratio of metal molybdenum and aluminum can be effectively regulated and controlled by the etching solution, the occurrence of the lateral etching phenomenon of the film layer is weakened, the strip width loss of the film layer is reduced, and the etching precision is improved.
In the present application, the etching solution contains 50 to 80 parts by weight of phosphoric acid, and illustratively, the parts by weight of phosphoric acid may be 50 parts, 55 parts, 60 parts, 62 parts, 65 parts, 68 parts, 70 parts, 75 parts, 78 parts, and 80 parts.
In the present application, the etching solution contains 1 to 10 parts of nitric acid. Illustratively, the parts by weight of nitric acid may be 1 part, 2 parts, 2.5 parts, 3 parts, 5 parts, 7.5 parts, 8 parts, 10 parts.
In the present application, the etching solution contains 10 to 30 parts of acetic acid. Illustratively, the acetic acid may be 10 parts, 15 parts, 17.5 parts, 19 parts, 20 parts, 25 parts, 30 parts by weight.
In the application, the etching solution contains 0.01-1 part of metal corrosion inhibitor. Illustratively, the metal corrosion inhibitor may be present in an amount of 0.01 parts, 0.02 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.5 parts, 0.75 parts, 1.0 parts by weight.
In the present application, the etching solution contains 0.01 to 1 part of a surfactant. Illustratively, the weight parts of the surfactant may be 0.01 parts, 0.02 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.5 parts, 0.75 parts, 1.0 parts.
In the embodiments of the present application, phosphoric acid, nitric acid, and acetic acid are commercially available reagents. The phosphine carboxylic acid may be aminotrimethylene phosphonic acid, 2-phosphonobutane-1, 2, 4-tricarboxylic acid, 2-hydroxyphosphonoacetic acid, and the like.
In the embodiment of the application, the etching solution contains the following components in parts by weight: 72-78 parts of phosphoric acid, 2.5-4.5 parts of nitric acid, 16-19 parts of acetic acid and the balance of water. The preferable contents of the phosphoric acid, the nitric acid and the acetic acid are more favorable for ensuring the etching rate of the whole etching solution and regulating the etching selection ratio and the etching precision of the molybdenum and the aluminum.
In the embodiment of the application, the etching solution contains 0.005-0.75 parts of nonylphenol polyoxyethylene ether, and the parts by weight of nonylphenol polyoxyethylene ether can be 0.005 parts, 0.01 parts, 0.02 parts, 0.03 parts, 0.05 parts, 0.1 parts, 0.15 parts, 0.2 parts and 0.25 parts. The etching solution contains 0.005-0.25 part of fatty alcohol-polyoxyethylene ether sulfate, and exemplarily, the weight parts of the fatty alcohol-polyoxyethylene ether sulfate can be 0.005 part, 0.01 part, 0.025 part, 0.03 part, 0.05 part, 0.1 part, 0.15 part, 0.2 part, 0.25 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part and 0.75 part. In some embodiments, the fatty alcohol-polyoxyethylene ether sulfate is sodium fatty alcohol-polyoxyethylene ether sulfate and/or ammonium fatty alcohol-polyoxyethylene ether sulfate. The fatty alcohol-polyoxyethylene ether sulfate is an ionic surfactant, the nonylphenol polyoxyethylene ether is a nonionic surfactant, and after the fatty alcohol-polyoxyethylene ether sulfate and the nonylphenol polyoxyethylene ether are compounded in a proper proportion, the cloud point of the nonylphenol polyoxyethylene ether can be improved, and the dispersibility of the nonylphenol polyoxyethylene ether in a system can be improved, so that the etching solution has better temperature resistance and can be kept stable at higher temperature.
In the embodiment of the application, the metal corrosion inhibitor further comprises phosphonate, and the phosphonate can be 2, 4-di-tert-butyl sodium phenoxyphosphate as an example. The phosphonate and the metal corrosion inhibitor can generate a certain synergistic effect, and particularly, under the condition that the phosphono-carboxylic acid compounds exist, the corrosion inhibition effect of the metal corrosion inhibitor can be effectively improved by the existence of a small amount of the phosphonate.
In some embodiments of the present disclosure, the metal corrosion inhibitor is a mixture of any one or more of sulfonated lignin, phosphine carboxylic acid, and thiobenzothiazole with potassium acetate. The existence of potassium acetate can improve the corrosion inhibition speed of organic corrosion inhibitors such as sulfonated lignin and the like on metal molybdenum, so that the consistency of the etching speed of aluminum and molybdenum is higher. Further, in the case of containing a phosphine carboxylic acid, a small amount of a phosphonate is preferably added. Thus greatly improving the corrosion inhibition effect of the phosphono-carboxylic acid. In other embodiments, the metal corrosion inhibitor is potassium acetate.
In the embodiment of the application, the mass ratio of the surfactant to the metal corrosion inhibitor is 1: (0.5-2). The proper mass ratio of the surfactant to the metal corrosion inhibitor can effectively improve the compounding effect of the surfactant and the metal corrosion inhibitor, thereby ensuring the etching selection ratio of the etching solution to molybdenum and aluminum.
In the embodiment of the present application, the pH of the etching solution is 1.5 to 2.5. The proper pH value can ensure the good stability and etching effect of the etching solution.
In a second aspect, the present application provides a method for preparing an etching solution, comprising the following steps:
mixing phosphoric acid, nitric acid, acetic acid, a surfactant, a metal corrosion inhibitor and water in proportion to obtain an etching solution; the etching solution comprises the following components in parts by weight: 50-80 parts of phosphoric acid, 1-10 parts of nitric acid, 10-30 parts of acetic acid, 0.01-1 part of metal corrosion inhibitor, 0.01-1 part of surfactant and the balance of water; wherein the surfactant comprises nonylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether sulfate; the metal corrosion inhibitor comprises at least one of potassium acetate, sulfonated lignin, phosphine carboxylic acid and sulfenyl benzothiazole.
The preparation method can obtain the etching solution only by mixing the raw materials, has simple process and high production efficiency, and is suitable for large-scale industrial production.
In a third aspect, the present application provides a method for processing a metal film, comprising contacting the etching solution provided in the first aspect of the present application or the etching solution prepared by the preparation method according to the second aspect with the metal film to perform etching; wherein the metal film material comprises an aluminum film, an aluminum alloy film, a molybdenum alloy film, a molybdenum-aluminum laminated film, an aluminum-molybdenum-aluminum laminated film and a molybdenum-aluminum-molybdenum laminated film. The treatment method is simple to operate and suitable for large-scale industrial production.
In the embodiment of the present application, the contacting includes immersing the metal film in the etching solution, or spraying/rinsing the etching solution on the metal film. Can be selected according to the actual production condition.
In the embodiment of the application, the etching time is 90s-110 s. The proper time can ensure that no residue is left after etching.
In the embodiment of the present application, the etching temperature is 40 ℃ to 70 ℃. The proper temperature can ensure the etching precision and the etching speed.
The etching solution provided by the application has the advantages of strong controllability, good etching uniformity, smooth etching angle and high precision, can finish the etching of materials in a short time, has no residue on the surface of a glass panel after etching, ensures that the loss of the critical dimension of the materials is less than 0.5 mu m, ensures that the coverage of a film on a substrate in the subsequent process is ensured, and is suitable for the production of a glass panel. And can simultaneously meet the etching requirements of aluminum films, aluminum alloy films, molybdenum alloy films, and molybdenum-aluminum laminated films, aluminum-molybdenum-aluminum laminated films and molybdenum-aluminum-molybdenum laminated films which are superposed in different thicknesses.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of a sample S6 obtained by etching the Mo-Al-Mo laminated film with the etching solution of example 6;
FIG. 2 is an SEM photograph of a sample S8 obtained by etching the Mo-Al-Mo laminated film with the etching solution of example 8;
FIG. 3 is an SEM photograph of a sample S9 obtained by etching the Mo-Al-Mo laminated film with the etching solution of example 9;
fig. 4 is an SEM photograph of a sample S10 obtained by etching the molybdenum-aluminum laminate film with the etching solution of example 10.
Detailed Description
The technical solution of the present application is described in detail by a plurality of examples.
Example 1
Uniformly mixing phosphoric acid, nitric acid, acetic acid, a metal corrosion inhibitor and water according to a certain proportion, and filtering to obtain the etching solution. The etching solution comprises the following components in parts by weight: 65 parts of phosphoric acid, 3 parts of nitric acid, 17.5 parts of acetic acid, 0.05 part of a metal corrosion inhibitor, specifically a mixture of potassium acetate, sulfonated lignin, 2-phosphonic butane-1, 2, 4-tricarboxylic acid and Thiobenzothiazole, 0.5 part of nonylphenol polyoxyethylene ether, 0.05 part of sodium fatty alcohol polyoxyethylene ether sulfate and the balance of water.
And (3) soaking the glass panel covered with the molybdenum-aluminum-molybdenum laminated film in the etching solution at 40 ℃ for 100s, wherein the thickness of each metal film in the thickness direction is 200nm, 3800nm and 500nm respectively. The etched sample was designated as S1.
Example 2
The difference between example 2 and example 1 is: the etching solution comprises the following components in parts by weight: 50 parts of phosphoric acid, 1 part of nitric acid, 10 parts of acetic acid, 0.01 part of a mixture of potassium acetate, sulfonated lignin, 2-phosphonic butane-1, 2, 4-tricarboxylic acid and sulfenyl benzothiazole, 0.01 part of nonylphenol polyoxyethylene ether, 0.05 part of fatty alcohol polyoxyethylene ether sodium sulfate and the balance of water. The etched sample was designated as S2.
Example 3
The difference between example 3 and example 1 is: the etching solution comprises the following components in parts by weight: 80 parts of phosphoric acid, 10 parts of nitric acid, 30 parts of acetic acid, 0.05 part of a mixture of potassium acetate, sulfonated lignin, 2-phosphonic butane-1, 2, 4-tricarboxylic acid and Thiobenzothiazole, 0.25 part of nonylphenol polyoxyethylene ether, 0.75 part of fatty alcohol polyoxyethylene ether sodium sulfate and the balance of water. The etched sample was designated as S3.
Example 4
The difference between example 4 and example 1 is: the etching solution contained 62 parts of phosphoric acid, 2.5 parts of nitric acid and 16 parts of acetic acid. The etched sample was designated as S4.
Example 5
The difference between example 5 and example 1 is: the etching solution contained 68 parts of phosphoric acid, 4.5 parts of nitric acid and 19 parts of acetic acid. The etched sample was designated as S5.
Example 6
The difference between example 6 and example 1 is: the metal corrosion inhibitor is a mixture of potassium acetate, sulfonated lignin, 2-phosphonic butane-1, 2, 4-tricarboxylic acid, phosphonate and sulfenyl benzothiazole. The etched sample was designated as S6.
Example 7
The difference between example 7 and example 1 is: the metal corrosion inhibitor is potassium acetate. The etched sample was designated as S7.
Example 8
The difference between example 8 and example 1 is: the thickness of each metal film in the thickness direction of the molybdenum-aluminum-molybdenum laminated film is 200nm, 3300nm and 500nm respectively. The etched sample was designated as S8.
Example 9
The difference between example 9 and example 1 is: the thickness of each metal film of the molybdenum-aluminum-molybdenum laminated film along the thickness direction is respectively 200nm, 2500nm and 500 nm. The etched sample was designated as S9.
Example 10
The difference between example 10 and example 1 is: the etching target was a molybdenum-aluminum laminated film, the thickness of the molybdenum layer was 800nm, and the thickness of the aluminum layer was 2000 nm. The etched sample was designated as S10.
Example 11
Example 11 differs from example 1 in that: the object of etching was a molybdenum film having a thickness of 2000 nm. The etched sample was designated as S11.
Example 12
Example 12 differs from example 1 in that: the etching target was an aluminum film having a thickness of 2000 nm. The etched sample was designated as S12.
In order to highlight the beneficial effects brought by the technical scheme of the embodiment of the application, the following comparative example is arranged.
Comparative example 1
The difference between comparative example 1 and example 1 is: does not contain a surfactant and a metal corrosion inhibitor. The etched sample was designated as DS 1.
Comparative example 2
The difference between comparative example 2 and example 1 is: does not contain metal corrosion inhibitor. The etched sample was designated as DS 2.
Comparative example 3
The difference between comparative example 3 and example 1 is: the surfactant is only fatty alcohol-polyoxyethylene ether sodium sulfate. The etched sample was designated as DS 3.
SEM tests are carried out on samples prepared in the above examples and comparative examples, and SEM pictures of the samples prepared in some examples can be seen in FIGS. 1 to 4. The critical dimension loss and the etching angle of the etched sample film layer can be directly measured from the SEM photograph. The test results of the examples and comparative examples are summarized in table 1.
Table 1 test results of metal films prepared in examples and comparative examples
As can be seen from the data in Table 1, the samples S1-S11 prepared in the examples of the present application have smaller critical dimension loss and etching angle (critical dimension loss less than 0.5 μm, etching angle less than 60 ℃ C.) and high etching cleanliness without material residue, compared with the samples DS1-DS3 prepared in the comparative examples. In addition, the etching solution of example 6 further added with phosphonate, and the result shows that the performance of the etching solution is improved more obviously. Therefore, the etching solution provided by the application has the advantages of strong controllability, good etching uniformity, smooth etching angle and high precision, the loss of the critical dimension of the etched material is less than 0.5 mu m, the etching angle is less than 60 degrees, and no residue is left on the surface of the glass panel.
The foregoing is illustrative of the present application and it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the application and are intended to be within the scope of the application.
Claims (10)
1. The etching solution is used for a metal film material, and is characterized by comprising the following components in parts by weight: 50-80 parts of phosphoric acid, 1-10 parts of nitric acid, 10-30 parts of acetic acid, 0.01-1 part of metal corrosion inhibitor, 0.01-1 part of surfactant and the balance of water; the surfactant comprises nonylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether sulfate; the metal corrosion inhibitor comprises at least one of potassium acetate, sulfonated lignin, phosphine carboxylic acid and thiobenzothiazole.
2. The etching solution of claim 1, wherein the etching solution comprises the following components in parts by weight: 0.005-0.75 parts of the nonylphenol polyoxyethylene ether; 0.005-0.25 part of fatty alcohol-polyoxyethylene ether sulfate.
3. The etching solution of claim 1, wherein the mass ratio of the surfactant to the metal corrosion inhibitor is 1: (0.5-2).
4. The etching solution of claim 1, wherein the metal corrosion inhibitor further comprises a phosphonate.
5. The etching solution of claim 1, wherein the etching solution comprises the following components in parts by weight: 72-78 parts of phosphoric acid, 2.5-4.5 parts of nitric acid, 16-19 parts of acetic acid and the balance of water.
6. The etching solution according to any one of claims 1 to 5, wherein the pH of the etching solution is 1.5 to 2.5.
7. A preparation method of an etching solution for a metal film material is characterized by comprising the following steps:
mixing phosphoric acid, nitric acid, acetic acid, a surfactant, a metal corrosion inhibitor and water in proportion to obtain an etching solution; the etching solution comprises the following components in parts by weight: 50-80 parts of phosphoric acid, 1-10 parts of nitric acid, 10-30 parts of acetic acid, 0.01-1 part of metal corrosion inhibitor, 0.01-1 part of surfactant and the balance of water; wherein the surfactant comprises nonylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether sulfate; the metal corrosion inhibitor comprises at least one of potassium acetate, sulfonated lignin, phosphine carboxylic acid and sulfenyl benzothiazole.
8. A method for processing a metal film is characterized by comprising the following steps:
contacting the etching liquid according to any one of claims 1 to 6 or the etching liquid prepared by the preparation method according to claim 7 with a metal film to etch the metal film; wherein the metal film material comprises an aluminum film, an aluminum alloy film, a molybdenum alloy film, a molybdenum-aluminum laminated film, an aluminum-molybdenum-aluminum laminated film and a molybdenum-aluminum-molybdenum laminated film.
9. The process of claim 8, wherein the etching time is 90s-110 s.
10. The process of claim 8, wherein the etching temperature is 40 ℃ to 70 ℃.
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