CN112921321A - Environment-friendly low-cost titanium-containing metal etching solution composition and use method thereof - Google Patents
Environment-friendly low-cost titanium-containing metal etching solution composition and use method thereof Download PDFInfo
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- 238000005530 etching Methods 0.000 title claims abstract description 135
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 65
- 239000002184 metal Substances 0.000 title claims abstract description 65
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000010936 titanium Substances 0.000 title claims abstract description 60
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 62
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 51
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 49
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 amino azole compound Chemical class 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 16
- 230000001590 oxidative effect Effects 0.000 claims abstract description 15
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- ANUQVPMOKIYKBZ-UHFFFAOYSA-N [Ti].[Ni].[Mo] Chemical compound [Ti].[Ni].[Mo] ANUQVPMOKIYKBZ-UHFFFAOYSA-N 0.000 claims description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- 229910052802 copper Inorganic materials 0.000 claims description 22
- 239000010949 copper Substances 0.000 claims description 22
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 19
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims description 18
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- 239000011733 molybdenum Substances 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 150000003868 ammonium compounds Chemical class 0.000 claims description 5
- QLSWIGRIBOSFMV-UHFFFAOYSA-N 1h-pyrrol-2-amine Chemical class NC1=CC=CN1 QLSWIGRIBOSFMV-UHFFFAOYSA-N 0.000 claims description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- AZUKLCJYWVMPML-UHFFFAOYSA-N 2-methyltetrazol-5-amine Chemical compound CN1N=NC(N)=N1 AZUKLCJYWVMPML-UHFFFAOYSA-N 0.000 claims description 3
- JSIAIROWMJGMQZ-UHFFFAOYSA-N 2h-triazol-4-amine Chemical compound NC1=CNN=N1 JSIAIROWMJGMQZ-UHFFFAOYSA-N 0.000 claims description 3
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 3
- 229940005991 chloric acid Drugs 0.000 claims description 3
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 3
- 229940077239 chlorous acid Drugs 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 3
- QYHFIVBSNOWOCQ-UHFFFAOYSA-N selenic acid Chemical compound O[Se](O)(=O)=O QYHFIVBSNOWOCQ-UHFFFAOYSA-N 0.000 claims description 3
- HUUBMTMJIQHAEN-UHFFFAOYSA-N triazole-1,4-diamine Chemical compound NC1=CN(N)N=N1 HUUBMTMJIQHAEN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000002671 adjuvant Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 abstract description 4
- 239000011737 fluorine Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 239000011574 phosphorus Substances 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 239000002699 waste material Substances 0.000 abstract 1
- FEPBITJSIHRMRT-UHFFFAOYSA-N 4-hydroxybenzenesulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C=C1 FEPBITJSIHRMRT-UHFFFAOYSA-N 0.000 description 15
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 14
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 10
- 229960002887 deanol Drugs 0.000 description 9
- 239000012972 dimethylethanolamine Substances 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012544 monitoring process Methods 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 150000007530 organic bases Chemical class 0.000 description 3
- 150000003460 sulfonic acids Chemical class 0.000 description 3
- 150000003672 ureas Chemical class 0.000 description 3
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical compound NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 238000003421 catalytic decomposition reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- MHVJUTLRTHDAOG-UHFFFAOYSA-N p-hydroxyphenylurea Natural products NC(=O)NC1=CC=C(O)C=C1 MHVJUTLRTHDAOG-UHFFFAOYSA-N 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- XVCKCCODMHCXJD-UHFFFAOYSA-N (4-aminophenyl)urea Chemical compound NC(=O)NC1=CC=C(N)C=C1 XVCKCCODMHCXJD-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241001124569 Lycaenidae Species 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 235000014987 copper Nutrition 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- BJAARRARQJZURR-UHFFFAOYSA-N trimethylazanium;hydroxide Chemical compound O.CN(C)C BJAARRARQJZURR-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 235000016804 zinc Nutrition 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
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The invention discloses an environment-friendly low-cost titanium-containing metal etching solution composition and a using method thereof, wherein the etching solution comprises a main agent and an auxiliary agent, wherein the main agent comprises the following components in percentage by mass: 1-20% of hydrogen peroxide, 1-10% of strong oxidizing acid, 1-10% of alkali compound, 0.01-5% of hydrogen peroxide stabilizer, 0.01-2% of amino azole compound and the balance of deionized water; the auxiliary agent comprises the following components in percentage by mass: 1-20% of strong oxidizing acid, 1-20% of alkali compound, 0.01-2% of amino azole compound and the balance of deionized water. The etching solution composition prepared by the invention is free of fluorine and phosphorus, environment-friendly, low in waste liquid treatment cost and high in copper ion loading capacity, and the etched metal has a good etching appearance and can meet the production requirements of ultra-fine and medium-small-size display products.
Description
Technical Field
The invention relates to the field of metal surface chemical treatment, in particular to an environment-friendly low-cost titanium-containing metal etching solution composition and a using method thereof.
Background
Etching (etching) is a technique for removing materials by using a chemical reaction or a physical impact action, and is mainly used for manufacturing printing intaglio and embossing plates such as coppers and zincs, reducing weight of instrument panels, and processing precision etching products such as electronic thin sheet parts/semiconductors in the aviation, machinery and chemical industries.
The etching liquid is a liquid that achieves the purpose of etching by eroding a material. Most of the existing commonly used etching solutions contain fluorine ions, so that although the etching rate is improved, the etching precision cannot be guaranteed, the loading capacity of the etching solutions on metal ions is not high, a large amount of etching solutions are generated in the etching process, the cost of the etching process is increased, and the environment-friendly requirement cannot be met.
In recent years, the etching process is most commonly applied to transistors and liquid crystal displays, a predetermined pattern is generated on a multi-layer metal layer composed of a plurality of metals such as copper, molybdenum and the like by an etching liquid, if an undercut phenomenon exists between the end of the metal layer of the pattern and a substrate, the coverage in a subsequent process is uneven, and further an unexpected open circuit is caused, so that the etching shape between the end of the metal layer and the substrate is very important for the yield of the transistors and the liquid crystal displays.
Disclosure of Invention
In view of the defects of the prior art, the invention provides an environment-friendly low-cost titanium-containing metal etching solution composition in a first aspect.
An environment-friendly low-cost titanium-containing metal etching solution composition comprises a main agent and an auxiliary agent.
Further, the main agent comprises the following components in percentage by mass: 1-20% of hydrogen peroxide, 1-10% of strong oxidizing acid, 0.01-10% of alkali compound, 0.01-5% of hydrogen peroxide stabilizer, 0.01-2% of amino azole compound and the balance of deionized water.
Further, the auxiliary agent comprises the following components in percentage by mass: 1-20% of strong oxidizing acid, 0.01-20% of alkali compound, 0.01-2% of amino azole compound and the balance of deionized water.
Further, the strong oxidizing acid in the main agent and the auxiliary agent is one or more of concentrated sulfuric acid, hypochlorous acid, nitric acid, selenic acid, chloric acid, chlorous acid, halogen acid, perhalogen acid, nitrous acid and permanganic acid.
Further, the alkali compounds in the main agent and the auxiliary agent are one or a combination of alcohol amine compounds and ammonium compounds.
Further, the hydrogen peroxide stabilizer is one or a combination of urea compounds and sulfonic acid compounds.
Furthermore, the amino azole compounds in the main agent and the auxiliary agent are one or more of 3-amino triazole, 4-amino triazole, 3, 5-diamino triazole, 5-amino tetrazole and 2-methyl-5-amino tetrazole.
The second aspect of the invention provides a use method of an environment-friendly low-cost titanium-containing metal etching solution composition, which comprises the following steps:
s1, preparing a main agent of the etching solution;
s2, preparing an etching solution auxiliary agent;
s3, contacting the titanium-containing metal with the etching solution main agent to etch the metal;
s4, the concentration of copper ions in the main agent of the etching solution is monitored, and the auxiliary agent is added into the main agent.
Further, the titanium-containing metal includes a copper film and a molybdenum titanium nickel film.
Further, the ratio of molybdenum in the molybdenum-titanium-nickel film is as follows: titanium: the mass percentage of the nickel is (3-10): (0-5): (0-5).
Compared with the prior art, the invention has the beneficial effects that:
1. the etching solution does not contain fluorine-containing compounds and phosphorus-containing compounds, reduces the treatment pressure and cost of the etching waste water, and meets the environment-friendly requirement.
2. In the etching solution system, the loading capacity of the etching solution to copper ions is improved under the combined action of the organic base and the nitric acid, the pH stability of the etching solution is maintained, and the rate of catalytic decomposition of hydrogen peroxide by the copper ions is relieved.
3. In the etching solution system, the metal corrosion inhibitor can interact with copper ions, and the etching rate of the copper film is slowed down under the combined action of organic alkali, so that the etching rates of different metal films are more balanced, and the titanium-containing metal obtained by etching has good etching appearance and can meet the production requirements of ultra-fine, medium and small-sized display products.
Drawings
FIG. 1 is an SEM photograph of a titanium-containing metal in etching of a titanium-containing metal 80s by using the etching solution of example 1 of the present invention.
FIG. 2 is an SEM photograph of a titanium-containing metal 87s etched by the etching solution of example 2 of the present invention.
FIG. 3 is an SEM photograph of a titanium-containing metal in the etching solution of example 3 of the present invention for etching the titanium-containing metal 85 s.
Detailed Description
In view of the defects of the prior art, the invention provides an environment-friendly low-cost titanium-containing metal etching solution composition in a first aspect.
An environment-friendly low-cost titanium-containing metal etching solution composition comprises a main agent and an auxiliary agent.
Further, the main agent comprises the following components in percentage by mass: 1-20% of hydrogen peroxide, 1-10% of strong oxidizing acid, 0.01-10% of alkali compound, 0.01-5% of hydrogen peroxide stabilizer, 0.01-2% of amino azole compound and the balance of deionized water.
Further, the main agent comprises the following components in percentage by mass: 5-15% of hydrogen peroxide, 1-5% of strong oxidizing acid, 0.01-10% of alkali compound, 0.01-3% of hydrogen peroxide stabilizer, 0.01-2% of amino azole compound and the balance of deionized water.
Further, the auxiliary agent comprises the following components in percentage by mass: 1-20% of strong oxidizing acid, 0.01-20% of alkali compound, 0.01-2% of amino azole compound and the balance of deionized water.
Further, the auxiliary agent comprises the following components in percentage by mass: 5-15% of strong oxidizing acid, 0.01-10% of alkali compound, 0.01-2% of amino azole compound and the balance of deionized water.
Further, the hydrogen peroxide is electronic grade hydrogen peroxide.
Further, the strong oxidizing acid of the main agent and the auxiliary agent is one or more of concentrated sulfuric acid, hypochlorous acid, nitric acid, selenic acid, chloric acid, chlorous acid, halogen acid, perhalogen acid, nitrous acid and permanganic acid.
Further, the strong oxidizing acid of the main agent and the auxiliary agent is one or more of concentrated sulfuric acid, nitric acid and nitrous acid.
Further, the strong oxidizing acid of the main agent and the auxiliary agent is nitric acid.
Further, the alkali compounds of the main agent and the auxiliary agent are one or a combination of alcohol amine compounds and ammonium compounds.
The alcohol amine compound includes ethylenediamine, propylenediamine, dimethylethanolamine, diethylaminopropylamine, diethylethanolamine, triethanolamine, isopropanolamine.
Further, the alcohol amine compounds of the main agent and the auxiliary agent are dimethyl ethanolamine.
The ammonium compound includes tetramethyl ammonium hydroxide, trimethyl ammonium hydroxide, ammonium acetate, ammonium chloride, ammonium sulfate, and ammonium nitrate.
Further, the ammonium compounds of the main agent and the auxiliary agent are both tetramethylammonium hydroxide.
Further, the hydrogen peroxide stabilizer is one or a combination of urea compounds and sulfonic acid compounds.
The urea compounds include p-hydroxyphenyl urea, p-aminophenyl urea, phenyl urea, thiourea and urea.
The sulfonic acid compounds include p-hydroxy benzenesulfonic acid and p-aminophenylsulfonic acid.
Furthermore, the amino azole compounds of the main agent and the auxiliary agent are one or more of 3-amino triazole, 4-amino triazole, 3, 5-diamino triazole, 5-amino tetrazole and 2-methyl-5-amino tetrazole.
Furthermore, the amino azole compounds of the main agent and the auxiliary agent are 5-aminotetrazole.
The second aspect of the invention provides a use method of an environment-friendly low-cost titanium-containing metal etching solution composition, which comprises the following steps:
s1, preparing a main agent of the etching solution;
s2, preparing an etching solution auxiliary agent;
s3, contacting the titanium-containing metal with the etching solution main agent, controlling the etching temperature and the etching time of the titanium-containing metal, and etching the metal;
s4, the concentration of copper ions in the main agent of the etching solution is monitored, and the auxiliary agent is added into the main agent.
Further, the titanium-containing metal includes a copper film and a molybdenum titanium nickel film.
Further, the ratio of molybdenum in the molybdenum-titanium-nickel film is as follows: titanium: the mass percentage of the nickel is (3-10): (0-5): (0-5).
Further, the ratio of molybdenum in the molybdenum-titanium-nickel film is as follows: titanium: the mass percentage ratio of nickel is (5-10): (0-3): (0-4).
Further, the ratio of molybdenum in the molybdenum-titanium-nickel film is as follows: titanium: the mass percentage of nickel is 6: 2: 2.
further, the thickness of the copper film is 3000-6000A.
Further, the thickness of the copper film is 4000-6000A.
Further, the thickness of the molybdenum titanium nickel film is 200-500A.
Further, the thickness of the molybdenum titanium nickel film is 200-400A.
Further, the etching temperature is 0-50 ℃.
Further, the etching temperature is 20-50 ℃.
Further, the etching temperature was 35 ℃.
Further, the etching time is 20-100 s.
Further, the etching time is 60-100 s.
Further, the etching time is 80-100 s.
Furthermore, the auxiliary agent is added in a way that the copper ions are increased by 100-200ppm per liter, and 0.01-1% of the auxiliary agent based on the mass of the main agent is supplemented into the etching solution system.
Furthermore, the auxiliary liquid is added in a way that the copper ions are increased by 100-150ppm per liter, and 0.01-0.5 percent of auxiliary agent based on the mass of the main agent is supplemented to the etching liquid system.
Furthermore, the auxiliary agent is added in a mode that every time the copper ions are increased by 100ppm, the auxiliary agent with the mass of 0.1 percent of the main agent is supplemented into the etching solution system.
The alkaline compound selected by the product is an organic alkaline compound, and the organic alkali and nitric acid act together in the etching solution system of the invention, so that the molybdenum oxide, nickel oxide, titanium oxide and other metal oxides are promoted to be dissolved into free metal ions and simultaneously complex copper ions, the loading capacity of the etching solution of the invention to the copper ions is improved, the pH stability of the etching solution can be maintained, and the rate of catalytic decomposition of hydrogen peroxide by the copper ions is relieved.
The metal corrosion inhibitor selected by the product can generate intermolecular interaction with metal ions to form a protective layer on the surface of copper metal, and the protective layer and the organic alkali contained in the product reduce the etching speed of the copper metal, so that the etching rates of different metals are more balanced, and the etching accuracy is further improved.
The service life of the etching solution is finally prolonged due to the combined action of various reasons.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, all the starting materials used are commercially available, unless otherwise specified.
Electronic grade Hydrogen peroxide, available from Hangzhou Jingxin chemical Co., Ltd, H2O235% by mass, CAS No.: 7722-84-1.
Nitric acid, CAS number: 7697-37-2.
Dimethylethanolamine, CAS No.: 108-01-0.
Tetramethylammonium hydroxide, CAS No.: 10424-65-4.
P-hydroxybenzenesulfonic acid, CAS No.: 98-67-9.
5-Aminotetrazole, CAS number: 4418-61-5.
Hydrofluoric acid, CAS No.: 7664-39-3.
Example 1
An environment-friendly low-cost titanium-containing metal etching solution composition comprises a main agent and an auxiliary agent.
The main agent comprises the following components in percentage by mass: 7.25 percent of hydrogen peroxide, 4.4 percent of nitric acid, 9.58 percent of tetramethyl ammonium hydroxide, 0.2 percent of p-hydroxybenzene sulfonic acid, 0.02 percent of 5-aminotetrazole and the balance of deionized water.
The auxiliary agent comprises the following components in percentage by mass: 9.45 percent of nitric acid, 23.15 percent of tetramethyl ammonium hydroxide, 0.3 percent of p-hydroxybenzene sulfonic acid, 0.04 percent of 5-aminotetrazole and the balance of deionized water.
An application method of an environment-friendly low-cost titanium-containing metal etching solution composition comprises the following steps:
soaking titanium-containing metal in a main agent of the etching solution, wherein the titanium-containing metal comprises a copper film and a molybdenum-titanium-nickel film, the thickness of the copper film is 5000A, the thickness of the molybdenum-titanium-nickel film is 300A, and the content of molybdenum in the molybdenum-titanium-nickel film is as follows: titanium: the mass percentage of nickel is 6: 2: etching at 2, 35 ℃ for 80 s; and monitoring the concentration of copper ions in the etching solution in the etching process, wherein 0.1 percent of auxiliary agent in the mass of the main agent is added into the etching solution when the concentration of the copper ions is increased by 100 ppm.
Example 2
An environment-friendly low-cost titanium-containing metal etching solution composition comprises a main agent and an auxiliary agent.
The main agent comprises the following components in percentage by mass: 7.25 percent of hydrogen peroxide, 2.86 percent of nitric acid, 7.28 percent of tetramethyl ammonium hydroxide, 0.25 percent of p-hydroxybenzene sulfonic acid, 0.02 percent of 5-aminotetrazole and the balance of deionized water.
The auxiliary agent comprises the following components in percentage by mass: 7.36 percent of nitric acid, 17.94 percent of tetramethyl ammonium hydroxide, 0.5 percent of p-hydroxybenzene sulfonic acid, 0.04 percent of 5-aminotetrazole and the balance of deionized water.
An application method of an environment-friendly low-cost titanium-containing metal etching solution composition comprises the following steps:
soaking titanium-containing metal in a main agent of the etching solution, wherein the titanium-containing metal comprises a copper film and a molybdenum-titanium-nickel film, the thickness of the copper film is 5000A, the thickness of the molybdenum-titanium-nickel film is 300A, and the content of molybdenum in the molybdenum-titanium-nickel film is as follows: titanium: the mass percentage of nickel is 6: 2: etching at 2, 35 ℃ for 87 s; and monitoring the concentration of copper ions in the etching solution in the etching process, wherein 0.1 percent of auxiliary agent in the mass of the main agent is added into the etching solution when the concentration of the copper ions is increased by 100 ppm.
Example 3
An environment-friendly low-cost titanium-containing metal etching solution composition comprises a main agent and an auxiliary agent.
The main agent comprises the following components in percentage by mass: 7.25% of hydrogen peroxide, 4.4% of nitric acid, 11.2% of dimethylethanolamine, 0.2% of p-hydroxybenzene sulfonic acid, 0.02% of 5-aminotetrazole and the balance of deionized water.
The auxiliary agent comprises the following components in percentage by mass: 9.45% of nitric acid, 29.8% of dimethylethanolamine, 0.3% of p-hydroxybenzene sulfonic acid, 0.04% of 5-aminotetrazole, and the balance of deionized water.
An application method of an environment-friendly low-cost titanium-containing metal etching solution composition comprises the following steps:
soaking titanium-containing metal in a main agent of the etching solution, wherein the titanium-containing metal comprises a copper film and a molybdenum-titanium-nickel film, the thickness of the copper film is 5000A, the thickness of the molybdenum-titanium-nickel film is 300A, and the content of molybdenum in the molybdenum-titanium-nickel film is as follows: titanium: the mass percentage of nickel is 6: 2: 2, etching at 35 ℃ for 85 s; and monitoring the concentration of copper ions in the etching solution in the etching process, wherein 0.1 percent of auxiliary agent in the mass of the main agent is added into the etching solution when the concentration of the copper ions is increased by 100 ppm.
Comparative example 1
An environment-friendly low-cost titanium-containing metal etching solution composition comprises a main agent and an auxiliary agent.
The main agent comprises the following components in percentage by mass: 7.25% of hydrogen peroxide, 0.08% of hydrofluoric acid, 4.4% of nitric acid, 11.2% of dimethylethanolamine, 0.2% of p-hydroxybenzene sulfonic acid, 0.02% of 5-aminotetrazole and the balance of deionized water.
The auxiliary agent comprises the following components in percentage by mass: 0.23% of hydrofluoric acid, 9.45% of nitric acid, 29.8% of dimethylethanolamine, 0.3% of p-hydroxybenzene sulfonic acid, 0.04% of 5-aminotetrazole, and the balance of deionized water.
An application method of an environment-friendly low-cost titanium-containing metal etching solution composition comprises the following steps:
soaking titanium-containing metal in a main agent of the etching solution, wherein the titanium-containing metal comprises a copper film and a molybdenum-titanium-nickel film, the thickness of the copper film is 5000A, the thickness of the molybdenum-titanium-nickel film is 300A, and the content of molybdenum in the molybdenum-titanium-nickel film is as follows: titanium: the mass percentage of nickel is 6: 2: 2, etching at 35 ℃ for 85 s; and monitoring the concentration of copper ions in the etching solution in the etching process, wherein 0.1 percent of auxiliary agent in the mass of the main agent is added into the etching solution when the concentration of the copper ions is increased by 100 ppm.
Comparative example 2
An environment-friendly low-cost titanium-containing metal etching solution composition comprises a main agent and an auxiliary agent.
The main agent comprises the following components in percentage by mass: 7.25% of hydrogen peroxide, 11.2% of dimethylethanolamine, 0.2% of p-hydroxybenzene sulfonic acid, 0.02% of 5-aminotetrazole, and the balance of deionized water.
The auxiliary agent comprises the following components in percentage by mass: 29.8 percent of dimethylethanolamine, 0.3 percent of p-hydroxybenzene sulfonic acid, 0.04 percent of 5-aminotetrazole and the balance of deionized water.
An application method of an environment-friendly low-cost titanium-containing metal etching solution composition comprises the following steps:
soaking titanium-containing metal in a main agent of the etching solution, wherein the titanium-containing metal comprises a copper film and a molybdenum-titanium-nickel film, the thickness of the copper film is 5000A, the thickness of the molybdenum-titanium-nickel film is 300A, and the content of molybdenum in the molybdenum-titanium-nickel film is as follows: titanium: the mass percentage of nickel is 6: 2: etching at 2, 35 ℃ for 130 s; and monitoring the concentration of copper ions in the etching solution in the etching process, wherein 0.1 percent of auxiliary agent in the mass of the main agent is added into the etching solution when the concentration of the copper ions is increased by 100 ppm.
Comparative example 3
An environment-friendly low-cost titanium-containing metal etching solution composition comprises a main agent and an auxiliary agent.
The main agent comprises the following components in percentage by mass: 7.25 percent of hydrogen peroxide, 4.4 percent of nitric acid, 0.2 percent of p-hydroxybenzene sulfonic acid, 0.02 percent of 5-aminotetrazole and the balance of deionized water.
The auxiliary agent comprises the following components in percentage by mass: 9.45 percent of nitric acid, 0.3 percent of p-hydroxybenzene sulfonic acid, 0.04 percent of 5-aminotetrazole and the balance of deionized water.
An application method of an environment-friendly low-cost titanium-containing metal etching solution composition comprises the following steps:
soaking titanium-containing metal in a main agent of the etching solution, wherein the titanium-containing metal comprises a copper film and a molybdenum-titanium-nickel film, the thickness of the copper film is 5000A, the thickness of the molybdenum-titanium-nickel film is 300A, and the content of molybdenum in the molybdenum-titanium-nickel film is as follows: titanium: the mass percentage of nickel is 6: 2: etching at 2, 35 ℃ for 120 s; and monitoring the concentration of copper ions in the etching solution in the etching process, wherein 0.1 percent of auxiliary agent in the mass of the main agent is added into the etching solution when the concentration of the copper ions is increased by 100 ppm.
Performance testing
The titanium-containing metals of the examples and comparative examples were tested for their etching effect and the results are reported in table 1.
TABLE 1
As can be seen from Table 1, the etching solutions of examples 1 to 3 of the present invention can achieve smaller CD-loss and slope angles within a wide range of the contents of the inorganic acid and the kinds and contents of the organic base. The etching effect of the etching solution of comparative example 1 shows that the etching solution of fluorine system can also obtain good etching morphology and copper carrying capacity, but the effect achieved by comparative example 1 is inferior to examples 1 to 3. The etching results of the etching solutions of comparative examples 2 to 3 show that certain amounts of inorganic acid and organic base are required in the etching solution system of the present invention, otherwise, etching of the metal film layer cannot be achieved.
Claims (10)
1. An environment-friendly low-cost titanium-containing metal etching solution composition is characterized by comprising a main agent and an auxiliary agent.
2. The etching solution composition as claimed in claim 1, wherein the main agent comprises the following components in percentage by mass: 1-20% of hydrogen peroxide, 1-10% of strong oxidizing acid, 0.01-10% of alkali compound, 0.01-5% of hydrogen peroxide stabilizer, 0.01-2% of amino azole compound and the balance of deionized water.
3. The etching solution composition as claimed in claim 1, wherein the adjuvant comprises, in mass percent: 1-20% of strong oxidizing acid, 0.01-20% of alkali compound, 0.01-2% of amino azole compound and the balance of deionized water.
4. The etching solution composition as claimed in any one of claims 2 to 3, wherein the strongly oxidizing acid in the main agent and the auxiliary agent is one or more of concentrated sulfuric acid, hypochlorous acid, nitric acid, selenic acid, chloric acid, chlorous acid, halogen acid, perhalogen acid, nitrous acid, and permanganic acid.
5. The etching solution composition according to any one of claims 2 to 3, wherein the alkali compounds in the main agent and the auxiliary agent are one or a combination of an alcohol amine compound and an ammonium compound.
6. The etching solution composition as claimed in claim 2, wherein the hydrogen peroxide stabilizer is one or a combination of urea compound and sulfonic acid compound.
7. The etching solution composition according to any one of claims 2 to 3, wherein the amino azole compounds in the main agent and the auxiliary agent are one or more of 3-amino triazole, 4-amino triazole, 3, 5-diamino triazole, 5-amino tetrazole, and 2-methyl-5-amino tetrazole.
8. The method for using the etching solution composition according to claim 1, comprising the steps of:
s1, preparing a main agent of the etching solution;
s2, preparing an etching solution auxiliary agent;
s3, contacting the titanium-containing metal with the etching solution main agent to etch the metal;
s4, the concentration of copper ions in the main agent of the etching solution is monitored, and the auxiliary agent is added into the main agent.
9. The method of claim 8, wherein the titanium-containing metal comprises a copper film and a molybdenum titanium nickel film.
10. The method of using the etching solution composition according to claim 9, wherein the ratio of molybdenum in the molybdenum titanium nickel film: titanium: the mass percentage of the nickel is (3-10): (0-5): (0-5).
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| CN116180084A (en) * | 2023-01-06 | 2023-05-30 | 江苏和达电子科技有限公司 | Copper-molybdenum alloy etching liquid composition and preparation method thereof |
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