CN112064032B - Supplementary liquid capable of prolonging service life of hydrogen peroxide etching liquid - Google Patents
Supplementary liquid capable of prolonging service life of hydrogen peroxide etching liquid Download PDFInfo
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- 238000005530 etching Methods 0.000 title claims abstract description 142
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000007788 liquid Substances 0.000 title claims description 58
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002738 chelating agent Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000000654 additive Substances 0.000 claims abstract description 13
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 13
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 7
- 239000012498 ultrapure water Substances 0.000 claims abstract description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 20
- 229910001431 copper ion Inorganic materials 0.000 claims description 20
- -1 methylene phosphonic acid Chemical compound 0.000 claims description 9
- 229940080258 tetrasodium iminodisuccinate Drugs 0.000 claims description 9
- GYBINGQBXROMRS-UHFFFAOYSA-J tetrasodium;2-(1,2-dicarboxylatoethylamino)butanedioate Chemical group [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC(C([O-])=O)NC(C([O-])=O)CC([O-])=O GYBINGQBXROMRS-UHFFFAOYSA-J 0.000 claims description 9
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 7
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 6
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 6
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical group OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 4
- 230000001502 supplementing effect Effects 0.000 claims description 4
- 229940120146 EDTMP Drugs 0.000 claims description 3
- KIDJHPQACZGFTI-UHFFFAOYSA-N [6-[bis(phosphonomethyl)amino]hexyl-(phosphonomethyl)amino]methylphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCCCCCN(CP(O)(O)=O)CP(O)(O)=O KIDJHPQACZGFTI-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- MRNZSTMRDWRNNR-UHFFFAOYSA-N bis(hexamethylene)triamine Chemical compound NCCCCCCNCCCCCCN MRNZSTMRDWRNNR-UHFFFAOYSA-N 0.000 claims 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 238000003486 chemical etching Methods 0.000 abstract description 2
- 239000007769 metal material Substances 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 10
- 239000004973 liquid crystal related substance Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000010949 copper Substances 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 8
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 description 8
- 229910052750 molybdenum Inorganic materials 0.000 description 8
- 239000011733 molybdenum Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000002035 prolonged effect Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 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
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000001039 wet etching Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical group [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GLULCKCBVYGUDD-UHFFFAOYSA-N 2-phosphonobutane-1,1,1-tricarboxylic acid Chemical class CCC(P(O)(O)=O)C(C(O)=O)(C(O)=O)C(O)=O GLULCKCBVYGUDD-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- YWMWZKYVGNWJPU-UHFFFAOYSA-N [bis[6-[bis(phosphonomethyl)amino]hexyl]amino]methylphosphonic acid Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCCCCCN(CP(O)(=O)O)CCCCCCN(CP(O)(O)=O)CP(O)(O)=O YWMWZKYVGNWJPU-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- C23F1/46—Regeneration of etching compositions
-
- 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
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
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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)
- Weting (AREA)
Abstract
本发明属于金属材料的化学法蚀刻用材料技术领域，具体涉及一种能提高过氧化氢系蚀刻液使用寿命的补充液。该补充液中各组分相对于整体组合物的总重量，包含4~20%的过硫酸铵、8~30%的螯合剂、4~20%的调节剂、2~10%的多功能添加剂以及使整体组合物达到100%的超纯水。本发明的补充液加入到持续蚀刻后接近失效的过氧化氢系蚀刻液后，能再次明显提高蚀刻液的使用寿命，可以达到节约蚀刻液使用量的目的，明显节约蚀刻成本，具有非常大的工业推广价值。The invention belongs to the technical field of materials for chemical etching of metal materials, and in particular relates to a supplementary solution that can improve the service life of a hydrogen peroxide-based etching solution. With respect to the total weight of the whole composition, each component in the replenishing solution contains 4-20% of ammonium persulfate, 8-30% of chelating agent, 4-20% of conditioner, and 2-10% of multifunctional additive And ultrapure water to make the overall composition 100%. After the supplementary solution of the present invention is added to the hydrogen peroxide-based etching solution that is close to failure after continuous etching, the service life of the etching solution can be remarkably improved again, the purpose of saving the usage amount of the etching solution can be achieved, the etching cost can be obviously saved, and the etching cost can be greatly reduced. Industrial promotion value.
Description
Technical Field
The invention belongs to the technical field of materials for chemical etching of metal materials, and particularly relates to a replenishing liquid capable of prolonging the service life of a hydrogen peroxide etching liquid.
Background
The liquid crystal display comprises a liquid crystal display panel and a backlight module, wherein the liquid crystal display panel comprises a CF substrate, a TFT array substrate and a liquid crystal material between the CF substrate and the TFT substrate. The direction of the liquid crystal molecules is controlled by supplying power to the TFT substrate or not, and the light of the backlight module is projected to the CF substrate to generate a picture.
The liquid crystal panel is the heart of the liquid crystal display, occupies more than 80% of the cost of the whole product, and the quality of the liquid crystal panel can directly influence the functional parameters of the display, such as color, brightness, contrast, visual angle and the like. To produce a liquid crystal panel, three complicated processes of "front-stage Array process, middle-stage Cell process, and rear-stage module assembly" are required. The TFT substrate is composed of a scanning signal line or a gate line transmitting a scanning signal, an image signal line or a data line transmitting an image signal, a thin film transistor connected to the gate line and the data line, a pixel electrode connected to the thin film transistor, and the like. The process of manufacturing the micro-circuit wiring of TFT-LCD is completed by a series of photoetching engineering, such as uniformly coating photoresist on a metal layer, then carrying out light irradiation imaging through a film with a pattern, etching the metal layer which is not covered by the photoresist, stripping and removing the unnecessary photoresist after the metal layer is formed into a desired shape, and the like.
Etching is a technique in which material is removed using a chemical reaction or physical impact. The etching techniques are classified into wet etching and dry etching, wherein the wet etching is performed by a chemical reaction between a specific etching solution and a thin film material to be etched, and the wet etching is still widely used in TFT-LCD due to advantages such as low equipment investment cost and good etching selectivity for a substrate.
In recent years, while the demand of liquid crystal displays is increasing, higher requirements are put on the picture precision of the displays, and the etching effect directly causes the quality of the manufacturing process of the TFT circuit board and affects the quality and precision of high-density wires. Aluminum is used for the metal wiring of the conventional TFT, and as the LCD becomes larger and higher in resolution, the lead wire connected to the TFT becomes longer, and the resistance of the lead wire also increases, causing a problem of signal delay, so that copper having a lower resistivity is used as a wiring material instead of aluminum. However, the bonding force between copper and the glass substrate is not good, and molybdenum needs to be introduced as a bonding layer on the glass substrate. The copper-molybdenum layer becomes the main structure of the TFT wiring.
The etching solution for etching the copper-molybdenum layer of the TFT mainly adopts a hydrogen peroxide system, such as: CN100494499C discloses a multi-layer copper-molybdenum etching solution, which comprises hydrogen peroxide, organic acid, phosphate, two additives containing nitrogen, and fluorine-containing compound. CN104480469A discloses a TFT copper molybdenum laminate etching solution composition, which comprises hydrogen peroxide, sulfuric acid, a stabilizer, a metal complexing agent, a surfactant, and an azole additive. CN102762770A discloses an etching solution for a multilayer film comprising a copper layer and a molybdenum layer, which comprises hydrogen peroxide, sulfuric acid or nitric acid, an organic acid, an amine compound, an azole compound, and a hydrogen peroxide stabilizer.
The above-described hydrogen peroxide-based etching solutions and the hydrogen peroxide-based etching solutions currently used in TFT manufacturing lines have a maximum service life in which the maximum allowable copper ion concentration in the etching solution does not exceed 7000ppm after the copper molybdenum layer is continuously etched by the etching solution. After the copper ion concentration of the etching solution exceeds 7000ppm, if the etching solution is continuously used, the etching parameters such as qualified etching angle and the like cannot be maintained, so the etching solution needs to be replaced, and at this time, only a small part of hydrogen peroxide in the etching solution is consumed, and a large amount of hydrogen peroxide and other components are not fully utilized. If the supplementing liquid can be provided and added into the etching liquid which is rapidly failed, the service life of the etching liquid can be continuously prolonged, the purpose of saving the using amount of the etching liquid can be achieved, and the etching cost can be saved. To achieve the above object, the present invention provides a replenishment solution capable of prolonging the service life of a hydrogen peroxide etching solution.
Disclosure of Invention
The invention aims to provide a supplementary liquid capable of prolonging the service life of a hydrogen peroxide etching liquid, wherein the supplementary liquid is added into the hydrogen peroxide etching liquid which is close to failure (when the concentration of copper ions is not lower than 6000 ppm) after continuous etching, so that the service life of the etching liquid can be obviously prolonged again, the purpose of saving the use amount of the etching liquid can be achieved, and the etching cost can be obviously saved.
In order to realize the purpose, the invention adopts the following technical scheme:
a can improve the supplementary solution composite of the service life of hydrogen peroxide etching solution, the said composite is made up of ammonium persulfate, chelating agent, regulator, multi-functional additive and ultrapure water;
the weight percentage of each component in the composition relative to the whole composition is respectively 4-20% of ammonium persulfate, 8-30% of chelating agent, 4-20% of regulator, 2-10% of multifunctional additive and ultrapure water which enables the whole composition to reach 100%;
the chelating agent is an organic phosphonic acid containing N atoms, and is selected from at least one of amino trimethylene phosphonic acid, ethylene diamine tetra methylene phosphonic acid, hexamethylene diamine tetra methylene phosphonic acid, diethylenetriamine pentamethylene phosphonic acid, dihexyltriamine pentamethylene phosphonic acid and polyamino polyether methylene phosphonic acid, preferably diethylenetriamine pentamethylene phosphonic acid and/or dihexyltriamine pentamethylene phosphonic acid;
the regulator is phosphonobutane tricarboxylic acid;
the multifunctional additive is tetrasodium iminodisuccinate;
the addition amount of the replenishment solution is 2 to 25 percent of the total amount of the original hydrogen peroxide etching solution, and is further 5 to 20 percent.
The above components are specifically described.
Ammonium persulfate: ammonium persulfate is an auxiliary oxidant in the supplementary liquid and has the function of assisting hydrogen peroxide in the original etching liquid to oxidize the TFT copper-molybdenum layer wiring. The reaction between ammonium persulfate, hydrogen peroxide and the copper layer can be represented by the following reaction formula:
S2O8 2-+H2O2+2H++2Cu→2Cu2++2SO4 2-+2H2O
the amount of ammonium persulfate accounts for 4-20% of the total weight of the supplementary liquid. If the amount of the ammonium persulfate is lower than 4 percent, the supplementary liquid does not obviously prolong the service life of the hydrogen peroxide etching liquid; when the amount of ammonium persulfate in the replenishment solution is more than 20%, the etching rate of the original hydrogen peroxide etching solution is changed, and the use process of the original etching solution cannot be maintained, which also causes the lack of remarkable improvement of the life of the hydrogen peroxide etching solution by the replenishment solution and the reduction of the utilization rate of the etching solution.
Chelating agent: through a great deal of research, the applicant finds that the organic phosphonic acid containing N atoms is most suitable to be selected as the chelating agent in the replenishing solution, the chelating agent has very strong chelating capacity on copper ions and molybdenum ions, and has good chemical stability, no toxicity and no pollution, and moreover, the organic phosphonic acid containing N atoms has a good stabilizing effect on hydrogen peroxide in the original hydrogen peroxide etching solution. The organic phosphonic acid containing an N atom is at least one selected from the group consisting of aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, dihexyltriaminepentamethylenephosphonic acid and polyaminopolyetherpolyetherpentamethylenephosphonic acid, and more preferably diethylenetriaminepentamethylenephosphonic acid and/or dihexyltriaminepentamethylenephosphonic acid.
After the original hydrogen peroxide etching solution is continuously etched, the most consumed component is the chelating agent or the complexing agent, so that the main component in the replenishing solution is the chelating agent, and the chelating agent accounts for 8-30% of the weight of the replenishing solution. If the amount of the chelating agent is less than 8%, the effect of the supplementary liquid for prolonging the service life of the etching liquid is not obvious, and if the amount of the chelating agent in the supplementary liquid is more than 30%, the pH value of the original etching liquid is reduced, the etching process of the original hydrogen peroxide etching liquid is changed, and the result is that the service life of the hydrogen peroxide etching liquid prolonged by the supplementary liquid is not obvious, and the utilization rate of the etching liquid becomes low as the regulator: the regulator is phosphonobutane tricarboxylic acid which plays two roles, wherein the phosphonobutane tricarboxylic acid can chelate copper and molybdenum ions, and the phosphonobutane tricarboxylic acid is used as a pH value regulator added into the original etching solution in the make-up solution, so that the pH value of the etching solution is regulated to be always stabilized in a smaller range in the subsequent life-prolonging continuous etching process, and the stability of the etching process is facilitated. The amount of regulator is 4~20%, if the amount of regulator is less than 4%, the effect that the replenishment improves etching solution life is not obvious, if the amount of regulator is higher than 20% in the replenishment, can make the pH value of former etching solution reduce, can't maintain former etching technology, and it is not obvious to lead to the replenishment to improve the life-span of hydrogen peroxide etching solution, and etching solution utilization ratio step-down multifunctional additive: the multifunctional additive is tetrasodium iminodisuccinate, and has the following functions: firstly, the tetrasodium iminodisuccinate is used as a stabilizer of the replenisher, the stability of the replenisher in the storage and transportation process is stabilized, secondly, the tetrasodium iminodisuccinate has good chelating capacity for copper and molybdenum, thirdly, the tetrasodium iminodisuccinate also has strong stability for hydrogen peroxide in the etching solution, and fourthly, the tetrasodium iminodisuccinate also has good buffering effect on the pH value of the etching solution. The amount of tetrasodium iminodisuccinate in the replenishment solution is 2-10%, the amount is too small to play the role, if the adjusting agent amount in the replenishment solution is higher than 10%, the pH value of the original etching solution is also higher, the etching process of the original hydrogen peroxide etching solution is changed, the service life of the hydrogen peroxide etching solution improved by the replenishment solution is not obvious, and the utilization rate of the etching solution is reduced.
In addition, the proportion of the following components in the replenishment liquid needs to meet the following conditions to ensure that the replenishment liquid is added into the original hydrogen peroxide etching liquid without causing the pH value of the original etching liquid to deviate: the ratio of the total weight of the chelating agent and the regulator to the weight of the multifunctional additive is 10: 1-2: 1, more preferably 6: 1-4: 1.
compared with the prior art, the invention has the advantages and beneficial effects that:
the supplementing liquid of the invention is added into the hydrogen peroxide etching liquid which is close to lose efficacy after continuous etching, the service life of the etching liquid can be obviously prolonged again, the maximum concentration of allowed copper ions in the etching liquid can be increased from 7000ppm to over 12000ppm from the beginning, the purpose of saving the use amount of the etching liquid can be achieved, and the etching cost is obviously saved.
Drawings
FIG. 1 is a sectional view of a Scanning Electron Microscope (SEM) showing a TFT substrate etched by an etching solution when the concentration of copper ions in the original hydrogen peroxide etching solution is 6000ppm and the concentration of copper ions in the etching solution is increased to 12000ppm by adding 15% of the replenishment solution of example 1; the etching angle was 53.6 degrees and CDloss was 0.89 um.
FIG. 2 is a top view of a Scanning Electron Microscope (SEM) of a TFT substrate in which etching of an original hydrogen peroxide etching solution was measured when the copper ion concentration of the etching solution was increased to 12000ppm after adding 15% of the replenishment solution of example 1 to 6000ppm of the original hydrogen peroxide etching solution; it can be seen that the etched substrate has no molybdenum residue and no undercut.
Detailed Description
The applicant will now describe in detail the technical solutions and effects of the present invention with reference to specific embodiments. It should be understood that the following examples are only examples, and the present invention is not limited to these examples.
The starting materials used in the following examples and comparative examples are commercially available in purities of analytical grade and above, e.g.ultrapure water, having an electrical conductivity of < 5. mu.S/cm.
Preparing supplementary solutions of examples 1 to 6, which can prolong the service life of the hydrogen peroxide etching solution, and supplementary solutions of comparative examples 1 to 8 according to the raw material types and the proportions shown in the following table 1;
the preparation method comprises the following steps: firstly adding ammonium persulfate into ultrapure water, stirring until the ammonium persulfate is completely dissolved, and then sequentially adding a chelating agent, a regulator and a multifunctional additive while stirring.
Table 1: replenisher composition and content for each example and comparative example
DTPMPA: diethylenetriamine penta (methylene phosphonic acid)
BHMTPMPA: dihexylenetriaminepentamethylenephosphonic acid [ Bis (hexamethyenetriaminepentamethylenephosphonic acid ]
PBTCA: phosphonobutane tricarboxylic acids
IDS: tetrasodium iminodisuccinate
Evaluation of Effect of the invention
Experimental TFT substrate: the TFT substrate is a patterned copper-molybdenum laminated film glass substrate provided by Shenzhen Huaxing photoelectric semiconductor display technology Limited, and the thickness of the copper layer is about
The thickness of the molybdenum layer is about
(molybdenum layer on glass substrate, copper layer on top of molybdenum layer).
Hydrogen peroxide-based etching solution: "etchant #1 (Cu)" hydrogen peroxide etching solution of fujiku, easy ai, korea, used by shenzhen huaxing photoelectric semiconductor display technology ltd, has a hydrogen peroxide concentration of 18 wt%, a maximum service life of maintaining etching characteristics of 7000ppm at the maximum allowed copper ion concentration in the etching solution, an abrupt boiling point of the etching solution of 11000ppm, and an etching angle of 35 ° to 60 ° and a CDloss of 1.1um or less when the copper ion concentration in the etching solution is less than 7000 ppm.
Supplementary liquid evaluation experiment: adding 100mL of the hydrogen peroxide etching solution into a beaker, adding 100mg of copper powder and 10mg of molybdenum powder, stirring at 35 ℃ until the copper powder and the molybdenum powder are completely dissolved, continuing for 6 times until the concentration of copper ions in the etching solution reaches 6000ppm, keeping the temperature of the etching solution at about 35 ℃, soaking a 10 x 10mm copper-molybdenum TFT substrate in the etching solution while magnetically stirring the etching solution, and etching for 80 seconds. After the etching, the substrate was washed with water and dried, and the cross-sectional shape, etching angle, and CDloss of the substrate were confirmed by a scanning electron microscope (model number: sigma 500). Then adding supplementary liquid with different proportions, and continuously testing the maximum allowable copper ion concentration of the etching liquid for maintaining the original etching characteristics (the etching angle is 35-60 degrees, the CDloss is less than 1.1 um) and the bumping point of the etching liquid.
And (3) evaluating the service life improvement effect of the etching solution after adding the supplementary solution: percentage of lifetime improvement (maximum allowable copper ion concentration for maintaining etching characteristics-7000)/7000
The maximum allowable copper ion concentration unit for maintaining etching characteristics is ppm, and the concentration value is taken in the formula
The etching solution utilization rate is the maximum allowable copper ion concentration/azeotrope point for maintaining the etching characteristics.
Evaluation results
The specific data of the performance evaluation of the replenisher of each example are shown in the following table 2:
table 2: results of Performance testing
Note: the proportion of the replenishment solution is the mass percentage of the replenishment solution added to the original hydrogen peroxide etching solution.
As can be seen from the above table 2, the service life of the original hydrogen peroxide etching solution can be obviously prolonged by only adding 5-20% of the replenishment solutions of the embodiments 1-6 of the present invention, the maximum concentration of the allowed copper ions in the etching solution can be increased from 7000ppm at the beginning to 12000-17000 ppm, the bumping point can be increased from 11000ppm at the beginning to 15000-23000 ppm, the service life of the etching solution is obviously prolonged, the percentage of the service life of the etching solution is increased to 70% -143%, and the utilization rate of the etching solution is further increased. The purpose of saving the use amount of the etching solution is achieved, the etching cost is obviously saved, and the method has great industrial value.
Compared with the supplementary liquid of comparative examples 1 to 8, which has different content percentages of the components defined by the invention, the supplementary liquid has no obvious effect of improving the service life of the original hydrogen peroxide etching liquid, the service life of the etching liquid is improved by only 14 to 57 percent, and the utilization rate of the etching liquid is low.
FIG. 1 is a sectional view of a Scanning Electron Microscope (SEM) showing a TFT substrate etched by an etching solution when the concentration of copper ions in the original hydrogen peroxide etching solution is 6000ppm and the concentration of copper ions in the etching solution is increased to 12000ppm by adding 15% of the replenishment solution of example 1; the etching angle was 53.6 degrees and CDloss was 0.89 um.
FIG. 2 is a top view of a Scanning Electron Microscope (SEM) of a TFT substrate in which etching of an original hydrogen peroxide etching solution was measured when the copper ion concentration of the etching solution was increased to 12000ppm after adding 15% of the replenishment solution of example 1 to 6000ppm of the original hydrogen peroxide etching solution; it can be seen that the etched substrate has no molybdenum residue and no undercut.
Claims (5)
1. The application of a replenishing liquid composition in prolonging the service life of a hydrogen peroxide etching liquid comprises the following steps: adding the replenishment liquid composition into the nearly ineffective hydrogen peroxide etching liquid, wherein the addition amount of the replenishment liquid composition is 2-25% of the total weight of the nearly ineffective hydrogen peroxide etching liquid;
the supplementary liquid composition consists of ammonium persulfate, a chelating agent, a regulator, a multifunctional additive and ultrapure water;
the weight percentage of each component in the composition relative to the whole composition is respectively 4-20% of ammonium persulfate, 8-30% of chelating agent, 4-20% of regulator, 2-10% of multifunctional additive and ultrapure water which enables the whole composition to reach 100%;
the weight ratio of the total weight of the chelating agent and the regulator to the weight of the multifunctional additive is 10: 1-2: 1;
the chelating agent is organic phosphonic acid containing N atoms;
the regulator is phosphonobutane tricarboxylic acid;
the multifunctional additive is tetrasodium iminodisuccinate.
2. Use according to claim 1, characterized in that: the chelating agent is selected from at least one of amino trimethylene phosphonic acid, ethylene diamine tetra methylene phosphonic acid, hexamethylene diamine tetra methylene phosphonic acid, diethylene triamine pentamethylene phosphonic acid, dihexylene triamine pentamethylene phosphonic acid and polyamino polyether methylene phosphonic acid.
3. Use according to claim 2, characterized in that: the chelating agent is diethylenetriamine pentamethylene phosphonic acid and/or dihexene triamine pentamethylene phosphonic acid.
4. The use according to any one of claims 1 to 3: the supplementing liquid composition is added into the near-failure hydrogen peroxide etching liquid, and the addition amount of the supplementing liquid composition is 5% -20% of the total weight of the near-failure hydrogen peroxide etching liquid.
5. Use according to claim 4, characterized in that: the near-failure hydrogen peroxide etching solution refers to an etching solution in which the concentration of copper ions is not less than 6000 ppm.
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| JP5604056B2 (en) * | 2009-05-15 | 2014-10-08 | 関東化学株式会社 | Etching solution for copper-containing laminated film |
| KR102002131B1 (en) * | 2012-08-03 | 2019-07-22 | 삼성디스플레이 주식회사 | Etchant composition and manufacturing method for thin film transistor using the same |
| KR20140118318A (en) * | 2013-03-28 | 2014-10-08 | 동우 화인켐 주식회사 | Etchant composition for copper-containing metal layer and preparing method of an array substrate for liquid crystal display using same |
| JP6354084B2 (en) * | 2013-04-16 | 2018-07-11 | メック株式会社 | Etching solution, replenisher, and wiring formation method |
| KR20150043569A (en) * | 2013-10-07 | 2015-04-23 | 주식회사 이엔에프테크놀로지 | Etching composition for copper and molibdenum containing film |
| CN104480469B (en) * | 2014-12-12 | 2018-02-23 | 江阴润玛电子材料股份有限公司 | A kind of TFT copper-molybdenums stacked film etchant and engraving method |
| CN108291314B (en) * | 2015-11-19 | 2020-09-11 | Oci有限公司 | Copper etching composition and hydrogen peroxide-based metal etching composition |
| CN107447217A (en) * | 2016-06-01 | 2017-12-08 | 东友精细化工有限公司 | Metal film etchant |
| CN106086891B (en) * | 2016-08-11 | 2018-10-26 | 江阴江化微电子材料股份有限公司 | A kind of advanced lines tablet copper titanium film acidic etching liquid |
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| CN110923713B (en) * | 2019-12-31 | 2020-12-08 | 成都中电熊猫显示科技有限公司 | Etching liquid for copper-molybdenum and alloy films and preparation method thereof |
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Denomination of invention: A supplementary solution that can improve the service life of hydrogen peroxide etching solution Granted publication date: 20220401 Pledgee: Agricultural Bank of China Limited Ezhou Gedian Development Zone Branch Pledgor: WUHAN DESYTEK NEW MATERIAL CO.,LTD. Registration number: Y2024980047484 |
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