CN101649202A - Etching bath composition for transparent conductive film - Google Patents
Etching bath composition for transparent conductive film Download PDFInfo
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- CN101649202A CN101649202A CN200910164091A CN200910164091A CN101649202A CN 101649202 A CN101649202 A CN 101649202A CN 200910164091 A CN200910164091 A CN 200910164091A CN 200910164091 A CN200910164091 A CN 200910164091A CN 101649202 A CN101649202 A CN 101649202A
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- etching bath
- bath composition
- transparent conductive
- conductive film
- oxalic acid
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/02—Etching, surface-brightening or pickling compositions containing an alkali metal hydroxide
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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
- C23F1/32—Alkaline compositions
Abstract
The invention relates to an etching bath composition for transparent conductive film, which has few indium oxalate precipitation in the corrosion processing for transparent conductive film of ITO filmused in liquid crystal display device and the like. The indium oxalate precipitation can be effectively prevented even if the concentration of indium is high in the etching bath in the transparent conductive film corrosion process, through the etching bath composition for transparent conductive film containing oxalic acid and alkaline compounds (except triethanolamine).
Description
Technical field
The present invention relates to the etching bath composition that a kind of nesa coating that is used for liquid-crystal display (LCD) and electroluminescent display (ELD) display element etc. is used.
Background technology
Nesa coating as being used for liquid-crystal display (LCD) and electroluminescent display (ELD) display element etc. has tin indium oxide (ITO), indium zinc oxide (IZO), Indium sesquioxide, stannic oxide, zinc oxide etc., wherein ITO film, IZO film are being widely used.As the layout method of nesa coating generally is after making nesa coating with film forming such as sputtering methods on the substrate of glass etc., forms the resist figure by photolithography, and the corrosion nesa coating forms the method for electrode pattern.
The corrosive fluid of nesa coating was to use the corrosive fluid that contains dissolved oxygen indium composition of (1) ferric chloride in aqueous solution, (2) acid iodide aqueous solution, (3) phosphate aqueous solution, (4) hydrochloric acid-aqueous nitric acid (chloroazotic acid) and (5) oxalic acid aqueous solution etc. in the past.
As the ITO film, be to use fundamental characteristics such as resistivity and the good many crystallizations ITO film of transmissivity as nesa coating in the past, but in recent years along with maximization, high precision int, the high performance of display element, require to improve working accuracy, the low temperatureization of technological temperature, high surface etc., as the nesa coating that satisfies these requirements, noncrystalline ITO film, IZO film have been brought into use.
The corrosive fluid of the nesa coating of noncrystalline ITO film, IZO film etc., the little oxalic acid aqueous solution of injury that is using cheapness, good stability widely, having practical corrosion speed and AI is connected up., with the corrosion of oxalic acid aqueous solution, there is the oxalic acid indium crystalline problem of separating out easily to nesa coating.
Usually, because corrosive fluid recycles in corrosion device repeatedly, so when using the corrosive fluid corrosion nesa coating that contains oxalic acid, the concentration of the indium in the corrosive fluid rises and separates out the oxalic acid indium easily.In case after separating out, just carry out crystalline growth, form thick crystallisate and paying in device as nuclear.Its result, the problem of the obstruction of the bad and strainer of the action of generation device, injury substrate etc.
Because the oxalic acid indium is extremely to be difficult to dissolved salt, so be difficult to be dissolved in the corrosive fluid, also is difficult in addition be dissolved in the water again.For this reason, in removal is dissolved in device separate out crystallisate the time, operation or remove with soup dissolving method such as remove by hand after the corrosive fluid in the device can only being discharged will be related to like this that productivity descends, the raising of cost.Can remove crystallisate or can only be to change strainer with certain methods plugged screen in addition, this still will be related to, and productivity descends, the problem of the raising of cost.Therefore, contain the corrosion of the corrosive fluid of oxalic acid to nesa coating for use, the problem that forms maximum is that the crystallization of oxalic acid indium is separated out easily.
As solution to the problems described above, can enumerate using above-mentioned oxalic acid Indium sesquioxide in addition to carry out the dissolved composition, but, ferric chloride in aqueous solution side etch amount is big, contains the shortcoming to the iron of the least good influence of semi-conductor.The acid iodide aqueous solution has the iodine that dissociates easily in addition, the shortcoming that poor stability and valency are high.Then wiring has injury to phosphate aqueous solution to AI, is easy to generate the shortcoming of etching residue.Have again, hydrochloric acid-nitric acid mixed solution (chloroazotic acid) exist through the time be changed significantly technology controlling and process difficulty, the shortcoming that can not transmit.
And then, be in the corrosion operation to the nesa coating of noncrystalline ITO film and IZO film etc. of corrosive fluid of principal constituent in order to oxalic acid, there is the problem that is easy to generate etching residue.
As the method that addresses these problems, the present inventor proposed to contain from oxalic acid and poly-sulfoacid compound and polyoxyethylene-polyoxypropylene block copolymers constitute select the group more than a kind or 2 kinds compound, the ITO film is with etching bath composition (patent documentation 1).The ITO film that has also proposed to contain oxalic acid and aminocarboxylic acid or trolamine in addition with etching bath composition (patent documentation 2), contain oxalic acid and carboxylic acid amorphousness ITO film with etching reagent (patent documentation 3), contain the ITO film of perfluoralkyl phosphate salt, oxalic acid and water and IZO film with etching bath composition (patent documentation 4), contain ITO film that oxalic acid and fluorine are tensio-active agent and IZO film usefulness etching bath composition (patent documentation 5) etc.These corrosive fluids that contain oxalic acid have practical corrosion speed can see the effect that prevents residue, but does not recognize the problem that the crystallization of oxalic acid indium is separated out fully, still is in unsolved always state.
And then, as the corrosive fluid that does not contain oxalic acid, the amorphousness ITO corrosive component (patent documentation 6) etc. that is made of the aqueous solution that contains thionamic acid and polyethylene oxide alkyl ethers vitriol, polyoxyethylene alkyl phenyl ether sulfate or polyoxyalkylene alkyl ether phosphate has been proposed.Though but these corrosive fluids that do not contain oxalic acid do not separate out the oxalic acid crystallization effect that prevents etching residue arranged, more but exist corrosion speed slow with the aqueous solution that contains oxalic acid, the problem of degradation under the productivity.
As previously discussed, in the known corrosive fluids as principal constituent such as mineral acid of the dissolved oxygen indium beyond the oxalic acid, have big problem in the point of corrosive characteristic and corrosion stability etc., using, still do not exist with oxalic acid be the corrosive fluid that the corrosive fluid of principal constituent is equal to good characteristic.In addition, also do not exist, in oxalic acid is the corrosive fluid of principal constituent, keep its excellent characteristic, and then can suppress the corrosive fluid that the crystallization of oxalic acid indium is separated out.
Therefore, now as to being that the corrosion process that the corrosive fluid of principal constituent is used for containing the nesa coating of indium prevents the countermeasure that crystallization is separated out with oxalic acid, be adopt after will using corrosive fluid with nano-film filtration regenerated method, to device keep in repair and adopt apparatus structure that crystallization is difficult to separate out etc. termly, be the mode (patent documentation 7 and non-patent literature 1) of on installing, carrying out countermeasure at present.
[patent documentation 1] spy opens the 2002-164332 communique
[patent documentation 2] spy opens the 2002-033304 communique
[patent documentation 3] spy opens the 2003-306676 communique
[patent documentation 4] spy opens the 2005-116542 communique
[patent documentation 5] spy opens the 2005-244083 communique
[patent documentation 6] spy opens the 2002-367974 communique
[patent documentation 7] spy opens the 2006-013158 communique
[non-patent literature 1] on December 17th, 2007 the 1st edition, distribution " the big complete or collected works of the up-to-date nesa coating " P556-P557 of the apparatus of information of Co., Ltd.
This shows that above-mentioned existing etching bath composition obviously still has inconvenience and defective, and demands urgently further being improved in the use.In order to solve the problem of above-mentioned existence, relevant manufacturer there's no one who doesn't or isn't seeks solution painstakingly, but do not see always that for a long time suitable design finished by development, and the general corrosion fluid composition can not address the above problem, this obviously is the problem that the anxious desire of relevant dealer solves.Therefore how to found a kind of new etching bath composition for transparent conductive film, real one of the current important research and development problem that belongs to, also becoming the current industry utmost point needs improved target.
Summary of the invention
Main purpose of the present invention is, overcome the defective that existing etching bath composition exists, and provide a kind of new etching bath composition for transparent conductive film, technical problem to be solved is to make its corrosion process at the nesa coating of amorphousness ITO that is used for liquid-crystal display and IZO etc., can prevent separating out of oxalic acid indium, can boost productivity and reduce cost.
The present inventor has carried out meticulous research in order to address the above problem, found to contain oxalic acid and, the etching bath composition for transparent conductive film of basic cpd has with oxalic acid is the good characteristic of the corrosive fluid of principal constituent, and can suppress oxalic acid indium crystalline and separate out, and then the result of research, finish up to of the present invention.
The object of the invention to solve the technical problems realizes by the following technical solutions.According to the etching bath composition for transparent conductive film that the present invention proposes, wherein relate to and contain oxalic acid and basic cpd (but, wherein except the trolamine).
The object of the invention to solve the technical problems also can be applied to the following technical measures to achieve further.
Aforesaid etching bath composition for transparent conductive film, wherein said basic cpd be from the oxyhydroxide of quaternary ammonium hydroxide class, basic metal class, alkanol amine (but, wherein except the trolamine) and hydroxyl amine constitute select among the group more than a kind or 2 kinds.
Aforesaid etching bath composition for transparent conductive film, wherein said pH value is 1.1-5.0.
Aforesaid etching bath composition for transparent conductive film, wherein and then contain from poly-sulfoacid compound, polyoxyethylene-polyoxypropylene block copolymers and sulfonate type anion surfactant and form the compound of selecting the group more than a kind or 2 kinds.
Aforesaid etching bath composition for transparent conductive film, wherein and then contain water-soluble polymers more than a kind or 2 kinds.
Aforesaid etching bath composition for transparent conductive film, it is the corrosion that is used to contain the Indium sesquioxide nesa coating.
Aforesaid etching bath composition for transparent conductive film, it has been to use above-mentioned etching bath composition for transparent conductive film.
The present invention compared with prior art has tangible advantage and beneficial effect.As known from the above, the reason that the crystallization of oxalic acid indium is separated out easily can be thought the low cause of solubleness of the indium in the oxalic acid aqueous solution.The meltage of finding indium in the oxalic acid aqueous solution in present inventors' the investigation is 300ppm, and the crystallization of oxalic acid indium is just separated out easily when surpassing above-mentioned concentration.Just, think that the meltage that makes the indium in the oxalic acid aqueous solution increases, and just can suppress the crystalline of oxalic acid indium and separate out.
Etching bath composition for transparent conductive film of the present invention, by containing basic cpd, it may not be very clear and definite can suppressing the reason that the crystallization of oxalic acid indium separates out, but can think in solution, raising along with pH, OH base and amine, quaternary ammonium generate complex compound than oxalic acid is easy with indium, have so just suppressed the generation of oxalic acid indium, have consequently increased the meltage of indium.
The etching bath composition for transparent conductive film of the application of the invention is separated out owing to suppressing oxalic acid indium crystalline in the corrosion process of nesa coating, can prolong the life of corrosive fluid.Can also alleviate in addition and remove the crystalline operation, can boost productivity reduces cost.
Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technique means of the present invention, and can be implemented according to the content of specification sheets, and for above-mentioned and other purposes, feature and advantage of the present invention can be become apparent, below especially exemplified by preferred embodiment, and conjunction with figs., be described in detail as follows.
Description of drawings
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Embodiment
Reach technique means and the effect that predetermined goal of the invention is taked for further setting forth the present invention, below in conjunction with accompanying drawing and preferred embodiment, to the etching bath composition for transparent conductive film that foundation the present invention proposes, its embodiment, step, feature and effect thereof, describe in detail as after.
Nesa coating of the present invention is meant the nesa coating, particularly amorphousness ITO film of formations such as tin indium oxide (ITO), indium zinc oxide (IZO) and Indium sesquioxide and the nesa coating that the IZO film constitutes.In addition, etching bath composition for transparent conductive film of the present invention is the etching bath composition that is used in the corrosion process in the manufacturing process of indicating meter and electroluminescent display etc., at above-mentioned nesa coating.
The concentration that is used for etching bath composition oxalic acid of the present invention, after considering to obtain the abundant corrosion speed in the practicality and not separating out oxalic acid crystallization etc., can suitably determine, but 0.1-10 weight % preferably, more preferably 0.3-8 weight % particularly preferably is 0.5-6 weight %.When the concentration of oxalic acid was hanged down, corrosion speed reduced, the tendency that has the oxalic acid crystallization to separate out when concentration of oxalic acid is high, if the concentration of oxalic acid when above-mentioned scope, just can obtain the corrosion speed in the practicality, in addition, had better not have because the oxalic acid crystalline is separated out the obstacle that is brought on storage and transport.
The basic cpd that is used for etching bath composition of the present invention, select having considered indium meltage and corrosion speed etc., but, etching bath composition of the present invention, the decline that it is characterized in that the corrosion speed after adding alkaline components reduces, so the balance of indium meltage and corrosion speed is extremely important.As the basic cpd that is used for etching bath composition of the present invention, typically can enumerate oxyhydroxide, alkanol amine (but removing the trolamine class) and the hydroxyl amine etc. of quaternary ammonium hydroxide class, basic metal class.
Particularly, can enumerate tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, choline etc. as the quaternary ammonium hydroxide class.
In addition, can enumerate for example sodium hydroxide, potassium hydroxide etc. as alkali hydroxide.
And then, as the alkanol amine, can enumerate monoalkanolamine class, dialkanol amine, remove three alkanol amines of trolamine etc.The monoalkanolamine class can be enumerated for example monoethanolamine, 2-methylamino ethanol, 2-ethyl amido alcohol, 2-(2-amino ethoxy) ethanol, 1-amino-2-propyl alcohol, single Propanolamine, dimethylaminoethanol and these salt etc.In addition,, for example can enumerate diethanolamine, N methyldiethanol amine, two butanolamines, and these salt etc. as the dialkanol amine.In the above-mentioned alkanol amine, from the viewpoint of the meltage of indium and corrosion speed etc., preferably monoalkanolamine class, dialkanol amine etc., more preferably monoalkanolamine class, most preferably monoethanolamine etc.
And then, as hydroxyl amine, can enumerate for example oxyamine, N-methyl oxyamine, N, N-dimethyl hydroxyl amine, N, N-diethyl oxyamine, sulfuric acid oxyamine, hydrochloric acid oxyamine etc., preferably oxyamine etc.
In addition.These basic cpd also can contain more than a kind or 2 kinds according to purposes.
The concentration that is used for the basic cpd of etching bath composition of the present invention, be to separate out in the crystallization of the meltage of having considered indium, oxalic acid indium, can determine aptly after the pH value of etching bath composition and corrosion speed etc., but 0.1-10 weight % preferably, 0.3-7 weight % more preferably, that outstanding especially is 0.5-5 weight %.When the concentration of basic cpd is hanged down, separate out the crystallization of oxalic acid indium easily, corrosion speed had the tendency of decline when concentration was high, and the concentration of basic cpd is when above-mentioned scope, just can be prevented effect and practical corrosion speed that the crystallization of oxalic acid indium is separated out fully, so be ideal.
The pH value of etching bath composition of the present invention, be the crystallization of the meltage of having considered indium, oxalic acid indium separate out and corrosion speed etc. after decision aptly, but 1.1-5.0 preferably, more preferably 1.2-4.0 particularly preferably is 1.3-3.0.When pH hangs down, separate out the crystallization of oxalic acid indium easily, corrosion speed had the tendency of decline when pH was high, and pH just can be prevented effect and practical corrosion speed that the crystallization of oxalic acid indium is separated out, fully so be ideal when above-mentioned scope.
In the etching bath composition of the present invention, when containing the pH value of composition of the present invention of oxalic acid and basic cpd and the pH that do not contain the composition of the same composition beyond the basic cpd and comparing, owing to add the variation delta pH of the pH value of basic cpd, be to separate out and corrosion speed etc. can determine aptly in the crystallization of considering indium meltage, oxalic acid indium, kind by the basic cpd that adds and concentration etc. are adjusted aptly.
The scope of Δ pH, 0.1-4.0 preferably, more preferably 0.3-3.0 particularly preferably is 0.5-2.0.Oxalic acid indium crystallization in Δ pH hour is separated out easily, and when Δ pH was big, corrosion speed had the tendency of decline, if Δ pH, just can be prevented effect and practical corrosion speed that the crystallization of oxalic acid indium is separated out fully in above-mentioned scope.So be ideal.
The corrosion speed of etching bath composition of the present invention, after considering treatment time and corrosion uniformly etc., the concentration of oxalic acid, can by adding basic cpd kind and concentration adjust aptly.
In addition, under the prerequisite that does not hinder above-mentioned effect, can and then contain the composition of removing etching residue in etching bath composition of the present invention.As the preferably poly-sulfoacid compound of the employed composition of this purpose, polyoxyethylene-polyoxypropylene block copolymers, sulfonate type anion surfactant etc.
As poly-sulfoacid compound, can enumerate naphthalene sulfonic acidformaldehyde condensation product and salt thereof, polystyrolsulfon acid and salt thereof, lignosulfonic acid and salt thereof etc.As sulfonic formaldehyde condensation compound and salt thereof, the trade(brand)name market that can enumerate Le ノ Star Network ス 1000C, 1500A, イ オ ネ Star ト D-2, the レ ベ ロ of Sanyo Application PHL (above, KCC of bundle nation), ロ one マ PWA-40 (サ Application ノ プ コ Co., Ltd.), デ モ one Le N (Kao Corp), Port リ テ イ N-100K (ラ イ オ Application Co., Ltd.), ラ ベ リ Application FH-P (worker industry System medicine Co., Ltd.) etc. particularly is on sale.As lignosulfonic acid and salt thereof, can enumerate with ソ Le Port one Le 9047K (Toho Chemical Industry Co., Ltd. (JP) Tokyo-To, Japan), サ Application エ キ ス trade(brand)names such as (Nippon Paper Chemicals Co., Ltd.) on sale particularly in the market.In these poly-sulfoacid compounds, contain the material of metal such as sodium, it is unfavorable using as electronic industry, by the processing of ion exchange resin etc., removes sodium and just can use.
Polyoxyethylene-polyoxypropylene block copolymers, ratio and molecular weight according to polyoxyethylene and polyoxytrimethylene have various models, concrete for example having with trade(brand)name ニ ユ one Port one Le PE series (Sanyo Chemical Industries, Ltd.), エ パ Application series (Di-ichi Kogyo Seiyaku Co., Ltd.) etc. of peddling on market.
As the sulfonate type anion surfactant, can enumerate dialkyl and salt, polyethylene oxide alkyl ethers sulfonic acid and salt thereof, polyoxyethylene allyl ethers sulfonic acid and the salt thereof etc. of the benzene sulfonamide acid esters of Witco 1298 Soft Acid sample for example and salt, alkyl sulfuric ester and salt thereof, sulfo-succinic acid.Wherein polyethylene oxide alkyl ethers sulfonic acid and salt thereof, polyoxyethylene allyl ethers sulfonic acid and salt thereof and since blowing ratio less be preferred, be commercially available with the trade(brand)name of ニ ユ one コ one Le series (Japanese emulsifying agent Co., Ltd.).Have, these compounds can contain more than a kind or 2 kinds according to purposes again.
The concentration of employed poly-sulfoacid compound, polyoxyethylene-polyoxypropylene block copolymers and/or sulfonate type anionic surfactant in the etching bath composition of the present invention, from can fully removing the effect viewpoint of etching residue, preferably 0.0001-10 weight % particularly preferably is 0.001-10 weight %.
And then etching bath composition of the present invention in the scope that does not hinder above-mentioned effect, can make it contain the composition that promising further inhibition oxalic acid indium is separated out.As the employed composition of such purpose, preferably prevent the water-soluble polymers of incrustation scale effect.
As water-soluble polymers, can enumerate polyacrylic acid, polymaleic acid, vinylformic acid-maleic acid, vinylformic acid-sulfonic acid based copolymer, vinylformic acid-styrol copolymer and these salt.Can enumerate for example commercially available product of the trade(brand)name of ア Network ア リ Star Network series (Nippon Shokubai Co., Ltd), ア ロ Application series (Toagosei Co., Ltd), Port リ テ イ series (ラ イ オ Application Co., Ltd.) etc. particularly.The metal that contains sodium etc. in these the water-soluble polymers is to be unsuitable for electronic industry to use, but processing such as spent ion exchange resin are operable after sodium removed.In addition, these water-soluble polymerss can contain more than a kind or 2 kinds according to purposes.
The concentration of employed water-soluble polymers in the etching bath composition of the present invention, from obtaining fully to suppress the viewpoint of the effect that crystallization separates out, preferably 0.001-10 weight % particularly preferably is 0.01-10 weight %.In addition, the molecular weight of these water-soluble polymers, 200-100 preferably, 000, particularly preferably be 500-10,000.
Etching bath composition of the present invention can use in room temperature or heating back, can suitably impose a condition and uses in order to obtain needed corrosion speed and etching time.
Use the caustic solution of the nesa coating of etching bath composition of the present invention, can enumerate with nozzle to the inject process of substrate jet etching fluid composition, substrate directly is immersed in method in the corrosive fluid, shakes substrate self or stirs the method etc. of the dip treating of corrosive fluid.
Below represented embodiments of the invention and comparative example, and then described the present invention in detail, but the present invention is not subjected to the restriction of these embodiment, can carry out various variations in not breaking away from technological thought scope of the present invention.
Embodiment
(composition of corrosive fluid)
The composition of in table 1, having represented the corrosive fluid of embodiments of the invention and comparative example.
Table 1
| Example No. | Oxalic acid | Basic cpd | Poly-sulfoacid compound | Water |
| Embodiment 1 | 3.4 weight % | TMAH 1.5 weight % | ??- | Residual amount |
| Embodiment 2 | 3.4 weight % | TMAH 2.0 weight % | ??- | Residual amount |
| Embodiment 3 | 3.4 weight % | TMAH 2.7 weight % | ??- | Residual amount |
| Embodiment 4 | 3.4 weight % | TMAH 3.8 weight % | ??- | Residual amount |
| Embodiment 5 | 0.5 weight % | TMAH 0.4 weight % | ??- | Residual amount |
| Embodiment 6 | 1.0 weight % | TMAH 0.7 weight % | ??- | Residual amount |
| Embodiment 7 | 5.0 weight % | TMAH 3.2 weight % | ??- | Residual amount |
| Embodiment 8 | 3.4 weight % | Choline 2.6 weight % | ??- | Residual amount |
| Embodiment 9 | 3.4 weight % | MEA 1.4 weight % | ??- | Residual amount |
| Embodiment 10 | 3.4 weight % | Oxyamine 0.8 weight % | ??- | Residual amount |
| Embodiment 11 | 3.4 weight % | Sodium hydroxide 0.7 weight % | ??- | Residual amount |
| Embodiment 12 | 3.4 weight % | TMAH 2.4 weight % | Moral More N 1.0 weight % | Residual amount |
| Embodiment 13 | 3.4 weight % | TMAH 3.0 weight % | Moral More N 1.0 weight % | Residual amount |
| Comparative example 1 | 3.4 weight % | ??- | ??- | Residual amount |
| Comparative example 2 | 0.5 weight % | ??- | ??- | Residual amount |
| Comparative example 3 | 1.0 weight % | ??- | ??- | Residual amount |
| Comparative example 4 | 5.0 weight % | ??- | ??- | Residual amount |
| Comparative example 5 | 3.4 weight % | ??- | Moral More N 1.0 weight % | Residual amount |
The TMAH tetramethyl ammonium hydroxide
The MEA monoethanolamine
The sodium salt of moral More N naphthalene sulfonic acidformaldehyde condensation product (Kao Corp's system)
(the solvability evaluation of indium)
Each represented in the table 1 corrosive fluid is heated to 50 ℃ on one side,, stirred 2～3 hours Yi Bian add the indium concentration of indium oxide powder (median size 1 μ m, purity 99.99%) up to regulation.After observe confirming that with eyes indium oxide powder fully dissolves, filter each corrosive fluid respectively with 0.2 μ m filter, filtered liquid is enclosed in rests in the container in the thermostatic bath that is set at 37 ℃, observe in every specific time, to confirm whether have crystalline to separate out with eyes.In addition, determine the pH of each corrosive fluid.In addition, the indium meltage in the corrosive fluid is that the weight from the indium that adds, the capacity of corrosive fluid and the variable quantity of the strainer weight before and after the filtration calculate.Its result is illustrated in the table 2.
Table 2
| Example No. | ??pH | The In meltage | Liquid stabilising |
| Embodiment 1 | ??1.3 | ??2.000ppm | ??○ |
| Embodiment 2 | ??1.5 | ??3.000ppm | ??○ |
| Embodiment 3 | ??1.8 | ??5.000ppm | ??○ |
| Embodiment 4 | ??3.0 | ??5.000ppm | ??○ |
| Embodiment 5 | ??2.0 | ??1.000ppm | ??○ |
| Embodiment 6 | ??1.8 | ??1.000ppm | ??○ |
| Embodiment 7 | ??1.5 | ??2.000ppm | ??○ |
| Embodiment 8 | ??1.5 | ??2.000ppm | ??○ |
| Embodiment 9 | ??1.5 | ??2.000ppm | ??○ |
| Embodiment 10 | ??1.5 | ??1.000ppm | ??○ |
| Embodiment 11 | ??1.3 | ??1.000ppm | ??○ |
| Embodiment 12 | ??1.5 | ??3.000ppm | ??○ |
| Embodiment 13 | ??1.8 | ??5.000ppm | ??○ |
| Comparative example 1 | ??1.0 | ??1.000ppm | ??× |
| Comparative example 2 | ??1.5 | ??1.000ppm | ??× |
| Comparative example 3 | ??1.3 | ??1.000ppm | ??× |
| Comparative example 4 | ??0.8 | ??1.000ppm | ??× |
| Comparative example 5 | ??0.9 | ??1.000ppm | ??× |
※ indium solvability judgement criteria
Do not separate out crystallization more than 0 168 hours (7 days)
* 24 hours (1 day) separates out crystallization with interior
As table 2 is represented, the such corrosive fluid that does not contain basic cpd of comparative example 1～5 as can be seen, the meltage of its indium is little, separates out crystallization at 24 hours with interior.In contrast, embodiments of the invention 1～13 contain the basic cpd corrosive fluid, the meltage of its indium is big, and separates out crystallization more than 168 hours (7 days), the stability of liquid is extremely good.It is that effectively etching bath composition of the present invention has the effect that extremely good inhibition oxalic acid indium is separated out that the meltage that increases indium from these results is as can be seen separated out the crystallization that suppresses the oxalic acid indium.In the etching bath composition of the present invention, the balance of the meltage of above-mentioned indium and stability and corrosion speed described later is a particularly important.
In addition, as comparative example 2 and 3, even with concentration of oxalic acid reduce, pH is controlled at 1.3～1.5 and can sees that also crystallization separates out, there is not effect so merely will contain the pH raising of the corrosive fluid of oxalic acid yet, by making it contain basic cpd, can suppress oxalic acid indium crystalline extremely effectively and separate out as can be seen.
(evaluation of corrosion speed)
Each corrosive fluid that table 1 is represented is heated to 40 ℃,
The substrate of the anticorrosive figure that forms was immersed in each corrosive fluid after 1 minute on the noncrystalline ITO film of thickness, after washing, drying, peeled off anticorrosive film, measured etching extent with the contact pin type film thickness gauge, calculated corrosion speed.Its result is illustrated in table 3.
Table 3
As table 3 is represented, the corrosive fluid that does not contain basic cpd of the corrosive fluid that contains basic cpd of the embodiment of the invention 1～13 and comparative example 1～5 relatively, though corrosion speed has some minimizings as can be seen, amorphousness ITO film had sufficient corrosion speed.
(evaluation of removing property of residue)
To on glass substrate, form the substrate of ITO film, use time of 1.4 times of the lucky etching time that calculates from corrosion speed to carry out corrosion treatment after, carry out the residue after the electron microscope observation evaluation corrosion.In addition, to on glass substrate, having formed silicon nitride (SiN) film, and then form the substrate of ITO film, use time of 1.4 times of the lucky etching time that calculates from corrosion speed to carry out corrosion treatment equally after, carry out the residue after the electron microscope observation evaluation corrosion.Its result is illustrated in table 4.
Table 4
The judgement criteria of removing property of ※ residue
Zero does not see residue fully
* see residue all sidedly
As table 4 is represented, as can be seen in the corrosive fluid that only contains oxalic acid of comparative example 1, seeing residue all sidedly on the glass substrate and on the SiN film, and the corrosive fluid that contains oxalic acid, basic cpd and poly-sulfoacid compound of embodiment 12 and 13 has with the identical residue of the corrosive fluid that contains oxalic acid and poly-sulfonic acid of comparative example 5 and removes ability.
From the result of above-mentioned table 1～4 etching bath composition of the present invention as can be seen, because the meltage of indium is big, and the liquid stabilising behind the dissolving indium is high, so have the effect that the crystallization of extremely good inhibition oxalic acid indium is separated out.
In addition, with do not contain basic cpd in the past with oxalic acid to be that the corrosive fluid of principal constituent has identical, sufficient corrosion speed in the practicality.
And then, with do not contain basic cpd in the past with oxalic acid be principal constituent corrosive fluid similarly, can obtain good residue and remove ability by adding poly-sulfoacid compound etc.
According to the present invention, use contains the etching bath composition of oxalic acid and basic cpd, will be on substrates such as glass film forming ITO and the nesa coating of IZO etc. corrode, can suppress effectively the crystallization of the oxalic acid indium in the corrosion device is separated out, prolong the work-ing life of corrosive fluid significantly, the exchange number of times of operation and strainer is removed in crystallization in can alleviator, can reach and boost productivity and reduce cost.Therefore, in the manufacturing technology field nesa coating that has used ITO and IZO etc., liquid-crystal display and electroluminescent display etc., be useful especially.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, though the present invention discloses as above with preferred embodiment, yet be not in order to limit the present invention, any those skilled in the art, in not breaking away from the technical solution of the present invention scope, when the technology contents that can utilize above-mentioned announcement is made a little change or is modified to the equivalent embodiment of equivalent variations, in every case be not break away from the technical solution of the present invention content, according to technical spirit of the present invention to any simple modification that above embodiment did, equivalent variations and modification all still belong in the scope of technical solution of the present invention.
Claims (7)
1, a kind of etching bath composition for transparent conductive film, it is characterized in that containing oxalic acid and, basic cpd.
2, etching bath composition for transparent conductive film according to claim 1, it is characterized in that described basic cpd be oxyhydroxide, alkanol amine from quaternary ammonium hydroxide class, basic metal class and hydroxyl amine constitute select the group more than a kind or 2 kinds.
3, etching bath composition for transparent conductive film according to claim 1 and 2 is characterized in that the pH value is 1.1-5.0.
4, etching bath composition for transparent conductive film according to claim 1 and 2 is characterized in that and then contains from poly-sulfoacid compound, polyoxyethylene-polyoxypropylene block copolymers and sulfonate type anion surfactant and forms the compound of selecting the group more than a kind or 2 kinds.
5, etching bath composition for transparent conductive film according to claim 1 and 2 is characterized in that and then contain the water-soluble polymers more than a kind or 2 kinds.
6, etching bath composition for transparent conductive film according to claim 1 and 2 is characterized in that containing the corrosion of the nesa coating of Indium sesquioxide.
7, a kind of caustic solution of nesa coating is characterized in that having used any described etching bath composition for transparent conductive film among the aforesaid right requirement 1-6.
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| JP2008209103A JP5354989B2 (en) | 2008-08-14 | 2008-08-14 | Etching composition for transparent conductive film |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103627400A (en) * | 2012-08-22 | 2014-03-12 | 易安爱富科技有限公司 | Etchant composition for molybdenum alloy film and indium oxide film |
| CN105938797A (en) * | 2015-03-05 | 2016-09-14 | 东友精细化工有限公司 | Etchant composition for etching an indium oxide layer and method of manufacturing a display substrate using the etchant composition |
| CN107446582A (en) * | 2016-05-31 | 2017-12-08 | 长濑化成株式会社 | Etching solution |
| CN113372916A (en) * | 2021-06-08 | 2021-09-10 | 安徽华晟新能源科技有限公司 | Film layer removing slurry, solar cell cutting method and semiconductor device scribing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5431014B2 (en) * | 2009-05-01 | 2014-03-05 | 関東化学株式会社 | Indium oxalate solubilizer composition |
| JP2012043897A (en) * | 2010-08-17 | 2012-03-01 | Dnp Fine Chemicals Co Ltd | Etchant for conductive film and etching method |
| JP5803708B2 (en) * | 2012-02-03 | 2015-11-04 | 豊田合成株式会社 | Manufacturing method of semiconductor light emitting device |
| JP6044337B2 (en) | 2012-12-28 | 2016-12-14 | 三菱瓦斯化学株式会社 | Etching solution and etching method for oxide of indium and gallium and oxygen or indium and gallium, zinc and oxygen |
| JP6261926B2 (en) | 2013-09-18 | 2018-01-17 | 関東化學株式会社 | Metal oxide etchant composition and etching method |
| KR102178949B1 (en) | 2013-11-21 | 2020-11-16 | 삼성디스플레이 주식회사 | Echtant and method for manufacturing display device using the same |
| KR102384563B1 (en) * | 2016-03-24 | 2022-04-08 | 동우 화인켐 주식회사 | Composition for Etching Indium Oxide Layer |
| KR102362556B1 (en) * | 2016-03-25 | 2022-02-14 | 동우 화인켐 주식회사 | Composition for Etching Indium Oxide Layer |
| KR102546609B1 (en) * | 2018-07-13 | 2023-06-23 | 오씨아이 주식회사 | Etching solution for silicon substrate |
| CN109234072A (en) * | 2018-11-02 | 2019-01-18 | 江阴江化微电子材料股份有限公司 | A kind of cleaning process of indium oxalate dissolving agent composition and etching machines |
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| CN1346864A (en) * | 2000-09-08 | 2002-05-01 | 关东化学株式会社 | Etching liquid composition |
| WO2003081658A1 (en) * | 2002-03-25 | 2003-10-02 | Nagase Chemtex Corporation | Etchant composition |
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| CN103627400A (en) * | 2012-08-22 | 2014-03-12 | 易安爱富科技有限公司 | Etchant composition for molybdenum alloy film and indium oxide film |
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| CN105938797A (en) * | 2015-03-05 | 2016-09-14 | 东友精细化工有限公司 | Etchant composition for etching an indium oxide layer and method of manufacturing a display substrate using the etchant composition |
| CN107446582A (en) * | 2016-05-31 | 2017-12-08 | 长濑化成株式会社 | Etching solution |
| CN113372916A (en) * | 2021-06-08 | 2021-09-10 | 安徽华晟新能源科技有限公司 | Film layer removing slurry, solar cell cutting method and semiconductor device scribing method |
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| Publication number | Publication date |
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| TW201026819A (en) | 2010-07-16 |
| JP5354989B2 (en) | 2013-11-27 |
| CN101649202B (en) | 2014-06-18 |
| KR101680758B1 (en) | 2016-11-29 |
| JP2010045253A (en) | 2010-02-25 |
| TWI519627B (en) | 2016-02-01 |
| KR20100021376A (en) | 2010-02-24 |
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