WO2021117478A1 - Etching liquid composition and etching method - Google Patents

Etching liquid composition and etching method Download PDF

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Publication number
WO2021117478A1
WO2021117478A1 PCT/JP2020/043660 JP2020043660W WO2021117478A1 WO 2021117478 A1 WO2021117478 A1 WO 2021117478A1 JP 2020043660 W JP2020043660 W JP 2020043660W WO 2021117478 A1 WO2021117478 A1 WO 2021117478A1
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Prior art keywords
etching
acid
silver
solution composition
etching solution
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PCT/JP2020/043660
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French (fr)
Japanese (ja)
Inventor
大津　猛
佳秀 齋尾
珠美 青木
大輔 大宮
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株式会社Adeka
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Publication of WO2021117478A1 publication Critical patent/WO2021117478A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/30—Acidic compositions for etching other metallic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process

Definitions

  • the present invention relates to an etching solution composition used for etching a silver-containing layer and an etching method using the same.
  • a printed wiring board or film having a circuit formed on its surface is widely used for mounting electronic components, semiconductor elements, and the like.
  • silver material a silver alloy having excellent properties such as conductivity and thermal conductivity for wiring used for such printed wiring boards and the like.
  • Patent Document 1 proposes an etching solution composition containing phosphoric acid, nitric acid, acetic acid, and water.
  • Patent Document 2 proposes an etching solution composed of an acidic aqueous solution containing ferric sulfate as an active ingredient.
  • Patent Document 3 proposes an etching solution composition containing nitric acid, sulfuric acid, hydrogen chloride, and water.
  • the silver material be removed by etching in the area other than the wiring part.
  • a finely divided wiring pattern is etched using a conventional etching solution composition, a residue of a silver material is likely to be generated. For this reason, there is a case where a problem such as a short circuit is likely to occur in the circuit wiring due to the residue of the silver material generated may occur.
  • the increase in the amount of side etching and the generation of residue greatly impair the electrical connection reliability of the circuit wiring.
  • the present invention has been made in view of the problems of the prior art, and the subject thereof is an etching solution composition capable of etching the silver-containing layer while suppressing the generation of side etching and residues. It is to provide things.
  • Another object of the present invention is to provide an etching method using this etching solution composition capable of etching a silver-containing layer while suppressing side etching and generation of residues.
  • an etching solution composition containing a specific component at a specific concentration can solve the above problems, and have completed the present invention. ..
  • etching solution composition used for etching a silver-containing layer, wherein (A) component: oxidant 0.1 to 20% by mass, (B) component: (i) dicarboxylic acid. It contains 0.5 to 40% by mass of at least one component of an ammonium salt of an acid and (ii) a combination of the dicarboxylic acid and an amine compound or an ammonium compound, and water, wherein the dicarboxylic acid is oxalic acid.
  • an etching solution composition which is an organic acid having an alkylene chain having 2 or less carbon atoms which is unsubstituted or substituted with a hydroxyl group is provided.
  • the oxidizing agent is preferably hydrogen peroxide.
  • the dicarboxylic acid is preferably succinic acid.
  • the component (B) is preferably ammonium succinate.
  • the etching solution composition of the present invention is suitable as a composition for etching a silver-containing layer containing silver or a silver alloy.
  • an etching method including a step of etching a silver-containing layer using the above-mentioned etching solution composition.
  • an etching solution composition capable of etching a silver-containing layer while suppressing side etching and generation of residues. Further, according to the present invention, it is possible to provide an etching method using this etching solution composition capable of etching a silver-containing layer while suppressing side etching and generation of residues.
  • etching means a technique of plastic molding or surface treatment utilizing the corrosive action of chemicals and the like. Specifically, a method of coating the necessary portion of the surface of the material to be used with an etching resist and dissolving and eroding the unnecessary portion with an etching solution composition to process the unnecessary portion into a desired shape can be mentioned.
  • the "silver-containing layer" in the present specification may be any layer containing silver.
  • Silver is, for example, natural silver (silver alone), silver oxide, etc., other silver components such as silver nanoparticles, silver nanoplates, and silver nanowires; other metals mainly composed of silver (eg, aluminum, silicon). , Titanium, chromium, copper, zinc, germanium, indium, tin, palladium, platinum, gold, neodymium, etc.).
  • the shape of the "silver-containing layer” is not particularly limited, and may be a metal film, a metal plate, a metal foil, metal particles, or a composite containing a resin and a metal.
  • metal means the silver-containing metal described above.
  • the “silver-containing layer” preferably contains the above silver in an amount of 1% by mass or more, and more preferably 5% by mass or more.
  • the etching solution composition is a composition (etching solution) used for etching a silver-containing layer, and contains the following components (A), (B), and water. It is an aqueous solution.
  • the component (A) is an oxidizing agent.
  • the oxidizing agent include n-methylmorpholine oxide, benzoyl peroxide, tetrabutylammonium peroxide monosulfate, ozone, ferric chloride, peroxoboic acid permanganate, chlorous acid, peroxosulfuric acid, ammonium peroxydisulfate, and the like.
  • oxidizing agents may be used alone or in combination of two or more.
  • the oxidizing agent is preferably hydrogen peroxide because a more remarkable effect can be obtained.
  • the concentration of the component (A) in the etching solution composition is 0.1 to 20% by mass, preferably 0.5 to 10% by mass, and more preferably 0.5 to 5% by mass.
  • concentration of the component (A) is less than 0.1% by mass, the etching rate is remarkably lowered, the productivity is lowered, and a residue is likely to be generated.
  • concentration of the component (A) exceeds 20% by mass, it becomes difficult to control the etching rate.
  • the component (B) is at least one of (i) an ammonium salt of a dicarboxylic acid and (ii) a combination of a dicarboxylic acid and an amine compound or an ammonium compound.
  • the dicarboxylic acid constituting the component (B) is oxalic acid or an organic acid having an alkylene chain having 2 or less carbon atoms, which is unsubstituted or substituted with a hydroxyl group.
  • Examples of the organic acid having an alkylene chain having 2 or less carbon atoms substituted with an unsubstituted or hydroxyl group include tartaric acid, malonic acid, and succinic acid. These organic acids can be used alone or in combination of two or more.
  • the dicarboxylic acid is preferably succinic acid because a more remarkable effect can be obtained.
  • an ammonium salt of a dicarboxylic acid is preferable.
  • the ammonium salt of the dicarboxylic acid include ammonium oxalate, ammonium succinate, and ammonium tartrate.
  • the ammonium salts of these dicarboxylic acids can be used alone or in combination of two or more.
  • the component (B) is preferably ammonium succinate because a more remarkable effect can be obtained.
  • amine compounds include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, octaethylenenonamine, nonaethylenedecamine, butylene diamine, pentamethylenediamine, and hexamethylene.
  • Chain amines such as diamine, heptamethylenediamine, tetramethylethylenediamine, pentamethyldiethylenetriamine, tetramethyltriethylenetetramine, pentamethyltriethylenetetramine, and hexamethyltriethylenetetramine; cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine , Cycloheptylamine, cyclooctylamine, cyclononylamine, cyclodecylamine, cycloundesylamine, and alicyclic amines of cyclododecylamine; aniline, 2-methylaniline, 3-methylaniline, 2,3-dimethylaniline , 4-Methylaniline, 5-Methylaniline, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, 5-ethylaniline, 2,4-dimethylaniline, 2,5
  • ammonium compound examples include ammonia, ammonium hydrogencarbonate, ammonium carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like. These ammonium compounds can be used alone or in combination of two or more.
  • the concentration of the component (B) in the etching solution composition is 0.5 to 40% by mass, preferably 1 to 30% by mass, and more preferably 2 to 10% by mass. If the concentration of the component (B) is less than 0.5% by mass, it becomes difficult to suppress side etching and the generation of residues. On the other hand, if the concentration of the component (B) exceeds 40% by mass, the component (B) may be difficult to dissolve.
  • the etching solution composition of this embodiment contains water. That is, the etching solution composition of the present embodiment is an aqueous solution in which the components (A) and (B) are dissolved in water.
  • the pH of the etching solution composition at 25 ° C. is preferably 5.5 to 10. If the pH of the etching solution is out of the above numerical range, it may be somewhat difficult to control the etching of the silver-containing layer.
  • the pH of the etching solution at 25 ° C. is more preferably pH 6 to 9 because the linearity of the formed wiring is improved.
  • the etching solution composition of the present embodiment may contain a well-known additive, if necessary, as long as the effects of the present invention are not impaired.
  • Additives that can be contained include reducing agents, surfactants, stabilizers, solubilizers, defoamers, specific gravity regulators, viscosity regulators, wettability improvers, polyalkylene glycols, organic acids, amino acids. Classes, azoles, pyrimidines, thioureas, amines, alkylpyrrolidones, organic chelating agents, polyacrylamides, persulfates, pH regulators and the like.
  • the concentration of the additive in the etching solution composition is preferably 0.001 to 50% by mass based on the entire etching solution composition.
  • the etching rate of the etching solution composition is high, it is preferable to add a reducing agent.
  • the reducing agent include metal powder, sodium nitrite, and sodium hypochlorite that can be dissolved in the etching solution composition.
  • surfactant examples include fluorine-based amphoteric surfactants such as fluoroalkyl betaine and fluoroalkyl polyoxyethylene ether; nonionic surfactants; and the like.
  • Stabilizers include, for example, amine compounds such as 2-amino-2-methyl-1-propanol, 1-amino-2-propanol, 2-aminoethanol, and tetramethylammonium hydroxide; 1,2,4- 1H-triazole, 1H-benzotriazole, 5-methyl-1H-benzotriazole, 3-amino-1H-1,2,4-triazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H- Azole such as tetrazole and 5-amino-1H-tetrazole; ureas such as phenylurea, allylurea, 1,3-dimethylurea, and thiourea; Aromatic sulfonic acids; alkane sulfonic acids such as methane sulfonic acid and ethane sulfonic acid; alcohols such as phenylethylene glycol, 1-propanol, 2-propano
  • the solubilizer is preferably a component that is miscible with water and can promote the removal of etching residues.
  • examples of the solubilizer include sulfolane, N-methylpyrrolidone, dimethyl sulfoxide and the like.
  • defoaming agent examples include a silicon defoaming agent, a long-chain alcohol defoaming agent, a fatty acid ester defoaming agent, a metal soap defoaming agent, and an ethylene oxide propylene oxide copolymer.
  • the specific gravity adjusting agent a solution in which a substance for adjusting the specific gravity is dissolved in a solvent or diluted water can be used.
  • the substance for adjusting the specific gravity any substance can be used as long as the solution does not corrode or exfoliate the silver-containing layer.
  • the substance for adjusting the specific gravity include pure water, ion-exchanged water, tap water, sugars such as sucrose, edible salt, urea and the like.
  • the viscosity modifier it is preferable to use one having compatibility with the etching solution composition.
  • the viscosity modifier include sorbitol, low molecular weight polyvinylpyrrolidone, polyvinyl alcohol, hydroxyethyl cellulose, an aqueous solution of hydroxypropyl cellulose, a sol of hydroxypropyl cellulose, and diluted water.
  • the wettability improving agent is added to the etching solution composition for the purpose of facilitating the removal of air existing in the slit groove of the silver-containing layer and obtaining a degreasing effect.
  • polyalkylene glycol for example, ethylene oxide or propylene oxide is blocked or randomly added to diols such as polyethylene glycol; polyethylene glycol dimethyl ether; ethylene glycol, propylene glycol, 1,3-butanol, and 1,4-butanol.
  • diols such as polyethylene glycol; polyethylene glycol dimethyl ether; ethylene glycol, propylene glycol, 1,3-butanol, and 1,4-butanol.
  • Polyalkylene glycol; etc. can be mentioned.
  • organic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, acrylic acid, crotonic acid, isocrotonic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, malein.
  • examples thereof include acids, fumaric acid, malic acid, tartaric acid, citric acid, glycolic acid, lactic acid, sulfamic acid, nicotinic acid, ascorbic acid, hydroxypivalic acid, levulinic acid, ⁇ -chloropropionic acid and the like.
  • amino acids examples include amino acids such as glycine, alanine, valine, leucine, serine, phenylalanine, tryptophan, glutamic acid, aspartic acid, lysine, and arginine and histidine; alkali metal salts and ammonium salts of these amino acids. Can be done.
  • azoles include alkyl imidazoles such as imidazole, 2-methyl imidazole, 2-undecyl-4-methyl imidazole, 2-phenyl imidazole, and 2-methyl benzo imidazole; benzo imidazole, 2-methyl benzo imidazole, 2 -Benzoimidazoles such as undecylbenzomidazole, 2-phenylbenzoimidazole, and 2-mercaptobenzomidazole; 1,2,3-triazole, 1,2,4-triazole, 5-phenyl-1,2,4- Triazole, 5-amino-1,2,4-triazole, 1,2,3-benzotriazole, 1-aminobenzotriazole, 4-aminobenzotriazole, 1-bisaminomethylbenzotriazole, 1-methyl-benzotriazole, Triazoles such as tririltriazole, 1-hydroxybenzotriazole, 5-methyl-1H-benzotriazole, and 5-chlorobenzotriazole; 1
  • pyrimidines examples include diaminopyrimidine, triaminopyrimidine, tetraaminopyrimidine, and mercaptopyrimidine.
  • thioureas examples include thiourea, ethylenethiourea, thiodiglycol, and mercaptan.
  • amines include diamylamine, dibutylamine, triethylamine, triamylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, ethanolisopropanolamine, diethanolisopropanolamine, ethanoldi.
  • examples thereof include isopropanolamine, polyallylamine, polyvinylpyridine, and hydrochlorides thereof.
  • alkylpyrrolidones include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-butyl-2-pyrrolidone, N-amyl-2-pyrrolidone, and N-.
  • Hexyl-2-pyrrolidone, N-heptyl-2-pyrrolidone, N-octyl-2-pyrrolidone and the like can be mentioned.
  • organic chelating agent examples include ethylenediamine tetraacetic acid, diethylenetriaminepentacetic acid, triethylenetetraminehexacetic acid, tetraethylenepentamineriacetic acid, pentaethylenehexamineoctacetic acid, nitrilotriacetic acid, and alkali metal (preferably sodium) salts thereof.
  • Aminocarboxylic acid-based chelating agents such as hydroxyethylidene diphosphonic acid, nitrilotrismethylenephosphonic acid, phosphonobutanetricarboxylic acid, and phosphonic acid-based chelating agents such as alkali metal (preferably sodium) salts thereof; oxalic acid, malon Divalent or higher valents of acids, succinic acid, glutaric acid, adipic acid, pimeric acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid, these anhydrides, and alkali metal (preferably sodium) salts thereof.
  • Examples thereof include a carboxylic acid compound, and a monoan anhydride or a dianhydride obtained by dehydrating a divalent or higher carboxylic acid compound.
  • concentration of the organic chelating agent in the etching solution composition may be, for example, 0.01 to 40% by mass.
  • polyacrylamides examples include polyacrylamide and tert-butylacrylamide sulfonic acid.
  • persulfate examples include ammonium persulfate, sodium persulfate, potassium persulfate and the like.
  • a pH adjuster is a component containing a base or an acid.
  • the base include amines, diglycolamines, triethanolamines, tetrabutylphosphonium hydroxides, primary amine compounds, secondary amine compounds, tertiary amine compounds and the like.
  • the acid include inorganic acids such as sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, and hydrofluoric acid; organic acids such as carboxylic acids, amino acids, hydroxycarboxylic acids, and polycarboxylic acids; and the like. Can be done.
  • etching solution composition of the present embodiment include, for example, a removing agent for a silver-containing layer, a surface smoothing agent, a surface roughening agent, a pattern-forming agent, and a cleaning solution of a silver component slightly adhering to a substrate. And so on.
  • the etching method of the present embodiment includes a step of etching the silver-containing layer using the above-mentioned etching solution composition. More specifically, first, a material in which a silver-containing layer (for example, a metal film) is formed in a predetermined region on a substrate is prepared, and an etching resist is used to mask a necessary portion of the silver-containing layer to mask a mask region. To form. Next, the silver-containing layer in the region other than the mask region (non-mask region) is removed by etching with the above-mentioned etching solution composition.
  • a material in which a silver-containing layer for example, a metal film
  • an etching resist is used to mask a necessary portion of the silver-containing layer to mask a mask region.
  • the silver-containing layer in the region other than the mask region is removed by etching with the above-mentioned etching solution composition.
  • the method for etching the silver-containing layer in the non-masked region is not particularly limited, and a general etching method can be used. For example, an etching method such as a dip type, a spray type, or a spin type can be mentioned. Further, the conditions for etching the silver-containing layer in the non-masked region are not particularly limited, and various well-known general methods such as batch type, flow type, redox potential of etchant, specific gravity, and auto-control type based on acid concentration are adopted. be able to.
  • a material having a silver-containing layer formed on a substrate is etched by a dip-type etching method
  • the material is immersed in an etching solution composition under appropriate etching conditions and then pulled up to contain silver on the substrate.
  • the layer can be etched.
  • the etching conditions in the dip-type etching method may be arbitrarily set according to the shape and film thickness of the silver-containing layer of the material to be etched.
  • the etching temperature for general etching is preferably 10 to 40 ° C, more preferably 20 to 40 ° C.
  • the temperature of the etching solution composition may rise due to the heat of reaction. Therefore, if necessary, it is preferable to control the temperature of the etching solution composition by a known means so as to maintain the temperature within the above range.
  • the etching time may be a time sufficient to complete the etching, and is not particularly limited. For example, if the film thickness of the silver-containing layer is about 1 nm to 1 ⁇ m, etching may be performed in the above temperature range for about 10 seconds to 1 hour.
  • the silver-containing layer on the substrate can be etched by spraying the etching solution composition onto the material under appropriate conditions. it can.
  • the etching conditions in the spray-type etching method may be arbitrarily set according to the shape and film thickness of the silver-containing layer.
  • the spray pressure when spraying the etching solution composition can be selected from the range of 0.01 to 1.0 MPa, preferably in the range of 0.02 to 0.1 MPa. , More preferably in the range of 0.03 to 0.08 MPa.
  • the spray pressure in the range of 0.03 to 0.08 MPa is particularly preferable because the difference between the upper width and the lower width of the silver-containing layer in the wiring portion can be made very small.
  • the etching temperature is preferably in the range of 10 to 50 ° C, more preferably in the range of 20 to 50 ° C.
  • the temperature of the etching solution composition may rise due to the heat of reaction. Therefore, if necessary, the temperature may be controlled by a known means so that the temperature of the etching solution composition can be maintained within the above range. Further, the etching time may be a time sufficient to complete the etching, and is not particularly limited. For example, if the film thickness is about 1 nm to 1 ⁇ m, etching may be performed in the above temperature range for about 10 seconds to 1 hour.
  • the etching method of the present embodiment further includes a step of adding a replenishing liquid to the etching liquid composition in order to recover the deterioration of the etching liquid composition due to repeated etching.
  • a replenisher is set in the etching apparatus in advance, the replenisher can be appropriately added to the etching solution composition.
  • the replenisher for example, an aqueous solution containing the above-mentioned component (A) and component (B) can be used.
  • the concentration of each component may be about 3 to 20 times the concentration of each component in the etching solution composition.
  • Each of the above-mentioned components essential or optionally used in the etching solution composition may be added to the supplement solution, if necessary.
  • the etching solution composition according to the embodiment of the present invention includes a printed wiring board for forming electrodes for a touch sensor, a packaging substrate that requires a fine pitch, and a subtractive method for COF and TAB. And can be suitably used for circuit formation of the semi-additive method.
  • etching solution composition ⁇ Preparation of etching solution composition> (Implemented compositions 1-9, comparative compositions 1-5)
  • Etching liquid compositions (implemented compositions 1 to 9 and comparative compositions 1 to 5) were prepared by mixing each component so as to have the formulations shown in Table 1.
  • the “pH value” in Table 1 is the pH value of the etching solution composition immediately after production at 25 ° C.
  • the numerical values in parentheses in Table 1 are the contents (mass%) of each component based on the entire etching solution composition.
  • Examples 1 to 9, Comparative Examples 1 to 5 A substrate having a layer (silver-containing layer) made of a silver-palladium-copper alloy (product name "APC", manufactured by Furuya Metal Co., Ltd.) having a thickness of 100 nm laminated on a glass substrate was prepared. A resist pattern having a width of 60 ⁇ m and an opening of 60 ⁇ m was formed on the silver-containing layer of this substrate using a negative dry film, and then cut into a size of 50 mm ⁇ 50 mm to obtain a test piece.
  • a substrate having a layer (silver-containing layer) made of a silver-palladium-copper alloy (product name "APC", manufactured by Furuya Metal Co., Ltd.) having a thickness of 100 nm laminated on a glass substrate was prepared.
  • a resist pattern having a width of 60 ⁇ m and an opening of 60 ⁇ m was formed on the silver-containing layer of this substrate using a negative dry film, and then cut into a size of
  • test pieces were evaluated by etching using the prepared etching solution compositions under the conditions of 35 ° C., a spray pressure of 0.05 MPa, and a predetermined etching treatment time (Table 2). Pattern was formed. In Comparative Example 1 and Comparative Example 2, a pattern having a desired shape could not be formed even after etching for 180 seconds or longer.

Abstract

Provided is an etching liquid composition capable of etching a silver-containing layer while suppressing the occurrence of side etching and the generation of residue. The present invention provides an etching liquid composition that is used for etching a silver-containing layer. The etching liquid composition contains: a component (A) which is 0.1-20 mass% of an oxidant; a component (B) which is 0.5-40 mass% of at least one of (i) an ammonium salt of a dicarboxylic acid and (ii) a combination of a dicarboxylic acid and an amine compound or an ammonium compound; and water. The dicarboxylic acid is an oxalic acid or an organic acid having an alkylene chain that is unsubstituted or substituted with a hydroxyl group and that has at most 2 carbon atoms.

Description

エッチング液組成物及びエッチング方法Etching liquid composition and etching method
　本発明は、銀含有層をエッチングするために用いるエッチング液組成物、及びそれを用いたエッチング方法に関する。 The present invention relates to an etching solution composition used for etching a silver-containing layer and an etching method using the same.
　表面に回路を形成したプリント配線板又はフィルムが、電子部品や半導体素子等を実装するために広く用いられている。このようなプリント配線板等に用いられる配線には、近年、導電性や熱伝導性等の性質に優れた銀又は銀合金（以下、纏めて「銀材料」とも記す）が使用される機会が増えている。 A printed wiring board or film having a circuit formed on its surface is widely used for mounting electronic components, semiconductor elements, and the like. In recent years, there has been an opportunity to use silver or a silver alloy (hereinafter collectively referred to as "silver material") having excellent properties such as conductivity and thermal conductivity for wiring used for such printed wiring boards and the like. is increasing.
　プリント配線板の製造する方法としては、ウエットエッチングによって銀材料の配線を形成する方法が多く採用されている。このようなウエットエッチングで用いられるエッチング液組成物については、これまでに多数報告されている。例えば、特許文献１では、燐酸、硝酸、酢酸、及び水を配合したエッチング液組成物が提案されている。また、特許文献２では、硫酸第２鉄を有効成分として含有する酸性水溶液からなるエッチング液が提案されている。さらに、特許文献３では、硝酸、硫酸、塩化水素、及び水を含有するエッチング液組成物が提案されている。 As a method for manufacturing a printed wiring board, a method of forming wiring made of silver material by wet etching is often adopted. Many etching solution compositions used in such wet etching have been reported so far. For example, Patent Document 1 proposes an etching solution composition containing phosphoric acid, nitric acid, acetic acid, and water. Further, Patent Document 2 proposes an etching solution composed of an acidic aqueous solution containing ferric sulfate as an active ingredient. Further, Patent Document 3 proposes an etching solution composition containing nitric acid, sulfuric acid, hydrogen chloride, and water.
特開２００４－１７６１１５号公報Japanese Unexamined Patent Publication No. 2004-176115 特開平１０－０６０６７１号公報Japanese Unexamined Patent Publication No. 10-060671 特開２０１７－１７１９９２号公報Japanese Unexamined Patent Publication No. 2017-171992
　しかしながら、配線パターンの微細化が進んだ結果、従来のエッチング液組成物を用いて銀材料をエッチングすると、サイドエッチング量が多くなる傾向にあり、銀材料で形成される配線部分が断線しやすくなる場合があった。 However, as a result of the progress of miniaturization of the wiring pattern, when the silver material is etched using the conventional etching solution composition, the amount of side etching tends to increase, and the wiring portion formed of the silver material is likely to be broken. There was a case.
　また、配線部分以外の領域については、エッチングによって銀材料が除去されることが望まれる。しかし、従来のエッチング液組成物を用いて微細化された配線パターンをエッチングすると、銀材料の残渣が生じやすい。このため、生じた銀材料の残渣に起因して回路配線で短絡が発生しやすくなる等の不具合が生ずる場合があった。サイドエッチング量の増加や残渣の発生は、回路配線の電気的な接続信頼性を大きく損なうことになる。 In addition, it is desirable that the silver material be removed by etching in the area other than the wiring part. However, when a finely divided wiring pattern is etched using a conventional etching solution composition, a residue of a silver material is likely to be generated. For this reason, there is a case where a problem such as a short circuit is likely to occur in the circuit wiring due to the residue of the silver material generated may occur. The increase in the amount of side etching and the generation of residue greatly impair the electrical connection reliability of the circuit wiring.
　したがって、本発明は従来技術に有する問題に鑑みてなされたものであり、その課題とするところは、サイドエッチング及び残渣の発生を抑制しながら、銀含有層をエッチングすることが可能なエッチング液組成物を提供することにある。また、本発明の課題とするところは、このエッチング液組成物を用いる、サイドエッチング及び残渣の発生を抑制しながら銀含有層をエッチングすることが可能なエッチング方法を提供することにある。 Therefore, the present invention has been made in view of the problems of the prior art, and the subject thereof is an etching solution composition capable of etching the silver-containing layer while suppressing the generation of side etching and residues. It is to provide things. Another object of the present invention is to provide an etching method using this etching solution composition capable of etching a silver-containing layer while suppressing side etching and generation of residues.
　本発明者らは、上記課題を解決すべく鋭意検討した結果、特定の成分を特定濃度で含有させたエッチング液組成物が上記課題を解決しうることを見出し、本発明を完成させるに至った。 As a result of diligent studies to solve the above problems, the present inventors have found that an etching solution composition containing a specific component at a specific concentration can solve the above problems, and have completed the present invention. ..
　すなわち、本発明によれば、銀含有層をエッチングするために用いられるエッチング液組成物であって、（Ａ）成分：酸化剤０．１～２０質量％、（Ｂ）成分：（ｉ）ジカルボン酸のアンモニウム塩、及び（ｉｉ）前記ジカルボン酸とアミン化合物若しくはアンモニウム化合物との組み合わせ、の少なくともいずれかの成分０．５～４０質量％、並びに水を含有し、前記ジカルボン酸が、シュウ酸、又は無置換若しくは水酸基で置換された炭素数２以下のアルキレン鎖を有する有機酸であるエッチング液組成物が提供される。 That is, according to the present invention, it is an etching solution composition used for etching a silver-containing layer, wherein (A) component: oxidant 0.1 to 20% by mass, (B) component: (i) dicarboxylic acid. It contains 0.5 to 40% by mass of at least one component of an ammonium salt of an acid and (ii) a combination of the dicarboxylic acid and an amine compound or an ammonium compound, and water, wherein the dicarboxylic acid is oxalic acid. Alternatively, an etching solution composition which is an organic acid having an alkylene chain having 2 or less carbon atoms which is unsubstituted or substituted with a hydroxyl group is provided.
　本発明においては、前記酸化剤が、過酸化水素であることが好ましい。 In the present invention, the oxidizing agent is preferably hydrogen peroxide.
　本発明においては、ジカルボン酸が、コハク酸であることが好ましい。 In the present invention, the dicarboxylic acid is preferably succinic acid.
　本発明においては、（Ｂ）成分が、コハク酸アンモニウムであることが好ましい。 In the present invention, the component (B) is preferably ammonium succinate.
　本発明のエッチング液組成物は、銀又は銀合金を含有する銀含有層をエッチングするための組成物として好適である。 The etching solution composition of the present invention is suitable as a composition for etching a silver-containing layer containing silver or a silver alloy.
　また、本発明によれば、上記のエッチング液組成物を用いて銀含有層をエッチングする工程を有するエッチング方法が提供される。 Further, according to the present invention, there is provided an etching method including a step of etching a silver-containing layer using the above-mentioned etching solution composition.
　本発明によれば、サイドエッチング及び残渣の発生を抑制しながら、銀含有層をエッチングすることが可能なエッチング液組成物を提供することができる。また、本発明によれば、このエッチング液組成物を用いる、サイドエッチング及び残渣の発生を抑制しながら銀含有層をエッチングすることが可能なエッチング方法を提供することができる。 According to the present invention, it is possible to provide an etching solution composition capable of etching a silver-containing layer while suppressing side etching and generation of residues. Further, according to the present invention, it is possible to provide an etching method using this etching solution composition capable of etching a silver-containing layer while suppressing side etching and generation of residues.
　以下、本発明の実施の形態について具体的に説明する。本明細書における「エッチング」とは、化学薬品等の腐食作用を利用した塑形又は表面加工による技法を意味する。具体的には、使用する素材表面の必要部分をエッチングレジストで被覆するとともに、エッチング液組成物を用いて不要部分を溶解・浸食して所望の形状に加工する手法を挙げることができる。 Hereinafter, embodiments of the present invention will be specifically described. As used herein, the term "etching" means a technique of plastic molding or surface treatment utilizing the corrosive action of chemicals and the like. Specifically, a method of coating the necessary portion of the surface of the material to be used with an etching resist and dissolving and eroding the unnecessary portion with an etching solution composition to process the unnecessary portion into a desired shape can be mentioned.
　本明細書における「銀含有層」は、銀を含有する層であればよい。銀は、例えば、自然銀（銀単体）、酸化銀等、銀ナノ粒子、銀ナノプレート、及び銀ナノワイヤー等の銀成分の他；銀を主体として微量の他の金属（例えば、アルミニウム、ケイ素、チタン、クロム、銅、亜鉛、ゲルマニウム、インジウム、錫、パラジウム、白金、金、及びネオジム等）を含有する銀合金であってもよい。 The "silver-containing layer" in the present specification may be any layer containing silver. Silver is, for example, natural silver (silver alone), silver oxide, etc., other silver components such as silver nanoparticles, silver nanoplates, and silver nanowires; other metals mainly composed of silver (eg, aluminum, silicon). , Titanium, chromium, copper, zinc, germanium, indium, tin, palladium, platinum, gold, neodymium, etc.).
　「銀含有層」の形状は、特に限定されず、金属膜、金属プレート、金属箔、金属粒子、樹脂と金属を含有する複合物であってもよい。本明細書における「金属」は、上記の銀を含有する金属を意味する。「銀含有層」は、上記の銀を１質量％以上含有することが好ましく、５質量％以上含有することがさらに好ましい。 The shape of the "silver-containing layer" is not particularly limited, and may be a metal film, a metal plate, a metal foil, metal particles, or a composite containing a resin and a metal. As used herein, the term "metal" means the silver-containing metal described above. The "silver-containing layer" preferably contains the above silver in an amount of 1% by mass or more, and more preferably 5% by mass or more.
　本発明の一実施形態であるエッチング液組成物は、銀含有層をエッチングするために用いられる組成物（エッチング液）であり、以下の（Ａ）成分、（Ｂ）成分、及び水を含有する水溶液である。
　（Ａ）成分：酸化剤
　（Ｂ）成分：（ｉ）ジカルボン酸のアンモニウム塩、及び（ｉｉ）前記ジカルボン酸とアミン化合物若しくはアンモニウム化合物との組み合わせ、の少なくともいずれかの成分 The etching solution composition according to an embodiment of the present invention is a composition (etching solution) used for etching a silver-containing layer, and contains the following components (A), (B), and water. It is an aqueous solution.
(A) Component: Oxidizing agent (B) Component: (i) Ammonium salt of dicarboxylic acid, and (ii) At least one component of the dicarboxylic acid and an amine compound or a combination of an ammonium compound.
　（Ａ）成分は酸化剤である。酸化剤としては、例えば、ｎ－メチルモルホリン酸化物、ベンゾイルペルオキシド、テトラブチルアンモニウム過酸化モノ硫酸、オゾン、塩化第二鉄、過マンガン酸ペルオキソホウ酸、過塩素酸、ペルオキソ硫酸、ペルオキシ二硫酸アンモニウム、過酢酸、尿素ヒドロペルオキシド、硝酸、亜塩素酸アンモニウム、塩素酸アンモニウム、ヨウ素酸アンモニウム、過ホウ酸アンモニウム、過塩素酸アンモニウム、過ヨウ素酸アンモニウム、過硫酸アンモニウム、亜塩素酸テトラメチルアンモニウム、塩素酸テトラメチルアンモニウム、ヨウ素酸テトラメチルアンモニウム、過ホウ酸テトラメチルアンモニウム、過塩素酸テトラメチルアンモニウム、過ヨウ素酸テトラメチルアンモニウム、過硫酸テトラメチルアンモニウム、及び過酸化水素等を挙げることができる。これらの酸化剤は、１種単独で又は２種以上を組み合わせてもよい。より顕著な効果が得られることから、酸化剤は過酸化水素であることが好ましい。 The component (A) is an oxidizing agent. Examples of the oxidizing agent include n-methylmorpholine oxide, benzoyl peroxide, tetrabutylammonium peroxide monosulfate, ozone, ferric chloride, peroxoboic acid permanganate, chlorous acid, peroxosulfuric acid, ammonium peroxydisulfate, and the like. Peracetic acid, urea hydroperoxide, nitric acid, ammonium chlorate, ammonium chlorate, ammonium iodate, ammonium perborate, ammonium perchlorate, ammonium periodate, ammonium persulfate, tetramethylammonium chlorate, tetra chlorate Examples thereof include methylammonium, tetramethylammonium iodate, tetramethylammonium perborate, tetramethylammonium perchlorate, tetramethylammonium periodate, tetramethylammonium persulfate, and hydrogen peroxide. These oxidizing agents may be used alone or in combination of two or more. The oxidizing agent is preferably hydrogen peroxide because a more remarkable effect can be obtained.
　エッチング液組成物中の（Ａ）成分の濃度は、０．１～２０質量％であり、好ましくは０．５～１０質量％、さらに好ましくは０．５～５質量％である。（Ａ）成分の濃度が０．１質量％未満であると、エッチング速度が著しく低下して生産性が低下するとともに、残渣が発生しやすくなる。一方、（Ａ）成分の濃度が２０質量％超であると、エッチング速度の制御が困難になる。 The concentration of the component (A) in the etching solution composition is 0.1 to 20% by mass, preferably 0.5 to 10% by mass, and more preferably 0.5 to 5% by mass. When the concentration of the component (A) is less than 0.1% by mass, the etching rate is remarkably lowered, the productivity is lowered, and a residue is likely to be generated. On the other hand, if the concentration of the component (A) exceeds 20% by mass, it becomes difficult to control the etching rate.
　（Ｂ）成分は、（ｉ）ジカルボン酸のアンモニウム塩、及び（ｉｉ）ジカルボン酸とアミン化合物若しくはアンモニウム化合物との組み合わせ、の少なくともいずれかの成分である。
　そして、この（Ｂ）成分を構成するジカルボン酸は、シュウ酸、又は無置換若しくは水酸基で置換された炭素数２以下のアルキレン鎖を有する有機酸である。無置換又は水酸基で置換された炭素数２以下のアルキレン鎖を有する有機酸としては、酒石酸、マロン酸、及びコハク酸等を挙げることができる。これらの有機酸は、１種単独で又は２種以上を組み合わせて用いることができる。より顕著な効果が得られることから、ジカルボン酸はコハク酸であることが好ましい。 The component (B) is at least one of (i) an ammonium salt of a dicarboxylic acid and (ii) a combination of a dicarboxylic acid and an amine compound or an ammonium compound.
The dicarboxylic acid constituting the component (B) is oxalic acid or an organic acid having an alkylene chain having 2 or less carbon atoms, which is unsubstituted or substituted with a hydroxyl group. Examples of the organic acid having an alkylene chain having 2 or less carbon atoms substituted with an unsubstituted or hydroxyl group include tartaric acid, malonic acid, and succinic acid. These organic acids can be used alone or in combination of two or more. The dicarboxylic acid is preferably succinic acid because a more remarkable effect can be obtained.
　また、（Ｂ）成分としては、ジカルボン酸のアンモニウム塩が好ましい。ジカルボン酸のアンモニウム塩としては、シュウ酸アンモニウム、コハク酸アンモニウム、及び酒石酸アンモニウム等を挙げることができる。これらのジカルボン酸のアンモニウム塩は、１種単独で又は２種以上を組み合わせて用いることができる。なかでも、より顕著な効果が得られることから、（Ｂ）成分はコハク酸アンモニウムであることが好ましい。 Further, as the component (B), an ammonium salt of a dicarboxylic acid is preferable. Examples of the ammonium salt of the dicarboxylic acid include ammonium oxalate, ammonium succinate, and ammonium tartrate. The ammonium salts of these dicarboxylic acids can be used alone or in combination of two or more. Among them, the component (B) is preferably ammonium succinate because a more remarkable effect can be obtained.
　アミン化合物としては、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、ヘキサエチレンヘプタミン、ヘプタエチレンオクタミン、オクタエチレンノナミン、ノナエチレンデカミン、ブチレンジアミン、ペンタメチレンジアミン、ヘキサメチレンジアミン、ヘプタメチレンジアミン、テトラメチルエチレンジアミン、ペンタメチルジエチレントリアミン、テトラメチルトリエチレンテトラミン、ペンタメチルトリエチレンテトラミン、及びヘキサメチルトリエチレンテトラミン等の鎖状アミン；シクロプロピルアミン、シクロブチルアミン、シクロペンチルアミン、シクロヘキシルアミン、シクロヘプチルアミン、シクロオクチルアミン、シクロノニルアミン、シクロデシルアミン、シクロウンデシルアミン、及びシクロドデシルアミンの脂環式アミン；アニリン、２－メチルアニリン、３－メチルアニリン、２，３－ジメチルアニリン、４－メチルアニリン、５－メチルアニリン、２－エチルアニリン、３－エチルアニリン、４－エチルアニリン、５－エチルアニリン、２，４－ジメチルアニリン、２，５－ジメチルアニリン、２－プロピルアニリン、及び２－ブチルアニリン等の芳香族アミン；等を挙げることができる。これらのアミン化合物は、１種単独で又は２種以上を組み合わせて用いることができる。 Examples of amine compounds include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, octaethylenenonamine, nonaethylenedecamine, butylene diamine, pentamethylenediamine, and hexamethylene. Chain amines such as diamine, heptamethylenediamine, tetramethylethylenediamine, pentamethyldiethylenetriamine, tetramethyltriethylenetetramine, pentamethyltriethylenetetramine, and hexamethyltriethylenetetramine; cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine , Cycloheptylamine, cyclooctylamine, cyclononylamine, cyclodecylamine, cycloundesylamine, and alicyclic amines of cyclododecylamine; aniline, 2-methylaniline, 3-methylaniline, 2,3-dimethylaniline , 4-Methylaniline, 5-Methylaniline, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, 5-ethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2-propylaniline, And aromatic amines such as 2-butylaniline; etc. These amine compounds can be used alone or in combination of two or more.
　アンモニウム化合物としては、アンモニア、炭酸水素アンモニウム、炭酸アンモニウム、水酸化テトラメチルアンモニウム、及び水酸化テトラエチルアンモニウム等を挙げることができる。これらのアンモニウム化合物は、１種単独で又は２種以上を組み合わせて用いることができる。 Examples of the ammonium compound include ammonia, ammonium hydrogencarbonate, ammonium carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like. These ammonium compounds can be used alone or in combination of two or more.
　エッチング液組成物中の（Ｂ）成分の濃度は、０．５～４０質量％であり、好ましくは１～３０質量％、さらに好ましくは２～１０質量％である。（Ｂ）成分の濃度が０．５質量％未満であると、サイドエッチング及び残渣の発生を抑制することが困難になる。一方、（Ｂ）成分の濃度が４０質量％超であると、（Ｂ）成分が溶解しにくくなる場合がある。 The concentration of the component (B) in the etching solution composition is 0.5 to 40% by mass, preferably 1 to 30% by mass, and more preferably 2 to 10% by mass. If the concentration of the component (B) is less than 0.5% by mass, it becomes difficult to suppress side etching and the generation of residues. On the other hand, if the concentration of the component (B) exceeds 40% by mass, the component (B) may be difficult to dissolve.
　本実施形態のエッチング液組成物は、水を含有する。すなわち、本実施形態のエッチング液組成物は、（Ａ）成分及び（Ｂ）成分が水に溶解した水溶液である。エッチング液組成物の２５℃におけるｐＨは、５．５～１０であることが好ましい。エッチング液のｐＨが上記の数値範囲外であると、銀含有層のエッチングの制御がやや困難になることがある。なお、形成される配線の直線性が向上することから、エッチング液の２５℃におけるｐＨはｐＨ６～９であることがさらに好ましい。 The etching solution composition of this embodiment contains water. That is, the etching solution composition of the present embodiment is an aqueous solution in which the components (A) and (B) are dissolved in water. The pH of the etching solution composition at 25 ° C. is preferably 5.5 to 10. If the pH of the etching solution is out of the above numerical range, it may be somewhat difficult to control the etching of the silver-containing layer. The pH of the etching solution at 25 ° C. is more preferably pH 6 to 9 because the linearity of the formed wiring is improved.
　本実施形態のエッチング液組成物には、本発明の効果を損なわない範囲で、必要に応じて、周知の添加剤を含有させることができる。含有させることができる添加剤としては、還元剤、界面活性剤、安定化剤、可溶化剤、消泡剤、比重調整剤、粘度調整剤、濡れ性改善剤、ポリアルキレングリコール、有機酸、アミノ酸類、アゾール類、ピリミジン類、チオ尿素類、アミン類、アルキルピロリドン類、有機キレート剤、ポリアクリルアミド類、過硫酸塩、及びｐＨ調整剤等を挙げることができる。エッチング液組成物中の添加剤の濃度は、エッチング液組成物全体を基準として、０．００１～５０質量％であることが好ましい。 The etching solution composition of the present embodiment may contain a well-known additive, if necessary, as long as the effects of the present invention are not impaired. Additives that can be contained include reducing agents, surfactants, stabilizers, solubilizers, defoamers, specific gravity regulators, viscosity regulators, wettability improvers, polyalkylene glycols, organic acids, amino acids. Classes, azoles, pyrimidines, thioureas, amines, alkylpyrrolidones, organic chelating agents, polyacrylamides, persulfates, pH regulators and the like. The concentration of the additive in the etching solution composition is preferably 0.001 to 50% by mass based on the entire etching solution composition.
　エッチング液組成物のエッチング速度が速い場合、還元剤を添加することが好ましい。還元剤としては、例えば、エッチング液組成物に溶解しうる金属粉、亜硝酸ナトリウム、及び次亜燐酸ナトリウム等を挙げることができる。 When the etching rate of the etching solution composition is high, it is preferable to add a reducing agent. Examples of the reducing agent include metal powder, sodium nitrite, and sodium hypochlorite that can be dissolved in the etching solution composition.
　界面活性剤としては、例えば、フルオロアルキルベタイン、及びフルオロアルキルポリオキシエチレンエーテル等のフッ素系両性界面活性剤；ノニオン系界面活性剤；等を挙げることができる。 Examples of the surfactant include fluorine-based amphoteric surfactants such as fluoroalkyl betaine and fluoroalkyl polyoxyethylene ether; nonionic surfactants; and the like.
　安定化剤としては、例えば、２－アミノ－２－メチル－１－プロパノール、１－アミノ－２－プロパノール、２－アミノエタノール、及び水酸化テトラメチルアンモニウム等のアミン化合物；１，２，４－１Ｈ－トリアゾール、１Ｈ－ベンゾトリアゾール、５－メチル－１Ｈ－ベンゾトリアゾール、３－アミノ－１Ｈ－１，２，４－トリアゾール、１Ｈ－テトラゾール、５－メチル－１Ｈ－テトラゾール、５－フェニル－１Ｈ－テトラゾール、及び５－アミノ－１Ｈ－テトラゾール等のアゾール類；フェニル尿素、アリル尿素、１，３－ジメチル尿素、及びチオ尿素等の尿素類；フェノールスルホン酸、ベンゼンスルホン酸、及びクレゾールスルホン酸等の芳香族スルホン酸類；メタンスルホン酸、及びエタンスルホン酸等のアルカンスルホン酸類；フェニルエチレングリコール、１－プロパノール、２－プロパノール、及び２－ブトキシエタノール等のアルコール類；等を挙げることができる。 Stabilizers include, for example, amine compounds such as 2-amino-2-methyl-1-propanol, 1-amino-2-propanol, 2-aminoethanol, and tetramethylammonium hydroxide; 1,2,4- 1H-triazole, 1H-benzotriazole, 5-methyl-1H-benzotriazole, 3-amino-1H-1,2,4-triazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H- Azole such as tetrazole and 5-amino-1H-tetrazole; ureas such as phenylurea, allylurea, 1,3-dimethylurea, and thiourea; Aromatic sulfonic acids; alkane sulfonic acids such as methane sulfonic acid and ethane sulfonic acid; alcohols such as phenylethylene glycol, 1-propanol, 2-propanol, and 2-butoxyethanol; and the like.
　可溶化剤は、水と混和可能であるとともに、エッチング残留物の除去を促進しうる成分であることが好ましい。可溶化剤としては、例えば、スルホラン、Ｎ－メチルピロリドン、及びジメチルスルホキシド等を挙げることができる。 The solubilizer is preferably a component that is miscible with water and can promote the removal of etching residues. Examples of the solubilizer include sulfolane, N-methylpyrrolidone, dimethyl sulfoxide and the like.
　消泡剤としては、例えば、シリコン消泡剤、長鎖アルコール消泡剤、脂肪酸エステル消泡剤、金属石鹸消泡剤、及びエチレンオキサイドプロピレンオキサイド共重合体等を挙げることができる。 Examples of the defoaming agent include a silicon defoaming agent, a long-chain alcohol defoaming agent, a fatty acid ester defoaming agent, a metal soap defoaming agent, and an ethylene oxide propylene oxide copolymer.
　比重調整剤としては、比重調整用の物質を溶媒に溶解させた溶液や、希釈水を用いることができる。比重調整用の物質としては、その溶液が銀含有層を腐食又は剥離させないものであれば用いることができる。比重調整用の物質としては、例えば、純水、イオン交換水、水道水、ショ糖等の糖類、食用塩、及び尿素等を挙げることができる。 As the specific gravity adjusting agent, a solution in which a substance for adjusting the specific gravity is dissolved in a solvent or diluted water can be used. As the substance for adjusting the specific gravity, any substance can be used as long as the solution does not corrode or exfoliate the silver-containing layer. Examples of the substance for adjusting the specific gravity include pure water, ion-exchanged water, tap water, sugars such as sucrose, edible salt, urea and the like.
　粘度調整剤としては、エッチング液組成物との相溶性を有するものを用いることが好ましい。粘度調整剤としては、例えば、ソルビトール、低分子量ポリビニルピロリドン、ポリビニルアルコール、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロースの水溶液、ヒドロキシプロピルセルロースのゾル、及び希釈水等を挙げることができる。 As the viscosity modifier, it is preferable to use one having compatibility with the etching solution composition. Examples of the viscosity modifier include sorbitol, low molecular weight polyvinylpyrrolidone, polyvinyl alcohol, hydroxyethyl cellulose, an aqueous solution of hydroxypropyl cellulose, a sol of hydroxypropyl cellulose, and diluted water.
　濡れ性改善剤は、銀含有層のスリット溝等に存在する空気を排除しやすくするとともに、脱脂効果等を得ること等を目的としてエッチング液組成物に添加される。 The wettability improving agent is added to the etching solution composition for the purpose of facilitating the removal of air existing in the slit groove of the silver-containing layer and obtaining a degreasing effect.
　ポリアルキレングリコールとしては、例えば、ポリエチレングリコール；ポリエチレングリコールジメチルエーテル；エチレングリコール、プロピレングリコール、１，３－ブタノール、１，４－ブタノール等のジオールに、エチレンオキサイドやプロピレンオキサイドをブロック又はランダムに付加させたポリアルキレングリコール；等を挙げることができる。 As the polyalkylene glycol, for example, ethylene oxide or propylene oxide is blocked or randomly added to diols such as polyethylene glycol; polyethylene glycol dimethyl ether; ethylene glycol, propylene glycol, 1,3-butanol, and 1,4-butanol. Polyalkylene glycol; etc. can be mentioned.
　有機酸としては、例えば、ギ酸、酢酸、プロピオン酸、酪酸、吉草酸、カプロン酸、アクリル酸、クロトン酸、イソクロトン酸、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、マレイン酸、フマル酸、リンゴ酸、酒石酸、クエン酸、グリコール酸、乳酸、スルファミン酸、ニコチン酸、アスコルビン酸、ヒドロキシピバリン酸、レブリン酸、及びβ－クロロプロピオン酸等を挙げることができる。 Examples of organic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, acrylic acid, crotonic acid, isocrotonic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, malein. Examples thereof include acids, fumaric acid, malic acid, tartaric acid, citric acid, glycolic acid, lactic acid, sulfamic acid, nicotinic acid, ascorbic acid, hydroxypivalic acid, levulinic acid, β-chloropropionic acid and the like.
　アミノ酸類としては、例えば、グリシン、アラニン、バリン、ロイシン、セリン、フェニルアラニン、トリプトファン、グルタミン酸、アスパラギン酸、リシン、及びアルギニン、ヒスチジン等のアミノ酸；これらのアミノ酸のアルカリ金属塩及びアンモニウム塩等を挙げることができる。 Examples of amino acids include amino acids such as glycine, alanine, valine, leucine, serine, phenylalanine, tryptophan, glutamic acid, aspartic acid, lysine, and arginine and histidine; alkali metal salts and ammonium salts of these amino acids. Can be done.
　アゾール類としては、例えば、イミダゾール、２－メチルイミダゾール、２－ウンデシル－４－メチルイミダゾール、２－フェニルイミダゾール、及び２－メチルベンゾイミダゾール等のアルキルイミダゾール類；ベンゾイミダゾール、２－メチルベンゾイミダゾール、２－ウンデシルベンゾイミダゾール、２－フェニルベンゾイミダゾール、及び２－メルカプトベンゾイミダゾール等のベンゾイミダゾール類；１，２，３－トリアゾール、１，２，４－トリアゾール、５－フェニル－１，２，４－トリアゾール、５－アミノ－１，２，４－トリアゾール、１，２，３－ベンゾトリアゾール、１－アミノベンゾトリアゾール、４－アミノベンゾトリアゾール、１－ビスアミノメチルベンゾトリアゾール、１－メチル－ベンゾトリアゾール、トリルトリアゾール、１－ヒドロキシベンゾトリアゾール、５－メチル－１Ｈ－ベンゾトリアゾール、及び５－クロロベンゾトリアゾール等のトリアゾール類；１Ｈ－テトラゾール、５－アミノ－１Ｈ－テトラゾール、５－メチル－１Ｈ－テトラゾール、５－フェニル－１Ｈ－テトラゾール、５－メルカプト－１Ｈ－テトラゾール、１－フェニル－５－メルカプト－１Ｈ－テトラゾール、１－シクロヘキシル－５－メルカプト－１Ｈ－テトラゾール、及び５，５’－ビス－１Ｈ－テトラゾール等のテトラゾール類；ベンゾチアゾール、２－メルカプトベンゾチアゾール、２－フェニルチアゾール、２－アミノベンゾチアゾール、２－アミノ－６－ニトロベンゾチアゾール、２－アミノ－６－メトキシベンゾチアゾール、及び２－アミノ－６－クロロベンゾチアゾール等のチアゾール類；等を挙げることができる。 Examples of azoles include alkyl imidazoles such as imidazole, 2-methyl imidazole, 2-undecyl-4-methyl imidazole, 2-phenyl imidazole, and 2-methyl benzo imidazole; benzo imidazole, 2-methyl benzo imidazole, 2 -Benzoimidazoles such as undecylbenzomidazole, 2-phenylbenzoimidazole, and 2-mercaptobenzomidazole; 1,2,3-triazole, 1,2,4-triazole, 5-phenyl-1,2,4- Triazole, 5-amino-1,2,4-triazole, 1,2,3-benzotriazole, 1-aminobenzotriazole, 4-aminobenzotriazole, 1-bisaminomethylbenzotriazole, 1-methyl-benzotriazole, Triazoles such as tririltriazole, 1-hydroxybenzotriazole, 5-methyl-1H-benzotriazole, and 5-chlorobenzotriazole; 1H-tetrazole, 5-amino-1H-tetrazole, 5-methyl-1H-tetrazole, 5 -Phenyl-1H-tetrazole, 5-mercapto-1H-tetrazole, 1-phenyl-5-mercapto-1H-tetrazole, 1-cyclohexyl-5-mercapto-1H-tetrazole, and 5,5'-bis-1H-tetrazole Tetrazoles such as: benzotriazole, 2-mercaptobenzotriazole, 2-phenylthiazole, 2-aminobenzotriazole, 2-amino-6-nitrobenzotriazole, 2-amino-6-methoxybenzotriazole, and 2-amino- Thiazols such as 6-chlorobenzotriazole; and the like can be mentioned.
　ピリミジン類としては、例えば、ジアミノピリミジン、トリアミノピリミジン、テトラアミノピリミジン、及びメルカプトピリミジン等を挙げることができる。 Examples of pyrimidines include diaminopyrimidine, triaminopyrimidine, tetraaminopyrimidine, and mercaptopyrimidine.
　チオ尿素類としては、例えば、チオ尿素、エチレンチオ尿素、チオジグリコール、及びメルカプタン等を挙げることができる。 Examples of thioureas include thiourea, ethylenethiourea, thiodiglycol, and mercaptan.
　アミン類としては、例えば、ジアミルアミン、ジブチルアミン、トリエチルアミン、トリアミルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノイソプロパノールアミン、ジイソプロパノールアミン、トリイソプロパノールアミン、エタノールイソプロパノールアミン、ジエタノールイソプロパノールアミン、エタノールジイソプロパノールアミン、ポリアリルアミン、ポリビニルピリジン、及びこれらの塩酸塩等を挙げることができる。 Examples of amines include diamylamine, dibutylamine, triethylamine, triamylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, ethanolisopropanolamine, diethanolisopropanolamine, ethanoldi. Examples thereof include isopropanolamine, polyallylamine, polyvinylpyridine, and hydrochlorides thereof.
　アルキルピロリドン類としては、例えば、Ｎ－メチル－２－ピロリドン、Ｎ－エチル－２－ピロリドン、Ｎ－プロピル－２－ピロリドン、Ｎ－ブチル－２－ピロリドン、Ｎ－アミル－２－ピロリドン、Ｎ－ヘキシル－２－ピロリドン、Ｎ－ヘプチル－２－ピロリドン、及びＮ－オクチル－２－ピロリドン等を挙げることができる。 Examples of alkylpyrrolidones include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-butyl-2-pyrrolidone, N-amyl-2-pyrrolidone, and N-. Hexyl-2-pyrrolidone, N-heptyl-2-pyrrolidone, N-octyl-2-pyrrolidone and the like can be mentioned.
　有機キレート剤としては、例えば、エチレンジアミン四酢酸、ジエチレントリアミン五酢酸、トリエチレンテトラミン六酢酸、テトラエチレンペンタミン七酢酸、ペンタエチレンヘキサミン八酢酸、ニトリロ三酢酸、及びこれらのアルカリ金属（好ましくはナトリウム）塩等のアミノカルボン酸系キレート剤；ヒドロキシエチリデンジホスホン酸、ニトリロトリスメチレンホスホン酸、ホスホノブタントリカルボン酸、及びこれらのアルカリ金属（好ましくはナトリウム）塩等のホスホン酸系キレート剤；シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、マレイン酸、フマル酸、リンゴ酸、酒石酸、クエン酸、これらの無水物、及びこれらのアルカリ金属（好ましくはナトリウム）塩等の２価以上のカルボン酸化合物、又は２価以上のカルボン酸化合物が脱水した一無水物や二無水物等を挙げることができる。エッチング液組成物中の有機キレート剤の濃度は、例えば０．０１～４０質量％であればよい。 Examples of the organic chelating agent include ethylenediamine tetraacetic acid, diethylenetriaminepentacetic acid, triethylenetetraminehexacetic acid, tetraethylenepentamineriacetic acid, pentaethylenehexamineoctacetic acid, nitrilotriacetic acid, and alkali metal (preferably sodium) salts thereof. Aminocarboxylic acid-based chelating agents such as hydroxyethylidene diphosphonic acid, nitrilotrismethylenephosphonic acid, phosphonobutanetricarboxylic acid, and phosphonic acid-based chelating agents such as alkali metal (preferably sodium) salts thereof; oxalic acid, malon Divalent or higher valents of acids, succinic acid, glutaric acid, adipic acid, pimeric acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid, these anhydrides, and alkali metal (preferably sodium) salts thereof. Examples thereof include a carboxylic acid compound, and a monoan anhydride or a dianhydride obtained by dehydrating a divalent or higher carboxylic acid compound. The concentration of the organic chelating agent in the etching solution composition may be, for example, 0.01 to 40% by mass.
　ポリアクリルアミド類としては、例えば、ポリアクリルアミド、及びｔｅｒｔ－ブチルアクリルアミドスルホン酸等を挙げることができる。 Examples of polyacrylamides include polyacrylamide and tert-butylacrylamide sulfonic acid.
　過硫酸塩としては、例えば、過硫酸アンモニウム、過硫酸ナトリウム、及び過硫酸カリウム等を挙げることができる。 Examples of the persulfate include ammonium persulfate, sodium persulfate, potassium persulfate and the like.
　ｐＨ調整剤は、塩基又は酸を含有する成分である。塩基としては、例えば、アミン、ジグリコールアミン、トリエタノールアミン、水酸化テトラブチルホスホニウム、一級アミン化合物、二級アミン化合物、及び三級アミン化合物等を挙げることができる。酸としては、例えば、硫酸、硝酸、リン酸、フッ化水素酸、及び臭化水素酸等の無機酸；カルボン酸、アミノ酸、ヒドロキシカルボン酸、及びポリカルボン酸等の有機酸；等を挙げることができる。 A pH adjuster is a component containing a base or an acid. Examples of the base include amines, diglycolamines, triethanolamines, tetrabutylphosphonium hydroxides, primary amine compounds, secondary amine compounds, tertiary amine compounds and the like. Examples of the acid include inorganic acids such as sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, and hydrofluoric acid; organic acids such as carboxylic acids, amino acids, hydroxycarboxylic acids, and polycarboxylic acids; and the like. Can be done.
　本実施形態のエッチング液組成物の具体的な用途としては、例えば、銀含有層向けの除去剤、表面平滑化剤、表面粗化剤、パターン形成用薬剤、基体に微量付着した銀成分の洗浄液等を挙げることができる。 Specific uses of the etching solution composition of the present embodiment include, for example, a removing agent for a silver-containing layer, a surface smoothing agent, a surface roughening agent, a pattern-forming agent, and a cleaning solution of a silver component slightly adhering to a substrate. And so on.
　次に、本発明の一実施形態であるエッチング方法について説明する。本実施形態のエッチング方法は、前述のエッチング液組成物を用いて銀含有層をエッチングする工程を有する。より具体的には、まず、基板上の所定領域に銀含有層（例えば、金属膜等）を形成した材料を用意し、エッチングレジストを用いて銀含有層の必要な部分をマスクしてマスク領域を形成する。次いで、マスク領域以外の領域（非マスク領域）の銀含有層を、前述のエッチング液組成物でエッチングして除去する。非マスク領域の銀含有層をエッチングする方法は特に限定されず、一般的なエッチング方法を用いることができる。例えば、ディップ式、スプレー式、スピン式等によるエッチング方法を挙げることができる。また、非マスク領域の銀含有層をエッチングする条件は特に限定されず、バッチ式、フロー式、エッチャントの酸化還元電位、比重、酸濃度によるオートコントロール式等の周知一般の様々な方式を採用することができる。 Next, an etching method according to an embodiment of the present invention will be described. The etching method of the present embodiment includes a step of etching the silver-containing layer using the above-mentioned etching solution composition. More specifically, first, a material in which a silver-containing layer (for example, a metal film) is formed in a predetermined region on a substrate is prepared, and an etching resist is used to mask a necessary portion of the silver-containing layer to mask a mask region. To form. Next, the silver-containing layer in the region other than the mask region (non-mask region) is removed by etching with the above-mentioned etching solution composition. The method for etching the silver-containing layer in the non-masked region is not particularly limited, and a general etching method can be used. For example, an etching method such as a dip type, a spray type, or a spin type can be mentioned. Further, the conditions for etching the silver-containing layer in the non-masked region are not particularly limited, and various well-known general methods such as batch type, flow type, redox potential of etchant, specific gravity, and auto-control type based on acid concentration are adopted. be able to.
　ディップ式のエッチング方法によって、基板上に銀含有層が形成された材料をエッチングする場合、この材料を適切なエッチング条件にてエッチング液組成物に浸漬した後、引き上げることで、基板上の銀含有層をエッチングすることができる。 When a material having a silver-containing layer formed on a substrate is etched by a dip-type etching method, the material is immersed in an etching solution composition under appropriate etching conditions and then pulled up to contain silver on the substrate. The layer can be etched.
　ディップ式のエッチング方法におけるエッチング条件は、被エッチング材料の銀含有層の形状や膜厚等に応じて任意に設定すればよい。一般的なエッチングを行う場合のエッチング温度は１０～４０℃とすることが好ましく、２０～４０℃とすることがさらに好ましい。エッチング液組成物の温度は反応熱により上昇することがある。このため、必要に応じて、エッチング液組成物の温度を上記の範囲内に維持するように公知の手段によって温度制御することが好ましい。また、エッチング時間は、エッチングが完了するのに十分な時間とすればよく、特に限定されない。例えば、銀含有層の膜厚が１ｎｍ～１μｍ程度であれば、上記の温度範囲で１０秒～１時間程度エッチングすればよい。 The etching conditions in the dip-type etching method may be arbitrarily set according to the shape and film thickness of the silver-containing layer of the material to be etched. The etching temperature for general etching is preferably 10 to 40 ° C, more preferably 20 to 40 ° C. The temperature of the etching solution composition may rise due to the heat of reaction. Therefore, if necessary, it is preferable to control the temperature of the etching solution composition by a known means so as to maintain the temperature within the above range. Further, the etching time may be a time sufficient to complete the etching, and is not particularly limited. For example, if the film thickness of the silver-containing layer is about 1 nm to 1 μm, etching may be performed in the above temperature range for about 10 seconds to 1 hour.
　スプレー式のエッチング方法によって、基板上に銀含有層が形成された材料をエッチングする場合、エッチング液組成物を適切な条件で材料に噴霧することで、基板上の銀含有層をエッチングすることができる。 When etching a material in which a silver-containing layer is formed on a substrate by a spray-type etching method, the silver-containing layer on the substrate can be etched by spraying the etching solution composition onto the material under appropriate conditions. it can.
　スプレー式のエッチング方法におけるエッチング条件は、銀含有層の形状や膜厚等に応じて任意に設定すればよい。例えば、一般的なエッチングを行う場合、エッチング液組成物を噴霧するときのスプレー圧は、０．０１～１．０ＭＰａの範囲から選択することができ、好ましくは０．０２～０．１ＭＰａの範囲、さらに好ましくは０．０３～０．０８ＭＰａの範囲である。スプレー圧を０．０３～０．０８ＭＰａの範囲とすると、配線部分の銀含有層の上部の幅と下部の幅との差を非常に小さくできるために特に好ましい。エッチング温度は、１０～５０℃の範囲が好ましく、２０～５０℃の範囲がさらに好ましい。エッチング液組成物の温度は、反応熱により上昇することがある。このため、必要に応じて、エッチング液組成物の温度を上記の範囲内に維持できるように公知の手段によって温度制御してもよい。また、エッチング時間は、エッチングが完了するのに十分な時間とすればよく、特に限定されない。例えば、膜厚１ｎｍ～１μｍ程度であれば、上記の温度範囲で１０秒～１時間程度エッチングすればよい。 The etching conditions in the spray-type etching method may be arbitrarily set according to the shape and film thickness of the silver-containing layer. For example, when performing general etching, the spray pressure when spraying the etching solution composition can be selected from the range of 0.01 to 1.0 MPa, preferably in the range of 0.02 to 0.1 MPa. , More preferably in the range of 0.03 to 0.08 MPa. The spray pressure in the range of 0.03 to 0.08 MPa is particularly preferable because the difference between the upper width and the lower width of the silver-containing layer in the wiring portion can be made very small. The etching temperature is preferably in the range of 10 to 50 ° C, more preferably in the range of 20 to 50 ° C. The temperature of the etching solution composition may rise due to the heat of reaction. Therefore, if necessary, the temperature may be controlled by a known means so that the temperature of the etching solution composition can be maintained within the above range. Further, the etching time may be a time sufficient to complete the etching, and is not particularly limited. For example, if the film thickness is about 1 nm to 1 μm, etching may be performed in the above temperature range for about 10 seconds to 1 hour.
　本実施形態のエッチング方法は、エッチングの繰り返しによるエッチング液組成物の劣化を回復させるために、エッチング液組成物に補給液を加える工程をさらに有することが好ましい。特に、オートコントロール式のエッチングの場合、エッチング装置に補給液を予めセットしておけば、エッチング液組成物に補給液を適宜添加することができる。補給液としては、例えば、前述の（Ａ）成分や（Ｂ）成分を含有する水溶液を用いることができる。各成分の濃度は、エッチング液組成物中の各成分の濃度の３～２０倍程度とすればよい。この補給液には、エッチング液組成物に必須又は任意で使用される前述の各成分を必要に応じて添加してもよい。 It is preferable that the etching method of the present embodiment further includes a step of adding a replenishing liquid to the etching liquid composition in order to recover the deterioration of the etching liquid composition due to repeated etching. In particular, in the case of auto-control type etching, if a replenisher is set in the etching apparatus in advance, the replenisher can be appropriately added to the etching solution composition. As the replenisher, for example, an aqueous solution containing the above-mentioned component (A) and component (B) can be used. The concentration of each component may be about 3 to 20 times the concentration of each component in the etching solution composition. Each of the above-mentioned components essential or optionally used in the etching solution composition may be added to the supplement solution, if necessary.
　上記のエッチング液組成物を用いる本発明の一実施形態であるエッチング方法によれば、サイドエッチングを抑制して精密な回路配線を形成することができる。このため、本発明の一実施形態であるエッチング液組成物は、タッチセンサー用の電極形成等のプリント配線基板の他、ファインピッチが要求されるパッケージ用基板、ＣＯＦ、ＴＡＢ用途のサブトラクティブ法、及びセミアディティブ法の回路形成に好適に使用することができる。 According to the etching method according to the embodiment of the present invention using the above-mentioned etching solution composition, side etching can be suppressed and a precise circuit wiring can be formed. Therefore, the etching solution composition according to the embodiment of the present invention includes a printed wiring board for forming electrodes for a touch sensor, a packaging substrate that requires a fine pitch, and a subtractive method for COF and TAB. And can be suitably used for circuit formation of the semi-additive method.
　以下、実施例及び比較例を用いて本発明をさらに詳細に説明する。しかしながら、本発明は以下の実施例等によって制限を受けるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited by the following examples and the like.
＜エッチング液組成物の調製＞
（実施組成物１～９、比較組成物１～５）
　表１に示す配合となるように各成分を混合してエッチング液組成物（実施組成物１～９及び比較組成物１～５）を調製した。表１中の「ｐＨ値」は、製造直後のエッチング液組成物の２５℃におけるｐＨ値である。また、表１中の括弧内の数値は、エッチング液組成物全体を基準とする各成分の含有量（質量％）である。 <Preparation of etching solution composition>
(Implemented compositions 1-9, comparative compositions 1-5)
Etching liquid compositions (implemented compositions 1 to 9 and comparative compositions 1 to 5) were prepared by mixing each component so as to have the formulations shown in Table 1. The “pH value” in Table 1 is the pH value of the etching solution composition immediately after production at 25 ° C. The numerical values in parentheses in Table 1 are the contents (mass%) of each component based on the entire etching solution composition.
Figure JPOXMLDOC01-appb-I000001
Figure JPOXMLDOC01-appb-I000001
＜エッチング方法＞
（実施例１～９、比較例１～５）
　厚さ１００ｎｍの銀－パラジウム－銅合金（製品名「ＡＰＣ」、フルヤ金属社製）からなる層（銀含有層）をガラス基板上に積層した基体を用意した。この基体の銀含有層上に、ネガ型ドライフィルムを用いて、幅６０μｍ、開口部６０μｍのレジストパターンを形成した後、５０ｍｍ×５０ｍｍのサイズに切断してテストピースを得た。得られたテストピースに対し、調製したエッチング液組成物をそれぞれ用いて、３５℃、スプレー圧０．０５ＭＰａ、及び所定のエッチング処理時間（表２）の条件でスプレー法によるエッチングを行って、評価用パターンを形成した。なお、比較例１及び比較例２については、１８０秒以上エッチング処理しても、目的とする形状のパターンを形成することができなかった。 <Etching method>
(Examples 1 to 9, Comparative Examples 1 to 5)
A substrate having a layer (silver-containing layer) made of a silver-palladium-copper alloy (product name "APC", manufactured by Furuya Metal Co., Ltd.) having a thickness of 100 nm laminated on a glass substrate was prepared. A resist pattern having a width of 60 μm and an opening of 60 μm was formed on the silver-containing layer of this substrate using a negative dry film, and then cut into a size of 50 mm × 50 mm to obtain a test piece. The obtained test pieces were evaluated by etching using the prepared etching solution compositions under the conditions of 35 ° C., a spray pressure of 0.05 MPa, and a predetermined etching treatment time (Table 2). Pattern was formed. In Comparative Example 1 and Comparative Example 2, a pattern having a desired shape could not be formed even after etching for 180 seconds or longer.
＜評価＞
（１）Ｓ．Ｅ．幅
　レーザー顕微鏡を使用して、エッチング処理前のレジストパターンのスペース幅（μｍ）、及びエッチング処理後にレジストパターンを剥離して観察される配線間のスペース幅（μｍ）を計測した。そして、下記式（１）により、Ｓ．Ｅ．幅（μｍ）を算出した。結果を表２に示す。
　Ｓ．Ｅ．幅（μｍ）＝（Ａ－Ｂ）／２　　・・・（１）
　　Ａ：レジストパターンのスペース幅（μｍ）
　　Ｂ：配線間のスペース幅（μｍ） <Evaluation>
(1) S. E. Width Using a laser microscope, the space width (μm) of the resist pattern before the etching treatment and the space width (μm) between the wires observed by peeling the resist pattern after the etching treatment were measured. Then, according to the following equation (1), S.I. E. The width (μm) was calculated. The results are shown in Table 2.
S. E. Width (μm) = (AB) / 2 ... (1)
A: Space width (μm) of resist pattern
B: Space width between wirings (μm)
（２）残渣
　エッチング処理後にレジストパターンを剥離し、電界放出型走査電子顕微鏡（ＦＥ－ＳＥＭ）を使用して、配線部分の銀含有層の表面における残渣の有無を確認した。残渣を確認できなかった場合を「無し」と評価し、残渣を確認できた場合を「有り」と評価した。結果を表２に示す。 (2) Residue After the etching treatment, the resist pattern was peeled off, and the presence or absence of residue on the surface of the silver-containing layer of the wiring portion was confirmed using a field emission scanning electron microscope (FE-SEM). The case where the residue could not be confirmed was evaluated as "none", and the case where the residue could be confirmed was evaluated as "present". The results are shown in Table 2.
Figure JPOXMLDOC01-appb-I000002
Figure JPOXMLDOC01-appb-I000002
　表２に示す結果から、酢酸アンモニウム、アジピン酸アンモニウム、又はクエン酸三アンモニウムを（Ｂ）成分として含有するエッチング液組成物を用いてエッチングすると、サイドエッチング量が多くなるとともに、銀含有層の表面に残渣が発生することがわかる（比較例３～５）。また、コハク酸やコハク酸ナトリウムを（Ｂ）成分として含有するが、アミン化合物やアンモニウム化合物との組み合わせでない場合、又はアンモニウム塩ではない場合には、ほとんどエッチングできなかったことがわかる（比較例１及び２）。これに対し、実施組成物１～９のエッチング液組成物を用いてエッチングした場合には、サイドエッチング量を抑制することができるとともに、残渣が発生せず、良好な回路配線が形成されることがわかる（実施例１～９）。

  From the results shown in Table 2, when etching is performed using an etching solution composition containing ammonium acetate, ammonium adipate, or triammonium citrate as the component (B), the amount of side etching increases and the surface of the silver-containing layer is increased. It can be seen that a residue is generated in (Comparative Examples 3 to 5). Further, it can be seen that when succinic acid or sodium succinate is contained as the component (B), but it is not a combination with an amine compound or an ammonium compound, or when it is not an ammonium salt, it can hardly be etched (Comparative Example 1). And 2). On the other hand, when etching is performed using the etching solution compositions of the implementation compositions 1 to 9, the amount of side etching can be suppressed, no residue is generated, and good circuit wiring is formed. Can be understood (Examples 1 to 9).

Claims (6)

  1. 　銀含有層をエッチングするために用いられるエッチング液組成物であって、
    　（Ａ）成分：酸化剤０．１～２０質量％、
    　（Ｂ）成分：（ｉ）ジカルボン酸のアンモニウム塩、及び（ｉｉ）前記ジカルボン酸とアミン化合物若しくはアンモニウム化合物との組み合わせ、の少なくともいずれかの成分０．５～４０質量％、並びに
    　水を含有し、
    　前記ジカルボン酸が、シュウ酸、又は無置換若しくは水酸基で置換された炭素数２以下のアルキレン鎖を有する有機酸であるエッチング液組成物。     An etching solution composition used for etching a silver-containing layer.
    Component (A): Oxidizing agent 0.1 to 20% by mass,
    (B) Component: Contains 0.5 to 40% by mass of at least one of (i) an ammonium salt of a dicarboxylic acid and (ii) a combination of the dicarboxylic acid and an amine compound or an ammonium compound, and water. ,
    An etching solution composition in which the dicarboxylic acid is oxalic acid or an organic acid having an alkylene chain having 2 or less carbon atoms substituted with an unsubstituted or hydroxyl group.
  2. 　前記酸化剤が、過酸化水素である請求項１に記載のエッチング液組成物。 The etching solution composition according to claim 1, wherein the oxidizing agent is hydrogen peroxide.
  3. 　前記ジカルボン酸が、コハク酸である請求項１又は２に記載のエッチング液組成物。 The etching solution composition according to claim 1 or 2, wherein the dicarboxylic acid is succinic acid.
  4. 　前記（Ｂ）成分が、コハク酸アンモニウムである請求項１又は２に記載のエッチング液組成物。 The etching solution composition according to claim 1 or 2, wherein the component (B) is ammonium succinate.
  5. 　前記銀含有層が、銀又は銀合金を含有する請求項１～４のいずれか一項に記載のエッチング液組成物。 The etching solution composition according to any one of claims 1 to 4, wherein the silver-containing layer contains silver or a silver alloy.
  6. 　請求項１～５のいずれか一項に記載のエッチング液組成物を用いて銀含有層をエッチングする工程を有するエッチング方法。

          An etching method comprising a step of etching a silver-containing layer using the etching solution composition according to any one of claims 1 to 5.
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