TW201803969A - Etching liquid composition and etching method - Google Patents

Abstract

The present invention is an etching solution composition useful for etching an indium oxide-based layer that can form an indium oxide-based layer with a small narrow width, good linearity, and a desired width even if it does not contain hydrogen chloride, and contains: (A ) 0.01 to 15% by mass of hydrogen peroxide; (B) 1 to 40% by mass of sulfuric acid; (C) (C-1) The following general formula (1): (R ¹ , R ² , and R ³ : hydrogen, carbon atoms) (1 to 8 alkyl groups, etc.) 0.01 to 10% by mass of the amido compound, or 0.01 to 20% by mass of the (C-2) amino acid compound; and water.

Description

Etching liquid composition and etching method

The present invention relates to an etchant composition and an etching method using the same. More specifically, the present invention relates to an etchant composition for etching an indium oxide-based layer and an etching method using the same.

Various techniques are known for wet etching of indium oxide-based layers used in transparent conductive films and the like. Among them, from the viewpoint of being inexpensive and having a good etching rate, an aqueous solution containing hydrochloric acid is often used as an etching solution composition.

For example, Patent Document 1 discloses an etching solution composition for indium-tin oxide (hereinafter also referred to as "ITO") containing ferric chloride and hydrochloric acid.

In addition, as for an etchant that does not use hydrochloric acid, for example, Patent Document 2 discloses an etchant of copper or a copper alloy, and an aqueous solution containing a second copper ion, an organic acid, a halogen ion, an azole, and a polyalkylene glycol.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2009-231427

[Patent Document 2] Japanese Patent Laid-Open No. 2006-111953

However, if an etching solution containing hydrogen chloride as the etching solution composition disclosed in Patent Document 1 is used to collectively etch an ITO layer or a laminated body composed of an ITO layer and a copper layer, it may easily occur: a substrate or a peripheral member Problems such as discoloration, roughening of the surface of the base material or the peripheral member, elution of metal components from the surface of the base material or the peripheral member, and poor linearity of the formed thin line occur.

In addition, if an etching solution containing no hydrogen chloride is used as the etchant disclosed in Patent Document 2, if the ITO layer or the laminated body composed of the ITO layer and the copper layer is collectively etched, the thickness of the formed thin line is large. It is difficult to form a thin line of a desired width, and the straightness of the thin line is reduced, and defects such as a defect appearing in the upper portion of the thin line. In addition, if the etching process is continued after the etching between the thin lines is finished, there may be a problem that the thin lines are further thinned.

Therefore, the present invention has been made to solve the above-mentioned problems, and an object thereof is to provide an indium oxide-based system capable of forming a thin line having a small narrow width, good linearity, and a desired width due to etching even without containing hydrogen chloride. A useful etchant composition for layer etching.

Furthermore, the object of the present invention is to provide a fine width with a small width due to etching, a small width at the upper part of a thin line, and a desired width can be suppressed even if hydrogen chloride is not contained. Even if the etching treatment is continued even after the etching between thin lines is completed, the etching solution composition in which the thin lines become thinner can be suppressed. Another object of the present invention is to provide an etching method using the above-mentioned etching solution composition.

The present inventors have made intensive studies in order to solve the above problems, and found that an etching solution composition containing a specific component can solve the above problems, and thus completed the present invention.

That is, the etching solution composition provided according to the present invention is an etching solution composition for etching an indium oxide-based layer, and contains: (A) hydrogen peroxide 0.01 to 15% by mass; (B) sulfuric acid 1 to 40% by mass; (C) (C-1) 0.01 to 10% by mass of the amido compound represented by the following general formula (1), or (C-2) 0.01 to 20% by mass of the amino acid compound; and water.

(In the above general formula (1), R ¹ , R ² , and R ³ each independently represent hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or may be carbon An alkyl group having 1 or 2 atoms is substituted with an aryl group having 6 to 8 carbon atoms).

The amino acid compound is preferably at least one selected from the group consisting of glutamic acid, a compound represented by the following general formula (2), and salts thereof. The amino acid compound is preferably at least one selected from the group consisting of glutamic acid, tyrosine, and phenylalanine.

(In the above general formula (2), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; R ² represents a hydrogen atom, a hydroxyl group, a halogen atom, or a nitro group; and A represents a carbon atom of 1 to 4 (Alkanediyl groups; n is a value from 1 to 5)

In the present invention, it is preferable to further contain (D) a halide ion supply source.

Furthermore, the etching method according to the present invention includes the step of etching the indium oxide-based layer using the above-mentioned etching solution composition.

According to the present invention, it is possible to provide an etchant composition for etching an indium oxide-based layer that can form a thin line having a small narrow width, a good linearity, and a desired width even if it does not contain hydrogen chloride, and has a desired width.

Furthermore, the present invention can provide a thin line with a small width due to etching, a defect in the upper part of the thin line that is suppressed, and a desired width can be formed. Even if the etching process is continued after the thin line is finished, the thin line can be suppressed from becoming thinner. Etching solution composition. The etching solution composition of the present invention can achieve the above-mentioned effects even when the indium oxide-based layer and the metal-based layer are collectively etched. Therefore, the etchant composition of the present invention is more suitable as an etchant for collectively etching a multilayer body composed of an indium oxide-based layer and a metal-based layer. Moreover, according to this invention, the etching method using the said etching liquid composition is provided.

Hereinafter, embodiments of the present invention will be specifically described. The term "etching" as used in this specification refers to a plastic forming or surface processing technique that utilizes corrosive effects such as chemicals. Specific uses of the etching solution composition of the present invention include, for example, a remover, a surface smoothing agent, a surface roughening agent, a pattern-forming agent, a cleaning solution with a small amount of components attached to a substrate, and the like. The etching solution composition of the present invention is more suitable as a removing agent because the removal rate of the layer containing indium oxide is fast. Moreover, if it is used for formation of a fine-shaped pattern having a three-dimensional structure, a pattern of a desired shape such as a rectangle can be obtained, and therefore it is more suitable as a pattern-forming agent.

The "indium oxide-based layer" in this specification is lifted before the layer containing indium oxide, and the rest is not particularly limited. The "indium oxide-based layer" is a collective term for a layer composed of one or more types selected from indium oxide, indium-tin oxide, and indium-zinc oxide, for example.

The "metal-based layer" in this specification is lifted before a layer made of a metal, and the rest is not particularly limited. The "metal layer" is a metal layer such as copper, nickel, titanium, chromium, silver, molybdenum, platinum, palladium, or a metal alloy represented by CuNi, CuNiTi, NiCr, Ag-Pd-Cu, etc.1 A collective term for layers composed of more than one species.

When the etching solution composition of the present invention is used to collectively perform an etching treatment on a laminated body of an indium oxide-based layer and a metal-based layer, the metal-based layer preferably contains copper in an amount of 10% by mass or more. Electrical layer. Examples of the conductive layer containing copper in an amount of 10% by mass or more include a conductive layer formed using metallic copper, or a conductive layer formed using copper alloys such as CuNi, CuNiTi, NiCr, and Ag-Pd-Cu. In addition, when the indium oxide-based layer is a layer containing indium-tin oxide, and the metal-based layer contains a layer of copper in an amount of 10% by mass or more, the required thin line can be formed with a higher precision and the etching speed can be higher. Also fast, so better.

The etching solution composition of the present invention contains (A) hydrogen peroxide (hereinafter also referred to as "(A) component"). The concentration of the component (A) in the etchant composition is in the range of 0.01 to 15% by mass. If the concentration of the component (A) is less than 0.01% by mass, the etching rate will be too slow, and the productivity will be significantly reduced. On the other hand, if the concentration of the component (A) exceeds 15% by mass, the etching rate will be too fast, making it difficult to control the etching rate. (A) The component concentration is preferably in the range of 0.1 to 12% by mass, and more preferably in the range of 1 to 10% by mass.

The etching solution composition of the present invention contains (B) sulfuric acid (hereinafter also referred to as "(B) component"). The concentration of the component (B) in the etchant composition is in the range of 1 to 40% by mass. If the concentration of the component (B) is less than 1% by mass, the etching rate will be too slow and productivity will decrease. On the other hand, if the concentration of the component (B) exceeds 40% by mass, the etching rate will be too fast, the etching rate will be difficult to control, or the components around the object to be etched, the photoresist, and the like may be deteriorated. (B) The component concentration is preferably in the range of 5 to 30% by mass, and more preferably in the range of 10 to 25% by mass.

The etching solution composition of the present invention contains: (C) (C-1) the amidine compound represented by the following general formula (1) (hereinafter also referred to as "(C-1) component"), or (C-2 ) Amino acid compound (hereinafter also referred to as "(C-2) component"). In addition, the components (C-1) and (C-2) are collectively recorded as "(C) ingredient".

In the general formula (1), R ¹ , R ² , and R ³ each independently represent hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or a carbon number 1 or 2 alkyl substituted aryl groups having 6 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, second butyl, third butyl, isobutyl, pentyl, and isopentyl. , Third pentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, third heptyl, n-octyl Group, isooctyl, third octyl, 2-ethylhexyl and the like.

Examples of alkenyl systems having 2 to 8 carbon atoms include vinyl, 1-methylvinyl, 2-methylvinyl, propenyl, butenyl, isobutenyl, pentenyl, hexenyl, and heptyl Alkenyl, octenyl, etc.

Examples of aryl groups having 6 to 8 carbon atoms substituted with alkyl groups having 1 or 2 carbon atoms include phenyl, 2-methylphenyl, 3-methylphenyl, and 4-methylphenyl. , 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl , 3,5-dimethylphenyl, etc.

Preferred specific examples of the amidine compound represented by the general formula (1) include, for example, formazan Amine, acetamidine, acetamidine propionate, acetamidine butyrate, N, N-dimethylformamide, N-methylformamide, N, N-diethylformamide, methacrylamide Amine, acrylamide, N-phenylformamide, benzamide, N-methylacetamide, N, N-dimethylacetamide and the like. Among these, when formamidine is used, the width (difference) between the width of the photoresist pattern and the width of a thin line formed by etching becomes smaller, and the linearity of the formed thin line is better, which is preferable.

The concentration of the (C-1) component in the etchant composition is in the range of 0.01 to 10% by mass. When the concentration of the component (C-1) is less than 0.01% by mass, the linearity of the thin line formed by the etching is reduced. On the other hand, if the concentration of the (C) -1 component exceeds 10% by mass, the etching rate will be too slow, resulting in a significant decrease in productivity. (C-1) The component concentration is preferably in the range of 0.05 to 5% by mass, and more preferably in the range of 0.1 to 1% by mass.

As the amino acid compound, any compound having one or more amine groups and one carboxyl group may be used, and a known general amino acid compound can be used. Specific examples of the amino acid compound include, for example, glycine, alanine, valine, leucine, serine, phenylalanine, tryptophan, glutamic acid, asparagine Acid, lysin, arginine, histidine, tyrosine, methionine, 4-chlorophenylalanine, 4-bromophenylalanine, 4-nitrophenylalanine, 3- (3,4-dihydrophenyl) alanine, α-methylphenylalanine, and salts thereof and the like. Examples of the salt system include alkali metal salts and ammonium salts. These amino acid compounds can be used alone or in combination of two or more.

The amino acid compound is preferably at least one selected from the group consisting of glutamic acid, a compound represented by the following general formula (2), and salts thereof. By containing these amino acid compounds in the etchant composition, the etching place for the indium oxide-based layer can be further reduced. The narrow width of the formed fine lines can efficiently form a fine line of a desired width. In addition, it is more effective to suppress the occurrence of defects in the upper part of the thin wires, and even if the etching process is continued after the etching between the thin wires is completed, the deterioration of the thin wires can be more effectively suppressed, which is preferable. As the particularly preferred amino acid compound, at least one selected from the group consisting of glutamic acid, tyrosine, and phenylalanine is used.

In the general formula (2), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. Examples of the hydrocarbon group having 1 to 4 carbon atoms include methyl, ethyl, propyl, butyl, second butyl, and third butyl.

In the general formula (2), R ² represents a hydrogen atom, a hydroxyl group, a halogen atom, or a nitro group. Examples of the halogen atom system include a fluorine atom, a chlorine atom, and a bromine atom.

In the general formula (2), A is an alkanediyl group having 1 to 4 carbon atoms. Examples of the alkanediyl system having 1 to 4 carbon atoms include methylene, ethylidene, and butylene.

In general formula (2), if (i) R ¹ is a hydrogen atom or a methyl group; (ii) R ² is a hydrogen atom or a hydroxyl group; or (iii) A is a methylene group, the indium oxide-based layer can be further reduced. The narrow width of the thin line formed by the etching process can form the thin line with a desired width efficiently. In addition, it is more effective to suppress the occurrence of defects in the upper part of the thin wires, and even if the etching process is continued after the etching between the thin wires is completed, the deterioration of the thin wires can be more effectively suppressed, which is preferable. In general formula (2), n is preferably 1 or 2.

The concentration of the (C-2) component in the etchant composition is in the range of 0.01 to 20% by mass. When the concentration of the component (C-2) is less than 0.01% by mass, the narrow width of the thin line formed by etching the indium oxide-based layer is increased. On the other hand, even if the concentration of the (C-2) component exceeds 20% by mass, the effect obtained by blending the (C-2) component cannot be improved. (C-2) The component concentration is preferably in the range of 0.05 to 15% by mass, and more preferably in the range of 0.1 to 10% by mass.

The etching solution composition of this invention contains water as an essential component other than (A) component, (B) component, and (C) component. In the etching solution composition of the present invention, as the components other than (A) component, (B) component, (C) component, and water, known additives may be blended within a range that does not impair the effects of the present invention. Examples of the additive system include a stabilizer of an etching solution composition, a solubilizing agent for each component, a defoaming agent, a pH adjusting agent, a specific gravity adjusting agent, a viscosity adjusting agent, a wettability improving agent, a chelating agent, an oxidizing agent, and a reducing agent. , Surfactants and so on. The concentration of these additives is generally in the range of 0.001 to 50% by mass.

Chelating agents can be exemplified by ethylenediaminetetraacetic acid, ethylenediaminetriaminepentaacetic acid, ethylenediaminetetraaminehexaacetic acid, tetraethyleneethylenepentamineamineacetate, pentaethyleneethylenehexaamineoctaacetate, nitrogen triacetate And amine carboxylic acid chelating agents such as alkali metal (preferably sodium) salts; hydroxyethylene diphosphonic acid, azotrimethylenephosphonic acid, phosphinobutanetricarboxylic acid, and the like Phosphonic acid-based chelating agents such as alkali metal (preferably sodium) salts; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, fumaric acid , Malic acid, tartaric acid, citric acid, such anhydrides, and alkali metal (preferably sodium) salts such as dibasic acids A compound, or a mono- or dianhydride dehydrated from a dicarboxylic acid compound or more. The concentration of these chelating agents generally ranges from 0.01 to 40% by mass.

When the etching rate is fast, it is preferable to use a reducing agent as an additive. Specific examples of the reducing agent include copper chloride, ferrous chloride, copper powder, and silver powder. The concentration of these reducing agents generally ranges from 0.01 to 10% by mass.

The etchant composition of the present invention preferably further contains (D) a halide ion supply source (hereinafter also referred to as "(D) component"). For example, when a thin line is formed by etching, by further containing the component (D), the difference (deviation) between the width of the photoresist pattern and the width of the thin line formed by etching can be further reduced.

Examples of the halide ion system supplied by the halide ion supply source include chloride ion, bromide ion, and iodide ion. As the halide ion supply source, for example, a water-soluble salt containing a halide ion can be used. Specific examples of the water-soluble salt containing a halide ion include halide salts such as sodium chloride and potassium chloride; ammonium chloride and the like. Among these, if a halide salt is used, etching can be performed at a better speed, so it is a better, more preferably alkali chloride salt, and particularly preferably sodium chloride.

The concentration of the (D) component in the etchant composition is preferably in the range of 0.00001 to 0.1% by mass. If the concentration of the (D) component is less than 0.00001% by mass, the effect of blending the (D) component may not be obtained. On the other hand, even if the concentration of the (D) component exceeds 0.1% by mass, the effect of blending the (D) component cannot be further improved. (D) The component concentration is more preferably in the range of 0.0001 to 0.01% by mass.

The etching method of the present invention includes a step of etching the indium oxide-based layer using the above-described etching solution composition of the present invention. By using the etchant composition of the present invention, it is possible to collectively etch a multilayer body composed of an indium oxide-based layer and a metal-based layer. The indium oxide-based layer system constituting the laminated body may be one layer, or may be two or more layers. In addition, the metal-based layer constituting the laminated body may be one layer, or may be two or more layers. The multilayer system can be configured with the metal-based layer on the upper layer of the indium oxide-based layer, or on the lower layer, or on both the upper and lower layers. Alternatively, the indium oxide-based layer and the metal-based layer may be alternately laminated.

The method of collectively performing etching on the indium oxide-based layer or the laminated body of the indium oxide-based layer and the metal-based layer is not particularly limited, and a general etching method can be used. For example, the etching method is performed according to an immersion method, a spray method, or a rotary method. For example, when using a dipping etching method to etch a substrate on which a Cu / ITO layer is formed on a PET substrate, the substrate can be dipped in an etchant composition under appropriate etching conditions and then pulled up. The Cu / ITO layer on the PET substrate is collectively etched.

The etching conditions of the immersion etching method are not particularly limited, and may be arbitrarily set according to the shape, film thickness, and the like of the substrate (the object to be etched). For example, the etching temperature is preferably 10 to 60 ° C, and more preferably 20 to 40 ° C. The temperature of the etchant composition rises due to the heat of reaction. Therefore, if necessary, the temperature of the etching solution composition may be maintained within the above-mentioned range, and the temperature may be controlled by a known method. The etching time is not particularly limited as long as it is sufficient time to complete the etching. For example, when the wiring of an electronic circuit substrate is manufactured, if the film thickness is about 5 to 500 nm, etching can be performed for about 10 to 600 seconds according to the above temperature range.

When the spray-type etching method is used to etch a substrate on which a Cu / ITO layer is formed on a PET substrate, Cu / ITO on the PET substrate can be sprayed on the substrate by spraying the etchant composition on the substrate under appropriate conditions. The layer is etched.

The etching conditions of the spray etching method are not particularly limited, and may be arbitrarily set in accordance with the shape, film thickness, etc. of the body to be etched. For example, the spraying condition can be selected from the range of 0.01 to 1.0 MPa, preferably 0.02 to 0.5 MPa, and more preferably 0.05 to 0.2 MPa. The etching temperature is preferably 10 to 60 ° C, and more preferably 20 to 40 ° C. The temperature of the etchant composition rises due to the heat of reaction. Therefore, if necessary, the temperature of the etching solution composition may be maintained within the above-mentioned range, and the temperature may be controlled by a known method. The etching time is not particularly limited as long as it is sufficient time to complete the etching. For example, when the wiring of the electronic circuit substrate is manufactured, if the film thickness is about 5 to 500 nm, it is only necessary to perform etching in the above temperature range for about 5 to 600 seconds.

In the etching method of the present invention, in order to restore the performance of the etching solution composition that is degraded by repeated etching, it is preferable to further include the step of adding a supplementary liquid to the etching solution composition. For example, in the case of the automatic control etching method described above, if a replenisher is installed in the etching device in advance, the replenisher can be added to the etchant composition. As the replenishing liquid system, for example, an aqueous solution containing (A) component, (B) component, (C) component and water; or an aqueous solution containing (C) component and water can be used. The concentration of each component in the aqueous solution (supplementary liquid) may be, for example, about 3 to 20 times the concentration of each component in the etching solution composition. In addition, as necessary, the above-mentioned respective components contained in an essential component or an arbitrary component contained in the etching solution composition of the present invention may be added as necessary.

The etching solution composition of the present invention and the etching method using the etching solution composition can be applied to electrodes or wirings mainly used for liquid crystal displays, plasma displays, touch panels, organic EL, solar cells, lighting appliances, etc. During processing.

[Example]

Hereinafter, the present invention will be described in detail using examples and comparative examples, but the present invention is not limited by these.

<Etching liquid composition (1)> (Examples I-1 to 12)

Using the amidine compound shown in Table 1, the components were mixed so that each component became the formulation shown in Table 2 to obtain an etchant composition (Examples I-1 to 12). In addition, water was prepared so that the total components would be 100% by mass.

(Comparative Examples I-1 to 5)

Each component was mixed so that each component might become the formulation shown in Table 3, and the etchant composition was obtained (comparative examples I-1 to 5). In addition, water was prepared so that the total components would be 100% by mass.

<Etching method (1)> (Example I-13 ~ 24)

A photoresist pattern having a width of 30 μm and an opening of 30 μm was formed on a glass substrate in which a ITO layer (15 nm) and a Cu layer (400 nm) were sequentially laminated, and a positive liquid photoresist was used. The photoresist pattern-formed substrate was cut into a length of 20 mm × width of 20 mm to obtain a test piece. With respect to the obtained test piece, the etching solution composition of Examples I-1 to 12 was used, and the etching treatment was performed by dipping at 35 ° C. for 1 minute to form a thin line.

(Comparative Examples I-6 to 10)

A photoresist pattern having a width of 30 μm and an opening of 30 μm was formed on a glass substrate in which a ITO layer (15 nm) and a Cu layer (400 nm) were sequentially laminated, and a positive liquid resist was used. The photoresist pattern-formed substrate was cut into a length of 20 mm × width of 20 mm to obtain a test piece. With respect to the obtained test piece, an etching solution composition of Comparative Examples I-1 to 5 was used, and an etching treatment was performed by dipping at 35 ° C. for 1 minute to form a thin line.

<Evaluation (1)>

Using a laser microscope, the linearity of the thin line and the deviation between the width of the photoresist pattern and the width of the thin line were evaluated. Regarding the linearity of the thin line, a thin line snakewalker that can be confirmed is rated as "-", and a thin line snakewalker that cannot be confirmed is rated as "+". Regarding the deviation between the width of the photoresist pattern and the width of the thin line, the absolute value “L ¹ ” of the difference between the width of the photoresist pattern before the etching process and the upper width of the formed thin line was calculated from the following formula (A), and Perform evaluation. When the value of "L ¹ " is "0", it means that the width of the photoresist pattern before the etching process is the same as the width of the formed thin line, and a thin line having a desired width is formed. On the other hand, the larger the value of "L ¹ ", the larger the difference between the width of the photoresist pattern before the etching process and the width of the formed thin line means that the thinner the required width cannot be formed. The evaluation results are shown in Table 4.

L ¹ = | (width of the photoresist pattern before the etching process)-(width of the upper part of the formed thin line) | ... (A)

From the results shown in Table 4, it was found that all of Examples I-13 to 24 formed thin lines with good linearity. In addition, the values of "L ¹ " in Examples I-13 to 24 are smaller than those in Comparative Examples I-1 to 5, and it is possible to form a thin line with a desired width. Among Examples I-13 to 19, the values of "L ¹ " of Examples I-13, I-14, and I-16 were particularly small. In addition, Examples I-20 to 24 use the etching solution composition of Examples I-8 to 12 containing the (D) component, compared to Examples I-13 to 19 using the embodiment without the (D) component. It was found that the etching solution composition of I-1 to 7 reduced the "L ¹ " value by about 50%.

<Etching liquid composition (2)> (Examples II-1 to 9)

Using the amino acid compounds shown in Table 5, each component was mixed so that it might become a formulation shown in Table 6, and the etchant composition was obtained (Example II-1-9). In addition, water was prepared so that the total components would be 100% by mass.

(Comparative Examples II-1 to 5)

Each component was mixed so that it might become a formulation shown in Table 7, and the etchant composition was obtained (comparative examples II-1 to 5). In addition, water was prepared so that the total components would be 100% by mass.

<Etching method (2)> (Examples II-10 to 18)

A photoresist pattern with a width of 10 μm and an opening of 10 μm was formed on a glass substrate in which a ITO layer (15 nm) and a Cu layer (400 nm) were sequentially laminated, and a positive liquid photoresist was used. The photoresist pattern-formed substrate was cut into a length of 20 mm × width of 20 mm to obtain a test piece. The obtained test piece was subjected to pattern etching (etching treatment) by a spray method using the etching solution composition of Examples II-1 to 9 under the conditions of 35 ° C. and a spray pressure of 0.05 MPa. The etching process is performed until it is visually confirmed that there is no residue between wirings. In addition, the "optimal etching time" in this specification means "an etching process time until there is no residue between wirings."

(Comparative Examples II-6 to 10)

Except that the etching solution compositions of Comparative Examples II-1 to 5 were used, pattern etching was performed by the spray method in the same manner as in Examples II-10 to 18 described above.

<Evaluation (2)>

Using a laser microscope, the state of the thin line and the deviation between the width of the photoresist pattern and the width of the thin line were evaluated. The state of the thin line was evaluated by confirming the presence or absence of a length of 3 μm or more in the corner of the thin line. Specifically, a person who cannot confirm a length defect of 3 μm or more is rated as “+”, and a person who can confirm a length defect of 3 μm or more is rated as “−”. Further, regarding the deviation between the width of the photoresist pattern and the width of the thin line, the absolute value “L ¹ ” of the width of the photoresist pattern before the etching process and the upper width of the formed thin line was calculated and evaluated. When the value of "L ¹ " is "0", it means that the width of the photoresist pattern before the etching process is the same as the width of the formed thin line, and a thin line having a desired width is formed. On the other hand, the larger the value of "L ¹ ", the larger the difference between the width of the photoresist pattern before the etching process and the width of the formed thin line means that the thinner the required width cannot be formed. Then, a case where the value of "L ¹ " is less than 3 µm is rated as "+", and a case where the value of "L ¹ " is 3 µm or more is rated as "-". The evaluation results are shown in Table 8.

From the results shown in Table 8, it was found that in Examples II-10 to 18, no defect having a length of 3 μm or more was confirmed, and the fine wire condition after the etching treatment was good. It was also found that the values of "L ¹ " in Examples II-10 to 18 were all less than 3 µm. From the above, it is known that if the etching solution composition of the present invention is used, even if the indium oxide-based layer and the metal-based layer are collectively subjected to an etching treatment, defects at the upper portion of the thin line can be suppressed, and a thin line having a desired width can be formed.

<Etching method (3)> (Examples II-19 to 27)

Except that the etching process time was set to twice the optimum etching time, the pattern etching was performed by the spray method in the same manner as in the aforementioned Examples II-10 to 18.

(Comparative Examples II-11 to 15)

Except that the etching solution compositions of Comparative Examples II-1 to 5 were used, pattern etching was performed by the spray method in the same manner as in Examples II-19 to 27 described above.

<Evaluation (3)>

"L ¹ " was calculated using a laser microscope, and the deviation between the width of the photoresist pattern and the width of the thin line was evaluated. The case where the value of "L ¹ " is less than 5 µm is rated as "++", the case where the value of "L ¹ " is 5 to 10 µm is rated as "+", and the case where the value of "L ¹ " exceeds 10 µm is rated as "-"". The evaluation results are shown in Table 9.

It is known from the results shown in Table 9 that, although Examples II-19 to 27 were subjected to an etching treatment that significantly exceeded the optimal etching time, a thin line of a desired width was formed, and thus the process range was wide. Among the examples II-19 to 24, since the fineness of the fine lines can be significantly suppressed, it is known that the etchant composition systems of the examples II-1 to 6 belong to a particularly excellent etchant.

Claims (5)

An etching solution composition is used for etching an indium oxide-based layer, and contains: (A) 0.01 to 15% by mass of hydrogen peroxide; (B) 1 to 40% by mass of sulfuric acid; (C) (C-1) 0.01 to 10% by mass of the amido compound represented by the following general formula (1), or 0.01 to 20% by mass of the (C-2) amino acid compound; and water;

(In the above general formula (1), R ¹ , R ² , and R ³ each independently represent hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or may be carbon An alkyl group having 1 or 2 atoms is substituted with an aryl group having 6 to 8 carbon atoms). The etching solution composition according to claim 1, wherein the amino acid compound is at least one selected from the group consisting of glutamic acid, a compound represented by the following general formula (2), and salts thereof;

(In the above general formula (2), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; R ² represents a hydrogen atom, a hydroxyl group, a halogen atom, or a nitro group; and A represents a carbon atom of 1 to 4 Alkanediyl; n is a value from 1 to 5). The etching solution composition according to claim 1 or 2, wherein the amino acid compound is at least one selected from the group consisting of glutamic acid, tyrosine, and phenylalanine. The etching solution composition according to claim 1, further comprising (D) a halide Ion supply. An etching method includes a step of etching an indium oxide-based layer using the etching solution composition of any one of claims 1 to 4.