Etching liquid composition, etching method and method for producing base material

Abstract

The present invention provides an etching liquid composition which is capable of sufficiently etching a copper-containing layer in the depth direction, while sufficiently suppressing side etching.　The present invention specifically provides an etching liquid composition which is used for the purpose of etching a copper-containing layer, and which is an aqueous solution that contains (A) a compound represented by general formula (1) (in general formula (1), each of R1 and R2 independently represents a hydrogen atom, an amino group, a thiol group, a phenyl group, or a carboxy group, provided that in cases where one of R1 and R2 is a hydrogen atom, the other is a thiol group, a phenyl group, or a carboxy group), (B) at least one component that is selected from the group consisting of a cupric ion and a ferric ion, (C) an acid, and water.

Description

Etching solution composition, etching method, and method for manufacturing substrate

[0001] The present invention relates to an etching solution composition containing specific components, an etching method using the same, and a method for manufacturing a substrate.

[0002] Known circuit formation methods for printed circuit boards, semiconductor package boards, and the like include an additive method in which a circuit pattern is added to a substrate later, and a subtractive method in which unnecessary portions of a metal foil on a substrate are removed to form a circuit pattern. Currently, etching, a subtractive method with low manufacturing costs, is generally used to manufacture printed circuit boards. In addition, with the recent trend toward higher performance and smaller size of electronic devices, there is a demand for finer patterns on printed circuit boards, and progress is being made in the development of etching solutions capable of forming fine patterns on substrates.

[0003] For example, Patent Document 1 discloses an etching solution capable of etching copper, which contains copper chloride, hydrochloric acid, and 5-amino-1H-tetrazole, 1H-tetrazole, or 5-methyl-1H-tetrazole. Patent Document 2 discloses an etching solution for a nickel-containing layer, which contains iron chloride, hydrogen chloride, and 5-aminotetrazole or benzotriazole.

[0004] JP 2021-116449 A JP 2018-178142 A

[0005] However, the etching solutions disclosed in Patent Documents 1 and 2 are unable to etch with high anisotropy, that is, are unable to etch sufficiently in the depth direction while sufficiently suppressing side etching, and therefore have the problem of being unable to form a fine pattern with the desired dimensional accuracy.

[0006] Therefore, the present invention aims to provide an etching solution composition that can sufficiently etch a copper-containing layer in the depth direction while sufficiently suppressing side etching. The present invention also aims to provide an etching method and a method for manufacturing a substrate using the etching solution composition.

[0007] As a result of extensive research into obtaining the above etching solution composition, the present inventors discovered that a composition containing specific components can solve the above problems, and thus arrived at the present invention.

[0008] That is, according to the present invention, there is provided an etching solution composition to be used for etching a copper-containing layer, which is an aqueous solution containing (A) a compound represented by the following general formula (1), (B) at least one component selected from the group consisting of cupric ions and ferric ions, (C) an acid, and water:

[0009] (In the general formula (1), R １ and R ２ each independently represents a hydrogen atom, an amino group, a thiol group, a phenyl group, or a carboxy group. １ and R ２ When one of the groups is a hydrogen atom, the other is a thiol group, a phenyl group, or a carboxy group.

[0010] The present invention also provides an etching method comprising the step of etching a copper-containing layer using the above-described etching solution composition.

[0011] Furthermore, according to the present invention, there is provided a method for manufacturing a substrate, which comprises the step of etching a copper-containing layer using the above-mentioned etching solution composition.

[0012] According to the present invention, an etching solution composition capable of sufficiently etching a copper-containing layer in the depth direction while sufficiently suppressing side etching can be provided. Furthermore, according to the present invention, an etching method and a method for manufacturing a substrate using the etching solution composition can be provided.

[0013] FIG. 10 is a cross-sectional view schematically showing the test substrate after etching.

[0014] An etching solution composition according to one embodiment of the present invention (hereinafter sometimes referred to as "the composition") is an aqueous solution containing: component (A): a compound represented by general formula (1) (hereinafter also simply referred to as "component (A)"), component (B): at least one component selected from the group consisting of cupric ions and ferric ions (hereinafter also simply referred to as "component (B)"), component (C): an acid (hereinafter also simply referred to as "component (C)"), and water.

[0015] The present composition is an etching solution composition used for etching a copper-containing layer. The copper-containing layer may include a layer containing at least one selected from the group consisting of copper and copper alloys. Examples of copper alloys include copper-silver alloys, copper-titanium alloys, copper-beryllium alloys, copper-nickel alloys, copper-iron alloys, and copper-aluminum alloys. In particular, the present composition is suitable as an etching solution composition used for etching a layer containing at least one selected from the group consisting of copper, copper-titanium alloys, copper-beryllium alloys, copper-nickel alloys, and copper-iron alloys. Furthermore, the present composition is preferably used for etching at least one layer selected from the group consisting of copper layers and copper alloy layers, and the copper-containing layer to be etched is more preferably a copper alloy layer. The copper alloy is more preferably at least one selected from the group consisting of copper-titanium alloys, copper-beryllium alloys, copper-nickel alloys, and copper-iron alloys. In particular, the present composition is particularly suitable as an etching solution composition used for etching copper-titanium alloys.

[0016] As used herein, "etching" refers to a plastic shaping or surface processing technique that utilizes the corrosive action of chemicals or the like. Specific uses of the present composition include, for example, removers, surface smoothing agents, surface roughening agents, pattern-forming agents, and cleaning solutions for components adhering in trace amounts to a substrate. When the present composition is used to form a finely shaped pattern having a three-dimensional structure, a pattern of a desired shape, such as a rectangle, can be obtained. Therefore, the present composition is suitable for use as a pattern-forming agent. Furthermore, since the present composition has a high removal rate for copper-containing layers, it can also be suitable for use as a remover.

[0017] The component (A) is a compound represented by the following general formula (1): One type of component (A) can be used alone, or two or more types can be used in combination.

[0018] (In general formula (1), R １ and R ２ each independently represents a hydrogen atom, an amino group, a thiol group, a phenyl group, or a carboxy group. １ and R ２ When one of the groups is a hydrogen atom, the other is a thiol group, a phenyl group, or a carboxy group.

[0019] Preferred specific examples of the compound represented by general formula (1) include compounds represented by the following chemical formulas No. 1 to No. 13. In the following chemical formulas No. 1 to No. 13, "Ph" represents a phenyl group.

[0020]

[0021] Among the compounds represented by general formula (1), R １ is a hydrogen atom or an amino group. ２ Among them, compounds in which R in general formula (1) is an amino group or a thiol group are preferred. １ is a hydrogen atom or an amino group, and R ２is an amino group or a thiol group. That is, among Chemical Formulas No. 1 to No. 13, the compounds represented by Chemical Formulas No. 1, No. 4, and No. 5 are more preferred.

[0022] The component (A) is a compound represented by the general formula (1) R １ and R ２ are all amino groups, i.e., the compound represented by Chemical Formula No. 4 is more preferred. By using the compound represented by Chemical Formula No. 4 as component (A), it is possible to etch the copper-containing layer with even higher anisotropy. That is, it is possible to etch the copper-containing layer more sufficiently in the depth direction while more sufficiently suppressing side etching.

[0023] The content of component (A) in the composition is preferably 0.01 to 10 mass%. By having the content of component (A) in this range, it is possible to etch the copper-containing layer with higher anisotropy. From this perspective, the content of component (A) in the composition is more preferably 0.05 to 8 mass%, even more preferably 0.1 to 5 mass%, and particularly preferably 0.2 to 3 mass%. In this specification, the content (mass%) of a component in the composition refers to the content (concentration) of that component based on the total mass of the composition.

[0024] In the present composition, the mass ratio of component (A) to the total of component (A) and component (B), {(A) / ((A)+(B))}, is preferably 0.001 to 0.3. When the mass ratio {(A) / ((A)+(B))} is within the above range, the copper-containing layer can be etched with higher anisotropy. From this viewpoint, the mass ratio {(A) / ((A)+(B))} is more preferably 0.003 to 0.2, even more preferably 0.005 to 0.1, and particularly preferably 0.01 to 0.06.

[0025] Component (B) is a cupric ion (copper (II) ion, Cu ２＋ ) and ferric ions (iron (III) ions, Fe ３＋) is at least one component selected from the group consisting of: copper(II) ions and ferric ions. Component (B) may be used alone or in combination. By incorporating a copper(II) compound, cupric ions can be incorporated into the composition. That is, a copper(II) compound can be used as a source of cupric ions. Furthermore, by incorporating an iron(III) compound, ferric ions can be incorporated into the composition. That is, an iron(III) compound can be used as a source of ferric ions.

[0026] Examples of copper (II) compounds include copper (II) chloride, copper (II) bromide, copper (II) sulfate, and copper (II) hydroxide. Examples of iron (III) compounds include iron (III) chloride, iron (III) bromide, iron (III) iodide, iron (III) sulfate, iron (III) nitrate, and iron (III) acetate. These copper (II) compounds and iron (III) compounds can be used alone or in combination of two or more. Among these compounds, copper (II) chloride and iron (III) chloride are preferred, and copper (II) chloride is more preferred, because they allow for easy control of the etching rate and enable a sufficient etching rate.

[0027] The content of component (B) in the present composition is preferably 1 to 35% by mass. By having the content of component (B) within this range, the etching rate can be easily controlled and a sufficient etching rate can be achieved. From these viewpoints, the content of component (B) in the present composition is more preferably 3 to 30% by mass, even more preferably 5 to 25% by mass, and particularly preferably 10 to 20% by mass. When cupric ions or ferric ions are used alone, the concentration of component (B) refers to the concentration of cupric ions or the concentration of ferric ions. Furthermore, when cupric ions and ferric ions are used in combination (mixed), the concentration refers to the sum of the concentrations of cupric ions and ferric ions. For example, when the etching solution composition contains 10% by mass of copper(II) chloride, the concentration of component (B) in this etching solution composition is approximately 4.7% by mass. Furthermore, for example, when the etching solution composition contains 10 mass% copper(II) chloride and 10 mass% iron(III) chloride, the concentration of the component (B) in this etching solution composition is approximately 8.2 mass%.

[0028] Component (C) is an acid. Component (C) is preferably an inorganic acid because it easily dissolves component (A) and provides a sufficient etching rate. Among inorganic acids, at least one selected from the group consisting of hydrogen chloride, nitric acid, and sulfuric acid is more preferred, and hydrogen chloride is even more preferred.

[0029] The content of component (C) in the composition is preferably 1 to 35% by mass. By having the content of component (C) in this range, problems such as corrosion of device components are less likely to occur, and a sufficient etching rate can be achieved. From these viewpoints, the content of component (C) in the composition is more preferably 1.5 to 25% by mass, even more preferably 2 to 20% by mass, and particularly preferably 2.5 to 15% by mass.

[0030] In the present composition, the mass ratio of component (C) to the total of components (A) and (B) {(C) / ((A)+(B))}} is preferably 0.01 to 0.5. When the mass ratio {(C) / ((A)+(B))} is within the above range, problems such as corrosion of device components are unlikely to occur, and a sufficient etching rate can be achieved. From these viewpoints, the mass ratio {(C) / ((A)+(B))} is more preferably 0.03 to 0.4, even more preferably 0.05 to 0.3, and particularly preferably 0.1 to 0.3.

[0031] The present composition contains water as an essential component and is an aqueous solution in which each component is dissolved in water. The water used is preferably water from which ionic substances and impurities have been removed, such as ion-exchanged water, pure water, or ultrapure water. The water content in the present composition is preferably 20 to 80% by mass, more preferably 20 to 70% by mass, and even more preferably 30 to 60% by mass.

[0032] Since the present composition can etch with higher anisotropy, it is preferable that it further contains (D) a specific gravity adjuster. Examples of component (D) include calcium chloride, potassium chloride, magnesium chloride, and sodium chloride. These can be used alone or in combination of two or more. In one embodiment, the present composition preferably further contains (D) at least one specific gravity adjuster selected from the group consisting of calcium chloride, potassium chloride, magnesium chloride, and sodium chloride. Among component (D), potassium chloride and sodium chloride are more preferred, and sodium chloride is even more preferred.

[0033] The content of component (D) in the present composition is preferably 0.1 to 15 mass%. By having the content of component (D) in this range, it is possible to etch the copper-containing layer with higher anisotropy. From this viewpoint, the content of component (D) in the present composition is more preferably 0.3 to 13 mass%, even more preferably 0.5 to 10 mass%, and particularly preferably 1 to 5 mass%.

[0034] Since the composition of the present invention can be etched with higher anisotropy, the specific gravity is preferably 1.2 to 1.6, and more preferably 1.3 to 1.5.

[0035] The present composition may contain well-known additives and solvents as components other than the above-described components (A), (B), (C), and (D), and water, provided that the effects of the present invention are not impaired. Examples of additives include stabilizers for the etching solution composition, solubilizers for each component, pH adjusters, viscosity adjusters, wettability improvers, chelating agents, oxidizing agents, reducing agents, and surfactants. These additives may be used alone or in combination of two or more. The content of each of the above additives in the present composition is preferably within the range of 0.001 to 50% by mass, more preferably within the range of 0.001 to 40% by mass, and even more preferably within the range of 0.001 to 30% by mass.

[0036] Examples of pH adjusters include inorganic acids other than component (C), such as sulfuric acid and nitric acid, and their salts; water-soluble organic acids and their salts; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide, strontium hydroxide, and barium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; quaternary ammonium hydroxides such as tetramethylammonium hydroxide and choline; organic amines such as ethylamine, diethylamine, triethylamine, and hydroxyethylamine; ammonium carbonate; ammonium bicarbonate; ammonia; and the like. These pH adjusters can be used alone or in combination of two or more. The content of the pH adjuster may be determined so that the pH of the etching solution composition is the desired pH.

[0037] Examples of chelating agents include aminocarboxylic acid chelating agents such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, tetraethylenepentamineheptaacetic acid, pentaethylenehexamineoctaacetic acid, nitrilotriacetic acid, and alkali metal (preferably sodium) salts thereof; phosphonic acid chelating agents such as hydroxyethylidene diphosphonic acid, nitrilotrismethylenephosphonic acid, phosphonobutanetricarboxylic acid, and alkali metal (preferably sodium) salts thereof; and divalent or higher carboxylic acid compounds such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, malic acid, tartaric acid, citric acid, anhydrides thereof, and alkali metal (preferably sodium) salts thereof, as well as monoanhydrides and dianhydrides obtained by dehydration of divalent or higher carboxylic acid compounds. The content (concentration) of the chelating agent in the etching solution composition is preferably within the range of 0.01 to 40% by mass, more preferably within the range of 0.05 to 30% by mass.

[0038] As the surfactant, cationic surfactants and amphoteric surfactants can be used. Examples of cationic surfactants include alkyl(alkenyl)trimethylammonium salts, dialkyl(alkenyl)dimethylammonium salts, alkyl(alkenyl)pyridinium salts, alkyl(alkenyl)dimethylbenzylammonium salts, alkyl(alkenyl)isoquinolinium salts, dialkyl(alkenyl)morphonium salts, polyoxyethylene alkyl(alkenyl)amines, alkyl(alkenyl)amine salts, polyamine fatty acid derivatives, amyl alcohol fatty acid derivatives, benzalkonium chloride, and benzethonium chloride. Examples of amphoteric surfactants include carboxybetaine, sulfobetaine, phosphobetaine, amide amino acid, and imidazolinium betaine surfactants. The content (concentration) of the surfactant in the etching solution composition is preferably within the range of 0.001 to 10% by mass.

[0039] Examples of solvents that can be used include alcohol-based solvents, ketone-based solvents, and ether-based solvents. Examples of alcohol-based solvents include methanol, ethanol, diethylene glycol, isopropyl alcohol, and 2-ethylhexanol. Examples of ketone-based solvents include methyl acetate, ethyl acetate, and propyl acetate. Examples of ether-based solvents include tetrahydrofuran and methyl cellosolve.

[0040] An etching method according to one embodiment of the present invention includes a step of etching a copper-containing layer using the present composition (etching solution composition) described above. A method for manufacturing a substrate according to one embodiment of the present invention also includes a step of etching a copper-containing layer using the etching solution composition described above. Both the etching method according to this embodiment and the method for manufacturing a substrate can employ steps from well-known general etching methods, except for using the etching solution composition described above.

[0041] As the material to be etched, among copper-containing layers, a layer containing at least one selected from the group consisting of copper, copper-titanium alloy, copper-beryllium alloy, copper-nickel alloy, and copper-iron alloy is preferred. Among these, a layer of at least one copper alloy selected from the group consisting of copper-titanium alloy, copper-beryllium alloy, copper-nickel alloy, and copper-iron alloy is more preferred, and a copper-titanium alloy is even more preferred.

[0042] Specific etching methods that can be used include, for example, immersion and spraying. Etching conditions can be adjusted appropriately depending on the composition of the etching solution composition used and the etching method. Furthermore, various well-known methods, such as a batch method, a flow method, and an auto-control method based on the oxidation-reduction potential, specific gravity, or acid concentration of the etchant, may be used.

[0043] The etching conditions are not particularly limited and can be set arbitrarily depending on the shape and film thickness of the object to be etched. For example, the etching solution composition is preferably sprayed at 0.01 to 0.20 MPa, more preferably at 0.05 to 0.15 MPa. The etching temperature is preferably 10 to 50°C, more preferably 20 to 50°C. Since the temperature of the etching solution composition may rise due to the heat of reaction, the temperature may be controlled by known means as necessary so as to be maintained within the above temperature range. The etching time may be set to a time that allows the object to be etched to be sufficiently etched.

[0044] According to the etching method and the method for manufacturing a substrate using the above-mentioned etching solution composition, a fine pattern having high anisotropy can be formed, and thus a substrate having a copper-containing layer on which a fine pattern having high anisotropy is formed can be manufactured. Therefore, the etching solution composition can be suitably used for subtractive processes for packaging substrates, COF, and TAB applications that require a fine pitch, in addition to printed wiring boards.

[0045] As described above in detail, one embodiment of the present invention can have the following configurations. [1] An etching solution composition used for etching a copper-containing layer, the etching solution composition being an aqueous solution containing: (A) a compound represented by the general formula (1) above; (B) at least one component selected from the group consisting of cupric ions and ferric ions; (C) an acid; and water. [2] The etching solution composition according to the above item [1], wherein the content of the component (A) is 0.01 to 10 mass %, the content of the component (B) is 1 to 35 mass %, and the content of the component (C) is 1 to 35 mass %. [3] The etching solution composition according to the above item [1] or [2], wherein the copper-containing layer is a copper alloy layer. [4] The etching solution composition according to the above item [3], wherein the copper alloy is at least one selected from the group consisting of a copper-titanium alloy, a copper-beryllium alloy, a copper-nickel alloy, and a copper-iron alloy. [5] The etching solution composition according to any one of [1] to [4] above, wherein the source of the component (B) is at least one selected from the group consisting of copper(II) chloride and iron(III) chloride. [6] The etching solution composition according to any one of [1] to [5] above, wherein the mass ratio of the component (A) to the total of the components (A) and (B) {(A) / ((A) + (B))}} is 0.001 to 0.3. [7] The etching solution composition according to any one of [1] to [6] above, wherein the mass ratio of the component (C) to the total of the components (A) and (B) {(C) / ((A) + (B))}} is 0.01 to 0.5. [8] The etching solution composition according to any one of [1] to [7] above, further comprising (D) at least one specific gravity adjuster selected from the group consisting of calcium chloride, potassium chloride, magnesium chloride, and sodium chloride. [9] The etching solution composition according to [8] above, wherein the content of the component (D) is 0.1 to 15 mass %.

[10] An etching method comprising a step of etching a copper-containing layer using the etching solution composition according to any one of [1] to [9] above.

[11] A method for producing a substrate, comprising a step of etching a copper-containing layer using the etching solution composition according to any one of [1] to [9] above.

[0046] EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0047] The component (A) used in the examples and comparative examples is as follows: a-1: Compound represented by the above chemical formula No. 1 a-2: Compound represented by the above chemical formula No. 4 a-3: Compound represented by the above chemical formula No. 5

[0048] In addition, the following compounds a-4 to a-6 were prepared as comparative compounds for component (A): a-4: Comparative compound 1 a-5: Comparative compound 2 a-6: Comparative compound 3

[0049]

[0050] The sources of the component (B) used in the examples and comparative examples are as follows: b-1: copper(II) chloride b-2: iron(III) chloride

[0051] The components (C) used in the examples and comparative examples are as follows: c-1: Hydrochloric acid c-2: Nitric acid c-3: Sulfuric acid

[0052] The component (D) used in the examples and comparative examples is as follows: d-1: Sodium chloride

[0053] Example 1 (Examples 1-1 to 1-11) and Comparative Example 1 (Comparative Examples 1-1 to 1-5) Etching solution compositions No. 1 to 16 were obtained by mixing the component (A) or a comparative component thereof, a source of the component (B), the component (C), the component (D), and water so as to obtain the compositions shown in Table 1.

[0054] The type of component (B) shown in Table 1 represents the type of supply source of component (B) (b-1 supplying cupric ions, b-2 supplying ferric ions), and the content (mass%) of component (B) represents the content of component (B) (cupric ions, ferric ions) supplied from the supply source. When the amount of cupric ions supplied by b-1 (copper (II) chloride) in the etching solution composition is 10 mass%, 16 mass%, or 20 mass%, the content of copper (II) chloride is 21.2 mass%, 33.9 mass%, and 42.3 mass%, respectively. When the amount of ferric ions supplied by b-2 (iron (III) chloride) in the etching solution composition is 16 mass%, the content of iron (III) chloride is 46.5 mass%. The balance in the composition of the etching solution composition shown in Table 1 (the total composition of component (A) or its comparative component, the supply source of component (B), component (C), and component (D)) is water. Furthermore, the content of component (C) shown in Table 1 is the content as an acid, and for example, when component (C) is c-1, it is the content of hydrogen chloride.

[0055]

[0056] Example 2 (Examples 2-1 to 2-11) and Comparative Example 2 (Comparative Examples 2-1 to 2-5) A substrate was prepared by laminating a 75 μm thick copper-titanium alloy (titanium content: 3% by mass) layer on a polyimide resin substrate (hereinafter sometimes simply referred to as "resin substrate"). A photoresist pattern with a pitch width of 120 μm (line width: 70 μm (see line width 6 in FIG. 1 ), openings: 50 μm) was formed on the copper-titanium alloy layer of this substrate to prepare a test substrate. The prepared test substrate was wet-etched by spraying the prepared etching solution composition for 300 seconds under conditions of a treatment temperature of 45° C. and a treatment pressure of 0.10 MPa. The resist pattern was then removed using a stripper to form a pattern (fine lines).

[0057] <Evaluation> A laser microscope was used to confirm the presence or absence of thin line formation and residual film. Furthermore, a focused ion beam processing and observation device (JIB-4000, manufactured by JEOL Ltd.) was used to process the cross section of the thin line, and the cross section of the thin line was observed with a scanning electron microscope (SEM). Then, the thin line width was measured from the SEM image of the cross section of the thin line. Specifically, referring to FIG. 1 , which is a cross-sectional view schematically showing the test substrate after etching, the width (top width) 4 on the resist 2 side of the cross section of the etched copper alloy layer 1 (thin line of the copper-titanium alloy layer) was measured, which was smaller than the width (bottom width) 5 on the resin base 3 side. The evaluation results and measurement results of (1) to (3) below are shown in Table 2. The absence of residual film (remaining etched portion) means that sufficient etching was achieved in the depth direction, making disconnections and short circuits less likely to occur. Furthermore, the smaller the one-side side etch width, the more suppressed side etching was.

[0058] (1) Presence or absence of fine line formation If a fine line was formed, it was evaluated as "++", and if no fine line was formed, it was evaluated as "--". (2) Presence or absence of residual film If no residual film was present, it was evaluated as "++", and if a residual film was present, it was evaluated as "--". (3) One-side side etch width It was calculated using the following formula. The unit is "μm". However, if no fine line was formed, it was marked as "immeasurable" because the width of the top of the fine line could not be measured. "One-side side etch width" = {"resist line width" - "measured value of the width of the top of the fine line"} / 2

[0059]

[0060] As shown in Table 2, in Examples 2-1 to 2-11, the one-side side etch width was 11.3 μm or less, and it was possible to form fine patterns with excellent dimensional accuracy while suppressing the occurrence of residual films. Among these, in Examples 2-2 to 2-7 and 2-11, the one-side side etch width was 9.2 μm or less, and it was possible to form fine patterns with even better dimensional accuracy while suppressing the occurrence of residual films. In particular, in Examples 2-2 and 2-5, the one-side side etch width was 8.9 μm or less, and it was possible to form fine patterns with particularly excellent dimensional accuracy while suppressing the occurrence of residual films. Of these, in Example 2-2 in particular, the one-side side etch width was 8.8 μm, and it was possible to form fine patterns with the highest dimensional accuracy while suppressing the occurrence of residual films. On the other hand, in Comparative Examples 2-1 and 2-2, the one-side side etch width was 25.2 μm or more, and it was possible to form patterns with inferior dimensional accuracy compared to Examples 2-1 to 2-11. Furthermore, no pattern was formed in Comparative Examples 2-3 to 2-5. From the above results, according to one embodiment of the present invention, it is possible to provide an etching solution composition, an etching method, and a method for manufacturing a substrate that are capable of forming a fine pattern that is less likely to produce a residual film that can cause disconnection or short-circuiting, has a small one-side side etch width, and has high anisotropy and excellent dimensional accuracy.

[0061] Example 3 (Examples 3-1 to 3-3) and Comparative Example 3 (Comparative Examples 3-1 to 3-2) Instead of the substrate in which a copper-titanium alloy layer was laminated on a resin substrate used in Example 2, a substrate in which a 75 μm-thick copper-beryllium alloy layer (beryllium content: 2% by mass) was laminated on a polyimide resin substrate was prepared. Except for using this substrate, a test substrate was prepared by forming a photoresist on the copper-beryllium alloy layer of the substrate in the same manner as in Example 2. This test substrate was then wet-etched using the prepared etching solution composition, and the resist was then removed to form a pattern (thin line). Furthermore, the width 4 on the resist 2 side (width above the thin line) of the cross section of the etched copper alloy layer 1 (thin line of the copper-beryllium alloy layer) was measured in the same manner as in Example 2, and the above-described evaluations (1) to (3) were performed. The evaluation results and measurement results are shown in Table 3.

[0062]

[0063] Example 4 (Examples 4-1 to 4-3) and Comparative Example 4 (Comparative Examples 4-1 to 4-2) Instead of the substrate in which a copper-titanium alloy layer was laminated on a resin substrate used in Example 2, a substrate in which a 75 μm-thick copper-nickel alloy layer (nickel content: 3% by mass) was laminated on a polyimide resin substrate was prepared. Except for using this substrate, a test substrate was prepared by forming a photoresist on the copper-nickel alloy layer of the substrate in the same manner as in Example 2. This test substrate was then wet-etched using the prepared etching solution composition, and the resist was then removed to form a pattern (thin line). Furthermore, the width 4 on the resist 2 side (width above the thin line) of the cross section of the etched copper alloy layer 1 (thin line of the copper-nickel alloy layer) was measured in the same manner as in Example 2, and the above-described evaluations (1) to (3) were performed. The evaluation results and measurement results are shown in Table 4.

[0064]

[0065] Example 5 (Examples 5-1 to 5-3) and Comparative Example 5 (Comparative Examples 5-1 to 5-2) Instead of the substrate in which a copper-titanium alloy layer was laminated on a resin substrate used in Example 2, a substrate in which a 75 μm-thick copper-iron alloy layer (iron content: 3% by mass) was laminated on a polyimide resin substrate was prepared. Except for using this substrate, a test substrate was prepared by forming a photoresist on the copper-iron alloy layer of the substrate in the same manner as in Example 2. This test substrate was then wet-etched using the prepared etching solution composition, and the resist was then removed to form a pattern (thin line). Furthermore, the width 4 on the resist 2 side (width above the thin line) of the cross section of the etched copper alloy layer 1 (thin line of the copper-iron alloy layer) was measured in the same manner as in Example 2, and the above-described evaluations (1) to (3) were performed. The evaluation results and measurement results are shown in Table 5.

[0066]

[0067] 1: Copper alloy layer 2: Resist 3: Resin base 4: Width of upper part of fine line 5: Width of lower part of fine line 6: Line width of resist

Claims

1. An etching solution composition used for etching a copper-containing layer, the etching solution composition being an aqueous solution containing: (A) a compound represented by the following general formula (1); (B) at least one component selected from the group consisting of cupric ions and ferric ions; (C) an acid; and water. (In the general formula (1), R １ and R ２ each independently represents a hydrogen atom, an amino group, a thiol group, a phenyl group, or a carboxy group. １ and R ２ When one of the groups is a hydrogen atom, the other is a thiol group, a phenyl group, or a carboxy group.

2. The etching solution composition according to claim 1, wherein the content of said component (A) is 0.01 to 10 mass %, the content of said component (B) is 1 to 35 mass %, and the content of said component (C) is 1 to 35 mass %.

3. The etching solution composition according to claim 1 or 2, wherein the copper-containing layer is a copper alloy layer.

4. The etching solution composition according to claim 3, wherein the copper alloy is at least one selected from the group consisting of a copper-titanium alloy, a copper-beryllium alloy, a copper-nickel alloy, and a copper-iron alloy.

5. The etching solution composition according to claim 1 or 2, wherein the source of the component (B) is at least one selected from the group consisting of copper (II) chloride and iron (III) chloride.

6. The etching solution composition according to claim 1 or 2, wherein a mass ratio of the component (A) to the total of the component (A) and the component (B), {(A) / ((A)+(B))}, is 0.001 to 0.

3.

7. The etching solution composition according to claim 1 or 2, wherein a mass ratio of the component (C) to the total of the component (A) and the component (B), {(C) / ((A)+(B))}, is 0.01 to 0.

5.

8. The etching solution composition according to claim 1 or 2, further comprising (D) at least one specific gravity adjuster selected from the group consisting of calcium chloride, potassium chloride, magnesium chloride, and sodium chloride.

9. The etching solution composition according to claim 8, wherein the content of the component (D) is 0.1 to 15 mass %.

10. An etching method comprising the step of etching a copper-containing layer using the etching solution composition according to claim 1 or 2.

11. A method for manufacturing a substrate, comprising the step of etching a copper-containing layer with the etching solution composition according to claim 1 or 2.

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